CN111378168A

CN111378168A - Combined energy absorption method and application thereof

Info

Publication number: CN111378168A
Application number: CN201910000101.1A
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Weng Qiumei
Priority date: 2019-01-01
Filing date: 2019-01-01
Publication date: 2020-07-07

Abstract

The invention discloses a combined energy absorption method and application thereof, wherein the combined energy absorption method adopts a combined hybrid dynamic polymer containing boron-containing dynamic covalent bonds, other dynamic covalent bonds and optional hydrogen bonds to absorb energy. The combined hybrid dynamic polymer can be used for preparing dynamic polymer materials with wide controllable range, rich structure and various performances by introducing boron-containing dynamic covalent bonds with different dynamic properties, other dynamic covalent bonds and optional hydrogen bonds. The polymer material has the functions of absorbing, dissipating, dispersing and the like impact energy when being subjected to physical impact. The dynamic polymer is used as an energy absorption material for energy absorption, has the functions of damping, buffering, impact resistance protection, noise elimination, sound insulation, shock absorption and the like, and can be applied to the aspects of body protection of sports and daily life, body protection of military police, explosion prevention, air-drop and air-drop protection, automobile collision prevention, impact resistance protection of electronic and electric products and the like.

Description

Combined energy absorption method and application thereof

Technical Field

The invention relates to a combined energy absorption method, in particular to a combined energy absorption method based on a combined hybrid dynamic polymer formed by boron-containing dynamic covalent bonds, other dynamic covalent bonds and optional hydrogen bonds and application thereof.

Background

In daily life and actual production processes, a method or means is often needed to avoid or mitigate the influence caused by physical impact in the forms of impact, vibration, explosion, sound and the like, wherein the energy absorption material is widely applied to absorb energy, so that the physical impact is effectively protected. The materials for absorbing energy are mainly metals, polymers, composite materials and the like. The energy loss sources of the polymer material are mainly the following: 1. energy is absorbed by the phenomenon that polymers have a high dissipation factor near their glass transition temperature. In the method, because the material is near the glass-transition temperature, the mechanical property of the material is sensitive to the temperature change, and the mechanical property of the material is easy to change violently along with the change of the environmental temperature in the use process, which brings difficulty to the use; 2. the energy absorption is carried out by utilizing the processes of breaking chemical bonds such as covalent bonds and the like, generating cracks in the material and even breaking the whole material, and the like, in the processes, the breaking of the covalent bonds, the macroscopic cracks and the breaking can not be recovered, and the mechanical property of the material is reduced, and after one or a few times of energy absorption processes, the material must be replaced in time to maintain the original property; 3. by utilizing the deformation, particularly the internal friction energy absorption between molecular chain segments caused by the large deformation of the rubber state or the viscoelastic state of the polymer, the method usually needs the large deformation of the material to generate a remarkable effect, and after the material is deformed with high energy loss, the material can not be recovered to the original shape, can not be used continuously and needs to be replaced. The novel impact-resistant and energy-absorbing material is a novel material proposed in recent years, and the appearance of the novel impact-resistant and energy-absorbing material has important practical value for the selection of the material and the performance research thereof. The impact-resistant energy-absorbing material with different configurations has excellent mechanical, bearing, impact-resistant and energy-absorbing characteristics, and also has other functions of damping, vibration reduction, sound absorption and noise reduction, stimulation response and the like, so that the requirements of high and new technical fields such as aerospace, precise instruments, automobile industry and the like on the material are met.

Energy absorbing protective materials currently on the market rely primarily on elastomeric foams or relatively soft compressible materials as the energy absorbing material. When the material is applied to human body protection or precision instrument protection, the main defects are that the shock absorption performance is limited, when severe impact is applied, the common protective material cannot effectively dissipate impact energy, and strong impact force still acts on a human body or equipment, so that the human body is injured or the equipment is damaged. There is a need to develop a new energy absorption method, especially to use a polymer with a new energy absorption and loss mechanism to absorb energy, so as to solve the problems in the prior art.

Disclosure of Invention

Against this background, the present invention provides a combined energy absorbing method and its use based on a combined hybrid dynamic polymer containing at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and optionally hydrogen bonds. The combined hybrid dynamic polymer can show good dynamic reversibility, can absorb and dissipate energy through reversible breakage of dynamic covalent bonds and hydrogen bonds, endows the dynamic polymer with good impact resistance protection performance, and can also show stimulation responsiveness, thereby providing a novel combined energy absorption method.

The invention is realized by the following technical scheme:

the invention relates to an energy absorption method based on a combined hybrid dynamic polymer, which is characterized in that the combined hybrid dynamic polymer is provided and is used as an energy absorption material for energy absorption; wherein the combinatorial hybrid dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonds; the boron-containing dynamic covalent bond contains boron atoms in the dynamic structure composition, and comprises fifteen bonds of organic boron anhydride bonds, inorganic boron anhydride bonds, organic-inorganic boron anhydride bonds, saturated five-membered ring organic borate bonds, unsaturated five-membered ring organic borate bonds, saturated six-membered ring organic borate bonds, unsaturated six-membered ring organic borate bonds, saturated five-membered ring inorganic borate bonds, unsaturated five-membered ring inorganic borate bonds, saturated six-membered ring inorganic borate bonds, unsaturated six-membered ring inorganic borate bonds, organic borate monoester bonds, inorganic borate monoester bonds, organic borate silicone bonds and inorganic borate silicone bonds; wherein the other dynamic covalent bonds do not contain boron atoms in their dynamic structural composition and include, but are not limited to, dynamic sulfide bonds, dynamic diselenide bonds, dynamic selenazone bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, dynamic covalent bonds based on reversible free radicals, combinable exchangeable acyl bonds, dynamic covalent bonds induced by steric effects, reversible addition fragmentation chain transfer dynamic covalent bonds, dynamic siloxane bonds, dynamic silicon ether bonds, exchangeable dynamic covalent bonds based on alkyltriazolium, unsaturated carbon-carbon double bonds capable of olefin cross metathesis, unsaturated carbon-carbon double bonds capable of alkyne cross metathesis, triple addition dynamic covalent bonds, [2+2] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, mercapto-Michael addition dynamic covalent bonds, or mercapto-metathesis bonds, An amine alkene-Michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkylsulfonium bond; wherein the presence of said boron-containing dynamic covalent bonds, other dynamic covalent bonds, and optionally hydrogen bonds is a requirement for forming or maintaining a polymer structure.

According to a preferred embodiment (first structure) of the present invention, the combinatorial hybrid dynamic polymer is a non-crosslinked structure comprising at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond.

According to a preferred embodiment (second structure) of the present invention, the combined hybrid dynamic polymer is a non-crosslinked structure comprising at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and hydrogen bonds.

According to a preferred embodiment (third structure) of the present invention, the composite hybrid dynamic polymer comprises only one dynamic covalent crosslinking network, and at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond crosslink are contained in the crosslinking network at the same time, and the crosslinking degree of the dynamic covalent bond crosslinks is above the gel point. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof.

According to a preferred embodiment (fourth structure) of the present invention, the composite hybrid dynamic polymer comprises only one dynamic covalent crosslinking network, and the crosslinking network comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and hydrogen bond crosslinking, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point. In this embodiment, the crosslinking degree of boron-containing dynamic covalent bond crosslinking and the crosslinking degree of hydrogen bond crosslinking may be at least the gel point thereof or at most the gel point thereof.

According to a preferred embodiment (the fifth structure) of the present invention, the composite hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network, which comprises at least one boron-containing dynamic covalent bond crosslink and has a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network is more than the gel point.

According to a preferred embodiment (sixth structure) of the present invention, the composite hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network, which comprises at least one boron-containing dynamic covalent bond crosslink and has a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; and further comprising hydrogen bonding crosslinks in at least one of the dynamic covalently crosslinked networks. In this embodiment, the degree of crosslinking in hydrogen bonding may be not less than the gel point thereof, or may be not more than the gel point thereof.

According to a preferred embodiment (seventh structure) of the present invention, the composite hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink, and the crosslinking degree of the dynamic covalent bond crosslink is above the gel point; the other crosslinking network is a hydrogen bonding crosslinking network, wherein the crosslinking degree of the hydrogen bonding crosslinking is above the gel point of the crosslinking network. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof.

According to a preferred embodiment (eighth structure) of the present invention, the composite hybrid dynamic polymer comprises three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network, which comprises at least one boron-containing dynamic covalent bond crosslink and has a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinked network is a hydrogen-bonded crosslinked network, wherein the degree of crosslinking of the hydrogen-bonded crosslinks is above its gel point.

According to a preferred embodiment (ninth structure) of the present invention, the composite hybrid dynamic polymer comprises three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network, which comprises at least one boron-containing dynamic covalent bond crosslink and has a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinked network is a dynamic covalent crosslinked network which contains at least one other dynamic covalent bond crosslink and the crosslinking degree of the crosslinked network reaches above the gel point.

According to a preferred embodiment (tenth configuration) of the present invention, the combinatorial hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising both at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network is more than the gel point. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof.

According to a preferred embodiment (eleventh structure) of the present invention, the composite hybrid dynamic polymer comprises only one dynamic covalent crosslinked network, and at least one other dynamic covalent crosslinking is contained in the crosslinked network, and the degree of crosslinking of the other dynamic covalent crosslinking is above the gel point, and a non-crosslinked dynamic polymer containing at least one boron-containing dynamic covalent linkage is dispersed in the crosslinked network.

According to a preferred embodiment (twelfth structure) of the present invention, the composite hybrid dynamic polymer comprises only one dynamic covalent crosslinked network, and at least one other dynamic covalent crosslinking is contained in the crosslinked network, and the degree of crosslinking of the other dynamic covalent crosslinking is above the gel point, and the dynamic polymer particles containing at least one boron-containing dynamic covalent linkage are dispersed in the crosslinked network.

Furthermore, according to a preferred embodiment of the present invention, a non-crosslinked polymer having a crosslinking degree below the gel point or a polymer particle having a crosslinking degree above the gel point may be dispersed in the crosslinked network, and the non-crosslinked polymer or the polymer particle may contain one or more of boron-containing dynamic covalent bonds, other dynamic covalent bonds, and supramolecular interactions, or may be formed by only common covalent bonds.

In addition, the present invention can also have other various dynamic polymer structure embodiments, one embodiment can comprise a plurality of same or different non-crosslinked polymer chains and/or crosslinked polymer networks, and the same crosslinked network can comprise different dynamic covalent bond crosslinks and/or different hydrogen bond crosslinks, wherein the hydrogen bond can be crosslinked with the dynamic covalent bond in the same crosslinked network or in each independent crosslinked network or partially interacted with the dynamic covalent crosslinked network, and can also be dispersed in the dynamic covalent crosslinked network in the form of a non-crosslinked polymer.

In embodiments of the present invention, the following combinations of boron-containing and other dynamic covalent bonds are preferred, respectively:

combination 1: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicone bond; at least one of a dynamic linkage, a dynamic diselenide linkage, a dynamic covalent linkage based on reversible radicals, a binding exchangeable acyl linkage, a dynamic covalent linkage based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent linkage, a dynamic silicon ether linkage, an exchangeable dynamic covalent linkage based on alkyltriazolium, a [2+2] cycloaddition dynamic covalent linkage, a [2+4] cycloaddition dynamic covalent linkage, a [4+4] cycloaddition dynamic covalent linkage, a mercapto-michael addition dynamic covalent linkage, a dynamic covalent linkage based on triazolinedione-indole, an aminoalkene-michael addition dynamic covalent linkage, a dynamic covalent linkage based on diazacarbene, a dynamic exchangeable trialkylsulfonium linkage combination;

and (3) combination 2: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one series of dynamic selenium-nitrogen bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds and amine alkene-Michael addition dynamic covalent bond combinations;

and (3) combination: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond combination;

and (4) combination: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one of a dynamic linkage, a dynamic diselenide linkage, a dynamic covalent linkage based on reversible radicals, a binding exchangeable acyl linkage, a dynamic covalent linkage based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent linkage, a dynamic silicon ether linkage, an exchangeable dynamic covalent linkage based on alkyltriazolium, a [2+2] cycloaddition dynamic covalent linkage, a [2+4] cycloaddition dynamic covalent linkage, a [4+4] cycloaddition dynamic covalent linkage, a mercapto-michael addition dynamic covalent linkage, a dynamic covalent linkage based on triazolinedione-indole, an aminoalkene-michael addition dynamic covalent linkage, a dynamic covalent linkage based on diazacarbene, a dynamic exchangeable trialkylsulfonium linkage combination;

and (3) combination 5: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one series of dynamic selenium-nitrogen bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds and amine alkene-Michael addition dynamic covalent bond combinations;

and (4) combination 6: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one member selected from the group consisting of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, and a triazolinedione-indole-based dynamic covalent bond.

Combinations of boron-containing dynamic covalent bonds and other dynamic covalent bonds included in the hybrid dynamic polymers provided in the present invention include, but are not limited to, the preferences set forth above, and can be reasonably combined and selected by one skilled in the art according to specific practical needs.

In embodiments of the invention, the optional hydrogen bond may be generated by the presence of a non-covalent interaction between any suitable hydrogen bonding groups. The hydrogen bond group may contain only a hydrogen bond donor, only a hydrogen bond acceptor, or both a hydrogen bond donor and a hydrogen bond acceptor, preferably both a hydrogen bond donor and a hydrogen bond acceptor.

In an embodiment of the present invention, the optional hydrogen bond is formed by hydrogen bond formation between hydrogen bond groups present at any one or more of the combined hybrid dynamic polymer chain backbone (including main chain and side chain/branch/branched chain backbone), side group, and end group. Wherein said hydrogen bonding groups may also be present in said composite hybrid dynamic polymer composition, such as a small molecule compound or filler.

In embodiments of the present invention, the linking group for linking the boron-containing dynamic covalent bond, the other dynamic covalent bond and/or the hydrogen bonding group may be selected from any one or more of a heteroatom linking group, a divalent or multivalent small molecule hydrocarbon group, a divalent or multivalent polymer chain residue, a divalent or multivalent inorganic small molecule chain residue, and a divalent or multivalent inorganic large molecule chain residue.

In embodiments of the present invention, the hybrid dynamic polymer and its raw material components may or may not have one or more glass transition temperatures. At least one of them is below 0 ℃, or between 0 and 25 ℃, or between 25 and 100 ℃, or above 100 ℃ for the glass transition temperature of the composite hybrid dynamic polymer.

In the embodiment of the invention, the form of the combined hybrid dynamic polymer can be solution, emulsion, paste, glue, common solid, elastomer, gel (including hydrogel, organic gel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), foam material and the like.

During the preparation process of the combined hybrid dynamic polymer, certain solvent, other auxiliary agents/additives and fillers which can be added/used can be added or used to jointly form the dynamic polymer material.

In the embodiment of the invention, the energy absorption method based on the combined hybrid dynamic polymer can be applied to body protection of sports and daily life and work, body protection of military police, explosion prevention, air drop and air drop protection, automobile collision prevention, damping, buffering, impact resistance protection, sound insulation, noise elimination and shock absorption of electronic and electric products.

Compared with the prior art, the invention has the following beneficial effects:

(1) in the combined energy absorption method provided by the invention, the combined hybrid dynamic polymer for energy absorption comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and optional hydrogen bonds, and based on the dynamic differences of different dynamic covalent bonds and hydrogen bonds, the energy absorption method can embody orthogonality and cooperativity and stimulation responsiveness. The boron-containing dynamic covalent bond contained in the dynamic polymer has stronger dynamic property, can carry out dynamic reversible balance under mild conditions, and is beneficial to energy absorption and recovery self-repair of the polymer material; and other dynamic covalent bonds contained in the dynamic polymer can show orthogonal dynamic reversibility along with the change of external stimuli, so that the polymer shows different response capacities to external stimuli such as heat, illumination, pH, oxidation reduction and the like, and further can have different energy absorption effects under different environmental conditions. By utilizing different boron-containing dynamic covalent bonds, other dynamic covalent bonds and optional hydrogen bond dynamic properties, the polymer can embody multiple response and energy absorption effects according to different environments in the application process, the tolerance of the material is improved, and the selective regulation and control on the energy absorption are lacked in the prior art system. In addition, the dynamic property of the dynamic covalent bond and the hydrogen bond can enable the dynamic covalent bond and the hydrogen bond to be bonded again, so that the dynamic polymer can still keep higher energy absorption effect after being used for many times, and the method has great advantages compared with the existing energy absorption method and technology.

(2) The combined hybrid dynamic polymer utilized by the combined energy absorption method provided by the invention has the advantages of rich structure, various performances and strong controllability. Boron-containing dynamic covalent bonds, other dynamic covalent bonds, and optionally hydrogen bonds are incorporated into the dynamic polymer structure and their respective advantages are integrated and exploited. By controlling the parameters of the molecular structure, the number of functional groups, the molecular weight and the like of the compound serving as the raw material, the combined hybrid dynamic polymer with different apparent characteristics, adjustable performance and wide application can be prepared. In the invention, for the dynamic polymer with a non-covalent crosslinking structure, the dynamic polymer can show sensitive dilatancy under the action of stress/strain, so that the mechanical energy can be more lost through viscous flow, and excellent impact resistance is shown; when the dynamic polymer with a dynamic covalent cross-linked structure generates a dilatant characteristic, the dynamic polymer is easy to generate viscosity-elasticity transformation, the strength of the material is improved while energy is absorbed, the dispersion of impact force is realized, and the impact damage is reduced.

(3) The combined hybrid dynamic polymer adopted in the invention can also show self-repairability, reusability and recyclability, so that the energy-absorbing material prepared by using the polymer has wider application range and longer service life. Because the common covalent crosslinking above the gel point does not exist, the dynamic polymer can show more sensitive dilatancy under the action of stress/strain, and is more favorable for being used as an impact-resistant energy-absorbing material.

These and other features and advantages of the present invention will become apparent with reference to the following description of embodiments, examples and appended claims.

Detailed Description

The invention relates to a combined energy absorption method and application thereof, which is characterized in that a combined hybrid dynamic polymer is provided and is used as an energy absorption material for energy absorption; wherein the combinatorial hybrid dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonds; the boron-containing dynamic covalent bond contains boron atoms in the dynamic structure composition, and comprises fifteen bonds of organic boron anhydride bonds, inorganic boron anhydride bonds, organic-inorganic boron anhydride bonds, saturated five-membered ring organic borate bonds, unsaturated five-membered ring organic borate bonds, saturated six-membered ring organic borate bonds, unsaturated six-membered ring organic borate bonds, saturated five-membered ring inorganic borate bonds, unsaturated five-membered ring inorganic borate bonds, saturated six-membered ring inorganic borate bonds, unsaturated six-membered ring inorganic borate bonds, organic borate monoester bonds, inorganic borate monoester bonds, organic borate silicone bonds and inorganic borate silicone bonds; wherein the other dynamic covalent bonds do not contain boron atoms in their dynamic structural composition and include, but are not limited to, dynamic sulfide bonds, dynamic diselenide bonds, dynamic selenazone bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, dynamic covalent bonds based on reversible free radicals, combinable exchangeable acyl bonds, dynamic covalent bonds induced by steric effects, reversible addition fragmentation chain transfer dynamic covalent bonds, dynamic siloxane bonds, dynamic silicon ether bonds, exchangeable dynamic covalent bonds based on alkyltriazolium, unsaturated carbon-carbon double bonds capable of olefin cross metathesis, unsaturated carbon-carbon double bonds capable of alkyne cross metathesis, triple addition dynamic covalent bonds, [2+2] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, mercapto-Michael addition dynamic covalent bonds, or mercapto-metathesis bonds, An amine alkene-Michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkylsulfonium bond. Wherein the presence of said boron-containing dynamic covalent bonds, other dynamic covalent bonds, and optionally hydrogen bonds is a requirement for forming or maintaining a polymer structure. In the present invention, once the boron-containing dynamic covalent bonds, other dynamic covalent bonds, and optional hydrogen bonds are dissociated, the polymer system can be decomposed into any one or any of the following secondary units: non-crosslinked units such as monomers, polymer chain fragments, polymer clusters, and the like, and even units such as crosslinked polymer fragments and the like; at the same time, interconversion and dynamic reversibility between the dynamic polymer and the units may be achieved by bonding and dissociation of boron-containing dynamic covalent bonds, other dynamic covalent bonds and optionally hydrogen bonds.

The invention also provides an impact resistance method, which is characterized in that the invention provides a combined hybrid dynamic polymer which is used as an impact resistance material to resist impact; wherein the combinatorial hybrid dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonding.

The invention also provides a damping method, which is characterized in that a combined hybrid dynamic polymer is provided and is used as a damping material for damping; wherein the combinatorial hybrid dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonding.

The invention also provides a buffering method, which is characterized in that a combined hybrid dynamic polymer is provided and is used as a buffering material for buffering; wherein the combinatorial hybrid dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonding.

The invention also provides a sound insulation method, which is characterized in that the invention provides a combined hybrid dynamic polymer which is used as a sound insulation material for sound insulation; wherein the combinatorial hybrid dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonding.

The invention also provides a noise elimination method, which is characterized in that a combined hybrid dynamic polymer is provided and is used as a noise elimination material for noise elimination; wherein the combinatorial hybrid dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonding.

In the present invention, the three-dimensional infinite network containing common covalent bond crosslinks is not present in the combined hybrid dynamic polymer, but there may be a common covalent bond crosslinked polymer component dispersed and filled in the form of particles (which may be particles of any morphology, including but not limited to spheres, platelets, fibers, irregular shapes).

The term "energy absorption" as used herein refers to the absorption, dissipation, dispersion, etc. of energy generated by physical impact in the form of impact, vibration, shock, explosion, sound, etc.

The term "polymerization (reaction/action)" used in the present invention refers to a process/action of chain extension, that is, a process of forming a product having a higher molecular weight from a reactant having a lower molecular weight by a reaction form of polycondensation, polyaddition, ring-opening polymerization, etc. The reactant may be a monomer, oligomer, prepolymer, or other compound having a polymerization ability (i.e., capable of polymerizing spontaneously or under the action of an initiator or an external energy). The product resulting from the polymerization of one reactant is called a homopolymer. The product resulting from the polymerization of two or more reactants is referred to as a copolymer. It is to be noted that "polymerization" referred to in the present invention includes a linear growth process of a reactant molecular chain, a branching process of a reactant molecular chain, a ring formation process of a reactant molecular chain, but does not include a crosslinking process of a reactant molecular chain; in embodiments of the invention, "polymerization" comprises a chain growth process resulting from non-covalent interactions of boron-containing dynamic covalent bonds, bonding of other dynamic covalent bonds and common covalent bonds, and hydrogen bonds.

The term "crosslinking (reaction/action)" as used in the present invention refers to the process of generating a three-dimensional infinite network type product by chemical and/or supramolecular chemical linkage between and/or within reactant molecules through the formation of dynamic covalent bonds and/or common covalent bonds and/or hydrogen bonds. During the crosslinking process, the polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which may be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. During the cross-linking of the reactants, the viscosity increases suddenly and gelation begins, the reaction point at which a three-dimensional infinite network is first reached, called the gel point, also called the percolation threshold. A crosslinked reaction product above the gel point (including the gel point, and the degree of crosslinking occurring elsewhere in the present invention includes the gel point in the description above its gel point) having a three-dimensional infinite network structure with the crosslinked network forming a unitary body and spanning the entire polymer structure; the crosslinked reaction products, which are below the gel point, do not form a three-dimensional infinite network structure and do not belong to a crosslinked network that can be integrated across the entire polymer structure. Unless otherwise specified, the term "crosslinked (topological structure) in the present invention includes only a three-dimensional infinite network (structure) having a crosslinking degree of not less than the gel point (including the gel point), and the term" uncrosslinked (structure) refers to a linear, cyclic, branched, etc. structure having a crosslinking degree of not more than the gel point, as well as a two-dimensional or three-dimensional cluster structure.

As used herein, a "dynamic covalent bond" refers to a type of covalent bond that is capable of undergoing reversible cleavage and formation under suitable conditions. The boron-containing dynamic covalent bonds and other dynamic covalent bonds are included in the present invention.

The term "ordinary covalent bond" as used herein refers to a covalent bond in the conventional sense other than dynamic covalent bond, which is difficult to break at ordinary temperature (generally not higher than 100 ℃) and ordinary time (generally less than 1 day), and includes, but is not limited to, ordinary carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen bond, carbon-nitrogen bond, carbon-sulfur bond, nitrogen-hydrogen bond, nitrogen-oxygen bond, hydrogen-oxygen bond, nitrogen-nitrogen bond, etc.

In embodiments of the invention, the combination hybrid dynamic polymer may or may not have one or more glass transition temperatures. At least one of them is lower than 0 ℃, or between 0 and 25 ℃, or between 25 and 100 ℃, or higher than 100 ℃ for the glass transition temperature of the composite hybrid dynamic polymer; wherein, the dynamic polymer with the glass transition temperature lower than 0 ℃ has better low-temperature service performance and is convenient to be used as a sealant, an elastomer, a gel and the like; the dynamic polymer with the glass transition temperature of 0-25 ℃ can be used at normal temperature and can be conveniently used as an elastomer, a sealant, gel, foam and a common solid; the dynamic polymer with the glass transition temperature of 25-100 ℃ has stronger mechanical property, and is convenient to obtain common solid, foam and gel at room temperature; the dynamic polymer with the glass transition temperature higher than 100 ℃ has good dimensional stability, mechanical strength and temperature resistance, and is favorable for being used as a stress bearing material and a high impact resistant material. For the dynamic polymer with the glass transition temperature lower than 25 ℃, the polymer can show excellent dynamic property, self-repairability, recoverability and stress impact sensitivity, and is convenient for realizing the dissipation of impact through the dynamic balance of boron-containing dynamic covalent bonds and other dynamic covalent bonds; for the dynamic polymer with the glass transition temperature higher than 25 ℃, the polymer can show good shape memory capacity, stress bearing capacity and impact resistance; in addition, the existence of the optional supermolecule hydrogen bond can further regulate and control the glass transition temperature of the dynamic polymer, and supplement the dynamic property, the crosslinking degree, the mechanical strength and the energy absorption effect of the dynamic polymer. For the dynamic polymers of the present invention, it is preferred that at least one glass transition temperature is not greater than 50 deg.C, more preferably at least one glass transition temperature is not greater than 25 deg.C, and most preferably no glass transition temperature is greater than 25 deg.C. Systems with individual glass transition temperatures of no more than 25 ℃ are particularly suitable for use as impact-resistant protective materials due to their good flexibility and flowability/creep at the temperature of daily use. The glass transition temperature of the dynamic polymer can be measured by a glass transition temperature measurement method commonly used in the art, such as DSC and DMA. In embodiments of the invention, the polymer glass transition temperature may be altered by chemical means.

In embodiments of the present invention, each raw material component of the combined hybrid dynamic polymer may have one or more glass transition temperatures, or may have no glass transition temperature, and at least one of the glass transition temperatures is lower than 0 ℃, or between 0 ℃ and 25 ℃, or between 25 ℃ and 100 ℃, or higher than 100 ℃, wherein the raw material of the compound with the glass transition temperature lower than 0 ℃ is convenient for low-temperature preparation and processing during the preparation of the dynamic polymer; the compound raw material with the glass transition temperature of 0-25 ℃ can be prepared, processed and molded at normal temperature; the compound raw material with the glass transition temperature of 25-100 ℃ can be molded by conventional heating equipment, and the manufacturing cost is low; the compound raw material with the glass transition temperature higher than 100 ℃ can be used for preparing high-temperature resistant materials with good dimensional stability and excellent mechanical properties. The dynamic polymer is prepared by utilizing a plurality of compound raw materials with different glass transition temperatures, so that the dynamic polymer with different glass transition temperatures in different ranges can be obtained, multiple comprehensive properties can be embodied, and the dynamic polymer has dynamic property and stability.

In embodiments of the invention, the combinatorial hybrid dynamic polymers and their compositions and polymer chain topologies in the feedstock components can be selected from linear, cyclic, branched, clustered, crosslinked, and combinations thereof.

Wherein, the linear structure means that the polymer molecular chain is in a regular or irregular long-chain linear shape and is generally formed by connecting a plurality of repeating units on a continuous length, and the side group in the polymer molecular chain generally does not exist in a branched chain; for "linear structures," they are generally formed by polymerization of monomers that do not contain long chain pendant groups by polycondensation, polyaddition, ring opening, or the like.

Wherein, the "cyclic" structure refers to that the polymer molecular chain exists in the form of cyclic chain, which includes cyclic structures in the form of single ring, multiple rings, bridged ring, nested ring, etc.; as the "cyclic structure", it can be formed by intramolecular and/or intermolecular cyclization of a linear or branched polymer, and can also be produced by ring-expanding polymerization or the like.

Wherein, the branched structure refers to a structure containing side chains, branched chains and the like on a polymer molecular chain, and comprises but is not limited to star-shaped, H-shaped, comb-shaped, dendritic, hyperbranched, combinations thereof and the like; for "side chain, branched chain and branched chain structures of polymer", it may have a multi-stage structure, for example, one or more stages of branches may be continued on the branches of the polymer molecular chain. As the "branched structure", there are a number of methods for its preparation, which are generally known to those skilled in the art, and which can be formed, for example, by polycondensation of monomers containing long-chain pendant groups, or by chain transfer of radicals during polyaddition, or by radiation and chemical reactions to extend branched structures out of linear molecular chains. The branched structure is further subjected to intramolecular and/or intermolecular reaction (crosslinking) to produce a cluster and a crosslinked structure.

The "cluster" structure refers to a two-dimensional/three-dimensional structure below the gel point, which is generated by intramolecular and/or intermolecular reaction of polymer chains.

Wherein, the "cross-linked" structure refers to a three-dimensional infinite network structure of the polymer.

The "combination type" structure refers to a polymer structure containing two or more of the above topological structures, for example, a ring-shaped chain is used as a side chain of a comb-shaped chain, the ring-shaped chain has side chains to form a ring-shaped comb-shaped chain, the ring-shaped chain and a straight chain form a tadpole-shaped chain and a dumbbell-shaped chain, and the combination structure also includes different rings, different branches, different clusters and combination structures of other topological structures.

In the embodiment of the invention, the combined hybrid dynamic polymer and the composition and raw material components thereof can have only one topological form of polymer, and can also be a mixture of polymers with multiple topological forms.

It should be noted that, in the present invention, the terms "species", "class" and "series" used for describing different structures are used in a range of series, which is larger than the class, that is, a series can have a plurality of classes, and a class can have a plurality of kinds. Even if the dynamic covalent bonds have the same basic structure, differences in properties may occur due to differences in the linking groups, substituents, isomers, and the like. In the present invention, dynamic covalent bonds having the same basic structure are generally regarded as the same structure, but they are regarded as different structures if the difference in properties is caused by the difference in a linker, a substituent, an isomer, or the like. The invention can be reasonably designed, selected and regulated according to the needs to obtain the best performance, which is also the advantage of the invention. In the present invention, different types of structures are preferably used, and more preferably different series of structures are used, in order to better regulate orthogonality.

According to a preferred embodiment (first structure) of the present invention, the combinatorial hybrid dynamic polymer is a non-crosslinked structure comprising at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond. In this embodiment, since the composite hybrid dynamic polymer has a non-crosslinked structure, when the dilatant characteristic occurs under a specific condition, the viscosity is easily increased, and the viscous loss is increased, so that the mechanical energy can be more lost by the viscous flow, and the impact resistance characteristic can be exhibited.

According to a preferred embodiment (second structure) of the present invention, the combined hybrid dynamic polymer is a non-crosslinked structure comprising at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and hydrogen bonds. In this embodiment, since the composite hybrid dynamic polymer has a non-crosslinked structure, when the dilatant characteristic occurs under specific conditions, the viscosity is easily increased, and the viscous loss is increased, so that the mechanical energy can be more lost by viscous flow, and excellent impact resistance is exhibited; meanwhile, the introduction of hydrogen bonds can generate synergistic and orthogonal effects, and is beneficial to improving the tolerance and the energy absorption effect of the material.

According to a preferred embodiment (third structure) of the present invention, the composite hybrid dynamic polymer comprises only one dynamic covalent crosslinking network, and at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond crosslink are contained in the crosslinking network at the same time, and the crosslinking degree of the dynamic covalent bond crosslinks is above the gel point. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof. The embodiment only contains one crosslinking network, has simple structure and excellent performance, and the boron-containing dynamic covalent bond and other dynamic covalent bonds can be used for providing energy absorption effect with orthogonality and/or cooperativity.

According to a preferred embodiment (fourth structure) of the present invention, the composite hybrid dynamic polymer comprises only one dynamic covalent crosslinking network, and the crosslinking network comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and hydrogen bond crosslinking, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point. In this embodiment, the crosslinking degree of boron-containing dynamic covalent bond crosslinking and the crosslinking degree of hydrogen bond crosslinking may be at least the gel point thereof or at most the gel point thereof. The energy absorbing material contains only one cross-linking network, has simple structure and excellent performance, and boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds can be used for providing energy absorbing effect with rich orthogonality and/or cooperativity.

According to a preferred embodiment (the fifth structure) of the present invention, the composite hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network, which comprises at least one boron-containing dynamic covalent bond crosslink and has a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network is more than the gel point. In the embodiment, the dissociation of one type of dynamic covalent bonds does not immediately cause the failure of the other type of dynamic covalent cross-linked network, and the structure and the performance of one dynamic covalent cross-linked network can be respectively regulated and controlled by designing the structures of the two dynamic covalent cross-linked networks and controlling the use conditions, so that the aim of reasonably regulating and controlling the performance of the dynamic polymer is fulfilled. In addition, by dispersing and blending the boron-containing dynamic covalent bond crosslinking network and other dynamic covalent bond crosslinking networks, discontinuous, partially continuous or bicontinuous dispersed phases can be respectively formed in a system, so that the respective dynamic characteristics are respectively embodied, stress induction and damage induction can be respectively carried out, and impact energy can be dispersed, absorbed and dissipated.

According to a preferred embodiment (sixth structure) of the present invention, the composite hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network, which comprises at least one boron-containing dynamic covalent bond crosslink and has a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; and further comprising hydrogen bonding crosslinks in at least one of the dynamic covalently crosslinked networks. In this embodiment, the degree of crosslinking in hydrogen bonding may be not less than the gel point thereof, or may be not more than the gel point thereof. In the embodiment, by designing the structures of the two dynamic covalent cross-linked networks and controlling the use conditions, the performances of boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds in different dynamic covalent cross-linked networks can be fully exerted, and outstanding orthogonality and cooperativity are obtained, so that a better energy absorption effect is achieved. In addition, the boron-containing dynamic covalent bond crosslinked network and other dynamic covalent bond crosslinked networks are mutually blended and dispersed, and can respectively form discontinuous, partially continuous or bicontinuous dispersed phases in a system, so that stress induction and damage induction can be respectively carried out, and impact energy can be dispersed, absorbed and dissipated.

According to a preferred embodiment (seventh structure) of the present invention, the composite hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink, and the crosslinking degree of the dynamic covalent bond crosslink is above the gel point; the other crosslinking network is a hydrogen bonding crosslinking network, wherein the crosslinking degree of the hydrogen bonding crosslinking is above the gel point of the crosslinking network. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof. In the embodiment, the introduction of the hydrogen bond crosslinking network can generate synergistic and orthogonal effects, and is beneficial to improving the tolerance and the energy absorption effect of the material.

According to a preferred embodiment (eighth structure) of the present invention, the composite hybrid dynamic polymer comprises three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network, which comprises at least one boron-containing dynamic covalent bond crosslink and has a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinked network is a hydrogen-bonded crosslinked network, wherein the degree of crosslinking of the hydrogen-bonded crosslinks is above its gel point. In the embodiment, the dynamic covalent cross-linked network and the hydrogen bond cross-linked network exist independently, and the networks can also be independent from each other in raw material composition, so that the dynamic polymer shows different orthogonality and cooperativity by utilizing the difference of the dynamic property and the stability between different cross-linked networks, and the energy absorption effect with the orthogonality is achieved. In addition, the boron-containing dynamic covalent bond crosslinked network, other dynamic covalent bond crosslinked networks and the hydrogen bond crosslinked network are mutually blended and dispersed, so that discontinuous, partially continuous or bicontinuous dispersed phases can be respectively formed in a system, stress induction and damage induction can be respectively carried out, and impact energy can be dispersed, absorbed and dissipated.

According to a preferred embodiment (ninth structure) of the present invention, the composite hybrid dynamic polymer comprises three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network, which comprises at least one boron-containing dynamic covalent bond crosslink and has a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinked network is a dynamic covalent crosslinked network which contains at least one other dynamic covalent bond crosslink and the crosslinking degree of the crosslinked network reaches above the gel point. In the embodiment, three dynamic covalent crosslinking networks exist independently, and the networks can also be independent from each other in raw material composition, so that the dynamic polymer shows different orthogonality and cooperativity by utilizing the difference of dynamic property and stability among different crosslinking networks, and the energy absorption effect with orthogonality is achieved. In addition, the boron-containing dynamic covalent bond crosslinked network and other dynamic covalent bond crosslinked networks are mutually blended and dispersed, and can respectively form discontinuous, partially continuous or bicontinuous dispersed phases in a system, so that stress induction and damage induction can be respectively carried out, and impact energy can be dispersed, absorbed and dissipated.

According to a preferred embodiment (tenth configuration) of the present invention, the combinatorial hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising both at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network is more than the gel point. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof. By designing the structures of the two dynamic covalent cross-linked networks and controlling the use conditions, the structure and the performance of one dynamic covalent cross-linked network can be respectively regulated and controlled, and the aim of reasonably regulating and controlling the energy absorption effect of the dynamic polymer is fulfilled.

According to a preferred embodiment (eleventh structure) of the present invention, the composite hybrid dynamic polymer comprises only one dynamic covalent crosslinked network, and at least one other dynamic covalent crosslinking is contained in the crosslinked network, and the degree of crosslinking of the other dynamic covalent crosslinking is above the gel point, and a non-crosslinked dynamic polymer containing at least one boron-containing dynamic covalent linkage is dispersed in the crosslinked network. In this embodiment, the non-crosslinked dynamic polymer is dispersed in the dynamic covalent crosslinked network, and when subjected to an external force and having dilatancy, can only produce viscosity increase, and give the polymer a hierarchical dilatancy effect, which acts to disperse, absorb and dissipate impact energy.

According to a preferred embodiment (twelfth structure) of the present invention, the composite hybrid dynamic polymer comprises only one dynamic covalent crosslinked network, and at least one other dynamic covalent crosslinking is contained in the crosslinked network, and the degree of crosslinking of the other dynamic covalent crosslinking is above the gel point, and the dynamic polymer particles containing at least one boron-containing dynamic covalent linkage are dispersed in the crosslinked network. In this embodiment, the dynamic polymer particles are dispersed in the dynamic covalent cross-linked network, which can provide dynamic supplementation and local viscosity and strength increase for the cross-linked network, thereby achieving good energy absorption effect.

Furthermore, according to a preferred embodiment of the present invention, a non-crosslinked polymer having a crosslinking degree below the gel point or a polymer particle having a crosslinking degree above the gel point may be dispersed in the crosslinked network, and the non-crosslinked polymer or the polymer particle may contain one or more of boron-containing dynamic covalent bonds, other dynamic covalent bonds, and supramolecular interactions, or may be formed by only common covalent bonds. The non-crosslinked polymer dispersed therein, the degree of crosslinking of which is below the gel point thereof, can provide dynamic or entanglement properties to the crosslinked network, thereby enhancing the energy-absorbing effect; while polymer particles dispersed therein having a degree of crosslinking above their gel point may provide filling and dynamic properties, and may achieve localized viscosity and strength increases upon strain.

In addition, the present invention can also have other various dynamic polymer structure embodiments, one embodiment can comprise a plurality of same or different non-crosslinked polymer chains and/or crosslinked polymer networks, and the same crosslinked network can comprise different dynamic covalent crosslinks and/or different hydrogen bond crosslinks, wherein the hydrogen bond can be in the same crosslinked network with the dynamic covalent crosslinks or in each independent crosslinked network or partially interact with the dynamic covalent crosslinked network, and can also be dispersed in the dynamic covalent crosslinked network in the form of a non-crosslinked polymer. The crosslinking degree of any crosslinking of any network in the combined hybrid dynamic polymer can be reasonably controlled so as to achieve the aim of regulating and controlling the balance structure and the dynamic performance; the crosslinking degrees of the dynamic covalent crosslinking and the hydrogen bonding crosslinking may be at least the respective gel point, at most the respective gel point, and preferably at least the respective gel point; when the dynamic covalent crosslinking reaches the gel point or above, the dynamic polymer can better show the advantage of dynamic property when being used as a stress/strain responsive material. In the present invention, when at least one crosslinking component is present, the different components (including the crosslinking component and the non-crosslinking component) may be dispersed, interspersed or partially interspersed with each other, but the present invention is not limited thereto. The structure of the combinatorial hybrid dynamic polymers of the present invention includes, but is not limited to, those mentioned above, and those skilled in the art can reasonably realize the structure according to the logic and context of the present invention.

The term "orthogonality" as used herein refers to different types of boron-containing dynamic covalent bonds, different types of other dynamic covalent bonds, and different types of hydrogen bonds, which can exhibit different dynamic reactivity and dynamic reversibility under different external conditions due to different dynamic properties, stability, dynamic reaction conditions, etc., so that the dynamic polymer can exhibit energy-absorbing effects of different dynamic covalent bonds and hydrogen bonds under different environmental conditions. Specifically, other dynamic covalent bonds do not generally exhibit dynamic reversibility at room temperature, and dynamic adjustment in the dynamic polymer system can be achieved only by boron-containing dynamic covalent bonds and optional hydrogen bonds; after the system is heated, illuminated, added with an oxidation-reduction agent, added with a catalyst, added with an initiator, illuminated, radiated, microwave and plasma, and the pH is adjusted, the dynamics of other corresponding dynamic covalent bonds under corresponding conditions can be triggered, and different types of other dynamic covalent bonds have different dynamic response capabilities to different environmental stimuli, for example, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds, amine alkene-Michael addition dynamic covalent bonds are sensitive to the change of the pH value, dynamic siloxane bonds, unsaturated carbon-carbon double bonds capable of generating olefin cross metathesis reaction, and unsaturated carbon-carbon triple bonds capable of generating alkyne cross metathesis reaction are required to be subjected to dynamic equilibrium reaction under the condition of the existence of the catalyst, by utilizing different reaction conditions, when one function is exerted, other functions are in a state of not being triggered, so that the orthogonality regulation is realized.

The term "synergy" as used herein means that different boron-containing dynamic covalent bonds, different other dynamic covalent bonds, and different hydrogen bonds can exhibit a dynamic reactivity and a dynamic reversibility which are compatible with each other and act synergistically under certain specific external conditions, so that the dynamic polymer can exhibit an energy absorption effect which is more excellent than the original single effect under specific environmental conditions. By selecting dynamic covalent bonds or optional hydrogen bonds that are capable of dynamic behavior under the same external stimulus conditions of heating, addition of redox agents, addition of catalysts, illumination, radiation, microwaves, plasma effects, pH, etc., one effect is effective while the other effect or effects are also capable of dynamic behavior under corresponding environmental conditions, producing a synergistic effect greater than the linear superposition of the two effects. For example, boron-containing dynamic covalent bonds, dynamic sulfide bonds, dynamic diselenide bonds, dynamic covalent bonds based on reversible radicals, associative exchangeable acyl bonds, dynamic covalent bonds based on steric effect induction, reversible addition fragmentation chain transfer dynamic covalent bonds, dynamic silicon ether bonds, exchangeable dynamic covalent bonds based on alkyltriazolium, 2+2 cycloaddition dynamic covalent bonds, [2+4] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, mercapto-michael addition dynamic covalent bonds, triazolinedione-indole-based dynamic covalent bonds, aminoalkene-michael addition dynamic covalent bonds, dinitrohetero carbene-based dynamic covalent bonds, and dynamically exchangeable trialkylsulfonium bonds may exhibit different dynamics with respect to changes in temperature, and may act synergistically under the action of heat; acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds and amine alkene-Michael addition dynamic covalent bonds are sensitive to the change of pH value and can synergistically play a role through the adjustment of acidity and alkalinity; the dynamic siloxane bonds, unsaturated carbon-carbon double bonds that can undergo olefin cross metathesis, and unsaturated carbon-carbon triple bonds that can undergo alkyne cross metathesis generally act synergistically by introducing a catalyst; by selecting proper reaction conditions and proper dynamic action, the cooperative regulation and control of the dynamic polymer can be realized.

In a preferred embodiment of the present invention, the combinatorial hybrid dynamic polymer may contain the boron-containing dynamic covalent bond, other dynamic covalent bonds, at any suitable position of the polymer; the dynamic covalent bonds and the optional hydrogen bonds in the dynamic polymer may function both independently and synergistically. For non-crosslinked dynamic covalent polymers, the polymer may contain dynamic covalent bonds on the backbone of the polymer backbone, or on the side chains/branches/branched chains of the polymer backbone; for the cross-linked network, the dynamic covalent bond can be contained on the cross-linked network chain skeleton, and the dynamic covalent bond can also be contained on the side chain/branched chain skeleton of the cross-linked network chain skeleton; the invention also does not exclude the inclusion of dynamic covalent bonds in the side and/or end groups of the polymer chain, other constituents of the polymer such as small molecules, fillers, etc. In embodiments of the present invention, the dynamic covalent bonds are preferably located on the backbone of the polymer backbone (for non-crosslinked structures) and on the backbone of the polymer crosslinked network chains (for crosslinked structures). The optional hydrogen bonds that may be formed between hydrogen bonding groups present at any one or more of any of the components in the composite hybrid dynamic polymer; wherein, the hydrogen bond group can be present on a dynamic polymer cross-linked network chain skeleton, can also be present on a side chain/branched chain skeleton of the cross-linked network chain skeleton, and can also be present on a side group and an end group of the cross-linked polymer; or can be present on the main chain skeleton, side chain/branched chain skeleton, side group and end group of the non-crosslinked polymer; may also be present in the combined hybrid dynamic polymer composition (e.g., small molecule compound or filler). The dynamic covalent bond and the hydrogen bond can be subjected to reversible fragmentation and regeneration under specific conditions; under appropriate conditions, dynamic covalent and hydrogen bonds at any position in the dynamic polymer can participate in dynamic reversible exchange.

The "backbone" as used herein refers to the chain length direction of the polymer chain. The "crosslinked network chain skeleton" refers to any chain segment constituting the crosslinked network skeleton. The term "main chain" as used herein, unless otherwise specified, refers to the chain having the highest number of links in the polymer structure. The side chain refers to a chain structure which is connected with a polymer main chain skeleton or a crosslinking network chain skeleton in a polymer structure and is distributed beside the chain skeleton, and the molecular weight of the chain structure is more than 1000 Da; wherein the branched or branched chain refers to a chain structure with a molecular weight of more than 1000Da branched from a polymer main chain skeleton or a cross-linked network chain skeleton or any other chain; in the present invention, for the sake of simplicity, the side chain, the branched chain, and the branched chain are collectively referred to as a side chain unless otherwise specified. Wherein, the side group refers to a chemical group with molecular weight not higher than 1000Da and a short side chain with molecular weight not higher than 1000Da which are connected with the polymer chain skeleton and distributed beside the chain skeleton in the polymer structure. For the side chain and the side group, the side chain and the side group can have a multi-stage structure, that is, the side chain can be continuously provided with the side group and the side chain, the side chain of the side chain can be continuously provided with the side group and the side chain, and the side chain also comprises chain structures such as branched chain and branched chain. The "terminal group" refers to a chemical group which is linked to the polymer chain skeleton in the polymer structure and is located at the end of the chain skeleton; in the present invention, the side groups may have terminal groups in specific cases. For hyperbranched and dendritic chains and their related chain structures, the polymer chains therein can be regarded as main chains, but in the present invention, the outermost chains are regarded as side chains and the remaining chains as main chains, unless otherwise specified. In the present invention, the "side chain", "side group" and "end group" also apply to small molecular monomers and large molecular monomers that undergo supramolecular polymerization by hydrogen bonding. For non-crosslinked structures, the polymer chain skeleton comprises a polymer main chain skeleton and chain skeletons such as polymer side chains, branched chains and the like; for the crosslinked structure, the polymer chain skeleton includes a skeleton of an arbitrary segment present in the crosslinked network (i.e., crosslinked network chain skeleton) and chain skeletons thereof such as side chains, branched chains, and branched chains.

The boron-containing dynamic covalent bond in the invention contains boron atoms in the dynamic structure composition, and comprises fifteen bonds of organic boron anhydride bonds, inorganic boron anhydride bonds, organic-inorganic boron anhydride bonds, saturated five-membered ring organic borate bonds, unsaturated five-membered ring organic borate bonds, saturated six-membered ring organic borate bonds, unsaturated six-membered ring organic borate bonds, saturated five-membered ring inorganic borate bonds, unsaturated five-membered ring inorganic borate bonds, saturated six-membered ring inorganic borate bonds, unsaturated six-membered ring inorganic borate bonds, organic borate monoester bonds, inorganic borate monoester bonds, organic borate silicone bonds and inorganic borate silicone bonds; wherein, each boron-containing dynamic covalent bond can comprise a plurality of boron-containing dynamic covalent bond structures. When the boron-containing dynamic covalent bonds are selected from two or more than two, the boron-containing dynamic covalent bonds can be selected from different structures in the same boron-containing dynamic covalent bond and can also be selected from different structures in different boron-containing dynamic covalent bonds, wherein in order to achieve orthogonal and/or synergistic energy absorption effects, the boron-containing dynamic covalent bonds are preferably selected from different structures in different boron-containing dynamic covalent bonds.

The organoboron anhydride linkages described herein are selected from, but not limited to, at least one of the following structures:

wherein each boron atom in the organoboron anhydride linkage is connected to at least one carbon atom by a boron-carbon bond, and at least one organic group is connected to the boron atom by said boron-carbon bond;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference in the same boron atom

Can be linked to form a ring, on different boron atomsMay be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical organoboronic anhydride bond structures may be exemplified by:

in the embodiment of the present invention, the organoboron anhydride linkages contained in the dynamic polymer may be formed by reacting organoboronic acid moieties contained in the compound raw materials with organoboronic acid moieties, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between the reactive groups contained in the organoboron anhydride linkages-containing compound raw materials.

The inorganic boron anhydride linkages described in this invention are selected from, but not limited to, the following structures:

wherein, Y₁、Y₂、Y₃、Y₄Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y₁、Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, Y₃、Y₄At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b, c, d denote each independently of Y₁、Y₂、Y₃、Y₄The number of connected connections; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b, c and d are 0; when Y is₁、 Y₂、Y₃、Y₄When each is independently selected from oxygen atom and sulfur atom, a, b, c and d are 1; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from nitrogen atom and boron atom, a, b, c and d are 2; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from silicon atoms, a, b, c and d are 3; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic boron anhydride bond structures are exemplified by:

in the embodiment of the present invention, the inorganic boron anhydride bond contained in the dynamic polymer may be formed by the reaction of an inorganic boric acid moiety contained in the compound raw material with an inorganic boric acid moiety, or the dynamic polymer may be introduced by the polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an inorganic boron anhydride bond.

The organic-inorganic boron anhydride linkage described in the present invention is selected from, but not limited to, the following structures:

wherein, Y₁、Y₂Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y₁、Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein, the boron atom in the structure is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b denote independently from Y₁、Y₂The number of connected connections; when Y is₁、Y₂When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a and b are 0; when Y is₁、Y₂When each is independently selected from oxygen atom and sulfur atom, a and b are 1; when Y is₁、Y₂When each is independently selected from nitrogen atom and boron atom, a and b are 2; when Y is₁、Y₂When each is independently selected from silicon atoms, a, b is 3; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical organic-inorganic boron anhydride bond structures may be exemplified by:

in embodiments of the present invention, the organic-inorganic boron anhydride linkages contained in the dynamic polymer may be formed by reaction of organic boronic acid moieties contained in the compound starting materials with inorganic boronic acid moieties, or may be introduced into the dynamic polymer by polymerization/crosslinking reactions between the reactive groups contained in the compound starting materials containing organic-inorganic boron anhydride linkages.

The saturated five-membered ring organic boric acid ester bond is selected from but not limited to the following structures:

wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring organoborate bond structures may be exemplified by:

in the embodiment of the present invention, the saturated five-membered ring organic boronic acid ester bond contained in the dynamic polymer may be formed by reacting a 1, 2-diol moiety contained in the compound raw material with an organic boronic acid moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the saturated five-membered ring organic boronic acid ester bond.

The unsaturated five-membered ring organic boric acid ester bond in the invention is selected from but not limited to the following structures:

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;

an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated five-membered ring organoboronate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or may not be substituted. Typical unsaturated five-membered ring organoborate bond structures may be exemplified by:

in the embodiment of the present invention, the unsaturated five-membered ring organic borate bond contained in the dynamic polymer may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an organic borate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the unsaturated five-membered ring organic borate bond.

The saturated six-membered ring organic boric acid ester bond in the invention is selected from, but not limited to, the following structures:

Can be linked to form a ring, on different carbon atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring organoboronate bond structures may be exemplified by:

in the embodiment of the present invention, the saturated six-membered ring organoboronate bond contained in the dynamic polymer may be formed by reacting a 1, 3-diol moiety contained in the compound raw material with an organoboronate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated six-membered ring organoboronate bond.

The unsaturated six-membered ring organic boric acid ester bond in the invention is selected from but not limited to the following structures:

an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring organoboronate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Or can be connected into a ring. Typical unsaturated six-membered ring organoboronate bond structures may be exemplified by:

in the embodiment of the present invention, the unsaturated six-membered ring organoboronic acid ester bond contained in the dynamic polymer may be formed by reacting a 2-hydroxymethylphenol moiety contained in the compound raw material with an organoboronic acid moiety, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated six-membered ring organoboronic acid ester bond.

In the invention, the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond are preferably selected from boron atoms and aminomethyl benzene groups in the structure (B)

Indicates the position to which the boron atom is attached); forming the saturated five-membered ring organic boric acidThe organic boric acid units of ester bonds, unsaturated five-membered ring organic boric acid ester bonds, saturated six-membered ring organic boric acid ester bonds and unsaturated six-membered ring organic boric acid ester bonds are preferably aminomethyl phenylboronic acid (ester) units.

As the aminomethyl phenylboronic acid (ester) element has higher reaction activity when reacting with the 1, 2-diol element and/or the catechol element and/or the 1, 3-diol element and/or the 2-hydroxymethylphenol element, the formed boron-containing dynamic covalent bond has stronger dynamic reversibility, can perform dynamic reversible reaction under milder neutral conditions, can show sensitive dynamic responsiveness and obvious energy absorption effect, and can embody greater advantages when being used as an energy absorption material.

Typical structures of such boron-containing dynamic covalent bonds are exemplified by:

the saturated five-membered ring inorganic borate ester bond in the invention is selected from but not limited to at least one of the following structures:

wherein, Y₁Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;

represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y₁The number of connected connections; when Y is₁When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is₁When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is₁When selected from silicon atoms, a is 3; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring inorganic borate bond structures are exemplified by:

in the embodiment of the present invention, the saturated five-membered ring inorganic borate bond contained in the dynamic polymer may be formed by reacting a 1, 2-diol moiety contained in the compound raw material with an inorganic borate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated five-membered ring inorganic borate bond.

The unsaturated five-membered ring inorganic borate bond in the invention is selected from but not limited to at least one of the following structures:

represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y₁The number of connected connections; when Y is₁When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is₁When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is₁When selected from silicon atoms, a is 3;

an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated five-membered ring inorganic borate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituentOr may be unsubstituted. Typical unsaturated five-membered ring inorganic borate bond structures may be exemplified by:

in the embodiment of the present invention, the unsaturated five-membered ring inorganic borate bond contained in the dynamic polymer may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an inorganic borate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated five-membered ring inorganic borate bond.

The saturated six-membered ring inorganic borate bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein, Y₁Selected from oxygen atoms, sulphur atoms, nitrogen atoms, boron atoms, silicon atoms, preferably oxygen atoms;

Can be linked to form a ring, on different carbon atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring inorganic borate estersThe key structure may be exemplified by:

in the embodiment of the present invention, the saturated six-membered ring inorganic borate bond contained in the dynamic polymer can be formed by reacting the 1, 3-diol moiety contained in the compound raw material with the inorganic borate moiety, or the dynamic polymer can be introduced by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the saturated six-membered ring inorganic borate bond.

The unsaturated six-membered ring inorganic borate bond in the invention is selected from but not limited to at least one of the following structures:

an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring inorganic borate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom

Can be connected into a ring, differentOn carbon atoms

Or can be connected into a ring. Typical unsaturated six-membered ring inorganic borate bond structures are exemplified by:

in the embodiment of the present invention, the unsaturated six-membered ring inorganic borate bond contained in the dynamic polymer may be formed by reacting a 2-hydroxymethylphenol moiety contained in the compound raw material with an inorganic borate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated six-membered ring inorganic borate bond.

The organoboronic acid monoester bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond; i is₁Selected from divalent linking groups; i is₂Selected from the group consisting of a double bond directly attached to two carbon atoms, a trivalent carbene group directly attached to two carbon atoms

A divalent non-carbon atom, a linking group containing at least two backbone atoms;

an aromatic ring of any number of members, preferably selected from six-membered rings; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different in the same carbon atom, boron atom

Can be connected into a ring, on different carbon atoms and boron atoms

Can also be connected into a ring or can be connected with I₁、I₂The substituent atoms (substituents) in the (A) form a ring together, the ring comprises but is not limited to an aliphatic ring, an ether ring, a condensation ring and a combination thereof, wherein the organic boric acid single ester bond formed after the 6 and 7 structures form the ring is not the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond which are described in the previous description. Typical organic boronic acid monoester bond structures are exemplified by:

in the embodiment of the present invention, the organic boronic acid monoester bond contained in the dynamic polymer may be formed by the reaction of a monool moiety contained in the compound raw material with an organic boronic acid moiety, or the dynamic polymer may be introduced by the polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the organic boronic acid monoester bond.

The inorganic boric acid monoester bond in the invention is selected from at least one of the following structures:

wherein, Y₁～Y₁₃Each independently of the otherIs selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y₁、Y₂；Y₃、Y₄；Y₅、Y₆、Y₇、Y₈；Y₉、Y₁₀、Y₁₁、Y₁₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; y is₁₄Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; i is₁Selected from divalent linking groups; i is₂Selected from the group consisting of a double bond directly attached to two carbon atoms, a trivalent carbene group directly attached to two carbon atoms

represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a to n each represent a linkage to Y₁～Y₁₄The number of connected connections; when Y is₁～Y₁₃When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a-m is 0; when Y is₁～Y₁₄When each is independently selected from oxygen atom and sulfur atom, a to n are 1; when Y is₁～Y₁₄When each is independently selected from nitrogen atom and boron atom, a to n are 2; when Y is₁～Y₁₄Each independently selected from silicon atoms, a to n is 3;

an aromatic ring of any number of members, preferably selected from six-membered rings; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Can also be connected into a ring or can be connected with I₁、I₂The substituted atoms (substituents) in the (A) form a ring together, the ring comprises but is not limited to aliphatic ring, ether ring, condensed ring and combination thereof, wherein the inorganic boric acid monoester bond formed after the 5, 6, 7 and 8 structures form the ring is not the saturated five-membered ring inorganic boric acid ester bond, the unsaturated five-membered ring inorganic boric acid ester bond, the saturated six-membered ring inorganic boric acid ester bond and the unsaturated six-membered ring inorganic boric acid ester bond which are described before. Typical inorganic boronic acid monoester bond structures are exemplified by:

in the embodiment of the present invention, the inorganic boronic acid monoester bond contained in the dynamic polymer may be formed by the reaction of a monool moiety contained in the compound raw material with an inorganic boronic acid moiety, or the dynamic polymer may be introduced by the polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing an inorganic boronic acid monoester bond.

The organic borate silicone bond in the invention is selected from but not limited to at least one of the following structures:

wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom

Can be connected into a ring, different from the originalOn the son

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical silicon organoborate bond structures may be exemplified by:

in the embodiment of the present invention, the organoboronate silicone bond contained in the dynamic polymer may be formed by reacting a silanol group contained in the compound raw material with an organoboronic acid group, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between the reactive groups contained in the organoboronate silicone bond-containing compound raw material.

The inorganic borate silicone bond in the invention is selected from but not limited to at least one of the following structures:

wherein, Y₁、Y₂、Y₃Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y₁、Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b, c denote each independently of Y₁、Y₂、 Y₃The number of connected connections; when Y is₁、Y₂、Y₃When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b and c are 0; when Y is₁、Y₂、Y₃Each of which isIndependently selected from oxygen atom and sulfur atom, a, b and c are 1; when Y is₁、Y₂、Y₃When each is independently selected from nitrogen atoms and boron atoms, a, b and c are 2; when Y is₁、Y₂、Y₃When each is independently selected from silicon atoms, a, b and c are 3; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic silicon borate ester bond structures include, for example:

in the embodiment of the present invention, the inorganic borate silicone bond contained in the dynamic polymer may be formed by the reaction of a silanol group contained in the compound raw material with an inorganic borate group, or the dynamic polymer may be introduced by the polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing an inorganic borate silicone bond.

The organic boronic acid moiety in the embodiments of the present invention is selected from, but not limited to, any of the following structures:

wherein, K₁、K₂、K₃Is a monovalent organic group or a monovalent organosilicon group directly bonded to an oxygen atom through a carbon atom or a silicon atom, selected from any of the following structures: small molecule hydrocarbyl, small molecule silyl, polymer chain residues; k₄Is a divalent organic or divalent organosilicon radical directly bonded to two oxygen atoms via a carbon atom or siliconThe atoms are directly linked to oxygen atoms and are selected from any of the following structures: a divalent small molecule hydrocarbon group, a divalent small molecule silane group, a divalent polymer chain residue; m₁ ⁺、M₂ ⁺、M₃ ⁺Is a monovalent cation, preferably Na⁺、K⁺、NH₄ ⁺；M₄ ²⁺Is a divalent cation, preferably Mg²⁺、Ca²⁺、Zn²⁺、Ba²⁺；X₁、X₂、X₃Is a halogen atom, preferably selected from chlorine and bromine atoms; d₁、D₂Is a group bound to a boron atom, D₁、D₂Are different and are each independently selected from hydroxyl (-OH), ester (-OK)₁) Salt group (-O)^-M₁ ⁺) Halogen atom (-X)₁) Wherein, K is₁、M₁ ⁺、X₁The definitions of (A) and (B) are consistent with those described above, and are not described herein again; wherein, the boron atom in the structure is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;

May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

The inorganic boronic acid moiety described in the embodiments of the present invention is selected from, but not limited to, the following structures:

wherein, W₁、W₂、W₃Each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, and oxygen atomA sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and W₁、W₂、W₃At least one selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;

represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein x, y, z each represent a linkage to W₁、W₂、W₃The number of connected connections; when W is₁、W₂、W₃X, y, z is 0 when each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom; when W is₁、W₂、W₃When each is independently selected from oxygen atom and sulfur atom, x, y and z are 1; when W is₁、W₂、W₃When each is independently selected from nitrogen atom and boron atom, x, y and z are 2; when W is₁、W₂、W₃Each independently selected from the group consisting of silicon atom, x, y, z ═ 3; difference on the same atom

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

The inorganic boric acid moiety described in the embodiment of the present invention is preferably introduced by using inorganic borane, inorganic boric acid, inorganic boric anhydride, inorganic borate ester, inorganic boron halide as a raw material.

The 1, 2-diol moiety described in the embodiments of the present invention is ethylene glycol

And substituted forms thereof which have been deprived of at least one non-hydroxyl hydrogen atom;

practice of the inventionThe 1, 3-diol moiety described in (1), which is 1, 3-propanediol

for the 1, 2-diol moiety and the 1, 3-diol moiety, they may be linear structures or cyclic group structures.

For linear 1, 2-diol motif structures, it may be selected from any one or several of the B-like structures and isomeric forms thereof:

class B:

for linear 1, 3-diol motif structures, it may be selected from any one or several of the C-like structures and isomeric forms thereof:

class C:

wherein R is₁～R₃Is a monovalent group attached to the 1, 2-diol moiety; r₄～R₈Is a monovalent group attached to the 1, 3-diol moiety;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein R is₁～R₈Each independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group and polymer chain residue.

Wherein, the isomeric forms of B1-B4 and C1-C6 are respectively and independently selected from any one of position isomerism, conformational isomerism and chiral isomerism.

For a cyclic 1, 2-diol elementary structure, two carbon atoms in an ethylene glycol molecule are connected through the same group; wherein, the cyclic group structure is 3-200 rings, preferably 3-10 rings, more preferably 3-6 rings, the number of the cyclic group structure is 1,2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic rings, ether rings, condensed rings, and combinations thereof; suitable cyclic group structures are exemplified by:

for cyclic 1, 3-diol motif structures, it can be formed by linking two carbon atoms in the 1, 3-propanediol molecule through the same group; wherein, the cyclic group structure is 3-200 rings, preferably 3-10 rings, more preferably 3-6 rings, the number of the cyclic group structure is 1,2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic rings, ether rings, condensed rings, and combinations thereof; suitable cyclic group structures are exemplified by:

the catechol moiety in the present invention is a catechol

And substituted forms thereof, hybridized forms thereof, and combinations thereof, having lost at least one non-hydroxyl hydrogen atom, suitable catechol motif structures being exemplified by:

the 2-hydroxymethylphenol moiety described in the present invention is a 2-hydroxymethylphenol

And substituted forms thereof and hybridized forms thereof and combinations thereof, with suitable 2-hydroxymethylphenol motifs such as:

the monool moiety in the embodiment of the present invention refers to a structural moiety consisting of a hydroxyl group and a carbon atom directly bonded to the hydroxyl group (

Wherein, the carbon atom can be a non-aromatic carbon atom, and can also be an aromatic carbon atom), and in the case that the 1, 2-diol unit, the catechol unit, the 1, 3-diol unit and the 2-hydroxymethylphenol unit form an unsaturated/saturated five-membered ring organic borate bond, an unsaturated/saturated six-membered ring organic borate bond, an unsaturated/saturated five-membered ring inorganic borate bond and an unsaturated/saturated six-membered ring inorganic borate bond, the monoalcohol unit is not the hydroxyl group in the 1, 2-diol unit, the catechol unit, the 1, 3-diol unit and the 2-hydroxymethylphenol unit, and besides this, the monoalcohol unit can also be selected from any suitable dihydric (polybasic) alcohol compound and/or any hydroxyl group in the group. Suitable structures containing monoalcohol moieties may be mentioned, for example:

the silanol moiety in the embodiment of the present invention refers to a structural moiety consisting of a silicon atom and a hydroxyl group or a group hydrolyzable to the silicon atom to obtain a hydroxyl group (

Or

Wherein Z can be selected from halogen, cyano, oxygen cyano, sulfur cyano, alkoxy, amino, sulfate group, borate group, acyl, acyloxy, acylamino, ketoxime group, alkoxide group and the like, and preferably halogen and alkoxy).

The boron-containing dynamic covalent bond selected by the invention has strong dynamic property and mild dynamic reaction condition, can realize the synthesis and dynamic reversible effect of the dynamic polymer under the conditions of no need of a catalyst, no need of high temperature, illumination or specific pH, can further improve the preparation efficiency, reduce the limitation of the use environment and expand the application range of the polymer.

Other dynamic covalent bonds described in the present invention, which do not contain a boron atom in their dynamic structural composition, include, but are not limited to, dynamic sulfur linkage, dynamic diselenide linkage, dynamic selenazone linkage, acetal dynamic covalent linkage, dynamic covalent linkage based on carbon-nitrogen double bonds, dynamic covalent linkage based on reversible free radicals, associative exchangeable acyl linkage, dynamic covalent linkage based on steric effect induction, reversible addition fragmentation chain transfer dynamic covalent linkage, dynamic siloxane linkage, dynamic silicon ether linkage, exchangeable dynamic covalent linkage based on alkyltriazolium, unsaturated carbon-carbon double bonds where olefin cross metathesis can occur, unsaturated carbon-carbon double bonds where alkyne cross metathesis can occur, 2+2 cycloaddition dynamic covalent linkage, [4+2] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, mercapto-michael addition dynamic covalent linkage, and the like, An amine alkene-Michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkylsulfonium bond; wherein, each series of other dynamic covalent bonds may comprise a plurality of types of other dynamic covalent bond structures. When two or more than two kinds of the other dynamic covalent bonds are selected, the other dynamic covalent bonds can be selected from different structures in the same kind of dynamic covalent bonds in the same series of other dynamic covalent bonds, can also be selected from different structures in different kinds of dynamic covalent bonds in the same series of other dynamic covalent bonds, and can also be selected from different structures in different series of other dynamic covalent bonds, wherein, in order to achieve orthogonal and/or synergistic energy absorption effects, the other dynamic covalent bonds are preferably selected from different structures in different series of other dynamic covalent bonds.

The dynamic sulfur-connecting bond comprises a dynamic disulfide bond and a dynamic polysulfide bond, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic; the dynamic sulfur linkage described in the present invention is selected from, but not limited to, the following structures:

wherein x is the number of S atoms, x is more than or equal to 2,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic sulfur linkage structures may be exemplified by:

in the embodiment of the invention, the dynamic reversible 'certain conditions' for activating dynamic sulfur-connecting bond includes, but is not limited to, temperature adjustment, addition of oxidation-reduction agent, addition of catalyst, addition of initiator, light irradiation, radiation, microwave, plasma action, pH adjustment and the like, for example, the dynamic sulfur-connecting bond can be broken to form sulfur radical by heating, so that the dynamic sulfur-connecting bond is dissociated and exchanged, the dynamic sulfur-connecting bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairability and reworkability, light irradiation can also lead the dynamic sulfur-connecting bond to be broken to form sulfur radical, so that the dissociation and exchange reaction of disulfide bond can be carried out, the dynamic sulfur-connecting bond is reformed after removing the light irradiation, so that the polymer can obtain self-repairability and reworkability, radiation, microwave and plasma can generate radical in the system to act with the dynamic sulfur-connecting bond, so that the self-repairability and reworkability can be obtained, so that the dynamic sulfur-connecting bond can be formed and exchanged, so that the process is accelerated and the self-repairability can be obtained, wherein the dynamic reversible catalyst includes, the dynamic hydrogen peroxide-oxidizing agent can be obtained by adding the hydrogen peroxide-oxidizing agent, the hydrogen peroxide-oxidizing agent can also include, the hydrogen peroxide-oxidizing agent can be obtained by heating, the hydrogen peroxide-oxidizing agent includes, the hydrogen peroxide-oxidizing agent includes, the hydrogen peroxide-bis-2-bis-phenyl-bis-phenyl-2-bis-phenyl-thiobenzone-2-bis (2-ethyl-bis (2-phenyl-bis-phenyl-ethyl-phenyl-ethyl-ketone-ethyl-2-bis (2-phenyl-bis-phenyl-bis (2-phenyl-bis (2-phenyl-ethyl-phenyl-ethyl-ketone), the hydrogen peroxide-ketone-bis (2-phenyl-ethyl-phenyl-2-phenyl-ketone), the hydrogen peroxide-bis (2-ethyl-phenyl-bis (2) initiator, 2-bis (2-phenyl) initiator, 2-bis (2) initiator, 2-phenyl-bis (2-phenyl) initiator, 2-bis (2) initiator, 2-bis (4) initiator, 2-bis (2) initiator, 2-bis (2.

In the embodiment of the present invention, the dynamic sulfur linkage contained in the dynamic polymer may be formed by a bond formation reaction of a sulfur radical by an oxidative coupling reaction of a mercapto group contained in a compound raw material, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a disulfide linkage. Among these, the compound raw material containing a disulfide bond is not particularly limited, and a polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, ester, amide, sulfur, and mercapto compound containing a disulfide bond are preferable, and a polyol, isocyanate, epoxy compound, alkene, and alkyne containing a disulfide bond are more preferable.

The dynamic double selenium bond can be activated under certain conditions, and dissociation, bonding and exchange reaction of the bond are carried out, so that the dynamic reversible characteristic is embodied; the dynamic diselenide bond described in the present invention is selected from, but not limited to, the following structures:

wherein,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic double selenium bond structures may be mentioned for example:

in the embodiment of the invention, the dynamic reversible 'certain conditions' for activating the dynamic bis-seleno bond includes but is not limited to temperature adjustment, addition of redox agent, addition of catalyst, addition of initiator, irradiation, radiation, microwave, plasma action and the like, so that the dynamic polymer shows good self-repairing property, recycling property, stimulation responsiveness and the like, for example, heating can lead the dynamic bis-seleno bond to be broken to form selenium free radical, so that dissociation and exchange reaction of the bis-seleno bond can be generated, the dynamic bis-seleno bond is reformed and stabilized after cooling, self-repairing property and reprocessing property can be displayed, the polymer containing the bis-seleno bond can obtain good self-repairing property by laser irradiation, free radical can be generated in the system by irradiation, microwave and plasma, and the dynamic repairing bis-seleno bond can be generated in the system to act with the dynamic repairing bis-seleno bond so that self-repairing property and reprocessing property can be obtained, the dynamic polymer can also be recycled by adding the redox agent in the system, wherein the dynamic bis-seleno bond can be promoted to be dissociated into alcohol, so that the polymer is dissociated, the dynamic initiator can be formed into bis-seleno-peroxide, the peroxide system can also include but is not limited to be generated, the peroxide-2-peroxide-2-ethyl-bis-benzoyl peroxide-ketone-2-disulfide (such as 2-ethyl-2-thiobenzone-2-bis-oxobenzene-2-bis-oxoacetone-bis-oxobenzene-oxoketone, bis-oxoketone-bis-oxoketone, bis-oxoketone, bis-oxoethyl-oxoketone, 2-oxoketone-bis-oxoketone, bis-oxoketone, bis-oxoketone, bis-oxoketone.

In the embodiment of the present invention, the dynamic diselenide bond contained in the dynamic polymer may be formed by an oxidative coupling reaction of selenol contained in the compound raw material or a bond-forming reaction of a selenium radical, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the diselenide bond. Among these, the compound having a diselenide bond is not particularly limited as a raw material, and a polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, diselenide (e.g., sodium diselenide, dichlorodiselenide) having a diselenide bond is preferable, and a polyol, isocyanate, epoxy compound, alkene, alkyne having a diselenide bond is more preferable.

The dynamic selenium-nitrogen bond can be activated under a certain condition, and dissociation, bonding and exchange reaction of the bond are carried out, so that the dynamic reversible characteristic is embodied; the dynamic seleno-nitrogen bond described in the present invention is selected from, but not limited to, the following structures:

wherein X is selected from halogen ions, preferably chloride ions and bromide ions,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic selenium nitrogen bond structures can be exemplified by:

in the embodiment of the present invention, the "certain condition" for activating the dynamic reversibility of the dynamic diselenide bond includes, but is not limited to, temperature regulation, addition of an acid-base catalyst, and the like, so that the dynamic polymer exhibits good self-repairing property, recycling property, stimulus responsiveness, and the like. Wherein, the acid-base catalyst can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, and cobalt carbonate. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf))₃) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.

In an embodiment of the invention, the dynamic selenazonium bond contained in the dynamic polymer can be formed by reacting a phenyl seleno halide contained in the compound starting material with a pyridine derivative.

The acetal dynamic covalent bond comprises a dynamic ketal bond, a dynamic acetal bond, a dynamic thioketal bond and a dynamic thioketal bond, can be activated under certain conditions, and generates bond dissociation, ketal reaction and exchange reaction, thereby reflecting the dynamic reversible characteristic; the "certain conditions" for activating the dynamic reversibility of acetal dynamic covalent bond means heating, appropriate acidic aqueous conditions, and the like. The acetal-based dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein, X₁、X₂、X₃、X₄Each independently selected from oxygen atom, sulfur atom, nitrogen atom, preferably from oxygen atom, sulfur atom; r₁、R₂Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; r₃、R₄Each independently selected from the group consisting of a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group, a divalent or polyvalent polymer chain residue;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein

May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical acetal-based dynamic covalent bond structures include, for example:

in the embodiment of the present invention, the acetal dynamic covalent bond can be dissociated in an acidic aqueous solution and formed under anhydrous acidic conditions, and has good pH stimulus responsiveness, so that dynamic reversibility can be obtained by adjusting an acidic environment.

In embodiments of the present invention, acids that may be used in the dynamic ketal reaction include, but are not limited to, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid, oxalic acid, carbonic acid, propionic acid, nonanoic acid, silicic acid, acetic acid, nitric acid, chromic acid, phosphoric acid, 4-chloro-benzenesulfinic acid, p-methoxybenzoic acid, 1, 4-phthalic acid, 4, 5-difluoro-2-nitrophenylacetic acid, 2-bromo-5-fluorophenylpropionic acid, bromoacetic acid, chloroacetic acid, phenylacetic acid, adipic acid, and the like. The acid used in the present invention may be in the form of a simple acid, an organic acid solution, an aqueous acid solution, or a vapor of an acid, without limitation. The invention can also use different states of the acid in a combined mode, such as promoting the formation of dynamic covalent bonds by using an organic solution of p-toluenesulfonic acid, and dissociating the dynamic covalent bonds by using an aqueous solution of hydrochloric acid to obtain recycling property and the like.

In an embodiment of the present invention, the acetal dynamic covalent bond contained in the dynamic polymer may be formed by condensation reaction of a ketone group, an aldehyde group, a hydroxyl group, and a thiol group contained in a compound raw material, may be formed by exchange reaction of the acetal dynamic covalent bond with an alcohol, a thiol, an aldehyde, and a ketone, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the acetal dynamic covalent bond. Among these, the raw material of the compound having the acetal dynamic covalent bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having the acetal dynamic covalent bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having the acetal dynamic covalent bond are more preferable.

The dynamic covalent bond based on the carbon-nitrogen double bond comprises a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond and a dynamic acylhydrazone bond, can be activated under certain conditions, and undergoes dissociation, condensation and exchange reaction of the dynamic covalent bond, so that the dynamic reversible characteristic is reflected; herein, the "certain condition" for activating the dynamic covalent bond dynamic reversibility based on a carbon-nitrogen double bond refers to an appropriate pH aqueous condition, an appropriate catalyst presence condition, a heating condition, a pressurizing condition, and the like. The dynamic covalent bond based on carbon-nitrogen double bond in the invention is selected from but not limited to at least one of the following structures:

wherein R is₁Is a divalent or polyvalent small molecule hydrocarbon group;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic covalent bond structures based on carbon-nitrogen double bonds may be mentioned, for example:

in the embodiment of the present invention, the suitable pH aqueous condition for promoting the dissociation and condensation reaction of the dynamic covalent bond based on carbon-nitrogen double bond refers to that the dynamic polymer is swelled in an aqueous solution with a certain pH value or the surface thereof is wetted with an aqueous solution with a certain pH value, so that the dynamic covalent bond based on carbon-nitrogen double bond in the dynamic polymer has dynamic reversibility. The aqueous solution can be all aqueous solution, or organic solution containing water, oligomer, plasticizer and ionic liquid. The pH of the aqueous solution selected varies depending on the type of the selected dynamic covalent bond based on carbon-nitrogen double bond, for example, for the dynamic phenylimide bond, an acidic solution having a pH of 6.5 or less may be selected for hydrolysis, and for the dynamic acylhydrazone bond, an acidic solution having a pH of 4 or less may be selected for hydrolysis.

Wherein, the acid-base catalyst for the dissociation, condensation and exchange reaction of the dynamic covalent bond based on carbon-nitrogen double bond can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methylSulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, and cobalt carbonate. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf))₃) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.

In the embodiment of the present invention, the dynamic covalent bond based on carbon-nitrogen double bond contained in the dynamic polymer may be formed by condensation reaction of a ketone group, an aldehyde group, an acyl group and an amino group, a hydrazine group, a hydrazide group contained in the compound raw material, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the dynamic covalent bond based on carbon-nitrogen double bond. Among these, the raw material of the compound having a dynamic covalent bond based on a carbon-nitrogen double bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic covalent bond based on a carbon-nitrogen double bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond based on a carbon-nitrogen double bond are more preferable.

The dynamic covalent bond based on the reversible free radical can be activated under certain conditions to form a reversible oxygen/sulfur/carbon/nitrogen free radical, and generates bonding or exchange reaction of the bond, so that the dynamic reversible characteristic is embodied; the "exchange reaction of dynamic covalent bonds based on reversible free radicals" refers to that intermediate reversible free radicals formed after the dissociation of old dynamic covalent bonds in the polymer form new dynamic covalent bonds elsewhere, so that the exchange of chains and the change of the topological structure of the polymer are generated. The dynamic covalent bond based on reversible free radicals in the present invention is selected from, but not limited to, at least one of the following structures:

wherein, X₁、X₂Is a sterically hindered divalent or polyvalent radical directly bonded to the nitrogen atom, each of which is independently selected from divalent or polyvalent C_3-20Alkyl, divalent or polyvalent cyclic C_3-20Alkyl, phenyl, benzyl, aryl, carbonyl, sulfone, phosphate and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropylidene, isobutylene, isoamylidene, isohexylidene, cyclohexylidene, phenylene, benzylidene, carbonyl, sulfone, phosphate; r' is a group directly linked to a carbon atom, each independently selected from a hydrogen atom, C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated, substituted, hybridized forms of the above groups and combinations thereof, R 'is preferably selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl, methylbenzyl, R' is more preferably selected from the group consisting of methyl, ethyl, isopropyl, phenyl, benzyl; wherein each W is independently selected from an oxygen atom, a sulfur atom; w₁Each independently selected from ether groups, thioether groups, secondary amine groups and substituents thereof, preferably from ether groups; w₂Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups and substituents thereof, carbonyl groups, thiocarbonyl groups, divalent methyl groups and substituents thereof, preferably from the group consisting of thioether groups, secondary amine groups and substituents thereofA substituent, a carbonyl group; w₃Each independently selected from ether groups, thioether groups; w₄Each independently selected from the group consisting of a direct bond, an ether group, a thioether group, a secondary amine group and substituents thereof, a carbonyl group, a thiocarbonyl group, a divalent methyl group and substituents thereof, preferably from the group consisting of a direct bond, an ether group, a thioether group; w, W at different locations₁、W₂、W₃、W₄The structures of the two groups can be the same or different; wherein R is₁Each independently selected from hydrogen atom, halogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residue, R₁Preferably selected from hydrogen atom, hydroxy group, cyano group, carboxy group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heteroaryl, substituted C_1-20Alkyl, substituted hetero C_1-20Alkyl radical, R₁More preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group, and R at different positions₁May be the same or different; wherein R is₂Each independently selected from hydrogen atom, cyano group, hydroxy group, phenyl group, phenoxy group, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein L 'is a divalent linking group selected from the group consisting of a single bond, a heteroatom linking group, and a divalent small hydrocarbon group, L' is preferably selected from the group consisting of acyl, acyloxy, acylthio, amido, oxyacyl, sulfuryl, phenylene, divalent C_1-20Alkyl, substituted divalent C_1-20Alkyl, substituted divalent C_1-20The heteroalkyl group, L 'is more preferably selected from acyl, oxyacyl, aminoacyl, phenylene, and L' at different positions may be the same or different; wherein V, V ' are independently selected from carbon atom and nitrogen atom, V, V ' at different positions can be the same or different, and when V, V ' is selected from nitrogen atom, it is connected with V, V

Is absent; wherein,

the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein, X₁And X₂On

Can be connected into a ring, and can form the following structure:

wherein, the ring is nitrogen-containing aliphatic ring, nitrogen-containing aromatic ring or their combination with any number of elements, at least one ring atom is nitrogen atom, the hydrogen atom on the ring atom can be substituted by any substituent or not, the ring is preferably nitrogen-containing five-membered ring or nitrogen-containing six-membered ring, and is optimally selected from 2,2,6, 6-tetramethyl-piperidine, 4,5, 5-tetramethyl-imidazole, 2,5, 5-tetramethyl pyrrole, maleimide, succinimide and triazone. Typical dynamic covalent bond structures based on reversible free radicals may be mentioned, for example:

in an embodiment of the present invention, the "certain conditions" for activating dynamic reversibility of dynamic covalent bond based on reversible free radical include, but are not limited to, temperature adjustment, addition of initiator, light irradiation, radiation, microwave, plasma action, etc., for example, the dynamic covalent bond may be cleaved by heating to form nitroxide radical/thioaza radical/carbon radical, thereby causing dissociation and exchange reaction of dynamic covalent bond, and the dynamic covalent bond may be reformed and stabilized after cooling, thereby allowing the polymer to obtain self-repairability and reworkability, the light irradiation may also cause the dynamic covalent bond to be cleaved to form nitroxide radical/thioaza radical/carbon radical, thereby causing dissociation and exchange reaction of dynamic covalent bond, and the dynamic covalent bond may be reformed after removing light irradiation, microwave and the like, thereby obtaining self-repairability and reworkability, the initiator may generate free radical, thereby promoting dissociation or exchange of dynamic covalent bond, thereby obtaining self-repairability or recycling of repairability, wherein the initiator includes any one of the following initiators, such as photoinitiator, including, bis (2-tert-butyl) benzoyloxybenzoyl-2-bis (2-butyl-2-p-2-butyl-2-oxoethyl-2-bis (p-2-propyl-2-bis (4-butyl-oxoethyl-2-bis (p-propyl-2-propyl-p-2-propyl-2-bis (preferably-2-bis (di-tert-butyl-propyl-butyl-2-propyl-p-propyl-2-butyl-2-p-2-propyl-p-2-propyl-peroxybenzoylperoxy-2-butyl-2-propyl-2-peroxy-2-propyl-peroxy.

In an embodiment of the present invention, the dynamic covalent bond based on the reversible radical contained in the dynamic polymer may be formed by a bonding reaction of a nitroxide radical, a nitrogen-sulfur radical, a carbon radical, a nitrogen radical contained in a compound raw material, or other suitable coupling reaction; it can be generated in situ in the polymer or can be introduced into the dynamic polymer by polymerization/crosslinking reactions between the reactive groups it contains using a compound starting material containing a dynamic covalent bond based on a reversible free radical. Among these, the raw material of the compound having a dynamic covalent bond based on a reversible radical is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic covalent bond based on a reversible radical are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond based on a reversible radical are more preferable.

The combinable exchangeable acyl bond can be activated under certain conditions, and can perform combinable acyl exchange reaction (such as combinable ester exchange reaction, combinable amide exchange reaction, combinable carbamate exchange reaction, combinable vinyl-inserting amide or vinyl-inserting carbamate exchange reaction and the like) with a nucleophilic group, so that the dynamic reversible characteristic is shown; wherein, the 'associative acyl exchange reaction' means that the associative exchangeable acyl bonds are firstly combined with nucleophilic groups to form an intermediate structure, and then the acyl exchange reaction is carried out to form a new dynamic covalent bond, thereby generating exchange of chains and change of a topological structure of the polymer, wherein the crosslinking degree of the polymer can be kept unchanged; wherein the "certain conditions" for activating the dynamic reversibility of the binding exchangeable acyl bond means suitable catalyst existence conditions, heating conditions, pressurizing conditions, etc.; the "nucleophilic group" refers to a reactive group such as hydroxyl, sulfhydryl and amino group, which is present in a polymer system for a binding acyl exchange reaction, and the nucleophilic group may be on the same polymer network/chain as the binding exchangeable acyl bond, may be on a different polymer network/chain, or may be introduced through a small molecule or a polymer containing the nucleophilic group. The binding exchangeable acyl bond as described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein, X₁、X₂Selected from carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; y is selected from the group consisting of an oxygen atom, a sulfur atom and a secondary amine group; z₁、Z₂Selected from oxygen atom, sulfur atom; r₅Selected from the group consisting of hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein, when X₁、X₂When it is an oxygen atom or a sulfur atom, R₁、R₂、R₃、R₄Is absent; when X is present₁、X₂When it is a nitrogen atom, R₁、R₃Exist, R₂、R₄Is absent, and R₁、 R₃Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present₁、X₂When it is a carbon atom or a silicon atom, R₁、R₂、R₃、R₄Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Wherein the binding exchangeable acyl bond is preferably selected from the group consisting of a binding exchangeable ester bond, a binding exchangeable thioester bond, a binding exchangeable amide bond, a binding exchangeable urethane bond, a binding exchangeable thiocarbamate bond, a binding exchangeable urea bond, a binding exchangeable vinyl amide bond, and a binding exchangeable vinyl carbamate bond. Typical binding exchangeable acyl bond structures may be exemplified by:

among them, the acyl bond having an exchangeable binding property to a nucleophilic group is more preferable, and typical structures thereof are, for example:

in the present invention, some of the bonded acyl exchange reactions need to be carried out under catalytic conditions, and the catalysts include catalysts for transesterification (including esters, thioesters, carbamates, thiocarbamates, etc.) and amine exchange (including amides, carbamates, thiocarbamates, ureas, vinylogous amides, vinylogous carbamates, etc.). By adding the catalyst, the occurrence of the combined acyl exchange reaction can be promoted, so that the dynamic polymer shows good dynamic characteristics.

Wherein the catalyst for the transesterification reaction may be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium carbonate, and cobalt carbonate. (3) The alkali metal of group IIA and its compounds are exemplified by calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, and magnesium ethoxide. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, and an aluminum alkoxide-based compound can be cited. (5) Tin compounds include inorganic tin compounds and organic tin compounds. Examples of the inorganic tin include tin oxide, tin sulfate, stannous oxide, and stannous chloride. Examples of the organotin include dibutyltin oxide, dibutyltin dilaurate, dibutyltin dichloride, tin tributylacetate, tributyltin chloride and trimethyltin chloride. Examples of the group IVB element compound (6) include titanium dioxide, tetramethyl titanate, isopropyl titanate, isobutyl titanate, tetrabutyl titanate, zirconium oxide, zirconium sulfate, zirconium tungstate, and tetramethyl zirconate. (7) Anionic layered column compounds, whose main component is generally composed of hydroxides of two metals, are known asThe double metal hydroxide LDH, the calcined product of which is LDO, may be exemplified by hydrotalcite { Mg }₆(CO₃)[Al(OH)₆]₂(OH)₄·4H₂O }. (8) Supported solid catalysts, which may be mentioned by way of example KF/CaO, K₂CO₃/CaO、KF/γ-Al₂O₃、K₂CO₃/γ-Al₂O₃、KF/Mg-La、K₂O/activated carbon, K₂CO₃Coal ash powder, KOH/NaX, KF/MMT (montmorillonite) and other compounds. (9) Examples of the organozinc compound include zinc acetate and zinc acetylacetonate. (10) Examples of the organic compound include 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene (TBD), 2-methylimidazole (2-MI), triphenylphosphine, and the like. Among them, preferred are organotin compounds, titanate compounds, organozinc compounds, supported solid catalysts, TBD, 2-MI; more preferably, TBD and zinc acetate are mixed and used for concerted catalysis, and 2-MI and zinc acetylacetonate are mixed and used for concerted catalysis.

Among them, the catalyst for amine exchange reaction can be selected from: nitric acid, hydrochloric acid, aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)₃) Montmorillonite KSF, hafnium tetrachloride (HfCl)₄)、Hf₄Cl₅O₂₄H₂₄、 HfCl₄KSF-polyDMAP, transglutaminase (TGase); divalent copper compounds, such as copper acetate; examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, copper acetate is preferable; sc (OTf)₃And HfCl₄Mixing and sharing synergistic catalysis; HfCl₄KSF-polyDMAP; the glycerol, the boric acid and the ferric nitrate hydrate are mixed to share the synergistic catalysis.

In the present embodiment, some of the coupling acyl exchange reactions may be performed by microwave irradiation or heating. For example, conventional urethane, thiourethane, and urea linkages may be usedHeating to 160-180 ℃, and carrying out an acyl exchange reaction under the pressure of 4 MPa; the vinylogous amide bond and the vinylogous carbamate bond can generate acyl exchange reaction through Michael addition when being heated to more than 100 ℃;

the urethane bond of the structure can be heated to more than 90 ℃ to carry out acyl exchange reaction with the molecular chain containing the phenolic hydroxyl or the benzyl hydroxyl structure. The present invention preferably performs the reversible reaction under normal temperature and normal pressure conditions by adding a catalyst that can be used for the binding acyl exchange reaction.

In the embodiment of the present invention, the exchangeable acyl bond for binding contained in the dynamic polymer may be formed by condensation reaction of acyl group, thioacyl group, aldehyde group, carboxyl group, acid halide, acid anhydride, active ester, isocyanate group contained in the compound raw material with hydroxyl group, amino group, mercapto group, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the exchangeable acyl bond for binding. Among these, the starting material of the compound having the exchangeable acyl bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having the exchangeable acyl bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having the exchangeable acyl bond are more preferable.

The dynamic covalent bond based on steric effect induction can be activated at room temperature or under a certain condition due to the fact that the dynamic covalent bond contains the large group with the steric effect, and the dissociation, bonding and exchange reaction of bonds occur, so that the dynamic reversible characteristic is embodied. The steric effect induced dynamic covalent bond is selected from, but not limited to, at least one of the following structures:

wherein，X₁、X₂Selected from carbon atoms, silicon atoms and nitrogen atoms, preferably carbon atoms, nitrogen atoms; z₁、Z₂Selected from oxygen atoms and sulfur atoms, preferably oxygen atoms; when X is present₁、X₂When it is a nitrogen atom, R₁、R₃Exist, R₂、R₄Is absent, and R₁、R₃Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present₁、X₂When it is a carbon atom or a silicon atom, R₁、R₂、R₃、R₄Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein R is_bIs a bulky group with steric hindrance directly bonded to the nitrogen atom, and is selected from C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, benzyl, methylbenzyl, most preferably selected from tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, methylbenzyl;

a nitrogen-containing ring having an arbitrary number of atoms, which may be an aliphatic ring or an aromatic ring, which may be an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, or a combination thereof, wherein the ring-forming atoms are each independently selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or another hetero atom, and the hydrogen atom on the ring-forming atom may or may not be substituted with any substituent, and the ring formed is preferably a pyrrole ring, an imidazole ring, a piperidine ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring; n represents the number of linkages to the ring-forming atoms of the cyclic group structure. Typical steric effect-based induced dynamic covalent bond structures may be exemplified by:

the large group with steric hindrance effect in the invention is directly connected with a nitrogen atom or forms a ring structure with the nitrogen atom, and can weaken the chemical bond strength between a carbon atom in carbonyl and thiocarbonyl and an adjacent nitrogen atom, so that the carbon-nitrogen bond shows the property of a dynamic covalent bond, and the dynamic reversible reaction can be carried out at room temperature or under certain conditions. It is to be noted that the larger the steric effect in the "bulky group having steric effect" is, the better, the moderate size is, and the appropriate dynamic reversibility of the carbon-nitrogen bond is imparted. The 'certain condition' for activating dynamic covalent bond dynamic reversibility induced by steric effect comprises but is not limited to action modes of heating, pressurizing, lighting, radiation, microwave, plasma action and the like, so that the dynamic polymer has good self-repairability, recycling property, stimulus responsiveness and the like. For example,

the dynamic covalent bond of the structure can carry out dynamic exchange reaction at 60 ℃, and shows dynamic characteristics.

In the present invention, the steric effect induced dynamic covalent bond is preferably selected from steric effect induced amide bond, steric effect induced urethane bond, steric effect induced thiourethane bond, and steric effect induced urea bond.

In an embodiment of the present invention, the steric effect induced dynamic covalent bond contained in the dynamic polymer may be formed by condensation reaction of an acyl group, a thioacyl group, an aldehyde group, a carboxyl group, an acid halide, an acid anhydride, an active ester, and an isocyanate group contained in a compound raw material with an amino group having a bulky group having steric effect attached thereto, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between reactive groups contained therein using a compound raw material containing the steric effect induced dynamic covalent bond. Among these, the raw material of the compound having a dynamic covalent bond induced by steric hindrance is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, or a carboxylic acid having a dynamic covalent bond induced by steric hindrance is preferably contained, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, or an alkyne having a dynamic covalent bond induced by steric hindrance is more preferably contained.

The reversible addition fragmentation chain transfer dynamic covalent bond can be activated in the presence of an initiator, and a reversible addition fragmentation chain transfer reaction is carried out, so that the dynamic reversible characteristic is embodied. The reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein R is₁～R₁₀Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; x₁、X₂、X₃Each independently selected from single bond, divalent or polyvalent small molecule hydrocarbon group, preferably from divalent C_1-20Alkyl groups and substituted forms thereof, hybridized forms thereof, and combinations thereof, more preferably selected from the group consisting of divalent isopropyl groups, divalent cumyl groups, divalent isopropyl ester groups, divalent isopropylcarboxyl groups, divalent isopropyl nitrile groups, divalent nitrile cumyl groups, divalent acrylic acid group n-mers, divalent acrylic ester group n-mers, divalent styrene group n-mers and substituted forms thereof, hybridized forms thereof, and combinations thereof, wherein n is greater than or equal to 2; z₁、Z₂、Z₃Each independently selected from a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbyl group, preferably from a heteroatom linking group having or associated with a group having an electro-absorption effect, a divalent or polyvalent small molecule hydrocarbyl group having or associated with a group having an electro-absorption effect; wherein as Z₂、Z₃Preferably, it can be selected from ether groups, thio groups, seleno groups, divalent silicon groups, divalent aminesA group, a divalent phosphoric acid group, a divalent phenyl group, a methylene group, an ethylene group, a divalent styryl group, a divalent isopropyl group, a divalent cumyl group, a divalent isopropyl ester group, a divalent isopropylcarboxyl group, a divalent isopropylnitrile group, a divalent nitrile isopropylphenyl group; wherein, the group having the electric absorption effect includes, but is not limited to, carbonyl group, aldehyde group, nitro group, ester group, sulfonic group, amido group, sulfone group, trifluoromethyl group, aryl group, cyano group, halogen atom, alkene, alkyne and combination thereof;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.

The reversible addition fragmentation chain transfer dynamic covalent bonds described herein are preferably polyacrylic and ester groups, polymethacrylic and ester groups, polystyrene, polymethylstyrene, allyl sulfide groups, dithioester groups, diseleno groups, trithiocarbonate groups, triselenocarbonate groups, diseleno thiocarbonate groups, dithioselenocarbonate groups, bisthioester groups, bisseleno groups, bistrothiocarbonate groups, bistriselenocarbonate groups, dithiocarbamato groups, diseleno carbamate groups, dithiocarbonate groups, diseleno carbonate groups, and derivatives thereof.

Typical reversible addition fragmentation chain transfer dynamic covalent bond structures may be exemplified by:

wherein n is the number of the repeating units, can be a fixed value or an average value, and n is more than or equal to 1.

The "reversible addition fragmentation chain transfer reaction" described in the present invention means that when a reactive radical reacts with the reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention to form an intermediate, the intermediate can be fragmented to form a new reactive radical and a new reversible addition fragmentation chain transfer dynamic covalent bond, and this process is a reversible process. This process is similar to, but not exactly identical to, the reversible addition fragmentation chain transfer process in reversible addition fragmentation chain transfer polymerization. Firstly, reversible addition fragmentation chain transfer polymerization is a solution polymerization process, and the reversible addition fragmentation chain transfer reaction can be carried out in solution or solid; in addition, in the reversible addition fragmentation chain transfer reaction, a proper amount of a substance capable of generating an active free radical can be added to generate the active free radical under a certain condition, so that the reversible addition fragmentation chain transfer dynamic covalent bond has good dynamic reversibility, and the progress of the reversible addition fragmentation chain transfer reaction is promoted.

Wherein, the initiator optionally used in the reversible addition-fragmentation chain transfer exchange reaction includes, but is not limited to, any one or any of photoinitiators such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and α -ketoglutaric acid, organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, tert-butylperoxypivalate, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, inorganic peroxides such as dimethoxyacetophenone, potassium peroxydisulfate, etc., preferably, 2-dimethoxybenzoyl peroxybenzoate, ammonium persulfate, and azobenzoperoxydisulfonitrile.

In an embodiment of the present invention, the reversible addition fragmentation chain transfer dynamic covalent bond contained in the dynamic polymer may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between the reactive groups contained therein using a compound starting material containing the reversible addition fragmentation chain transfer dynamic covalent bond.

The dynamic siloxane bond can be activated under the condition of catalyst or heating, and siloxane exchange reaction is carried out, so that the dynamic reversible property is embodied; the term "siloxane exchange reaction" refers to the formation of new siloxane bonds elsewhere with concomitant dissociation of old siloxane bonds, resulting in exchange of chains and a change in polymer topology. The dynamic siloxane bond described in the present invention is selected from, but not limited to, the following structures:

wherein,

may be looped or not looped.

In the present invention, the siloxane reaction is carried out in the presence of a catalyst or under heating, wherein the dynamic siloxane bond is preferably subjected to a siloxane bond exchange reaction in the presence of a catalyst. The catalyst can promote the siloxane equilibrium reaction, so that the dynamic polymer has good dynamic characteristics. Among them, the catalyst for the siloxane equilibrium reaction can be selected from: (1) examples of the alkali metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, and calcium hydroxide. (2) Examples of the alkali metal alkoxide and the alkali metal polyalcohol salt include potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium propoxide, potassium n-butoxide, potassium isobutoxide, sodium t-butoxide, potassium t-butoxide, lithium pentoxide, potassium ethylene glycol, sodium glycerol, potassium 1, 4-butanediol, sodium 1, 3-propanediol, lithium pentaerythritol, and sodium cyclohexanolate. (3) Examples of the silicon alkoxide include potassium triphenylsilanolate, sodium dimethylphenylsilicolate, lithium tri-tert-butoxysilicolate, potassium trimethylsilolate, sodium triethylsilanolate, lithium (4-methoxyphenyl) dimethylsilolate, tri-tert-pentoxysilicolate, potassium diphenylsilanediol, and potassium benzyltrimethylammonium bis (catechol) phenylsilicolate. (4) Examples of the quaternary ammonium bases include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), trimethylbenzylammonium hydroxide, tetrabutylammonium hydroxide, (1-hexadecyl) trimethylammonium hydroxide, methyltriethylammonium hydroxide, phenyltrimethylammonium hydroxide, tetra-N-hexylammonium hydroxide, tetrapropylammonium hydroxide, tetraoctylammonium hydroxide, triethylbenzylammonium hydroxide, choline, [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt, phenyltriethylammonium hydroxide, N, N, N-trimethyl-3- (trifluoromethyl) aniline hydroxide, N-ethyl-N, N-dimethyl-ethylammonium hydroxide, tetradecylammonium hydroxide, tetrapentylammonium hydroxide, N, N, n-trimethyl-1-adamantylammonium hydroxide, forty-eight alkyl ammonium hydroxide, N-dimethyl-N- [3- (thioxo) propyl ] -1-nonane ammonium hydroxide inner salt, (methoxycarbonylsulfamoyl) triethylammonium hydroxide, 3-sulfopropyldodecyl dimethyl betaine, 3- (N, N-dimethyl palmitylamino) propane sulfonate, methacryloylethyl sulfobetaine, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt, tributylmethyl ammonium hydroxide, tris (2-hydroxyethyl) methyl ammonium hydroxide, tetradecyl sulfobetaine, and the like. In the present invention, the catalyst used for the siloxane equilibrium reaction is preferably a catalyst of quaternary ammonium base, silanol type, or alkali metal hydroxide type, and more preferably a catalyst of lithium hydroxide, potassium trimethylsilanolate, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), or the like.

In the embodiment of the present invention, the dynamic siloxane bond contained in the dynamic polymer may be formed by a condensation reaction between a silicon hydroxyl group and a silicon hydroxyl group precursor contained in the compound raw material, or may be formed by a reactive group contained in the compound raw material containing a dynamic siloxane bond through the silicon hydroxyl group precursor contained in the compound raw materialIn the presence of a polymerization/crosslinking reaction between the two polymers. Among these, the raw material of the compound having a dynamic siloxane bond is not particularly limited, and a polyol, a polyamine, an isocyanate, a siloxane compound, a hydrosiloxane compound, an epoxy compound, an alkene, and an alkyne having a dynamic siloxane bond are preferable, and a polyol, an isocyanate, a siloxane compound, a hydrosiloxane compound, and an alkene having a dynamic siloxane bond are more preferable. Wherein the silicon hydroxyl precursor refers to a structural unit (Si-X) consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group and is connected with the silicon atom₁) Wherein X is₁Groups which are hydrolyzable to give hydroxyl groups may be selected from the group consisting of halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide groups. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO₄CH₃，Si-OB(OCH₃)₂，Si-NH₂，Si-N(CH₃)₂，Si-OCH₃，Si-COCH₃， Si-OCOCH₃，Si-CONH₂，Si-O-N＝C(CH₃)₂，Si-ONa。

The dynamic silicon ether bond can be activated under the heating condition, and generates a silicon ether bond exchange reaction, so that the dynamic reversible characteristic is embodied; the "exchange reaction of the silyl ether bond" refers to the formation of a new silyl ether bond elsewhere with concomitant dissociation of the old silyl ether bond, resulting in exchange of the chains and a change in the topology of the polymer. The dynamic silicon ether linkage described in the present invention is selected from, but not limited to, the following structures:

wherein,

may be looped or not looped. Among them, the dynamic silicon ether bond is more preferably selected from the following structures:

in the embodiment of the present invention, the dynamic silicon ether bond contained in the dynamic polymer may be formed by condensation reaction of a silicon hydroxyl group contained in a compound raw material, a silicon hydroxyl group precursor and a hydroxyl group in the system, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction of a reactive group contained in a compound raw material containing a dynamic silicon ether bond. Among these, the raw material of the compound having a dynamic silicon ether bond is not particularly limited, and a polyol, a polyamine, an isocyanate, a siloxane compound, a hydrosilation compound, an epoxy compound, an alkene, and an alkyne having a dynamic silicon ether bond are preferable, and a polyol, an isocyanate, a siloxane compound, a hydrosilation compound, and an alkene having a dynamic silicon ether bond are more preferable. Wherein the silicon hydroxyl precursor refers to a structural unit (Si-X) consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group and is connected with the silicon atom₁) Wherein X is₁Groups which are hydrolyzable to give hydroxyl groups may be selected from the group consisting of halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide groups. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO₄CH₃，Si-OB(OCH₃)₂，Si-NH₂，Si-N(CH₃)₂，Si-OCH₃，Si-COCH₃， Si-OCOCH₃，Si-CONH₂，Si-O-N＝C(CH₃)₂，Si-ONa。

The exchangeable dynamic covalent bond based on the alkyl triazolium can be activated under certain conditions, and can perform dynamic exchange reaction with the halogenated alkyl, so that the exchangeable dynamic covalent bond based on the alkyl triazolium shows dynamic reversible characteristics. The alkyl triazolium-based exchangeable dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:

wherein, X^—Is negative ion selected from bromide ion and iodide ion, preferably bromide ion;

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical interchangeable dynamic covalent bond structures based on alkyltriazolium are exemplified by:

in the embodiment of the present invention, the haloalkyl group, which may be an aliphatic haloalkyl group or an aromatic haloalkyl group, may be present in any suitable terminal group, side group and/or side chain in the dynamic polymer, or may be present in any suitable form in other components such as small molecules, oligomers, etc., and may be on the same polymer network/chain with exchangeable dynamic covalent bonds based on alkyltriazolium, or on different polymer networks/chains, or may be introduced through small molecules or polymers containing haloalkyl groups.

In the present embodiment, the "certain conditions" for activating the dynamic reversibility of exchangeable dynamic covalent bonds based on alkyltriazolium means in the presence of a halogenated alkyl group and a solvent and under suitable conditions of temperature, humidity and the like.

In the embodiment of the present invention, the raw material compound containing the alkyl triazolium-based exchangeable dynamic covalent bond is not particularly limited, but preferably contains an alkyl triazolium-based exchangeable dynamic covalent bond, an epoxy-based compound, an alkyl vinyl chloride, a vinyl chloride.

The unsaturated carbon-carbon double bond capable of generating the olefin cross-metathesis double decomposition reaction can be activated in the presence of a catalyst, and generates the olefin cross-metathesis double decomposition reaction, so that the dynamic reversible characteristic is embodied; wherein, the olefin cross metathesis double decomposition reaction refers to the carbon skeleton rearrangement reaction between unsaturated carbon-carbon double bonds catalyzed by metal catalyst; wherein, the rearrangement reaction refers to the generation of new carbon-carbon double bonds at other places and the dissociation of old carbon-carbon double bonds, thereby generating the exchange of chains and the change of polymer topological structure. The structure of the unsaturated carbon-carbon double bond capable of undergoing olefin cross metathesis reaction in the present invention is not particularly limited, and is preferably selected from the following structures having low steric hindrance and high reactivity:

in embodiments of the present invention, the catalyst for catalyzing olefin cross metathesis reaction includes, but is not limited to, metal catalysts based on ruthenium, molybdenum, tungsten, titanium, palladium, nickel, etc.; among them, the catalyst is preferably a catalyst based on ruthenium, molybdenum, tungsten, more preferably a ruthenium catalyst having higher catalytic efficiency and being insensitive to air and water, particularly a catalyst which has been commercialized such as Grubbs 'first generation, second generation, third generation catalysts, Hoveyda-Grubbs' first generation, second generation catalysts, etc. Among these, examples of catalysts useful in the present invention for catalyzing olefin cross metathesis reactions include, but are not limited to, the following:

wherein Py is₃Is composed of

Mes is

Ph is phenyl, Et is ethyl, i-Pr is isopropyl, t-Bu is tert-butyl, and PEG is polyethylene glycol.

The unsaturated carbon-carbon triple bond capable of generating alkyne cross-metathesis reaction can be activated in the presence of a catalyst, and generates alkyne cross-metathesis reaction, thereby showing dynamic reversible property; wherein, the alkyne cross metathesis double decomposition reaction refers to the carbon skeleton rearrangement reaction between unsaturated carbon-carbon triple bonds catalyzed by a metal catalyst; the rearrangement reaction refers to the formation of new triple bonds between carbon and the dissociation of old triple bonds between carbon and carbon, resulting in exchange of chains and change of polymer topology. The structure of the unsaturated carbon-carbon triple bond in which the alkyne cross metathesis reaction can occur in the present invention is not particularly limited, and is preferably selected from the structures shown below which are small in steric hindrance and high in reactivity:

in embodiments of the present invention, the catalyst for catalyzing alkyne cross-metathesis reaction includes, but is not limited to, metal catalysts based on molybdenum, tungsten, and the like; among them, the catalyst is preferably a catalyst having compatibility with the functional group, such as catalysts 15 to 20 in the exemplified structure, etc.; the catalyst is also preferably a catalyst having higher catalytic efficiency and being insensitive to air, such as catalysts 1, 18-20, etc. in the exemplified structure; the catalyst is also preferably a catalyst which can function catalytically at ambient temperature or in the ambient temperature range, such as catalyst 11 in the illustrated construction. Examples of catalysts useful in the present invention for catalyzing alkyne cross metathesis reactions include, but are not limited to, the following:

wherein Py is₃Is composed of

Ph is phenyl and t-Bu is tert-butyl.

In the embodiment of the present invention, the unsaturated carbon-carbon double bond capable of undergoing olefin cross metathesis reaction and the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross metathesis reaction contained in the dynamic polymer may be derived from a selected polymer precursor already containing the unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond, or may be generated or introduced on the basis of a polymer precursor not containing the unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond. However, since the reaction conditions for forming the carbon-carbon double bond/carbon-carbon triple bond are generally harsh, it is preferable to use a polymer precursor having carbon-carbon double bond/carbon-carbon triple bond to carry out the reaction, thereby achieving the purpose of introducing carbon-carbon double bond/carbon-carbon triple bond.

Among them, polymer precursors which already contain unsaturated carbon-carbon double bonds/unsaturated carbon-carbon triple bonds include, by way of example and not limitation, butadiene rubber, 1, 2-butadiene rubber, isoprene rubber, polynorbornene, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, polychloroprene, brominated polybutadiene, ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), unsaturated polyester, unsaturated polyether and its copolymer, 1, 4-butylene glycol, 1, 5-di-p-hydroxyphenyl-1, 4-pentadien-3-one, unsaturated carbon-carbon triple bonds, Glyceryl monoricinoleate, maleic acid, fumaric acid, trans-methylbutenedioic acid (mesaconic acid), cis-methylbutenedioic acid (citraconic acid), chloromaleic acid, 2-methylenesuccinic acid (itaconic acid), 4' -diphenylenedicarboxylic acid, 1, 5-di-p-hydroxyphenyl-1, 4-pentadien-3-one, fumaroyl chloride, 1, 4-phenylenediacryloyl chloride, citraconic anhydride, maleic anhydride, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, dimethyl citraconate, 1, 4-dichloro-2-butene, 1, 4-dibromo-2-butene, etc., and oligomers having a carbon-carbon double bond/carbon-carbon triple bond in the terminal-functionalized chain skeleton may also be used.

The [2+2] cycloaddition dynamic covalent bond is formed based on the [2+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic; wherein, the [2+2] cycloaddition reaction refers to a reaction that one unsaturated double bond and another unsaturated double bond or unsaturated triple bond respectively provide 2 pi electrons to react and add with each other to form a quaternary ring structure. The [2+2] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein D is₁～D₆Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, preferably from carbon atom, D₁、D₂At least one of them is selected from carbon atoms or nitrogen atoms; a is₁～a₆Respectively represent with D₁～D₆The number of connected connections; when D is present₁～D₆Each independently selected from an oxygen atom and a sulfur atom₁～a₆0; when D is present₁～D₆Each independently selected from the group consisting of nitrogen atoms,a₁～a₆1 is ═ 1; when D is present₁～D₆Each independently selected from carbon atoms, a₁～a₆＝2；Q₁～Q₆Each independently selected from carbon atoms, oxygen atoms; b₁～b₆Respectively represent and Q₁～Q₆The number of connected connections; when Q is₁～Q₆Each independently selected from oxygen atoms, b₁～b₆0; when Q is₁～Q₆Each independently selected from carbon atoms, b₁～b₆＝2；

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typically [2+2]]Examples of cycloaddition dynamic covalent bond structures are:

in an embodiment of the present invention, the unsaturated double bond for performing the [2+2] cycloaddition reaction may be selected from a carbon-carbon double bond, a carbon-oxygen double bond, a carbon-sulfur double bond, a carbon-nitrogen double bond, a nitrogen-nitrogen double bond; unsaturated triple bonds, which may be selected from carbon-carbon triple bonds, for forming said [2+2] cycloaddition dynamic covalent bond; wherein, the unsaturated double bond and the unsaturated triple bond are preferably directly connected with an electroabsorption effect group or an electrosupply effect group, and the electroabsorption effect group comprises but is not limited to carbonyl, aldehyde group, nitro, ester group, sulfonic group, acylamino, sulfonyl, trifluoromethyl, aryl, cyano, halogen atom, alkene, alkyne and combination thereof; the electron donating effector groups include, but are not limited to, hydroxyl, p-methoxyphenyl, thioether, amino, secondary amine, tertiary amine, methyl, ethyl, isopropyl, isobutyl, and combinations thereof.

In the embodiment of the present invention, the [2+2] cycloaddition dynamic covalent bond contained in the dynamic polymer may be formed by [2+2] cycloaddition reaction between unsaturated carbon-carbon double bonds, azo groups, carbonyl groups, aldehyde groups, thiocarbonyl groups, imino groups, cumulative diene groups, ketene groups contained in compound raw materials, or between the unsaturated carbon-carbon triple bonds and the compound raw materials, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in compound raw materials containing [2+2] cycloaddition dynamic covalent bonds, wherein the compound raw materials containing unsaturated carbon-carbon double bonds are preferably ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, butenedicarboxylic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α -unsaturated nitro compounds, cyclooctene, norbornene, maleic anhydride, p-propargyl dicarboxylic acid, butynedicarboxylic acid, azodicarboxylate, bisthioester, maleimide, fullerene, and derivatives of the above compounds, and the like, and wherein the raw materials containing [2+2] cycloaddition dynamic covalent bond, the compound containing [2+2] cycloaddition, alkyne, isocyanate, the compound containing no limitation is particularly preferred.

The [4+2] cycloaddition dynamic covalent bond is formed based on the [4+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic; wherein the [4+2] cycloaddition reaction refers to a reaction in which 4 pi electrons are provided by a diene group and 2 pi electrons are provided by a dienophile group to form a cyclic group structure by addition. The [4+2] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein, K₁、K₂、K₅～K₁₀Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K₁、K₂Or K₅、K₆Or K₇、 K₈Or K₉、K₁₀At least one atom selected from carbon atom or nitrogen atom; c. C₁～c₁₀Respectively represent and K₁～K₁₀The number of connected connections; when K is₁、 K₂、K₅～K₁₀Each independently selected from an oxygen atom and a sulfur atom, c₁、c₂、c₅～c₁₀0; when K is₁、K₂、K₅～K₁₀Each independently selected from nitrogen atoms, c₁、c₂、c₅～c₁₀1 is ═ 1; when K is₁、K₂、K₅～K₁₀Each independently selected from carbon atoms, c₁、c₂、c₅～c₁₀＝2；K₃、K₄Each independently selected from oxygen atom, sulfur atom, nitrogen atom; c. C₃、c₄Respectively represent and K₃、K₄The number of connected connections; when K is₃、K₄Each independently selected from an oxygen atom and a sulfur atom, c₃、c₄0; when K is₃、K₄Each independently selected from nitrogen atoms, c₃、c₄＝1；I₁、I₂Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, an amide group, an ester group, a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, a 1, 2-diethylene group, a 1, 2-vinylidene group, a 1,1' -vinyl group, substituted forms of a secondary amine group, an amide group, an ester group;

the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the structure of the cyclic group is preferably benzene ring, naphthalene ring, anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic group structure;

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical [4+2]]Examples of cycloaddition dynamic covalent bond structures are:

wherein, the [4+2] cycloaddition dynamic covalent bond can be connected with the light-control locking element to form the light-control DA structure. The light-operated locking element can react with the dynamic covalent bond and/or the light-operated locking element under a specific illumination condition to change the structure of the dynamic covalent bond, thereby achieving the purpose of locking/unlocking DA reaction; wherein, when the dynamic covalent bond is locked, it is unable or more difficult to perform DA equilibrium reaction, and when the dynamic covalent bond is unlocked, it is able to perform DA equilibrium reaction, realizing dynamic characteristics.

In the invention, the light control locking element comprises the following structural units:

wherein,

Can be linked to form a ring, on different atoms

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;

a photo-controlled [4+2] cycloaddition dynamic covalent bond attached to a photo-control locking motif, preferably selected from at least one of the following general structures:

wherein, K₁、K₂、K₃、K₄、K₅、K₆Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K₁、K₂Or K₃、 K₄Or K₅、K₆At least one of them is selected from carbon atoms; a is₁、a₂、a₃、a₄、a₅、a₆Respectively represent and K₁、K₂、K₃、K₄、K₅、K₆The number of connected connections; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from an oxygen atom and a sulfur atom₁、a₂、a₃、a₄、a₅、a₆0; when K is₁、K₂、K₃、K₄、K₅、K₆Each independently selected from nitrogen atoms, a₁、a₂、a₃、a₄、a₅、a₆1 is ═ 1; when K is₁、K₂、K₃、K₄、 K₅、K₆Each independently selected from carbon atoms, a₁、a₂、a₃、a₄、a₅、a₆＝2；I₁、I₂、I₃Each independently absent or each independently selected from the group consisting of an oxygen atom, a 1,1 '-carbonyl group, a methylene group and substituted forms thereof, a 1, 2-ethylene group and substituted forms thereof, a 1,1' -vinyl group and substituted forms thereof; when I is₁、 I₂、I₃Each independently absent, b ═ 2; when I is₁、I₂、I₃Each independently selected from the group consisting of an oxygen atom, 1 '-carbonyl, methylene and substituted forms thereof, 1, 2-ethylene and substituted forms thereof, 1' -vinyl and substituted forms thereof, b ═ 1; m is selected from the group consisting of an oxygen atom, a nitrogen atom, a divalent alkoxy chain: (

n ═ 2, 3, 4), preferably an oxygen atom or a nitrogen atom; c represents the number of connections to M; when M is selected from an oxygen atom, a divalent alkoxy chain, c ═ 0; when M is selected from nitrogen atoms, c ═ 1; c₁、C₂、C₃、C₄、C₅、C₆Represent carbon atoms in different positions; difference on the same atom

Can be linked to form a ring, on different atoms

Can also be connected into a ring,among them, K is preferred₁And K₂K to₃And K₄K to₅And K₆C to₁And C₂C to₃And C₄C to₅And C₆Forming a ring; the ring may be any number of rings, preferably five-membered and six-membered rings, which may be aliphatic, aromatic, ether, condensed, or combinations thereof, the ring-forming atoms are each independently selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, selenium atoms, or other heteroatoms, and the hydrogen atoms on the ring-forming atoms may be substituted with any substituent or not; wherein, K₁And K₂K to₃And K₄K to₅And K₆The ring formed between preferably has the following structure:

C₁and C₂C to₃And C₄The ring formed between preferably has the following structure:

C₅and C₆The ring formed between preferably has the following structure:

in the embodiment of the present invention, the diene group used for the [4+2] cycloaddition reaction may be any suitable group containing conjugated diene and its derivatives, such as butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and its derivatives, etc.; dienophile groups for forming the [4+2] cycloaddition dynamic covalent bonds containing any suitable unsaturated double or triple bonds, such as carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-sulfur double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, and the like; wherein, the diene group, unsaturated double bond or unsaturated triple bond in the dienophile group are preferably directly connected with the electric absorption effect group or the electric supply effect group, and the electric absorption effect group comprises but is not limited to carbonyl, aldehyde group, nitro group, ester group, sulfonic group, acylamino group, sulfonyl group, trifluoromethyl, aryl, cyano group, halogen atom, alkene, alkyne and combination thereof; the electron donating effector groups include, but are not limited to, hydroxyl, p-methoxyphenyl, thioether, amino, secondary amine, tertiary amine, methyl, ethyl, isopropyl, isobutyl, and combinations thereof.

In the embodiment of the present invention, the [4+2] cycloaddition dynamic covalent bond contained in the dynamic polymer may be formed by [4+2] cycloaddition reaction between a compound raw material containing a diene group and a compound raw material containing a dienophile group, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a [4+2] cycloaddition dynamic covalent bond, wherein the compound raw material containing a diene group may be selected from butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and derivatives thereof, and wherein the compound raw material containing a dienophile group may be selected from ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, butenedicarboxylic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α -unsaturated nitro compound, cyclooctene, norbornene, maleic acid, p-benzoquinone, butynedicarboxylic acid, azodicarboxylate, bisanhydride, maleimide, and compounds containing a cyclic addition of more preferably a compound containing a 4+ 2-epoxy group, a maleimide group, a compound containing a cycloaddition of a maleimide group, a more preferably a compound containing a fullerene group, a compound, a sulphur, a compound containing a mercapto group, and a compound containing a more preferably a cycloaddition of a 4+ 2-epoxy group, a compound.

The [4+4] cycloaddition dynamic covalent bond is formed based on the [4+4] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic; wherein the [4+4] cycloaddition reaction refers to a reaction in which two conjugated diene groups each provide 4 pi electrons to form a cyclic group structure by addition. The [4+4] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:

wherein,

the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the structure of the cyclic group is preferably benzene ring, naphthalene ring, anthracene ring, aza benzene, aza naphthalene, aza anthracene and substituted forms of the above groups; i is₆～I₁₄Each independently selected from the group consisting of an oxygen atom, a sulfur atom, an amide group, an ester group, an imine group, and a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, 1, 2-diethylene, 1, 2-vinylidene, an amide group, an ester group, and an imine group;

Can be linked to form a ring, on different atoms

And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typically [4+4]]Examples of cycloaddition dynamic covalent bond structures are:

in an embodiment of the present invention, the conjugated diene group used for the [4+4] cycloaddition reaction may be any suitable group containing conjugated diene and its derivatives, such as benzene, anthracene, naphthalene, furan, cyclopentadiene, cyclohexadiene, pyrone, pyridone and its derivatives, and the like.

In the embodiment of the present invention, the [4+4] cycloaddition dynamic covalent bond contained in the dynamic polymer may be formed by a [4+4] cycloaddition reaction between the compound raw materials containing the conjugated diene group, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between the reactive groups contained therein using the compound raw materials containing the [4+4] cycloaddition dynamic covalent bond.

In the embodiment of the present invention, the "certain condition" for activating the dynamic reversibility of the [2+2] cycloaddition dynamic covalent bond, [4+4] cycloaddition dynamic covalent bond includes, but is not limited to, the action modes of temperature regulation, catalyst addition, illumination, radiation, microwave, etc. For example, the [2+2] cycloaddition dynamic covalent bond can be dissociated by heating at a higher temperature, and then the [2+2] cycloaddition dynamic covalent bond is reformed by heating at a lower temperature; furan and maleimide can carry out a [4+2] cycloaddition reaction at room temperature or under a heating condition to form a dynamic covalent bond, the formed dynamic covalent bond can be dissociated at a temperature higher than 110 ℃, and the dynamic covalent bond can be reformed through cooling. For another example, the [2+2] cycloaddition dynamic covalent bond can be subjected to [2+2] cycloaddition reaction under the long-wavelength light irradiation condition to form a dynamic covalent bond, and then the dynamic covalent bond is dissociated under the short-wavelength light irradiation condition to obtain an unsaturated carbon-carbon double bond again; for example, the cinnamoyl unsaturated carbon-carbon double bond can be subjected to a [2+2] cycloaddition reaction under the ultraviolet irradiation condition that the lambda is more than 280nm to form a dynamic covalent bond, and the bond dissociation is carried out under the ultraviolet irradiation condition that the lambda is less than 280nm to obtain the cinnamoyl unsaturated carbon-carbon double bond again; the coumarin unsaturated carbon-carbon double bond can be subjected to [2+2] cycloaddition reaction under the condition that lambda is larger than 319nm ultraviolet irradiation to form a dynamic covalent bond, and the bond dissociation is carried out under the condition that lambda is smaller than 319nm ultraviolet irradiation to obtain the coumarin unsaturated carbon-carbon double bond again. For another example, anthracene and maleic anhydride can undergo a [4+2] cycloaddition reaction under ultraviolet irradiation at λ 250 nm to form a dynamic covalent bond. For another example, anthracene can undergo a [4+4] cycloaddition reaction under uv irradiation at λ 365nm to form a dynamic covalent bond, and then undergo bond dissociation under uv irradiation at λ less than 300 nm. In addition, the [2+2], [4+4] cycloaddition reaction can be carried out under the catalytic condition of a catalyst to form a dynamic covalent bond, wherein the catalyst comprises but is not limited to Lewis acid, Lewis base and metal catalyst; the lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkylmetal compound, borane, boron trifluoride and its derivatives, arylboron difluoride, scandium trifluoroalkylsulfonate, and the like, preferably titanium tetrachloride, aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, iron tribromide, iron trichloride, tin tetrachloride, borane, boron trifluoride etherate, scandium trifluoromethanesulfonate; the Lewis bases, which include, but are not limited to, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), azacyclocarbene (NHC), quinidine, quinine, etc.; the metal catalyst includes, but is not limited to, catalysts based on iron, cobalt, palladium, ruthenium, nickel, copper, silver, gold, molybdenum, and examples of the metal catalyst used in the present invention for catalyzing the [2+2], [4+4] cycloaddition include, but are not limited to, the following:

the dynamic covalent bond of the mercapto-Michael addition can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, so that the dynamic reversible characteristic is embodied; the dynamic covalent thiol-michael addition bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein X is selected from ketone group, ester group, amide group, thiocarbonyl group and sulfone group; y is an electron withdrawing effect group including, but not limited to, aldehyde groups, carboxyl groups, nitro groups, phosphate groups, sulfonate groups, amide groups, sulfone groups, trifluoromethyl groups, cyano groups, halogen atoms, and combinations thereof;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein the difference is on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Or may be linked to form a ring, the carbon atom being attached to X

May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical mercapto-michael addition dynamic covalent bond structures may be exemplified by:

in the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the thiol-michael addition dynamic covalent bond include, but are not limited to, temperature adjustment, catalyst addition, pH adjustment, and the like. For example, the dissociated mercapto-michael addition dynamic covalent bonds can be regenerated by heating or exchanged to allow the polymer to achieve self-repairability and re-processability. For another example, for a thiol-michael addition dynamic covalent bond, it can be dissociated with a neutral or weakly alkaline solution to be in a dynamic reversible equilibrium. As another example, the presence of a catalyst that promotes the formation and exchange of dynamic covalent bonds, such mercapto-Michael addition reaction catalysts include, but are not limited to, Lewis acids, organophosphates, organo-base catalysts, nucleophilic catalysts, ionic liquid catalysts, and the like; the Lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkyl metal compound, borane, boron trifluoride and its derivative, aryl boron difluoride, scandium trifluoroalkyl sulfonate, etc.; the organic phosphide includes, but is not limited to potassium phosphate, tri-n-propyl phosphine, dimethyl phenyl phosphine, methyl diphenyl phosphine, triphenyl phosphine; organic base catalysts including, but not limited to, ethylenediamine, triethanolamine, triethylamine, pyridine, diisopropylethylamine, and the like; the nucleophilic catalyst comprises 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylguanidine, 1, 5-diazabicyclo [4,3,0] non-5-ene, 1, 8-diazabicyclo [5,4,0] -undec-7-ene, 1,5, 7-triazabicyclo [4,4,0] dec-5-ene, 1, 4-diazabicyclo [2,2,2] octane, imidazole and 1-methylimidazole; the ionic liquid catalyst includes but is not limited to 1-butyl-3-methylimidazolium hexafluorophosphate, 1- (4-sulfonic) butylpyridine, 1-butyl-3-methylimidazolium tetrahydroborate, 1-allyl-3-methylimidazolium chloride and the like.

In the embodiment of the present invention, the mercapto-michael addition dynamic covalent bond contained in the dynamic polymer may be formed by a mercapto-michael addition reaction using a mercapto group contained in a compound raw material with a conjugated olefin or a conjugated alkyne, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained therein using a compound raw material containing a mercapto-michael addition dynamic covalent bond. Wherein the compound material containing conjugated olefin or conjugated alkyne can be selected from acrolein, acrylic acid, acrylate, propiolate, methacrylate, acrylamide, methacrylamide, acrylonitrile, crotonate, butenedioate, butynedioate, itaconic acid, cinnamate, vinyl sulfone, maleic anhydride, maleimide and derivatives thereof; among these, the raw material of the compound having a dynamic covalent bond of mercapto-michael addition is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, an ester, and an amide having a dynamic covalent bond of mercapto-michael addition are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond of mercapto-michael addition are more preferable.

The amine alkene-Michael addition dynamic covalent bond can be activated under a certain condition, and undergoes bond dissociation, bonding and exchange reaction, so that the dynamic reversible characteristic is embodied; the amine alkene-michael addition dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:

wherein,

In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the amine alkene-michael addition dynamic covalent bond include, but are not limited to, temperature adjustment, pH adjustment, and the like. For example, for amine alkene-Michael addition dynamic covalent bonds, a weakly acidic (pH 5.3) solution can be used to cause dissociation and thus dynamic reversible equilibrium. As another example, the dissociated amine alkene-Michael addition dynamic covalent bond can be regenerated by heating at 50-100 deg.C or exchanged to allow the polymer to achieve self-repairability and re-processability.

In an embodiment of the present invention, the amine alkene-michael addition dynamic covalent bond contained in the dynamic polymer may be formed by preparing an intermediate product from terephthalaldehyde, malonic acid, and malonic diester as raw materials, and reacting the intermediate product with an amino compound through amine alkene-michael addition.

The dynamic covalent bond based on triazoline diketone-indole can be activated under certain conditions, and bond dissociation, bonding and exchange reaction are carried out, so that the dynamic reversible characteristic is embodied; the dynamic covalent bond based on triazolinedione-indole described in the present invention is selected from, but not limited to, the following structures:

wherein,

In the embodiment of the present invention, the "certain conditions" for activating the dynamic covalent bond dynamic reversibility based on triazolinedione-indole include, but are not limited to, temperature regulation, pressurization, addition of a catalyst, and the like. For example, the indole and the oxazoline diketone can generate a dynamic covalent bond based on triazoline diketone-indole at the temperature of 0 ℃, the bond dissociation is realized by heating, and the dynamic covalent bond is regenerated by cooling or the exchange of the dynamic covalent bond is carried out, so that the polymer can obtain self-repairability and reprocessing property. For another example, for dynamic covalent bonds based on triazolinedione-indole, they may optionally be dissociated in neutral or slightly alkaline solution to be in dynamic reversible equilibrium. As another example, the presence of a catalyst capable of promoting the formation and exchange of dynamic covalent bonds, said addition reaction catalyst being selected from Lewis acids; the lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkyl metal compound, borane, boron trifluoride and its derivative, aryl boron difluoride, scandium trifluoroalkyl sulfonate, and the like.

In an embodiment of the present invention, the dynamic covalent bond based on triazolinedione-indole contained in the dynamic polymer may be formed by an alder-olefin addition reaction using a bisoxazolinedione group and derivatives thereof contained in a compound raw material and indole and derivatives thereof. Wherein the indole or its derivative is selected from indole-3-propionic acid, indole-3-butyric acid, indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carboxylic acid, 4- (aminomethyl) indole, 5- (aminomethyl) indole, 3- (2-hydroxyethyl) indole, indole-4-methanol, indole-5-methanol, 3-mercaptoindole, 3-acetylenoindole, 5-amino-2 phenylindole, 2-phenyl-1H-indol-6 amine, 2-phenyl-1H-indol-3-acetaldehyde, (2-phenyl-1H-indol-3-alkyl) carboxylic acid, 6-amino-2-phenyl-1H-indole-3-carboxylic acid Ethyl ester, 2- (2-aminophenyl) indole, 2-phenylindole-3-acetonitrile, 4, 6-diamidino-2-phenylindole dihydrochloride, and the like.

The dynamic covalent bond based on the dinitrogen heterocarbene can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond are generated, so that the dynamic reversible characteristic is embodied; the dinitrogabine-based dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:

wherein,

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; in which, on different carbon atoms

May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical bis-azacarbene based dynamic covalent bond structures may be exemplified by:

wherein Me represents a methyl group, Et represents an ethyl group, nBu represents an n-butyl group, Ph represents a phenyl group, and Mes represents a trimethylphenyl group.

In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the double-nitrogen heterocarbene-based dynamic covalent bond include, but are not limited to, temperature regulation, solvent addition and other action modes. For example, the polymer can obtain self-repairability and reworkability by heating the dynamic covalent bond based on the diazacarbone under the temperature condition of higher than 90 ℃ to dissociate the dynamic covalent bond into a diazacarbone structure, and then reducing the temperature to regenerate the dynamic covalent bond or exchange the dynamic covalent bond.

In an embodiment of the present invention, the dynamic covalent bond based on the diazacarbone contained in the dynamic polymer may be formed by using the diazacarbone group contained in the compound raw material itself or by reacting it with a thiocyano group.

The hexahydrotriazine dynamic covalent bond can be activated under certain conditions, and generates bond dissociation, bonding and exchange reaction, so as to embody the dynamic reversible characteristic; the "certain condition" for activating the dynamic reversibility of the hexahydrotriazine dynamic covalent bond refers to an appropriate pH condition, heating condition, or the like. The hexahydrotriazine dynamic covalent bond in the invention is selected from but not limited to at least one of the following structures:

wherein,

refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical hexahydrotriazine dynamic covalent bond structures may be mentioned, for example:

in the embodiment of the invention, the suitable pH condition for carrying out the hexahydrotriazine dynamic covalent bond dynamic reversible reaction refers to that the dynamic polymer is swelled in a solution with a certain pH value or the surface of the dynamic polymer is wetted by a solution with a certain pH value, so that the hexahydrotriazine dynamic covalent bond in the dynamic polymer shows dynamic reversibility. For example, hexahydrotriazine dynamic covalent bonds can be dissociated at a pH < 2 and reformed at neutral pH, allowing the polymer to be self-healing and re-processing. Wherein, the acid-base reagent for adjusting pH can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and compounds thereof include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, brilliant carbonate, and potassium tert-butoxide. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamineHydrochloride, butyraldehyde oxime, benzaldoxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)₃) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, copper acetate, and potassium tert-butoxide are preferable.

In the embodiment of the present invention, the hexahydrotriazine dynamic covalent bond contained in the dynamic polymer can be formed by performing a polycondensation reaction between an amino group and an aldehyde group contained in a compound raw material under a low temperature condition (e.g., 50 ℃) to form a hexahydrotriazine dynamic covalent bond of the (I) type, and then heating under a high temperature condition (e.g., 200 ℃) to form a hexahydrotriazine dynamic covalent bond of the (II) type; the starting compounds containing hexahydrotriazine dynamic covalent bonds can also be used to introduce dynamic polymers by polymerization/crosslinking reactions between the reactive groups they contain. Among these, the starting materials of the hexahydrotriazine compound having a dynamic covalent bond are not particularly limited, and polyols, isocyanates, epoxy compounds, alkenes, alkynes, carboxylic acids, esters, and amides having a dynamic covalent bond of hexahydrotriazine are preferable, and polyols, isocyanates, epoxy compounds, alkenes, alkynes having a dynamic covalent bond of hexahydrotriazine are more preferable.

The dynamic exchangeable trialkyl sulfonium bond can be activated under the heating condition, and performs alkyl exchange reaction, so that the dynamic exchangeable trialkyl sulfonium bond has dynamic reversible characteristics; wherein the "transalkylation reaction" refers to the formation of new trialkylsulfonium bonds elsewhere with concomitant dissociation of old trialkylsulfonium bonds, resulting in exchange of chains and changes in polymer topology. In the present invention, the transalkylation reaction is preferably carried out under the heating conditions of 130-160 ℃. The dynamically exchangeable trialkylsulfonium linkage described in this invention is selected from, but not limited to, the following structures:

wherein, X^—Selected from sulfonates, preferably benzenesulfonates, more preferably p-bromobenzenesulfonates;

In an embodiment of the present invention, the dynamic exchangeable trialkylsulfonium bond contained in the dynamic polymer can be formed by a mercapto-michael addition reaction between a mercapto group contained in a compound raw material and an unsaturated carbon-carbon double bond, and a sulfonate is added as an alkylating agent.

Other dynamic covalent bonds in the invention can be kept stable under specific conditions, so as to achieve the purpose of providing a balanced structure and mechanical strength, and can also show dynamic reversibility under other specific conditions, so that the material can be completely self-repaired, recycled and plastically deformed; meanwhile, due to the existence of different types of other dynamic covalent bonds, the polymer can show different response effects to external stimuli such as heat, illumination, pH, oxidation reduction and the like, and dynamic reversible balance can be promoted or slowed down in a proper environment by selectively controlling external conditions, so that the dynamic polymer is in a required state.

combination 1: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicone bond; dynamic linkage, dynamic diselenide linkage, dynamic covalent linkage based on reversible radicals, associative exchangeable acyl linkage, dynamic covalent linkage induced based on steric effects, reversible addition fragmentation chain transfer dynamic covalent linkage, dynamic silicon ether linkage, exchangeable dynamic covalent linkage based on alkyltriazolium, [2+2] cycloaddition dynamic covalent linkage, [2+4] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, mercapto-michael addition dynamic covalent linkage, dynamic covalent linkage based on triazolinedione-indole, aminoalkene-michael addition dynamic covalent linkage, dynamic covalent linkage based on diazacarbene, dynamic exchangeable trialkylsulfonium linkage. The boron-containing dynamic covalent bonds selected in the combination have good regulation and control performance and rich structure selectivity, and dynamic polymers with different topological structures and different energy absorption effects can be prepared by controlling parameters such as the molecular structure, the number of functional groups, the molecular weight and the like of organic boric acid elements in the boron-containing dynamic covalent bonds; the selected other dynamic covalent bonds can realize the dynamic reversible balance of the dynamic covalent bonds through conventional means such as temperature regulation, illumination and the like, so that the dynamic polymer can embody richer energy absorption effect, is simple and convenient to operate and low in cost, and can control the energy absorption degree by regulating and controlling the temperature and the illumination frequency.

And (3) combination 2: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; dynamic selenium-nitrogen bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds, and amine alkene-Michael addition dynamic covalent bond combinations. The boron-containing dynamic covalent bonds selected in the combination have good regulation and control performance and rich structure selectivity, and dynamic polymers with different topological structures and different energy absorption effects can be prepared by controlling parameters such as the molecular structure, the number of functional groups, the molecular weight and the like of organic boric acid elements in the boron-containing dynamic covalent bonds; the other selected dynamic covalent bonds can dynamically respond to the change of the pH value, are usually suitable for preparing gel materials, and can realize the dissipation of the polymer materials to external stress by regulating and controlling the pH value of the swelling agent.

And (3) combination: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one member selected from the group consisting of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, and a triazolinedione-indole-based dynamic covalent bond. The boron-containing dynamic covalent bonds selected in the combination have good regulation and control performance and rich structure selectivity, and dynamic polymers with different topological structures and different energy absorption effects can be prepared by controlling parameters such as the molecular structure, the number of functional groups, the molecular weight and the like of organic boric acid elements in the boron-containing dynamic covalent bonds; the other dynamic covalent bonds are generally required to perform dynamic equilibrium reaction of the dynamic covalent bonds in the presence of a catalyst, and after the catalyst or a composite component containing the catalyst is added into a system, the other dynamic covalent bonds can show dynamic characteristics under mild conditions, so that the boron-containing dynamic covalent bonds are combined and matched to show a hierarchical rich energy absorption effect.

And (4) combination: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; dynamic linkage, dynamic diselenide linkage, dynamic covalent linkage based on reversible radicals, associative exchangeable acyl linkage, dynamic covalent linkage induced based on steric effects, reversible addition fragmentation chain transfer dynamic covalent linkage, dynamic silicon ether linkage, exchangeable dynamic covalent linkage based on alkyltriazolium, [2+2] cycloaddition dynamic covalent linkage, [2+4] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, mercapto-michael addition dynamic covalent linkage, dynamic covalent linkage based on triazolinedione-indole, aminoalkene-michael addition dynamic covalent linkage, dynamic covalent linkage based on diazacarbene, dynamic exchangeable trialkylsulfonium linkage. The boron-containing dynamic covalent bond selected in the combination has a simple and stable structure, can show sensitive dilatancy under the action of external force, and has good viscous loss to absorb energy; the selected other dynamic covalent bonds can realize the dynamic reversible balance of the dynamic covalent bonds through conventional means such as temperature regulation, illumination and the like, so that the dynamic polymer can embody richer energy absorption effect, is simple and convenient to operate and low in cost, and can control the energy absorption degree by regulating and controlling the temperature and the illumination frequency.

And (3) combination 5: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; dynamic selenium-nitrogen bonds, acetal dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, hexahydrotriazine dynamic covalent bonds, and amine alkene-Michael addition dynamic covalent bond combinations. The boron-containing dynamic covalent bond selected in the combination has a simple and stable structure, can show sensitive dilatancy under the action of external force, and has good viscous loss to absorb energy; the other selected dynamic covalent bonds can dynamically respond to the change of the pH value, are usually suitable for preparing gel materials, and can realize the dissipation of the polymer materials to external stress by regulating and controlling the pH value of the swelling agent.

And (4) combination 6: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one member selected from the group consisting of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, and a triazolinedione-indole-based dynamic covalent bond. The boron-containing dynamic covalent bond selected in the combination has a simple and stable structure, can show sensitive dilatancy under the action of external force, and has good viscous loss to absorb energy; the other dynamic covalent bonds are generally required to perform dynamic equilibrium reaction of the dynamic covalent bonds in the presence of a catalyst, and after the catalyst or a composite component containing the catalyst is added into a system, the other dynamic covalent bonds can show dynamic characteristics under mild conditions, so that the boron-containing dynamic covalent bonds are combined and matched to show a hierarchical rich energy absorption effect.

In the embodiment of the present invention, in the process of introducing a dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in a raw material of a compound having a dynamic covalent bond, the type and mode of reaction for introducing a dynamic covalent bond are not particularly limited, and the following reaction is preferred: the reaction of isocyanate with amino, hydroxyl, mercapto, carboxyl and epoxy group, the reaction of carboxylic acid, acyl halide, acid anhydride and active ester with amino, hydroxyl and mercapto, the reaction of epoxy group with amino, hydroxyl and mercapto, thiol-ene click reaction, acrylate free radical reaction, acrylamide free radical reaction, double bond free radical reaction, Michael addition reaction of alkene-amine, azide-alkyne click reaction, tetrazole-alkene cycloaddition reaction and silicon hydroxyl condensation reaction; more preferably, the reaction can be carried out rapidly at a temperature of not higher than 100 ℃, including but not limited to the reaction of isocyanate group with amino group, hydroxyl group, mercapto group, carboxyl group, the reaction of acyl halide, acid anhydride with amino group, hydroxyl group, mercapto group, acrylate radical reaction, acrylamide radical reaction, and thiol-ene click reaction.

The reactive group in the embodiments of the present invention refers to a group capable of undergoing chemical reaction and/or physical action to form a common covalent bond and/or dynamic covalent bond and/or hydrogen bond spontaneously or under the conditions of an initiator or light, heating, irradiation, catalysis, etc., and suitable groups include, but are not limited to: hydroxyl, carboxyl, carbonyl, acyl, amide, acyloxy, amino, aldehyde, sulfonic, sulfonyl, thiol, alkenyl, alkynyl, cyano, oxazinyl, oxime, hydrazine, guanidino, halogen, isocyanate, anhydride, epoxy, hydrosilyl, acrylate, acrylamide, maleimide, succinimide, norbornene, azo, azide, heterocyclic, triazolinedione, carbon, oxygen, sulfur, selenium, hydrogen bonding, and the like; hydroxyl, amino, mercapto, alkenyl, isocyanate, epoxy, acrylate, acrylamide, oxygen radical, sulfur radical, hydrogen bonding group are preferred. The reactive group plays a role in a system, namely, derivatization reaction is carried out to prepare a hydrogen bond group, and common covalent bond and/or dynamic covalent bond and/or hydrogen bond are directly formed between the compound per se or between the compound and other compounds or between the compound and reaction products of the compound through the reaction of the reactive group, so that the molecular weight of the compound and/or the reaction products of the compound is increased/the functionality of the compound is increased, and polymerization or crosslinking is formed between the compound and/or the reaction products of the compound.

The other dynamic covalent bonds in the present invention are in dynamic reversible equilibrium, thereby having dynamic reversibility and exhibiting good dynamic and energy-absorbing effects, which usually need to be made dynamic reversible by means of temperature adjustment, addition of redox agents, addition of catalysts, light, radiation, microwaves, plasma action, pH adjustment, etc. among them, the temperature adjustment means that can be used in the present invention include, but are not limited to, water bath heating, oil bath heating, electric heating, microwave heating, and laser heating, etc. the type of light used in the present invention is not limited, preferably Ultraviolet (UV), infrared (ir), visible light, laser, chemiluminescence, more preferably UV, ir, visible light, etc. the radiation used in the present invention includes, but is not limited to, high-energy ionizing rays such as α rays, β rays, gamma rays, x-rays, electron beams, etc. the plasma action used in the present invention refers to catalysis using ionized gas-like substances composed of positive and negative ions generated after atoms and atomic groups are ionized, the microwave used in the present invention refers to electromagnetic waves having a frequency of 300MHz to 300 GHz.

The hydrogen bond in the present invention is any suitable supramolecular interaction established by hydrogen bond, and is generally a hydrogen bond link between Z and Y through hydrogen atom covalently linked to atom Z with large electronegativity and atom Y with large electronegativity and small radius, which is mediated by hydrogen, to form Z-H … Y, wherein Z, Y is any suitable atom with large electronegativity and small radius, which may be the same kind of element or different kind of element, and is selected from atoms of F, N, O, C, S, Cl, P, Br, I, etc., more preferably from F, N, O atom, and more preferably from O, N atom. The hydrogen bond can exist as supramolecular polymerization and/or crosslinking and/or intrachain cyclization, namely the hydrogen bond can only play a role of connecting two or more chain segment units to increase the size of a polymer chain but not play a role of supramolecular crosslinking, or the hydrogen bond only plays a role of interchain supramolecular crosslinking, or only plays a role of intrachain cyclization, or the combination of any two or more of the three.

In embodiments of the present invention, the hydrogen bonds may be any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by a donor (H, i.e., a hydrogen atom) and an acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of hydrogen bonding groups, each H … Y combining into one tooth. In the following formula, the hydrogen bonding of monodentate, bidentate and tridentate hydrogen bonding groups is schematically illustrated, respectively.

The more the number of teeth of the hydrogen bond, the greater the synergistic effect and the greater the strength of the hydrogen bond. In the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. If the number of teeth of the hydrogen bond is large, the strength is large, the dynamic property of the hydrogen bond action is weak, and the hydrogen bond can play a role in promoting the dynamic polymer to keep an equilibrium structure and improving the mechanical properties (modulus and strength). If the number of teeth of the hydrogen bond is small, the strength is low, the dynamic property of the hydrogen bond action is strong, and the dynamic property can be provided together with the dynamic covalent bond for energy absorption. In embodiments of the invention, preferably no more than four teeth hydrogen bonding are involved.

In embodiments of the invention, the hydrogen bonding may be generated by non-covalent interactions that exist between any suitable hydrogen bonding groups. The hydrogen bond group may contain only a hydrogen bond donor, only a hydrogen bond acceptor, or both a hydrogen bond donor and a hydrogen bond acceptor, preferably both a hydrogen bond donor and a hydrogen bond acceptor.

The hydrogen bond donor in the present invention may be any suitable hydrogen atom-containing donor group, preferably containing at least one of the following structural elements:

more preferably contains

The hydrogen bond acceptor in the present invention may be an acceptor group containing any suitable electronegative atom (e.g., O, N, S, F, etc.), preferably containing at least one of the following structural components:

wherein A is selected from oxygen atom and sulfur atom; d is selected from nitrogen atom and mono-substituted alkyl; x is selected from halogen atoms.

The hydrogen bond group containing both a hydrogen bond donor and a hydrogen bond acceptor in the present invention may be any suitable hydrogen bond group containing a hydrogen bond donor and a hydrogen bond acceptor, and preferably contains at least one of the following structural components:

in the present invention, the hydrogen bonding groups may be present only on the polymer chain backbone (including the main chain and the side chain/branch chain backbone), referred to as backbone hydrogen bonding groups, wherein at least part of the atoms are part of the chain backbone; or may be present only on pendant groups of the polymer chain backbone (including the main chain and the side chain/branch/branched chain backbone), referred to as pendant hydrogen bonding groups, wherein pendant hydrogen bonding groups may also be present on the multilevel structure of pendant groups; or may be present only on the polymer chain backbone/end groups of the small molecule, referred to as end hydrogen bonding groups; or can be simultaneously present on at least two of the polymer chain skeleton, the side group and the end group; the hydrogen bonding groups may also be present in the composite hybrid dynamic polymer composition, such as a small molecule compound or filler. When hydrogen bonding groups are present on at least two of the backbone, pendant group, and terminal group of the polymer chain at the same time, hydrogen bonding may occur between hydrogen bonding groups in different positions, for example, the backbone hydrogen bonding group may form hydrogen bonding with the pendant group hydrogen bonding group in a specific case.

In the embodiment of the present invention, the backbone hydrogen bond group preferably contains any one or more of the following structural components:

wherein W is selected from oxygen atom and sulfur atom; x is selected from oxygen atom, sulfur atom, nitrogen atom and carbon atom; wherein a is the number of D's attached to the X atom; when X is selected from an oxygen atom or a sulfur atom, a ═ 0, D is absent; when X is selected from nitrogen atoms, a ═ 1; when X is selected from carbon atoms, a ═ 2; d is selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues, preferably from hydrogen atoms;

refers to a linkage to a polymer backbone, a cross-linked network chain backbone, a side chain backbone (including multilevel structures thereof), a side group (including multilevel structures thereof), or any other suitable group/atom; the cyclic group structure is a non-aromatic or aromatic nitrogen heterocyclic group containing at least one N-H bond, at least two ring-forming atoms are nitrogen atoms, the cyclic group structure can be a micromolecular ring or a macromolecule ring, and the cyclic group structure is preferably a 3-50-membered ringMore preferably from 3 to 10 membered rings; the ring-forming atoms of the cyclic group structure are each independently a carbon atom, a nitrogen atom or other hetero atom, and the hydrogen atoms on the respective ring-forming atoms may or may not be substituted. In embodiments of the present invention, the backbone hydrogen bonding group is preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazoles, imidazoles, imidazolines, triazoles, purines, porphyrins, and derivatives of the above.

Suitable backbone hydrogen bonding groups are exemplified by (but the invention is not limited to):

in the embodiment of the present invention, the pendant hydrogen bonding group/terminal hydrogen bonding group preferably contains any one or more of the following structural components:

wherein W is selected from oxygen atom and sulfur atom; x is selected from oxygen atom, sulfur atom, nitrogen atom and carbon atom; wherein a is the number of D's attached to the X atom; when X is selected from an oxygen atom or a sulfur atom, a ═ 0, D is absent; when X is selected from nitrogen atoms, a ═ 1; when X is selected from carbon atoms, a ═ 2; d is selected from hydrogen atom, heteroatom group, small molecule alkyl, preferably hydrogen atom; i is a divalent linking group selected from the group consisting of a single bond, a heteroatom linking group, and a divalent small molecule hydrocarbon group; q is a terminal group selected from a hydrogen atom, a heteroatom group, a small molecule hydrocarbon group;

refers to a linkage to a polymer backbone, a cross-linked network chain backbone, a side chain backbone (including multilevel structures thereof), a side group (including multilevel structures thereof), or any other suitable group/atom; i, D, Q wherein any two or more of them may be linked together to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof; in the form of a ringThe group structure is a non-aromatic or aromatic nitrogen heterocyclic group containing at least one N-H bond, at least two ring-forming atoms are nitrogen atoms, and the ring-forming group structure is preferably a 3-50-membered ring, more preferably a 3-10-membered ring; the ring-forming atoms of the cyclic group structure are each independently a carbon atom, a nitrogen atom or other hetero atom, and the hydrogen atoms on the respective ring-forming atoms may or may not be substituted. In embodiments of the present invention, the pendant/terminal hydrogen bonding groups are preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazoles, imidazoles, imidazolines, triazoles, purines, porphyrins, and derivatives of the above.

Suitable pendant/terminal hydrogen bonding groups may have the following exemplary structure (but the invention is not limited thereto) in addition to the above-described backbone hydrogen bonding group structure:

wherein m and n are the number of repeating units, and may be fixed values or average values, and are preferably less than 20, and more preferably less than 5.

In the embodiment of the present invention, the hydrogen bonding groups forming hydrogen bonding may be complementary combinations of different hydrogen bonding groups or self-complementary combinations of the same hydrogen bonding groups, as long as the groups can form proper hydrogen bonding. Some combinations of hydrogen bonding groups may be exemplified as follows, but the invention is not limited thereto:

the hydrogen bond groups on other optional components in the composition of the combined hybrid dynamic polymer, such as small molecules, polymers and fillers, can refer to the skeleton hydrogen bond group, the side group hydrogen bond and the end group hydrogen bond group, and are not described again here.

In the embodiment of the present invention, it is preferable that the hybrid dynamic polymer contains at least one of backbone hydrogen bonding groups, side hydrogen bonding groups, and end hydrogen bonding groups. By way of example, in a preferred embodiment of the invention, the dynamic polymer contains only backbone hydrogen bonding groups; in another preferred embodiment of the invention, the dynamic polymer contains only pendant hydrogen bonding groups; in another preferred embodiment of the invention, the dynamic polymer contains only terminal hydrogen bonding groups; in another preferred embodiment of the present invention, the dynamic polymer contains only backbone hydrogen bonding groups and pendant hydrogen bonding groups; in another preferred embodiment of the present invention, the dynamic polymer contains only backbone hydrogen bonding groups and terminal hydrogen bonding groups; in another preferred embodiment of the present invention, the dynamic polymer contains only pendant and terminal hydrogen bonding groups; in another preferred embodiment of the invention, the dynamic polymer contains skeleton hydrogen bond groups, side group hydrogen bond groups and end group hydrogen bond groups; the invention is not limited thereto.

In the embodiment of the present invention, since some hydrogen bonds have no directionality and selectivity, in a specific case, hydrogen bonding interactions can be formed between hydrogen bonding groups at different positions, hydrogen bonding interactions can be formed between hydrogen bonding groups at the same or different positions in the same or different polymer molecules, and hydrogen bonding interactions can also be formed between hydrogen bonding groups contained in other components in the polymer, such as optional other polymer molecules, fillers, small molecules, and the like. In the present invention, intrachain rings may be formed in addition to interchain crosslinks. It is to be noted that the present invention does not exclude that some of the hydrogen bonding actions formed do not form interchain crosslinking actions nor intrachain rings, but only non-crosslinking polymerization, grafting, and the like. In embodiments of the present invention, it is preferred that at least one of the backbone hydrogen bonding groups, the side group hydrogen bonding groups, the end group hydrogen bonding groups form interchain crosslinks between the same respective hydrogen bonding groups and/or interchain crosslinks between at least two different types of hydrogen bonding groups. By way of example, in one embodiment of the present invention, it is preferred that interchain crosslinks be formed between backbone hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks be formed between pendant hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks be formed between terminal hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks are formed between backbone hydrogen bonding groups and pendant hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks are formed between backbone hydrogen bonding groups and terminal hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks are formed between the pendant and terminal hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks are formed between backbone hydrogen bonding groups, pendant hydrogen bonding groups and terminal hydrogen bonding groups; the invention is not limited thereto.

In the invention, the same hybrid dynamic polymer can contain one or more than one hydrogen bonding group, and the same cross-linking network can also contain one or more than one hydrogen bonding group, that is, the dynamic polymer can contain one hydrogen bonding group or the combination of a plurality of hydrogen bonding groups. The hydrogen bonding groups may be formed by any suitable chemical reaction, for example: formed by covalent reaction between carboxyl groups, acid halide groups, acid anhydride groups, ester groups, amide groups, isocyanate groups and amino groups; formed by covalent reaction between isocyanate groups and hydroxyl, mercapto and carboxyl groups; formed by covalent reaction between the succinimide ester group and amino, hydroxyl, sulfhydryl groups.

In embodiments of the invention, hydrogen bonding groups may be introduced in any suitable composition and at any suitable time, including but not limited to from monomers, while forming a prepolymer, while forming a dynamic covalent crosslink, after forming a dynamic covalent crosslink. Preferably at the same time as the prepolymer is formed and the covalent crosslinking is dynamic. In order to avoid the influence of the formation of hydrogen bond crosslinking after the introduction of the hydrogen bond group on the operations of mixing, dissolving and the like, the hydrogen bond group can also be subjected to closed protection, and then the deprotection is carried out after a proper time (such as the formation of dynamic covalent crosslinking at the same time or after).

In the invention, different boron-containing dynamic covalent bonds and other dynamic covalent bonds have different strengths and dynamics, and different hydrogen bond structures and performances thereof are different, so that the strength, dynamics, responsiveness, energy absorption effect and the like of the dynamic polymer can be adjusted in a large range on the basis of containing at least two types of dynamic covalent bonds and adding the hydrogen bonds; meanwhile, the dynamic polymer can be conveniently hybridized by regulating and controlling the number of the introduced dynamic covalent bonds and hydrogen bonds and the linking structure of the dynamic covalent bonds and hydrogen bonds and the polymer chain, so that the dynamic polymer with controllable dynamic property and glass transition temperature can be obtained. The boron-containing dynamic covalent bonds in the dynamic polymer can have dynamic characteristics under mild conditions, so that energy absorption is achieved by reversible breakage and shear thickening of the bonds to dissipate energy, and other dynamic covalent bonds can show dynamic characteristics under specific conditions, so that the dynamic polymer can show different energy absorption effects under different external stimulation conditions; the dynamic properties of the boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds are different, and the dynamic properties of different types of boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds are different, so that the dynamic polymer can generate different energy dissipation effects in the application process, the tolerance and the energy absorption effect of the material can be improved, and the energy absorption effect can be selectively controlled by adjusting external stimulation conditions. Due to the dynamic covalent bond containing boron, other dynamic covalent bonds and the difference of hydrogen bond dynamics and response conditions, the dynamic polymer with multiple responsivity and energy absorption effect can be prepared.

The topology of the linking group for linking the boron-containing dynamic covalent bond, other dynamic covalent bond and/or hydrogen bond group is not particularly limited, and may be linear, branched, multi-armed, star, H, comb, dendrimer, monocyclic, polycyclic, spiro, fused ring, bridged ring, chain with cyclic structure, two-dimensional and three-dimensional cluster type and combinations thereof, and the topology of the linking group is preferably linear, branched, star, comb, dendrimer, two-dimensional and three-dimensional cluster type, more preferably linear or branched. For the connecting group with straight chain type and straight chain type structures, the molecular chain motion energy barrier is low, the molecular chain motion capability is strong, the processing and forming are facilitated, the polymer can be enabled to show quick self-repairability, and sensitive dilatancy is shown under the stress/strain action, so that more mechanical energy can be lost through viscous flow, and the excellent impact resistance characteristic is shown. For the connecting base with two-dimensional and three-dimensional cluster structures, the topological structure is stable, good mechanical property and thermal stability can be provided for the dynamic polymer, the dynamic polymer can be endowed with quick viscoelasticity transformation, the material is easy to obtain a balanced structure under an impacted state, the dispersion of impact force is realized, and the impact damage is reduced.

For simplicity of description, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or. For example, the term "comprising dynamic covalent and hydrogen bonds at the side groups and/or end groups of the polymer chains" and/or "as used herein means comprising dynamic covalent and hydrogen bonds at the side groups of the polymer chains, or at the end groups of the polymer chains, or at the side groups and end groups of the polymer chains. The conjunction "and/or" appearing elsewhere in the specification of the invention is intended to be such meaning.

The combined hybrid dynamic polymer contains at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond, and the strength, structure, dynamics, responsiveness, formation conditions and the like of different types of dynamic covalent bonds are different, so that the synergistic and orthogonal energy absorption effect can be achieved, and the structure and performance of the material are more adjustable. In addition, by selectively controlling other conditions (such as adding auxiliary agents, adjusting reaction temperature, performing illumination and the like), the dynamic covalent chemical equilibrium can be accelerated or quenched to be in a required state under a proper environment.

In the embodiment of the invention, the form of the combined hybrid dynamic polymer can be solution, emulsion, paste, gum, common solid, elastomer, gel (including hydrogel, organogel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), foam material and the like, wherein the content of soluble small molecular weight components in the common solid and the foam material is generally not higher than 10 wt%, and the content of small molecular weight components in the gel is generally not lower than 50 wt%. Solutions, emulsions, pastes, glues, ordinary solids, elastomers, gels, and foams are characterized and advantageous. The solution and the emulsion have good fluidity, can fully show shear thickening effect in fluid, and can also be used for preparing an impact-resistant coating by utilizing the coating property. Pastes are typically concentrated emulsions and gums are typically concentrated solutions or low glass transition temperature polymers that can exhibit good plasticity and fillability. The shape and volume of the common solid are fixed, the common solid has better mechanical strength and can not be restrained by an organic swelling agent or water. Elastomers have the general properties of ordinary solids, but at the same time have better elasticity and are softer, which is advantageous for providing damping/energy absorbing capabilities. The gel has good flexibility, can embody better energy absorption characteristic and rebound resilience, and is suitable for preparing the energy absorption material with the damping effect. The foam material has the advantages of low density, lightness and high specific strength, can also overcome the problems of brittleness of part of common solids and low mechanical strength of gel, and has good elasticity, energy absorption and soft and comfortable characteristics. Materials of different morphologies may have suitable uses in different fields.

In the embodiment of the invention, the combined hybrid dynamic polymer gel can be obtained by crosslinking in a swelling agent (including one or a combination of water, an organic solvent, an oligomer, a plasticizer and an ionic liquid), or can be obtained by swelling with the swelling agent after the preparation of the dynamic polymer is finished. Of course, the present invention is not limited to this, and those skilled in the art can implement the present invention reasonably and effectively according to the logic and context of the present invention.

In the preparation process of the dynamic polymer foam material, three methods, namely a mechanical foaming method, a physical foaming method and a chemical foaming method, are mainly adopted to foam the dynamic polymer.

The mechanical foaming method is that during the preparation of dynamic polymer, large amount of air or other gas is introduced into emulsion, suspension or solution of polymer via strong stirring to form homogeneous foam, which is then physically or chemically changed to form foam. Air can be introduced and an emulsifier or surfactant can be added to shorten the molding cycle.

Wherein, the physical foaming method is to realize the foaming of the polymer by using the physical principle in the preparation process of the dynamic polymer, and the method comprises the following steps: (1) inert gas foaming, i.e. by pressing inert gas into molten polymer or pasty material under pressure, then raising the temperature under reduced pressure to expand the dissolved gas and foam; (2) evaporating, gasifying and foaming low-boiling-point liquid, namely pressing the low-boiling-point liquid into the polymer or dissolving the liquid into the polymer (particles) under certain pressure and temperature conditions, heating and softening the polymer, and evaporating and gasifying the liquid to foam; (3) dissolving out method, i.e. soaking liquid medium into polymer to dissolve out solid matter added in advance to make polymer have lots of pores and be foamed, for example, mixing soluble matter salt with polymer, etc. first, after forming into product, placing the product in water to make repeated treatment, dissolving out soluble matter to obtain open-cell foamed product; (4) the hollow/foaming microsphere method is that hollow microspheres are added into the material and then compounded to form closed-cell foamed polymer; (5) a filling foamable particle method of mixing filled foamable particles first and then foaming the foamable particles in a molding or mixing process to obtain a foamed polymer material; (6) the freeze-drying method is that the dynamic polymer is swelled in a volatile solvent to be frozen, and then the solvent is escaped in a sublimation manner under the condition of approximate vacuum, thereby obtaining the porous sponge-like foam material. Among them, it is preferable to carry out foaming by a method of dissolving an inert gas and a low boiling point liquid in the polymer.

The chemical foaming method is a method for generating gas and foaming along with chemical reaction in the dynamic polymer foaming process, and includes, but is not limited to, the following methods: (1) the thermal decomposition type foaming method is a method of foaming by using a gas released by decomposition of a chemical foaming agent after heating. (2) The foaming process in which the polymer components interact to produce a gas utilizes a chemical reaction between two or more of the components in the foaming system to produce an inert gas (e.g., carbon dioxide or nitrogen) to cause the polymer to expand and foam. In order to control the polymerization reaction and the foaming reaction to be carried out in balance in the foaming process and ensure that the product has better quality, a small amount of catalyst and foam stabilizer (or surfactant) are generally added. Among these, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.

In an embodiment of the present invention, the structure of the dynamic polymer foam material relates to three structures, namely an open-cell structure, a closed-cell structure and a semi-open and semi-closed structure; dynamic polymer foams are classified according to their hardness into three categories, soft, hard and semi-hard; dynamic polymer foams can be further classified by their density into low-foaming, medium-foaming and high-foaming.

The initiator, catalyst and redox agent for activating/adjusting other dynamic covalent bond dynamic equilibrium reactions described in the foregoing of the present invention can be directly dispersed in the polymer component for use, or can be used in the form of a composite, for example, coated or loaded on an organic, inorganic or polymer carrier by a physical or chemical method, or coated in a microcapsule or a microcatheter together with other components having high fluidity under dynamic reaction conditions, etc. When the initiator, catalyst and redox agent are used alone, they are compatible with the polymer components and optionally various groups of the various auxiliary fillers. The reasonable selection of the carrier can enhance the dispersibility of the initiator, the catalyst, the redox agent or the compound component thereof in the polymer component and reduce the particle size of the cluster, thereby improving the reaction efficiency, reducing the use amount and lowering the cost. Proper selection of the coating material also avoids deactivation of the additive during the preparation or operation of the composition.

The organic carrier for coating the initiator, the catalyst and the redox agent is not particularly limited, and examples of the organic carrier can be selected from paraffin, polyethylene glycol and the like, the method for coating the additive in the organic carrier is a known and disclosed technical means, and a common preparation method is selected for the invention. For example, a preferred preparation method for coating with paraffin as the organic carrier is: fully blending the selected additive, paraffin and surfactant in a paraffin melting state, and pouring the blend into water which is stirred at a certain rotating speed and has the temperature higher than the melting point of the paraffin; stirring until the blending liquid reaches a stable state, and adding ice water to quickly cool the water to below the melting point of paraffin; stopping stirring, and filtering to obtain the paraffin-coated composite component.

The carrier for loading the initiator, the catalyst and the redox agent on the organic or inorganic carrier through physical adsorption or chemical reaction is not particularly limited, and can be selected from polystyrene resin particles, magnetic nanoparticles, silica gel particles, molecular sieves, other mesoporous materials and the like as examples, a method for loading the additive on the organic or inorganic carrier is a known and disclosed technical means, and a common preparation method is selected in the invention.

The present invention also allows for the encapsulation of initiators, catalysts, redox agents and other optional adjuvants in polymer-shell microcapsules. Among them, the polymer as the outer wall of the microcapsule is not particularly limited, and includes, but is not limited to, the following: natural polymers such as gum arabic, agar, etc., semisynthetic polymers such as cellulose derivatives, and synthetic polymers such as polyolefin, polyester, polyether, polyurethane, polyurea-aldehyde, polyamide, polyvinyl alcohol, polysiloxane, etc., and the usual preparation method is selected for the present invention.

In the preparation process of the combined hybrid dynamic polymer, in addition to the initiator, the catalyst and the redox agent which are used for activating/adjusting other dynamic covalent bond dynamic equilibrium reactions, certain solvent, other auxiliary agents/additives and fillers which can be added/used can be added or used to jointly form the dynamic polymer material.

The other additive/additive which can be added/used can improve the material preparation process, improve the product quality and yield, reduce the product cost or endow the product with certain specific application performance. The auxiliary agent is selected from any one or any several of the following auxiliary agents: auxiliary agents for synthesis, including catalysts; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; an auxiliary agent for improving mechanical properties, comprising a toughening agent; the processing performance improving additives comprise a lubricant and a release agent; the auxiliary agents for softening and lightening comprise a plasticizer, a foaming agent and a dynamic regulator; the auxiliary agents for changing the surface performance comprise an antistatic agent, an emulsifier and a dispersant; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; flame retardant and smoke suppressant aids including flame retardants; other auxiliary agents include nucleating agents, rheological agents, thickening agents and leveling agents.

The fillers that can be added/used include, but are not limited to, inorganic non-metallic fillers, organic fillers, organometallic compound fillers.

The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, argil, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene oxide, fullerene, carbon nano tube, molybdenum disulfide, silica, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, nano silica, nano Fe₃O₄Particulate, nano gamma-Fe₂O₃Particulate, nano MgFe₂O₄Particulate, nano-MnFe₂O₄Granular, nano CoFe₂O₄Particles, quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots)Lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), upconversion crystal particles (including but not limited to NaYF)₄:Er、CaF₂:Er、Gd₂(MoO₄)₃:Er、Y₂O₃:Er、Gd₂O₂S:Er、 BaY₂F₈:Er、LiNbO₃:Er,Yb,Ln、Gd₂O₂:Er,Yb、Y₃Al₅O₁₂:Er,Yb、TiO₂:Er,Yb、YF₃:Er,Yb、Lu₂O₃:Yb,Tm、 NaYF₄:Er,Yb、LaCl₃:Pr、NaGdF₄:Yb,Tm@NaGdF₄Core-shell nanostructure of Ln, NaYF₄:Yb,Tm、Y2BaZnO₅:Yb,Ho、NaYF₄:Yb,Er@NaYF₄Core-shell nanostructures of Yb, Tm, NaYF₄:Yb,Tm@NaGdF₄Core-shell nanostructure of Yb), oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass beads, resin beads, glass powder, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, silicon carbide fibers, ceramic fibers, whiskers and the like. In one embodiment of the present invention, inorganic non-metallic fillers having electrical conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, are preferred, which facilitate obtaining a composite material having electrical conductivity and/or electrothermal function. In another embodiment of the present invention, the non-metallic filler having the heat generating function under the action of infrared and/or near-infrared light and/or electromagnetic is preferably selected from graphene, graphene oxide, carbon nanotube, nano-Fe₃O₄The composite material which can be heated by infrared and/or near infrared light is conveniently obtained. Good heating performance, especially remote control heating performance, and is beneficial to obtaining controllable shape memory, self-repairing performance and the like. In another embodiment of the present invention, inorganic non-metallic fillers with thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, are preferred, which facilitate obtaining composite materials with thermal conductivity.

The metalFillers, including metal compounds, include, but are not limited to, any one or any of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano-metal particles including, but not limited to, nano-gold particles, nano-silver particles, nano-palladium particles, nano-iron particles, nano-cobalt particles, nano-nickel particles, nano-CoPt₃Particles, nano FePt particles, nano FePd particles, nickel-iron bimetal magnetic nanoparticles and other nano metal particles capable of heating under at least one of infrared, near infrared, ultraviolet and electromagnetic action; liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys. In one embodiment of the present invention, fillers that can be heated electromagnetically and/or near-infrared, including but not limited to nanogold, nanosilver, and nanopalladium, are preferred for remote heating. In another embodiment of the present invention, liquid metal fillers are preferred, which can enhance the thermal and electrical conductivity of the flexible substrate while maintaining the flexibility and ductility of the substrate.

The organic filler comprises any one or more of ① natural organic filler, ② synthetic resin filler, ③ synthetic rubber filler, ④ synthetic fiber filler, ⑤ foamable polymer particles, ⑥ conjugated polymer and ⑦ organic functional dye/pigment, and the organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal property and the like has important significance to the invention and can fully utilize the properties to obtain multifunctionality.

The organic metal compound filler contains a metal organic complex component, wherein a metal atom is directly connected with a carbon atom to form a bond (including a coordination bond, a sigma bond and the like), and the metal organic complex component can be a small molecule or a large molecule and can be in an amorphous or crystal structure. Metal organic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat, and the like.

Wherein the type of filler added is not limited, but depends mainly on the desired material properties, and calcium carbonate, clay, carbon black, and the like are preferred,Graphene, (hollow) glass beads, nano-Fe₃O₄Particles, nano-silica, quantum dots, up-conversion metal particles, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, nano-metal particles, synthetic rubber, synthetic fibers, synthetic resin, resin microbeads, organometallic compounds, organic materials having photo-thermal properties. The amount of the filler used is not particularly limited, but is generally 1 to 30% by weight. In the embodiment of the invention, the filler can be selectively modified and then dispersed and compounded or directly connected into a polymer chain, so that the dispersibility, the compatibility, the filling amount and the like can be effectively improved, and the filler has important significance particularly on the action of photo-thermal, electromagnetic heat and the like.

In the preparation process of the hybrid dynamic polymer, the addition amount of each component of the dynamic polymer is not particularly limited, and can be adjusted by those skilled in the art according to the actual preparation situation and the target polymer performance.

Due to the fact that the dynamic covalent bonds and optional hydrogen bonds of different types are contained, in the application process of the combined hybrid dynamic polymer, on one hand, swelling flow with stimulation responsiveness can be shown, so that mechanical energy is lost through viscous flow, and on the other hand, the multiple absorption of energy can be achieved through reversible fragmentation by utilizing the difference of dynamic covalent bonds containing boron, other dynamic covalent bonds and optional hydrogen bond dynamics and responsiveness in the polymer. By proper component selection and formula design of the dynamic polymer, polymer fibers, films, plates, foams, gels and the like with excellent energy absorption effects can be prepared. The dynamic polymer is used as an energy absorption material for energy absorption, and can embody good effects of damping, shock absorption, sound insulation, noise elimination, impact resistance and the like, thereby having wide application in the fields of life, production, sports, leisure, entertainment, military affairs, police affairs, security, medical care and the like. For example, the dynamic polymer can be applied to the manufacture of damping shock absorbers for the vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings, and can dissipate a large amount of energy to play a damping effect when being vibrated, thereby effectively mitigating the vibration of a vibrator; the swelling flow property of the dynamic polymer can be utilized to generate the change of polymerization degree and crosslinking degree, the flexibility and strong elasticity are changed, the effect of effectively dispersing impact force is achieved, and the material can be used as an energy-absorbing buffer material to be applied to the aspects of buffer packaging materials, sports protection products, impact protection products, military and police protection materials and the like, so that the vibration and impact of articles or human bodies under the action of external force, including shock waves generated by explosion and the like, are reduced; the dynamic polymer can also be used for preparing speed lockers of roads and bridges, and for manufacturing anti-seismic shear plates or cyclic stress bearing tools; the energy-absorbing material with the shape memory function can be designed and applied to specific occasions, such as personalized and customized energy-absorbing protectors. The prepared combined hybrid dynamic polymer with different glass transition temperatures and different surface morphologies can also be applied to different fields according to specific properties; for example, for solid materials (e.g., general solid materials, foam materials) having a high glass transition temperature and high hardness, it is suitable for application in fields requiring high-strength energy-absorbing materials, such as automobile outer bumpers, so as to be able to better protect automobiles and drivers/passengers from a car accident impact; for another example, soft materials with low glass transition temperatures (e.g., elastomers, gels) are suitable for energy absorbing applications in human body protection, precision instruments, fragile objects, etc., and are convenient for form-fitting/conforming applications. The combined energy absorption method provided by the invention is particularly suitable for carrying out impact resistance protection on human bodies, animal bodies, articles and the like, for example, the material is used as a protective clothing to protect the bodies in daily life, production and sports; preparing explosion-proof tents, blankets, walls, bulletproof glass interlayer glue, interlayer plates and the like, and performing explosion-proof protection on articles; the product can be made into other protective articles/appliances, and can be applied to the aspects of air-drop and air-drop protection, automobile anti-collision, impact resistance protection of electronic and electric appliances, and the like.

In addition, the combined hybrid dynamic polymer can be applied to other various suitable fields according to the energy absorption characteristics embodied by the combined hybrid dynamic polymer, and the combined hybrid dynamic polymer can be expanded and implemented by a person skilled in the art according to actual needs.

The dynamic polymer materials of the present invention are further described below in conjunction with certain embodiments. The specific examples are intended to illustrate the present invention in further detail, and are not intended to limit the scope of the present invention.

Example 1

Taking AIBN as an initiator, reacting 3- (2-hydroxyethyl) phenylboronic acid pinacol ester with acryloyl chloride to prepare a phenylboronic acid ester acrylate monomer, and then carrying out free radical polymerization on the phenylboronic acid ester acrylate monomer, methyl methacrylate and mercapto methyl methacrylate to obtain an acrylate copolymer (a).

Adding a certain amount of toluene solvent into a dry and clean reaction bottle, adding 8mmol of acrylate copolymer (a) into the reaction bottle, stirring and dissolving completely, then dropwise adding a proper amount of acetic acid aqueous solution for hydrolysis for 30min, adding a proper amount of anhydrous sodium sulfate, introducing nitrogen, heating to 80 ℃, removing water and removing oxygen for reaction for 3h, then adding a proper amount of triethylamine, manganese dioxide and 0.04mol of polycaprolactone diol, continuing to stir for reaction for 3h, then adding 5 wt% of titanium alloy powder, 5 wt% of ceramic powder and 10 wt% of calcium sulfate, stirring uniformly, continuing to react for 2h, after the reaction is completed, pouring the polymer solution into a proper mold, placing the mold in a vacuum oven at 80 ℃ for 24h to remove the solvent, then cooling to room temperature and placing for 30min to obtain a milky white polymer solid sample with glossiness, preparing a dumbbell-shaped sample with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0), performing tensile test by using a tensile testing machine, measuring the tensile rate of 10mm/min, measuring the tensile strength of the sample as 12.10 +/-2.52.52, tensile modulus of the sample, and performing a bionic impact buffer effect on a skeleton capable of generating a bionic polymer capable of generating impact buffer effect on the outside and generating the bionic bone.

Example 2

Adding 2,2,6, 6-tetramethyl-1-oxypiperidine into a mixed solution of styrene and benzoyl peroxide, heating to 90 ℃ under the protection of nitrogen, and reacting for 20 hours to obtain a compound (a), wherein the molar ratio of the benzoyl peroxide to the 2,2,6, 6-tetramethyl-1-oxypiperidine is 1: 2; adding an ethanol solution in which the compound (a) is dissolved into a KOH aqueous solution, and carrying out reflux reaction for 16h under the protection of nitrogen to obtain a compound (b); then the compound (b) reacts with an equimolar amount of isocyano ethyl methacrylate to obtain a methacrylate monomer (c). An equimolar amount of 2,2,6, 6-tetramethyl-1- (1-phenylethoxy) -4-piperidinol was reacted with isocyanoethyl methacrylate to prepare a methacrylate monomer (d). Taking potassium persulfate as an initiator, taking a methacrylate monomer (c) and methyl methacrylate as raw materials, and carrying out free radical polymerization to obtain a copolymer acrylate 1; the copolymerized acrylate 2 is obtained by radical polymerization using potassium persulfate as an initiator and a methacrylate monomer (d) and methyl methacrylate as raw materials.

The silane copolymerization modified acrylate (e) is obtained by radical polymerization using potassium persulfate as an initiator and 3- (dimethoxymethylsilyl) propyl acrylate and methyl acrylate as raw materials.

Acrylic acid and 2-hydroxy chalcone are used as raw materials, a chalcone acrylate monomer is prepared through condensation reaction, potassium persulfate is used as an initiator, the chalcone acrylate monomer and methyl acrylate are used as raw materials, and copolymerization modified acrylate (f) is obtained through free radical polymerization.

Adding a certain amount of toluene solvent into a dry clean three-neck flask, adding 2mmol triethyl borate and 3mmol silane copolymerization modified acrylate (e), dropwise adding a proper amount of acetic acid aqueous solution for hydrolysis for 30min, adding a proper amount of triethylamine, stirring and mixing for 10min, reacting for 4h under the condition of 60 ℃ water bath to prepare a first network, adding 3mmol 1 and 3mmol 2 of copolymerization acrylate, heating to 100 ℃ for reaction for 2h to prepare a second network, adding 3mmol (f) copolymerization modified acrylate, 1 wt% barite powder, 2 wt% gypsum, 1 wt% carbon black and 0.3 wt% sodium dodecyl benzene sulfonate, continuing to react for 2h after ultrasonic treatment for 20min, pouring the polymer solution into a proper boron-containing mold after the reaction is completed, placing in a vacuum oven at 80 ℃ for 12h for removing the solvent, then placing in an ultraviolet light at 280nm for irradiation for 30min, then cooling to room temperature for placing for 30min to obtain a hard solid polymer sample, and obtaining the polymer sample which can be used as a tensile testing material with the dynamic damping effect under the conditions of 80.0 mm 80.0 × 10.0.0. 10.0 × (2.0.0.0 mm), wherein the tensile stress of the tensile strength can be measured by using a sample under the condition of an orthogonal damping stress test, and the dynamic stress test under the condition that the tensile stress of a sample under the condition of a tensile test of a sample with the tensile stress of a tensile test of a tensile strength of a sample under the tensile test of a tensile test sample under the tensile strength of a tensile strength of 10.10.10.10.10 mm.

Example 3

Trimethylolpropane and ethylene oxide are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, and hydroxyl-terminated three-arm polyethylene oxide is synthesized through cationic ring-opening polymerization.

Adding 0.04mol of hydroxyl-terminated three-arm polyethylene oxide and 0.03mol of 1, 4-phenyl diboronic acid into a dry and clean reaction bottle, adding a proper amount of triethylamine, stirring and mixing uniformly, heating to 80 ℃, and reacting for 5 hours to form a first network; then adding 3mmol of polyoxypropylene triol with the molecular weight of about 5,000, 1.5mmol of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) ethylenediamine (a) and 6mmol of 1, 2-bis (4-phenyl isocyanate) disulfide, and continuing to react for 2 hours to obtain the polyurethane-based dynamic polymer elastomer which has certain viscoelasticity and can be stretched and expanded in a large range under the action of external force.

Example 4

2-formylphenylboronic acid and polyether amine with the molecular weight of about 1000 are used as raw materials, the molar ratio of the raw materials to the polyether amine is controlled to be 2:1, the raw materials are dissolved in a toluene solvent, a proper amount of sodium borohydride is added as a reducing agent, and the aminomethyl phenylboronic acid end-capped polyether amine is synthesized through a Petasis reaction.

Weighing 7.5g of aminomethyl phenylboronic acid terminated polyetheramine and 1.5g of pentaerythritol in a dry and clean flask, adding 100ml of epoxidized soybean oil and 0.08g of bentonite, placing the mixture at 60 ℃ for continuously stirring and mixing, after mixing for 30min, dropwise adding a proper amount of triethylamine, heating to 80 ℃, continuing to react for 3h, adding 0.68g of N, N' -di-tert-butyl hexanediamine and 2.1g of trimethyl-1, 6-hexamethylene diisocyanate, reacting for 2h in a nitrogen atmosphere, and obtaining a dynamic polymer elastomer with good resilience after the reaction is finished.

Example 5

Adding 0.1mol of diethanolamine and a certain amount of anhydrous methanol into a dry three-neck flask, uniformly stirring at room temperature, adding 0.2mol of methyl acrylate, stirring at 35 ℃ for 4h, vacuumizing to remove excessive methanol and methyl acrylate, reacting the mixture with trimethylolpropane in a dropwise manner at 115 ℃ under the catalysis of p-toluenesulfonic acid to obtain a primary intermediate product, reacting the primary intermediate product with 3- (bis (2-hydroxyethyl) amino) methyl propionate to obtain a secondary intermediate product, and blocking by using 3-propylene isocyanate to obtain the hyperbranched compound (a).

4-mercaptomethylbenzeneboronic acid and gamma-mercaptopropyldimethylmethoxysilane are used as raw materials, the molar ratio of the raw materials to the raw materials is controlled to be 1:2, and a trimercapto compound (b) is obtained through condensation reaction at the temperature of 60 ℃.

4-mercaptomethylbenzyl boronic acid and 2-mercaptoethanol are used as raw materials, the molar ratio of the raw materials to the raw materials is controlled to be 1:2, and a trimercapto compound (c) is obtained through condensation reaction at the temperature of 60 ℃.

The preparation method comprises the steps of adding 0.01mol of hyperbranched compound (a) into a dry and clean reaction bottle, adding a certain amount of chloroform solvent for dissolving, introducing nitrogen gas for removing water and oxygen for 1h, adding 0.3 wt% of AIBN and 1.0 wt% of triethylamine, slowly adding 0.015mol of 1, 8-octanedithiol, 0.01mol of trimercapto compound (d), 0.01mol of trimercapto compound (b), 0.01mol of trimercapto compound (c) and 3mmol of 4-bromobenzenesulfonic acid butyl ester (e) in sequence, continuing to react for 6h under the condition of nitrogen protection at 60 ℃, pouring a polymer solution into a proper mold, placing the mold into a vacuum oven at 50 ℃ for 12h for drying, and finally obtaining the dynamic polymer elastomer with good resilience, preparing the dumbbell-type sample with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0), performing tensile test by using a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 3.52 +/-1.15 MPa, the tensile modulus is 5.0-4.0 mm, the sample is a dumbbell-type sample, the sample can be recovered under the normal stress absorption, the stress of the normal impact, the stress, the sample can be recovered, the sample after the sample is recovered, the sample is the sample, the sample can be used as the material with the normal stress, the stress of the sample can be recovered, the sample after the sample, the sample is recovered, the sample.

Example 6

Adding 2mol of 1,1,1,3,3, 3-hexamethyldisilazane and 2mol of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine into a nitromethane solution, heating to 50 ℃, stirring for reaction, adding 2mol of sodium acetate and DMF under a nitrogen atmosphere to prepare an intermediate product, cooling the reaction solution to 0 ℃, dropwise adding 1mol of disulfide dichloride, continuously stirring for reaction for 15min, pouring into cold water, collecting the product, dissolving in n-hexane, and adding Na₂SO₄Drying, purifying, dissolving the product in methanol solvent, adding appropriate amount of K₂CO₃The mixture was stirred at room temperature for 4 hours, purified and recrystallized from methanol to obtain the dihydroxy compound (a).

Dissolving 1 molar amount of diglycerol ether and 2 molar amounts of 1-aminoethylboronic acid in a proper amount of THF solvent, and carrying out condensation reaction at 80 ℃ by using triethylamine as a catalyst to obtain a boronic acid ester compound (b).

Taking methylene dithio-dimethanol and ethylene oxide as raw materials, and KOH as a catalyst, and synthesizing hydroxyl-terminated polyethylene oxide through cationic ring-opening polymerization.

Weighing 20g of hydroxyl-terminated polyethylene oxide in a dry clean flask, heating to 110 ℃ to remove water for 1h, adding 4.8g of dihydroxy compound (a), 3.5g of borate compound (b), 8.4g of toluene diisocyanate, 12g of acetone and 0.2g of stannous octoate, reacting for 3h under the condition of 80 ℃ nitrogen protection, after the reaction is finished, removing the acetone in vacuum, cooling to room temperature to finally obtain a polyurethane-based elastomer, preparing the polyurethane-based elastomer into a dumbbell-shaped sample bar with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0), performing tensile test by using a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is measured to be 2.78 +/-0.86 MPa, the tensile modulus is 5.73 +/-1.52 MPa, and the elongation at break is 1034 +/-354%, and the prepared polymer material has good toughness and excellent compression property, can be applied to automobile parts as a damping material, plays the roles of reducing noise and reducing vibration on the surface of the automobile and realizing self-repairing by heating.

Example 7

Weighing equimolar amounts of 2-aminomethylphenylboronic acid and 2- (4-aminobutyl) propane-1, 3-diol, dissolving in a proper amount of chloroform solvent, and carrying out condensation reaction at 80 ℃ with triethylamine as a catalyst to obtain the boronic acid ester compound.

Weighing 50g of low molecular weight polyethylene, 1g of maleic anhydride and 0.1g of dicumyl peroxide, uniformly mixing, melting and mixing by using a small extruder, and granulating to obtain maleic anhydride grafted polyethylene, wherein the extrusion temperature is 160 ℃.

The preparation method comprises the steps of adding 25g of maleic anhydride grafted polyethylene, 1.5g of borate compound, 1.6g of 7-aminocoumarin and 10mg of BHT antioxidant into a dry and clean three-neck flask, heating to 160 ℃ under the protection of nitrogen, carrying out melting stirring and mixing for 1h, then adding 0.25g of p-toluenesulfonic acid, 3.0g of plasticizer DOP and 0.5g of dimethyl silicone oil, continuing to react for 3h under the protection of nitrogen, pouring into a suitable mold, carrying out compression molding at 120 ℃ by using a molding press, cooling to room temperature, standing for 30min, irradiating and curing for 2h by 350nm ultraviolet light to obtain a polyvinyl polymer sample, preparing a dumbbell-shaped sample with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0) mm, carrying out a tensile test by using a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 5.71 +/-1.34 MPa, the tensile modulus is 10.25 +/-2.83 MPa, the elongation at break is 715%, the scratch rate is 205%, placing the sample in a self-repairing instrument for a self-repairing polyvinyl polymer sample, and placing the sample in a self-repairing instrument for a self-repairing polyvinyl polymer sample under the selected from a dynamic ultraviolet light-absorbing instrument, wherein the sample can be used as a self-repairing material which can be placed under the noise-absorbing cushion under the noise-absorbing ultraviolet light with.

Example 8

Reacting 6-bromo-1-hexene with excessive sodium azide to obtain 6-azido-1-hexene; 1 molar equivalent of propargyl acrylate and 1 molar equivalent of 6-azido-1-hexene were reacted in cyclohexanone at 90 ℃ for 3 hours to obtain the diolefin compound (a).

Polymerizing ethylene under the catalysis of Zr-FI catalyst to generate vinyl-terminated polyethylene, and then carrying out mercaptan-olefin click addition reaction on the vinyl-terminated polyethylene and 4-mercaptophenylboronic acid to obtain the organic boric acid compound (b).

Taking AIBN as an initiator and triethylamine as a catalyst, and carrying out a thiol-ene click reaction on propenyl boric acid and 1,3, 5-triazine-2, 4, 6-trithiol to prepare the organic boric acid compound (c), wherein the molar ratio of the propenyl boric acid to the 1,3, 5-triazine-2, 4, 6-trithiol is 3: 1.

The modified polysilsesquioxane (d) is prepared by taking mercaptopropyl triethoxysilane as a raw material and ferric trichloride and HCl as catalysts, performing hydrolytic condensation to obtain mercapto-modified polysilsesquioxane, and then partially blocking by utilizing quantitative vinylcyclopropane.

Dissolving 0.03mol of tetraboric acid, 0.02mol of organic boric acid compound (c) and 8mmol of organic boric acid compound (b) in a certain amount of toluene solvent, and adding a proper amount of calcium chloride for dehydrationHeating the mixture to 80 ℃, and stirring and reacting for 5 hours to form a first network. Then adding 0.02mol of modified polysilsesquioxane (d), 0.04mmol of diene compound (a), 0.04mol of 1, 11-dibromo-undecane, 3 wt% of organic bentonite and 1 wt% of nano Fe₃O₄Uniformly mixing 1 wt% of metal osmium heteroaromatic ring particles, 0.3 wt% of sodium dodecyl benzene sulfonate and 0.2 wt% of photoinitiator DMPA, reacting for 20min under ultraviolet irradiation to form a second network, pouring the reaction solution into a proper mould, placing the mould in a vacuum oven at 60 ℃ for 12h for further reaction and drying, cooling to room temperature, and placing for 30min to obtain a rubber-state heat-conducting polyolefin polymer sample. It is made into

80.0 × 10.0.0 10.0 × (2.0-4.0) mm dumbbell-shaped sample strips are subjected to tensile test by using a tensile testing machine, the tensile rate is 50mm/min, the tensile strength of the sample is 3.12 +/-1.05 MPa, the tensile modulus is 5.26 +/-1.78 MPa, and the elongation at break is 578 +/-250%.

Example 9

Mixing and dissolving equal molar amount of cyclooctadiene and m-chloroperoxybenzoic acid in a certain amount of acetonitrile solvent, dropwise adding a proper amount of H₂SO₄Stirring and reacting at room temperature to obtain 5-cyclooctene-1, 2-diol; the polyoctene polyol and cyclooctene are mixed in a molar ratio of 1:2, and under the action of a Grubbs second-generation catalyst (1, 3-bis (2,4, 6-trimethylphenyl) -2- (imidazolidinylidene) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium), the polyoctene polyol is prepared.

2-formylphenylboronic acid and methylamine are used as raw materials, toluene is used as a solvent, sodium borohydride is used as a reducing agent, the (2- (methylamino) methyl) phenylboronic acid is synthesized through a Petasis reaction, and then the (2- (methylamino) methyl) phenylboronic acid is respectively subjected to alkylation reaction and esterification reaction with 1, 6-dibromohexane and 1, 2-diol propane to prepare the aminomethyl phenylboronic acid ester compound (a), wherein the alkylation reaction solvent is DMF, the catalyst is potassium carbonate, the reaction temperature is 90 ℃, the esterification reaction catalyst is anhydrous sulfuric acid, and the reaction temperature is 90 ℃.

Dissolving 5.4g of polyoctenamei polyol in 100ml of toluene solvent, adding 4mg of BHT antioxidant, mixing and stirring uniformly, adding 1.0 mol% of aminomethyl phenylboronic acid ester compound (a), dropwise adding a small amount of acetic acid aqueous solution, hydrolyzing for 30min, adding a certain amount of triethylamine, heating to 65 ℃, and continuing to stir for reaction for 2 h. Then introducing nitrogen to remove water for 1h, adding 0.25g of terephthalaldehyde and a proper amount of p-toluenesulfonic acid, stirring and mixing, reacting for 2h under the condition of nitrogen protection, then adding 0.02g of ruthenium-based catalyst 2, continuing to react for 6h at 65 ℃, pouring the pasty polymer solution into a proper mould, placing the mould in a vacuum oven at 50 ℃ to dry for 12h to remove a solvent, cooling to room temperature and placing for 30min to finally obtain a colloidal polymer sample, wherein the colloidal polymer sample can show good resilience and dilatancy, the colloidal polymer sample is slowly pressed by fingers, the material shows viscous deformation, and the material shows temporary rigidity under quick knocking. In this embodiment, the obtained polymer material can be used to manufacture a high-efficiency damping material for impact protection.

Example 10

Taking vinyl boronic acid pinacol ester and cyclopentadiene as raw materials, controlling the molar ratio of the vinyl boronic acid pinacol ester to the cyclopentadiene to be 1:1, and taking aluminum trichloride as a catalyst to prepare boric acid ester modified norbornene (a) through a Diels-Alder reaction; the method comprises the steps of taking dipropylene glycol diacrylate and cyclopentadiene as raw materials, controlling the molar ratio of the dipropylene glycol diacrylate to the cyclopentadiene to be 1:2, and taking aluminum trichloride as a catalyst to prepare a norbornene compound (b) through a Diels-Alder reaction.

150ml of toluene solvent is added into a dry and clean reaction bottle, then 0.02mol of borate modified norbornene (a) and 4mmol of norbornene compound (b) are added, metallocene catalyst/methylaluminoxane is taken as a catalytic system, and the crosslinking polynorbornene compound with the borate lateral group is prepared by addition polymerization reaction at 70 ℃.

Adding 200ml of o-dichlorobenzene solvent into a dry and clean reaction bottle, adding 0.02mol of ammonium borate, dropwise adding a proper amount of acetic acid aqueous solution, hydrolyzing for 30min, adding a proper amount of triethylamine, adjusting the pH of the solution to 7.5-8, stirring and mixing for 10min, adding 5mmol of crosslinked polynorbornene compound with a borate side group, stirring and mixing for 10min, adding 6 mol% of 2-methylimidazole and 5 mol% of copper acetate, adding a small amount of anhydrous sodium sulfate, heating to 80 ℃, stirring and reacting for 3h, pouring into a proper mold, placing into a vacuum oven at 60 ℃, continuously reacting for 12h, cooling to room temperature, placing for 30min, finally obtaining a colloidal polymer sample which has good resilience and can be subjected to tensile extension to show ultra-toughness, pressing with a finger, making the colloidal polymer sample into a boron-containing dumbbell type sample with the size of 80.0 × 10.0.0 (2.0-10.0 × (2.0-4.0) mm, performing a tensile test by using a tensile testing machine, obtaining a boron-containing dumbbell type material with the tensile strength of 50mm/min, the tensile strength of 3.0.78, and the tensile strength of the material under normal temperature, and using other dynamic energy absorption characteristics of a dynamic energy absorption coefficient of a dynamic absorption coefficient of a dynamic covalent bond under normal temperature, and a normal temperature, wherein the tensile test shows a dynamic absorption of 18..

Example 11

Adding a proper amount of 2-mercaptoethanol and petroleum ether into a reaction bottle, cooling to 0 ℃ by using an ice water bath, dropwise adding a mixed solution of disulfide dichloride and petroleum ether, and controlling the molar ratio of the 2-mercaptoethanol to the disulfide dichloride to be 3:1, stirring for 4 hours after the addition is finished, washing the reaction mixture by distilled water, separating out an organic phase, drying by anhydrous calcium chloride, distilling petroleum ether by a water pump under reduced pressure at room temperature, and then distilling under reduced pressure under heating in a water bath to obtain the bis (2-hydroxy) ethyl tetrasulfide (a).

Adding a certain amount of selenium into an aqueous solution dissolved with sodium borohydride under a stirring state, stirring and reacting for 25min, and then keeping the temperature through a short steam bath to ensure that the selenium is completely dissolved to obtain a brownish red sodium diselenide solution; then adding the sodium diselenide solution into an anhydrous tetrahydrofuran solution dissolved with 2-bromoethanol under the protection of nitrogen, and reacting at 50 ℃ for 6 hours to obtain a yellow transparent 2,2' -diselenide ethanol solution (b).

An amino compound (c) is obtained by condensation reaction of equimolar amounts of 2-aminoethylaminoboronic acid and 2- (4-aminobutyl) propane-1, 3-diol as starting materials with tetrahydrofuran as a solvent at 50 ℃ and a pH of 8.

The low molecular weight ethylene propylene rubber is used as a raw material, dibenzoyl peroxide is used as a cross-linking agent to react to form a small cluster structure, and maleic anhydride is grafted on the surface of the cluster to obtain the maleic anhydride grafted ethylene propylene rubber.

Weighing 5.5g of maleic anhydride grafted ethylene propylene rubber, adding 30ml of epoxidized soybean oil, 10ml of tricresyl phosphate, 2.52g of bis (2-hydroxy) ethyl tetrasulfide (a), 2.48g of 2,2' -diselenyl diethanol (b), 0.5g of amino compound (c), 0.04g of p-toluenesulfonic acid, 1.0mg of BHT antioxidant, 1.0g of montmorillonite, 1.2g of carbon black and 0.35g of ferric oxide into a reaction bottle, introducing nitrogen for protection, heating to 80 ℃, stirring for reaction for 2 hours, then placing the reaction liquid into a proper mold, continuing the reaction for 5 hours in a vacuum oven at 80 ℃, then cooling to room temperature, standing for 30 minutes, taking out a sample from the mold, and obtaining the ethylene propylene rubber dynamic polymer material. In this embodiment, the polymer rubber can be used as an energy-absorbing and shock-absorbing pad for manufacturing shoes or sporting goods, and the polymer material can exhibit different buffering and shock-absorbing effects under illumination and heating conditions, and has orthogonality and cooperativity.

Example 12

The graft modified polyisoprene rubber (a) is prepared by taking polyisoprene with molecular weight of about 5,000 and 3-mercaptoindole as raw materials and DMPA as a photoinitiator through mercaptan-olefin click addition reaction under the condition of ultraviolet irradiation. Taking hydroxyl-terminated 1, 3-polybutadiene and dichlorodimethylsilane as raw materials, taking toluene as a solvent, and absorbing HCl generated by the reaction by triethylamine to prepare chlorosilane-terminated polybutadiene (b).

200ml of toluene solvent is measured in a dry clean reaction bottle, 6g of chlorosilane-terminated polybutadiene (b) and 1.4g of ethylboric acid are added, an appropriate amount of acetic acid aqueous solution is dropwise added for hydrolysis for 30min, an appropriate amount of triethylamine is added, the mixture is stirred and mixed for 10min, the mixture is heated to 80 ℃ for stirring reaction for 3h, 15g of graft modified polyisoprene rubber (a) is added for stirring dissolution, nitrogen is introduced for removing water and removing oxygen for 1h, 3.82g of triazolinedione compound (b) is added, the mixture is reacted for 4h under an ice bath condition in a nitrogen atmosphere, 0.05g of ruthenium-based catalyst 7 is added, the reaction solution is poured into a suitable mold, the mold is placed into an 80 ℃ vacuum oven for reaction and drying for 24h, the reaction is cooled to room temperature, a polymer sample with certain elasticity is finally obtained, the polymer sample is made into an 80.0 × 10.0.0 mm 10.0 × (2.0-4.0) mm-sized dumbbell-shaped sample, a tensile testing machine is utilized, the tensile rate is 50mm/min, the sample is measured, the tensile strength of the sample is 3.55 +/-1.02 MPa, the tensile modulus of the sample, the sample is 5.74, the sample is measured, the sample is placed in a dumbbell-type dumbbell-shaped sample capable of a shoe-shaped, the shoe-shaped pad capable of exhibiting excellent-shaped, the shoe-shaped dynamic damping-shaped pad capable of damping-shaped shoe with a slightly-shaped damping effect, the shoe-shaped damping.

Example 13

The brominated butyl rubber and the 4-mercaptomethylbenzeneboronic acid are dissolved in a xylene solvent, uniformly stirred and dispersed, and then irradiated for 30min under the ultraviolet condition by taking DMPA as a photoinitiator, and then dried for 12h in a vacuum oven at 80 ℃ to obtain the phenylboronic acid grafted modified butyl rubber.

The brominated butyl rubber and the 3-mercapto-1, 2-propylene glycol are dissolved in a xylene solvent, uniformly stirred and dispersed, and then irradiated for 30min under the ultraviolet condition by using DMPA as a photoinitiator, and then dried for 12h in a vacuum oven at 80 ℃ to obtain the glycol grafted modified butyl rubber.

Weighing 16g of phenylboronic acid graft modified rubber, 14g of diol graft modified rubber and 5g of brominated butyl rubber, uniformly mixing, adding the mixture into a small internal mixer, mixing for 20min, adding 4.0g of foaming agent AC, 2.4g of dimercapto compound (a), 0.07g of photoinitiator DMPA, 0.08g of ruthenium-based catalyst 1, 1.2g of zinc stearate, 1.5g of tribasic lead sulfate, 2g of white carbon black, 0.05g of barium stearate, 0.1g of stearic acid, 0.1g of antioxidant 168 and 0.2g of antioxidant 1010, continuously mixing for 20min, taking out the mixed material, cooling, placing the mixed material in a double-roll machine to prepare a sheet, cooling at room temperature, cutting into pieces, taking out the prepared polymer sheet, reacting for 15min under ultraviolet irradiation, placing in a vacuum box at 80 ℃ for 4h to further react and dry, then cooling to room temperature, placing the mixed sheet in a mold, placing the mixed sheet in a proper mold, performing compression molding by using a flat vulcanizing machine to obtain a rubber insole, placing the rubber sheet in a universal compression testing machine, placing the rubber, the rubber compression molding, the rubber.

Example 14

Trimethylolpropane and propylene oxide are used as raw materials, KOH is used as a catalyst, hydroxyl-terminated polypropylene oxide is synthesized through cationic ring-opening polymerization, 1 molar amount of hydroxyl-terminated three-arm polypropylene oxide and 3 molar amounts of acrylic acid are subjected to esterification reaction to obtain three-arm polypropylene oxide triacrylate, and the three-arm polypropylene oxide triacrylate and 3 molar amounts of 3-mercapto-1, 2-propanediol are subjected to thiol-ene click reaction to obtain the 1, 2-diol-terminated three-arm polypropylene oxide.

The supermolecule compound (a) is prepared by the steps of capping polyether amine with the molecular weight of 800 by methylene diisocyanate, then capping by pentaerythritol, and then reacting with 1, 6-hexamethylene diisocyanate and 1- (2-hydroxyethyl) -2-imidazolidinone in sequence.

Adding 0.03mol of triethyl borate into a dry and clean reaction bottle, dropwise adding an appropriate amount of acetic acid aqueous solution, hydrolyzing for 30min, adding an appropriate amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, adding 0.02mol of 1, 2-diol-terminated three-arm polypropylene oxide, uniformly mixing, reacting for 3h at 60 ℃ to prepare a first network, adding 0.03mol of polyetheramine D2,000, 6mmol of paraformaldehyde, heating to 50 ℃ under stirring to react for 30min to form a second network, adding 0.02mol of a compound (a) into the reaction bottle, adding 5 wt% of graphene powder and 0.2 wt% of sodium dodecylbenzenesulfonate, oscillating and uniformly mixing, continuing to react for 3h, pouring the reaction solution into a suitable mold, placing in a vacuum oven at 60 ℃ for 24h to further react and dry, cooling to room temperature, placing for 30min, finally obtaining a colloidal polymer material dispersed with graphene, which shows a certain viscoelasticity and good thermal stability, performing tensile stress test on a tensile stress of a sample prepared by a tensile stress test by a tensile tester with a tensile stress test under the condition that the tensile stress of 0.2 mm, the sample is 0.2 mm, and the tensile stress of a specimen is 0.2 mm, wherein the sample is 0.2 mm, the tensile stress of a tensile test sample can be detected by a tensile tester under the tensile test sample is 0.2 mm, and the tensile test sample is performed under the tensile test method under the tensile test of a tensile test sample by a tensile test sample with the tensile test of a tensile test method under the tensile test method under.

Example 15

Dissolving a certain amount of trimethylolpropane in a hydrochloric acid solution, adding a proper amount of 3-hydroxy-2, 2-dimethylpropionaldehyde, stirring and reacting for 24 hours under the protection of argon at 90 ℃, wherein the molar ratio of the trimethylolpropane to the 3-hydroxy-2, 2-dimethylpropionaldehyde is 3:2, then uniformly mixing a proper amount of intermediate product with allyl bromide and NaOH powder, adding tetrabutylammonium bromide as a phase transfer catalyst, heating to 70 ℃, stirring and reacting for 24 hours, and preparing the diene compound (a).

4-hydroxystyrene and formaldehyde are taken as raw materials, and are refluxed with zinc nitrate hexahydrate for 24 hours to synthesize the 2- (hydroxymethyl) -4-vinylphenol.

2.5 mol of diene compound (a), 1mol of 2- (hydroxymethyl) -4-vinylphenol, 1.5 mol of pentaerythritol tetramercaptoacetate and 0.02 wt% of photoinitiator DMPA are mixed uniformly, poured into a glass plate mold clamped with a silica gel gasket, irradiated for 10min under ultraviolet light, and subjected to mercaptan-olefin click addition reaction to prepare the cross-linked compound (b) with 2-hydroxymethyl phenol.

Adding 200ml of deionized water into a three-neck flask, adding 5g of sodium borate, dropwise adding an appropriate amount of acetic acid for hydrolysis for 30min, then adding an appropriate amount of NaOH, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, then adding 40g of a crosslinking compound (b), heating to 60 ℃, stirring and dissolving, and continuing to stir and react for 5h at 60 ℃ to obtain a polymer hydrogel, wherein the polymer hydrogel is prepared into a block sample with the size of 20.0 × 20.0.0 20.0 × 20.0.0 mm, a compression performance test is carried out by using a universal testing machine, the compression rate is 2mm/min, the compression strength of the sample is measured to be 0.39 +/-0.08 MPa, and the obtained polymer hydrogel has certain viscosity, good resilience and good biocompatibility, can be used as a biocompatible gel as a buffer layer between mechanical bones, and can be hydrolyzed and regenerated in a phosphate buffer solution.

Example 16

Diethylene glycol diacrylate and 3-mercapto phenylboronic acid are used as raw materials, the molar ratio of the diethylene glycol diacrylate to the 3-mercapto phenylboronic acid is controlled to be 1:2, AIBN is used as an initiator, triethylamine is used as a catalyst, and the phenylboronic acid compound (a) is prepared through a mercapto-Michael addition reaction.

Using glycerol and propylene oxide as raw materials, using boron trifluoride diethyl etherate as a catalyst, synthesizing hydroxyl-terminated three-arm polypropylene oxide through cation ring-opening polymerization, performing esterification reaction on 1mol of hydroxyl-terminated three-arm polypropylene oxide and 3mol of acrylic acid to obtain three-arm polypropylene oxide triacrylate, and performing thiol-ene click reaction on the three-arm polypropylene oxide triacrylate and 3mol of mercaptomethyl diethoxysilane to obtain silane-terminated three-arm polypropylene oxide (b).

Trimethylolpropane and epoxypropane are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, hydroxyl-terminated three-arm polypropylene oxide is synthesized through cationic ring-opening polymerization, and then the hydroxyl-terminated three-arm polypropylene oxide and equimolar amount of acrylic acid are subjected to esterification reaction to obtain olefin-terminated three-arm polypropylene oxide.

Weighing a certain amount of tetrahydrofuran solvent, adding 0.02mol of silane-terminated three-arm polypropylene oxide (b), stirring and dissolving completely, adding 0.03mol of phenylboronic acid compound (a), adding a proper amount of triethylamine, and reacting for 3h at 50 ℃ to form a first network. Then 0.02mol of olefin-terminated three-arm polypropylene oxide, 0.03mol of 1, 6-hexanedithiol, 2 wt% of photocatalyst DMPA, 0.02 wt% of BHT antioxidant, 6 mol% of 2-methylimidazole and 5 mol% of copper acetate are added, and after the reactants are completely dissolved by stirring, the reactants react for 15min under the irradiation of ultraviolet light to form a second network. Pouring the reaction liquid into a proper mould, placing the mould in a vacuum oven at 60 ℃ for 24h for further reaction and drying, then cooling to room temperature and placing for 30min to finally obtain a colloidal polymer sample with certain elasticity, wherein the colloidal polymer sample can be stretched within a certain range. In the using process, the material shows good viscoelasticity, has good vibration isolation and stress buffering effects, and simultaneously shows excellent hydrolysis resistance. In this example, the polymer sample was used as an impact resistant protective gasket.

Example 17

AIBN is used as an initiator, 4-acrylamide sodium phenylboronate and vinyl pyrrolidone are used as raw materials, and the vinyl pyrrolidone-borate copolymer is obtained through free radical polymerization. AIBN is used as an initiator, 3-acrylamide dopamine and vinyl pyrrolidone are used as raw materials, and the vinyl pyrrolidone-dopamine copolymer is obtained through free radical polymerization. Taking AIBN as an initiator and hydroxyethyl acrylate, 2-aminoethyl acrylate and vinyl pyrrolidone as raw materials, and carrying out free radical polymerization to obtain the vinyl pyrrolidone-hydroxyl-amino copolymer.

Measuring 200ml of 1-ethyl-3-methylimidazole tetrafluoroborate in a dry and clean three-neck flask, adding 12g of vinyl pyrrolidone-borate copolymer and 13g of vinyl pyrrolidone-dopamine copolymer, heating, stirring and mixing uniformly, continuing stirring and mixing for 30min, dropwise adding a small amount of 1mol/L NaOH solution, and reacting in a constant-temperature water bath at 60 ℃ for 4h to obtain a first network polymer; then 15g of vinyl pyrrolidone-hydroxyl-amino copolymer, 1.34g of terephthalaldehyde and a proper amount of p-toluenesulfonic acid are added, the mixture is stirred and dissolved completely, the mixture is refluxed and reacted at 65 ℃ under the protection of nitrogen, 5g of calcium carbonate is added after the polymer solution has certain viscosity, the mixture is subjected to ultrasonic treatment for 1min to uniformly disperse the calcium carbonate in the mixture, and the mixture is continuously placed in a constant-temperature water bath at 60 ℃ to react for 2 h. And after the reaction is finished, obtaining the dynamic polymer ionic liquid gel dispersed with calcium carbonate. The polymer gel sample has certain viscosity on the surface and good resilience, and can quickly rebound after being pressed by fingers, and certain tensile toughness is embodied. After the polymer gel is cut by a blade, the sections are jointed and placed in an oven at 60 ℃ for 2-3h, and the gel can be bonded again. In the embodiment, the prepared polymer gel can be used as a bionic material of human-like soft tissues by utilizing the rebound resilience, self-repairability and shape memory capacity of the polymer gel, so that the buffering and shock-absorbing effects are achieved, and in addition, the dynamic property and the buffering effect of the polymer gel can be adjusted by utilizing a pH buffer solution, so that the dynamic polymer material is ensured to have the orthogonality regulation and control effects under different environmental conditions.

Example 18

1- (3-hydroxypropyl) -3, 6-dimethyl pyrimidine-2, 4-diketone and acryloyl chloride are used as raw materials to react to prepare the acrylic pyrimidone (a). Taking AIBN as an initiator, and carrying out free radical polymerization on vinyl pyrrolidone and acrylic pyrimidone (a) to obtain a pyrimidone-vinyl pyrrolidone copolymer. Taking AIBN as an initiator, and carrying out free radical polymerization on vinyl pyrrolidone and 2, 3-dihydroxypropyl acrylate to obtain the vinyl pyrrolidone-diol copolymer.

Weighing 10g of pyrimidone-vinyl pyrrolidone copolymer in a dry clean beaker, adding 100ml of deionized water, continuously stirring and dissolving at 50 ℃, adding 1.5g of diboron trioxide after complete dissolution, adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, mixing for 10min, adding 5g of vinyl pyrrolidone-glycol copolymer, continuously stirring to dissolve and mix in the process, heating to 80 ℃ after complete dissolution, reacting for 1h, adding 5 wt% of carbon nano tubes, 3 wt% of mica sheets and 0.5 wt% of sodium dodecyl benzene sulfonate, ultrasonically treating for 20min, reacting for 2h at 80 ℃, continuously increasing the viscosity of the solution along with the reaction, heating and reacting for 2h to obtain a polymer sample, irradiating for 2h under 350nm ultraviolet light, finally obtaining the double-network conductive hydrogel dispersed with the carbon nano tubes, wherein the double-network conductive hydrogel has good rebound resilience, is prepared into a 20.0. × 20.0.0 mm × mm-sized sample, a compressive stress test is carried out, and a universal conductive material with the compressive stress, has the characteristics of 0.74 mm and the characteristics of the compressive stress, and the compressive stress of the material can be prepared into a material with the characteristics of the compressive stress, the material of the material.

Example 19

Dissolving 2g of selenocysteine hydrochloride into 120mL of dichloromethane, adding 5g of triethylamine under a stirring state, cooling to 0-5 ℃, slowly adding 2.5g of acryloyl chloride, reacting under stirring at room temperature for 24 hours under the protection of nitrogen, and distilling under reduced pressure to obtain the N, N' -bis (acryloyl) selenocysteine.

Using AIBN as an initiator, and initiating N 'N-dimethylacrylamide, N' -bis (acryloyl) selenocysteine and 3-acrylamidophenylboronic acid to perform RAFT free radical polymerization under the condition of water bath at 60 ℃ to obtain acrylamide copolymerization modified boric acid.

Weighing 12.0g of acrylamide copolymerization modified boric acid and 4.5g of polyvinyl alcohol in a dry and clean beaker, adding 100ml of deionized water, placing the beaker in a water bath kettle at 60 ℃, stirring the mixed solution evenly by continuous stirring, then dropwise adding a small amount of 1mol/L ammonia water solution, heating for reaction for 1h, then adding 3g of graphene and 0.15g of sodium dodecyl benzene sulfonate, stirring for 30min at 60 ℃, then adding 0.08g of bentonite, continuing stirring and mixing for reaction for 3h at 60 ℃, pouring the viscous polymer solution into a proper mould, placing the mould in a vacuum oven at 50 ℃ for continuous reaction for 4h, then cooling to room temperature and placing for 30min to finally obtain the polymer hydrogel dispersed with graphene, wherein the polymer hydrogel has certain elasticity and surface viscosity, can be stretched, prepared into a block sample with the size of 20.0 × 20.0.0 20.0 × 20.0.0 mm, performing compression performance test by using a testing machine, measuring the compression rate to be 2mm/min, the compression strength of the sample to be 0.88MPa, cutting and placing the polymer in a universal thermal gel oven with the functions of cutting, and adding a thermal stress sensing filler to the hydrogel, and then placing the gel in the gel with the gel capable of self-repairing function at 14 MPa.

Example 20

Taking potassium persulfate as an initiator, and carrying out free radical polymerization on 4-acrylamido phenylboronic acid sodium salt and N-isopropyl acrylamide to obtain a phenylboronic acid-acrylamide copolymer; taking potassium persulfate as an initiator, and carrying out free radical polymerization on 3-acrylamide dopamine and N-isopropylacrylamide to obtain a dopamine-acrylamide copolymer; taking potassium persulfate as an initiator, and carrying out free radical polymerization on 2-aminoethyl acrylate and N-isopropylacrylamide to obtain the amino-acrylamide copolymer.

Taking a certain amount of phosphate buffer solution (pH 7.0), adding 5mmol of dopamine-acrylamide copolymer and 5mmol of phenylboronic acid-acrylamide copolymer, and placing in a water bath kettle at 60 ℃ for heating reaction for 2 hours to obtain a first network polymer; then 0.01mol of amino-acrylamide copolymer and 0.1mol of terephthalaldehyde are added, stirred and dissolved completely, and reacted for 30min at room temperature; then adding 5 wt% of surface modified Fe₃O₄And (3) carrying out ultrasonic treatment on the particles, 5 wt% of metal magnetic powder and 1 wt% of bentonite for 1min to uniformly disperse the metal particles in the particles, then placing the mixture in a constant-temperature water bath at the temperature of 60 ℃ to react for 1h, and obtaining the double-network hydrogel dispersed with the magnetic particles after the reaction is finished. In the embodiment, the obtained polymer magnetic gel can be used as an intelligent buffer gel material with magnetic field responsiveness, and can realize multiple responsiveness to the gel material by two means of heating and pH adjustment, so that the orthogonality regulation capability based on boron-containing dynamic covalent bonds and other dynamic covalent bonds is embodied.

Example 21

Adding 0.04mol of polyethylene glycol 800 and 0.02mol of dihydroxyamine compound (a) into a dry and clean reaction bottle, adding a proper amount of triethylamine, stirring and mixing uniformly, adding 0.02mol of ethyl boric acid, 0.01mol of trimethyloylmethane and 0.03mol of aldehyde-terminated polyethylene glycol 2,000, heating to 60 ℃ under the protection of nitrogen, and reacting for 24 hours to obtain a viscous polymer sample which can show obvious dilatancy and the shear thickening effect of the polymer sample can respond to the change of temperature and pH(ii) a The apparent viscosity of the polymer fluid was measured using a rotational viscometer at 25 ℃ with a constant shear rate of 0.1s^-1The apparent viscosity of the polymer fluid was measured to be 6,500 mPas. The polymer samples produced can be used to coat or impregnate fabrics or textiles to make impact protective garments or athletic pads.

Example 22

Adding a certain amount of anhydrous toluene into a reaction bottle, adding 5g of polyethylene glycol 800 and a proper amount of tert-butyl alcohol solution dissolved with potassium tert-butoxide, uniformly mixing, introducing nitrogen for 20min, dropwise adding 3ml of ethyl bromoacetate, stirring at room temperature for 24h, dissolving in a methanol solvent after purification, slowly adding a hydrazine hydrate methanol solution, stirring at room temperature for 24h, filtering and purifying to obtain the hydrazide-terminated polyethylene glycol (a).

Measuring 200ml of tetrahydrofuran solvent in a reaction bottle, adding 0.03mol of tributyl borate, dropwise adding an appropriate amount of acetic acid aqueous solution for hydrolysis for 30min, adding an appropriate amount of triethylamine, adjusting the pH of the solution to 7.5-8, shaking and mixing for 10min, adding 0.04mol of polyoxypropylene triol with the molecular weight of about 2,000, shaking and mixing uniformly, heating to 60 ℃ under the protection of nitrogen for reaction for 3h to prepare a first network, introducing nitrogen to remove water for 1h, adding 0.03mol of hydrazide-terminated polyethylene glycol (a) and 0.02mol of 1,3, 5-benzenetricarboxylic acid for reaction for 24h, adding 5 wt% of graphene powder and 0.2 wt% of sodium dodecyl benzene sulfonate, shaking and mixing uniformly for reaction for 2h to obtain a dynamic polymer with a double network, pouring the reaction liquid into a suitable mold, placing the mold in a vacuum oven at 60 ℃ for further reaction and drying, cooling to room temperature for 30min to obtain a colloidal state polymer dispersed with graphene, performing tensile stress test on a tensile dumbbell material with the tensile strength of 3580 mm, and tensile strength of the sample under the condition that the tensile strength of a specimen is 0.53 mm, and the tensile strength of a specimen is measured by a specimen under a rapid tensile test condition that the tensile stress of 0.0.0.0.0 mm, and a specimen is 0.53 mm, and a specimen under the tensile test of a specimen under the tensile strength of a specimen under the tensile test condition that the tensile test of a specimen under the tensile test of a specimen under the tensile strength of a tensile test of a tensile strength of a specimen under the tensile strength of a tensile test of a tensile.

Example 23

The dopamine-styrene copolymer is prepared by taking benzoyl peroxide as an initiator and utilizing styrene and 3-acrylamide dopamine through free radical copolymerization.

The method comprises the following steps of (1) reacting trimethylolpropane with equal molar weight and acetone by taking petroleum ether as a solvent and p-toluenesulfonic acid as a catalyst to obtain a compound (a); then preparing an intermediate product by reacting the intermediate product with 4-chloromethyl styrene under the catalysis of sodium hydride, then preparing a compound (b) by using methanol as a solvent under the catalysis of hydrochloric acid, and finally reacting the compound (b) with 2 molar equivalents of ethyl chloroformate by using triethylamine as a catalyst to prepare a compound (c); then toluene is used as solvent, potassium tert-butoxide is used as catalyst, and the compound (d) is prepared by ring-opening polymerization under the condition of 0 ℃.

Adding a certain amount of toluene solvent into a dry and clean reaction bottle, adding 0.03mol of tricresyl borate into the reaction bottle, dropwise adding a proper amount of acetic acid aqueous solution for hydrolysis for 30min, then adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, then adding 10mmol of dopamine-styrene copolymer, heating to 60 ℃ for dissolution through stirring, continuing to react for 4h at 60 ℃ to obtain a first network, removing oxygen through argon for 1h, then adding 10g of styrene, 5.2g of compound (d) and 0.8 wt% of benzoyl peroxide, heating to 80 ℃ under the protection of nitrogen for reaction for 2h, then adding 1 wt% of potassium tert-butoxide for uniform mixing to form a second network, placing the mixed solution into a proper mold, drying for 24h in a vacuum oven at 60 ℃ for 60 ℃ to obtain a polymer hard solid, wherein the surface of the polymer is smooth, has a certain glossiness, and has certain hardness and mechanical strength, and the tensile strength of 80.0. ×.0. × (2.0 mm-4.84), and the tensile strength of a sample is measured by using a tensile testing machine, wherein the sample is a tensile strength of a sample bar of 20.54 mm, and the sample is 20 MPa.

Example 24

Mixing mercapto-p-phenol and 3-chloro-2-chloromethyl-1-propylene in a molar ratio of 2:1 by taking methanol as a solvent and sodium methoxide as a catalyst, and reacting for 16 hours under a heating condition to obtain dihydric alcohol containing allyl sulfide group; and (b) taking tetrahydrofuran as a solvent and triethylamine as a catalyst, reacting dihydric alcohol containing allyl sulfide with acryloyl chloride, and controlling the reaction temperature to be 0-25 ℃ to synthesize the diene compound (b) containing allyl sulfide. AIBN is used as an initiator, and styrene and 4-vinylpyridine are subjected to free radical copolymerization to prepare the styrene-pyridine copolymer.

Adding 200ml of dichloromethane solvent into a dry and clean reaction bottle, introducing argon to remove water and oxygen for 1h, adding 8g of styrene, 1g of 4-vinylphenylboronic acid, 2.3g of diene compound (b) containing allyl sulfide group, 0.1g of photoinitiator DMPA and 1.2 wt% of benzoyl peroxide, heating to 80 ℃ under the protection of argon to react for 5h, adding a small amount of anhydrous sodium sulfate, and continuing to heat and react for 2h to form a first network; then 5g of styrene-pyridine copolymer and 0.61g of phenyl selenium bromide (a) are added, stirred and mixed for 1h, and then the product is placed in a suitable mould and dried in a vacuum oven at 80 ℃ for 24h, and finally, hard semitransparent polymer solid is obtained, wherein the surface of the solid is smooth, and has certain glossiness and surface hardness. In the embodiment, the prepared polymer sample can be used as a device shell to protect and buffer articles, and when cracks appear on the surface of the polymer sample, the sample can be heated at 130 ℃ to realize self-repairing of the cracks.

Example 25

Adding 0.02mol of 2,2, 4-trimethylhexane diisocyanate into a three-neck flask, carrying out vacuum dehydration for 2h at 120 ℃, cooling to 45 ℃, adding 12ml of DMF for dissolving and diluting, introducing argon for protection, dissolving 0.01mol of N, N-bis (2-hydroxyethyl) cinnamamide and a small amount of butyl tin dilaurate ethyl ester solution in 40ml DMF, dropwise adding the solution into a reaction bottle at a constant speed, heating to 70 ℃ for reaction for 3h, adding 0.01mol of polyethylene glycol 400, and continuing the reaction for 6h at 70 ℃ to obtain the polyurethane containing the cinnamamide side group.

Adding a certain amount of dichloromethane solvent into a three-neck flask, adding 5mmol of 1, 2-bis (chlorodimethylsilyl) ethane, 4mmol of polyethylene glycol 800 and 5mmol of sodium borate, dropwise adding a proper amount of acetic acid aqueous solution, hydrolyzing for 30min, adding a proper amount of triethylamine, heating to 80 ℃ for reaction for 4h, then 10g of polyurethane containing cinnamamide side groups is added to continue to react for 1 hour, 5 wt% of mixed powder of titanium dioxide, ultramarine, chrome yellow, phthalocyanine blue and soft carbon black which are ground in advance, 3 wt% of organic bentonite, 3 wt% of nano-silicon dioxide, 5 wt% of hydroxyethyl cellulose, 2 wt% of dibutyltin dilaurate, trace fluorescent whitening agent KSN and light stabilizer 770 are added to be stirred and mixed evenly, standing for 12h, coating the coating on the surface of a base material, and irradiating for 30min under 280nm ultraviolet light to obtain the coating with energy absorption characteristic.

Example 26

Adding 15g of 2, 4-di-tert-butylphenol, 10g of 4-hydroxymandelic acid and 30ml of acetic acid into a reaction bottle, heating to 95 ℃, uniformly mixing, adding 0.09ml of methanesulfonic acid, continuing to react for 3h, cooling overnight, filtering and purifying to obtain an intermediate product 1, dissolving the intermediate product 1 in an NaOH aqueous solution, heating to 80 ℃ under the protection of nitrogen, adding a proper amount of 3-chloro-1, 2-propanediol, continuing to react for 3h, cooling to room temperature, adding a hydrochloric acid aqueous solution, heating to 80 ℃, continuing to react for 1h, purifying to obtain an intermediate product 2, uniformly mixing the intermediate product 2 with di-tert-butyl peroxide and benzene, irradiating by ultraviolet light at 30 ℃ for 90min, and purifying to obtain a compound (a).

Dissolving 2.5g of trimethyl borate in 200ml of toluene solvent, dropwise adding an appropriate amount of acetic acid aqueous solution for hydrolysis for 30min, then adding an appropriate amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, then adding 25g of polyoxypropylene triol with the molecular weight of about 2,000, stirring and mixing uniformly, heating to 80 ℃ for mixing reaction, after mixing and stirring reaction for 4h, adding 0.2g of talcum powder, 0.1g of dibutyltin dilaurate and 0.4g of silicone oil foam stabilizer, stirring and mixing uniformly at a high speed, adding 12.5g of compound (a) and 33.6g of hexamethylene diisocyanate, mixing rapidly, stirring for 30s at a high speed, when the mixture foams white and foams, pouring into an appropriate mold, placing the mold at 80 ℃ for molding and foaming for 12h to ensure complete reaction and polymerization, finally obtaining a polyurethane-based foam material, preparing a 20.0 × 20.0.0. 20.0 × 20.0.0 mm-sized bulk sample, performing a compression performance test by using a compression testing machine, placing the polyurethane-based foam material under a heating condition that the polyurethane-based foam material can achieve excellent compression performance, and can be used as a buffering cushion material when the polyurethane-based foam material, the polyurethane-based foam material can be used under the mechanical compression performance test, and the polyurethane-based foam material can be used under the polyurethane-based foam material can be applied under the polyurethane-based foam material when the mechanical-based foam material has the excellent-based foam material under the excellent-based cushion material can be used under.

Example 27

AIBN is used as an initiator, styrene and 4-chloromethyl styrene are subjected to free radical copolymerization to prepare a styrene-chloromethyl styrene copolymer, and the styrene-chloromethyl styrene copolymer reacts with 9-anthracene methanol serving as a raw material, NaH serving as a catalyst and THF serving as a solvent at the temperature of 65 ℃ to prepare the styrene copolymer (a). The styrene-phenylboronic acid copolymer (b) is prepared by radical copolymerization of styrene and 4-vinylphenylboronic acid using AIBN as initiator. Equimolar amounts of 2-aminoethyl acrylate and ethoxycarbonyl isocyanate are catalyzed by triethylamine to obtain an acrylate monomer containing a hydrogen bond group, and then AIBN is used as an initiator to copolymerize with styrene through free radicals to obtain hydrogen bond group copolymerization modified styrene (c).

Adding 200ml of toluene solvent into a dry clean reaction bottle, adding 15g of styrene-phenylboronic acid copolymer (b) and 1.36g of pentaerythritol, pouring 50ml of n-hexane solvent, heating to 80 ℃, stirring for dissolving, dropwise adding a proper amount of triethylamine, reacting for 4 hours, adding 10g of styrene copolymer (a), 0.2 wt% of photoinitiator DMPA and 10g of hydrogen bond group copolymerization modified styrene (c), continuously stirring for reacting for 2 hours, placing the mixed solution into a proper mold, irradiating for 30 minutes by 365nm ultraviolet light under a nitrogen atmosphere, drying for 24 hours in a vacuum oven at 60 ℃, and finally obtaining a polymer hard solid which has a smooth surface and a certain glossiness and has certain hardness and mechanical strength, preparing a dumbbell-shaped sample strip with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0), performing tensile test by using a tensile testing machine, wherein the tensile rate is 10mm/min, the tensile strength of the sample is 9.14 +/-3.10 MPa, the tensile modulus is 23.56 +/-5.12, and the sample has certain self-repairing performance and can be used for preparing a rigid sheet material with certain impact resistance.

Example 28

Reacting 4-aminobenzene boric acid with a styrene-maleic anhydride copolymer by taking p-toluenesulfonic acid as a catalyst to prepare the phenylboronic acid graft modified styrene-maleic anhydride copolymer.

Taking 50g of phenylboronic acid modified styrene-maleic anhydride copolymer, 6.8g of pentaerythritol, 2.36g of N-aminoethyl-S-aminoethyl dithiocarbamate, 0.18g of p-toluenesulfonic acid, 0.25g of stannous octoate, 1.8g of di-N-butyltin dilaurate, 5.8g of dioctyl phthalate, 10g of foaming agent F141b, 0.2g of photoinitiator DMPA, 0.24g of stearic acid, 0.06g of antioxidant 168 and 0.12g of antioxidant 1010, uniformly mixing, adding into a small internal mixer for banburying and blending, controlling the mixing temperature to be below 40 ℃, taking out a sample after mixing, filling into a compression mold, closing the mold for pressurizing and heating, the molding temperature being 100-110 ℃, the molding time being 15-20min, the pressure being 10MPa, then taking out, placing in a vacuum oven at 80 ℃ for 6h for further reaction and drying, finally obtaining a polystyrene-based polymer foam sample, preparing the polystyrene-based polymer foam sample into a 20.0. 20.0 × 20.0. 20.0 × 20.0.0 mm-mm size, performing a compression test by using a high-compression rate compression strength test, and performing a high-quality heat insulation and thermal insulation test on the sample.

Example 29

Adding a proper amount of 3,3 '-trithiocarbonate dipropionate and triphenylphosphine into a reaction bottle, adding an anhydrous tetrahydrofuran solution of hydroxyethyl acrylate under an anaerobic condition, then dropwise adding a toluene solution of ethyl azodicarboxylate, controlling the molar ratio of the 3, 3' -trithiocarbonate dipropionate to the hydroxyethyl acrylate to be 1:2, controlling the reaction temperature to be 10 ℃, and finishing the reaction after the dropwise addition is finished to obtain the diene compound (a) containing trithiocarbonate.

The organic boric acid-silane modified silicone oil (b) is prepared by taking methyl mercapto silicone oil with the molecular weight of about 60,000, dimethyl vinyl borate and methyl vinyl diethoxy silane as raw materials and DMPA as a photoinitiator through a thiol-ene click reaction under the condition of ultraviolet irradiation. Taking ethanethiol and isocyanate ethyl acrylate as raw materials, reacting to obtain an acrylate monomer containing thiocarbamate groups, and then reacting the acrylate monomer with methyl mercapto silicone oil with the molecular weight of about 60,000 by taking DMPA as a photoinitiator, and under the condition of ultraviolet irradiation, carrying out thiol-ene click reaction to obtain the modified silicone oil (c) containing side hydrogen bond groups.

Adding 25ml of organic boric acid-silane modified silicone oil (b) into a three-neck flask, heating to 80 ℃, adding a small amount of deionized water, dropwise adding 2ml of triethylamine, and carrying out polymerization reaction for 3 hours under a stirring state to form a first network; then 20ml of methylmercapto silicone oil with molecular weight of about 60,000, 2g of diene compound (a) containing trithiocarbonate and 0.2 wt% of photoinitiator DMPA are added and mixed for 1h, then 30ml of methylmercapto silicone oil (c) containing side hydrogen bond groups are added and mixed for 1h, then the polymer is poured into a proper mould, and is irradiated by 365nm ultraviolet light for 30min under nitrogen atmosphere, and is reacted for 12h under the condition of 80 ℃, and then is cooled to room temperature and is placed for 30min, finally a rubbery transparent polymer sample is obtained, which has certain surface elasticity and can be stretched and extended in a large range (the elongation at break can reach 5000%). In this embodiment, the dynamic polymer can be used as a bulletproof glass interlayer adhesive with self-repairing property, which can show different energy absorption and buffering properties under heating or illumination conditions.

Example 30

Hydroxyl-terminated methyl hydrogen-containing silicone oil with the molecular weight of about 3,000 and 9-vinyl anthracene are used as raw materials, and hydrosilylation is carried out under the catalysis condition of a platinum-olefin complex Pt (dvs) to prepare modified silicone oil (a).

Methyl terminated methyl hydrogen silicone oil with molecular weight of about 3,000 and ethyl 5-hexene-1-radical carbamate are used as raw materials, and the modified silicone oil (b) is prepared by hydrosilylation under the catalysis condition of platinum-olefin complex Pt (dvs).

Adding 20ml of modified silicone oil (a) and 50ml of liquid paraffin into a three-neck flask, adding 0.03mol of boron trioxide, dropwise adding an appropriate amount of acetic acid aqueous solution for hydrolysis for 30min, then adding an appropriate amount of triethylamine, heating to 80 ℃ for reaction for 5h, then introducing nitrogen to remove water and remove oxygen for 1h, then adding 0.01 wt% of BHT antioxidant and 0.06mol of 1, 8-bis (maleimide) -3, 6-dioxaoctane, stirring and dissolving completely, adding a small amount of tin tetrachloride and 15ml of modified silicone oil (b), heating to 80 ℃ under the condition of nitrogen protection for reaction for 12h, then cooling to room temperature and standing for 30min, and finally obtaining the polymer colloid with certain viscoelasticity. When a quick knock is made on the sample, it can show temporary rigidity, playing the effect of dissipating stress, and when the stress is slowly exerted on the surface of the sample, it shows viscous deformable characteristic, and can be used as an anti-impact protective pad applied to fitness equipment.

Example 31

Hydroxyl-terminated methyl vinyl silicone oil with the molecular weight of about 3,000 and 3-mercapto-1-propanol are taken as raw materials, a proper amount of DMPA is added to be taken as a photoinitiator, and the modified silicone oil (a) is prepared through a thiol-ene click reaction under the condition of ultraviolet irradiation.

The modified silicone oil (b) was prepared by hydrosilylation using methyl hydrogen silicone oil having a molecular weight of about 3,000 and 2-methyl-2-propyl (2-oxo-3-buten-1-yl) carbamate as raw materials under the catalysis of a platinum-ene complex Pt (dvs).

Adding 1.46g of triethyl borate into a three-neck flask, dropwise adding an appropriate amount of acetic acid aqueous solution, hydrolyzing for 30min, adding 20ml of modified silicone oil (a) and 1.2g of siloxane compound (c), adding an appropriate amount of triethylamine, heating to 80 ℃ for reaction for 4h, adding 15ml of modified silicone oil (b), heating and blending, cooling to room temperature, standing for 30min, preparing into 80.0 × 10.0.0 10.0 × (2.0-4.0) mm dumbbell-shaped sample strips by using a mold, performing tensile test by using a tensile testing machine at a tensile rate of 50mm/min, measuring the tensile strength of the sample to be 1.83 +/-0.28 MPa, the tensile modulus to be 3.12 +/-1.55 MPa and the elongation at break to be 2000%, and obtaining a soft damping surface of a polymer sample with super-toughness and capable of performing large-range tensile extension under the action of external stress.

Example 32

Controlling the molar ratio of methyl-terminated hydrosiloxane (molecular weight is about 4000) to 4-allyl catechol to be 1:2, adding 1% of Pt (dvs) -THF solution as a catalyst, and carrying out hydrosilylation under the protection of nitrogen to obtain the catechol double-terminated siloxane.

Octamethylcyclotetrasiloxane and phenyl tri (dimethylsiloxy) silane are used as raw materials, concentrated sulfuric acid is used as a catalyst, a ring-opening polymerization method is used for synthesizing three-terminal hydrogen polysiloxane, 1% of Pt (dvs) -THF solution is added to be used as a catalyst, and the three-terminal hydrogen polysiloxane and quantitative propylene diisopropyl borate are subjected to hydrosilylation reaction under the condition of nitrogen protection to obtain the three-arm borate terminated siloxane.

And (2) putting dibenzoyl peroxide in a flask, drying in high vacuum for 15min, then uniformly mixing the dibenzoyl peroxide with octamethylcyclotetrasiloxane, heating to 120 ℃ to react for 2h, filtering the solution by using a neutral active aluminum sieve, and drying to obtain the dimeric cyclotetrasiloxane (a).

Adding 120ml of anhydrous toluene solvent into a dry and clean three-neck flask, adding 6.2ml of octamethylcyclotetrasiloxane and 1.2ml of dimeric cyclotetrasiloxane (a), heating to 110 ℃, rapidly adding a proper amount of tetramethylammonium hydroxide under the stirring state, and continuously reacting for 4 hours to obtain a first network. Adding 15ml of three-armed borate terminated siloxane into a flask, dropwise adding a small amount of 20% acetic acid aqueous solution, heating to 80 ℃, mixing and stirring for 30min, adding 25ml of catechol double terminated siloxane and 5mg of BHT antioxidant, continuously stirring for 30min, adding 1.5ml of triethylamine, continuously reacting for 1h at 80 ℃, adding 5 wt% of graphene powder to obtain a polymer sample with higher viscosity, pouring the polymer sample into a proper mold, placing the polymer sample in a vacuum oven at 80 ℃ for 4-6h for further reaction, cooling to room temperature, placing for 30min to obtain a light yellow transparent viscous sample, coating the sample on the surface of a substrate as a protective coating, and playing a role in impact protection on the substrate through the synergistic effect of boron-containing dynamic covalent bonds and other dynamic covalent bonds.

Example 33

Under the anhydrous and oxygen-free conditions, AIBN is used as an initiator, triethylamine is used as a catalyst, chloroform is used as a solvent, and equimolar vinyl boric acid and 1, 6-hexanedithiol are subjected to mercaptan-olefin click addition reaction at the temperature of 80 ℃ to obtain the boric acid double-end-capped compound.

Reacting equimolar 1,3,5, 7-tetravinyl-1, 3,5, 7-tetramethylcyclotetrasiloxane and 1,3,5, 7-tetramethylcyclotetrasiloxane under the catalysis of chloroplatinic acid, and fully reacting to obtain dimeric cyclotetrasiloxane (a); then the material and 3-mercapto-1, 2-propanediol are subjected to thiol-ene click reaction in a dichloromethane solvent according to the molar ratio of 1:1 to prepare dimeric cyclotetrasiloxane (b) with diol.

Adding 120ml of anhydrous toluene solvent into a dry and clean three-neck flask, adding 4.8ml of 1,3,5, 7-tetramethylcyclotetrasiloxane, 3ml of dicyclo-tetrasiloxane (b) with glycol and 0.5mg of BHT antioxidant, heating to 110 ℃, rapidly adding a proper amount of tetramethylammonium hydroxide and a platinum-olefin complex Pt (dvs) catalyst under a stirring state, continuing to react for 4 hours, then adding 0.31g of sodium borate and a small amount of acetic acid aqueous solution, stirring and mixing for 30 minutes, heating to 80 ℃ to react for 2 hours, then pouring into a proper mould, placing in a vacuum oven at 80 ℃ for further reaction for 4-6 hours, then cooling to room temperature and placing for 30 minutes, and finally obtaining light yellow polymer colloid. The prepared dynamic polymer colloid is soft and has good toughness, and products with different appearance sizes can be customized according to the shape of the die. In addition, the polymeric elastomers also exhibit good moisture resistance. The sample after being pulled apart is stressed at the section and placed in a mold at 60 ℃ for 3-4h, and the section can be bonded again, and the sample has recyclability. In this embodiment, the polymer sample can be used as a custom-built energy absorber.

Example 34

Uniformly mixing methyl mercapto silicone rubber with the molecular weight of 30,000 with vinyl pinacol borate, adding a proper amount of photoinitiator DMPA, and carrying out thiol-ene click reaction under the ultraviolet irradiation condition to obtain the borate grafted modified silicone rubber.

Uniformly mixing methyl mercapto silicone rubber with the molecular weight of 30,000 and gamma-mercaptopropyl methyl dimethoxy silane, adding a proper amount of photoinitiator DMPA, and preparing the silane graft modified silicone rubber through thiol-ene click reaction under the condition of ultraviolet irradiation.

Weighing 18g of borate ester graft modified silicone rubber, 10g of silane graft modified silicone rubber and 2g of methyl silicone rubber particles, adding the mixture into a small internal mixer, mixing for 20min, adding 10g of silicon dioxide, 12g of titanium dioxide, 1.75g of ferric oxide and 0.035g of silicone oil, continuously mixing for 30min to ensure that the additive and the rubber material are fully and uniformly mixed, taking out the rubber material, placing the rubber material in a double-roller machine to press into a sheet, cooling at room temperature, cutting the sheet, soaking the prepared polymer sheet in 90 ℃ alkaline water for pre-crosslinking, taking out, placing the sheet in a 80 ℃ vacuum oven for 6h for further reaction and drying, remixing the dried rubber compound, adding 1.2g of 1,1,3,3,5, 5-hexamethyl-1, 5-divinyl trisiloxane, 3g of gallium-indium liquid alloy, 0.03g of photoinitiator DMPA, 0.8g of tetramethylammonium hydroxide, 0.3g of sodium trimethylsilanolate, 0.05g of antioxidant 168, 0.1g of antioxidant, continuing mixing for 20min, 0.3g of antioxidant, 0.84 min under 120 ℃, obtaining a tensile strength of 10.80 mm, a tensile strength of.

Example 35

Weighing 0.02mol of p-aminophenol triglycidyl epoxy resin, adding the p-aminophenol triglycidyl epoxy resin into a three-neck flask, heating to 60 ℃, introducing nitrogen, keeping the temperature for 1h, adding 0.03mol of suberic acid, 6 mol% of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and 5 mol% of zinc acetate, gradually heating to 130 ℃ under the stirring state, reacting for 5h at the temperature, sequentially adding 0.04mol of boric acid, a small amount of anhydrous calcium chloride, 5 wt% of glass microfiber, 2 wt% of silane coupling agent KH550 and 0.8 wt% of sodium dodecyl benzene sulfonate, stirring for 10min, adding 5 wt% of bentonite, mixing uniformly, and continuing to stir and react for 4h at 130 ℃. When the viscosity of the mixture rises to a certain stage, pouring a yellow viscous polymer sample into a proper mould, placing the mould in a vacuum oven at 80 ℃ for continuous reaction for 4h, then cooling to room temperature and placing for 30min to finally obtain the hard epoxy resin curing material, wherein the surface of the hard epoxy resin curing material is smooth and has higher surface hardness and compressive strength, and after the hard epoxy resin curing material is broken off, the glass microfibers are observed to be uniformly distributed in the matrix. In this embodiment, the polymer material can be used as a housing protection component of an electrical switching device, a printed circuit chassis, and an instrument panel electronic packaging material, and can protect the internal devices from impact.

Example 36

Dissolving 0.028g of stannous octoate in 0.5ml of toluene solvent, pouring into a reaction bottle, adding 50g of lactide and 1.9g of pentaerythritol, uniformly mixing, heating to 160 ℃, reacting for 3 hours, dissolving the product in dichloromethane, precipitating by using ethanol, repeatedly washing for 10 times, and drying for 24 hours under nitrogen atmosphere to obtain the hydroxyl-terminated four-arm polylactide.

The tetraboric acid compound (a) is prepared by taking vinyl boric acid and pentaerythritol tetra-3-mercaptopropionate as raw materials, controlling the molar ratio of the vinyl boric acid to the pentaerythritol tetra-3-mercaptopropionate to be 4:1, taking AIBN as an initiator and triethylamine as a catalyst through a thiol-ene click reaction.

4-hydroxystyrene and formaldehyde are taken as raw materials, the raw materials and zinc nitrate hexahydrate are refluxed for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, methanol is taken as a solvent, AIBN is taken as an initiator, triethylamine is taken as a catalyst, and the hydroxymethyl phenol compound (b) is prepared by the mercaptan-olefin click addition reaction of the methanol and 1, 6-hexanedithiol.

Weighing 100ml of dichloromethane solvent in a reaction bottle, adding 0.5mol of hydroxyl-terminated four-arm polylactide, 1mol of terephthalaldehyde, 0.5 wt% of p-toluenesulfonic acid, 0.35 wt% of tris (nonylphenyl) phosphite and 0.02mol of stannous octoate catalyst, heating to 65 ℃ under the nitrogen protection condition after complete dissolution and stirring, stirring and reacting for 4 hours, adding 0.5mol of tetraboric acid compound (a) and 1mol of hydroxymethyl phenol compound (b) into the reaction bottle, adding an appropriate amount of triethylamine, reacting for 4 hours at 60 ℃, adding 1 wt% of metal osmium heteroaromatic particles and 1 wt% of nano silver particles, shaking and mixing uniformly, continuing to react for 2 hours, pouring the polymer solution into a suitable mold, placing in a vacuum oven at 60 ℃ for 24 hours for drying and further reaction, cooling to room temperature for 30 minutes, finally obtaining a milky-white semitransparent polymer solid sample with gloss, preparing a tensile strength of 80.0 × 10.0.0 (10.0 ×) (2.0-4.0) mm, testing a tensile strength of a tensile dumbbell material with a tensile strength of 13.76 mm, and obtaining a sample with a tensile strength of 13.76 mm and a tensile strength of 13.76 mm.

Example 37

The amino-terminated compound (a) is obtained by condensation reaction at 60 ℃ by using equimolar amounts of 2-aminoethylaminoboronic acid and dopamine as raw materials and tetrahydrofuran as a solvent. 1, 6-hexamethylene diisocyanate and furfuryl alcohol are used as raw materials, dichloromethane is used as a solvent, stannous octoate is used as a catalyst, the molar ratio of the raw materials to the dichloromethane is controlled to be 1:2, the reaction is carried out for 2 hours at room temperature under the protection of nitrogen, and the reflux reaction is carried out for 2 hours to prepare a difuran compound (b).

Weighing 0.02mol of polybutadiene epoxy resin (c) with the molecular weight of about 2,000, adding the polybutadiene epoxy resin (c) into a three-neck flask, heating to 80 ℃, introducing nitrogen for 1h, adding an appropriate amount of triethylamine, slowly adding 0.02mol of boric acid under stirring, stirring for reaction for 1h, slowly adding 0.02mol of amino-terminated compound (a), continuously stirring for reaction for 1h, adding 0.05mol of N- (2-aminoethyl) maleimide, continuously heating for reaction for 2h, adding 0.05mol of difuran compound (b), mixing and stirring for 1h, placing a polymer sample into a suitable mold, placing the polymer sample into a vacuum oven for drying for 24h, cooling to room temperature, finally obtaining an epoxy resin elastomer with toughness and high elongation, wherein the epoxy resin elastomer has good electrical insulation, weather resistance and impact toughness, a dumbbell type sample with the size of 80.0 × 10.0.0 (10.0 ×) (2.0-4.0) mm is prepared, a tensile test is carried out by using a tensile testing machine with the tensile rate of 50mm/min, the tensile strength of the sample is 3.0.78, the sample is prepared into a dumbbell type sample with the tensile strength of 80.0.0.0 mm, the sample is prepared into a dumbbell type sample with the elastic strain response of a normal tensile testing machine, the elastic strain response of the elastic strain of the elastic elastomer is changed under the normal strain of the elastic elastomer under the elastic strain of.

Example 38

Adding 1.2g of sodium tetraborate, 7.5g of hydroxyl-terminated polybutadiene with the molecular weight of about 4,000 and 120ml of toluene into a dry and clean three-neck flask, adding a small amount of acetic acid aqueous solution, stirring and mixing for 30min, dropwise adding a small amount of BHT antioxidant, heating to 120 ℃, continuously mixing for 30min, dropwise adding a small amount of triethylamine, and reacting for 3h under the nitrogen protection condition to obtain a first network; then adding 2.58g of butynediol, 3.42g of butynedioic acid, 3g of polyoxypropylene triol with the molecular weight of about 3,000, 4.12g of dicyclohexylcarbodiimide condensing agent and 0.468g of catalyst 4-dimethylaminopyridine, stirring and mixing uniformly, reacting for 4h under the reflux condition, then adding the ruthenium-based catalyst 10, continuing to react for 2h, pouring the viscous reaction liquid into a proper mould, placing the mould into a vacuum oven at 80 ℃ for 24h for further reaction, cooling to room temperature, and standing for 30min to finally obtain a massive polymer sample with certain viscoelasticity. When a quick knock is made on the sample, it can show temporary rigidity, playing the effect of dissipating stress, and when the stress is slowly exerted on the surface of the sample, it shows viscous deformable characteristic, and can be used as an anti-impact protective pad applied to fitness equipment.

Example 39

The preparation method comprises the steps of extracting limonene oxide from orange peels, carrying out polymerization reaction on the limonene oxide and carbon dioxide under the catalysis of β -diimine zinc at 25 ℃ for 24 hours to obtain polycarbonate PLimC, and carrying out thiol-ene click reaction on the polycarbonate PLimC, AIBN serving as an initiator and triethylamine serving as a catalyst, and quantitative neopentyl glycol [4- (mercaptomethyl) phenyl ] borate, N-phenyl-3-mercaptopropionamide and 3-mercaptoindole to obtain a polycarbonate compound (a).

4-hydroxystyrene and formaldehyde are taken as raw materials, and are refluxed with zinc nitrate hexahydrate for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, and then methanol is taken as a solvent, AIBN is taken as an initiator, triethylamine is taken as a catalyst, and the mixture and 1, 6-hexanedithiol are subjected to mercaptan-olefin click addition reaction to prepare the hydroxymethyl phenol double-end-capped compound (b).

A certain amount of chloroform solvent was poured into a dry clean flask, and then 5mmol of polycarbonate compound (a) was added thereto and dissolved by stirring, dropwise adding an appropriate amount of acetic acid aqueous solution for hydrolysis for 30min, adding 0.02mol of hydroxymethyl phenol double-end-capped compound (b) and an appropriate amount of pyridine, stirring and mixing for 10min, heating to 60 ℃ for reaction for 3h, then introducing nitrogen to remove water and remove oxygen for 1h, then adding 4mg of BHT antioxidant, 0.04mol of triazolinedione compound (c), 2mmol of diphenyl carbonate, 0.01mol of zinc acetate and 0.01mol of triethylamine, reacting for 4 hours in nitrogen atmosphere under ice bath condition, then placing the mixed solution in a proper mould and drying in a vacuum oven at 50 ℃ for 24 hours to finally obtain a hard polymerization block sample, wherein the prepared polymer sample has hard texture, excellent mechanical strength and surface hardness, and can be used as an anti-impact protective cover or an anti-impact instrument panel.

Example 40

Polycaprolactone diacrylate is prepared by taking polycaprolactone diol with the molecular weight of about 10,000 and acryloyl chloride as raw materials, controlling the molar ratio of the polycaprolactone diol to the acryloyl chloride to be 1:2 and carrying out acylation reaction.

The tetraboric acid compound is prepared by taking vinyl boric acid and pentaerythritol tetramercaptoacetate as raw materials, controlling the molar ratio of the vinyl boric acid to the pentaerythritol tetramercaptoacetate to be 4:1, taking AIBN as an initiator and triethylamine as a catalyst through mercaptan-olefin click addition reaction.

4-hydroxystyrene and formaldehyde are taken as raw materials, and are refluxed with zinc nitrate hexahydrate for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, and then methanol is taken as a solvent, AIBN is taken as an initiator, triethylamine is taken as a catalyst, and the mixture and pentaerythritol tetramercapto acetate are subjected to mercaptan-olefin click addition reaction to prepare the polyol compound (a).

Adding 0.02mol of polyol compound (a) into a dry clean reaction bottle, stirring and dissolving completely, then adding 0.02mol of tetraboric acid compound and a proper amount of triethylamine, placing the mixture in a water bath kettle at 60 ℃ for heating and reacting for 3h, then adding 8mmol of polycaprolactone diacrylate, 4mmol of pentaerythritol tetramercapto acetate, 0.2 wt% of photoinitiator DMPA, 0.01 wt% of BHT antioxidant, 6 wt% of 2-methylimidazole and 5 wt% of copper acetate, mixing and stirring for 1h, then pouring the polymer solution into a proper mold, irradiating for 20min by using ultraviolet light, then placing the mold in a vacuum oven at 60 ℃ for 24h for further reaction and drying, then cooling to room temperature for 30min, finally obtaining a film-shaped dynamic polymer sample, cutting the sample into a dumbbell-shaped sample bar with the size of 80.0.08 +/-0.02 mm, performing a tensile test by using a tensile testing machine with the tensile rate of 50mm/min, measuring the tensile strength of the sample to be 2.54 +/-0.77 MPa, the tensile modulus to be 4.86 +/-1.255, cutting the dumbbell-shaped sample into a dumbbell-shaped sample, placing the sample into a film-shaped plastic film, cutting buffer film, and providing the plastic film, and repeatedly using a protective film with the plastic film, cutting process, wherein the plastic film has the tensile strength of the plastic film, the plastic film can be repeatedly used for preparing the plastic film, and the plastic film, the plastic film.

EXAMPLE 41

Weighing 3g of terephthalaldehyde, dissolving in 50ml of absolute ethanol, adding 8.9g of diethyl malonate, 0.2g of piperidine and 0.2g of acetic acid, carrying out reflux reaction for 12 hours under the argon atmosphere, and then cooling and purifying to obtain the compound (a).

Weighing 5.0g of ethylene-vinyl alcohol copolymer and 0.82g of 1, 4-benzenediboronic acid in a reaction bottle, uniformly mixing, heating to 110 ℃, reacting for 2 hours, then adding 2.0g of compound (a) and 1.6g of triethylenetetramine in the reaction bottle, uniformly stirring, cooling to room temperature, standing for 6 hours, heating to 50 ℃, standing for 10 hours, and finally obtaining the crosslinked polymer film. The obtained polymer film has soft texture, certain strength and toughness, can be expanded within a certain range, and has certain tear resistance. In this embodiment, the obtained polymer material can be used as an outer packaging material having high barrier properties and flexibility, and can protect the inner articles.

Example 42

Reacting quantitative diphenylmethane diisocyanate and polyoxypropylene glycol PPG-700 to prepare the isocyanate-terminated polyether. 2-formylphenylboronic acid and polyether amine with the molecular weight of about 1000 are used as raw materials, the molar ratio of the raw materials to the polyether amine is controlled to be 2:1, the raw materials are dissolved in a toluene solvent, a proper amount of sodium borohydride is added as a reducing agent, and the aminomethyl phenylboronic acid end-capped polyether amine is synthesized through a Petasis reaction.

1.8g of the hexafluorocyclopentene compound (a) was weighed and dissolved in 10ml of a toluene solvent, 0.96g N- (2-hydroxyethyl) maleimide was added, and the reaction was stirred at 90 ℃ for 24 hours, and washed and purified with ethyl acetate and deionized water to obtain the hexafluorocyclopentene compound (b).

Weighing 8g of aminomethyl phenylboronic acid end-capped polyetheramine and 5g of four-arm polyethylene glycol (c) with the molecular weight of about 3,000 in a dry and clean reaction bottle, placing the mixture at 60 ℃ for continuously stirring and mixing, after mixing for 30min, dropwise adding a proper amount of triethylamine, heating to 80 ℃, continuing to react for 3h to obtain a first network, and crushing a product into small particles; taking another reaction bottle, adding 200ml of THF solvent, vacuumizing to remove water for 1h, then adding 0.02mol of hexafluorocyclopentene compound (b), 0.01mol of dinitrocarbene compound (d) and 0.04mol of isocyanate terminated polyether, heating to 60 ℃, reacting for 3h in nitrogen atmosphere, then adding 15g of first network polymer small particles, 10 wt% of carbon nanotubes, introducing nitrogen for protection, continuing to react for 2h, then placing in a vacuum oven at 80 ℃ for 6h for further reaction and drying, and finally obtaining the conductive polyurethane-based dynamic polymer elastomer which has good resilience, can be used as conductive adhesive with a self-repairing function, is used for damping and buffering of precise instruments or electronic products, and can show different dynamic and self-repairing effects under different illumination conditions.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims

1. A combined energy absorption method is characterized in that a combined hybrid dynamic polymer is provided and is used as an energy absorption material for energy absorption; wherein the combinatorial hybrid dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonds; wherein the presence of said boron-containing dynamic covalent bonds, other dynamic covalent bonds, and optionally hydrogen bonds is a requirement for forming or maintaining a polymer structure.

2. The method of claim 1, wherein the boron-containing dynamic covalent bond is selected from the group consisting of an organoborane bond, an inorganic borane bond, an organic-inorganic borane bond, a saturated five-membered ring organoborate bond, an unsaturated five-membered ring organoborate bond, a saturated six-membered ring organoborate bond, an unsaturated six-membered ring organoborate bond, a saturated five-membered ring inorganic borate bond, an unsaturated five-membered ring inorganic borate bond, a saturated six-membered ring inorganic borate bond, an unsaturated six-membered ring inorganic borate bond, an organoborate monoester bond, an inorganic borate monoester bond, an organoborate silicone bond, and an inorganic borate silicone bond.

3. The method according to claim 2, wherein the organoboron anhydride linkages are selected from at least one of the following structures:

the inorganic boron anhydride linkage is selected from the following structures:

wherein, Y₁、Y₂、Y₃、Y₄Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, and Y₁、Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, Y₃、Y₄At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a, b, c, d are each independently of Y₁、Y₂、Y₃、Y₄The number of connected connections; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b, c and d are 0; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from oxygen atom and sulfur atom, a, b, c and d are 1; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from nitrogen atom and boron atom, a, b, c and d are 2; when Y is₁、Y₂、Y₃、Y₄When each is independently selected from silicon atoms, a, b, c and d are 3;

the organic-inorganic boron anhydride linkage selected from the following structures:

wherein, Y₁、Y₂Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, and Y₁、Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a and b are each independently of Y₁、Y₂The number of connected connections; wherein, the boron atom in the structure is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; when Y is₁、Y₂When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a and b are 0; when Y is₁、Y₂When each is independently selected from oxygen atom and sulfur atom, a and b are 1; when Y is₁、Y₂When each is independently selected from nitrogen atom and boron atom, a and b are 2; when Y is₅、Y₆When each is independently selected from silicon atoms, a, b is 3;

the saturated five-membered ring organic boric acid ester bond is selected from the following structures:

the unsaturated five-membered ring organic boric acid ester bond is selected from the following structures:

represents an aromatic ring with any number of elements, and the aromatic ring contains two adjacent carbon atoms which are positioned in an unsaturated five-membered ring organic borate bond;

the saturated six-membered ring organic boric acid ester bond is selected from the following structures:

the unsaturated six-membered ring organic boric acid ester bond is selected from the following structures:

represents an aromatic ring of any number of elements, and the aromatic ring contains two adjacent carbon atoms, which are located in an unsaturated six-membered ring organoboronate bond;

the saturated five-membered ring inorganic borate ester bond is selected from at least one of the following structures:

wherein, Y₁Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a represents a group represented by the formula₁The number of connected connections; when Y is₁When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is₁When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is₁When selected from silicon atoms, a is 3;

the unsaturated five-membered ring inorganic borate ester bond is selected from at least one of the following structures:

represents an aromatic ring with any number of elements, and the aromatic ring contains two adjacent carbon atoms which are positioned in an unsaturated five-membered ring inorganic borate bond;

the saturated six-membered ring inorganic borate ester bond is selected from at least one of the following structures:

wherein, Y₁Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a represents a group represented by the formula₁The number of connected connections; when Y is₁When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is₁When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is₁When selected from silicon atoms, a ═3；

The unsaturated six-membered ring inorganic borate ester bond is selected from at least one of the following structures:

an aromatic ring of any number of elements, the aromatic ring containing two adjacent carbon atoms, which is located in an unsaturated six-membered ring inorganic borate bond;

the organic boric acid monoester bond is selected from at least one of the following structures:

wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond; i is₁Selected from divalent linking groups; i is₂Selected from the group consisting of a double bond directly to two carbon atoms, a trivalent carbene group directly to two carbon atoms, a divalent non-carbon atom, a linking group comprising at least two backbone atoms;

an aromatic ring having an arbitrary number of elements; wherein, the organic boric acid monoester bonds formed after the 6 and 7 structures are formed into rings are not the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond;

the inorganic boric acid monoester bond is selected from at least one of the following structures:

wherein, Y₁～Y₁₃Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, and Y₁、Y₂；Y₃、Y₄；Y₅、Y₆、Y₇、Y₈；Y₉、Y₁₀、Y₁₁、Y₁₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; y is₁₄Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; i is₁Selected from divalent linking groups; i is₂Selected from the group consisting of a double bond directly to two carbon atoms, a trivalent carbene group directly to two carbon atoms, a divalent non-carbon atom, a linking group comprising at least two backbone atoms; wherein a to n each represents Y₁～Y₁₄The number of connected connections; when Y is₁～Y₁₃When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a-m is 0; when Y is₁～Y₁₄When each is independently selected from oxygen atom and sulfur atom, a to n are 1; when Y is₁～Y₁₄When each is independently selected from nitrogen atom and boron atom, a to n are 2; when Y is₁～Y₁₄Each independently selected from silicon atoms, a to n is 3;

an aromatic ring having an arbitrary number of elements; wherein, the inorganic boric acid monoester bonds formed after the structures of 5, 6, 7 and 8 are cyclized are not the saturated five-membered ring inorganic boric acid ester bond, the unsaturated five-membered ring inorganic boric acid ester bond, the saturated six-membered ring inorganic boric acid ester bond and the unsaturated six-membered ring inorganic boric acid ester bond;

the organic borate silicone bond is selected from at least one of the following structures:

the inorganic borate silicon ester bond is selected from at least one of the following structures:

wherein, Y₁、Y₂、Y₃Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, and Y₁、Y₂At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a, b and c are each independently of Y₁、Y₂、Y₃The number of connected connections; when Y is₁、Y₂、Y₃When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b and c are 0; when Y is₁、Y₂、Y₃When the atom is selected from oxygen atom and sulfur atom, a, b and c are 1; when Y is₁、Y₂、Y₃When the atoms are selected from nitrogen atoms and boron atoms, a, b and c are 2; when Y is₁、Y₂、Y₃When each is independently selected from silicon atoms, a, b and c are 3.

4. The combined energy absorbing method of claim 1, wherein the other dynamic covalent bond is selected from the group consisting of a dynamic sulfur linkage, a dynamic diselenide linkage, a dynamic selenazone linkage, an acetal dynamic covalent bond, a dynamic covalent bond based on a carbon-nitrogen double bond, a dynamic covalent bond based on a reversible radical, an exchangeable acyl bond for binding, a dynamic covalent bond induced by steric effects, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, a, An amine alkene-Michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine dynamic covalent bond, and a dynamically exchangeable trialkylsulfonium bond.

5. The energy absorbing method of claim 4, wherein the dynamic sulfur linkage is selected from the following structures:

wherein x is the number of S atoms and is more than or equal to 2;

the dynamic double selenium bond is selected from the following structures:

the dynamic selenium-nitrogen bond is selected from the following structures:

wherein X is selected from halide ions;

the acetal dynamic covalent bond is selected from at least one of the following structures:

wherein, X₁、X₂、X₃、X₄Each independently selected from oxygen atom, sulfur atom, nitrogen atom; r₁、R₂Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; r₃、R₄Each independently selected from the group consisting of a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group, a divalent or polyvalent polymer chain residue;

the dynamic covalent bond based on carbon-nitrogen double bond is selected from at least one of the following structures:

wherein R is₁Is a divalent or polyvalent small molecule hydrocarbon group;

the dynamic covalent bond based on the reversible free radical is selected from at least one of the following structures:

wherein, X₁、X₂Is a sterically hindered divalent or polyvalent radical directly bonded to the nitrogen atom, each of which is independently selected from divalent or polyvalent C_3-20Alkyl, divalent or polyvalent cyclic C_3-20Alkyl, phenyl, benzyl, aromatic, carbonyl, sulfone, phosphate, and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof; r' is a group directly linked to a carbon atom, each independently selected from a hydrogen atom, C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aromatic and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof; wherein each W is independently selected from an oxygen atom, a sulfur atom; w₁Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups, and substituents thereof; w₂Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups and substituents thereof, carbonyl groups, thiocarbonyl groups, divalent methyl groups and substituents thereof; w₃Each independently selected from ether groups, thioether groups; w₄Each independently selected from the group consisting of a direct bond, an ether group, a thioether group, a secondary amine group and substituents thereof, a carbonyl group, a thiocarbonyl group, a dicarbonyl groupA monovalent methyl group and a substituent thereof; w, W at different locations₁、W₂、W₃、W₄The structures of (A) are the same or different; wherein R is₁Each independently selected from hydrogen atom, halogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residue, R at different positions₁The same or different; wherein R is₂Each independently selected from hydrogen atom, cyano group, hydroxy group, phenyl group, phenoxy group, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein, L 'is a divalent linking group selected from a single bond, a heteroatom linking group and a divalent small molecule hydrocarbon group, and L' at different positions is the same or different; wherein V, V ' are each independently selected from carbon atom, nitrogen atom, V, V ' at different positions are the same or different, and when V, V ' is selected from nitrogen atom, it is connected to V, V

Is absent; wherein,

the cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms;

the binding exchangeable acyl bond is selected from at least one of the following structures:

wherein, X₁、X₂Selected from carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; y is selected from the group consisting of an oxygen atom, a sulfur atom and a secondary amine group; z₁、Z₂Selected from oxygen atom, sulfur atom; r₅Selected from the group consisting of hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein, when X₁、X₂When it is an oxygen atom or a sulfur atom, R₁、R₂、R₃、R₄Is absent; when X is present₁、X₂When it is a nitrogen atom, R₁、R₃Exist, R₂、R₄Is absent, and R₁、R₃Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present₁、X₂When it is a carbon atom or a silicon atom, R₁、R₂、R₃、R₄Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;

the dynamic covalent bond based on steric effect induction is selected from at least one of the following structures:

wherein, X₁、X₂Selected from carbon atoms, silicon atoms and nitrogen atoms; z₁、Z₂Selected from oxygen atoms and sulfur atoms; when X is present₁、X₂When it is a nitrogen atom, R₁、R₃Exist, R₂、R₄Is absent, and R₁、R₃Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present₁、X₂When it is a carbon atom or a silicon atom, R₁、R₂、R₃、R₄Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein R is_bIs a bulky group with steric effect directly connected with nitrogen atom and selected from C_3-20Alkyl, ring C_3-20Alkyl, phenyl, benzyl, aromatic and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof;

the reversible addition fragmentation chain transfer dynamic covalent bond is selected from at least one of the following structures:

wherein R is₁～R₁₀Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; x₁、X₂、X₃Each independently selected from single bond, divalent or polyvalent small molecule alkyl; z₁、Z₂、Z₃Each independently selected from single bonds, heteroatom linking groups, divalent or polyvalent small molecule hydrocarbon groups;

the dynamic siloxane bond is selected from the following structures:

the dynamic silicon ether bond is selected from the following structures:

the alkyl triazolium-based exchangeable dynamic covalent bond is selected from the following structures:

wherein, X^-Is negative ion selected from bromide ion and iodide ion;

the unsaturated carbon-carbon double bond capable of olefin cross metathesis reaction is selected from the following structures:

the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross metathesis reaction is selected from the following structures:

the [2+2] cycloaddition dynamic covalent bond is selected from at least one of the following structures:

wherein D is₁～D₆Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, D₁、D₂At least one of them is selected from carbon atoms or nitrogen atoms; a is₁～a₆Respectively represent with D₁～D₆The number of connected connections; when D is present₁～D₆Each independently selected from an oxygen atom and a sulfur atom₁～a₆0; when D is present₁～D₆Each independently selected from nitrogen atoms, a₁～a₆1 is ═ 1; when D is present₁～D₆Each independently selected from carbon atoms, a₁～a₆＝2；Q₁～Q₆Each independently selected from carbon atoms, oxygen atoms; b₁～b₆Respectively represent and Q₁～Q₆The number of connected connections; when Q is₁～Q₆Each independently selected from oxygen atoms, b₁～b₆0; when Q is₁～Q₆Each independently selected from carbon atoms, b₁～b₆＝2；

The [4+2] cycloaddition dynamic covalent bond is selected from at least one of the following structures:

wherein, K₁、K₂、K₅～K₁₀Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K₁、K₂Or K₅、K₆Or K₇、K₈Or K₉、K₁₀At least one atom selected from carbon atom or nitrogen atom; c. C₁～c₁₀Respectively represent and K₁～K₁₀The number of connected connections; when K is₁、K₂、K₅～K₁₀Each independently selected from an oxygen atom and a sulfur atom, c₁、c₂、c₅～c₁₀0; when K is₁、K₂、K₅～K₁₀Each independently selected from nitrogen atoms, c₁、c₂、c₅～c₁₀1 is ═ 1; when K is₁、K₂、K₅～K₁₀Each independently selected from carbon atoms, c₁、c₂、c₅～c₁₀＝2；K₃、K₄Each independently selected from oxygen atom, sulfur atom, nitrogen atom; c. C₃、c₄Respectively represent and K₃、K₄The number of connected connections; when K is₃、K₄Each independently selected from an oxygen atom and a sulfur atom, c₃、c₄0; when K is₃、K₄Each independently selected from nitrogen atoms, c₃、c₄＝1；I₁、I₂Each independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule alkyl;

the cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms; n represents the number of linkages to the ring-forming atoms of the cyclic group structure;

the [4+4] cycloaddition dynamic covalent bond is selected from at least one of the following structures:

wherein,

the cyclic group structure is aromatic ring or hybrid aromatic ring, and the ring atoms of the cyclic group structure are independently selected from carbon atom, nitrogen atom or other hetero atomsAn atom; i is₆～I₁₄Each independently selected from oxygen atom, sulfur atom, amido, ester group, imino, divalent small molecule alkyl;

the dynamic covalent bond of the mercapto-Michael addition is selected from at least one of the following structures:

wherein X is selected from ketone group, ester group, amide group, thiocarbonyl group and sulfone group; y is an electron withdrawing effect group selected from the group consisting of aldehyde groups, carboxyl groups, nitro groups, phosphate groups, sulfonic acid groups, amide groups, sulfone groups, trifluoromethyl groups, cyano groups, halogen atoms, and combinations thereof;

the amine alkene-Michael addition dynamic covalent bond is selected from the following structures:

the dynamic covalent bond based on triazolinedione-indole is selected from the following structures:

the dynamic covalent bond based on the diazacarbene is selected from at least one of the following structures:

the hexahydrotriazine dynamic covalent bond is selected from at least one of the following structures:

the dynamically exchangeable trialkylsulfonium linkage is selected from the following structures:

wherein, X^-Selected from the group consisting of sulfonate salts.

6. The method of claim 1, wherein the hybrid dynamic polymer has one of the following structures:

the first method comprises the following steps: the combined hybrid dynamic polymer is a non-crosslinked structure and contains at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond;

and the second method comprises the following steps: the combined hybrid dynamic polymer is a non-crosslinked structure and contains at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and a hydrogen bond;

and the third is that: the combined hybrid dynamic polymer only contains one dynamic covalent cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond cross-link, and the cross-linking degree of the dynamic covalent bond cross-link is above the gel point;

and fourthly: the combined hybrid dynamic polymer only contains one dynamic covalent crosslinking network, and the crosslinking network simultaneously contains at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and hydrogen bond crosslinking, and the crosslinking degree of the dynamic covalent bond crosslinking is above the gel point;

and a fifth mode: the combined hybrid dynamic polymer comprises two crosslinking networks, wherein one crosslinking network is a dynamic covalent crosslinking network which comprises at least one boron-containing dynamic covalent crosslinking and the crosslinking degree of the boron-containing dynamic covalent crosslinking reaches above a gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point;

and a sixth mode: the combined hybrid dynamic polymer comprises two crosslinking networks, wherein one crosslinking network is a dynamic covalent crosslinking network which comprises at least one boron-containing dynamic covalent crosslinking and the crosslinking degree of the boron-containing dynamic covalent crosslinking reaches above a gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; and further comprising hydrogen bonding crosslinks in at least one of said dynamic covalent crosslink networks;

seventh, the method comprises: the combined hybrid dynamic polymer comprises two crosslinking networks, wherein one crosslinking network is a dynamic covalent crosslinking network and simultaneously comprises at least one boron-containing dynamic covalent bond crosslinking and at least one other dynamic covalent bond crosslinking, and the crosslinking degree of the dynamic covalent bond crosslinking is more than the gel point of the dynamic covalent bond crosslinking; the other crosslinking network is a hydrogen bond crosslinking network, wherein the crosslinking degree of the hydrogen bond crosslinking is above the gel point;

an eighth method: the combined hybrid dynamic polymer contains three crosslinking networks, wherein one crosslinking network is a dynamic covalent crosslinking network which contains at least one boron-containing dynamic covalent crosslinking and the crosslinking degree of the boron-containing dynamic covalent crosslinking reaches more than the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinking network is a hydrogen bond crosslinking network, wherein the crosslinking degree of the hydrogen bond crosslinking is above the gel point;

ninth, the method comprises the following steps: the combined hybrid dynamic polymer contains three crosslinking networks, wherein one crosslinking network is a dynamic covalent crosslinking network which contains at least one boron-containing dynamic covalent crosslinking and the crosslinking degree of the boron-containing dynamic covalent crosslinking reaches more than the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the last crosslinking network reaches above the gel point;

the tenth way: the combined hybrid dynamic polymer comprises two crosslinking networks, wherein one crosslinking network is a dynamic covalent crosslinking network and simultaneously comprises at least one boron-containing dynamic covalent bond crosslinking and at least one other dynamic covalent bond crosslinking; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point;

an eleventh aspect: the combined hybrid dynamic polymer only contains one dynamic covalent cross-linked network, and the cross-linked network contains at least one other dynamic covalent cross-linked, and the cross-linking degree of the other dynamic covalent cross-linked is above the gel point, and the non-cross-linked dynamic polymer containing at least one boron-containing dynamic covalent bond is dispersed in the cross-linked network;

the twelfth way: the combined hybrid dynamic polymer only contains one dynamic covalent cross-linked network, and the cross-linked network contains at least one other dynamic covalent cross-link, the cross-linking degree of the other dynamic covalent cross-link is above the gel point, and dynamic polymer particles containing at least one boron-containing dynamic covalent bond are dispersed in the cross-linked network.

7. The combined energy absorbing method according to claim 6, characterized in that non-crosslinked polymers with a crosslinking degree below the gel point or polymer particles with a crosslinking degree above the gel point are dispersed in the combined hybrid dynamic polymer crosslinked network, and the non-crosslinked polymers or the polymer particles contain one or more of boron-containing dynamic covalent bonds, other dynamic covalent bonds, supramolecular action, or are formed by ordinary covalent bonds only.

8. The method of claim 1, wherein the boron-containing dynamic covalent bonds and other dynamic covalent bonds are selected from the group consisting of:

9. The combined energy absorbing method according to claim 1, wherein the formulation components constituting the combined hybrid dynamic polymer composition comprise any one or more of the following additives/agents: auxiliaries/additives, fillers;

wherein, the auxiliary agent/additive is selected from any one or more of the following components: catalysts, initiators, redox agents, antioxidants, light stabilizers, heat stabilizers, toughening agents, lubricants, mold release agents, plasticizers, foaming agents, dynamic modifiers, antistatic agents, emulsifiers, dispersants, colorants, fluorescent whitening agents, delustering agents, flame retardants, nucleating agents, rheological agents, thickeners, and leveling agents;

wherein, the filler is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers, organometallic compound fillers.

10. -combined energy absorption method according to any of claims 1, 9, characterized in that the morphology of the combined hybrid dynamic polymer has any of the following: solutions, emulsions, pastes, glues, common solids, elastomers, gels, foams.

11. A combined energy absorbing method according to any one of claims 1 and 9, characterized in that it is applied for damping, cushioning, impact protection, sound insulation, sound damping, shock absorption.