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WO2018137506A1 - Polymère dynamique ayant une structure réticulée hybridée et applications associée - Google Patents

Polymère dynamique ayant une structure réticulée hybridée et applications associée Download PDF

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Publication number
WO2018137506A1
WO2018137506A1 PCT/CN2018/072457 CN2018072457W WO2018137506A1 WO 2018137506 A1 WO2018137506 A1 WO 2018137506A1 CN 2018072457 W CN2018072457 W CN 2018072457W WO 2018137506 A1 WO2018137506 A1 WO 2018137506A1
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Prior art keywords
dynamic
polymer
linking
covalent
network
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English (en)
Chinese (zh)
Inventor
郭琼玉
徐晖
张欢
梁愫
林淦
欧阳勇
翁文桂
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Weng Qiumei
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Weng Qiumei
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/08—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/04—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing boron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/02—Polythioethers; Polythioether-ethers

Definitions

  • the invention relates to the field of smart polymers, in particular to a dynamic polymer having a hybrid crosslinked network composed of common covalent bonds, dynamic covalent bonds and supramolecular hydrogen bonds, and an application thereof.
  • the traditional three-dimensional network structure is generally formed by ordinary covalent cross-linking.
  • the common covalent bond has high bond energy, which gives the polymer good stability and stress carrying capacity, so it occupies in the cross-linking of the polymer. Larger proportion.
  • the cross-linking density is low, the cross-linking effect is often not reflected, especially the mechanical properties are poor; and if the cross-linking density is high, the cross-linked polymer is often caused to be hard. It is brittle; and the general chemical cross-linking lacks dynamics. Once chemical cross-linking is formed, the cross-linking itself cannot be changed, and the properties of the polymer material are immobilized.
  • the present invention is directed to the above background, and provides a dynamic polymer having a hybrid crosslinked network structure, wherein at least one covalent crosslinked network is included, wherein common covalent bond crosslinks reach above the gel point; A valence inorganic silicic acid silicate bond and a supramolecular hydrogen bond formed by a side hydrogen bond group.
  • the dynamic polymer exhibits excellent dynamic reversibility while exhibiting certain mechanical strength and good toughness, and can exhibit functional characteristics such as stimuli responsiveness, self-repairing, and self-adhesiveness.
  • a dynamic polymer having a hybrid crosslinked structure comprising at least one covalent crosslinked network in which the degree of crosslinking of ordinary covalent crosslinks reaches above its gel point; and simultaneously contains dynamic covalent inorganic silicon borate The bond and the supramolecular hydrogen bonding formed by the side hydrogen bonding groups.
  • the dynamic polymer has only one network, and the network includes both common covalent crosslinks, dynamic covalent crosslinks, and supramolecular hydrogen bond crosslinks, wherein common covalent crosslinks reach Above the gel point, the dynamic covalent cross-linking is achieved by a silicon silicate linkage, which is formed by the participation of pendant hydrogen bonding groups.
  • the dynamic polymer consists of two networks, the first network comprising common covalent crosslinks and dynamic covalent crosslinks, wherein the common covalent crosslinks reach Above the gel point, the dynamic covalent cross-linking is achieved by an inorganic boronic acid silicate bond, which does not contain the side hydrogen bond group on both the side group and the side chain; the second network does not contain covalent bond crosslinks.
  • the polymer chain has the side hydrogen bond group present and participates in hydrogen bond crosslinking.
  • the dynamic polymer consists of two networks, the first network comprising common covalent crosslinks and supramolecular hydrogen bond crosslinks, wherein the common covalent crosslinks are achieved.
  • the supramolecular hydrogen bonding cross-linking is carried out by a side hydrogen bonding group; the second network does not contain ordinary covalent cross-linking, but contains the inorganic boric acid silicide bond to participate in the formation of dynamic covalent cross-linking. In association, it does not contain the side hydrogen bond group.
  • the dynamic polymer consists of two networks, the first network comprising common covalent crosslinks and supramolecular hydrogen bond crosslinks, wherein the common covalent crosslinks are achieved. Above the gel point, the supramolecular hydrogen bond crosslinking is achieved by the side hydrogen bonding group; the second network contains the common covalent crosslinks and the inorganic boric acid silicide bond to form a dynamic covalent cross. In combination, wherein the ordinary covalent cross-linking reaches above its gel point, it does not contain the side hydrogen bond group.
  • the dynamic polymer is composed of two networks, and the first network includes common covalent crosslinks, dynamic covalent crosslinks, and supramolecular hydrogen bond crosslinks, wherein The cross-linking of the valence reaches above its gel point, the dynamic covalent cross-linking is achieved by a silicon silicate bond, the supramolecular hydrogen bond cross-linking is formed by a side hydrogen bond group; the second network does not contain The covalent bond crosslinks, but the polymer chain has a side hydrogen bond group and participates in the formation of hydrogen bond crosslinks.
  • the dynamic polymer is composed of two networks, and the first network includes common covalent crosslinks, dynamic covalent crosslinks, and supramolecular hydrogen bond crosslinks, wherein The cross-linking of the valence reaches above its gel point, the dynamic covalent cross-linking is achieved by a silicon silicate bond, the supramolecular hydrogen bond cross-linking is formed by a side hydrogen bond group; the second network contains ordinary Covalent cross-linking and inorganic boronic acid silicate bond participate in the formation of dynamic covalent crosslinks, but they do not contain the pendant hydrogen bond groups.
  • the dynamic polymer is composed of two networks, and the first network includes common covalent crosslinks, dynamic covalent crosslinks, and supramolecular hydrogen bond crosslinks, wherein The valence cross-linking reaches above its gel point, the dynamic covalent cross-linking is achieved by a silicon silicate bond, the supramolecular hydrogen bond cross-linking is formed by a side hydrogen bond group; the second network contains an inorganic The silicic acid silicate bond participates in the formation of dynamic covalent crosslinks and supramolecular hydrogen bond crosslinks, which are achieved by the side hydrogen bond groups.
  • the dynamic polymer is composed of two networks, and the first network includes common covalent crosslinks, dynamic covalent crosslinks, and supramolecular hydrogen bond crosslinks, wherein The valence cross-linking reaches above its gel point, the dynamic covalent cross-linking is achieved by a silicon silicate bond, the supramolecular hydrogen bond cross-linking is formed by a side hydrogen bond group; the second network contains both Covalent cross-linking, dynamic covalent cross-linking, and supramolecular hydrogen bonding cross-linking, wherein common covalent cross-linking reaches above its gel point, said dynamic covalent cross-linking is achieved by inorganic boronic acid silicate linkages,
  • the supramolecular hydrogen bonding crosslinks are formed by the side hydrogen bonding groups; however, the first and second networks described above are not identical.
  • the dynamic polymer is composed of three networks, and the first network contains a common covalent cross-linking and an inorganic boric acid silicide bond to participate in the formation of dynamic covalent cross-linking, but it does not Containing the side hydrogen bond group; the second network does not contain covalent bond crosslinks, but the side hydrogen bond group is present on the polymer chain, and the hydrogen bond crosslinks participating in the side hydrogen bond group are formed
  • the third network contains both common covalent crosslinks, dynamic covalent crosslinks, and supramolecular hydrogen bond crosslinks, wherein common covalent crosslinks reach above their gel point, and the dynamic covalent crosslinks are made up of inorganic boric acid.
  • the silyl ester bond is achieved, and the supramolecular hydrogen bond crosslinking is formed by the participation of a side hydrogen bond group.
  • the dynamic polymer is composed of three networks, and the first network contains a dynamic covalent cross-linking and a supramolecular hydrogen bond cross-linking which are formed by inorganic boronic acid borate bonds. Supramolecular hydrogen bond cross-linking is achieved by the side hydrogen bonding group, but does not contain ordinary covalent cross-linking; the second network does not contain covalent bond cross-linking, but the side exists on the polymer chain a hydrogen bond group and forming a hydrogen bond crosslink involving the side hydrogen bond group; the third network includes both common covalent crosslinks, dynamic covalent crosslinks, and supramolecular hydrogen bond crosslinks, wherein common covalent Crosslinking reaches above its gel point, said dynamic covalent cross-linking being effected by inorganic boronic acid silicate linkages which are formed by the participation of pendant hydrogen bonding groups.
  • the dynamic polymer is composed of three networks, and the first network contains a dynamic covalent cross-linking and a supramolecular hydrogen bond cross-linking which are formed by inorganic boronic acid borate bonds.
  • the supramolecular hydrogen bond cross-linking is achieved by the side hydrogen bond group, but there is no common covalent cross-linking;
  • the second and third networks both contain common covalent cross-linking, dynamic covalent cross-linking and super Molecular hydrogen bonding cross-linking in which ordinary covalent cross-linking reaches above its gel point, said dynamic covalent cross-linking is achieved by an inorganic boronic acid silicate bond, said supramolecular hydrogen bonding cross-linking by a side hydrogen bond
  • the group participated in the formation, but the 2nd and 3rd networks were different.
  • the dynamic polymer is composed of three networks, the first network is a common covalent cross-linking network, does not contain dynamic covalent bonds and hydrogen bonds; the second network is dynamic covalent The crosslinked network does not contain hydrogen bond crosslinks; the third network is a hydrogen bond crosslinked network in which the side hydrogen bond groups participate, and does not contain dynamic covalent crosslinks and ordinary covalent crosslinks.
  • the dynamic polymer is composed of two networks, the first network is a common covalent crosslinked network, does not contain dynamic covalent bonds and hydrogen bonds; the second network is the side Hydrogen bonding group participates in a hydrogen bonding cross-linking network, which does not contain dynamic covalent cross-linking and common covalent cross-linking; a non-crosslinked dynamic covalent polymer containing a dynamic covalent inorganic boronic acid silic silicate bond is dispersed in the above two networks in.
  • the dynamic polymer is composed of two networks, the first network is a common covalent cross-linking network, does not contain dynamic covalent bonds and hydrogen bonds; the second network is dynamic covalent
  • the crosslinked network does not contain hydrogen bond crosslinks and ordinary covalent crosslinks; non-crosslinked supramolecular polymers containing side hydrogen bonds are dispersed in the above two networks.
  • the dynamic polymer is composed of a network
  • the cross-linking network is a common covalent cross-linking network, does not contain dynamic covalent bond cross-linking and hydrogen bond cross-linking; contains dynamic covalent
  • a non-crosslinked dynamic covalent polymer of an inorganic boronic acid silicate bond and a non-crosslinked dynamic supramolecular polymer containing a side hydrogen bond are dispersed in the above network.
  • the dynamic polymer is composed of a network
  • the cross-linking network is a common covalent cross-linking network, does not contain dynamic covalent bond cross-linking and hydrogen bond cross-linking
  • a non-crosslinked dynamic polymer of a valence inorganic silicic acid silicate bond and a side hydrogen bond is dispersed in the above network.
  • the dynamic polymer is composed of a network
  • the crosslinked network is a common covalent crosslinked network, and optionally contains hydrogen bonding crosslinks in which the side hydrogen bonds participate
  • the dynamic covalent inorganic boronic acid silicate linkage crosslinked dynamic covalent polymer is dispersed in the network in the form of particles containing optional hydrogen bonding crosslinks involving the side hydrogen bonds.
  • the present invention can also have various other hybrid cross-linking network structure implementations. Those skilled in the art can be reasonably effective according to the logic and context of the present invention. Realized.
  • the inorganic boronic acid silicate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor.
  • the inorganic boron compound refers to a boron-containing compound in which a boron atom in a compound is not bonded to a carbon atom through a boron-carbon bond.
  • the silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor means any suitable compound containing a silanol group and/or a silanol group precursor at the terminal of the compound.
  • the silicon-containing compound is selected from the group consisting of a small molecule silicon-containing compound and a macromolecular silicon-containing compound, and may be an organic or inorganic compound including silica.
  • the silicon-containing compound may have any suitable topology including, but not limited to, linear, cyclic (including but not limited to monocyclic, polycyclic, bridged, nested), branched (including but not limited to comb type) , star, dendritic, hyperbranched), 2D/3D clusters, and combinations thereof.
  • the pendant hydrogen bonding group is a hydrogen bonding group on the pendant and/or side chain backbone, which may be any suitable hydrogen bonding group.
  • one side hydrogen bond group has both a hydrogen bond acceptor and a hydrogen bond donor; or a partial side hydrogen bond group may have a hydrogen bond donor, and the other part of the side hydrogen bond group contains a hydrogen bond acceptor; It contains both a receptor and a donor.
  • the acceptor of the side hydrogen bond group in the present invention preferably contains at least one of the structures represented by the following formula (1).
  • A is selected from the group consisting of an oxygen atom and a sulfur atom
  • D is selected from a nitrogen atom and a CR group
  • X is a halogen atom; Any one selected from the group consisting of a suitable atom, group, segment, cluster; wherein R is selected from the group consisting of a hydrogen atom, a substituted atom, and a substituent.
  • the donor of the side hydrogen bond group in the present invention preferably contains at least one of the structures represented by the following formula (2).
  • the structures represented by the general formulae (1) and (2) may be a side group, an end group, a linear structure, a branched chain structure containing a side group, or a cyclic structure or the like.
  • the ring structure may be a single ring structure, a polycyclic structure, a spiro ring structure, a fused ring structure, a bridge ring structure, a nested ring structure, or the like.
  • the side hydrogen bond group preferably contains both the structures represented by the general formulae (1) and (2).
  • the side hydrogen bond group is preferably selected from the group consisting of an amide group, a carbamate group, a thiocarbamate group, a urea group, a pyrazole, an imidazole, an imidazoline, a triazole, an anthracene, a porphyrin, and Their derivatives.
  • the dynamic polymer composition having a hybrid crosslinked structure may be in the form of a common solid, an elastomer, a gel (including a hydrogel, an organogel, an oligomer swollen gel, Plasticizer swollen gel, ionic liquid swollen gel), foam, and the like.
  • the dynamic polymer having a hybrid crosslinked structure may be selectively added to other polymers, additives, and fillers that may be added/used during the preparation process to form a dynamic polymer.
  • the other polymer that can be added/used is selected from any one or more of the following: a natural polymer compound, a synthetic resin, a synthetic rubber, a synthetic fiber;
  • the additive which can be added/used is selected from any one or more of the following: catalyst, initiator, antioxidant, light stabilizer, heat stabilizer, crosslinking agent, curing agent, chain extender, toughening Agent, coupling agent, lubricant, mold release agent, plasticizer, foaming agent, dynamic regulator, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, matting agent, flame retardant, Nucleating agent, rheological agent, thickener, leveling agent;
  • the filler that can be added/used is selected from any one or more of the following: an inorganic non-metallic filler, a metal filler, and an organic filler.
  • the dynamic polymer having a hybrid crosslinked structure has a wide range of properties, and has broad application prospects, and specifically, can be applied to a shock absorber, a cushioning material, and a soundproofing.
  • the present invention has the following beneficial effects:
  • a dynamic polymer having a hybrid crosslinked structure of the present invention combines common covalent cross-linking, dynamic covalent inorganic silicon borate bonds, and supramolecular hydrogen bonds, and fully utilizes and combines various bonding functions. advantage.
  • common covalent cross-linking provides a strong and stable network structure for dynamic polymers, the polymer can maintain a balanced structure, that is, dimensional stability; and the introduction of dynamic covalent inorganic silicon borate bonds and super in the polymer After molecular hydrogen bonding, the dynamics of dynamic covalent bonds and hydrogen bonds can impart excellent dynamics to the material, including but not limited to weak bond properties and dynamic bond properties, particularly dilatancy.
  • dynamic covalent bonds and hydrogen bonds can be broken in the form of "sacrificial bonds", which dissipate a large amount of energy and provide sufficient toughness for the crosslinked polymer, so that the crosslinked polymer has crosslinks.
  • the inherent mechanical strength and stability of the structure also has excellent tensile toughness and tear resistance; its dilatancy can provide excellent energy dispersion and absorption for the material, and obtain excellent damping, shock absorption and resistance. Impact and other properties.
  • the dynamic covalent bond and the hydrogen bond are orthogonal to each other, coordinate and supplement, and obtain the most ideal performance. This is not possible with a single key combination.
  • orthogonality/sequence dynamics and response and fracture/dissociation under stress can be obtained to maximize multiple responses, energy absorption, and shape. Memory and other functions. This is not available in the prior art.
  • the side hydrogen bonding group is involved in the formation of a supramolecular hydrogen bond, since the side hydrogen bond is usually suspended from the main chain skeleton
  • the side side has flexible adjustability in terms of density, distribution, structure, etc., and can conveniently adjust the glass transition temperature of the polymer, especially the glass transition temperature of the hydrogen bond involved in the formation, and the hydrogen bond formed.
  • the dynamics, etc. therefore have outstanding advantages.
  • the dynamic reversible bond of the dynamic polymer having a hybrid crosslinked structure of the present invention has strong dynamic reactivity and mild dynamic reaction conditions. Compared with other existing dynamic covalent systems, the invention fully utilizes the inorganic boronic acid silicate bond to have good thermal stability and high dynamic reversibility, and can be realized without catalyst, high temperature, illumination or specific pH.
  • the synthesis and dynamic reversibility of dynamic polymers improve the preparation efficiency and reduce the limitations of the use environment, extending the application range of the polymer.
  • a dynamic polymer having a hybrid crosslinked structure can exhibit functional characteristics.
  • the polymer can exhibit stimuli responsiveness and dilatancy.
  • the polymer can respond to external stimuli such as external force, temperature, pH, light, etc., and change its state.
  • the dynamically reversible silicon silicate bond and the supramolecular hydrogen bond can be re-bonded by changing the external conditions after the fracture, so that the material has plasticity, self-repairing and other functional properties, which prolongs the service life of the polymer. It can be applied to many special fields.
  • the invention relates to a dynamic polymer having a hybrid crosslinked structure, which comprises at least one covalent cross-linking network, wherein the degree of cross-linking of common covalent cross-linking reaches above its gel point; and contains dynamic covalent inorganic A silyl borate bond and a supramolecular hydrogen bond formed by a side hydrogen bond group.
  • polymerization is a growth process/action of a chain, including a process of synthesizing a product having a higher molecular weight by a reaction form such as polycondensation, polyaddition, ring-opening polymerization or the like.
  • the reactants are generally compounds such as monomers, oligomers, and prepolymers which have a polymerization ability (that is, can be polymerized spontaneously or can be polymerized by an initiator or an external energy).
  • the product obtained by polymerization of one reactant is referred to as a homopolymer.
  • a product obtained by polymerization of two or more reactants is referred to as a copolymer.
  • the "polymerization" described in the present invention includes a linear growth process of a reactant molecular chain, a branching process including a reactant molecular chain, a ring-forming process including a reactant molecular chain, and a reaction.
  • the cross-linking process of molecular chains includes a linear growth process of a reactant molecular chain, a branching process including a reactant molecular chain, a ring-forming process including a reactant molecular chain, and a reaction.
  • crosslinking refers to the formation of a supramolecular chemical linkage between a reactant molecule and/or a reactant molecule by chemical and/or hydrogen bonding of a common covalent bond or a dynamic covalent bond.
  • the polymer chains In the cross-linking process, the polymer chains generally grow in the two-dimensional/three-dimensional direction, gradually forming clusters (which can be two-dimensional or three-dimensional), and then develop into three-dimensional infinite networks.
  • cross-linking in the present invention refers to a three-dimensional infinite network structure above the gel point, including non-crosslinking including linear, branched, cyclic, two-dimensional clusters and gel points.
  • a structure below the gel point such as a three-dimensional cluster structure.
  • the "gel point" described in the present invention means that the viscosity of the reactants suddenly increases during the crosslinking process, and gelation occurs, and the reaction point when a first three-dimensional network is reached, which is also called percolation. Threshold. a crosslinked product above the gel point having a three-dimensional infinite network structure, the crosslinked network forming a whole and spanning the entire polymer structure; the crosslinked product below the gel point, which is only a loose link structure, and The three-dimensional infinite network structure is not formed, and does not belong to a cross-linked network that can form a whole across the entire polymer structure.
  • the "ordinary covalent bond" as used in the present invention refers to a covalent bond other than a dynamic covalent bond in the conventional sense, at a usual temperature (generally not higher than 100 ° C) and a usual time (generally Less than 1 day) is less difficult to break, including but not limited to common carbon-carbon bonds, carbon-oxygen bonds, carbon-hydrogen bonds, carbon-nitrogen bonds, carbon-sulfur bonds, nitrogen-hydrogen bonds, nitrogen-oxygen bonds. , hydrogen-oxygen bond, nitrogen-nitrogen bond, and the like.
  • the "dynamic covalent bond” refers to an inorganic boronic acid borate bond.
  • said inorganic boronic acid silicate bond which may be at any suitable position on the polymer chain, either on the polymer backbone backbone or on the polymer side chains and/or branches and/or fractions Cross-chain skeleton and / or cross-linking links.
  • the invention also does not exclude the inclusion of inorganic boronic acid silicate linkages on the pendant and/or terminal groups of the polymer chain. Since the boron atom is a trivalent structure, the formation of the inorganic boronic acid borate by the polymerization process can result in the formation of a bifurcation and can be further crosslinked.
  • the inorganic boronic acid silicate bond can be on the crosslinked polymer network or on the non-crosslinked polymer, nor can it be on small molecules.
  • skeleton refers to a structure in the chain length direction of a polymer chain.
  • the "backbone”, for a crosslinked polymer, refers to any segment present in the backbone of the crosslinked network; for a non-crosslinked polymer, unless otherwise specified, refers to a link The longest segment.
  • the “side chain” refers to a chain structure which is connected to the main chain skeleton of the polymer and distributed on the side of the main chain skeleton; wherein the "branched” / "bifurcation chain” may be The side chain can also be other chain structures that branch off from any chain.
  • side group refers to a chemical group which is bonded to an arbitrary chain of the polymer and distributed on the side of the chain.
  • side chains branched chains
  • side groups it may have a multi-stage structure, ie the side chains/branches may continue to have side groups and side chains/branches, side chains/branched sides Chains/branches can continue to have side groups and side chains/branches.
  • end group refers to a chemical group attached to an arbitrary chain of the polymer and located at the end of the chain.
  • the branch can also be regarded as the main chain, but in the present invention, the outermost branch is regarded as a branch, and the rest is regarded as a main chain.
  • the branched/branched chains of the present invention are considered to be side chains.
  • the "side hydrogen bond group” refers to a hydrogen bond group carried on the side chain of the polymer chain and/or the side chain backbone, which may be on the crosslinked polymer network, It can also be on non-crosslinked polymers.
  • the side hydrogen bond group may form a hydrogen bond with a side hydrogen bond group, or may form a hydrogen bond with a hydrogen bond group on the backbone of the polymer backbone, or may form a hydrogen bond with the surface of the organic/inorganic filler.
  • the group forms a hydrogen bond and can also form a hydrogen bond with the hydrogen bond group in the auxiliary/additive/solvent, but the present invention is not limited thereto, and the hydrogen bond bonding of these side hydrogen bond groups may be collectively referred to.
  • Side hydrogen bond (action) may form a hydrogen bond with a side hydrogen bond group, or may form a hydrogen bond with a hydrogen bond group on the backbone of the polymer backbone, or may form a hydrogen bond with the surface of the organic/inorganic filler.
  • the group forms a hydrogen bond and can also form a hydrogen bond with the hydrogen bond group in the auxiliary/additive/solvent, but the present invention is not limited thereto, and the hydrogen bond bonding of these side hydrogen bond groups may be collectively
  • the present invention may further comprise hydrogen bonding other than side hydrogen bonding, including but not limited to hydrogen bonding between the main chain skeleton hydrogen bonding group and the main chain skeleton hydrogen bonding group, and main chain skeleton hydrogen bonding groups and ends Hydrogen bonding between hydrogen bond groups.
  • the hydrogen bonding may be polymerization, intrachain cyclization, interchain crosslinking, grafting, pendant functionalization, preferably polymerization, intrachain cyclization. Role, cross-linking between chains.
  • the side hydrogen bonding groups are extremely flexible in terms of structure and properties, and thus can impart properties not achievable by other hydrogen bonding of the dynamic polymer.
  • the dynamic polymer comprises at least one covalent cross-linking network, wherein the common covalent cross-linking reaches above the gel point, that is, the dynamic polymer contains at least one gel point or more.
  • a covalent crosslinked network in this covalently crosslinked network, it may also contain dynamic covalent crosslinks and/or supramolecular hydrogen bond crosslinks.
  • the dynamic polymer may comprise, in addition to the at least one common covalent cross-linking network, one or more common covalent cross-linking networks and/or dynamic covalent cross-linking and/or supramolecular hydrogen-bond cross-linking. The internet.
  • the dynamic covalent inorganic silicon silicate bond and/or the hydrogen bond based on the side hydrogen bond group may be on the crosslinked network or not on the crosslinked network, that is, containing the dynamic covalent inorganic boron silicate bond and
  • the component of the supramolecular hydrogen bonding based on the side hydrogen bond group may be non-crosslinked (below the gel point) and may not be on a common covalently crosslinked network.
  • the dynamic covalent inorganic boronic acid silicate bond and/or the supramolecular hydrogen bonding based on the side hydrogen bond group participate in the crosslinking, more preferably on the same crosslinked network as the common covalent crosslinking.
  • the common covalent cross-linking in the same dynamic polymer system may have one or more, that is, any suitable common covalent cross-linking topology, chemical structure, reaction mode, and Combination, etc.
  • at least one cross-linking network in a dynamic polymer system may be a single network, or may have multiple networks blended with each other, or may have multiple networks interpenetrating.
  • Blending and interpenetration may also be present, and the like; wherein two or more networks may be the same or different; it may be that the partial network contains only ordinary covalent crosslinks and the partial network contains only inorganic boronate linkages and/or a combination of side hydrogen bonding crosslinks, or a combination comprising only ordinary covalent crosslinks and partially containing both common covalent crosslinks and inorganic borate bonds and/or side hydrogen bond crosslinks, or portions only containing Inorganic borate bonds and/or side hydrogen bond crosslinks and partially simultaneously comprise a combination of common covalent crosslinks and inorganic borate bonds and/or side hydrogen bond crosslinks, or both networks generally contain a common
  • the valency crosslinks are crosslinked with inorganic borate bonds and/or side hydrogen bonds, but the invention is not limited thereto.
  • Crosslinking in a single network can be a combination of one or more of ordinary covalent crosslinks, dynamic covalent crosslinks, and hydrogen bond crosslinks.
  • the ordinary covalent cross-linking reaches above the gel point in at least one network, which ensures that even in the case of only one network, the polymer can maintain a balanced structure, that is, in the usual The state may be (at least partially) insoluble in the unmelted solid.
  • there may be interactions between different networks ie dynamic covalent and/or supramolecular effects, which may also be independent of one another.
  • the dynamic polymer of the hybrid crosslinked network has only one network (the first network structure), characterized in that the network includes both common covalent crosslinks and dynamic covalent crosslinks.
  • Crosslinking with supramolecular hydrogen bonds wherein, the common covalent cross-linking is achieved by an ordinary covalent bond, and the common covalent cross-linking reaches above the gel point of the common covalent cross-linking; the dynamic covalent cross-linking is achieved by an inorganic boric acid silicide bond;
  • the supramolecular hydrogen bonding crosslinks comprise a side hydrogen bond.
  • This network structure is the simplest, but it can combine three different bonding modes in one network to achieve the best orthogonal synergy effect.
  • the dynamic polymer of the hybrid crosslinked network is composed of two networks (second network structure), characterized in that the first network includes common covalent crosslinks and dynamic co- Valence cross-linking, wherein the ordinary covalent cross-linking reaches above its gel point; the dynamic covalent cross-linking is achieved by an inorganic boronic acid silicate bond, and the side and side chains do not contain the side Hydrogen bond group.
  • the second network does not contain a common covalent bond and an inorganic boronic acid silicate bond crosslink, but a side hydrogen bond group exists on the side group and/or the side chain skeleton of the polymer chain and participates in hydrogen bond crosslinking; in the network structure
  • the equilibrium structure is maintained by ordinary covalent cross-linking in the first network and the inorganic boronic acid silicate bond therein provides covalent dynamics, providing supramolecular dynamics by side hydrogen bonding in the second network.
  • the dynamic polymer of the hybrid crosslinked network is composed of two networks (a third network structure), characterized in that the first network comprises common covalent crosslinks and supramolecules. Hydrogen bond cross-linking, wherein the ordinary covalent cross-linking reaches above its gel point; the supramolecular hydrogen bond cross-linking is caused by side hydrogen bonds present on the side chain and/or side chain backbone of the polymer chain The group is involved in the implementation.
  • the second network does not contain ordinary covalent crosslinks, but contains dynamic covalent crosslinks formed by inorganic boronic acid silicate bonds, which do not contain the side hydrogen bond groups on both the side groups and the side chains.
  • the equilibrium structure is maintained by ordinary covalent cross-linking in the first network, and the covalent dynamics are provided by the inorganic boronic acid silicate bond in the second network, and the superhydrogen cross-linking in the first network provides super-crossing.
  • the covalent dynamics are provided by the inorganic boronic acid silicate bond in the second network, and the superhydrogen cross-linking in the first network provides super-crossing.
  • the dynamic polymer of the hybrid crosslinked network is composed of two networks (fourth network structure), characterized in that the first network comprises common covalent crosslinks and supramolecules. Hydrogen bond cross-linking, wherein the ordinary covalent cross-linking reaches above its gel point; the supramolecular hydrogen bond cross-linking is caused by side hydrogen bonds present on the side chain and/or side chain backbone of the polymer chain The group is involved in the implementation.
  • the second network comprises dynamic covalent cross-linking of common covalent cross-linking and inorganic boronic acid silicate bond formation, wherein the common covalent cross-linking reaches above its gel point, and its side groups and side chains are It does not contain the side hydrogen bond group.
  • the equilibrium structure is maintained by ordinary covalent cross-linking in the first network and the second network, and the covalent dynamics are provided by the inorganic boronic acid silicate bond in the second network, and the side hydrogen bonds in the first network are passed.
  • Crosslinking provides supramolecular dynamics.
  • the dynamic polymer of the hybrid cross-linking network is composed of two networks (fifth network structure), characterized in that the first network is the first network structure;
  • the second network does not contain covalent bond crosslinks, but side hydrogen groups are present on the pendant and/or side chain backbones of the polymer chain and participate in the formation of hydrogen bond crosslinks.
  • the equilibrium structure and the inorganic boronic acid silicate bond therein provide covalent dynamics through covalent cross-linking in the first network; supermolecular dynamics are provided by side hydrogen bonding in the first and second networks Sex.
  • the dynamic polymer of the hybrid cross-linking network is composed of two networks (sixth network structure), characterized in that the first network is the first network structure;
  • the second network contains dynamic covalent cross-linking of ordinary covalent cross-linking and inorganic boronic acid silicate bond formation, but does not contain the side hydrogen bond group on both the side group and the side chain.
  • the equilibrium structure and the inorganic boronic acid silicate bond are provided by the common covalent cross-linking in the first network and the second network to provide covalent dynamics; and the superhydrogen crosslinking in the first network provides super-crossing.
  • the dynamic polymer of the hybrid cross-linking network is composed of two networks (the seventh network structure), characterized in that the first network is the first network structure;
  • the second network contains a dynamic covalent cross-linking and a supramolecular hydrogen bond cross-linking which are formed by the inorganic boronic acid silicate bond, which is present on the side chain and/or side chain backbone of the polymer chain.
  • the side hydrogen bond groups are involved in the implementation.
  • the equilibrium structure and the inorganic boronic acid silicate bond are provided by the common covalent cross-linking in the first network and the second network to provide covalent dynamics; the side hydrogen bonds in the first network and the second network Crosslinking provides supramolecular dynamics.
  • the dynamic polymer of the hybrid cross-linking network is composed of two networks (the eighth network structure), characterized in that the first network and the second network are both the first type.
  • the structure described by the network, but the first and second networks described above are different.
  • Such a difference may be, for example, a difference in the main structure of the polymer chain, a different crosslink density of the covalently crosslinked, a different composition of the side chain and/or the side chain of the polymer chain, a side chain of the polymer chain and/or a side chain.
  • the hydrogen bond groups on the difference are equal.
  • the purpose of accurately controlling the dynamic polymer performance can be achieved.
  • the dynamic polymer of the hybrid crosslinked network is composed of three networks (the ninth network structure), characterized in that the first network contains common covalent crosslinks and inorganic
  • the silicic acid borate bond participates in the formation of dynamic covalent cross-linking, but does not contain the side hydrogen bond group on both the side group and the side chain;
  • the second network does not contain ordinary covalent cross-linking and dynamic covalent cross-linking,
  • a side hydrogen bond group exists on the side group and/or the side chain skeleton of the polymer chain, and hydrogen bond crosslinking is formed by the side hydrogen bond group;
  • the third network is the first network structure.
  • the equilibrium structure and the inorganic boronic acid silicate bond are provided by the common covalent cross-linking in the first network and the third network to provide covalent dynamics through the side hydrogen bonding in the second and third networks.
  • the joint provides supramolecular dynamics.
  • the dynamic polymer of the hybrid crosslinked network is composed of three networks (tenth network structure), characterized in that the first network contains inorganic silicon silicate bond to participate in formation.
  • Dynamic covalent cross-linking and supramolecular hydrogen bonding cross-linking is achieved by side hydrogen bonding groups present on the polymer chain side groups and/or side chain backbone, but does not contain ordinary Covalent cross-linking;
  • the second network does not contain ordinary covalent cross-linking and dynamic covalent cross-linking, but there are side hydrogen bonding groups on the side groups and/or side chains of the polymer chain, and through the side hydrogen bonds
  • the group participates in the formation of hydrogen bond crosslinks;
  • the third network is the first network structure described.
  • the equilibrium structure is maintained by ordinary covalent cross-linking in the third network, and the covalent dynamics are provided by the inorganic boronic acid silicate bond in the first and third networks, through the first, second, and third networks.
  • the side hydrogen bond cross-linking provides supramolecular dynamics.
  • the dynamic polymer of the hybrid crosslinked network is composed of three networks (the eleventh network structure), characterized in that the first network contains an inorganic boronic acid borate bond.
  • Dynamic covalent cross-linking and supramolecular hydrogen bonding cross-linking, the supramolecular hydrogen bonding cross-linking is achieved by side hydrogen bonding groups present on the polymer chain side groups and/or side chain backbone, but does not exist Common covalent cross-linking; both the 2nd and 3rd networks are the first network structure described, but the 2nd and 3rd networks are different.
  • the equilibrium structure and the inorganic boronic acid silicate bond therein provide covalent dynamics through ordinary covalent cross-linking in the first, second, and third networks, through the side hydrogen in the first and third networks.
  • Bond cross-linking provides supramolecular dynamics.
  • the dynamic polymer of the hybrid cross-linking network is composed of three networks (the twelfth network structure), wherein the first network is a common covalent cross-linking network. Does not contain dynamic covalent bonds and hydrogen bonds; the second network is a dynamic covalent cross-linking network, does not contain hydrogen bond cross-linking; the third network is the hydrogen bond cross-linking network formed by the side hydrogen bond groups, excluding Dynamic covalent cross-linking and common covalent cross-linking.
  • the three networks are independent and synergistic.
  • the dynamic polymer of the hybrid cross-linking network is composed of two networks (the thirteenth network structure), wherein the first network is a common covalent cross-linking network. Does not contain dynamic covalent bonds and hydrogen bonds; the second network is a hydrogen bond cross-linking network in which the side hydrogen bond groups participate, without dynamic covalent cross-linking and common covalent cross-linking; containing dynamic covalent inorganic boric acid
  • the non-crosslinked dynamic covalent polymer of the silicon ester bond is dispersed in the above two networks.
  • the first network is used to provide a balanced structure
  • the second network is used to provide dynamic supramolecular cross-linking
  • the non-crosslinked dynamic covalent polymer is used to provide additional viscosity.
  • the dynamic polymer of the hybrid cross-linking network is composed of two networks (fourteenth network structure), wherein the first network is a common covalent cross-linking network. Does not contain dynamic covalent bonds and hydrogen bonds; the second network is a dynamic covalent cross-linking network, which does not contain hydrogen bond cross-linking and common covalent cross-linking; non-cross-linked supramolecular polymers containing side hydrogen bonds are dispersed in the above In both networks.
  • the first network is used to provide a balanced structure
  • the second network is used to provide dynamic covalent cross-linking
  • the non-crosslinked dynamic supramolecular polymer is used to provide additional viscosity.
  • the dynamic polymer of the hybrid crosslinked network is composed of a network (the fifteenth network structure), characterized in that the crosslinked network is a common covalent crosslinked network, and Containing dynamic covalent bond crosslinking and hydrogen bonding crosslinking; a non-crosslinked dynamic covalent polymer containing a dynamic covalent inorganic boronic acid silicate bond and a non-crosslinked dynamic supramolecular polymer containing a side hydrogen bond dispersed in the above network .
  • Common covalent cross-linking networks are used to provide a balanced structure, non-crosslinked dynamic covalent and supramolecular polymers are used to provide additional viscosity.
  • the dynamic polymer of the hybrid crosslinked network is composed of a network (the sixteenth network structure), characterized in that the crosslinked network is a common covalent crosslinked network, and It contains dynamic covalent bond crosslinks and hydrogen bond crosslinks; a non-crosslinked dynamic polymer containing both a dynamic covalent inorganic boronic acid borate bond and a side hydrogen bond is dispersed in the above network.
  • Common covalent cross-linking networks are used to provide a balanced structure, non-crosslinked dynamic covalent and supramolecular polymers are used to provide additional viscosity.
  • the dynamic polymer of the hybrid crosslinked network is composed of a network (the seventeenth network structure), characterized in that the crosslinked network is a common covalent crosslinked network, and Selectively containing hydrogen bonding crosslinks in which the side hydrogen bonds are involved; a dynamic covalent polymer crosslinked by a dynamic covalent inorganic boronic acid silicate bond is dispersed in the network in the form of particles, optionally containing the side Hydrogen bonding involves hydrogen bonding crosslinks.
  • a common covalent cross-linking network is used to provide a balanced structure, and the cross-linked dynamic covalent polymer is dispersed in a particle shape in a crosslinked network for providing additional viscosity and strength.
  • the present invention may have other various hybrid cross-linking network structure embodiments, and one embodiment may include three or more identical or different.
  • the network the same network can contain different common covalent crosslinks and / or different dynamic covalent crosslinks and / or different hydrogen bond crosslinks
  • the network structure can be dispersed / filled with dynamic covalent bonds and / Or a non-crosslinked polymeric component or crosslinked particles of the hydrogen bond (including but not limited to fibers, flakes, and any suitable irregular shape).
  • the side hydrogen bonding groups in the covalently crosslinked network cannot form hydrogen bonds with each other, and it is necessary to form hydrogen bonds with other components added.
  • Inorganic boronic acid silicate linkages are used to provide covalent dynamic properties including, but not limited to, plasticity, self-healing, and dilatancy; hydrogen bonding by the formation of side hydrogen bonding groups provides additional energy to the polymer as reversible physical crosslinking on the one hand
  • the strength, on the one hand can take advantage of its good dynamic properties, giving stress/strain responsiveness, super toughness, self-healing, shape memory and other properties.
  • the number and distribution of side hydrogen bonding groups of the polymer are not limited.
  • the number and distribution of side hydrogen bond groups on the polymer segment between the two covalent crosslinks are not limited.
  • the segment between any two covalent cross-linking points may contain the side hydrogen bond group, or the segment between the partial cross-linking points may have a side hydrogen bond group;
  • each segment contains not less than 2 of said side hydrogen bonding groups on a segment between covalent crosslinking points containing a side hydrogen bonding group, and more preferably each segment contains not less than 5
  • the side hydrogen bonding group; the number of the side hydrogen bonding groups in the entire covalent crosslinking network is also not limited, preferably on the average segment between each of the two covalent crosslinking points Not less than 0.1 of the side hydrogen bond groups, more preferably not less than 1 of the side hydrogen bond groups.
  • the dynamic polymers of the present invention can exhibit a wide variety of dynamic properties and responsiveness to external stimuli including, but not limited to, self-healing Saturation, temperature responsiveness, stress/strain responsiveness, especially dilatancy.
  • self-healing Saturation temperature responsiveness
  • stress/strain responsiveness especially dilatancy.
  • the inorganic boronic acid silicate bond and the hydrogen bond do not interact with ordinary covalent crosslinking and the two together act to produce a crosslinked polymer, the dynamic polymer system expands even under stress/strain.
  • the performance which does not contribute to the elastic properties, only increases the viscosity of the system, which contributes to the loss of mechanical energy through the viscous.
  • the dynamic polymer system undergoes dilatancy When the gel point is reached, the viscous-elastic transition or the elasticity is enhanced, and the effect below the gel point will increase the viscosity, so that the viscous loss of the external force can be generated while effectively reducing the damage of the external force.
  • the dynamic polymer system will only undergo viscous-elastic transition or elastic reinforcement when expansion occurs, so that external force can occur. Part of the viscous loss can also minimize the damage of external forces. Different situations have their own characteristics and advantages.
  • the dynamic polymer may have one or more glass transition temperatures or may have no glass transition temperature.
  • the glass transition temperature of the dynamic polymer at least one of which is lower than 0 ° C, or between 0-25 ° C, or between 25-100 ° C, or higher than 100 ° C; wherein, the glass transition Dynamic polymers with a temperature below 0 °C have good low temperature performance and are convenient for use as sealants, elastomers, gels, etc.
  • Dynamic polymers with a glass transition temperature between 0 and 25 ° C can be beneficial in It can be conveniently used as an elastomer, sealant, gel, foam and ordinary solids at room temperature.
  • Dynamic polymers with a glass transition temperature between 25 and 100 ° C are convenient for obtaining ordinary solids and foams above room temperature. And gel; dynamic polymer with glass transition temperature higher than 100 °C, its dimensional stability, mechanical strength, temperature resistance is good, and it is beneficial to be used as a stress-carrying material and a high impact material.
  • dynamic polymers with a glass transition temperature below 25 °C it can exhibit excellent dynamics, self-healing and recyclability; it can be good for dynamic polymers with a glass transition temperature higher than 25 °C.
  • Shape memory ability, stress carrying capacity and impact resistance; in addition, the presence of supramolecular hydrogen bonds can further regulate the glass transition temperature of dynamic polymers, dynamics of dynamic polymers, cross-linking degree, mechanical The intensity is supplemented.
  • the dynamic polymer in the present invention it is preferred that at least one glass transition temperature is not higher than 50 ° C, further preferably at least one glass transition temperature is not higher than 25 ° C, and most preferably each glass transition temperature is not higher than 25 ° C.
  • Each system having a glass transition temperature of not higher than 25 ° C is particularly suitable for use as a self-healing material or an energy absorbing material because of its good flexibility and flowability/creep property at daily use temperatures.
  • the glass transition temperature of the dynamic polymer can be measured by a method for measuring the glass transition temperature which is common in the art, such as DSC and DMA.
  • each raw material component of the dynamic polymer may also have one or more glass transition temperatures, or may have no glass transition temperature, and its glass transition temperature is at least one lower than 0 ° C. Or at between 0-25 ° C, or between 25-100 ° C, or above 100 ° C, wherein the compound material having a glass transition temperature of less than 0 ° C facilitates low temperature preparation and processing in the preparation of dynamic polymers;
  • the compound raw material having a glass transition temperature of 0-25 ° C can be prepared and processed at normal temperature; the compound raw material having a glass transition temperature of 25-100 ° C can be formed by using a conventional heating device, and the manufacturing cost is low;
  • a compound material having a glass transition temperature higher than 100 ° C can be used to prepare a high temperature resistant material having good dimensional stability and excellent mechanical properties.
  • the inorganic boronic acid silicate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor.
  • the inorganic boron compound refers to a boron-containing compound in which a boron atom in a compound is not bonded to a carbon atom through a boron-carbon bond.
  • the inorganic boron compound is selected from the group consisting of, but not limited to, boric acid, boric acid esters, borate salts, boric anhydrides, and boron halides.
  • the boric acid may be orthoboric acid, metaboric acid or tetraboric acid.
  • Borate esters include alkyl and allyl borate/triorgano borate hydrolyzed to boric acid in the presence of water, such as trimethyl borate, triethyl borate, triphenyl borate, tribenzyl borate, Tricyclohexyl borate, tris(methylsilyl) borate, tri-tert-butyl borate, tri-n-pentyl borate, tri-sec-butyl borate, DL-menthyl borate, tris(4) -Chlorophenyl)borate, 2,6-di-tert-butyl-4-tolyldibutyl orthoborate, tris(2-methoxyethyl)borate, benzyldihydroborate Ester, diphenylhydroborate, isopropanol pinacol borate, triethanolamine borate, and the like.
  • water such as trimethyl borate, triethyl borate, triphenyl borate, tribenzy
  • Suitable boronic acid anhydride includes, in addition to the formula B 2 O 3 is typically boron oxide, also including but not limited trialkoxy boroxine and derivatives thereof, e.g. trimethoxy boroxine, tris isopropoxide Alkyl boroxane, 2,2'-oxybis[4,4,6-trimethyl-1,3,2-dioxaboroxane, and the like.
  • Suitable borate salts include, but are not limited to, diammonium pentaborate, sodium tetraborate decahydrate (borax), potassium pentaborate, magnesium diborate, calcium monoborate, barium triborate, zinc metaborate, tripotassium borate, original Iron borate.
  • Suitable boron halides include, but are not limited to, boron trifluoride, boron trichloride, boron tribromide, boron triiodide, diboron tetrachloride, and the like.
  • Suitable inorganic boron compounds further include partial hydrolyzates of the foregoing borate esters.
  • the inorganic boron compound is boron oxide of the formula B 2 O 3 [CAS Registry Number #1303-86-2] or boric acid of the general formula H 3 BO 3 [CAS Registry Number #10043-35-3].
  • the chemical structural formula of a suitable inorganic boron compound is as follows, but the invention is not limited thereto:
  • the silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor means any suitable compound containing a silanol group and/or a silanol group precursor in the structure of the compound.
  • the silicon-containing compound is selected from the group consisting of a small molecule silicon-containing compound and a macromolecular silicon-containing compound, and may be an organic or inorganic compound including silica.
  • the silicon-containing compound may have any suitable topology including, but not limited to, linear, cyclic (including but not limited to monocyclic, polycyclic, bridged, nested), branched (including but not limited to comb type) , star, dendritic, hyperbranched), 2D/3D clusters, and combinations thereof.
  • the silanol group in the present invention refers to a structural unit (Si-OH) composed of a silicon atom and a hydroxyl group connected to the silicon atom, wherein the silanol group may be a silanol group (ie, a silyl group)
  • the silicon atom is connected to at least one carbon atom through a silicon carbon bond, and at least one organic group is bonded to the silicon atom through the silicon carbon bond, or may be an inorganic silicon hydroxy group (ie, the silicon atom in the silicon hydroxy group is not Attached to the organic group), preferably a silicone hydroxyl group.
  • one hydroxyl group (-OH) in the silanol group is a functional group.
  • the silanol precursor as described in the present invention refers to a structural unit (Si-Z) composed of a silicon atom and a group capable of hydrolyzing a hydroxyl group connected to the silicon atom, wherein Z is Hydrolyzed to give a hydroxyl group, which may be selected from the group consisting of halogen, cyano, oxocyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketone oxime Base, alkoxide group, and the like.
  • one of the silyl hydroxyl precursors which can be hydrolyzed to give a hydroxyl group (-Z) is a functional group.
  • the silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor may be any suitable compound containing a terminal group and/or a pendant silanol group and/or a silanol precursor, including small molecules and a macromolecular compound wherein the group or segment linking the silicon-containing hydroxyl group and/or the silanol precursor can be any suitable group or segment including, but not limited to, a carbon/carbon chain structure, a carbon hetero group/carbon Chain structure, carbon element/carbon element chain structure, carbon element group/carbon element chain structure, element group/element chain structure, hetero element group/hetero element chain structure.
  • the carbon-based/carbon chain structure means that the group/chain skeleton consists only of carbon atoms;
  • the carbon-hetero/carbon hetero-chain structure means that the group/chain skeleton contains a hetero atom in addition to the carbon atom, wherein Heteroatoms include, but are not limited to, oxygen, nitrogen, sulfur;
  • carbon element/carbon chain structure meaning that the group/chain skeleton contains elemental atoms in addition to carbon atoms, wherein element atoms include, but are not limited to, P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir;
  • carbon element/carbon element chain structure meaning that the group/chain skeleton contains hetero atoms and element atoms in addition to carbon atoms;
  • / Element chain structure means that the group/chain skeleton contains only element atoms;
  • the hetero element group/element hetero chain structure means that the group/chain structure contains only element atoms and hetero atoms.
  • Suitable silicon-containing compounds of the silicon-containing hydroxyl group and/or silicic acid hydroxyl precursor can be exemplified as follows, and the present invention is not limited to this:
  • n, x, y, and z are the number of repeating units, and may be a fixed value or an average value.
  • any suitable inorganic boron compound and a silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor may be used to form an inorganic boronic acid silicate bond, preferably an inorganic boric acid and a silicon hydroxy group-containing macromolecular compound.
  • Inorganic boric acid and a macromolecular compound containing a silicon hydroxy precursor, an inorganic borate (salt) and a silanol-containing macromolecular compound to form an inorganic boronic acid silicate bond more preferably an inorganic boric acid and a silanol-containing macromolecular compound
  • the inorganic borate ester and the silanol-containing macromolecular compound form an inorganic boronic acid silicate bond, and it is more preferred to use an inorganic borate ester and a silanol-containing macromolecular compound to form an inorganic boronic acid silicate bond.
  • the dynamic polymer may be obtained by forming an inorganic boronic acid silicate bond, or a compound containing the inorganic boronic acid silicate bond may be prepared to be repolymerized/crosslinked/blended to generate The dynamic polymer.
  • a Si atom participating in the formation of BO-Si on the silicon-containing compound containing a linker may form up to three BO-Sis, which share one Si atom; and since the boron atom is The trivalent structure, the inorganic boronic acid borate produced by the polymerization process can easily cause bifurcation and can be further crosslinked.
  • any polymer/segment of any other raw material, dynamic polymer component other than the silicon-containing compound may have any suitable topology including, but not limited to, linear, cyclic (including but not limited to single ring) , multi-ring, nested ring, bridged ring), branching (including but not limited to star-shaped, H-shaped, comb-like, dendritic, hyperbranched), two-dimensional/three-dimensional clusters, three-dimensional infinite network cross-linking structure, and the above The combination form.
  • the polymer chain has pendant groups, side chains, and branches, and the side groups, side chains, and branches may continue to have pendant groups, side chains, and branches, that is, may have a multistage structure.
  • 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, and the dynamics of hydrogen bond crosslinking is weak, which can promote the dynamic polymer to maintain a balanced structure and improve the mechanical properties (modulus and strength). If the number of teeth of the hydrogen bond is small, the strength is low, and the hydrogen bond cross-linking is strong, and the dynamic covalent inorganic boronic acid silicate bond can be used together to provide dynamic properties such as self-healing properties and energy absorbing properties. In an embodiment of the invention, hydrogen bonds of no more than four teeth are preferred as crosslinks.
  • the number of teeth is a number of hydrogen bonds composed of a donor (D, that is, a hydrogen atom) of a side hydrogen bond group and an acceptor (A, that is, an electronegative atom accepting a hydrogen atom), and each DA combination is one. Teeth (as shown in the following formula, hydrogen bonding of one, two, and three-tooth hydrogen bonding groups, respectively).
  • the pendant hydrogen bonding group may be any suitable hydrogen bonding group.
  • one side hydrogen bond group has both a hydrogen bond acceptor and a hydrogen bond donor; or a partial side hydrogen bond group may have a hydrogen bond donor, and the other part of the side hydrogen bond group contains a hydrogen bond acceptor; It contains both a receptor and a donor.
  • the acceptor of the side hydrogen bond group in the present invention preferably contains at least one of the structures represented by the following formula (1).
  • A is selected from the group consisting of an oxygen atom and a sulfur atom
  • D is selected from a nitrogen atom and a CR group
  • X is a halogen atom; Any one selected from the group consisting of a suitable atom, group, segment, cluster; wherein R is selected from the group consisting of a hydrogen atom, a substituted atom, and a substituent.
  • the number of carbon atoms of R is not particularly limited, but the number of carbon atoms is preferably from 1 to 20, and more preferably from 1 to 10.
  • the structure of R is not particularly limited and includes, but is not limited to, a linear structure, a branched structure containing a side group, or a cyclic structure.
  • the cyclic structure is not particularly limited and may be selected from an aliphatic ring, an aromatic ring, a sugar ring, and a condensed ring, and is preferably an aliphatic ring.
  • R When it is a substituent, R may contain a hetero atom, and may contain a hetero atom.
  • R may be selected from a hydrogen atom, a halogen atom, a C 1-20 hydrocarbon group, a C 1-20 heteroalkyl group, a substituted C 1-20 hydrocarbon group or a substituted heterohydrocarbyl group.
  • the substituted atom or the substituent in R is not particularly limited, and is any one selected from the group consisting of a halogen atom, a hydrocarbon group substituent, and a hetero atom-containing substituent.
  • R is a hydrogen atom, a halogen atom, a C 1-20 alkyl group, a C 1-20 alkenyl group, an aryl group, an aromatic hydrocarbon group, a C 1-20 aliphatic hydrocarbon group, a heteroaryl group, a heteroaryl hydrocarbon group, and a C 1-20 group. Any atom or group of an alkoxyacyl group, an aryloxyacyl group, a C 1-20 alkylthio acyl group, an arylthio acyl group, or a substituted form of any one of the groups.
  • R may be selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, Indenyl, fluorenyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl , eicosyl, allyl, propenyl, vinyl, phenyl, methylphenyl, butylphenyl, benzyl, methoxycarbonyl, ethoxycarbonyl, phen
  • butyl includes, but not limited to, n-butyl group and tert-butyl group.
  • Octyl groups include, but are not limited to, n-octyl, 2-ethylhexyl.
  • the substituted atom or the substituent is selected from any one of a halogen atom, a hydrocarbon group substituent, and a hetero atom-containing substituent.
  • the donor of the side hydrogen bond group in the present invention preferably contains at least one of the structures represented by the following formula (2).
  • the structures represented by the general formulae (1) and (2) may be a side group, an end group, a linear structure, a branched chain structure containing a side group, or a cyclic structure or the like.
  • the ring structure may be a single ring structure, a polycyclic structure, a spiro ring structure, a fused ring structure, a bridge ring structure, a nested ring structure, or the like.
  • the side hydrogen bond group preferably contains both the structures represented by the general formulae (1) and (2).
  • the side hydrogen bond group is preferably selected from the group consisting of an amide group, a carbamate group, a thiocarbamate group, a urea group, a pyrazole, an imidazole, an imidazoline, a triazole, an anthracene, a porphyrin, and Their derivatives.
  • Suitable side groups and/or side hydrogen bond groups on the side chain (including the branched/bifurcation chain) backbone are, for example, but the invention is not limited thereto:
  • n and n are the number of repeating units, and may be a fixed value or an average value, preferably less than 20, more preferably less than 5.
  • the terminal hydrogen bonding group may be identical to the side hydrogen bonding group.
  • a suitable crosslinked network skeleton and a main chain skeleton hydrogen bond group on the non-crosslinked main chain skeleton may be, for example, but the present invention is not limited thereto:
  • the hydrogen bonding group forming a hydrogen bond may be a complementary combination between different hydrogen bonding groups, or a self-complementary combination between the same hydrogen bonding groups, as long as the group It is sufficient to form a suitable hydrogen bond.
  • Some combinations of hydrogen bonding groups can be exemplified as follows, but the present invention is not limited to this:
  • the same polymer may contain more than one of the above-mentioned side hydrogen bond groups, and the same network may contain more than one of the above-mentioned side hydrogen bond groups, and may also contain other optional hydrogen bonds.
  • Group. The compound to which the side hydrogen bond group and the optional other hydrogen bond group can be introduced is not particularly limited, and the type and mode of the reaction for forming the hydrogen bond group are not particularly limited.
  • formed by a covalent reaction between a carboxyl group, an acid halide group, an acid anhydride group, an ester group, an amide group, an isocyanate group and an amino group formed by a covalent reaction between an isocyanate group and a hydroxyl group, a thiol group, or a carboxyl group; Formation by a covalent reaction between a succinimide group and an amino group, a hydroxyl group, or a thiol group.
  • the supramolecular hydrogen bond crosslinking in the crosslinked network may have any suitable degree of crosslinking, which may be above its gel point or below its gel point.
  • the supramolecular hydrogen bonding cross-linking may be generated during dynamic covalent cross-linking of the dynamic polymer; or may be pre-generated by supramolecular hydrogen bonding and then subjected to dynamic covalent cross-linking; After the valence cross-linking is formed, supramolecular hydrogen bonding cross-linking occurs in the dynamic polymer subsequent molding process, but the present invention is not limited thereto.
  • the dynamic polymer composition having a hybrid crosslinked structure may be in the form of a common solid, an elastomer, a gel (including a hydrogel, an organogel, an oligomer swollen gel, a plasticizer swollen gel, an ionic liquid swollen gel, a foam, etc., wherein the content of the soluble small molecular weight component contained in the ordinary solid and solid foam is generally not more than 10% by weight, and the content of the small molecular weight component contained in the gel is generally Generally not less than 50% by weight.
  • a gel including a hydrogel, an organogel, an oligomer swollen gel, a plasticizer swollen gel, an ionic liquid swollen gel, a foam, etc.
  • Ordinary solids have the advantages of high strength, fixed shape and volume, high density, and are suitable for high-strength explosion-proof walls or instrument casings; elastomers have the general properties of ordinary solids, but have better elasticity and better softness. Better damping, shock absorption, sound insulation, noise reduction and other energy absorption properties; gel has the advantages of softness, good energy absorption and elasticity, suitable for preparing high damping energy absorbing materials; and foam has low density It has the advantages of light weight and high specific strength, and its soft foam material also has good elasticity and energy absorption.
  • the dynamic polymer gel may be obtained by crosslinking in a swelling agent (including one of water, an organic solvent, an oligomer, a plasticizer, an ionic liquid, or a combination thereof), or After the preparation of the dynamic polymer is completed, swelling is obtained by using a swelling agent.
  • a swelling agent including one of water, an organic solvent, an oligomer, a plasticizer, an ionic liquid, or a combination thereof.
  • the dynamic polymer is mainly foamed by three methods: mechanical foaming method, physical foaming method and chemical foaming method.
  • the mechanical foaming method is to introduce a large amount of air or other gas into the emulsion, suspension or solution of the polymer into a uniform foam by vigorous stirring during the preparation of the dynamic polymer, and then pass through the physics. Or chemical changes make it gelatinize and solidify into a foam.
  • air can be introduced and an emulsifier or surfactant can be added.
  • the physical foaming method utilizes physical principles to achieve foaming of the polymer in the preparation process of the dynamic polymer, and generally includes the following five methods: (1) an inert gas foaming method, that is, adding Pressing the inert gas into the molten polymer or the paste material under pressure, and then heating the pressure under reduced pressure to expand and foam the dissolved gas; (2) evaporating the gasification foam by using a low-boiling liquid, that is, pressing the low-boiling liquid Into the polymer or under certain pressure and temperature conditions, the liquid is dissolved into the polymer particles, and then the polymer is heated and softened, and the liquid is vaporized by evaporation to foam; (3) dissolution method, that is, liquid The medium is immersed in the polymer to dissolve the solid substance added in advance, so that a large amount of pores appear in the polymer to be foamed, such as mixing the soluble substance salt, starch, etc.
  • an inert gas foaming method that is, adding Pressing the inert gas into the
  • foaming is preferably carried out by a method in which an inert gas and a low-boiling liquid are dissolved in a polymer.
  • the physical foaming method has the advantages of less toxicity in operation, lower cost of foaming raw materials, and no residual body of foaming agent.
  • the chemical foaming method is a method of foaming along with a chemical reaction in a dynamic polymer foaming process, and generally comprises the following two methods: (1) a thermal decomposition type foaming agent The bubble method, that is, the gas liberated by heating with a chemical foaming agent is foamed. (2) A foaming method in which a polymer component interacts to generate a gas, that is, a chemical reaction occurring between two or more components in a foaming system to generate an inert gas such as carbon dioxide or nitrogen to cause a polymer Expand and foam.
  • a small amount of a catalyst and a foam stabilizer (or a surfactant) are generally added.
  • dynamic polymer foam materials are mainly formed by three methods: compression foam molding, injection foam molding and extrusion foam molding.
  • the molding foam molding the process is relatively simple and easy to control, and can be divided into one-step method and two-step method.
  • One-step molding means that the mixed material is directly put into the cavity for foam molding; the two-step method refers to pre-expansion treatment of the mixed material, and then into the cavity for foam molding.
  • the one-step molding foam molding is more convenient to operate than the two-step method and the production efficiency is high, it is preferable to carry out the compression foam molding by the one-step method.
  • the injection foam molding process and equipment are similar to ordinary injection molding, and the bubble nucleation stage is heated and rubbed to make the material into a melt state after the material is added to the screw, and the foaming agent is passed.
  • the control of the metering valve is injected into the material melt at a certain flow rate, and then the foaming agent is uniformly mixed through the mixing elements of the screw head to form a bubble core under the action of the nucleating agent.
  • Both the expansion stage and the solidification setting stage occur after the end of the filling cavity. When the cavity pressure drops, the expansion process of the bubble core occurs, and the bubble body solidifies and sets as the mold cools down.
  • the extrusion foam molding, the process and equipment are similar to ordinary extrusion molding, the foaming agent is added to the extruder before or during the extrusion process, and the melt flows through the pressure at the head. Upon falling, the blowing agent volatilizes to form the desired foamed structure. Because it can not only achieve continuous production, but also is more competitive in cost than injection foam molding, it is currently the most widely used foam molding technology.
  • the structure of the dynamic polymer foam material involves three types of open-cell structures, closed-cell structures, and half-open half-close structures.
  • the open-cell structure the cells and the cells are connected to each other or completely connected, and the single or three-dimensional can pass through a gas or a liquid, and the bubble diameter ranges from 0.01 to 3 mm.
  • the closed-cell structure has an independent cell structure, and the inner cell is separated from the cell by a wall membrane, and most of them are not connected to each other, and the bubble diameter is 0.01-3 mm.
  • the cells contained in the cells are connected to each other and have a semi-open structure.
  • the foam structure which has formed a closed cell it can also be made into an open-cell structure by mechanical pressure or chemical method, and those skilled in the art can select according to actual needs.
  • dynamic polymer foam materials can be classified into soft, hard and semi-rigid according to their hardness classification: (1) flexible foam at 23 ° C and 50% relative humidity.
  • the elastic modulus of the foam is less than 70 MPa;
  • the rigid foam has a modulus of elasticity greater than 700 MPa at 23 ° C and 50% relative humidity;
  • a semi-hard (or semi-soft) foam between The foam between the above two types has a modulus of elasticity between 70 MPa and 700 MPa.
  • the dynamic polymer foam material can be further classified into low foaming, medium foaming, and high foaming according to its density.
  • a low foaming foam material having a density of more than 0.4 g/cm 3 and a foaming ratio of less than 1.5
  • a medium foamed foam material having a density of 0.1 to 0.4 g/cm 3 and a foaming ratio of 1.5 to 9
  • a foamed foam having a density of less than 0.1 g/cm 3 and a foaming ratio of greater than 9.
  • a raw material formulation component for preparing a dynamic polymer in addition to the inorganic boron compound and the silicon-containing compound, other polymers, auxiliaries, and fillers that can be added/used, and these add/use materials can be The form of blending, participating in the chemical reaction together with the reaction product of the inorganic boron compound and the silicon-containing compound as a dynamic polymer formulation component having a hybrid crosslinked structure, or improving the processability during the preparation of the dynamic polymer effect.
  • the other polymers that can be added/used can be used as additives in the system to improve material properties, impart new properties to materials, improve material use and economic benefits, and achieve comprehensive utilization of materials.
  • Other polymers which may be added/used may be selected from natural polymer compounds, synthetic resins, synthetic rubbers, synthetic fibers.
  • the present invention does not limit the properties of the added polymer and the molecular weight thereof, and may be an oligomer or a high polymer depending on the molecular weight, and may be a homopolymer or a copolymer depending on the polymerization form. In the specific use process, it should be selected according to the performance of the target material and the needs of the actual preparation process.
  • the other polymer that can be added/used is selected from a natural high molecular compound, it may be selected from any one or any of the following natural high molecular compounds: natural rubber, chitosan, chitin, natural protein, and the like.
  • the other polymer that can be added/used is selected from a synthetic resin
  • it may be selected from any one or any of the following synthetic resins: polychlorotrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, polyvinyl chloride.
  • polyvinylidene chloride low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polybenzimidazole , polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene glycol, polyester, polyethersulfone, polyarylsulfone, poly Ether ether ketone, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polyacrylate, polyacrylonitrile, polyphenylene ether, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high impact Polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyurea, polyvinyl acetate, ethylene-propy
  • the other polymer that can be added/used is selected from synthetic rubber
  • it may be selected from any one or any of the following synthetic rubbers: isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, Butyl rubber, ethylene propylene rubber, silicone rubber, fluororubber, polyacrylate rubber, urethane rubber, chloroether rubber, thermoplastic elastomer, and the like.
  • the other polymer that can be added/used is selected from synthetic fibers, it may be selected from any one or any of the following synthetic fibers: viscose fiber, cuprammonium fiber, diethyl ester fiber, triethyl ester fiber, polyamide. Fiber, polyester fiber, polyurethane fiber, polyacrylonitrile fiber, polyvinyl chloride fiber, polyolefin fiber, fluorine-containing fiber, and the like.
  • polymers which may be added/used during the preparation of the polymer material are preferably natural rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polyacrylic acid. Ester, epoxy resin, phenolic resin, isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, butyl rubber, ethylene propylene rubber, silicone rubber, urethane rubber, thermoplastic elastomer.
  • the additive that can be added/used can improve the material preparation process, improve product quality and yield, reduce product cost, or impart a unique application property to the product.
  • the additive which can be added/used is selected from any one or any of the following auxiliary agents: a synthetic auxiliary agent, including a catalyst, an initiator, a stabilizing auxiliary agent, including an antioxidant, a light stabilizer, and a heat stabilizer.
  • Additives for improving mechanical properties including chain extenders, toughening agents, coupling agents; additives for improving processability, including lubricants, mold release agents; softening and lightening additives, including plasticizers , foaming agent, dynamic regulator; additives to change the surface properties, including antistatic agents, emulsifiers, dispersants; additives to change the color, including colorants, fluorescent whitening agents, matting agents; flame retardant and inhibit Tobacco additives, including flame retardants; other additives, including nucleating agents, rheological agents, thickeners, leveling agents.
  • the catalyst in the auxiliary agent is capable of accelerating the reaction rate of the reactants in the reaction process by changing the reaction pathway and reducing the activation energy of the reaction.
  • the catalyst includes, but is not limited to: (1) a catalyst for polyurethane synthesis: an amine catalyst such as triethylamine, triethylenediamine, bis(dimethylaminoethyl)ether, 2-(2-Dimethylamino-ethoxy)ethanol, trimethylhydroxyethylpropanediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, N-(dimethylaminopropyl) Diisopropanolamine, N,N,N'-trimethyl-N'-hydroxyethyl bisamine ethyl ether, tetramethyldipropylene triamine, N,N-dimethylcyclohexylamine ,N,N,N',N'-tetramethylalkylenediamine,
  • Catalyst for polyolefin synthesis such as Ziegler-Natta catalyst, ⁇ -allyl nickel, alkyl lithium catalyst, metallocene catalyst, diethylaluminum chloride, titanium tetrachloride, titanium trichloride, trifluoro Boron ether complex, magnesium oxide, dimethylamine, cuprous chloride, triethylamine, sodium tetraphenylborate, antimony trioxide, sesquiethylaluminum chloride, vanadium oxychloride, triisobutylene Aluminum, nickel naphthenate, rare earth naphthenic acid, and the like.
  • Ziegler-Natta catalyst such as Ziegler-Natta catalyst, ⁇ -allyl nickel, alkyl lithium catalyst, metallocene catalyst, diethylaluminum chloride, titanium tetrachloride, titanium trichloride, trifluoro Boron ether complex, magnesium oxide, dimethylamine, cuprous chloride, triethylamine
  • the CuAAC reaction is synergistically catalyzed by a monovalent copper compound and an amine ligand.
  • the monovalent copper compound may be selected from a Cu(I) salt such as CuCl, CuBr, CuI, CuCN, CuOAc, etc.; or may be selected from a Cu(I) complex such as [Cu(CH 3 CN) 4 ]PF 6 , [Cu(CH 3 CN) 4 ]OTf, CuBr(PPh 3 ) 3 , etc.; it can also be formed in situ from elemental copper and divalent copper compounds (such as CuSO 4 , Cu(OAc) 2 );
  • the (I) salt is preferably CuBr and CuI, and the Cu(I) complex is preferably CuBr(PPh 3 ) 3 .
  • the amine ligand may be selected from tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), tris[(1-tert-butyl-1H-1, 2,3-triazol-4-yl)methyl]amine (TTTA), tris(2-benzimidazolylmethyl)amine (TBIA), hydrated phenanthroline sodium disulfonate, etc.; among them, amine ligand TBTA and TTTA are preferred.
  • Thiol-ene reaction catalyst photocatalyst, such as benzoin dimethyl ether, 2-hydroxy-2-methylphenylacetone, 2,2-dimethoxy-2-phenylacetophenone, etc.; nucleophilic A reagent catalyst such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine or the like.
  • the amount of the catalyst to be used is not particularly limited and is usually from 0.01 to 2% by weight.
  • the initiator in the additive which can be added/used, which can cause activation of the monomer molecule during the polymerization reaction to generate a radical, increase the reaction rate, and promote the reaction, including but not limited to any one of the following or Several initiators: organic peroxides, such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, diperoxydicarbonate (4 -tert-butylcyclohexyl)ester, t-butylperoxybenzoate, t-butyl peroxypivalate, di-tert-butyl peroxide, dicumyl hydroperoxide; azo compounds such as azo Diisobutyronitrile (AIBN), azobisisoheptanenitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, etc.; wherein the initiator is preferably
  • antioxidant in the additive which can be added/used, which can delay the oxidation process of the polymer sample, ensure the material can be smoothly processed and prolong its service life, including but not limited to any one of the following or Several antioxidants: hindered phenols such as 2,6-di-tert-butyl-4-methylphenol, 1,1,3-tris(2-methyl-4hydroxy-5-tert-butylphenyl) Butane, tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol Sulfur-containing hindered phenols such as 4,4'-thiobis-[3-methyl-6-tert-butylphenol], 2,2'-thiobis-[4-methyl-6-tert Butylphenol]; a triazine-based hindered phenol such as 1,3,5-bis[ ⁇ -(3,
  • the light stabilizer in the additive which can be added/used can prevent photoaging of the polymer sample and prolong its service life, including but not limited to any one or any of the following light stabilizers: light shielding agent Such as carbon black, titanium dioxide, zinc oxide, calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2,4,6- Tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-s-triazine, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; pioneer UV absorption Agents such as p-tert-butylphenyl salicylate, bisphenol A disalicylate; UV quenchers such as bis(3,5-di-tert-but
  • the heat stabilizer in the additive which can be added/used can make the polymer sample not undergo chemical change due to heat during processing or use, or delay the change to achieve the purpose of prolonging the service life, including but It is not limited to any one or any of the following heat stabilizers: lead salts such as tribasic lead sulfate, lead dibasic phosphite, lead dibasic stearate, lead dibasic lead, trisalt Lead methoxide, lead silicate, lead stearate, lead salicylate, lead dibasic phthalate lead, basic lead carbonate, silica gel coprecipitated lead silicate; metal soap: such as hard Cadmium citrate, barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds such as di-n-butyltin dilaurate, di-n-octyl dilaurate, maleic acid Butyltin, di-maleic acid monooctyl ester di-
  • the cross-linking agent in the auxiliary agent is used in the dynamic polymer to be used for cross-linking reactant components, which can bridge the polymer molecules of the linear type to make a plurality of linear molecules
  • Cross-linking into a network structure can further increase the crosslink density and crosslink strength of the polymer, improve the heat resistance and service life of the polymer, and improve the mechanical properties and weather resistance of the material, including but not limited to Any one or more of the following crosslinking agents: polypropylene glycol glycidyl ether, zinc oxide, aluminum chloride, aluminum sulfate, chromium nitrate, ethyl orthosilicate, methyl orthosilicate, p-toluenesulfonic acid, p-toluene Sulfonyl chloride, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, butyl acrylate, aluminum isopropoxide, zinc acetate, titanium acetylacet
  • the crosslinking agent is preferably dicumyl peroxide (DCP), benzoyl peroxide (BPO), or 2,4-dichlorobenzoyl peroxide (DCBP).
  • DCP dicumyl peroxide
  • BPO benzoyl peroxide
  • DCBP 2,4-dichlorobenzoyl peroxide
  • the amount of the crosslinking agent to be used is not particularly limited and is usually from 0.1 to 5% by weight.
  • the curing agent in the auxiliary agent which is used in combination with the reactant component in the dynamic polymer that needs to be cured, can enhance or control the curing reaction of the reactant component during the polymerization, including but not limited to the following Any one or more curing agents: amine curing agents such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, hexamethylenetetramine, m-phenylenediamine; anhydride curing Agents such as phthalic anhydride, maleic anhydride, pyromellitic dianhydride; amide curing agents such as low molecular polyamides; imidazoles such as 2-methylimidazole, 2-ethyl-4- Methylimidazole, 2-phenylimidazole; boron trifluoride complex, and the like.
  • amine curing agents such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropyl
  • the curing agent is preferably ethylenediamine (EDA), diethylenetriamine (DETA), phthalic anhydride or maleic anhydride, and the amount of the curing agent to be used is not particularly limited, and is usually from 0.5 to 1% by weight.
  • the chain extender in the additive/additive additive can react with a reactive group on the reactant molecular chain to expand the molecular chain and increase the molecular weight, and is generally used for preparing an additive polyurethane/polyurea.
  • chain extenders including but not limited to any one or any of the following chain extenders: polyol chain extenders, such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, 1 , 4-butanediol, 1,6-hexanediol, hydroquinone dihydroxyethyl ether (HQEE), resorcinol bishydroxyethyl ether (HER), p-hydroxyethyl bisphenol A; Polyamine chain extenders such as diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tetraethyldibenzylidenediamine, t
  • the toughening agent in the additive which can be added/used can reduce the brittleness of the polymer sample, increase the toughness, and improve the load bearing strength of the material, including but not limited to any one or any of the following toughening agents: Methyl acrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and modified product thereof, acrylonitrile-butadiene-styrene copolymer, acrylonitrile- Butadiene copolymer, ethylene propylene rubber, EPDM rubber, cis-butyl rubber, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, etc.; among them, the toughening agent is preferably ethylene propylene rubber or propylene.
  • ABS Nitrile-butadiene-styrene copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • MBS methyl methacrylate-butadiene-styrene copolymer resin
  • CPE Chlorinated polyethylene resin
  • the amount of the toughening agent to be used is not particularly limited and is usually from 5 to 10% by weight.
  • the coupling agent in the additive which can be added/used can improve the interfacial properties of the polymer sample and the inorganic filler or the reinforcing material, reduce the viscosity of the material melt during the plastic processing, and improve the dispersion of the filler.
  • any one or any of the following coupling agents organic acid chromium complex, silane coupling agent, titanium An acid ester coupling agent, a sulfonyl azide coupling agent, an aluminate coupling agent, etc.; wherein the coupling agent is preferably ⁇ -aminopropyltriethoxysilane (silane coupling agent KH550), ⁇ -(2 , 3-glycidoxypropyl)propyltrimethoxysilane (silane coupling agent KH560).
  • the amount of the coupling agent to be used is not particularly limited and is usually from 0.5 to 2% by weight.
  • the lubricant in the additive that can be added/used can improve the lubricity of the polymer sample, reduce friction, and reduce interfacial adhesion performance, including but not limited to any one or any of the following lubricants: saturation Hydrocarbons and halogenated hydrocarbons, such as paraffin wax, microcrystalline paraffin, liquid paraffin, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids such as stearic acid, hydroxystearic acid; fatty acid esters, such as fatty acid lower alcohol esters , fatty acid polyol esters, natural waxes, ester waxes and saponified waxes; aliphatic amides such as stearic acid amide or stearic acid amide, oleamide or oleic acid amide, erucamide, N, N'-ethylene double hard Fatty acid amide; fatty alcohols and polyols such as stearyl alcohol, cetyl alcohol, pentaerythritol; metal soap
  • the release agent is preferably dimethicone or polyethylene glycol.
  • the amount of the releasing agent to be used is not particularly limited and is usually from 0.5 to 2% by weight.
  • plasticizer in the additive that can be added/used, which can increase the plasticity of the polymer sample, such that the hardness, modulus, softening temperature and embrittlement temperature of the polymer decrease, elongation, flexibility and Increased flexibility, including but not limited to any one or any of the following plasticizers: phthalates: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate Ester, diheptyl phthalate, diisononyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl phthalate, butyl phthalate, phthalate Dicyclohexyl formate, bis(tridecyl) phthalate, di(2-ethyl)hexyl terephthalate; phosphates such as tricresyl phosphate, diphenyl-2-ethyl Hexyl ester; fatty acid esters such as di(2-ethy
  • the foaming agent in the additive which can be added/used can foam the polymer sample into pores, thereby obtaining a lightweight, heat-insulating, sound-insulating, elastic polymer material, including but not limited to the following One or any of several blowing agents: physical blowing agents such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene Butane, diethyl ether, methyl chloride, dichloromethane, dichloroethylene, dichlorodifluoromethane, chlorotrifluoromethane; inorganic foaming agents such as sodium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate; organic foaming agents, Such as N, N'-dinitropentamethyltetramine, N, N'-dimethyl-N, N'-dinitrosophthalamide, azodicarbonamide,
  • the blowing agent is preferably sodium hydrogencarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N, N'-dinitropentamethyltetramine (foaming agent H), N, N' -Dimethyl-N,N'-dinitroso-terephthalamide (foaming agent NTA), physical microsphere foaming agent, and the amount of the foaming agent to be used are not particularly limited, and are generally 0.1 to 30% by weight. .
  • the dynamic modifier in the additive that can be added/used can enhance the dynamic polymer dynamics in order to obtain optimal desired properties, typically with free hydroxyl or free carboxyl groups, or can give or accept Electron pair compounds include, but are not limited to, water, sodium hydroxide, alcohols (including silanols), carboxylic acids, Lewis acids, Lewis bases, and the like.
  • the amount of the dynamic regulator used is not particularly limited and is usually from 0.1 to 10% by weight.
  • the antistatic agent in the additive which can be added/used can guide or eliminate the harmful charge accumulated in the polymer sample, so that it does not cause inconvenience or harm to production and life, including but not limited to any of the following Or any of several antistatic agents: anionic antistatic agents, such as alkyl sulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate diethanolamine salts, potassium p-nonyldiphenyl ether sulfonate, Phosphate derivatives, phosphates, polyethylene oxide alkyl ether alcohol esters, phosphate derivatives, fatty amine sulfonates, sodium butyrate sulfonate; cationic antistatic agents, such as fatty ammonium hydrochloride , lauryl trimethyl ammonium chloride, dodecyl trimethylamine bromide, alkyl hydroxyethyl dimethyl ammonium perchlorate; zwitterionic antistatic agent,
  • the emulsifier in the additive which can be added/used can improve the surface tension between various constituent phases in the polymer mixture containing the auxiliary agent to form a uniform and stable dispersion system or emulsion,
  • emulsifiers including but not limited to any one or any of the following emulsifiers: anionic, such as higher fatty acid salts, alkyl sulfonates, alkyl benzene sulfonates, alkyl groups Sodium naphthalene sulfonate, succinate sulfonate, petroleum sulfonate, fatty alcohol sulfate, castor oil sulfate, sulfated butyl ricinate, phosphate ester, fatty acyl-peptide condensate; cationic Such as alkyl ammonium salt, alkyl quaternary ammonium salt, alkyl pyridinium salt; zwitterionic type, such as carboxy
  • the dispersing agent in the additive which can be added/used can disperse the solid floc in the polymer mixture into fine particles and suspend in the liquid, uniformly dispersing solid and liquid particles which are difficult to be dissolved in the liquid, and simultaneously It also prevents sedimentation and agglomeration of the particles to form a stable suspension, including but not limited to any one or any of the following dispersants: anionic, such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, petroleum sulphur Sodium; cationic; nonionic, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic type, such as silicate, condensed phosphate; wherein the dispersing agent is preferably dodecyl Sodium benzenesulfonate, naphthalene methylene sulfonate (dispersant N), fatty alcohol polyoxyethylene ether.
  • the amount of the dispersant to be used is not particularly
  • the colorant in the additive which can be added/used can make the polymer product exhibit the desired color and increase the surface color, including but not limited to any one or any of the following colorants: inorganic pigments, such as Titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine blue, chrome green, carbon black; organic pigments, such as Lisol Baohong BK, lake red C, blush, Jiaji R red, turnip Red, permanent solid red HF3C, plastic red R and clomo red BR, permanent orange HL, fast yellow G, Ciba plastic yellow R, permanent yellow 3G, permanent yellow H 2 G, indigo blue B, Indigo green, plastic purple RL, aniline black; organic dyes, such as thioindigo, reduced yellow 4GF, Shilin blue RSN, salt-based rose essence, oil-soluble yellow, etc.; among them, the colorant is selected according to the color requirements of the sample It does not need to be specially limited.
  • the fluorescent whitening agent in the additive which can be added/used enables the dyed substance to obtain a fluorite-like sparkling effect including, but not limited to, any one or any of the following fluorescent whitening agents: a stilbene type, a coumarin type, a pyrazoline type, a benzooxazole type, a phthalimide type, etc., wherein the fluorescent whitening agent is preferably sodium stilbene biphenyl disulfonate (fluorescent whitening) Agent CBS), 4,4-bis(5-methyl-2-benzoxazolyl)stilbene (fluorescent brightener KSN), 2,2-(4,4'-distyryl)bisbenzene And oxazole (fluorescent brightener OB-1).
  • the amount of the fluorescent whitening agent to be used is not particularly limited and is usually from 0.002 to 0.03 % by weight.
  • the matting agent in the additive that can be added/used can cause diffuse reflection when the incident light reaches the surface of the polymer, and produces a low-gloss matt and matte appearance, including but not limited to any one of the following or Several matting agents: precipitated barium sulfate, silica, hydrous gypsum powder, talc powder, titanium dioxide, polymethyl urea resin, etc.; wherein the matting agent is preferably silica.
  • the amount of the matting agent to be used is not particularly limited and is usually from 2 to 5% by weight.
  • the flame retardant in the additive which can be added/used can increase the flame resistance of the material, including but not limited to any one or any of the following flame retardants: phosphorus, such as red phosphorus, tricresyl phosphate Ester, triphenyl phosphate, tricresyl phosphate, toluene diphenyl phosphate; halogen-containing phosphates such as tris(2,3-dibromopropyl)phosphate, tris(2,3-dichloropropyl) phosphate Ester; organic halides, such as high chlorine content chlorinated paraffin, 1,1,2,2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentanane; inorganic flame retardants, such as trioxide Bismuth, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants, such as chloro-bromic anhydride, bis(2,3-dibromopropyl) fum
  • the nucleating agent in the additive which can be added/used can shorten the material molding cycle and improve the transparency of the product by changing the crystallization behavior of the polymer, accelerating the crystallization rate, increasing the crystal density, and promoting the grain size miniaturization.
  • the purpose of physical mechanical properties such as surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance, etc., including but not limited to any one or any of the following nucleating agents: benzoic acid, Diacid, sodium benzoate, talc, sodium p-phenolate, silica, dibenzylidene sorbitol and its derivatives, ethylene propylene rubber, ethylene propylene diene rubber, etc.; wherein the nucleating agent is preferably silica , Dibenzylidene sorbitol (DBS), EPDM rubber.
  • the amount of the nucleating agent to be used is not particularly limited and is usually from 0.1 to 1% by weight.
  • the rheological agent in the additive which can be added/used can ensure good coating property and appropriate coating thickness of the polymer in the coating process, prevent sedimentation of solid particles during storage, and can improve the re-coating thereof.
  • Dispersibility including but not limited to any one or any of the following rheological agents: inorganic, such as barium sulfate, zinc oxide, alkaline earth metal oxides, calcium carbonate, lithium chloride, sodium sulfate, magnesium silicate, gas phase Silica, water glass, colloidal silica; organometallic compounds such as aluminum stearate, aluminum alkoxide, titanium chelate, aluminum chelate; organic, such as organic bentonite, hydrogenated castor oil / amide wax , isocyanate derivative, acrylic emulsion, acrylic copolymer, polyethylene wax, cellulose ester, etc.; wherein, the rheological agent is preferably organic bentonite, polyethylene wax, hydrophobically modified alkaline swellable emulsion (
  • the thickener in the additive which can be added/used can impart good thixotropy and proper consistency to the polymer mixture, thereby satisfying the stability and application properties during production, storage and use.
  • the need including but not limited to any one or any of the following thickeners: low molecular substances such as fatty acid salts, alkyl dimethylamine oxides, fatty acid monoethanolamides, fatty acid diethanolamides, fatty acid isoforms Propionamide, sorbitan tricarboxylate, glycerol trioleate, cocoamidopropyl betaine, titanate coupling agent; high molecular substances, such as bentonite, artificial hectorite, fine powder silica, colloid Aluminum, animal protein, polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, crotonic acid copolymer, polyacrylamide, polyvinylpyrrolidone, polyether, etc.; wherein the thickener is preferably hydroxy coconut oil II
  • the leveling agent in the additive which can be added/used can ensure the smoothness and uniformity of the polymer coating film, improve the surface quality of the coating film, and improve the decorativeness, including but not limited to any one or any of the following Leveling agent: polydimethylsiloxane, polymethylphenylsiloxane, polyacrylate, silicone resin, etc.; wherein the leveling agent is preferably polydimethylsiloxane or polyacrylate.
  • the amount of the leveling agent to be used is not particularly limited and is usually from 0.5 to 1.5% by weight.
  • additives which may be added/used are preferably catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, chain extenders, toughening agents, plasticizers, foaming agents, Flame retardant, dynamic regulator.
  • the filler mainly plays the following roles in the dynamic polymer: 1 reducing the shrinkage rate of the molded article, improving the dimensional stability, surface smoothness, smoothness, and flatness or mattness of the product; 2 adjusting the polymer Viscosity; 3 to meet different performance requirements, such as improving the impact strength and compressive strength of polymer materials, hardness, stiffness and modulus, improving wear resistance, increasing heat distortion temperature, improving conductivity and thermal conductivity; 4 improving pigment coloration Effect; 5 imparts light stability and chemical resistance; 6 plays a compatibilizing role, which can reduce costs and improve the competitiveness of products in the market.
  • the filler is selected from any one or any of the following fillers: an inorganic non-metallic filler, a metal filler, and an organic filler.
  • the inorganic non-metallic filler includes, but is not limited to, any one or more of the following: calcium carbonate, clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon, quartz, mica powder, clay, Asbestos, asbestos fiber, feldspar, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene, graphene oxide, carbon nanotubes, molybdenum disulfide, slag, flue ash, wood flour and shell powder , diatomaceous earth, red mud, wollastonite, silicon aluminum black, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, niobium Stone, iron mud, white mud, alkali mud, (hollow) glass beads, foamed microspheres, foamable particles, glass powder, cement, glass fiber,
  • an inorganic non-metallic filler having conductivity including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fiber, is preferably used to conveniently obtain a composite having electrical conductivity and/or electrothermal function. material.
  • a non-metallic filler having a heat generating function under the action of infrared and/or near-infrared light including but not limited to graphene, graphene oxide, carbon nanotubes, and convenient use of infrared rays.
  • an inorganic non-metallic filler having thermal conductivity including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, and a composite for facilitating thermal conductivity is preferred. material.
  • the metal filler including metal compounds, including but not limited to any one or any of the following: metal powder, fiber, including but not limited to powders, fibers of copper, silver, nickel, iron, gold, etc. 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 Fe 3 O 4 particles, nano ⁇ -Fe 2 O 3 particles, Nano-MgFe 2 O 4 particles, nano-MnFe 2 O 4 particles, nano-CoFe 2 O 4 particles, nano-CoPt 3 particles, nano-FePt particles, nano-FePd particles, nickel-iron bimetallic magnetic nanoparticles and others in infrared, near-infrared, ultraviolet At least one kind of nano metal particles that can generate heat under electromagnetic action; liquid metal, including but not limited to mercury, gallium, gallium indium liquid alloy, gallium indium tin liquid alloy, other gallium-based liquid metal alloy; metal organic compound molecule, Crystals
  • the present invention can be preferably electromagnetic and / or near-infrared heating fillers, including but not limited to nano-gold, nano silver, nano Pd, nano Fe 3 O 4, for sensing heat.
  • a liquid metal filler is preferred to facilitate obtaining a composite material having good thermal conductivity, electrical conductivity, and ability to maintain flexibility and ductility of the substrate.
  • the organometallic compound molecules and crystals which can generate heat under at least one of infrared, near-infrared, ultraviolet, and electromagnetic are preferable, and on the one hand, the composite is facilitated, and the other side is improved in the efficiency of inducing heat generation and heating. effect.
  • the organic filler includes, but is not limited to, any one or more of the following: fur, natural rubber, synthetic rubber, synthetic fiber, synthetic resin, cotton, cotton linters, hemp, jute, linen, asbestos, cellulose, acetic acid Cellulose, shellac, chitin, chitosan, lignin, starch, protein, enzyme, hormone, lacquer, wood flour, shell powder, glycogen, xylose, silk, rayon, vinylon, phenolic microbeads, Resin beads, etc.
  • the type of filler to be added is not limited, and is mainly determined according to the required material properties, and preferably calcium carbonate, barium sulfate, talc, carbon black, graphene, (hollow) glass microbeads, foamed microspheres, glass fibers,
  • the amount of the filler used for the carbon fiber, the metal powder, the natural rubber, the chitosan, the protein, and the resin microbead is not particularly limited and is usually from 1 to 30% by weight.
  • a certain proportion of the raw materials may be mixed by mixing in any suitable material known in the art to prepare a dynamic polymer, which may be a batch, semi-continuous or continuous process mixture; Similarly, dynamic polymers can be formed in a batch, semi-continuous or continuous process.
  • the mixing modes employed include, but are not limited to, solution agitation mixing, melt agitation mixing, kneading, kneading, opening, melt extrusion, ball milling, etc., wherein solution agitation mixing, melt agitation mixing, and melt extrusion are preferred.
  • the form of energy supply during material mixing includes, but is not limited to, heating, illumination, radiation, microwave, ultrasound.
  • the molding methods used include, but are not limited to, extrusion molding, injection molding, compression molding, tape casting, calender molding, and casting molding.
  • a specific method for preparing a dynamic polymer by stirring and mixing a solution is usually carried out by stirring and dispersing the raw materials in a dissolved or dispersed form in a respective solvent or a common solvent in a reactor.
  • the mixing reaction temperature is controlled at 0 to 200 ° C, preferably 25 to 120 ° C, more preferably 25 to 80 ° C, and the mixing and stirring time is controlled to be 0.5 to 12 h, preferably 1 to 4 h.
  • the product obtained after the mixing and stirring may be poured into a suitable mold and placed at 0 to 150 ° C, preferably 25 to 80 ° C, for 0 to 48 hours to obtain a polymer sample.
  • a solvent sample may be selected as a solvent, a gel, or the like, or a solid polymer sample in the form of a film, a block, a foam, or the like may be selected by removing the solvent.
  • an initiator in a solvent to initiate polymerization to obtain a dynamic polymer by solution polymerization or to add a dispersing agent and an oil-soluble initiator to prepare a suspension for suspension polymerization or
  • the slurry is polymerized to initiate polymerization to obtain a dynamic polymer, or an initiator and an emulsifier are added to prepare an emulsion to initiate polymerization by emulsion polymerization to obtain a dynamic polymer.
  • the methods of solution polymerization, suspension polymerization, slurry polymerization, and emulsion polymerization employed are all known to those skilled in the art and widely used, and can be adjusted according to actual conditions, and will not be further developed here.
  • the solvent used in the above preparation method should be selected according to the actual conditions such as the reactants, products and reaction processes, including but not limited to any one of the following solvents or a mixed solvent of any of several solvents: deionized water, acetonitrile, acetone, Butanone, benzene, toluene, xylene, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, methanol, ethanol, chloroform, dichloromethane, 1,2-dichloroethane, dimethyl sulfoxide, Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isopropyl acetate, n-butyl acetate, trichloroethylene, mesitylene, dioxane, Tris buffer, citrate buffer, acetic acid Buffer solution, phosphate buffer solution, boric acid buffer solution, etc.; preferably deionized
  • the solvent may also be selected from the group consisting of an oligomer, a plasticizer, and an ionic liquid;
  • the oligomer includes, but is not limited to, a polyethylene glycol oligomer, a polyvinyl acetate oligomer, and a polybutyl acrylate. a polymer, a liquid paraffin or the like;
  • the plasticizer may be selected from the class of plasticizers in the additive which may be added, and is not described herein;
  • the ionic liquid generally consists of an organic cation and an inorganic anion.
  • the cation is usually an alkyl quaternary ammonium ion, an alkyl quaternary phosphonium ion, a 1,3-dialkyl substituted imidazolium ion, an N-alkyl substituted pyridinium ion, etc.; the anion is usually a halogen ion, a tetrafluoroborate ion, and a hexa Fluoride ions, also CF 3 SO 3 - , (CF3SO 2 ) 2 N - , C 3 F 7 COO - , C 4 F 9 SO 3 - , CF 3 COO - , (CF 3 SO 2 ) 3 C - , (C 2 F 5 SO 2 ) 3 C - , (C 2 F 5 SO 2 ) 2 N - , SbF 6 - , AsF 6 -, and the like.
  • a hydrogel can be obtained by using deionized water to prepare a dynamic polymer and selectively retaining it; when an organic solvent is used to prepare a dynamic polymer and it is selected to be retained, an organogel can be obtained; When preparing a dynamic polymer and selecting to retain it, an oligomer swollen gel can be obtained; when a dynamic polymer is prepared by using a plasticizer and selected to retain it, a plasticizer swollen gel can be obtained; using an ionic liquid to prepare When the dynamic polymer is selected and retained, an ionic liquid swollen gel can be obtained.
  • the liquid concentration of the compound to be disposed is not particularly limited depending on the structure, molecular weight, solubility, and desired dispersion state of the selected reactant, and a preferred compound liquid concentration is 0.1 to 10 mol/L, and more preferably 0.1 to 1 mol/L.
  • a specific method for preparing a dynamic polymer by melt-mixing usually by directly stirring or mixing the raw materials in a reactor, and then stirring and mixing the mixture, generally in the case where the raw material is a gas, a liquid or a solid having a low melting point.
  • the mixing reaction temperature is controlled at 0 to 200 ° C, preferably 25 to 120 ° C, more preferably 25 to 80 ° C
  • the mixing and stirring time is controlled to be 0.5 to 12 h, preferably 1 to 4 h.
  • the product obtained after the mixing and stirring may be poured into a suitable mold and placed at 0 to 150 ° C, preferably 25 to 80 ° C, for 0 to 48 hours to obtain a polymer sample.
  • melt polymerization and gas phase polymerization are all known to those skilled in the art and widely used, and can be adjusted according to actual conditions, and will not be developed in detail here.
  • a specific method for preparing a dynamic polymer by melt extrusion mixing is usually carried out by adding a raw material to an extruder for extrusion blending at an extrusion temperature of 0 to 280 ° C, preferably 50 to 150 ° C.
  • the reaction product can be directly cast into a suitable size, or the obtained extruded sample can be crushed and then sampled by an injection molding machine or a molding machine.
  • the injection temperature is 0-280 ° C, preferably 50-150 ° C
  • the injection pressure is preferably 60-150 MPa
  • the molding temperature is 0-280 ° C, preferably 25-150 ° C, more preferably 25-80 ° C
  • the molding time is 0.5-60 min, preferably
  • the molding pressure is preferably 4-15 MPa at 1-10 min.
  • the spline can be placed in a suitable mold and placed at 0-150 ° C, preferably 25-80 ° C, for 0-48 h to give the final polymer sample.
  • the molar equivalent ratio of the inorganic boron compound to the (poly)siloxane compound to be used in the preparation of the dynamic polymer should be in an appropriate range, preferably in the range of 0.1 to 10, more preferably in the range of 0.3 to 3, more preferably The range of 0.8 to 1.2. In the actual preparation process, those skilled in the art can adjust according to actual needs.
  • the amount of the raw materials of the dynamic polymer components is not particularly limited, and those skilled in the art can adjust according to the actual preparation conditions and the properties of the target polymer.
  • the dynamic polymer properties are widely adjustable and have broad application prospects, and are important in military aerospace equipment, functional coatings and coatings, biomedicine, biomedical materials, energy, construction, bionics, smart materials, and the like. Applications.
  • the dynamic polymer Based on the dilatancy and dynamics of the dynamic polymer, the dynamic polymer has excellent energy absorption performance, and is capable of absorbing and reducing mechanical energy including vibration, vibration, impact, explosion, sound wave, etc., and thus the dynamic polymerization
  • an energy absorbing material it can be used as an effective energy absorbing method. It can be applied to the production of damping dampers for vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings. When the polymer material is subjected to vibration, it can be used.
  • the dynamic energy and dynamic difference of the dynamic covalent bond and the hydrogen bond can also be used as a shape memory material, and when the external force is removed, the deformation of the material during the loading process can be recovered.
  • Stress-sensitive polymer materials are prepared by dynamic reversibility and stress rate dependence of dynamic polymers. Some of them can be used to prepare magic toys and fitness materials with stress/strain response, and can also be used to prepare roads and bridges.
  • the speed locker can also be used to make seismic shear plates or cyclic stress bearing tools, or to make stress monitoring sensors.
  • the inorganic boronic acid silicate bond and the hydrogen bond are used as the sacrificial bond, they can be sequentially fractured by an external force, and the hydrogen bond is first broken and then the inorganic boronic acid silicate bond is broken, and a large amount of energy is absorbed to impart a polymer.
  • the material has excellent toughness, so that it can obtain excellent tough polymer materials, which are widely used in military, aerospace, sports, energy, construction and other fields.
  • Trimethyl borate and dimethylmethoxy-3-butene silane were mixed at a molar ratio of 1:3, heated to 60 ° C and dissolved by stirring, and then a small amount of water was added to continue the reaction for 4 h to obtain a silyl borate.
  • the trivinyl compound 1a of the bond was
  • the 1,5-hexadien-3-ol and ethyl isocyanate were mixed in an equimolar ratio, and triethylamine was used as a catalyst to carry out a reaction in dichloromethane to obtain a compound 1b having a pendant group having a urethane group.
  • the polymer product can be used as a sheet or coating having certain energy absorbing properties and having tear resistance.
  • DMPA photoinitiator benzoin dimethyl ether
  • organopolysiloxane containing a side hydrogen bond group and trimethyl borate are mixed in a molar ratio of 1:1 to a Si-OCH 3 group and a B-OR group, and the mixture is heated to 80 ° C and uniformly mixed, and then 4 ml is added.
  • the polymer product can undergo large deformation under the action of small pressure or tensile force, but can exhibit high elasticity when it is rapidly stretched or beaten, and its electrical conductivity can change significantly with pressure or tension, and can be used as Force sensor.
  • the organopolysiloxane prepared above and boric acid are mixed according to a molar ratio of Si-OCH 3 group and B-OH group: 1:1, heated to 60 ° C and reacted for 16 hours by stirring to obtain a common covalent value.
  • N-allyl-1H-benzimidazol-2-amine and 5-butane-2-yl-5-prop-2-enyl-1,3-diazinenon-2,4,6 - Triketone is mixed in a molar ratio of 10:10:3, swelled in the first network polymer, added 5wt% carbon nanotubes, sonicated for 5min, then added 5mol% AIBN as an initiator, heated to 80 ° C for 8h,
  • a dynamic polymer containing a common covalent cross-linking, a side hydrogen bonding group, and a silicic acid silicate bond is prepared by radical polymerization.
  • the polymer product has good toughness and can be prepared into a polymer sealant and a sandwich adhesive.
  • 3-Aminopropylmethyldimethoxysilane and adipyl chloride are mixed at a molar ratio of 2:1, and triethylamine is used as a catalyst to react in anhydrous dichloromethane to prepare a disiloxane compound. .
  • the above disiloxane compound and boric acid are mixed in a molar ratio of 1:1 to a Si-OCH 3 group and a B-OR group, and heated to 60 ° C for 8 hours by stirring to obtain a dynamic bond containing a boronic borate bond.
  • the polymer acts as the first network polymer.
  • allyl mercaptan and 2-thiophene isocyanate were dissolved in methylene chloride at a molar ratio of 1:1, and catalyzed by triethylamine to obtain an olefin monomer 4b containing a thiourethane group.
  • the olefin monomer 4a, the olefin monomer 4b and the diallyl sulfide are thoroughly mixed at a molar ratio of 50:50:3, 80 parts of epoxidized soybean oil is added, stirred well, and then swollen in the first network polymer, and then A dynamic polymer organogel swelled with epoxidized soybean oil containing common covalent cross-linking, side hydrogen bonding groups and silicic acid silicate bond was prepared by free radical polymerization by adding 5 mol% of AIBN.
  • This epoxidized soybean oil-swellable dynamic polymer organogel has soft elasticity and can be used to make an energy absorbing material for impact protection.
  • the dynamic polymer ionic liquid gel is displaced from the ionic liquid by deionized water, and the deionized water is replaced once every 12 hours, and replaced by 4 times, thereby obtaining a common covalent cross-linking, a side hydrogen bonding group and boric acid.
  • Dynamic polymer hydrogel with a silicone bond is displaced from the ionic liquid by deionized water, and the deionized water is replaced once every 12 hours, and replaced by 4 times, thereby obtaining a common covalent cross-linking, a side hydrogen bonding group and boric acid.
  • the hydrogel prepared in this example has a modulus of 13 kPa, a strain of 15 times, and a breaking stress of 69 kPa.
  • the hydrogel can be used as a cushioning packaging material for fragile items.
  • DMPA benzoin dimethyl ether
  • the epoxy acetyl ricinoleic acid swelled organogel prepared in this example has a modulus of 20 kPa, a strain of 15 times, and a breaking stress of 100 kPa.
  • This organogel can be used to prepare airborne and airborne impact resistant materials.
  • the above polycarbonate PLimC and 2-aminoethanethiol and 2-tert-butoxycarbonylaminoethanethiol are mixed at a ratio of a double bond group and a thiol group of 10:5:5, and 0.3 wt% of AIBN is added to obtain a polymerization.
  • 0.2 wt% of dibutyltin dilaurate, 0.2 wt% of triethylenediamine, 4 wt% of polymer foamed microspheres, and 80 wt% are added to the above-mentioned polycarbonate having an amino group and a urethane group.
  • the first network polymer fully stirred evenly, and finally added 20wt% hexamethylene diisocyanate, quickly stirred by professional equipment to produce bubbles, then quickly injected into the mold, cured at room temperature for 30min, then cured at 80 ° C
  • a binary interpenetrating network composite foam containing ordinary covalent cross-linking, side hydrogen bonding groups and silicon borate bonds was obtained.
  • the foam has good chemical resistance and can be used as a substitute for glass products, a rigid packaging box and a decorative sheet. It has toughness and durability, and has good biodegradability. Sex.
  • 4-Amino-3,5-difluorophenylethyl ester 1.0 g, potassium permanganate 8.5 g, 8.6 g of ferrous sulfate heptahydrate, dissolved in 30 ml of LDCM, refluxed overnight to give the azobenzene product.
  • an organopolysiloxane having a terminal olefin group at a pendant group (molecular weight of about 6000) and a compound of 1,4-dimercaptobutane and 3-mercaptopropyltrimethoxysilane according to a double bond and two fluorenyl groups Mixing molar ratio of 20:2:16, adding 0.2wt% photoinitiator benzoin dimethyl ether (DMPA), stirring well, and then UV irradiation in UV cross-linking instrument for 4h, prepared a common covalent cross-linking And an organopolysiloxane having a side hydrogen bonding group.
  • DMPA photoinitiator benzoin dimethyl ether
  • the above organopolysiloxane and boric acid are mixed according to a molar ratio of Si-OCH 3 group and B-OH group: 1:1, and the mixture is heated to 80 ° C and uniformly mixed, and then 100 mL of 1-butyl-3-methylimidazolium hexafluoride is added.
  • Phosphate ([C 4 MIM] PF 6 ) ionic liquid fully swelled in the first network, and then added a small amount of 20% acetic acid solution, and the polymerization reaction is carried out under stirring to prepare a common covalent cross-linking, High-strength ionic liquid dynamic polymer gel with side hydrogen bonding groups and silicon borate bonds.
  • the ionic liquid gel has a modulus of 36 kPa, a strain of 32 times, and a breaking stress of 200 kPa.
  • This product can be used as a stress-carrying material in a fine mold, which can bear the stress and at the same time have a certain deformability and play a buffering role.
  • an organopolysiloxane having a terminal olefin group (molecular weight of about 3,000) and 4'4-dimercaptodiphenyl sulfide and 3-mercaptopropyltrimethoxysilane as a double bond and two fluorenyl groups The compound was mixed at a molar ratio of 2:1:1, and 0.2% by weight of a photoinitiator benzoin dimethyl ether (DMPA) was added with respect to 2-tert-butoxycarbonylaminoethanethiol. After stirring well, it was placed in an ultraviolet cross-linker. UV irradiation for 4 h gave a preparation of an organopolysiloxane containing common covalent crosslinks.
  • DMPA photoinitiator benzoin dimethyl ether
  • the above organopolysiloxane containing ordinary covalently crosslinked and 2,6-di-tert-butyl-4-tolyldibutyl orthoboroate have a molar ratio of terminal siloxane to boric acid ester of 1:1. After mixing and heating to 80 ° C to mix well, add 4 ml of deionized water, add a small amount of acetic acid dropwise, and carry out polymerization under stirring to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond. As the first network polymer.
  • the polymer product can be used as an impact resistant material.
  • the molar ratio of the double bond to the fluorenyl group is 100:96:1.
  • 0.2 wt% of photoinitiator benzoin dimethyl ether (DMPA) was added, and after stirring well, ultraviolet irradiation was carried out for 4 h in an ultraviolet crosslinker to obtain an organopolysiloxane containing a side hydrogen bond group.
  • the above-mentioned organopolysiloxane containing a side hydrogen bond group and 2,6-di-tert-butyl-4-tolyldibutyl orthoboroate have a molar ratio of terminal siloxane to boric acid ester of 1:1. After mixing and heating to 80 ° C to mix well, 4 ml of deionized water was added, and polymerization was carried out under stirring to prepare a dynamic polymer containing common covalent cross-linking, side hydrogen bonding groups and silicic acid borate bonds. As the first network polymer.
  • the product exhibits good viscoelasticity, good isolation shock and stress buffering, and also exhibits excellent hydrolysis resistance.
  • the terpene oxide extracted from the orange peel is polymerized with 100 psi of carbon dioxide under the catalysis of ⁇ -diimine zinc to obtain a polycarbonate PLimC.
  • the above polycarbonates PLimC and ⁇ -mercaptopropylmethyldimethoxysilane, N-[(2-mercaptoethyl)carbamoyl]propionamide, and di(2-mercaptoethyl) adipate are The ratio of the double bond group to the thiol group is 20:10:8:2, and 0.6 wt% of AIBN is added, and a polycarbonate having a common covalent crosslink, a side hydrogen bond group and a silanol precursor is obtained by a click reaction. .
  • the polymer is prepared into a film, exhibits superior comprehensive properties, has a certain tensile strength and good tear resistance, and can be stretched to a greater extent.
  • Such dynamic polymers can be used to make functional films, or can be used as films for automobiles and furniture, or as stretch wrap films, which are very scratch resistant.
  • Polyhydroxyethyl acrylate (molecular weight: about 1,000) was obtained by radical polymerization using hydroxyethyl acrylate as a monomer.
  • the polyacrylate having a trimethoxysilane group in the above side group and boric acid are mixed in a molar ratio of 1:1 to a Si-OCH 3 group and a B-OH group, and the mixture is heated to 80 ° C and uniformly mixed, and then stirred under stirring.
  • the polymerization was carried out for 8 hours to obtain a dynamic polymer containing a silicon borate bond as the first network polymer.
  • the 1,4-butadien-3-ol and methyl isocyanate were mixed in an equimolar ratio, and triethylamine was used as a catalyst to carry out a reaction in dichloromethane to obtain a compound 12b having a pendant group having a urethane group.
  • Compound 12a, compound 12b and 1,8-diazido-3,5-dioxaoctane are mixed at a molar ratio of 1:1:2, swelled in the first network, and added to the plasticizer o-benzene.
  • the dioctyl dicarboxylate 0.1 wt% of the catalyst CuBr(PPh 3 ) 3 and tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl are added to the monomer.
  • the amine (TBTA) was stirred and mixed at room temperature for 12 hours to obtain a dioctyl phthalate-swelling organogel.
  • the dioctyl phthalate-swelled organogel prepared in this example has a modulus of 22 kPa, a strain of 18 times, and a breaking stress of 100 kPa.
  • This organogel can be used to prepare airborne and airborne impact resistant materials.
  • DMPA photoin dimethyl ether
  • the polymer sample has a large viscosity and a very good tensile toughness, and can be stretched to a large extent without breaking (breaking elongation of up to 600%).
  • the polymer can be used as an electronic packaging material or an adhesive to avoid damage and gas leakage.
  • the above copolymer and trimethyl borate are mixed according to a molar ratio of Si-OCH 3 group and B-OR group 1:1, and the mixture is heated to 80 ° C and uniformly mixed, and then 4 ml of deionized water is added and stirred under stirring.
  • the polymerization reaction produces a dynamic polymer containing a common covalent crosslink and a silicic acid borate bond as the first network polymer.
  • 1,3-diphenylpropane-2,2-dithiol and compound 14a, compound 14b are mixed at a molar ratio of 1:1:3, and then swelled in the first network polymer and the second network polymer, Ultraviolet radiation was placed in an ultraviolet crosslinker for 8 h to obtain a dynamic polymer containing common covalent crosslinks, side hydrogen bond groups, and silicon borate bonds.
  • the polymer product can be used to prepare a military and police protective material.
  • the above copolymer and triethyl borate are mixed according to a molar ratio of Si-OCH 3 group and B-OR group 1:1, and the mixture is heated to 80 ° C and mixed uniformly, and then 4 ml of deionized water is added and stirred under stirring.
  • the polymerization reaction produces a dynamic polymer containing a side hydrogen bond group and a silicon borate bond as the first network polymer.
  • a certain amount of hydrogen-bonding group-containing monomer 15a and cyclooctene are mixed, and the ratio of the molar ratio of the two is controlled to be about 1:2.
  • the Grubbs second-generation catalyst is used as a catalyst, and dichloromethane is used as a solvent to obtain a side group.
  • the above copolymer and trimethyl borate are mixed according to a molar ratio of Si-OCH 3 group and B-OR group of 1:1, and then 1.0 g of expanded graphite, 1.0 g of ammonium polyphosphate is added, and fully swelled in the first network polymerization.
  • the second network polymer after heating to 80 ° C and mixing uniformly, 10 ml of deionized water is added, and polymerization is carried out under stirring to prepare a kind of common covalent cross-linking, side hydrogen bond group and boric acid. A dynamic polymer of silicon ester bonds.
  • the polymer product can be used for vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings.
  • the polymer material When the polymer material is subjected to vibration, it can dissipate a large amount of energy to dampen the vibration, thereby effectively alleviating the vibration.
  • the above copolymer and boric acid are mixed according to a molar ratio of Si-OCH 3 group and B-OH group 1:1, and the mixture is heated to 80 ° C and mixed uniformly. Then, 6 ml of deionized water is added, and polymerization is carried out under stirring. A dynamic polymer containing a side hydrogen bond group and a silicon borate bond was prepared as the first network polymer.
  • DMPA photoinitiator benzoin dimethyl ether
  • the molar ratio of the above-mentioned organopolysiloxane containing a side hydrogen bond group and the Si-OR group of the 2,6-di-tert-butyl-4-tolyldibutyl orthoborate and the B-OR group is 1: 1 mixing, heating to 80 ° C to mix well, adding 4 ml of deionized water, polymerization under stirring, to prepare a dynamic polymerization containing common covalent cross-linking, side hydrogen bonding groups and silicon borate bonds As a second network polymer.
  • the above copolymer and trimethyl borate are mixed in a molar ratio of 1:1 to the Si-OCH 3 group and the B-OR group, and are sufficiently swollen in the first network polymer and the second network polymer, and the temperature is raised to 80 ° C. After uniformly mixing, 10 ml of deionized water was added, and polymerization was carried out under stirring to prepare a dynamic polymer containing a common covalently crosslinked, a side hydrogen bond group and a silicon borate bond.
  • the polymer product can be used as an energy absorbing cushioning material in cushioning packaging materials.
  • a vinyl group-containing carbamate compound 17a at both ends is obtained by reacting 3-isocyanatopropene and 3-hydroxy-1-propene in an equimolar ratio.
  • 1,3-diphenylpropane-2,2-dithiol and compound 17a, triacrylamide are mixed according to a molar ratio of 9:6:2, and placed in an ultraviolet cross-linking instrument for ultraviolet light for 8 hours to obtain a common A cross-linked polymer as the first network polymer.
  • the polymer product can be used to prepare magical toys and fitness materials with stress response.
  • the olefin monomer 18a and the tert-butyl acrylate were thoroughly mixed at a molar ratio of 50:50, and 5 mol% of AIBN was further added, and a dynamic polymer containing a side hydrogen bond group was prepared by radical polymerization as a second network polymer.
  • the polymer product can be used to prepare speed lockers for roads and bridges.
  • methallyldichlorosilane and 1,10-fluorene dithiol are mixed at a molar ratio of 2:1, AIBN is used as an initiator, and triethylamine is used as a catalyst to obtain a kind of thiol-ene click reaction.
  • a silicon-containing compound of a silicon hydroxy precursor is used.
  • the silicon-containing compound of the silicic hydroxyl precursor and boric acid are mixed at a molar ratio of 3:4, stirred well and uniformly mixed, and after heating to 80 ° C, 4 ml of deionized water is added, and polymerization is carried out for 8 hours under stirring to prepare a polymerization reaction.
  • Ethyl methacrylate and 2-(1H-imidazol-4-yl)ethyl methacrylate were prepared by radical polymerization according to a molar ratio of 200:1, adding 3 mol% of AIBN as an initiator.
  • a non-crosslinked supramolecular polymer (having a molecular weight of about 3,000) containing a side hydrogen bond, and swelling the non-crosslinked polymer containing a side hydrogen bond in the first network polymer and the second network polymer to obtain A dynamic polymer containing common covalent crosslinks, side hydrogen bond groups, and silicon borate bonds.
  • the polymer product can be used to make seismic shear plates or cyclic stress bearing tools.
  • Dipropionyl adipate and 1,3,5-tris(azidomethyl)benzene are mixed at a molar ratio of 3:2, and 0.1 wt% of the catalyst CuBr(PPh 3 ) 3 and three are added relative to the monomer [ (1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), stirred well and reacted at 60 ° C for 4 h to obtain a common covalent cross-linking
  • the polymer acts as the first network polymer.
  • silyl-terminated polyethylene glycol having a molecular weight of about 5,000
  • boric acid compound containing a boronic acid borate bond are mixed at a molar ratio of siloxane to boric acid ester of about 1:1, and a small amount of water is added at 80 ° C. After stirring uniformly, the reaction was carried out for 6 hours to prepare a non-crosslinked dynamic polymer containing a silicon borate bond as a second network polymer.
  • the polymer product can be used to make damping dampers for a variety of motor vehicles and machinery.
  • Adipoyl chloride and polyoxypropylene triol are reacted in a molar ratio of acid chloride to hydroxyl group of about 1:1 to obtain a polymer containing ordinary covalent crosslinking.
  • 5-Aminopentyldimethylmethoxysilane and tri-n-pentyl borate are mixed in an equimolar ratio, heated to 60 ° C and dissolved by stirring, and then added with a small amount of water for 3 h to obtain a silicon borate.
  • An ester bond borate compound is
  • the above organohydrogen group containing a side hydrogen bond group and the above borate compound containing a boronic acid borate bond are mixed in a molar ratio of 1:1 to a Si-OCH 3 group and a B-OR group, and a small amount is added dropwise. 20% acetic acid aqueous solution, further adding 5 wt% graphene powder, stirring at 50 ° C, and then continuing the reaction for 4 h to prepare a non-crosslinked dynamic polymer containing a side hydrogen bond group and a silicon borate bond.
  • the non-crosslinked dynamic polymer containing a side hydrogen bond group and a silicon borate bond is swollen in the first network polymer to obtain a bond containing a common covalent crosslink, a side hydrogen bond group, and a silicic acid borate bond.
  • Dynamic polymer Dynamic polymer.
  • the polymer product exhibits good viscoelastic properties, good isolation shock and stress buffering, and can be used as an elastic cushioning gasket.
  • the obtained rubber-based dynamic polymer material has good resilience and can be applied as a rubber cushioning material to the field of sporting goods.

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Abstract

L'invention concerne un polymère dynamique ayant une structure réticulée hybridée, comprenant une réticulation covalente commune et comprenant également des effets d'une liaison ester de borate de silicium inorganique covalente dynamique et d'une liaison hydrogène supramoléculaire formée avec la participation d'un groupe de liaison hydrogène latéral, la réticulation covalente commune étant au niveau ou au-dessus de la température de gélatinisation du polymère. Le présent polymère dynamique combine la liaison ester de borate de silicium inorganique covalente dynamique et la liaison hydrogène supramoléculaire, fournit une grande réversibilité dynamique, et présente des caractéristiques fonctionnelles telles qu'une réactivité à un stimulus et des propriétés d'auto-cicatrisation ; de plus, la réticulation covalente commune confère en outre au polymère un certain degré d'intensité et de stabilité. De plus, la présence de la liaison ester de borate de silicium inorganique et de la liaison hydrogène permet également au polymère de fournir un effet d'absorption d'énergie élevé et d'effectuer une trempe et un amortissement d'un matériau dans une structure spécifique. Le polymère dynamique est applicable dans la fabrication d'un matériau d'amortissement absorbant les chocs, d'un matériau de protection résistant aux chocs, d'un matériau auto-cicatrisant, et d'un matériau élastique.
PCT/CN2018/072457 2017-01-25 2018-01-12 Polymère dynamique ayant une structure réticulée hybridée et applications associée Ceased WO2018137506A1 (fr)

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CN117144693A (zh) * 2023-08-24 2023-12-01 浙江禾欣科技有限公司 一种与聚氨酯面层树脂结合力优良的有机硅树脂及其制备方法
CN117466625A (zh) * 2023-10-31 2024-01-30 烟台美丰机械集团有限公司 复合碳纤维的碳陶刹车盘的复合工艺
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CN120574464A (zh) * 2025-06-09 2025-09-02 湖南毅远信科技股份有限公司 一种高压直流电缆用交联聚乙烯材料及其制备方法
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