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WO2018137505A1 - Polymère ou composition dynamique présentant une structure de liaison hybride, et application associée - Google Patents

Polymère ou composition dynamique présentant une structure de liaison hybride, et application associée Download PDF

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Publication number
WO2018137505A1
WO2018137505A1 PCT/CN2018/072455 CN2018072455W WO2018137505A1 WO 2018137505 A1 WO2018137505 A1 WO 2018137505A1 CN 2018072455 W CN2018072455 W CN 2018072455W WO 2018137505 A1 WO2018137505 A1 WO 2018137505A1
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bond
dynamic
polymer
group
inorganic
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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
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C08J2383/08—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
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Definitions

  • the invention relates to the field of smart polymers, in particular to a dynamic polymer or composition having a hybrid bonding structure composed of dynamic covalent bonds and supramolecular hydrogen bonds and its application.
  • Polymers are also developing in the direction of functionalization, intelligence and refinement on the basis of basic performance.
  • Polymer materials are also expanded from structural materials to functional materials with effects of light, electricity, sound, magnetism, biomedicine, biomimetic, catalysis, matter separation and energy conversion, such as separation materials, biological materials, and intelligence.
  • New polymer materials with functional effects such as materials, energy storage materials, photoconductive materials, nano materials, and electronic information materials.
  • the research on the relationship between polymer structure and properties also goes from macroscopic to microscopic, from qualitative to quantitative, from static to dynamic, and gradually realizes the synthesis and preparation of polymers capable of achieving the desired functions at the molecular design level.
  • the present invention in view of the above background, provides a dynamic polymer or composition having a hybrid bonding structure comprising a dynamic inorganic boronic acid silicate bond, an optional inorganic boron oxyboron bond, and a supramolecular hydrogen bond, the dynamic polymerization
  • the material or composition orthogonally combines the dynamic inorganic boronic acid silicate bond and the optional inorganic boron oxyboron bond with the supramolecular hydrogen bond, and fully utilizes and exerts its dynamic reversibility.
  • the dynamic polymer or composition has excellent dynamic reversibility, and can exhibit functional characteristics such as stimuli responsiveness, plasticity, self-healing property, recyclability, reworkability, and good energy absorption and toughness.
  • a dynamic polymer or composition having a hybrid bonding structure comprising polymerized and/or crosslinked with a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron boron bond (BOB) a dynamically covalent polymer component in which any one B atom is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and optionally - O-; wherein at least a portion of the dynamic polymer molecules carry a hydrogen bonding group, the hydrogen bonding group participating in the formation of a hydrogen bond.
  • a dynamic inorganic boron silicate bond BO-Si
  • BOB optional inorganic boron boron bond
  • At least a portion of the dynamic polymer molecule carries a hydrogen bonding group, preferably a group having a hydrogen bonding group attached to the Si atom on the polysiloxane chain bonded to the B atom. And / or segments.
  • ingredients include, but are not limited to, other polymers, small molecules, fillers, which may also carry hydrogen bonding groups.
  • the dynamic polymer or composition is a non-crosslinked structure in which the gel point is not reached by the combination of an inorganic boronic acid borate bond, an optional inorganic boron boron bond, and a hydrogen bond.
  • Crosslinked structure Including inorganic silicon borate bonds and optional inorganic boron boron bonds, all dynamic covalent bonds are not sufficient to form dynamic covalent crosslinks above the gel point; and hydrogen bonding is not sufficient to form gel points or more. Hydrogen bond cross-linking; the sum of dynamic covalent bonds and hydrogen bonds is also insufficient to form a crosslinked structure above the gel point.
  • the dynamic polymer or composition is a crosslinked structure in which the dynamic polymer contains an inorganic boric acid silicate bond and an optional inorganic boron oxyboron bond, and cannot reach the gel point or higher.
  • the dynamic polymer or composition is a crosslinked structure in which the dynamic polymer contains an inorganic boric acid silicate bond and an optional inorganic boron oxyboron bond, and cannot reach the gel point or higher.
  • Covalent cross-linking; the inorganic boronic acid silicate bond and the inorganic boron oxyboron bond are excluded, and the hydrogen bonding reaches the hydrogen bond cross-linking above the gel point.
  • the dynamic polymer or composition is a crosslinked structure in which the inorganic boronic acid silicate bond in the dynamic covalent polymer component reaches a dynamic covalent cross-linking above the gel point, and no inorganic Boron boron boron bond; after the inorganic silicon silicate bond is excluded, the hydrogen bond acts below the gel point of the hydrogen bond crosslink.
  • the dynamic polymer or composition is a crosslinked structure in which the inorganic boronic acid silicate bond and the inorganic boron oxyboron bond in the dynamic covalent polymer component reach a dynamic covalent state above the gel point.
  • Cross-linking, the inorganic boronic acid silicate bond is above the gel point of the dynamic covalent cross-linking; after the inorganic boronic acid silicate bond and the inorganic boron oxyborate bond are excluded, the hydrogen bond acts below the gel point of the hydrogen bond cross-linking.
  • the dynamic polymer or composition is a crosslinked structure in which the inorganic boronic acid silicate bond in the dynamic covalent polymer component reaches a dynamic covalent cross-linking above the gel point, and no inorganic Boron boron boron bond; after the exclusion of the inorganic boronic acid silicate bond, the hydrogen bonding action is also above the gel point of the hydrogen bond crosslinking.
  • the dynamic polymer or composition is a crosslinked structure in which the inorganic boronic acid silicate bond and the inorganic boron oxyboron bond in the dynamic covalent polymer component reach a dynamic covalent state above the gel point.
  • Crosslinking, the inorganic boronic acid silicate bond is above the gel point of dynamic covalent crosslinking; after excluding the inorganic boronic acid silicate bond and the inorganic boron oxyborate bond, the hydrogen bonding is also above the gel point of the hydrogen bond crosslinking.
  • the dynamic polymer or composition comprises dynamics of polymerization and/or cross-linking with a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron oxyborium bond (BOB).
  • a covalent polymer component in which any one B atom is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and an optional -O
  • At least a portion of the (poly)siloxane group has a hydrogen bonding group on its pendant and/or side chain.
  • the dynamic polymer or composition comprises polymerized and/or crosslinked with a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron boron bond (BOB).
  • a dynamically covalent polymer component in which any one B atom is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and optionally - O-; at least a portion of the (poly)siloxane group has a hydrogen bonding group on a pendant group and/or a side chain; wherein the sum of the inorganic boronic acid silicate bond and the optional inorganic boron oxyboron bond is The cross-linking gel point is below.
  • the dynamic polymer or composition comprises polymerized and/or crosslinked with a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron boron bond (BOB).
  • a dynamically covalent polymer component in which any one B atom is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and optionally - O-; at least a portion of the (poly)siloxane group has a hydrogen bonding group on its pendant and/or side chain; wherein the inorganic boronic acid silicate bond reaches a dynamic covalent cross-linking above the gel point.
  • the dynamic polymer system may comprise one or more polymers.
  • a crosslinked network When a crosslinked network is present, it may be composed of one or more crosslinked networks, or may contain both non-crosslinked polymer components.
  • the dynamic polymer consists of only one crosslinked network, the dynamic covalent cross-linking and supramolecular hydrogen bonding cross-linking are simultaneously contained in the cross-linked network structure; when the dynamic polymer contains both cross-linking and
  • the non-cross-linking component may be uniformly blended/interspersed in the cross-linked network, or may be unevenly dispersed in the cross-linked network; the plurality of non-cross-linking components may be uniformly or incompatiblely blended. / Interspersed.
  • the invention also provides an energy absorbing method, characterized in that a dynamic polymer or composition having a hybrid bonding structure is provided, and energy absorption is performed as an energy absorbing material, wherein the dynamic structure of the hybrid bonding structure is provided.
  • the polymer or composition comprises a dynamic covalent polymer component formed by polymerizing or crosslinking or simultaneously polymerizing and crosslinking a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron oxy boron bond (BOB), Any one of the B atoms is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and an optional -O-;
  • the dynamic polymer molecules carry hydrogen bonding groups which participate in the formation of hydrogen bonds.
  • the inorganic boronic acid silicate bond is formed by reacting an inorganic boron compound with a siloxane 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 the compound is not bonded to a carbon atom through a boron-carbon bond, and the inorganic boron compound is selected from the group consisting of, but not limited to, boric acid, borate, boric anhydride, Boron halide and the like.
  • the (poly)siloxane compound containing a silicon hydroxy group and/or a silanol precursor means that the terminal of the compound contains a silanol group and/or a silanol precursor, and the main chain or the host structure is intentionally suitable ( Poly) compounds of the siloxane structure.
  • the hydrogen bond group is characterized in that a hydrogen bond group has both a hydrogen bond acceptor and a hydrogen bond donor; or a part of the hydrogen bond group may have a hydrogen bond donor. Another part of the hydrogen bond group contains a hydrogen bond acceptor.
  • the acceptor of the 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 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 dynamic polymer or composition having a hybrid bonding structure may be in the form of a solution, an emulsion, a paste, 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 solid foam, and the like.
  • the dynamic polymer or composition having a hybrid bonding structure may be selectively added to other polymers, additives, and fillers that may be added/used during the preparation process. Form a dynamic polymer or composition.
  • the dynamic polymer or composition properties are widely adjustable and have a wide range of applications. Specifically, it can be applied to the production of shock absorbers, cushioning materials, soundproof materials, sound absorbing materials, impact protection materials, sports protection products, military and police protective products, self-healing coatings, self-healing sheets, and Repair adhesives, bulletproof glass interlayer adhesives, energy storage device materials, tough materials, shape memory materials, seals, toys, force sensors and other products.
  • the present invention has the following beneficial effects:
  • the dynamic polymer hybrid bonding structure of the present invention incorporates a dynamic covalent inorganic silicon borate bond, a supramolecular hydrogen bond, and an optional inorganic boron boron bond, and fully utilizes and combines the bonding functions.
  • the advantage is that the dynamic covalent bond and the hydrogen bond are orthogonal to each other and coordinated to complement. This is not possible with a single key combination. Based on the differences in dynamics, responsiveness and strength between different bonds, orthogonality/sequence dynamics and response and fracture/dissociation under stress can be obtained to maximize multiple responses, energy absorption, and self-dependence. Repair, shape memory and other functions. This is not available in the prior art.
  • the dynamic covalent bond in the present invention is only linked by an inorganic boronic acid silicate bond and an optional boron oxyboron bond on the polymer network/polymer backbone chain, and the skeletal chain of the dynamic polymer is only (poly) silicon.
  • Oxygenane can fully exert the advantages of low temperature and flexibility of (poly)siloxane, which is beneficial to the dynamics of the polymer; the side group/side chain/branched/bifurcation of the (poly)siloxane skeleton chain Hydrogen bonding groups on the chain further contribute to the dynamics of hydrogen bonding.
  • the dynamic polymer has a rich structure and various properties.
  • the number of functional groups in the starting compound, the molecular structure, the molecular weight, and/or introducing a reactive group, a group that promotes dynamics, a functional group, and/or a composition of the raw material in the raw material compound Dynamic polymers with different structures can be prepared, so that dynamic polymers can exhibit a variety of properties to meet the needs of different applications.
  • Dynamic reversible bonds in dynamic polymers have strong dynamic reactivity and mild dynamic reaction conditions.
  • 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 polymers.
  • by selectively controlling other conditions such as adding auxiliaries, adjusting the reaction temperature, etc.
  • it is possible to accelerate or quench the dynamic covalent chemical equilibrium in a suitable environment in a desired state which is now Some supramolecular chemistry and dynamic covalent systems are difficult to do.
  • Dynamic polymers can exhibit functional properties. By adjusting the dynamic components in the dynamic polymer, 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 inorganic boronic acid 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, and prolongs the service life of the polymer. It enables it to be applied to certain special fields.
  • the present invention relates to a dynamic polymer or composition having a hybrid bonding structure characterized by comprising a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron boron bond (BOB) polymerization and / or cross-linked dynamic covalent polymer component, wherein any one B atom is connected to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is (poly) siloxane An alkyl group and optionally -O-; wherein at least a portion of said dynamic covalent polymer molecules carry a hydrogen bonding group that participates in the formation of a hydrogen bond.
  • a dynamic inorganic boron silicate bond BO-Si
  • BOB optional inorganic boron boron bond
  • the dynamic covalent polymer is polymerized/crosslinked by a dynamic covalent bond using an inorganic boronic silicate bond (BO-Si) bond and an optional inorganic boron oxyborium bond (BOB). to make.
  • Said inorganic boronic acid silicate bond and inorganic boron oxyboron bond which may be at any suitable position of the dynamic polymer chain backbone, either on the polymer backbone backbone or on the polymer side chains and/or branches Chain and/or bifurcated chain backbone and/or crosslinked links.
  • the invention also does not exclude the inclusion of inorganic boronic acid silicate linkages and/or inorganic boron oxyboron linkages on the pendant and/or terminal groups of the polymer chain, but the inorganic boronic silicate linkages of the present invention and optional inorganic boron oxyborides
  • the bond produces at least a polymerization. Since the boron atom is a trivalent structure, the formation of the inorganic boronic acid silicate and the inorganic boron oxyboron bond in the polymerization process by a suitable raw material component can easily cause bifurcation and can be further crosslinked.
  • the dynamic covalent polymerization/crosslinking system in the dynamic polymer is degraded once the inorganic boronic acid silicate bond and the inorganic boron oxyboron bond contained in the dynamic polymer are partially or completely dissociated; the dynamic covalent The bond is completely dissociated, and when the hydrogen bond is also completely dissociated, the polymer system can be decomposed into any one or any of the following secondary non-crosslinking units: monomer, polymer chain fragment, polymer cluster Units and the like; at the same time, mutual conversion and dynamic reversibility can be achieved between the dynamic polymer and the above units by reversible bonding and dissociation of inorganic boronic acid silicate bonds, inorganic boron oxyboron bonds, and hydrogen bonds.
  • polymerization reaction is a process of increasing the chain/action, including the 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 reaction mainly refers to the formation of a two-dimensional, three-dimensional cluster type by chemical and/or hydrogen bonding supramolecular chemical bonding of covalent bonds between reactant molecules and/or reactant molecules. And/or the process of three-dimensional infinite mesh-like products.
  • 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" as used in the embodiment of the present invention refers to an inorganic boronic acid silicate bond and an inorganic boron oxyborate bond which participate in polymerization/crosslinking.
  • the inorganic boron boron boron bond is an optional dynamic covalent bond, which can be adjusted and controlled according to the selection of the reaction material and the formulation ratio.
  • the inorganic boron boron bond is less dynamic and has a lower responsiveness than the inorganic boronic acid silicate bond. The inorganic boron boron bond can therefore be used to adjust the dynamics of the dynamic polymer.
  • the dynamic covalent polymer molecules carry hydrogen bonding groups, that is, all of the dynamic covalent polymer molecules may have hydrogen bonding groups or only some of them may be dynamically polymerized.
  • the molecule has a hydrogen bonding group.
  • any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and optionally -O-, the hydrogen bonding group is not attached or participates as part of the linking group. Connect any two or more B atoms.
  • the hydrogen bond group may be present at all or a portion of a suitable position of the polymer molecule, including but not limited to The pendant/side chain of the (poly)siloxane unit, the end group of the dynamic covalent polymer molecule, the end segment backbone/side group/side chain of the dynamic covalent polymer molecule; the end segment refers to A segment of the dynamic covalent bond is connected to only one end.
  • the Si atoms of the (poly)siloxane group are attached to a group and/or a segment having a hydrogen bonding group.
  • the (poly)siloxane unit attached to the B atom may not be bonded to a group and/or a segment having a hydrogen bond group.
  • a group having a hydrogen bonding group and/or a segment are attached to a Si atom on a polysiloxane chain bonded to a B atom, which facilitates dynamic covalent bond and hydrogen bond to function positively.
  • the hydrogen bond group participates in the formation of a hydrogen bond.
  • the hydrogen bonding may be polymerization, intrachain chain formation, or interchain crosslinking.
  • hydrogen bonding can be achieved by hydrogen bonding groups in the same compound/polymer, or by hydrogen bonding groups in different compounds/polymers.
  • the (poly) siloxane group which is the main structure of the main chain or - (SiR 1 R 2 -O) n - units, wherein, n-siloxane units (SiR 1 R 2
  • the number of -O) which is an integer greater than or equal to 1, may be a fixed value or an average value;
  • R 1 and R 2 are groups/segments attached to a silicon atom, each independently selected from H, a halogen atom, and any other suitable organic and inorganic groups / segments include a hydroxyl group, and other reactive organic group; preferably an organic group / segment, more preferably a carbon-containing organic radical / segment;
  • R 1 preferably at least partly And/or R 2 is a group and/or a segment with a hydrogen bonding group.
  • the (poly)siloxane-based linker 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, H, star, dendritic, hyperbranched), 2D/3D clusters, even crosslinked particles, and combinations thereof.
  • the dynamic polymer contained in the dynamic polymer molecule may have one or more arbitrary suitable topologies including, but not limited to, linear, cyclic (including but not limited to single ring, multiple Rings, nested rings, bridged rings), 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 structures, and combinations thereof form.
  • suitable topologies including, but not limited to, linear, cyclic (including but not limited to single ring, multiple Rings, nested rings, bridged rings), 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 structures, and combinations thereof form.
  • any crosslinked network is a dynamic crosslinked network comprising dynamic covalent crosslinks and/or supramolecular hydrogen bond crosslinks; once the dynamic crosslinks dissociate, the crosslinked structures are dissociated.
  • the composition of the dynamic polymer contains filled conventional covalently crosslinked particles (including fibers and flake particles).
  • the dynamic polymer or composition is a non-crosslinked structure in which the gel point is not reached by the combination of an inorganic boronic acid borate bond, an optional inorganic boron boron bond, and a hydrogen bond.
  • Crosslinked structure Including inorganic silicon borate bonds and optional inorganic boron boron bonds, all dynamic covalent bonds are not sufficient to form dynamic covalent crosslinks above the gel point; and hydrogen bonding is not sufficient to form gel points or more. Hydrogen bond cross-linking; the sum of dynamic covalent bonds and hydrogen bonds is also insufficient to form a crosslinked structure above the gel point.
  • the polymer system is still a non-crosslinked structure and has a rheological property corresponding to a non-crosslinked structure.
  • the topology of the non-crosslinked dynamic covalent polymer may have a linear form, a ring shape (including but not limited to a single ring, a polycyclic ring, a bridged ring, a nested ring), and branching (including but not limited to These include, but are not limited to, comb, H, star, dendritic, hyperbranched, clusters, and combinations thereof.
  • the polymer chain has a side group, a side chain, a bifurcated chain, a branch, and the side groups, side chains, bifurcation chains, and branches can continue to have side groups, side chains, bifurcation chains, and branches, that is, Has a multi-level structure.
  • the dynamic polymer or composition is a crosslinked structure in which the dynamic covalent polymer comprises an inorganic boronic acid silicate bond and an optional inorganic boron oxyboron bond, and the condensation cannot be achieved.
  • the dynamic polymer or composition is a crosslinked structure in which the dynamic covalent polymer component comprises an inorganic boronic acid silicate bond and an optional inorganic boron oxyboron bond. Covalent cross-linking above the gel point; the inorganic boronic acid silicate bond and the optional inorganic boron oxyboron bond are excluded, and the hydrogen bonding reaches the hydrogen bond cross-linking above the gel point. Once the hydrogen bonds are completely dissociated, the polymer system will not form a crosslinked structure.
  • the dynamic polymer or composition is a crosslinked structure in which the inorganic boronic acid silicate bond in the dynamic covalent polymer component reaches a dynamic covalent cross-linking above the gel point, and no inorganic Boron boron boron bond; after the inorganic silicon silicate bond is excluded, the hydrogen bond acts below the gel point of the hydrogen bond crosslink. Once the dynamic covalent bond is completely dissociated, the polymer system will not form a crosslinked structure.
  • the dynamic polymer or composition is a crosslinked structure in which the inorganic boronic acid silicate bond and the inorganic boron oxyboron bond in the dynamic covalent polymer component reach a dynamic covalent state above the gel point.
  • Cross-linking, the inorganic boronic acid silicate bond is above the gel point of the dynamic covalent cross-linking; after the inorganic boronic acid silicate bond and the inorganic boron oxyborate bond are excluded, the hydrogen bond acts below the gel point of the hydrogen bond cross-linking.
  • the dynamic polymer or composition is a crosslinked structure in which the inorganic boronic acid silicate bond in the dynamic covalent polymer component reaches a dynamic covalent cross-linking above the gel point, and no inorganic Boron boron boron bond; after the exclusion of the inorganic boronic acid silicate bond, the hydrogen bonding action is also above the gel point of the hydrogen bond crosslinking. Even if one of the dynamic covalent bonds and the hydrogen bonds are completely dissociated, the polymer system can maintain a dynamic crosslinked structure.
  • the dynamic polymer or composition is a crosslinked structure in which the inorganic boronic acid silicate bond and the inorganic boron oxyboron bond in the dynamic covalent polymer component reach a dynamic covalent state above the gel point.
  • Crosslinking, the inorganic boronic acid silicate bond is above the gel point of dynamic covalent crosslinking; after excluding the inorganic boronic acid silicate bond and the inorganic boron oxyborate bond, the hydrogen bonding is also above the gel point of the hydrogen bond crosslinking. Even if one of the dynamic covalent bonds and the hydrogen bonds are completely dissociated, the polymer system can maintain a dynamic crosslinked structure.
  • the dynamic polymer or composition comprises dynamics of polymerization and/or cross-linking with a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron oxyborium bond (BOB).
  • a covalent polymer component in which any one B atom is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and an optional -O
  • At least a portion of the (poly)siloxane group has a hydrogen bonding group on its pendant and/or side chain.
  • the dynamic polymer or composition comprises polymerized and/or crosslinked with a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron boron bond (BOB).
  • a dynamically covalent polymer component in which any one B atom is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and optionally - O-; at least a portion of the (poly)siloxane group has a hydrogen bonding group on a pendant group and/or a side chain; wherein the sum of the inorganic boronic acid silicate bond and the optional inorganic boron oxyboron bond is The cross-linking gel point is below.
  • the dynamic polymer or composition comprises polymerized and/or crosslinked with a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron boron bond (BOB).
  • a dynamically covalent polymer component in which any one B atom is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and optionally - O-; at least a portion of the (poly)siloxane group has a hydrogen bonding group on its pendant and/or side chain; wherein the inorganic boronic acid silicate bond reaches a dynamic covalent cross-linking above the gel point.
  • the dynamic polymer or constituent system may comprise one or more polymers.
  • a crosslinked network When a crosslinked network is present, it may be composed of one or more crosslinked networks, or may contain both non-crosslinked polymer components.
  • the dynamic polymer consists of only one crosslinked network, the dynamic covalent cross-linking and supramolecular hydrogen bonding cross-linking are simultaneously contained in the cross-linked network structure; when the dynamic polymer consists of two or more
  • a crosslinked network is constructed, it may be composed of two or more cross-linked networks which are mutually blended, or may be composed of two or more cross-linked networks interpenetrated, or two or more parts may be mutually Interspersed and/or blended crosslinked network, but the invention is not limited thereto; wherein two or more crosslinked networks may be the same or different, and may be partially containing only supramolecular hydrogen bonding, or Each crosslinked network contains both a combination of dynamic covalent crosslinking and supramolecular hydrogen bonding.
  • the non-crosslinked components may be uniformly blended/interspersed in the crosslinked network, or may be unevenly dispersed in the crosslinked network; between the plurality of non-crosslinked components Blend/interpenetrate can be evenly or incompatible.
  • Blend/interpenetrate can be evenly or incompatible.
  • some of the polymers may have only hydrogen bonds, and some or all of the polymers may contain both dynamic covalent bonds and hydrogen bonds.
  • the dynamic polymer of the present invention when dynamic covalent crosslinking reaches above the gel point of dynamic covalent crosslinking in at least one crosslinked network, it is ensured that even in the case of only one crosslinked network, even if all When the supramolecular hydrogen bond is dissociated, the polymer may also have a crosslinked structure under specific conditions. When two or more crosslinked networks are present, there may be interactions between the different crosslinked networks (including the dynamic covalent boronic borate linkages and/or supramolecular hydrogen bonding), or they may be independent of one another.
  • the inorganic boronic acid silicate bond and the inorganic boron oxyboron bond have differences in dynamics, responsiveness and strength, the two are different from the hydrogen bond in terms of dynamicity, responsiveness and strength, so the dynamic covalent bond Designed in combination with hydrogen bonding, it regulates polymer structure and achieves desirable and diverse properties.
  • dynamic difference sequential dynamic behavior can be generated; by responsiveness, orthogonal and/or synergistic and/or sequential responses can be generated; based on the difference in intensity, multiple levels of external force dissociation can be generated.
  • the polymers of the present invention can exhibit stress/strain responsiveness, particularly dilatancy properties.
  • the dynamic polymer When the dynamic polymer is a non-crosslinked structure, even if the system expands, it will remain in a viscous flow state without generating an elastic state, which is beneficial to completely lose mechanical energy through the viscous flow.
  • the dynamic polymer When the dynamic polymer is a dynamically crosslinked structure, the system will undergo viscous elastic transformation or elastic reinforcement when the expansion flow occurs, and the viscous loss is avoided while reducing or reducing the material damage under the force. Both situations have their own characteristics and advantages.
  • the crosslinked network structure of the dynamic polymer may be blended and/or interspersed with one or more of the dynamic polymers containing the BO-Si bond and the optional BOB bond.
  • the topology of the other polymers may have a linear shape, a ring shape (including but not limited to a single ring, a polycyclic ring, a bridged ring, a nested ring), and branching (including but not limited to including but not limited to Comb, H, star, dendritic, hyperbranched), clusters or even crosslinked particles and combinations thereof.
  • the polymer chain has a side group, a side chain, a bifurcated chain, a branch, and the side groups, side chains, bifurcation chains, and branches can continue to have side groups, side chains, bifurcation chains, and branches, that is, Has a multi-level structure.
  • present invention may have other various hybrid embodiments, and those skilled in the art can implement the logic and the context of the present invention reasonably and effectively.
  • the invention also provides an energy absorbing method, characterized in that a dynamic polymer or composition having a hybrid bonding structure is provided, and energy absorption is performed as an energy absorbing material, wherein the dynamic structure of the hybrid bonding structure is provided.
  • the polymer or composition comprises a dynamic covalent polymer component formed by polymerizing or crosslinking or simultaneously polymerizing and crosslinking a dynamic inorganic boron silicate bond (BO-Si) and an optional inorganic boron oxy boron bond (BOB), Any one of the B atoms is bonded to three -O-, and any one of the divalent or bivalent or higher linking groups connecting at least two B atoms is a (poly)siloxane group and an optional -O-;
  • the dynamic polymer molecules carry hydrogen bonding groups which participate in the formation of hydrogen bonds.
  • 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 borate bond may be formed by reacting an inorganic boron compound with a siloxane 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 (poly)siloxane compound containing a silicon hydroxy group and/or a silanol precursor means that the structure of the compound contains a silanol group and/or a silanol precursor, and the main chain or the host structure is any suitable (poly) a compound of a siloxane structure.
  • the main chain or main structure of the (poly)siloxane consists of -(SiR 1 R 2 -O) n - units, wherein n is the number of siloxane units (SiR 1 R 2 -O), which is greater than Or an integer equal to 1, which may be a fixed value or an average value; R 1 and R 2 are groups/segments attached to a silicon atom, each independently selected from H, a halogen atom, and any other suitable organic or inorganic group.
  • a cluster/segment comprising a hydroxyl group, and other reactive organic groups; preferably an organic group/segment, more preferably a carbon-containing organic group/segment; preferably at least a portion of R 1 and/or R 2 is carried a group and/or a segment of a hydrogen bonding group.
  • the other reactive organic groups are only used for graft modification of (poly)siloxane, such as obtaining hydrogen bond groups, changing hydrophobicity, linking fluorophores, etc., and are not used for linking silicon borate containing inorganic boronic acid. The group/segment of the bond.
  • the (poly)siloxane compound containing a silicon hydroxy group and/or a silanol precursor is selected from the group consisting of a small molecule siloxane compound and a macromolecular polysiloxane compound, and may be an organic or inorganic compound including silica.
  • the (poly)siloxane compound can 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, H, star, dendritic, hyperbranched), 2D/3D clusters, even crosslinked particles, 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.
  • One (poly)siloxane may contain a plurality of silyl groups, a plurality of Si atoms may contain a hydroxyl group, and the same Si atom may also contain a plurality of hydroxyl groups.
  • 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.
  • Suitable silanols precursors example such as: Si-Cl, Si-CN , Si-CNS, Si-CNO, Si-SO 4 CH 3, Si-OB (OCH 3) 2, Si-NH 2, Si-N ( CH 3 ) 2 , Si-OCH 3 , Si-COCH 3 , Si-OCOCH 3 , Si-CONH 2 ,
  • Si-ON C(CH 3 ) 2 , Si-ONa.
  • one of the silanol precursors can be hydrolyzed to give a silyl group.
  • Si-Z is a functional group.
  • One (poly)siloxane may contain a plurality of silanol precursors, a plurality of Si atoms may contain a Z group, and the same Si atom may also contain a plurality of Z groups.
  • the silanols can be at the end of the polymer chain or at the side groups of the polymer chain; likewise, for organopolysiloxanes containing silicon hydroxy precursors, the silanol precursor can be in the polymer
  • the ends of the chains can also be pendant to the polymer chain.
  • the silanol/silicon hydroxy body can likewise be end groups or pendant groups.
  • the (poly)siloxane compound containing a silicon hydroxy group and/or a silanol group precursor can be exemplified as follows, and the present invention is not limited to this:
  • any suitable combination of an inorganic boron compound and a siloxane compound may be used to form an inorganic boronic acid silicate bond, preferably an inorganic boronic acid and a silicon hydroxy group-containing organopolysiloxane, an inorganic boronic acid and a silicon-containing hydroxy precursor.
  • Organopolysiloxane, inorganic borate (salt) and organopolysiloxane containing silicon hydroxy group to form a silicon borate bond more preferably inorganic boric acid and silicon-containing hydroxyl group organopolysiloxane, inorganic boric acid
  • the ester and the organopolysiloxane containing a silicon hydroxy group form a silicon borate bond, and it is more preferred to use an inorganic borate and an organopolysiloxane containing a silicon hydroxy group to form a silicon borate bond.
  • the inorganic boron boron boron bond may be formed in any suitable manner, preferably by inorganic dehydration with boric acid, and by the de-alcoholization of inorganic boronic acid with an inorganic boronic acid ester.
  • a silicon atom on a (poly)siloxane group preferably bonded to a boron atom may be bonded to the hydrogen bond group, or may be contained in a polymer system.
  • Other compounds contain hydrogen bonding groups including, but not limited to, other carbon chain polymers, carbon chain polymers, elemental polymers, preferably siloxanes, to improve compatibility.
  • the hydrogen bonding group may be attached to the silicon atom of the (poly)siloxane group/compound by any suitable chemical reaction, and may be formed before or after or simultaneously with the formation of the inorganic boronic silicate bond Hydrogen bond group.
  • the number of teeth that form a hydrogen bond to the hydrogen bond group 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 dynamics of the hydrogen bond crosslinking is strong, and the dynamic performance such as self-healing property and energy absorption property can be better provided. In an embodiment of the invention, hydrogen bonding of no more than four teeth is preferred.
  • the number of teeth is a number of hydrogen bonds composed of a donor (D, that is, a hydrogen atom) of a hydrogen bond group and a receptor (A, that is, an electronegative atom accepting a hydrogen atom), and each DA is combined into one tooth.
  • D that is, a hydrogen atom
  • A that is, an electronegative atom accepting a hydrogen atom
  • the hydrogen bonding group may be any suitable hydrogen bonding group.
  • one hydrogen bond group has both a hydrogen bond acceptor and a hydrogen bond donor; or a part of the hydrogen bond group may contain a hydrogen bond donor, and another part of the hydrogen bond group may contain a hydrogen bond acceptor; Body and donor.
  • the acceptor of the 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 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 hydrogen bond group preferably contains both the structures represented by the general formulae (1) and (2).
  • the 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 the like. Derivatives.
  • the hydrogen bond group attached to the silicon atom of the (poly)siloxane group/compound contains both a hydrogen bond donor and a acceptor so that it can be directly Hydrogen bonding is formed without the need for other components, simplifying the polymer composition and preparation process.
  • the pendant hydrogen bonding group on the pendant group and the terminal hydrogen bonding group on the terminal group may have the following structure, 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.
  • more than one of the above-mentioned side hydrogen bond groups may be contained in the same polymer, and more than one of the above-described side hydrogen bond groups may be contained in the same network.
  • the compound to which the side hydrogen bond group can be introduced is not particularly limited, and the type and mode of the reaction for forming the 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.
  • Preferred backbone hydrogen bonding groups on the appropriate polymer component backbone and/or side chain/branched/branched chain backbone are for example (but the 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 dynamic polymer may be formed by forming an inorganic boronic silicate bond and an optional inorganic boron oxyboron bond, or may be prepared by first containing the inorganic boronic silicate bond and optionally The inorganic boron boron bond-bonded compound is repolymerized/crosslinked to form the dynamic polymer.
  • the dynamic polymer or composition having a hybrid bonding structure may be in the form of a solution, an emulsion, a paste, 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 gel The content of the small molecular weight component contained in the content is generally not less than 50% by weight.
  • the dynamic polymer ordinary solid has a fixed shape and volume, high strength and high density, and is suitable for high-strength explosion-proof wall or instrument casing;
  • the elastic body has the general property of ordinary solid, but the elasticity is better and the softness is more High, more suitable as energy absorbing material such as damping/damping;
  • dynamic polymer gel is soft in texture, has good energy absorption and elasticity, and is suitable for preparing high damping energy absorbing materials;
  • dynamic polymer foam material has density The soft foam material also has good elasticity and energy absorbing properties when it is low in weight, light in weight, and high in specific strength.
  • 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.
  • the raw material formulation component for preparing the dynamic polymer, in addition to the inorganic boron compound and the (poly)siloxane compound, includes other polymers, additives, and fillers that can be added/used, which can be added/
  • the use may be in the form of blending, participating in a 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 bonding structure, or in the preparation of the dynamic polymer. Improve the performance of processing.
  • 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, polysulfide 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 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 amides; fatty alcohols and polyols such as stearyl alcohol, cetyl alcohol, pentaerythritol; metal
  • 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 solution, an emulsion, a paste, a gel, or the like, or a solid polymer in the form of a film, a block, a foam, or the like may be selected to remove the solvent. sample.
  • 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 dilatancy and dynamics of dynamic polymers By utilizing the dilatancy and dynamics of dynamic polymers, it can be applied to oil well production, fuel explosion protection, etc. It can also be used to prepare speed locks for roads and bridges; it can also be used to make damping shock absorbers. It is used for vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings. 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. It can also be used as energy absorption.
  • the cushioning material is applied to cushioning packaging materials, sports protective products, impact protection products, and protective materials for military and police, thereby reducing vibration and impact of articles or human bodies under external force, including shock waves generated by explosions; Energy materials, sound insulation, noise reduction, etc.
  • the dynamic energy and dynamic difference between the dynamic covalent bond and the hydrogen bond can also be used as a shape memory material.
  • the deformation of the material during the loading process can be recovered;
  • stress-sensitive polymer materials can be prepared, and some can be used to prepare toys and fitness materials with magical effects of fluidity and elastic conversion, and can also be used to make seismic shear plates. Or a cyclic stress bearing tool or a stress monitoring sensor.
  • dynamic polymers Taking full advantage of the dynamic properties of dynamic polymers, it can be prepared with self-repairing adhesive, which can be applied to the adhesive of various materials. It can also be used as bullet-proof glass interlayer adhesive. It can also be used for preparation with good plasticity and can be recovered and repaired.
  • the polymer sealing adhesive can be designed to produce a scratch-resistant coating with self-repairing function, thereby prolonging the service life of the coating and achieving long-lasting corrosion protection of the base material. It has shown great application potential in the fields of military industry, aerospace, electronics and bionics.
  • 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.
  • the surface strength of the polymer material is low and amorphous. Under the action of external force, the material is easy to stretch and exhibits good tensile toughness, and can be stretched to a large extent without breaking (elongation at break exceeds 2000). %). When defects appeared on the surface, it was heated in a vacuum oven at 60 ° C for 4 hours, and the defects disappeared.
  • the dynamic polymer can remain transparent for a long period of time, and the polymer can be used as a super hot melt adhesive or a room temperature self-adhesive material with self-healing properties, and can also be used as a medium for a speed locker for a bridge. And road construction.
  • methoxy-terminated polydimethyl-methylhydrogen silicone oil low silicon-based hydrogen content
  • acrylamine to control the active hydrogen atom of polydimethyl-methylhydrosilane oil in the reaction (direct and
  • the ratio of the number of moles of the hydrogen atom to which Si is bonded to the number of moles of the double bond in the acrylamine is about 1:1, and an addition reaction is carried out using chloroplatinic acid as a catalyst to obtain a methyl silicone oil having a polyamino group in a side group. That is, a polyorganopolyamine.
  • the above polyorganopolyamine and 4-fluorophenyl isocyanate are mixed at a molar ratio of amino group to isocyanate of 1:1, and triethylamine is used as a catalyst to react in dichloromethane to obtain a pendant group containing a ureido group and Trimethoxysilane group organopolysiloxane.
  • the foamed material was made into a block sample having a size of 20.0 ⁇ 20.0 ⁇ 20.0 mm, and a compression test was performed using a universal testing machine at a compression rate of 2 mm/min, and the compressive strength of the sample was measured to be 0.76 ⁇ 0.12 MPa.
  • the obtained silicone foam material has excellent heat insulation performance, and has the advantages of small density, high specific strength, good dimensional stability, recyclability and self-repair, and can be applied to refrigerators, freezers and pipes. In the field of insulation, it can also be used as building insulation material.
  • 3-Aminopropyldimethylmethoxysilane and boric acid were mixed in an equimolar ratio, and after heating to 60 ° C to dissolve by stirring, a small amount of water was added to react for 3 hours to obtain a boric acid compound containing a silicon borate bond.
  • the above-mentioned organopolysiloxane containing a side hydrogen bond group and the above-mentioned boric acid compound containing a silicon borate bond are mixed at a molar ratio of Si-OCH 3 group and B-OR group 1:1, and the temperature is raised to 80 ° C to be uniformly mixed. Thereafter, 4 ml of deionized water and 1 g of talc having a particle diameter of 50 nm were added, and polymerization was carried out under stirring to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond.
  • the obtained polymer sample has a rubbery shape and can be stretched in a wide range at a slow stretching rate to cause creep; however, if it is rapidly stretched, it exhibits an elastic characteristic and can be quickly restored by pressing with a finger.
  • This product can be used as a toy with magical elasticity.
  • the methoxy-terminated polymethylvinylsiloxane (molecular weight about 4500) and 2-tert-butoxycarbonylaminoethanethiol are mixed in a molar ratio of 1:1 to thiol, and added to 2-tert-butoxy 0.2% by weight of carbonyl aminoethanethiol photoinitiator benzoin dimethyl ether (DMPA), after being fully stirred, placed in an ultraviolet cross-linker for 4 h, to obtain an organopolysilicon containing a side hydrogen bond group.
  • DMPA carbonyl aminoethanethiol photoin dimethyl ether
  • 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.
  • Mix and warm to 80 ° C to mix well add 4.2g microsphere foaming agent, 2g ammonium polyphosphate, 3g carbon black, 3g 1000 mesh conductive carbon black, 2.5g ferric oxide, 4ml deionized water, stir for 30s After the mixture was uniformly mixed, the reaction was further stirred for 4 hours in a nitrogen atmosphere to prepare a soft foamed polysiloxane material containing a side hydrogen bond group and a silicon borate bond.
  • the reaction product was poured into a suitable mold, placed in a vacuum oven at 60 ° C for 24 hours, then cooled to room temperature for 30 minutes, and foamed by a flat vulcanizing machine, wherein the molding temperature was 140-150 ° C, molding time For 10-15min, the pressure is 10MPa, the surface of the sample is pressed with a finger, the sample can rebound quickly, showing good elasticity, and the sample can also be extended within a certain range.
  • the cross-linked polymer sample has high toughness, resilience, and flame retardancy, and can be made into a flame-retardant filling material, and the surface is coated with a fabric such as leather or cloth to form a soft furniture.
  • N-allyl-1H-imidazole-1-carboxamide and 5-vinyl-2-pyrrolidone are mixed well in a molar ratio of 1:2, dissolved in 1-butyl-3-methylimidazolium hexafluorophosphate Salt ([C 4 MIM] PF 6 ) ionic liquid, adding 5 mol% of AIBN as an initiator, fully swelled in the first network polymer, stirred well, and then poured into a glass plate mold with a silica gel gasket In the ultraviolet cross-linking device for 10 h, a dynamic polymer ionic liquid gel containing a side hydrogen bond group and a silicon borate bond is obtained.
  • the dynamic polymer ionic liquid gel was replaced by deionized water to remove the ionic liquid, and the deionized water was replaced once every 12 hours, and replaced four times, thereby obtaining a dynamic polymerization containing a side hydrogen bond group and a silicon borate bond. Hydrogel.
  • the hydrogel prepared in this example has a modulus of 13 kPa, a strain of up to 16 times, and a breaking stress of 59 kPa.
  • the hydrogel can be used as a cushioning packaging material for fragile items.
  • 3-Chloropropyldimethylmethoxysilane and boric acid were mixed in an equimolar ratio, and after heating to 60 ° C to dissolve by stirring, a small amount of water was added for 3 hours to obtain a boric acid compound containing a boronic borate bond.
  • the above-mentioned organopolysiloxane containing a hydrogen bond group in the side group and the above-mentioned boric acid compound containing a silicon borate bond are mixed at a molar ratio of siloxane to boric acid 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 side hydrogen bond group and a silicon borate bond.
  • N-allyl-1H-benzimidazol-2-amine, 5-butan-2-yl-5-prop-2-enyl-1,3-diazinenon-2,4,6 - Triketone is mixed at a molar ratio of 1:1, and 100 g of the mixture and 100 g of the obtained dynamic polymer are added, and 5 mol% of AIBN is added as an initiator and 5 wt% of carbon fiber, and heated to 80 ° C for 8 h, and subjected to radical polymerization.
  • a dynamic polymer containing a side hydrogen bond group and a silicon borate bond is obtained.
  • the mechanical properties of the dynamic polymer tensile strength of 9.8 MPa and elongation at break of 750%.
  • the product has good toughness and can be used to prepare polymer sealing glue, self-repairing adhesive and interlayer adhesive. Moreover, it has strong mechanical properties and excellent impact resistance, and can be used for preparing an impact resistant protective pad.
  • 3-bromopropyldimethylmethoxysilane and tripotassium 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 hours to obtain a silicon borate-containing bond. Borate compound.
  • the above-mentioned fluorine group-containing polyorganosiloxane containing a hydrogen bond group and the above-mentioned borate compound containing a boronic acid borate bond are mixed in a molar ratio of SiOCH 3 and BOK of about 1:1, and a small amount of water is added thereto. After stirring uniformly at °C, the reaction was carried out for 6 hours to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond.
  • 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 scratch resistant and can be recycled and reused.
  • a methoxy-terminated polymethylphenyl-methylvinylsiloxane (molecular weight of about 8,000) and 2-mercaptoimidazole are mixed in a molar ratio of a double bond to a mercapto group of 1:1, and 0.2 wt% of light is added.
  • the initiator benzoin dimethyl ether (DMPA) was stirred and placed in an ultraviolet cross-linker for 4 h to obtain an organopolysiloxane containing a side hydrogen bond group.
  • the above-mentioned organopolysiloxane having a hydrogen bond group in the pendant group and the isopropanol pinacol borate are mixed at a molar ratio of Si-OCH 3 and B-OR of 1:1, and a small amount of water is added at 60 ° C. After stirring uniformly, the reaction was carried out for 8 hours to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond as the first network polymer.
  • 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.
  • methoxy-terminated polymethylvinylsiloxane molecular weight about 3000
  • 5-mercaptomethyluracil molecular weight about 3000
  • a photoinitiator 0.2% by weight of a photoinitiator is added.
  • Benzoin dimethyl ether (DMPA) after sufficient agitation, was placed in an ultraviolet cross-linker for 4 h to obtain an organopolysiloxane containing a side hydrogen bond group.
  • organopolysiloxane containing a side hydrogen bond group and 2,6-di-tert-butyl-4-tolyldibutyl orthoborate are mixed at a molar ratio of Si-OCH 3 and B-OR of 1:1. After heating to 80 ° C and mixing uniformly, 4 ml of deionized water was added, and polymerization was carried out under stirring to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond as the first network polymer. .
  • the product exhibits good viscoelasticity, good isolation shock and stress buffering, and also exhibits excellent hydrolysis resistance.
  • the healing of the damaged portion can be achieved by heating to re-form, and the self-repair and recycling of the material can be realized.
  • the organopolysiloxane having a hydrogen bond group in the above-mentioned pendant group and the diphenylhydroborate are mixed at a molar ratio of 1:1 to the Si-OCH 3 group and the B-OR group, and the mixture is heated to 80 ° C to be mixed. After homogenization, 2 ml of deionized water and 30 mg of graphene were added, ultrasonically dispersed, swollen in the first network, and polymerization was carried out under stirring to prepare a dynamic polymerization containing a side hydrogen bond group and a silicon borate bond. Things.
  • the polymer sample can be used as an electronic packaging material or an adhesive, which can be recycled and reused during use, and the polymer sample has a long service life; and because the conductivity can occur with pressure or tension Sensitive response, suitable as a force sensor.
  • the ratio of the number of moles of double bonds in ethyl)-N'-2-propen-1-yl-urea is about 1:1, and an addition reaction is carried out using chloroplatinic acid as a catalyst to obtain a hydrogen bond group of a pendant group.
  • Organopolysiloxane Organopolysiloxane.
  • organopolysiloxane containing a side hydrogen bond group and tris(4-chlorophenyl) borate are mixed at a molar ratio of Si-OCH 3 group and B-OR group 1:1, and the temperature is raised to 80 ° C. After uniformly mixing, 4 ml of deionized water was added, and polymerization was carried out under stirring to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond as the first network polymer.
  • the above polycarbonate PLimC and 2-aminoethanethiol, 2-tert-butoxycarbonylaminoethanethiol are mixed in a ratio of double bond group and sulfhydryl group of 10:5:5, and 0.3 wt% of AIBN and 4 wt% are added.
  • the polymer foamed microspheres and 80% by weight of the first network polymer were quickly stirred by professional equipment to generate bubbles, and then quickly injected into the mold, cured at room temperature for 30 min, and then cured at 80 ° C for 4 h to obtain a A binary interpenetrating network composite foam with a side hydrogen bond group and a silicon borate bond.
  • 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.
  • the polymer product has a certain viscoelasticity and exhibits a colloidal state.
  • the surface of the sample is smooth, soft, has good resilience and a certain compressive strength, and can be stretched to some extent. It was made into a dumbbell-shaped spline of 80.0 ⁇ 10.0 ⁇ (2.0-4.0) mm, and tensile test was performed by a tensile tester at a tensile rate of 50 mm/min, and the tensile strength of the sample was measured to be 6.28 ⁇ 1.44 MPa. The tensile modulus was 11.16 ⁇ 1.75 MPa, and the elongation at break was 423 ⁇ 148%. After scratching the surface of the polymer with a blade, the scratches were applied and placed in an oven at 80 ° C for 6 hours, and the scratches were self-healing.
  • 5-Aminopentyldimethylmethoxysilane and tri-butylborate 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 hours to obtain a silicon borate.
  • a borate compound of the bond is obtained.
  • the above-mentioned organopolysiloxane 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 Si-OCH 3 group and B-OR group, and a small amount is added dropwise.
  • the 20% aqueous acetic acid solution was stirred at 50 ° C, and then 2 ml of triethylamine was added dropwise to continue the reaction for 4 h to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond. 1 network polymer.
  • a certain amount of hydrogen-bonding group-containing monomer 13a and cyclooctene are mixed and dissolved in dichloromethane, and the ratio of the molar ratio of the two is controlled to be about 1:2, and the first network polymerization is added to 80 wt% of the monomer.
  • the polymer sample not only exhibits very good tensile toughness, but also has good plasticity and resilience; it can be prepared into different shapes according to the size of the mold, and the depression can be quickly recovered after pressing the surface. It can be made into various types of seals.
  • the above polyorganopolyamine and 2-mercaptoisothiocyanate are mixed at a molar ratio of amino group to isocyanate of 1:1, and triethylamine is used as a catalyst to react in dichloromethane to obtain a side group containing thiourea.
  • the above-mentioned side group contains a thiourea group organopolysiloxane and boric acid 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, and then a small amount of water is added thereto.
  • the polymerization was carried out under stirring to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond 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 14b containing a thiourethane group.
  • the olefin monomer 14a and the olefin monomer 14b are thoroughly mixed at a molar ratio of 50:50, 80 parts of epoxy soybean oil is added, stirred well, and then swollen in the first network polymer, and then 5 mol% of AIBN is added to pass the free radical.
  • Polymerization prepared a epoxidized soybean oil-swellable dynamic polymer organogel containing a side hydrogen bond group and a silicon borate bond.
  • the epoxidized soybean oil-swelled polymer organogel not only exhibits good mechanical properties, but also has self-repairing, pH response and other functional characteristics.
  • the prepared organogel has excellent toughness, and the network structure of the gel is not damaged by external force. Dynamic polymer gels are widely used in targeted drug release, cell separation and labeling, protein adsorption and separation due to their unique mechanical properties, flexibility and permeability.
  • the above-mentioned organopolysiloxane containing a side hydrogen bond group and boric acid are mixed 1:1 according to a molar ratio of a Si—OCH 3 group and a B-OH group, and the mixture is heated to 80° C. and uniformly mixed, and then 100 mL of 1-butyl- 3-methylimidazolium hexafluorophosphate ([C 4 MIM] PF 6 ) ionic liquid, fully swelled in the first network, and then added 45 mg of graphene and a small amount of water, and polymerized under stirring to prepare a kind High-strength ionic liquid dynamic polymer gel with side hydrogen bonding groups and silicon borate bonds.
  • the ionic liquid gel has a modulus of 32 kPa, a strain of 27 times, and a fracture stress of 176 kPa.
  • This product can be used as a stress-carrying material in a fine mold. It has a load-bearing effect and a certain deformability. It acts as a buffer. When cracks or breakage occur, it can also be repaired by heating.
  • 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.
  • Deionized water was subjected to 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 above-mentioned organopolysiloxane containing a side hydrogen bond group and benzyl dihydroborate are mixed in a molar ratio of 1:1 to a Si-OCH 3 group and a B-OR group, and are sufficiently swollen to the first network polymer.
  • Meta-interpenetrating network dynamic polymer After heating to 80 ° C and mixing uniformly, 4 ml of deionized water was added, and a small amount of acetic acid was added dropwise, and the reaction was further stirred in a nitrogen atmosphere for 4 h to prepare a kind of a side containing a hydrogen bond group and a silicon borate bond.
  • the polymer sample not only exhibits a certain strength, but also exhibits excellent toughness. It can be used as a sealing strip, sealing ring or elastic cushioning pad; the material shows good performance during use. Viscoelastic, with good isolation shock and stress buffering effect, also shows excellent hydrolysis resistance. When the surface is damaged, the healing of the damaged portion can be achieved by heating to re-form, and the self-repair and recycling of the material can be realized.
  • the above organopolysiloxane containing a side hydrogen bond group and a trimethoxysilane group and triethyl borate are mixed 1:1 according to a molar ratio of the Si—OCH 3 group and the B-OR group, and the temperature is raised to 80° C. After uniformly mixing, 4 ml of deionized water was added, and polymerization was carried out under stirring to prepare a dynamic polymer containing a side hydrogen bond group and a silicon borate bond as the first network polymer.
  • the surface of the polymer product is smooth and has a certain surface hardness.
  • the glass microfibers are uniformly distributed in the matrix, and the cross-section is placed in an oven at 120 ° C for 12 h (in this process, the cross section can be selected) With a slight wetting), the material can be reshaped and exhibits recyclability compared to conventional epoxy cured materials.
  • the polymer material can be used for manufacturing electrical switching devices, printed circuit boards, electronic components of instrument panel electronic packaging materials, and can also be used for fixing various electronic components and metal parts in use.
  • the polymer material has a long service life.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne un polymère ou une composition dynamique présentant une structure de liaison hybride, comprenant une liaison ester inorganique dynamique de borate de silicium, et une liaison bore-oxygène-bore inorganique en option et une liaison hydrogène supramoléculaire. Le polymère dynamique combine orthogonalement la liaison ester inorganique dynamique du borate de silicium et la liaison bore-oxygène-bore inorganique en option avec la liaison hydrogène supramoléculaire, en utilisant et en développant complètement les réversibilités dynamiques différentes des deux, et en obtenant une excellente sensibilité aux stimuli, une excellente autoréparation et d'excellentes propriétés fonctionnelles analogues, notamment un bon rendement de l'absorption d'énergie. Le polymère dynamique peut être largement utilisé pour fabriquer des matériaux d'amortissement, des matériaux de protection contre les chocs, des matériaux auto-réparateurs, des matériaux ductiles et analogues.
PCT/CN2018/072455 2017-01-25 2018-01-12 Polymère ou composition dynamique présentant une structure de liaison hybride, et application associée Ceased WO2018137505A1 (fr)

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CN110698733A (zh) * 2019-10-14 2020-01-17 福建五持恒科技发展有限公司 石墨烯天然橡胶高分子冰上止滑混合发泡材料及其制备方法
CN112876774A (zh) * 2019-11-29 2021-06-01 合肥杰事杰新材料股份有限公司 一种聚丙烯材料及其制备方法

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CN111378141B (zh) * 2019-01-01 2023-04-07 厦门天策材料科技有限公司 一种力致响应超分子聚合物
CN114805418B (zh) * 2022-04-14 2023-12-26 深圳市明粤科技有限公司 一种粘结剂、芯片互连材料及其制备方法和半导体器件
CN115068669B (zh) * 2022-06-08 2023-05-26 湖南工业大学 一种三重网络多孔栓塞微球及其制备方法

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CN105111470A (zh) * 2015-08-13 2015-12-02 四川大学 一种可逆共价交联聚硅氧烷弹性体及其制备方法与应用
CN105646872A (zh) * 2016-02-26 2016-06-08 翁秋梅 一种动态聚合物材料

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US5258437A (en) * 1991-06-27 1993-11-02 Shin-Etsu Chemical Co., Ltd. Silicone putty compositions
CN101343421A (zh) * 2008-08-28 2009-01-14 上海交通大学 pH调控释放的动态聚合物封装体系的制备方法
WO2013127989A1 (fr) * 2012-03-02 2013-09-06 Fundación Cidetec Matériau élastomère autorégénérant
CN105111470A (zh) * 2015-08-13 2015-12-02 四川大学 一种可逆共价交联聚硅氧烷弹性体及其制备方法与应用
CN105646872A (zh) * 2016-02-26 2016-06-08 翁秋梅 一种动态聚合物材料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110698733A (zh) * 2019-10-14 2020-01-17 福建五持恒科技发展有限公司 石墨烯天然橡胶高分子冰上止滑混合发泡材料及其制备方法
CN112876774A (zh) * 2019-11-29 2021-06-01 合肥杰事杰新材料股份有限公司 一种聚丙烯材料及其制备方法

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