WO2018137508A1 - Dynamic polymer with hybrid cross-linked structure and application thereof - Google Patents

Dynamic polymer with hybrid cross-linked structure and application thereof Download PDF

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WO2018137508A1
WO2018137508A1 PCT/CN2018/072461 CN2018072461W WO2018137508A1 WO 2018137508 A1 WO2018137508 A1 WO 2018137508A1 CN 2018072461 W CN2018072461 W CN 2018072461W WO 2018137508 A1 WO2018137508 A1 WO 2018137508A1
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dynamic
polymer
group
atoms
covalent
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PCT/CN2018/072461
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French (fr)
Chinese (zh)
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徐晖
郭琼玉
张欢
梁愫
林淦
欧阳勇
翁文桂
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翁秋梅
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Definitions

  • the invention relates to the field of smart polymers, in particular to a dynamic polymer having a hybrid crosslinked network composed of a common covalent bond and an inorganic boronic acid silicate bond and an application thereof.
  • Conventional polymers are generally composed of common covalent bonds, which have a high bond energy and give the polymer good stability and stress carrying capacity.
  • the dynamic covalent bond is a kind of chemical bond that can undergo reversible reaction under certain conditions. It is more stable than non-covalent bond, but the bond energy is weaker than the common covalent bond.
  • Dynamic covalent bond can be realized by controlling external conditions. The break and formation. The introduction of dynamic covalent bonds into polymers is a viable way to form new smart polymers.
  • dynamic covalent bonds have the dynamic reversible properties of non-covalent interactions in supramolecular chemistry on the basis of common covalent bonds, while avoiding supramolecular non- Covalent interactions have weak bond bonds, poor stability, and are susceptible to external factors. Therefore, by introducing a dynamic covalent bond into the polymer, it is hopeful that a polymer having a good overall performance can be obtained.
  • the components such as polymer form an infinite three-dimensional network structure, which can improve the performance of the polymer in terms of thermal stability, mechanical properties, solvent resistance, etc., and can obtain good performance and application value.
  • Polymer material For conventional crosslinked polymers, they are generally classified into a chemically crosslinked type or a physically crosslinked type. Chemically crosslinked polymers are generally formed by cross-linking of common covalent bonds. Once formed, they are very stable and have good mechanical properties. Physically crosslinked polymers are generally formed by cross-linking through non-covalent interactions. It is dynamically reversible, and the properties of the crosslinked structure and polymer are variability.
  • cross-linked polymers currently in common use are often composed of a single common covalent bond or a single dynamic covalent bond, and the structural and dynamic properties are not well organically combined in the polymer.
  • the reversible effect of dynamics and the ability to regulate are also very limited, so there is a need to develop a new type of polymer to solve the problems in the prior art.
  • the present invention is directed to the above background, and provides a carbon chain/carbon heterochain dynamic polymer having a hybrid crosslinked structure comprising at least one common covalent crosslinked network, and further comprising a dynamic covalent inorganic boronic acid borate key.
  • the dynamic polymer exhibits excellent dynamic reversibility while exhibiting certain mechanical strength and good toughness, and can exhibit functions such as stimuli responsiveness, self-adhesiveness, energy absorption, and certain self-repairability. characteristic.
  • a dynamic polymer having a hybrid crosslinked structure comprising at least one common covalent crosslinked network, and at least one of said common covalently crosslinked network backbones is a carbon chain or a carbon hetero chain structure; a valence inorganic silicic acid silicate bond, wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is linked to three -O-, and some of them are based on different BO-Si dynamic covalent bonds of different B atoms
  • the Si atoms are connected by a linking group L, and are partially connected via a linking group Y based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms; the linking group L, which is contained on the dynamic polymer backbone skeleton
  • the carbon atom; the linker Y which is in the structure of the dynamic polymer backbone backbone, contains only (poly)siloxane units.
  • the dynamic polymer has only one network, and the network contains both common covalent crosslinks and dynamic covalent inorganic silicon borate linkages, wherein The valence crosslinks above its gel point and its crosslinked network backbone is a carbon chain or carbon heterochain structure; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is connected to three -O-, and Some of the Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and some Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group Y;
  • the linker L which contains a carbon atom on the backbone of the dynamic polymer backbone, the structure of the linker Y on the dynamic polymer backbone backbone contains only (poly)siloxane units.
  • the dynamic polymer contains two networks; the first network contains only ordinary covalent crosslinks, and the covalently crosslinked network backbone is a carbon chain Or a carbon heterocyclic structure; the crosslinking formed by the dynamic covalent inorganic boronic acid silicate bond in the second network reaches above the gel point, and does not contain ordinary covalent cross-linking above the gel point, wherein the dynamic covalent Any one of the B atoms of the inorganic boronic acid silicate bond is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on different B atoms.
  • the different Si atoms in the BO-Si dynamic covalent bond are linked by a linker Y; the linker L, which contains a carbon atom on the backbone of the dynamic polymer backbone, which is in the dynamic state
  • the structure on the backbone of the polymer backbone contains only (poly)siloxane units.
  • the dynamic polymer contains two networks; the first network is as described in the first network structure; and the second network contains only ordinary covalent cross-linking And not containing the dynamic covalent inorganic boronic acid borate bond; wherein at least one of the common covalent crosslinked network backbones is a carbon chain or a carbon heterochain structure; wherein any of the dynamic covalent inorganic boronic acid borate bonds
  • a B atom is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and some are based on BO-Si dynamic covalent of different B atoms.
  • the different Si atoms in the bond are connected by a linker Y; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, said linker Y being on the backbone of the dynamic polymer backbone
  • the structure contains only (poly)siloxane units.
  • the dynamic polymer contains two networks; the first network and the second network are both the first network structure, and at least one of the ordinary
  • the covalently crosslinked network backbone is a carbon chain or a carbon heterochain structure, but the first and second networks are different.
  • a difference may be, for example, a difference in the main structure of the polymer chain, a difference in the crosslinking density of the covalently crosslinked, a difference in the composition of the side chain and/or the side chain of the polymer chain, and the like.
  • the dynamic polymer contains at least one network containing only common covalent crosslinks, at least one of the common covalent crosslinked network backbones a polymer which is a carbon chain or a carbon hetero chain structure and crosslinked by a dynamic covalent inorganic boronic acid silicate bond is dispersed in the network in the form of particles; wherein any one of the dynamic covalent inorganic boron silicate bonds is B
  • the atom is connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on the BO-Si dynamic covalent bond of different B atoms.
  • the different Si atoms are connected by a linker Y; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the dynamic polymer backbone backbone, is only Contains (poly)siloxane units.
  • the dynamic polymer contains only one network, and the network only contains ordinary covalent crosslinks, and the common covalent crosslinked network skeleton is a carbon chain. Or a carbon heterochain structure, and a non-crosslinked polymer containing a dynamic covalent inorganic boronic acid silicate bond dispersed in the network; wherein the dynamic covalent inorganic boron silicate bond is any one of B atoms and three - O-linkage, and in which some Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected by a linker L, and partly based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms
  • the linker Y is linked; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the backbone of the dynamic polymer backbone, contains only (poly)silicon Oxytomane unit.
  • the dynamic polymer contains two networks, and both the first network and the second network contain only ordinary covalent crosslinks, and at least one of the ordinary
  • the covalently crosslinked network backbone is a carbon chain or a carbon heterochain structure; the first network and the second network may be the same or different, preferably different; in which at least one network is dispersed with a non-crossing containing a dynamic covalent inorganic boronic acid borate bond a bipolymer; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is linked to three -O-, and a part of which is based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms
  • the linking group L is connected, and the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through a linking group Y; the linking group L, which contains a carbon atom on the backbone of the dynamic polymer
  • the inorganic boronic acid silicate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor.
  • the inorganic boron compound refers to a boron-containing compound in which a boron atom in 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, boric acid ester, borate, boric acid. Anhydride, boron halide, and the like.
  • the silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor means that the terminal group and/or the pendant group of the compound contains a silyl group and/or a silanol precursor group.
  • any one of the B atoms of the dynamic covalent inorganic boronic acid borate bond is bonded to three -O-, and a part of the Si atom in the BO-Si dynamic covalent bond based on a different B atom passes through the linking group.
  • L is connected, and at the same time, the Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through a linking group Y;
  • the linking group L which contains carbon atoms on the dynamic polymer backbone, the connection Base Y, which contains only (poly)siloxane units
  • a raw material component for preparing a dynamic polymer includes, in addition to the inorganic boron compound and the silicon-containing compound, other polymers, adjuvants, and fillers that can be added/used.
  • the other polymer is selected from any one or more of the following: a natural polymer compound, a synthetic resin, a synthetic rubber, a synthetic fiber;
  • the auxiliary agent is selected from any one or more of the following: a catalyst, an initiator, an antioxidant, a light stabilizer, a heat stabilizer, a crosslinking agent, a curing agent, a chain extender, a toughening agent, Coupling agent, lubricant, mold release agent, plasticizer, foaming agent, dynamic regulator, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, matting agent, flame retardant, nucleation Agent, rheological agent, thickener, leveling agent;
  • the filler is selected from any one or more of the following: an inorganic non-metallic filler, a metal filler, and an organic filler.
  • the dynamic polymer or a composition thereof comprises, but is not limited to, a common solid, a gel (including a hydrogel, an organogel, an oligomer swollen gel, a plasticizer, and a swelling agent).
  • a gel including a hydrogel, an organogel, an oligomer swollen gel, a plasticizer, and a swelling agent.
  • Glue ionic liquid swelling gel
  • foam ionic liquid swelling gel
  • an energy absorbing method characterized in that a dynamic polymer having a hybrid crosslinked structure is provided and energy absorption is performed as an energy absorbing material, wherein the dynamic polymerization And comprising at least one common covalent crosslinked network, and at least one of said common covalent crosslinked network backbones is a carbon chain or a carbon hetero chain structure; and wherein it comprises a dynamic covalent inorganic boronic acid borate linkage, wherein said dynamic Any one of the B atoms of the inorganic boronic acid borate bond is connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and partly based on different B The different Si atoms in the BO-Si dynamic covalent bond of the atom are connected by a linker Y; the linker L, which contains a carbon atom on the dynamic polymer backbone; the linker Y, which is in a dynamic
  • the dynamic polymer having a hybrid crosslinked structure has a wide range of properties, and has broad application prospects. Specifically, it can be applied to fabricating a shock absorber, a buffer material, and an anti-wearing agent.
  • the present invention has the following beneficial effects:
  • the dynamic polymer hybrid crosslinked network structure of the present invention combines ordinary covalent cross-linking and inorganic boric acid silicide bond cross-linking, and fully utilizes and combines the respective advantages.
  • common covalent cross-linking provides a strong and stable network structure for dynamic polymers, the polymer can maintain a balanced structure, that is, dimensional stability; and dynamic covalent inorganic silicon borate bond cross-linking is a dynamic polymer. It provides a covalent dynamic network structure that can be reversibly changed spontaneously or under the influence of the outside world, thereby realizing the "dynamic and static combination" of dynamic covalent bonds and common covalent bonds, and exhibits synergy in the polymer network.
  • the inorganic boronic acid silicate bond of the present invention enables the crosslinked polymer to be promptly and rapidly externally due to its high dynamic reversibility and stress sensitivity. Force to react; compared with the existing supramolecular cross-linked polymer, the inorganic boronic acid silicate bond in the present invention can dissipate more energy during the fracture process due to its covalent property, thereby better Improve the energy absorption properties and toughness of the material. Moreover, the fracture of the inorganic boronic acid silicate bond is reversible, reversible, and imparts durability to the material.
  • the polymer Based on the strong dynamics of the inorganic boronic acid silicate bond, the polymer can exhibit dilatancy, resulting in a transition from creep to high elasticity, and the ability to disperse the impact force is greatly improved, thereby achieving an excellent impact resistance; Due to the existence of common covalent cross-linking, the polymer is self-supporting, eliminating the trouble of using a pouch to encapsulate the polymer but may leak, and has excellent practicability. By adopting the design idea adopted by the invention, the traditional crosslinked polymer has the characteristics of low elongation at break, poor toughness and excellent resistance while retaining the mechanical strength and stability of the traditional crosslinked polymer. Impact performance, which is not possible with the prior art.
  • a dynamic polymer having a hybrid crosslinked structure of the present invention which comprises two different linking groups L and a linking group Y, by adjusting the ratio of the two and the structural modification of the two linking groups.
  • the dynamic polymers with different structures are prepared, so that the dynamic polymers can exhibit a variety of properties to meet the application needs of different occasions.
  • the hybrid crosslinked dynamic polymer has a rich structure, various properties, and a wide range of raw material sources.
  • 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 to provide dynamic polymers with a wide variety of properties.
  • the inorganic boron compound has a wide range of sources, stable properties and low price, which greatly reduces the synthesis cost of the dynamic polymer, simplifies the preparation process, and enables the obtained hybrid crosslinked dynamic polymer material to be obtained. More efficient investment in practical production applications has expanded the field of application of materials.
  • the dynamic reversible bond in the hybrid crosslinked dynamic polymer has strong dynamic reactivity and mild dynamic reaction conditions.
  • the present invention makes full use of boric acid ester bond and has good thermal stability and high dynamic reversibility, and can realize dynamic polymerization without catalyst, high temperature and illumination.
  • the synthesis and dynamic reversibility of the material while improving the preparation efficiency, also reduces the limitations of the use environment, and expands the application range of the polymer.
  • by selectively controlling other conditions such as adding auxiliaries, adjusting the reaction temperature, etc.
  • the present invention relates to a dynamic polymer having a hybrid crosslinked structure comprising at least one common covalent crosslinked network, and at least one of said common covalently crosslinked network backbones is a carbon chain or a carbon hetero chain structure;
  • the invention comprises a dynamic covalent inorganic boronic acid borate bond, wherein any one of the B atoms of the dynamic covalent inorganic boronic acid borate bond is connected to three -O-, and a part of the BO-Si dynamic covalent bond based on different B atoms
  • the different Si atoms in the middle are connected by a linking group L, and at the same time, based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms, are connected through a linking group Y;
  • the linking group L which is contained in the dynamic polymer main
  • the carbon atom on the chain backbone, the linker Y, which is on the dynamic polymer backbone backbone contains only (poly)siloxane units.
  • polymerization is a growth process/action of a chain, including a process of synthesizing a product having a higher molecular weight by a reaction form such as polycondensation, polyaddition, ring-opening polymerization or the like.
  • the reactants are generally compounds such as monomers, oligomers, and prepolymers which have a polymerization ability (that is, can be polymerized spontaneously or can be polymerized by an initiator or an external energy).
  • the product obtained by polymerization of one reactant is referred to as a homopolymer.
  • a product obtained by polymerization of two or more reactants is referred to as a copolymer.
  • the "polymerization" described in the present invention includes a linear growth process of a reactant molecular chain, a branching process including a reactant molecular chain, a ring-forming process including a reactant molecular chain, and a reaction.
  • the cross-linking process of molecular chains includes a linear growth process of a reactant molecular chain, a branching process including a reactant molecular chain, a ring-forming process including a reactant molecular chain, and a reaction.
  • crosslinking refers to the formation of two-dimensional, three-dimensional clusters and further three-dimensional infinite network formation by chemical bonding of covalent bonds between reactant molecules and/or reactant molecules.
  • the process of the product In the cross-linking process, the polymer chains generally grow in the two-dimensional/three-dimensional direction, gradually forming clusters (which can be two-dimensional or three-dimensional), and then develop into three-dimensional infinite networks.
  • the cross-linking structure in the present invention refers specifically to a three-dimensional infinite network structure above the gel point, including non-crosslinking including linear, branched, cyclic, two-dimensional clusters and gel points. The structure of the three-dimensional cluster structure is equal to the gel point below.
  • 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 A three-dimensional infinite network structure is not formed, and only a small number of three-dimensional network structures exist locally, and it does not belong to a cross-linked network that can form a whole across the entire polymer structure.
  • the "ordinary covalent bond" as used in the present invention refers to a covalent bond other than a dynamic covalent bond in the conventional sense, at a usual temperature (generally not higher than 100 ° C) and a usual time (generally Less than 1 day) is less difficult to break, including but not limited to common carbon-carbon bonds, carbon-oxygen bonds, carbon-hydrogen bonds, carbon-nitrogen bonds, carbon-sulfur bonds, nitrogen-hydrogen bonds, nitrogen-oxygen bonds. , hydrogen-oxygen bond, nitrogen-nitrogen bond, and the like.
  • the "dynamic covalent bond” refers to an inorganic boronic acid borate bond.
  • the dynamic covalent bond may be present on the side chain and/or side chain and/or the branch and/or the bifurcation chain of the backbone chain in addition to the polymer backbone chain and / or lower levels of side groups and / or side chains and / or branches and / or fork chains.
  • the invention also does not exclude the inclusion of a boronic borate linkage on the pendant and/or end groups of the polymer chain.
  • Only dynamic covalent bonds on the backbone of the crosslinked network can constitute dynamic covalent crosslinks. Under suitable conditions, dynamic covalent bonds at any position in the dynamic polymer can participate in dynamic reversible exchange.
  • the total effective crosslink degree of the polymer system will decrease.
  • the number of inorganic boronic acid silicate bonds (the ratio of all bonds) on the skeleton between any two of the most common common covalent crosslinking points containing inorganic boronic acid silicate bonds is not limited, and may be one or more, preferably only One. When only one is included, the dynamic polymer structure is more regular and the dynamics are more controllable.
  • the linker L and the linker Y are both at least divalent, and both may have any suitable topology, including but not limited to linear, ring (including but not limited to single ring) , multi-ring, nested ring, bridged ring), branching (including but not limited to star, H, comb, dendritic, hyperbranched), two-dimensional and three-dimensional clusters, and any suitable combination of the above structures, It is even particles having ordinary covalent cross-linking (including fibers and flake particles); both of them may be homopolymers or copolymers.
  • the linking group L may be a linking group having a carbon atom on a skeleton having a low molecular weight or a high molecular weight, preferably a polymer linking group having a molecular weight of more than 1000 Da, and more preferably having a carbon atom of not less than 20 in the skeleton.
  • the linker L skeleton further contains an optional hetero atom and/or an element atom which can form an elemental organic group, wherein the hetero atom optionally contained may be any suitable hetero atom, including but not limited to O, N.
  • S optionally containing element atoms may be any suitable elemental atoms including, but not limited to, P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir.
  • the linking group L is directly bonded to the Si atom of the B-O-Si bond through a carbon atom, and both the dynamics of the B-O-Si bond and the performance of the carbon atom-containing linking group L can be utilized to the utmost.
  • the carbon atom-containing linking group L may have any one or more glass transition temperatures, and a glass transition temperature higher than room temperature may give a better rigidity and modulus to the dynamic polymer, and a glass transition temperature lower than room temperature.
  • the carbon atom-containing linking group L is preferably a hydrocarbon group, a polyolefin group, a polyether group, a polyester group, a polyurethane group, a polyurea group, a polythiourethane group, a polyacrylate group, a polyacrylamide group, a poly Carbonate group, polyethersulfone group, polyarylsulfone group, polyetheretherketone group, polyimide group, polyamide group, polyamine group, polyphenylene ether group, polyphenylene sulfide group, polyphenylsulfone group, However, the invention is not limited to this.
  • the linker Y is a (poly)siloxane, which may also have any one or more glass transition temperatures, but is generally lower than room temperature.
  • a dynamic polymer may contain different linking groups L and a linking group Y; in addition to the linking group L and the linking group Y, there may be other linking groups, which are not limited in the present invention, but preferably only There are a linker L and a linker Y.
  • the linker L and the linker Y simultaneously impart excellent adjustability to properties such as mechanical properties and dynamic properties, because the linker Y has a low glass transition temperature, is suitable for obtaining strong dynamics and softness, and the like; More suitable for good mechanical properties.
  • one or more polymers may be included, but at least one network of common covalent crosslinks is included, that is, at least one network is crosslinked by ordinary covalent bonds and reaches a gel. Point above.
  • the dynamic covalent inorganic silicon borate bonds may form crosslinks together in a common covalently bonded network, or may form a dynamic covalent crosslinked network independently or in a non-crosslinked chain. Since at least one network of common covalent crosslinks is included, the polymer system of the present invention can maintain a balanced structure even when all the dynamic bonds are completely dissociated, that is, the basic shape can be maintained without completeness. Melt and dissolve. Maintaining a balanced structure means being self-supporting and critical to many uses of polymers such as seals, tires, etc.
  • skeleton refers to a structure in the chain length direction of a polymer chain.
  • backbone refers to any segment present on the backbone of the crosslinked network, including the backbone and crosslinks on the infinite three-dimensional network backbone; wherein the polymer
  • the crosslinks between the chains can be one atom, one single bond, one group, one segment, one cluster, and the like.
  • the "backbone”, unless otherwise specified, refers to the chain with the most links; wherein the “side chain” refers to the same polymer main The chain structure in which the chain skeletons are connected and distributed on the side of the skeleton; wherein the "branched” / "bifurcation chain” may be a side chain or other chain structure branched from any chain.
  • the "side group” refers to a chemical group which is bonded to an arbitrary chain of the polymer and distributed on the side of the chain.
  • side chains For “side chains”, “branched chains” and “side groups”, it may have a multi-stage structure, ie the side chains/branches may continue to have side groups and side chains/branches, side chains/branched sides Chains/branches can continue to have side groups and side chains/branches.
  • end group refers to a chemical group attached to an arbitrary chain and located at the end of the chain.
  • the branch can also be considered a backbone, but usually the outermost branch is considered only a branch.
  • the dynamic polymer may have one or more glass transition temperatures or may have no glass transition temperature.
  • the glass transition temperature of the dynamic polymer at least one of which is lower than 0 ° C, or between 0-25 ° C, or between 25-100 ° C, or higher than 100 ° C; wherein, the glass transition Dynamic polymers with a temperature below 0 °C have good low temperature performance and are convenient for use as sealants, elastomers, gels, etc.
  • Dynamic polymers with a glass transition temperature between 0 and 25 ° C can be beneficial in It can be conveniently used as an elastomer, sealant, gel, foam and ordinary solids at room temperature.
  • Dynamic polymers with a glass transition temperature between 25 and 100 ° C are convenient for obtaining ordinary solids and foams above room temperature. And gel; dynamic polymer with glass transition temperature higher than 100 °C, its dimensional stability, mechanical strength, temperature resistance is good, and it is beneficial to be used as a stress-carrying material and a high impact material.
  • dynamic polymers with a glass transition temperature below 25 °C it can exhibit excellent dynamics, self-healing and recyclability; it can be good for dynamic polymers with a glass transition temperature higher than 25 °C.
  • Shape memory ability, stress carrying capacity and impact resistance; in addition, the presence of supramolecular hydrogen bonds can further regulate the glass transition temperature of dynamic polymers, dynamics of dynamic polymers, cross-linking degree, mechanical The intensity is supplemented.
  • the dynamic polymer in the present invention it is preferred that at least one glass transition temperature is not higher than 50 ° C, further preferably at least one glass transition temperature is not higher than 25 ° C, and most preferably each glass transition temperature is not higher than 25 ° C.
  • Each system having a glass transition temperature of not higher than 25 ° C is particularly suitable for use as a self-healing material or an energy absorbing material because of its good flexibility and flowability/creep property at daily use temperatures.
  • the glass transition temperature of the dynamic polymer can be measured by a method for measuring the glass transition temperature which is common in the art, such as DSC and DMA.
  • each raw material component of the dynamic polymer may also have one or more glass transition temperatures, or may have no glass transition temperature, and its glass transition temperature is at least one lower than 0 ° C. Or at between 0-25 ° C, or between 25-100 ° C, or above 100 ° C, wherein the compound material having a glass transition temperature of less than 0 ° C facilitates low temperature preparation and processing in the preparation of dynamic polymers;
  • the compound raw material having a glass transition temperature of 0-25 ° C can be prepared and processed at normal temperature; the compound raw material having a glass transition temperature of 25-100 ° C can be formed by using a conventional heating device, and the manufacturing cost is low;
  • a compound material having a glass transition temperature higher than 100 ° C can be used to prepare a high temperature resistant material having good dimensional stability and excellent mechanical properties.
  • the inorganic boronic acid silicate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor.
  • the inorganic boron compound refers to a boron-containing compound in which a boron atom in a compound is not bonded to a carbon atom through a boron-carbon bond.
  • the inorganic boron compound is selected from the group consisting of, but not limited to, boric acid, boric acid esters, borate salts, boric anhydrides, and boron halides.
  • the boric acid may be orthoboric acid, metaboric acid or tetraboric acid.
  • Borate esters include alkyl and allyl borate/triorgano borate hydrolyzed to boric acid in the presence of water, such as trimethyl borate, triethyl borate, triphenyl borate, tribenzyl borate, Tricyclohexyl borate, tris(methylsilyl) borate, tri-tert-butyl borate, tri-n-pentyl borate, tri-sec-butyl borate, DL-menthyl borate, tris(4) -Chlorophenyl)borate, 2,6-di-tert-butyl-4-tolyldibutyl orthoborate, tris(2-methoxyethyl)borate, benzyldihydroborate Ester, diphenylhydroborate, isopropanol pinacol borate, triethanolamine borate, and the like.
  • water such as trimethyl borate, triethyl borate, triphenyl borate, tribenzy
  • Suitable boronic acid anhydride includes, in addition to the formula B 2 O 3 is typically boron oxide, also including but not limited trialkoxy boroxine and derivatives thereof, e.g. trimethoxy boroxine, tris isopropoxide Alkyl boroxane, 2,2'-oxybis[4,4,6-trimethyl-1,3,2-dioxaboroxane, and the like.
  • Suitable borate salts include, but are not limited to, diammonium pentaborate, sodium tetraborate decahydrate (borax), potassium pentaborate, magnesium diborate, calcium monoborate, barium triborate, zinc metaborate, tripotassium borate, original Iron borate.
  • Suitable boron halides include, but are not limited to, boron trifluoride, boron trichloride, boron tribromide, boron triiodide, diboron tetrachloride, and the like.
  • Suitable inorganic boron compounds further include partial hydrolyzates of the foregoing borate esters.
  • the inorganic boron compound is boron oxide of the formula B 2 O 3 [CAS Registry Number #1303-86-2] or boric acid of the general formula H 3 BO 3 [CAS Registry Number #10043-35-3].
  • the chemical structural formula of a suitable inorganic boron compound is as follows, but the invention is not limited thereto:
  • the silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor means that the terminal group and/or the pendant group of the compound contains a silyl group and/or a silanol precursor group.
  • the silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor may itself contain a linking group L and/or a linking group Y, or may form a linking group L and/or a linking group by a suitable chemical reaction. Y.
  • the linking group L contains a carbon atom on the backbone of the dynamic polymer backbone, particularly a carbon-containing polymer linking group, a dynamic polymer backbone skeleton having rich structure and various properties can be obtained, in particular, the presence of the main chain skeleton carbon. It is convenient to obtain higher dynamic polymer mechanical properties and printability.
  • the above silicon-containing compound containing a linker Y or a silicon-containing hydroxyl group and/or a silanol precursor containing a linker Y by a suitable chemical reaction is a (poly)siloxane compound, meaning that the terminal of the compound contains a silanol group and / or a silyl hydroxyl precursor end group, and the main chain and / or side chain and / or other chain structure connected to the end group is any suitable (poly) siloxane structure and inorganic boron silicate which can be formed
  • the bond (BO-Si) contains the compound of the above-mentioned linker Y.
  • the main chain or main structure of the (poly)siloxane or the like is composed of -(SiR 1 R 2 -O) n - units, wherein n is a siloxane unit (SiR 1 R 2 -O)
  • the number of ) is an integer greater than or equal to 1, and 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 the like.
  • Suitable organic, inorganic groups/segments include hydroxyl groups, as well as other reactive organic groups; preferably organic groups/segments, more preferably carbon-containing organic groups/segments.
  • 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, 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.
  • one of the silanol precursors which can be hydrolyzed to give a siloxy 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.
  • n, x, y, and z are the number of repeating units, and may be a fixed value or an average value.
  • 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 also be at the end group or pendant group.
  • 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:
  • n, x, y, and z are the number of repeating units, and may be a fixed value or an average value.
  • any suitable inorganic boron compound and a compound containing a silicon hydroxy group and/or a silanol precursor may be used to form an inorganic boronic acid silicate bond, preferably an inorganic boric acid and a silanol group-containing macromolecular compound, inorganic boric acid.
  • a macromolecular compound containing a silicon-containing hydroxy precursor, an inorganic borate (salt) and a silanol-containing macromolecular compound to form an inorganic boronic acid silicate bond more preferably an inorganic boronic acid and a silicon-containing hydroxyl group-containing macromolecular compound, inorganic boron
  • the acid ester and the silanol-containing macromolecular compound form an inorganic boronic acid silicate bond, and it is more preferred to use an inorganic boronic acid ester and a silicon-containing hydroxyl group-containing macromolecular compound to form an inorganic boronic acid silicate bond.
  • the dynamic polymer may be obtained by forming an inorganic boronic acid silicate bond, or a compound containing the inorganic boronic acid silicate bond may be prepared to be repolymerized/crosslinked to generate the dynamic. polymer.
  • a Si atom participating in the formation of BO-Si on the silicon-containing compound may form up to three BO-Si bonds, which share one Si atom; and since the boron atom is In the trivalent structure, the polymerization process produces the inorganic silicon silicate bond which can easily cause bifurcation and can be further crosslinked.
  • the dynamic polymer has only one network, and the network contains both common covalent crosslinks and dynamic covalent inorganic silicon borate linkages, wherein The valence crosslinks above its gel point and its crosslinked network backbone is a carbon chain or carbon heterochain structure; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is connected to three -O-, and Some of the Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and some Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group Y;
  • the linker L which contains a carbon atom on the backbone of the dynamic polymer backbone, the structure of the linker Y on the dynamic polymer backbone backbone contains only (poly)siloxane units.
  • a balanced structure can be maintained by ordinary covalent cross-linking, and the inorganic boronic acid silicate bond can provide additional dynamic covalent cross-linking and dynamic covalentity, and the obtained dynamic polymer not only has self-supporting properties, but also has Significantly dilatant to produce elasticity, excellent structural simplicity.
  • the dynamic polymer contains two networks; the first network contains only ordinary covalent crosslinks, and the covalently crosslinked network backbone is a carbon chain Or a carbon heterocyclic structure; the crosslinking formed by the dynamic covalent inorganic boronic acid silicate bond in the second network reaches above the gel point, and does not contain ordinary covalent cross-linking above the gel point, wherein the dynamic covalent Any one of the B atoms of the inorganic boronic acid silicate bond is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on different B atoms.
  • the different Si atoms in the BO-Si dynamic covalent bond are linked by a linker Y; the linker L, which contains a carbon atom on the backbone of the dynamic polymer backbone, which is in the dynamic state
  • the structure on the backbone of the polymer backbone contains only (poly)siloxane units.
  • the equilibrium structure is maintained by ordinary covalent cross-linking in the first network, and the inorganic boronic acid silicate bond in the second network provides dynamic covalentity, the two networks are orthogonal to each other, and can be minimized in preparation. Limit to the mutual interference of the composition of the raw materials.
  • the dynamic polymer contains two networks; the first network is as described in the first network structure; and the second network contains only ordinary covalent cross-linking And not containing the dynamic covalent inorganic boronic acid borate bond; wherein at least one of the common covalent crosslinked network backbones is a carbon chain or a carbon heterochain structure; wherein any of the dynamic covalent inorganic boronic acid borate bonds
  • a B atom is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and some are based on BO-Si dynamic covalent of different B atoms.
  • the different Si atoms in the bond are connected by a linker Y; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, said linker Y being on the backbone of the dynamic polymer backbone
  • the structure contains only (poly)siloxane units.
  • the equilibrium structure is maintained by common covalent cross-linking in the first network and the second network, and the inorganic boronic acid silicate bond in the first network provides dynamic covalentity, and the two common covalent cross-linkings provide double
  • the network structure has outstanding advantages in mechanical properties, coupled with additional dynamic covalent cross-linking, the mechanical properties can be sublimated.
  • the dynamic polymer contains two networks; the first network and the second network are both the first network structure, and at least one of the ordinary
  • the covalently crosslinked network backbone is a carbon chain or a carbon heterochain structure, but the first and second networks are different.
  • Such a difference may be, for example, a difference in the structure of the polymer chain main body, a difference in the crosslinking density of the covalently crosslinked, a difference in the composition of the side chain of the polymer chain and/or the side chain, and the like.
  • the purpose of accurately controlling the dynamic polymer performance can be achieved.
  • the dynamic polymer contains at least one network containing only common covalent crosslinks, at least one of the common covalent crosslinked network backbones a polymer which is a carbon chain or a carbon hetero chain structure and crosslinked by a dynamic covalent inorganic boronic acid silicate bond is dispersed in the network in the form of particles; wherein any one of the dynamic covalent inorganic boron silicate bonds is B
  • the atom is connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on the BO-Si dynamic covalent bond of different B atoms.
  • the linker L contains a carbon atom on the backbone of the dynamic polymer backbone
  • the linker Y which is on the dynamic polymer backbone backbone, is only Contains (poly)siloxane units.
  • the common covalent cross-linking provides a balanced structure
  • the dynamic polymer crosslinked by the inorganic boronic acid silicate bond is dispersed in the form of particles in a common covalent cross-linking network, which can provide local dilatancy when subjected to force.
  • the hardness and strength of the material increase, achieving the purpose of organically regulating energy dispersion.
  • the dynamic polymer contains only one network, and the network only contains ordinary covalent crosslinks, and the common covalent crosslinked network skeleton is a carbon chain. Or a carbon heterochain structure, and a non-crosslinked polymer containing a dynamic covalent inorganic boronic acid silicate bond dispersed in the network; wherein the dynamic covalent inorganic boron silicate bond is any one of B atoms and three - O-linkage, and in which some Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected by a linker L, and partly based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms
  • the linker Y is linked; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the backbone of the dynamic polymer backbone, contains only (poly)silicon Oxytomane unit.
  • the linker L contains a carbon atom on the
  • the dynamic polymer contains two networks, and both the first network and the second network contain only ordinary covalent crosslinks, and at least one of the ordinary
  • the covalently crosslinked network backbone is a carbon chain or a carbon heterochain structure; the first network and the second network may be the same or different, preferably different; in which at least one network is dispersed with a non-crossing containing a dynamic covalent inorganic boronic acid borate bond a bipolymer; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is linked to three -O-, and a part of which is based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms
  • the linking group L is connected, and the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through a linking group Y; the linking group L, which contains a carbon atom on the backbone of the dynamic polymer
  • two common covalent crosslinked networks provide a balanced structure and excellent mechanical properties as a dual network structure, and the dilatancy of the non-crosslinked dynamic polymer dispersed therein can provide complete viscosity when stressed. Loss, which plays a strong role in energy absorption.
  • the present invention may have other various hybrid cross-linking network structure embodiments, and one embodiment may include three or more identical or different Network, the same network can contain different common covalent cross-linking and / or different dynamic inorganic boronic acid silicate bond cross-linking, the chemical structure, topology, cross-linking degree of each network can be the same or different, network structure
  • the crosslinked and/or non-crosslinked polymer component may be dispersed/filled therein, and each component may further contain a skeleton hydrogen bond group.
  • Inorganic boronic acid silicate bonds are used to provide covalent dynamic properties, including but not limited to plasticity and self-healing properties, which can be used to impart stress/strain responsiveness, super toughness, self-healing, shape memory, etc. .
  • plasticity and self-healing properties which can be used to impart stress/strain responsiveness, super toughness, self-healing, shape memory, etc. .
  • an energy absorbing method characterized in that a dynamic polymer having a hybrid crosslinked structure is provided and energy absorption is performed as an energy absorbing material, wherein the dynamic polymerization And comprising at least one common covalent crosslinked network, and at least one of said common covalent crosslinked network backbones is a carbon chain or a carbon hetero chain structure; and wherein it comprises a dynamic covalent inorganic boronic acid borate linkage, wherein said dynamic Any one of the B inorganic silicon borate bonds is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and partly based on different B The different Si atoms in the BO-Si dynamic covalent bond of the atom are connected by a linker Y; the linker L, which contains a carbon atom on the dynamic polymer backbone; the linker Y, which is in a dynamic polymerization
  • a hydrogen bond group on a polymer backbone backbone means that at least a portion of the atoms in the group are directly involved in building a continuous polymer backbone or Crosslinking the polymer backbone or crosslinks on the backbone of the network.
  • the skeleton hydrogen bond group may be formed during polymer polymerization/crosslinking, that is, by forming the hydrogen bond group to cause polymerization/crosslinking; or may be pre-formed and then polymerized/crosslinked.
  • the backbone hydrogen bonding group may be selected, for example, from an amide group, a urethane group, a thiourethane group, a silyl carbamate group, a urea group, and based on the above a derivative of a group.
  • Preferred are carbamate groups, urea groups and derivatives thereof.
  • the following structure can be mentioned, but the present invention is not limited to this:
  • 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:
  • more than one of the above-described skeleton hydrogen bond groups may be contained in the same polymer, and more than one of the above-described skeleton hydrogen bond groups may be contained in the same network.
  • the compound into which the skeleton 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.
  • the dynamic polymer composition having a hybrid crosslinked structure may be in the form of a common solid, an elastomer, a gel (including a hydrogel, an organogel, an oligomer swollen gel, Plasticizer swollen gel, ionic liquid swollen gel), foam, and the like.
  • the dynamic polymer ordinary solid has a fixed shape and volume, high strength and high density, and is suitable for use in a high-strength explosion-proof wall or an instrument casing;
  • the elastomer has the general property of ordinary solids, but is softer and more elastic.
  • the dynamic polymer gel has soft texture, good energy absorption and elasticity, and is suitable for preparing high damping energy absorbing materials.
  • Dynamic polymer foam materials have the advantages of low density, light weight and high specific strength of general foam. Its soft foam material also has good elasticity and energy absorption.
  • the dynamic polymer gel may be obtained by crosslinking in a swelling agent (including one of water, an organic solvent, an oligomer, a plasticizer, an ionic liquid, or a combination thereof), or After the preparation of the dynamic polymer is completed, swelling is obtained by using a swelling agent.
  • a swelling agent including one of water, an organic solvent, an oligomer, a plasticizer, an ionic liquid, or a combination thereof.
  • the dynamic polymer is mainly foamed by three methods: mechanical foaming method, physical foaming method and chemical foaming method.
  • the mechanical foaming method is to introduce a large amount of air or other gas into the emulsion, suspension or solution of the polymer into a uniform foam by vigorous stirring during the preparation of the dynamic polymer, and then pass through the physics. Or chemical changes make it gelatinize and solidify into a foam.
  • air can be introduced and an emulsifier or surfactant can be added.
  • the physical foaming method utilizes physical principles to achieve foaming of the polymer in the preparation process of the dynamic polymer, and generally includes the following five methods: (1) an inert gas foaming method, that is, adding Pressing the inert gas into the molten polymer or the paste material under pressure, and then heating the pressure under reduced pressure to expand and foam the dissolved gas; (2) evaporating the gasification foam by using a low-boiling liquid, that is, pressing the low-boiling liquid Into the polymer or under certain pressure and temperature conditions, the liquid is dissolved into the polymer particles, and then the polymer is heated and softened, and the liquid is vaporized by evaporation to foam; (3) dissolution method, that is, liquid The medium is immersed in the polymer to dissolve the solid substance added in advance, so that a large amount of pores appear in the polymer to be foamed, such as mixing the soluble substance salt, starch, etc.
  • an inert gas foaming method that is, adding Pressing the inert gas into the
  • foaming is preferably carried out by a method in which an inert gas and a low-boiling liquid are dissolved in a polymer.
  • the physical foaming method has the advantages of less toxicity in operation, lower cost of foaming raw materials, and no residual body of foaming agent.
  • the chemical foaming method is a method of foaming along with a chemical reaction in a dynamic polymer foaming process, and generally comprises the following two methods: (1) a thermal decomposition type foaming agent The bubble method, that is, the gas liberated by heating with a chemical foaming agent is foamed. (2) A foaming method in which a polymer component interacts to generate a gas, that is, a chemical reaction occurring between two or more components in a foaming system to generate an inert gas such as carbon dioxide or nitrogen to cause a polymer Expand and foam.
  • a small amount of a catalyst and a foam stabilizer (or a surfactant) are generally added.
  • dynamic polymer foam materials are mainly formed by three methods: compression foam molding, injection foam molding and extrusion foam molding.
  • the molding foam molding the process is relatively simple and easy to control, and can be divided into one-step method and two-step method.
  • One-step molding means that the mixed material is directly put into the cavity for foam molding; the two-step method refers to pre-expansion treatment of the mixed material, and then into the cavity for foam molding.
  • the one-step molding foam molding is more convenient to operate than the two-step method and the production efficiency is high, it is preferable to carry out the compression foam molding by the one-step method.
  • the injection foam molding process and equipment are similar to ordinary injection molding, and the bubble nucleation stage is heated and rubbed to make the material into a melt state after the material is added to the screw, and the foaming agent is passed.
  • the control of the metering valve is injected into the material melt at a certain flow rate, and then the foaming agent is uniformly mixed through the mixing elements of the screw head to form a bubble core under the action of the nucleating agent.
  • Both the expansion stage and the solidification setting stage occur after the end of the filling cavity. When the cavity pressure drops, the expansion process of the bubble core occurs, and the bubble body solidifies and sets as the mold cools down.
  • the extrusion foam molding, the process and equipment are similar to ordinary extrusion molding, the foaming agent is added to the extruder before or during the extrusion process, and the melt flows through the pressure at the head. Upon falling, the blowing agent volatilizes to form the desired foamed structure. Because it can not only achieve continuous production, but also is more competitive in cost than injection foam molding, it is currently the most widely used foam molding technology.
  • the structure of the dynamic polymer foam material involves three types of open-cell structures, closed-cell structures, and half-open half-close structures.
  • the open-cell structure the cells and the cells are connected to each other or completely connected, and the single or three-dimensional can pass through a gas or a liquid, and the bubble diameter ranges from 0.01 to 3 mm.
  • the closed-cell structure has an independent cell structure, and the inner cell is separated from the cell by a wall membrane, and most of them are not connected to each other, and the bubble diameter is 0.01-3 mm.
  • the cells contained in the cells are connected to each other and have a semi-open structure.
  • the foam structure which has formed a closed cell it can also be made into an open-cell structure by mechanical pressure or chemical method, and those skilled in the art can select according to actual needs.
  • dynamic polymer foam materials can be classified into soft, hard and semi-rigid according to their hardness classification: (1) flexible foam at 23 ° C and 50% relative humidity.
  • the elastic modulus of the foam is less than 70 MPa;
  • the rigid foam has a modulus of elasticity greater than 700 MPa at 23 ° C and 50% relative humidity;
  • a semi-hard (or semi-soft) foam between The foam between the above two types has a modulus of elasticity between 70 MPa and 700 MPa.
  • the dynamic polymer foam material can be further classified into low foaming, medium foaming, and high foaming according to its density.
  • a low foaming foam material having a density of more than 0.4 g/cm 3 and a foaming ratio of less than 1.5
  • a medium foamed foam material having a density of 0.1 to 0.4 g/cm 3 and a foaming ratio of 1.5 to 9
  • a foamed foam having a density of less than 0.1 g/cm 3 and a foaming ratio of greater than 9.
  • 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 crosslinked structure, or in the preparation of a dynamic polymer. Improve the performance of processing.
  • the other polymers that can be added 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 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 is selected from natural polymer compounds, it may be selected from any one or any of the following natural polymer compounds: natural rubber, chitosan, chitin, natural protein, and the like.
  • the other polymer that can be added 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, poly Vinylidene chloride, low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polybenzimidazole, poly Ethylene terephthalate, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene glycol, polyester, polyethersulfone, polyarylsulfone, polyether ether Ketone, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polyacrylate, polyacrylonitrile, polyphenylene ether, polypropylene, polyphenylene sulf
  • the other polymer that can be added is selected from synthetic rubber
  • it may be selected from any one or any of the following synthetic rubbers: isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, butyl Rubber, ethylene propylene rubber, silicone rubber, fluororubber, polyacrylate rubber, urethane rubber, chloroether rubber, thermoplastic elastomer, etc.
  • the other polymer that can be added 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 that may be added during the preparation of the polymer material are preferably natural rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polyacrylate, 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.
  • natural rubber polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polyacrylate, Epoxy resin, phenolic resin, isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, butyl rubber, ethylene propylene rubber
  • 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 is selected from any one or any of the following auxiliary agents: a synthesis auxiliary agent, including a catalyst, an initiator, a stabilization aid, including an antioxidant, a light stabilizer, a heat stabilizer; Additives for mechanical properties, including crosslinkers, curing agents, chain extenders, toughening agents, coupling agents; additives to improve processing properties, including lubricants, mold release agents; softening and lightening additives , including plasticizers, foaming agents, dynamic regulators; 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 smoke suppressing additives, including flame retardants; other additives, including nucleating agents, rheological agents, thickeners, leveling agents.
  • the catalyst in the additive which can be added/used can accelerate the reaction rate of the reactant in the reaction process by changing the reaction route and reducing the activation energy of the reaction.
  • the catalyst includes, but is not limited to: (1) a catalyst for polyurethane synthesis: an amine catalyst such as triethylamine, triethylenediamine, bis(dimethylaminoethyl)ether, 2-(2-Dimethylamino-ethoxy)ethanol, trimethylhydroxyethylpropanediamine, N,N-bis(dimethylaminopropyl)isopropanolamine, N-(dimethylaminopropyl) Diisopropanolamine, N,N,N'-trimethyl-N'-hydroxyethyl bisamine ethyl ether, tetramethyldipropylene triamine, N,N-dimethylcyclohexylamine ,N,N,N',N'-tetramethylalkylenediamine
  • Catalyst for polyolefin synthesis such as Ziegler-Natta catalyst, ⁇ -allyl nickel, alkyl lithium catalyst, metallocene catalyst, diethylaluminum chloride, titanium tetrachloride, titanium trichloride, trifluoro Boron ether complex, magnesium oxide, dimethylamine, cuprous chloride, triethylamine, sodium tetraphenylborate, antimony trioxide, sesquiethylaluminum chloride, vanadium oxychloride, triisobutylene Aluminum, nickel naphthenate, rare earth naphthenic acid, and the like.
  • Ziegler-Natta catalyst such as Ziegler-Natta catalyst, ⁇ -allyl nickel, alkyl lithium catalyst, metallocene catalyst, diethylaluminum chloride, titanium tetrachloride, titanium trichloride, trifluoro Boron ether complex, magnesium oxide, dimethylamine, cuprous chloride, triethylamine
  • the CuAAC reaction is synergistically catalyzed by a monovalent copper compound and an amine ligand.
  • the monovalent copper compound may be selected from a Cu(I) salt such as CuCl, CuBr, CuI, CuCN, CuOAc, etc.; or may be selected from a Cu(I) complex such as [Cu(CH 3 CN) 4 ]PF 6 , [Cu(CH 3 CN) 4 ]OTf, CuBr(PPh 3 ) 3 , etc.; it can also be formed in situ from elemental copper and divalent copper compounds (such as CuSO 4 , Cu(OAc) 2 );
  • the (I) salt is preferably CuBr and CuI, and the Cu(I) complex is preferably CuBr(PPh 3 ) 3 .
  • the amine ligand may be selected from tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), tris[(1-tert-butyl-1H-1, 2,3-triazol-4-yl)methyl]amine (TTTA), tris(2-benzimidazolylmethyl)amine (TBIA), hydrated phenanthroline sodium disulfonate, etc.; among them, amine ligand TBTA and TTTA are preferred.
  • Thiol-ene reaction catalyst photocatalyst, such as benzoin dimethyl ether, 2-hydroxy-2-methylphenylacetone, 2,2-dimethoxy-2-phenylacetophenone, etc.; nucleophilic A reagent catalyst such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine or the like.
  • the amount of the catalyst to be used is not particularly limited and is usually from 0.01 to 2% by weight.
  • the initiator in the additive which can be added/used, which can cause activation of the monomer molecule during the polymerization reaction to generate a radical, increase the reaction rate, and promote the reaction, including but not limited to any one of the following or Several initiators: organic peroxides, such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, diperoxydicarbonate (4 -tert-butylcyclohexyl)ester, t-butylperoxybenzoate, t-butyl peroxypivalate, di-tert-butyl peroxide, dicumyl hydroperoxide; azo compounds such as azo Diisobutyronitrile (AIBN), azobisisoheptanenitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, etc.; wherein the initiator is preferably
  • antioxidant in the additive which can be added/used, which can delay the oxidation process of the polymer sample, ensure the material can be smoothly processed and prolong its service life, including but not limited to any one of the following or Several antioxidants: hindered phenols such as 2,6-di-tert-butyl-4-methylphenol, 1,1,3-tris(2-methyl-4hydroxy-5-tert-butylphenyl) Butane, tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol Sulfur-containing hindered phenols such as 4,4'-thiobis-[3-methyl-6-tert-butylphenol], 2,2'-thiobis-[4-methyl-6-tert Butylphenol]; a triazine-based hindered phenol such as 1,3,5-bis[ ⁇ -(3,
  • the light stabilizer in the additive which can be added/used can prevent photoaging of the polymer sample and prolong its service life, including but not limited to any one or any of the following light stabilizers: light shielding agent Such as carbon black, titanium dioxide, zinc oxide, calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2,4,6- Tris(2-hydroxy-4-n-butoxyphenyl)-1,3,5-s-triazine, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate; pioneer UV absorption Agents such as p-tert-butylphenyl salicylate, bisphenol A disalicylate; UV quenchers such as bis(3,5-di-tert-but
  • the heat stabilizer in the additive which can be added/used can make the polymer sample not undergo chemical change due to heat during processing or use, or delay the change to achieve the purpose of prolonging the service life, including but It is not limited to any one or any of the following heat stabilizers: lead salts such as tribasic lead sulfate, lead dibasic phosphite, lead dibasic stearate, lead dibasic lead, trisalt Lead methoxide, lead silicate, lead stearate, lead salicylate, lead dibasic phthalate lead, basic lead carbonate, silica gel coprecipitated lead silicate; metal soap: such as hard Cadmium citrate, barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds such as di-n-butyltin dilaurate, di-n-octyl dilaurate, maleic acid Butyltin, di-maleic acid monooctyl ester di-
  • the cross-linking agent in the additive which can be added which is used in the dynamic polymer to be cross-linked, and which can bridge the polymer molecules in the on-line type, so that multiple The linear molecules are bonded to each other to form a network structure, which can further increase the crosslinking density and crosslinking strength of the polymer, improve the heat resistance and service life of the polymer, and improve the mechanical properties and weather resistance of the material, including
  • the crosslinking agent is preferably dicumyl peroxide (DCP), benzoyl peroxide (BPO), or 2,4-dichlorobenzoyl peroxide (DCBP).
  • DCP dicumyl peroxide
  • BPO benzoyl peroxide
  • DCBP 2,4-dichlorobenzoyl peroxide
  • the amount of the crosslinking agent to be used is not particularly limited and is usually from 0.1 to 5% by weight.
  • the curing agent in the additive which can be added can enhance or control the curing reaction of the reactant component in the polymerization process, including but It is not limited to any one or any of the following curing agents: an amine curing agent such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, hexamethylenetetramine, m-phenylenediamine; An acid anhydride curing agent such as phthalic anhydride, maleic anhydride, pyromellitic dianhydride; an amide curing agent such as a low molecular polyamide; an imidazole such as 2-methylimidazole or 2-ethyl 4-methylimidazole, 2-phenylimidazole; boron trifluoride complex, and the like.
  • an amine curing agent such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, hexamethylenetetramine, m
  • the curing agent is preferably ethylenediamine (EDA), diethylenetriamine (DETA), phthalic anhydride or maleic anhydride, and the amount of the curing agent to be used is not particularly limited, and is usually from 0.5 to 1% by weight.
  • the chain extender in the additive/additive additive can react with a reactive group on the reactant molecular chain to expand the molecular chain and increase the molecular weight, and is generally used for preparing an additive polyurethane/polyurea.
  • chain extenders including but not limited to any one or any of the following chain extenders: polyol chain extenders, such as ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane, pentaerythritol, 1 , 4-butanediol, 1,6-hexanediol, hydroquinone dihydroxyethyl ether (HQEE), resorcinol bishydroxyethyl ether (HER), p-hydroxyethyl bisphenol A; Polyamine chain extenders such as diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tetraethyldibenzylidenediamine, t
  • the toughening agent in the additive which can be added/used can reduce the brittleness of the polymer sample, increase the toughness, and improve the load bearing strength of the material, including but not limited to any one or any of the following toughening agents: Methyl acrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and modified product thereof, acrylonitrile-butadiene-styrene copolymer, acrylonitrile- Butadiene copolymer, ethylene propylene rubber, EPDM rubber, cis-butyl rubber, styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, etc.; among them, the toughening agent is preferably ethylene propylene rubber or propylene.
  • ABS Nitrile-butadiene-styrene copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • MBS methyl methacrylate-butadiene-styrene copolymer resin
  • CPE Chlorinated polyethylene resin
  • the amount of the toughening agent to be used is not particularly limited and is usually from 5 to 10% by weight.
  • the coupling agent in the additive which can be added/used can improve the interfacial properties of the polymer sample and the inorganic filler or the reinforcing material, reduce the viscosity of the material melt during the plastic processing, and improve the dispersion of the filler.
  • any one or any of the following coupling agents organic acid chromium complex, silane coupling agent, titanium An acid ester coupling agent, a sulfonyl azide coupling agent, an aluminate coupling agent, etc.; wherein the coupling agent is preferably ⁇ -aminopropyltriethoxysilane (silane coupling agent KH550), ⁇ -(2 , 3-glycidoxypropyl)propyltrimethoxysilane (silane coupling agent KH560).
  • the amount of the coupling agent to be used is not particularly limited and is usually from 0.5 to 2% by weight.
  • the lubricant in the additive that can be added/used can improve the lubricity of the polymer sample, reduce friction, and reduce interfacial adhesion performance, including but not limited to any one or any of the following lubricants: saturation Hydrocarbons and halogenated hydrocarbons, such as paraffin wax, microcrystalline paraffin, liquid paraffin, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids such as stearic acid, hydroxystearic acid; fatty acid esters, such as fatty acid lower alcohol esters , fatty acid polyol esters, natural waxes, ester waxes and saponified waxes; aliphatic amides such as stearic acid amide or stearic acid amide, oleamide or oleic acid amide, erucamide, N, N'-ethylene double hard Fatty acid amide; fatty alcohols and polyols such as stearyl alcohol, cetyl alcohol, pentaerythritol; metal soap
  • the release agent is preferably dimethicone or polyethylene glycol.
  • the amount of the releasing agent to be used is not particularly limited and is usually from 0.5 to 2% by weight.
  • plasticizer in the additive that can be added/used, which can increase the plasticity of the polymer sample, such that the hardness, modulus, softening temperature and embrittlement temperature of the polymer decrease, elongation, flexibility and Increased flexibility, including but not limited to any one or any of the following plasticizers: phthalates: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate Ester, diheptyl phthalate, diisononyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl phthalate, butyl phthalate, phthalate Dicyclohexyl formate, bis(tridecyl) phthalate, di(2-ethyl)hexyl terephthalate; phosphates such as tricresyl phosphate, diphenyl-2-ethyl Hexyl ester; fatty acid esters such as di(2-ethy
  • the foaming agent in the additive which can be added/used can foam the polymer sample into pores, thereby obtaining a lightweight, heat-insulating, sound-insulating, elastic polymer material, including but not limited to the following One or any of several blowing agents: physical blowing agents such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene Butane, diethyl ether, methyl chloride, dichloromethane, dichloroethylene, dichlorodifluoromethane, chlorotrifluoromethane; inorganic foaming agents such as sodium hydrogencarbonate, ammonium carbonate, ammonium hydrogencarbonate; organic foaming agents, Such as N, N'-dinitropentamethyltetramine, N, N'-dimethyl-N, N'-dinitrosophthalamide, azodicarbonamide,
  • the blowing agent is preferably sodium hydrogencarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N, N'-dinitropentamethyltetramine (foaming agent H), N, N' -Dimethyl-N,N'-dinitroso-terephthalamide (foaming agent NTA), physical microsphere foaming agent, and the amount of the foaming agent to be used are not particularly limited, and are generally 0.1 to 30% by weight. .
  • the dynamic modifier in the additive that can be added/used can enhance the dynamic polymer dynamics in order to obtain optimal desired properties, typically with free hydroxyl or free carboxyl groups, or can give or accept Electron pair compounds include, but are not limited to, water, sodium hydroxide, alcohols (including silanols), carboxylic acids, Lewis acids, Lewis bases, and the like.
  • the amount of the dynamic regulator used is not particularly limited and is usually from 0.1 to 10% by weight.
  • the antistatic agent in the additive which can be added/used can guide or eliminate the harmful charge accumulated in the polymer sample, so that it does not cause inconvenience or harm to production and life, including but not limited to any of the following Or any of several antistatic agents: anionic antistatic agents, such as alkyl sulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate diethanolamine salts, potassium p-nonyldiphenyl ether sulfonate, Phosphate derivatives, phosphates, polyethylene oxide alkyl ether alcohol esters, phosphate ester 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
  • 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 are preferably catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, chain extenders, toughening agents, plasticizers, foaming agents, flame retardants Agent, dynamic regulator.
  • the coloring effect of the pigment; 5 imparts light stability and chemical resistance; 6 acts as a compatibilizing agent, which can reduce the cost and improve the competitiveness of the product in the market.
  • the filler which can be added 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 gel or the like, or a solvent may be selected to remove the solvent to form a solid polymer sample in the form of a film, a block, a foam or the like.
  • an initiator in a solvent to initiate polymerization to obtain a dynamic polymer by solution polymerization, or to add a dispersing agent and an oil-soluble initiator to prepare a suspension for suspension polymerization or
  • the slurry is polymerized to initiate polymerization to obtain a dynamic polymer, or an initiator and an emulsifier are added to prepare an emulsion to initiate polymerization by emulsion polymerization to obtain a dynamic polymer.
  • the methods of solution polymerization, suspension polymerization, slurry polymerization, and emulsion polymerization employed are all known to those skilled in the art and widely used, and can be adjusted according to actual conditions, and will not be further developed here.
  • the solvent used in the above preparation method should be selected according to the actual conditions such as the reactants, products and reaction processes, including but not limited to any one of the following solvents or a mixed solvent of any of several solvents: deionized water, acetonitrile, acetone, Butanone, benzene, toluene, xylene, ethyl acetate, diethyl ether, methyl tert-butyl ether, tetrahydrofuran, methanol, ethanol, chloroform, dichloromethane, 1,2-dichloroethane, dimethyl sulfoxide, Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isopropyl acetate, n-butyl acetate, trichloroethylene, mesitylene, dioxane, Tris buffer, citrate buffer, acetic acid Buffer solution, phosphate buffer solution, boric acid buffer solution, etc.; preferably deionized
  • the solvent may also be selected from the group consisting of an oligomer, a plasticizer, and an ionic liquid;
  • the oligomer includes, but is not limited to, a polyethylene glycol oligomer, a polyvinyl acetate oligomer, and a polybutyl acrylate. a polymer, a liquid paraffin or the like;
  • the plasticizer may be selected from the class of plasticizers in the additive which may be added, and is not described herein;
  • the ionic liquid generally consists of an organic cation and an inorganic anion.
  • the cation is usually an alkyl quaternary ammonium ion, an alkyl quaternary phosphonium ion, a 1,3-dialkyl substituted imidazolium ion, an N-alkyl substituted pyridinium ion, etc.; the anion is usually a halogen ion, a tetrafluoroborate ion, and a hexa Fluoride ions, also CF 3 SO 3 - , (CF3SO 2 ) 2 N - , C 3 F 7 COO - , C 4 F 9 SO 3 - , CF 3 COO - , (CF 3 SO 2 ) 3 C - , (C 2 F 5 SO 2 ) 3 C - , (C 2 F 5 SO 2 ) 2 N - , SbF 6 - , AsF 6 -, and the like.
  • a hydrogel can be obtained by using deionized water to prepare a dynamic polymer and selectively retaining it; when an organic solvent is used to prepare a dynamic polymer and it is selected to be retained, an organogel can be obtained; When preparing a dynamic polymer and selecting to retain it, an oligomer swollen gel can be obtained; when a dynamic polymer is prepared by using a plasticizer and selected to retain it, a plasticizer swollen gel can be obtained; using an ionic liquid to prepare When the dynamic polymer is selected and retained, an ionic liquid swollen gel can be obtained.
  • the liquid concentration of the compound to be disposed is not particularly limited depending on the structure, molecular weight, solubility, and desired dispersion state of the selected reactant, and a preferred compound liquid concentration is 0.1 to 10 mol/L, and more preferably 0.1 to 1 mol/L.
  • a specific method for preparing a dynamic polymer by melt-mixing usually by directly stirring or mixing the raw materials in a reactor, and then stirring and mixing the mixture, generally in the case where the raw material is a gas, a liquid or a solid having a low melting point.
  • the mixing reaction temperature is controlled at 0 to 200 ° C, preferably 25 to 120 ° C, more preferably 25 to 80 ° C
  • the mixing and stirring time is controlled to be 0.5 to 12 h, preferably 1 to 4 h.
  • the product obtained after the mixing and stirring may be poured into a suitable mold and placed at 0 to 150 ° C, preferably 25 to 80 ° C, for 0 to 48 hours to obtain a polymer sample.
  • melt polymerization and gas phase polymerization are all known to those skilled in the art and widely used, and can be adjusted according to actual conditions, and will not be developed in detail here.
  • a specific method for preparing a dynamic polymer by melt extrusion mixing is usually carried out by adding a raw material to an extruder for extrusion blending at an extrusion temperature of 0 to 280 ° C, preferably 50 to 150 ° C.
  • the reaction product can be directly cast into a suitable size, or the obtained extruded sample can be crushed and then sampled by an injection molding machine or a molding machine.
  • the injection temperature is 0-280 ° C, preferably 50-150 ° C
  • the injection pressure is preferably 60-150 MPa
  • the molding temperature is 0-280 ° C, preferably 25-150 ° C, more preferably 25-80 ° C
  • the molding time is 0.5-60 min, preferably
  • the molding pressure is preferably 4-15 MPa at 1-10 min.
  • the spline can be placed in a suitable mold and placed at 0-150 ° C, preferably 25-80 ° C, for 0-48 h to give the final polymer sample.
  • the molar equivalent ratio of the inorganic boron compound to the (poly)siloxane compound to be used in the preparation of the dynamic polymer should be in an appropriate range, preferably in the range of 0.1 to 10, more preferably in the range of 0.3 to 3, more preferably The range of 0.8 to 1.2. In the actual preparation process, those skilled in the art can adjust according to actual needs.
  • the amount of the raw materials of the dynamic polymer components is not particularly limited, and those skilled in the art can adjust according to the actual preparation conditions and the properties of the target polymer.
  • the dynamic polymer properties are widely adjustable and have broad application prospects, and are important in military aerospace equipment, functional coatings and coatings, biomedicine, biomedical materials, energy, construction, bionics, smart materials, and the like. Applications.
  • the dilatancy and dynamics of dynamic polymers By utilizing the dilatancy and dynamics of dynamic polymers, it can be applied to the production of damping dampers for vibration isolation of various motor vehicles, mechanical equipment, bridges, buildings, and when the polymer material is subjected to vibration. It can dissipate a large amount of energy to dampen the effect, thereby effectively alleviating the vibration; it can also be used as an energy absorbing cushioning material for cushioning packaging materials, sports protection products, impact protection products, and military and police protective materials, thereby Reduce the shock and impact of objects or the human body under external forces, including noise and shock waves generated by explosions.
  • the dynamic properties of the silicon borate bond can also be used as a shape memory material.
  • the preparation of stress-sensitive polymer materials can also be used to prepare speed locks for roads and bridges, and can also be used for making seismic shears.
  • Plate or cyclic stress bearing tool or used to make stress monitoring sensors.
  • the inorganic boronic acid silicate bond When used as a sacrificial bond, it can absorb a large amount of energy and impart excellent toughness to the polymer material, thereby obtaining a polymer material having excellent toughness, which is widely used in military, aerospace, sports, energy. , construction and other fields.
  • hydroxyl terminated polybutadiene (HTPB) and toluene diisocyanate (2,4-TDI) are thoroughly mixed, and a small amount of glycerol is added as a crosslinking agent to control the NCO:OH in the reaction is about 1.2:1, that is, 2, A slight excess of 4-TDI, covalently cross-linked to give a polyurethane with a double bond in the pendant group (molecular weight of about 18,000).
  • the polymer product has good toughness, its conductivity can change with sensitivity due to changes in pressure and tension, and has a force sensing function, which can be used as a force sensor.
  • Trimethyl borate and dimethylmethoxy-3-butene silane were mixed at a molar ratio of 1:3, heated to 60 ° C and dissolved by stirring, and then a small amount of water was added to continue the reaction for 4 h to obtain a silyl borate.
  • the trivinyl compound 2a of the bond was obtained by the reaction for 4 h.
  • the polymer product can be used as a sheet or coating having some self-healing properties and tear resistance.
  • 3-Aminopropylmethyldimethoxysilane and adipyl chloride are mixed at a molar ratio of 2:1, and triethylamine is used as a catalyst to react in anhydrous dichloromethane to prepare a disiloxane compound. .
  • the terminal silylhydroxy poly(dimethyl-methylphenyl)siloxane, the above disiloxane compound, isopropanol pinacol borate according to Si-OH, Si-OCH 3 group and B-OR group The molar ratio of the group is 1:1:2, a small amount of 20% acetic acid aqueous solution is added dropwise, and the mixture is uniformly stirred at 50 ° C, and then reacted for 8 hours to prepare a dynamic polymer containing a silicon borate bond as the first network. polymer.
  • N, N'-methylenebisacrylamide, lutidine dithiol, trimethylolpropane tris(3-mercaptopropionate) are mixed according to a molar ratio of 20:20:1, and added to 120 wt%.
  • the epoxy acetyl ricinoleic acid swelled organogel prepared in this example has a modulus of 22 kPa, a strain of 16 times, and a breaking stress of 89 kPa.
  • This organogel can be used to prepare airborne and airborne impact resistant materials.
  • 1,3-diphenylpropane-2,2-dithiol and compound 4a, tripropyleneamine are mixed according to a molar ratio of 9:6:2, and placed in an ultraviolet cross-linking instrument for ultraviolet light for 8 hours to obtain a skeleton-containing hydrogen.
  • a bond group and a generally covalently crosslinked polymer are used as the first network polymer.
  • the polymer product can be used to make seismic shear plates or cyclic stress bearing tools.
  • the terpene oxide extracted from the orange peel is polymerized with 100 psi of carbon dioxide under the catalysis of ⁇ -diimine zinc to obtain a polycarbonate PLimC.
  • the above polycarbonates PLimC and N-[(2-mercaptoethyl)carbamoyl]propionamide, bis(2-mercaptoethyl) adipate are 10:9:1 according to the ratio of the double bond group and the thiol group.
  • the polymer sample has a large viscosity and a very good tensile toughness, and can be stretched to a large extent without breaking (breaking elongation of up to 600%).
  • the polymer can be used as an electronic packaging material or an adhesive, which can self-repair the small cracks that occur, and can avoid material damage and gas leakage.
  • tert-butyl methacrylate and compound 6a as monomers, controlling the molar ratio of the two to 10:1, a common covalently crosslinked polymer containing a skeleton hydrogen bond group was prepared by radical polymerization (molecular weight It is 7500) as the first network polymer.
  • the polymer is prepared into a film, exhibits superior comprehensive properties, has a certain tensile strength and good tear resistance, and can be stretched to a greater extent.
  • Such dynamic polymers can be used to make functional films, or can be used as films for automobiles and furniture, or as stretch wrap films, which are very scratch resistant.
  • Silicone hydroxy-terminated and pendant olefinic group-containing organopolysiloxane (molecular weight of about 2000) and 2,6-di-tert-butyl-4-tolyldibutyl orthoboroate according to terminal siloxane Mixing with the boric acid ester molar ratio of 1:1, heating to 80 ° C and mixing uniformly, adding 6 ml of deionized water, and carrying out polymerization under stirring to prepare an organopolysiloxane containing a silicon borate bond.
  • the polymer product can be used to prepare a military and police protective material.
  • Dipropionyl adipate and 1,3,5-tris(azidomethyl)benzene are mixed at a molar ratio of 3:2, and 0.1 wt% of the catalyst CuBr(PPh 3 ) 3 and three are added relative to the monomer [ (1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), stirred well and reacted at 60 ° C for 4 h to obtain a common covalent cross-linking
  • the polymer acts as the first network polymer.
  • the dynamic polymer containing a silicon borate bond cross-linking was added to a small extruder for extrusion blending at an extrusion temperature of 120 ° C, and the obtained extruded spline was subjected to granulation to obtain elastic small particles.
  • the elastic small particles were dispersed in the first network polymer in a solvent, and then placed in an oven at 50 ° C for 24 hours to remove the solvent, and then cooled to room temperature for 30 minutes to obtain a common covalent cross-linking and silicic acid borate bond.
  • Dynamic polymer
  • the polymer product exhibits good viscoelasticity, good isolation shock and stress buffering effect, and also exhibits excellent hydrolysis resistance.
  • 1,11-dichloro-1,1,3,3,5,5,7,7,9,9,11,11-dodecylhexasiloxane the above pendant group contains a diethoxysilane group
  • the grafted polyethylene and trimethyl borate are mixed according to the molar ratio of Si-Cl, Si-OCH 2 CH 3 group and B-OCH 3 group 1:3:4, and a small amount of water and 2.3 g of white carbon are added.
  • the above dynamic polymer containing a silicon borate bond cross-linking was added to a small extruder for extrusion blending at an extrusion temperature of 120 ° C, and the obtained extruded spline was subjected to granulation to obtain elastic small particles.
  • the elastic small particles were dispersed in the first network polymer in a solvent, and then placed in an oven at 50 ° C for 24 hours to remove the solvent, and then cooled to room temperature for 30 minutes to obtain a common covalent cross-linking and silicic acid borate bond.
  • Dynamic polymer Dynamic polymer.
  • the dynamic polymer has strong mechanical properties and excellent impact resistance, and can be used for preparing an impact resistant protective pad.
  • n-butyl methacrylate and trimethylolpropane trimethacrylate as monomers, controlling the molar ratio of the two to be 60:1, adding 3 mol% of AIBN as an initiator, and preparing by free radical polymerization.
  • a copolymer of n-butyl methacrylate and trimethylolpropane trimethacrylate (molecular weight of about 8,000) was obtained, that is, a polymer containing a common covalent crosslinked network was obtained.
  • the polymer product exhibits good viscoelastic properties, good isolation shock and stress buffering, and can be used as an elastic cushioning gasket.
  • the terpene oxide extracted from the orange peel is polymerized with 100 psi of carbon dioxide under the catalysis of ⁇ -diimine zinc to obtain a polycarbonate PLimC.
  • the polymer product can be used to make seismic shear plates or cyclic stress bearing tools.
  • the polymer product can be used to make damping dampers for a variety of motor vehicles and machinery.

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Abstract

A dynamic polymer with a hybrid cross-linked structure, comprising a common covalent crosslinking network with at least one carbon chain or carbon heterochain skeleton, and simultaneously comprises a dynamic covalent inorganic borate silicon ester bond. The common covalent crosslinking imparts the polymer with a certain strength and stability. The presence of the inorganic borate silicon ester bond allows the polymer to have good dynamic reversibility, thereby realizing functional properties such as stimuli responsiveness; it also enables good energy absorption in the polymer and can toughen and damp the material under specific structural configurations. The dynamic polymer can be used to make shock absorbing materials, anti-impact protection materials, self-repairing materials, tough materials, force sensors, and the like.

Description

具有杂化交联结构的动态聚合物及其应用Dynamic polymer with hybrid crosslinked structure and its application 技术领域Technical field
本发明涉及智能聚合物领域，具体涉及一种由普通共价键和无机硼酸硅酯键构成的具有杂化交联网络的动态聚合物及其应用。The invention relates to the field of smart polymers, in particular to a dynamic polymer having a hybrid crosslinked network composed of a common covalent bond and an inorganic boronic acid silicate bond and an application thereof.
背景技术Background technique
传统的聚合物一般由普通共价键构成，普通共价键由于具有较高的键能，赋予了聚合物以良好的稳定性和应力承载能力。而动态共价键则是一类可以在一定条件下进行可逆反应的化学键，它比非共价键稳定，但键能又弱于普通共价键，通过控制外界的条件可以实现动态共价键的断裂和形成。将动态共价键引入聚合物，是一种形成新型智能聚合物的可行方法。在聚合物中引入动态共价键的意义在于，动态共价键在普通共价键的基础上，具有超分子化学中非共价相互作用所具有的动态可逆特性，同时又规避了超分子非共价相互作用本身键能较弱，稳定性较差，易受外界因素影响的缺陷。因此，通过在聚合物中引入动态共价键，有希望能够获得具有良好综合性能的聚合物。Conventional polymers are generally composed of common covalent bonds, which have a high bond energy and give the polymer good stability and stress carrying capacity. The dynamic covalent bond is a kind of chemical bond that can undergo reversible reaction under certain conditions. It is more stable than non-covalent bond, but the bond energy is weaker than the common covalent bond. Dynamic covalent bond can be realized by controlling external conditions. The break and formation. The introduction of dynamic covalent bonds into polymers is a viable way to form new smart polymers. The significance of introducing dynamic covalent bonds into polymers is that dynamic covalent bonds have the dynamic reversible properties of non-covalent interactions in supramolecular chemistry on the basis of common covalent bonds, while avoiding supramolecular non- Covalent interactions have weak bond bonds, poor stability, and are susceptible to external factors. Therefore, by introducing a dynamic covalent bond into the polymer, it is hopeful that a polymer having a good overall performance can be obtained.
通过交联的手段使得聚合物等组分形成无限三维网络结构，能够使得聚合物在热稳定性、力学性能、耐溶剂性等方面的性能得以提高，并可以获得具有良好使用性能和应用价值的聚合物材料。对于传统的交联聚合物，其一般分为化学交联型或者是物理交联型。化学交联型聚合物一般通过普通共价键交联形成，一旦形成，则非常稳定，力学性能也比较优良；物理交联型聚合物一般通过非共价相互作用交联形成，其突出的特点是具有动态可逆性，交联结构和聚合物的性能具有可变性。而目前普遍使用的交联聚合物，其往往是由单一的普通共价键或单一的动态共价键所构成，还无法良好地将结构性与动态性在聚合物中进行有机地结合，其动态性的可逆效果以及调控能力也十分有限，因此需要发展出一种新型的聚合物以解决现有技术中存在的问题。By means of cross-linking, the components such as polymer form an infinite three-dimensional network structure, which can improve the performance of the polymer in terms of thermal stability, mechanical properties, solvent resistance, etc., and can obtain good performance and application value. Polymer material. For conventional crosslinked polymers, they are generally classified into a chemically crosslinked type or a physically crosslinked type. Chemically crosslinked polymers are generally formed by cross-linking of common covalent bonds. Once formed, they are very stable and have good mechanical properties. Physically crosslinked polymers are generally formed by cross-linking through non-covalent interactions. It is dynamically reversible, and the properties of the crosslinked structure and polymer are variability. However, the cross-linked polymers currently in common use are often composed of a single common covalent bond or a single dynamic covalent bond, and the structural and dynamic properties are not well organically combined in the polymer. The reversible effect of dynamics and the ability to regulate are also very limited, so there is a need to develop a new type of polymer to solve the problems in the prior art.
发明内容Summary of the invention
本发明针对上述背景，提供了一种具有杂化交联结构的碳链/碳杂链动态聚合物，其中包含至少一个普通共价交联网络，同时其中还包含有动态共价无机硼酸硅酯键。所述的动态聚合物在具有一定的力学强度和良好的韧性的同时，也表现出优良的动态可逆性，并可体现出刺激响应性、自粘性、吸能性、一定的自修复性等功能特性。The present invention is directed to the above background, and provides a carbon chain/carbon heterochain dynamic polymer having a hybrid crosslinked structure comprising at least one common covalent crosslinked network, and further comprising a dynamic covalent inorganic boronic acid borate key. The dynamic polymer exhibits excellent dynamic reversibility while exhibiting certain mechanical strength and good toughness, and can exhibit functions such as stimuli responsiveness, self-adhesiveness, energy absorption, and certain self-repairability. characteristic.
本发明通过如下技术方案予以实现：The invention is implemented by the following technical solutions:
一种具有杂化交联结构的动态聚合物，其中包含至少一个普通共价交联网络，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；同时其中包含动态共价无机硼酸硅酯键，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子；所述的连接基Y，其处于动态聚合物主链骨架的结构仅含有(聚)硅氧烷单元。A dynamic polymer having a hybrid crosslinked structure comprising at least one common covalent crosslinked network, and at least one of said common covalently crosslinked network backbones is a carbon chain or a carbon hetero chain structure; a valence inorganic silicic acid silicate bond, wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is linked to three -O-, and some of them are based on different BO-Si dynamic covalent bonds of different B atoms The Si atoms are connected by a linking group L, and are partially connected via a linking group Y based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms; the linking group L, which is contained on the dynamic polymer backbone skeleton The carbon atom; the linker Y, which is in the structure of the dynamic polymer backbone backbone, contains only (poly)siloxane units.
在本发明的一个实施方式中(第一种网络结构)，所述动态聚合物只有一个网络，该网络中同时含有普通共价交联和动态共价无机硼酸硅酯键交联，其中普通共价交联达到其凝胶点以上并且其交联网络骨架为碳链或碳杂链结构；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通 过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。In one embodiment of the invention (the first network structure), the dynamic polymer has only one network, and the network contains both common covalent crosslinks and dynamic covalent inorganic silicon borate linkages, wherein The valence crosslinks above its gel point and its crosslinked network backbone is a carbon chain or carbon heterochain structure; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is connected to three -O-, and Some of the Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and some Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group Y; The linker L, which contains a carbon atom on the backbone of the dynamic polymer backbone, the structure of the linker Y on the dynamic polymer backbone backbone contains only (poly)siloxane units.
在本发明的另一个实施方式中(第二种网络结构)，所述动态聚合物含有两个网络；第1网络中仅含普通共价交联，并且其共价交联网络骨架为碳链或碳杂链结构；第2网络中以动态共价无机硼酸硅酯键形成的交联达到其凝胶点以上，不含凝胶点以上的普通共价交联，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。In another embodiment of the invention (second network structure), the dynamic polymer contains two networks; the first network contains only ordinary covalent crosslinks, and the covalently crosslinked network backbone is a carbon chain Or a carbon heterocyclic structure; the crosslinking formed by the dynamic covalent inorganic boronic acid silicate bond in the second network reaches above the gel point, and does not contain ordinary covalent cross-linking above the gel point, wherein the dynamic covalent Any one of the B atoms of the inorganic boronic acid silicate bond is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on different B atoms. The different Si atoms in the BO-Si dynamic covalent bond are linked by a linker Y; the linker L, which contains a carbon atom on the backbone of the dynamic polymer backbone, which is in the dynamic state The structure on the backbone of the polymer backbone contains only (poly)siloxane units.
在本发明的另一个实施方式中(第三种网络结构)，所述动态聚合物含有两个网络；第1网络如所述第一种网络结构；第2网络中仅含普通共价交联，不含所述动态共价无机硼酸硅酯键；其中，至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。In another embodiment of the present invention (a third network structure), the dynamic polymer contains two networks; the first network is as described in the first network structure; and the second network contains only ordinary covalent cross-linking And not containing the dynamic covalent inorganic boronic acid borate bond; wherein at least one of the common covalent crosslinked network backbones is a carbon chain or a carbon heterochain structure; wherein any of the dynamic covalent inorganic boronic acid borate bonds A B atom is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and some are based on BO-Si dynamic covalent of different B atoms. The different Si atoms in the bond are connected by a linker Y; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, said linker Y being on the backbone of the dynamic polymer backbone The structure contains only (poly)siloxane units.
在本发明的另一个实施方式中(第四种网络结构)，所述动态聚合物含有两个网络；第1网络和第2网络均为所述第一种网络结构，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构，但所述的第1和第2网络不同。这种不相同，可以举例如，聚合物链主体结构不同、共价交联的交联密度不同、聚合物链侧基和/或侧链的组成不同等。In another embodiment of the present invention (fourth network structure), the dynamic polymer contains two networks; the first network and the second network are both the first network structure, and at least one of the ordinary The covalently crosslinked network backbone is a carbon chain or a carbon heterochain structure, but the first and second networks are different. Such a difference may be, for example, a difference in the main structure of the polymer chain, a difference in the crosslinking density of the covalently crosslinked, a difference in the composition of the side chain and/or the side chain of the polymer chain, and the like.
在本发明的另一个实施方式中(第五种网络结构)，所述动态聚合物含有至少一个网络，该些网络中仅含有普通共价交联，至少一个所述普通共价交联网络骨架为碳链或碳杂链结构，并且以动态共价无机硼酸硅酯键交联的聚合物以颗粒形式分散在所述网络中；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。In another embodiment of the invention (fifth network structure), the dynamic polymer contains at least one network containing only common covalent crosslinks, at least one of the common covalent crosslinked network backbones a polymer which is a carbon chain or a carbon hetero chain structure and crosslinked by a dynamic covalent inorganic boronic acid silicate bond is dispersed in the network in the form of particles; wherein any one of the dynamic covalent inorganic boron silicate bonds is B The atom is connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on the BO-Si dynamic covalent bond of different B atoms. The different Si atoms are connected by a linker Y; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the dynamic polymer backbone backbone, is only Contains (poly)siloxane units.
在本发明的另一个实施方式中(第六种网络结构)，所述动态聚合物仅含有一个网络，该网络中仅含有普通共价交联，所述普通共价交联网络骨架为碳链或碳杂链结构，并且含有动态共价无机硼酸硅酯键的非交联聚合物分散在所述网络中；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。In another embodiment of the present invention (sixth network structure), the dynamic polymer contains only one network, and the network only contains ordinary covalent crosslinks, and the common covalent crosslinked network skeleton is a carbon chain. Or a carbon heterochain structure, and a non-crosslinked polymer containing a dynamic covalent inorganic boronic acid silicate bond dispersed in the network; wherein the dynamic covalent inorganic boron silicate bond is any one of B atoms and three - O-linkage, and in which some Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected by a linker L, and partly based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms The linker Y is linked; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the backbone of the dynamic polymer backbone, contains only (poly)silicon Oxytomane unit.
在本发明的另一个实施方式中(第七种网络结构)，所述动态聚合物含有两个网络，第1网络和第2网络中均仅含普通共价交联，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；第1网络和第2网络可以相同或者不同，优选不同；在其中至少一个网络中分散有含有动态共价无机硼酸硅酯键的非交联聚合物；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原 子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。In another embodiment of the present invention (seventh network structure), the dynamic polymer contains two networks, and both the first network and the second network contain only ordinary covalent crosslinks, and at least one of the ordinary The covalently crosslinked network backbone is a carbon chain or a carbon heterochain structure; the first network and the second network may be the same or different, preferably different; in which at least one network is dispersed with a non-crossing containing a dynamic covalent inorganic boronic acid borate bond a bipolymer; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is linked to three -O-, and a part of which is based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms The linking group L is connected, and the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through a linking group Y; the linking group L, which contains a carbon atom on the backbone of the dynamic polymer backbone The linker Y, which is on the dynamic polymer backbone backbone, contains only (poly)siloxane units.
在本发明的实施方式中，所述的无机硼酸硅酯键(B-O-Si)由无机硼化合物和含硅羟基和/或硅羟基前驱体的含硅化合物反应而成。In an embodiment of the invention, the inorganic boronic acid silicate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor.
其中，所述无机硼化合物是指化合物中的硼原子不与碳原子通过硼碳键相连的含硼化合物，所述无机硼化合物选自包括但不限于硼酸、硼酸酯、硼酸盐、硼酸酐、卤化硼等。Wherein, 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, boric acid ester, borate, boric acid. Anhydride, boron halide, and the like.
所述含硅羟基和/或硅羟基前驱体的含硅化合物，是指化合物的端基和/或侧基含有硅羟基和/或硅羟基前驱体基团。The silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor means that the terminal group and/or the pendant group of the compound contains a silyl group and/or a silanol precursor group.
在本发明中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物骨架上的碳原子，所述的连接基Y，其仅含有(聚)硅氧烷单元In the present invention, any one of the B atoms of the dynamic covalent inorganic boronic acid borate bond is bonded to three -O-, and a part of the Si atom in the BO-Si dynamic covalent bond based on a different B atom passes through the linking group. L is connected, and at the same time, the Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through a linking group Y; the linking group L, which contains carbon atoms on the dynamic polymer backbone, the connection Base Y, which contains only (poly)siloxane units
在本发明的实施方式中，用于制备动态聚合物的原料组分，除所述的无机硼化合物和含硅化合物之外，还包括可添加/使用的其他聚合物、助剂、填料。In an embodiment of the present invention, a raw material component for preparing a dynamic polymer includes, in addition to the inorganic boron compound and the silicon-containing compound, other polymers, adjuvants, and fillers that can be added/used.
其中，所述的其他聚合物选自以下任一种或任几种：天然高分子化合物、合成树脂、合成橡胶、合成纤维；Wherein, the other polymer is selected from any one or more of the following: a natural polymer compound, a synthetic resin, a synthetic rubber, a synthetic fiber;
其中，所述的助剂选自以下任一种或任几种：催化剂、引发剂、抗氧剂、光稳定剂、热稳定剂、交联剂、固化剂、扩链剂、增韧剂、偶联剂、润滑剂、脱模剂、增塑剂、发泡剂、动态调节剂、抗静电剂、乳化剂、分散剂、着色剂、荧光增白剂、消光剂、阻燃剂、成核剂、流变剂、增稠剂、流平剂；Wherein, the auxiliary agent is selected from any one or more of the following: a catalyst, an initiator, an antioxidant, a light stabilizer, a heat stabilizer, a crosslinking agent, a curing agent, a chain extender, a toughening agent, Coupling agent, lubricant, mold release agent, plasticizer, foaming agent, dynamic regulator, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, matting agent, flame retardant, nucleation Agent, rheological agent, thickener, leveling agent;
其中，所述的填料选自以下任一种或任几种：无机非金属填料、金属填料、有机填料。Wherein, the filler is selected from any one or more of the following: an inorganic non-metallic filler, a metal filler, and an organic filler.
在本发明的实施方式中，所述的动态聚合物或其组成的形态包括但不限于普通固体、凝胶(包括水凝胶、有机凝胶、齐聚物溶胀凝胶、增塑剂溶胀凝胶、离子液体溶胀凝胶)、泡沫。In an embodiment of the invention, the dynamic polymer or a composition thereof comprises, but is not limited to, a common solid, a gel (including a hydrogel, an organogel, an oligomer swollen gel, a plasticizer, and a swelling agent). Glue, ionic liquid swelling gel), foam.
在本发明的实施方式中，提供一种吸能方法，其特征在于，提供一种具有杂化交联结构的动态聚合物并以其作为吸能材料进行吸能，其中，所述的动态聚合物包含至少一个普通共价交联网络，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；同时其中包含动态共价无机硼酸硅酯键，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物骨架上的碳原子；所述的连接基Y，其处于动态聚合物骨架的结构仅含有(聚)硅氧烷单元。In an embodiment of the present invention, there is provided an energy absorbing method, characterized in that a dynamic polymer having a hybrid crosslinked structure is provided and energy absorption is performed as an energy absorbing material, wherein the dynamic polymerization And comprising at least one common covalent crosslinked network, and at least one of said common covalent crosslinked network backbones is a carbon chain or a carbon hetero chain structure; and wherein it comprises a dynamic covalent inorganic boronic acid borate linkage, wherein said dynamic Any one of the B atoms of the inorganic boronic acid borate bond is connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and partly based on different B The different Si atoms in the BO-Si dynamic covalent bond of the atom are connected by a linker Y; the linker L, which contains a carbon atom on the dynamic polymer backbone; the linker Y, which is in a dynamic polymerization The structure of the skeleton contains only (poly)siloxane units.
在本发明的实施方式中，所述具有杂化交联结构的动态聚合物性能大范围可调，具有广阔的应用前景，具体来说，可将其应用于制作减震器、缓冲材料、抗冲击防护材料、运动防护制品、军警防护制品、自修复性涂层、自修复性板材、自修复性粘结剂、防弹玻璃夹层胶、储能器件材料、韧性材料、形状记忆材料、玩具、力传感器等制品。In the embodiment of the present invention, the dynamic polymer having a hybrid crosslinked structure has a wide range of properties, and has broad application prospects. Specifically, it can be applied to fabricating a shock absorber, a buffer material, and an anti-wearing agent. Impact protection materials, sports protection products, military and police protective products, self-healing coatings, self-healing sheets, self-healing adhesives, bulletproof glass interlayer adhesives, energy storage device materials, ductile materials, shape memory materials, toys, Products such as force sensors.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明的动态聚合物杂化交联网络结构中结合了普通共价交联和无机硼酸硅酯键交联，充分利用并结合了各自的优点。其中，普通共价交联为动态聚合物提供了一个强而稳定的网络结构，聚合物可以保持平衡结构，也即尺寸稳定性；而动态共价无机硼酸硅酯键交联则为动态聚合物提供了一个共价的可自发地或在外界作用下可逆变化的动态网络结构，从而实现了动态共价键与普通共价键的“动静结合”，在聚合物网络中表现出协同作用。(1) The dynamic polymer hybrid crosslinked network structure of the present invention combines ordinary covalent cross-linking and inorganic boric acid silicide bond cross-linking, and fully utilizes and combines the respective advantages. Among them, common covalent cross-linking provides a strong and stable network structure for dynamic polymers, the polymer can maintain a balanced structure, that is, dimensional stability; and dynamic covalent inorganic silicon borate bond cross-linking is a dynamic polymer. It provides a covalent dynamic network structure that can be reversibly changed spontaneously or under the influence of the outside world, thereby realizing the "dynamic and static combination" of dynamic covalent bonds and common covalent bonds, and exhibits synergy in the polymer network.
(2)相比于传统的普通共价交联聚合物，本发明中的无机硼酸硅酯键能够凭借其较高的动态可逆性以及应力敏感性，使得交联聚合物能够及时、迅速地对外力做出反应；而相比于现有的超分子交联聚合物，本发明中的无机硼酸硅酯键又因其共价性质在断裂过程中能够耗 散更多的能量，从而更好地提升材料的吸能特性和韧性。而且无机硼酸硅酯键的断裂是可逆的，可复原的，赋予材料以耐用性。基于无机硼酸硅酯键的强动态性，聚合物可以表现出胀流性，从而产生从蠕变性到高弹性的转变，对冲击力分散的能力大大提高，从而达到优异的抗冲击效果；而且由于普通共价交联的存在，聚合物具有自支撑性，免去采用囊袋对聚合物进行装裹但却可能泄露的麻烦，具有优异的实用性。利用本发明所采用的设计思路，在保留了传统交联聚合物力学强度、稳定性等特性的同时，改变了传统交联聚合物断裂伸长率低，韧性差的缺陷，又具有优异的抗冲击性能，这是现有技术所无法达到的。(2) Compared with the conventional common covalently crosslinked polymer, the inorganic boronic acid silicate bond of the present invention enables the crosslinked polymer to be promptly and rapidly externally due to its high dynamic reversibility and stress sensitivity. Force to react; compared with the existing supramolecular cross-linked polymer, the inorganic boronic acid silicate bond in the present invention can dissipate more energy during the fracture process due to its covalent property, thereby better Improve the energy absorption properties and toughness of the material. Moreover, the fracture of the inorganic boronic acid silicate bond is reversible, reversible, and imparts durability to the material. Based on the strong dynamics of the inorganic boronic acid silicate bond, the polymer can exhibit dilatancy, resulting in a transition from creep to high elasticity, and the ability to disperse the impact force is greatly improved, thereby achieving an excellent impact resistance; Due to the existence of common covalent cross-linking, the polymer is self-supporting, eliminating the trouble of using a pouch to encapsulate the polymer but may leak, and has excellent practicability. By adopting the design idea adopted by the invention, the traditional crosslinked polymer has the characteristics of low elongation at break, poor toughness and excellent resistance while retaining the mechanical strength and stability of the traditional crosslinked polymer. Impact performance, which is not possible with the prior art.
(3)本发明的一种具有杂化交联结构的动态聚合物，其中包含有两种不同的连接基L和连接基Y，通过调节两者的比例以及两种连接基的结构修饰，可制备出具有不同结构的动态聚合物，从而使动态聚合物体现出丰富各异的性能，满足不同场合的应用需求。(3) A dynamic polymer having a hybrid crosslinked structure of the present invention, which comprises two different linking groups L and a linking group Y, by adjusting the ratio of the two and the structural modification of the two linking groups. The dynamic polymers with different structures are prepared, so that the dynamic polymers can exhibit a variety of properties to meet the application needs of different occasions.
(4)本发明中杂化交联动态聚合物的结构丰富，性能多样，原料来源广泛易得。通过调整原料化合物中的官能团数、分子结构、分子量和/或在原料化合物中引入具有反应性的基团、促进动态性的基团、具有功能性的基团和/或调整原料组成等参数，可制备出具有不同结构的动态聚合物，从而使动态聚合物体现出丰富各异的性能。作为原料组分之一的无机硼化合物来源广泛、性质稳定且价格便宜，很大程度上降低了动态聚合物的合成成本，简化了制备流程，使得制得的杂化交联动态聚合物材料能够更为高效地投入实际生产应用，扩展了材料的应用领域。(4) In the present invention, the hybrid crosslinked dynamic polymer has a rich structure, various properties, and a wide range of raw material sources. By adjusting 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 to provide dynamic polymers with a wide variety of properties. As one of the raw material components, the inorganic boron compound has a wide range of sources, stable properties and low price, which greatly reduces the synthesis cost of the dynamic polymer, simplifies the preparation process, and enables the obtained hybrid crosslinked dynamic polymer material to be obtained. More efficient investment in practical production applications has expanded the field of application of materials.
(5)杂化交联动态聚合物中动态可逆键的动态反应性强、动态反应条件温和。相比于现有的其他动态共价体系，本发明充分利用了硼酸酯键兼具有的良好的热稳定性和高动态可逆性，可在无需催化剂、无需高温、光照条件下实现动态聚合物的合成和动态可逆性，在提高了制备效率的同时，也降低了使用环境的局限性，扩展了聚合物的应用范围。此外，通过可选择性地控制其他条件(如加入助剂、调整反应温度等)，能够在适当的环境下，加速或淬灭动态共价化学平衡，使其处于所需的状态，这在现有的超分子化学以及动态共价体系里面是较难做到的。(5) The dynamic reversible bond in the hybrid crosslinked dynamic polymer has strong dynamic reactivity and mild dynamic reaction conditions. Compared with other existing dynamic covalent systems, the present invention makes full use of boric acid ester bond and has good thermal stability and high dynamic reversibility, and can realize dynamic polymerization without catalyst, high temperature and illumination. The synthesis and dynamic reversibility of the material, while improving the preparation efficiency, also reduces the limitations of the use environment, and expands the application range of the polymer. In addition, 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.
参考下述实施方式说明、实施例和所附权利要求书，本发明的这些和其他特征以及优点将变得显而易见。These and other features and advantages of the present invention will become apparent from the description and appended claims appended claims.
具体实施方式detailed description
本发明涉及一种具有杂化交联结构的动态聚合物，其中包含至少一个普通共价交联网络，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；同时其中包含动态共价无机硼酸硅酯键，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。本发明中所用术语“聚合”(反应)为链的增长过程/作用，包括反应物通过缩聚、加聚、开环聚合等反应形式合成具有更高分子量的产物的过程。在这其中，反应物一般为具有聚合能力(即能够自发地进行聚合，或者能够在引发剂或外加能作用下进行聚合)的单体、低聚物、预聚物等化合物。由一种反应物进行聚合得到的产物称为均聚物。由两种或两种以上反应物进行聚合得到的产物称为共聚物。需要指出的是，在本发明中所述的“聚合”，其包含反应物分子链的线性增长过程，包含反应物分子链的支化过程，包含反应物分子链的成环过程，也包含反应物分子链的交联过程。The present invention relates to a dynamic polymer having a hybrid crosslinked structure comprising at least one common covalent crosslinked network, and at least one of said common covalently crosslinked network backbones is a carbon chain or a carbon hetero chain structure; The invention comprises a dynamic covalent inorganic boronic acid borate bond, wherein any one of the B atoms of the dynamic covalent inorganic boronic acid borate bond is connected to three -O-, and a part of the BO-Si dynamic covalent bond based on different B atoms The different Si atoms in the middle are connected by a linking group L, and at the same time, based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms, are connected through a linking group Y; the linking group L, which is contained in the dynamic polymer main The carbon atom on the chain backbone, the linker Y, which is on the dynamic polymer backbone backbone, contains only (poly)siloxane units. The term "polymerization" (reaction) as used in the present invention is a growth process/action of a chain, including a process of synthesizing a product having a higher molecular weight by a reaction form such as polycondensation, polyaddition, ring-opening polymerization or the like. Among them, 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. It should be noted that 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.
本发明中所用术语“交联”(反应)，指的是反应物分子间和/或反应物分子内通过共价键的化学连接形成具有二维、三维团簇并进而形成三维无限网状型产物的过程。在交联过程中，聚合物链一般先在二维/三维方向不断增长，逐步形成团簇(可以是二维或者三维)，再发展 为三维无限网络。除非特别说明，本发明中的交联结构特指凝胶点以上(含，下同)三维无限网络结构，非交联包括线型、支化、环状、二维团簇和凝胶点以下的三维团簇结构等凝胶点以下的结构。The term "crosslinking" (reaction) as used in the present invention refers to the formation of two-dimensional, three-dimensional clusters and further three-dimensional infinite network formation by chemical bonding of covalent bonds between reactant molecules and/or reactant molecules. The process of the product. In the cross-linking process, the polymer chains generally grow in the two-dimensional/three-dimensional direction, gradually forming clusters (which can be two-dimensional or three-dimensional), and then develop into three-dimensional infinite networks. Unless otherwise specified, the cross-linking structure in the present invention refers specifically to a three-dimensional infinite network structure above the gel point, including non-crosslinking including linear, branched, cyclic, two-dimensional clusters and gel points. The structure of the three-dimensional cluster structure is equal to the gel point below.
本发明中所述的“凝胶点”，表示的是反应物在交联过程中，粘度突增，开始出现凝胶化现象，初次达到一个三维无限网络时的反应点，也称为渗滤阈值。处于凝胶点以上的交联产物，其具有三维无限网络结构，交联网络构成一个整体并横跨整个聚合物结构；处于凝胶点以下的交联产物，其仅为松散的链接结构，并未形成三维无限网络结构，仅在局部存在少量的三维网络结构，并不属于横跨整个聚合物结构的能够构成一个整体的交联网络。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 A three-dimensional infinite network structure is not formed, and only a small number of three-dimensional network structures exist locally, and it does not belong to a cross-linked network that can form a whole across the entire polymer structure.
本发明中所述的“普通共价键”，指的即是传统意义上的除动态共价键以外的共价键，在通常温度下(一般不高于100℃)和通常时间内(一般小于1天)较难发生断裂，其包括但不仅限于通常的碳-碳键、碳-氧键、碳-氢键、碳-氮键、碳-硫键、氮-氢键、氮-氧键、氢-氧键、氮-氮键等。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.
在本发明的实施方式中，所述的“动态共价键”，指的是无机硼酸硅酯键。所述的动态共价键除存在于聚合物骨架链上之外，还可以存在于骨架链的侧基和/或侧链和/或支链和/或分叉链上及其下一级和/或下多级的侧基和/或侧链和/或支链和/或分叉链上。本发明也不排除在聚合物链的侧基和/或端基上含有硼酸硅酯键。其中只有交联网络骨架上的动态共价键才能构成动态共价交联。在合适的条件下，动态聚合物中任何位置的动态共价键都可以参与动态可逆交换。在动态聚合物的交联网络结构中，构成动态共价交联的动态共价键一旦解离，聚合物体系的总有效交联度将降低。在任意两个最近的含有无机硼酸硅酯键的普通共价交联点之间骨架上的无机硼酸硅酯键数量(占所有键的比例)没有限制，可以是一个或者多个，优选仅含有一个。仅含有一个时，动态聚合物结构更加规整，动态性更加可控。In an embodiment of the invention, the "dynamic covalent bond" refers to an inorganic boronic acid borate bond. The dynamic covalent bond may be present on the side chain and/or side chain and/or the branch and/or the bifurcation chain of the backbone chain in addition to the polymer backbone chain and / or lower levels of side groups and / or side chains and / or branches and / or fork chains. The invention also does not exclude the inclusion of a boronic borate linkage on the pendant and/or end groups of the polymer chain. Only dynamic covalent bonds on the backbone of the crosslinked network can constitute dynamic covalent crosslinks. Under suitable conditions, dynamic covalent bonds at any position in the dynamic polymer can participate in dynamic reversible exchange. In the crosslinked network structure of the dynamic polymer, once the dynamic covalent bond constituting the dynamic covalent crosslink is dissociated, the total effective crosslink degree of the polymer system will decrease. The number of inorganic boronic acid silicate bonds (the ratio of all bonds) on the skeleton between any two of the most common common covalent crosslinking points containing inorganic boronic acid silicate bonds is not limited, and may be one or more, preferably only One. When only one is included, the dynamic polymer structure is more regular and the dynamics are more controllable.
在本发明的实施方式中，所述连接基L和连接基Y均至少为二价，两者均可以有任意合适的拓扑结构，包括但不限于线型、环状(包括但不限于单环、多环、嵌套环、桥环)、支化(包括但不限于星型、H型、梳型、树枝状、超支化)、二维和三维团簇，以及以上结构的任意合适组合，甚至是具有普通共价交联的颗粒(包括纤维和片状颗粒)；两者也均可以是均聚物，也可以是共聚物。其中，所述连接基L可以是低分子量或高分子量的骨架上含有碳原子的连接基，优选为分子量大于1000Da的高分子连接基，更优选其骨架上含有的碳原子数量不低于20的分子量大于1000Da的高分子连接基。所述连接基L骨架上还含有可选的杂原子和/或可以形成元素有机基的元素原子，其中，可选地含有的杂原子可以是任意合适的杂原子，包括但不限于O、N、S；可选地含有的元素原子可以是任意合适的元素原子，包括但不限于P、Si、Se、Ni、Co、Pt、Ru、Ti、Al、Ir。优选连接基L通过碳原子直接与B-O-Si键的Si原子相连接，既可以获得B-O-Si键的动态性，又可以最大限度地利用含碳原子连接基L的性能。所述含碳原子的连接基L可以有任意一个或多个玻璃化转变温度，高于室温的玻璃化转变温度可赋予动态聚合物更好的刚性和模量，低于室温的玻璃化转变温度可赋予动态共聚物更好的柔软性、拉伸率和可塑性。所述含碳原子的连接基L优选为烃基、聚烯烃基、聚醚基、聚酯基、聚氨酯基、聚脲基、聚硫代胺酯基、聚丙烯酸酯基、聚丙烯酰胺基、聚碳酸酯基、聚醚砜基、聚芳砜基、聚醚醚酮基、聚酰亚胺基、聚酰胺基、聚胺基、聚苯醚基、聚苯硫醚基、聚苯砜基，但本发明不仅限于此。所述的连接基Y为(聚)硅氧烷，其也可以有任意一个或者多个玻璃化转变温度，但通常均低于室温。根据本发明的实施方式，一个动态聚合物中可以含有不同的连接基L和连接基Y；除连接基L和连接基Y外还可以有其他的连接基，本发明不做限制，但优选仅有连接基L和连接基Y。连接基L和连接基Y的同时存在赋予材料力学性能、动态性等性能优异的可调性，因为连接基Y具有低玻璃化转变温度，适合获得强动态性和柔软度等；而连接基L更适合获得良好的力学性能。In an embodiment of the invention, the linker L and the linker Y are both at least divalent, and both may have any suitable topology, including but not limited to linear, ring (including but not limited to single ring) , multi-ring, nested ring, bridged ring), branching (including but not limited to star, H, comb, dendritic, hyperbranched), two-dimensional and three-dimensional clusters, and any suitable combination of the above structures, It is even particles having ordinary covalent cross-linking (including fibers and flake particles); both of them may be homopolymers or copolymers. Wherein, the linking group L may be a linking group having a carbon atom on a skeleton having a low molecular weight or a high molecular weight, preferably a polymer linking group having a molecular weight of more than 1000 Da, and more preferably having a carbon atom of not less than 20 in the skeleton. A polymeric linker having a molecular weight greater than 1000 Da. The linker L skeleton further contains an optional hetero atom and/or an element atom which can form an elemental organic group, wherein the hetero atom optionally contained may be any suitable hetero atom, including but not limited to O, N. And S; optionally containing element atoms may be any suitable elemental atoms including, but not limited to, P, Si, Se, Ni, Co, Pt, Ru, Ti, Al, Ir. It is preferred that the linking group L is directly bonded to the Si atom of the B-O-Si bond through a carbon atom, and both the dynamics of the B-O-Si bond and the performance of the carbon atom-containing linking group L can be utilized to the utmost. The carbon atom-containing linking group L may have any one or more glass transition temperatures, and a glass transition temperature higher than room temperature may give a better rigidity and modulus to the dynamic polymer, and a glass transition temperature lower than room temperature. It imparts better softness, elongation and plasticity to the dynamic copolymer. The carbon atom-containing linking group L is preferably a hydrocarbon group, a polyolefin group, a polyether group, a polyester group, a polyurethane group, a polyurea group, a polythiourethane group, a polyacrylate group, a polyacrylamide group, a poly Carbonate group, polyethersulfone group, polyarylsulfone group, polyetheretherketone group, polyimide group, polyamide group, polyamine group, polyphenylene ether group, polyphenylene sulfide group, polyphenylsulfone group, However, the invention is not limited to this. The linker Y is a (poly)siloxane, which may also have any one or more glass transition temperatures, but is generally lower than room temperature. According to an embodiment of the present invention, a dynamic polymer may contain different linking groups L and a linking group Y; in addition to the linking group L and the linking group Y, there may be other linking groups, which are not limited in the present invention, but preferably only There are a linker L and a linker Y. The linker L and the linker Y simultaneously impart excellent adjustability to properties such as mechanical properties and dynamic properties, because the linker Y has a low glass transition temperature, is suitable for obtaining strong dynamics and softness, and the like; More suitable for good mechanical properties.
在本发明的动态聚合物中，可以包含一种或者多种聚合物，但至少包含一个普通共价交联的网络，也即至少有一个网络是以普通共价键进行交联并且达到凝胶点以上。所述动态共价无机硼酸硅酯键可以在普通共价键交联的网络中一起构成交联，也可以独立形成动态共价交联网络，也可以在非交联链中。因为至少包含一个普通共价交联的网络，所以即使在所有的动态键完全解离的情况下，本发明的聚合物体系也可以保持平衡结构，也即可以保持基本的形状并不出现完全的熔融和溶解。保持平衡结构意味着可以自支撑，对聚合物的许多使用至关重要，例如密封圈、轮胎等。In the dynamic polymer of the present invention, one or more polymers may be included, but at least one network of common covalent crosslinks is included, that is, at least one network is crosslinked by ordinary covalent bonds and reaches a gel. Point above. The dynamic covalent inorganic silicon borate bonds may form crosslinks together in a common covalently bonded network, or may form a dynamic covalent crosslinked network independently or in a non-crosslinked chain. Since at least one network of common covalent crosslinks is included, the polymer system of the present invention can maintain a balanced structure even when all the dynamic bonds are completely dissociated, that is, the basic shape can be maintained without completeness. Melt and dissolve. Maintaining a balanced structure means being self-supporting and critical to many uses of polymers such as seals, tires, etc.
在本发明中，“骨架”指的是聚合物链的链长方向上结构。对交联聚合物而言，所述的“主链”，指的是存在于交联网络骨架上的任意链段，其包括无限三维网络骨架上的主链和交联链接；其中，聚合物链之间的交联链接可以为一个原子、一个单键、一个基团、一个链段、一个团簇等。对非交联结构的聚合物而言，所述的“主链”，如非特别说明，指的是链节最多的链；其中，所述的“侧链”，指的是同聚合物主链骨架相连接而分布在骨架旁侧的链结构；其中，所述的“支链”/“分叉链”可以是侧链也可以是其他从任意链分叉出来的链结构。其中，所述的“侧基”，指的是同聚合物任意链相连接而分布在链旁侧的化学基团。对于“侧链”、“支链”和“侧基”，其可具有多级结构，也即侧链/支链可以继续带有侧基和侧链/支链，侧链/支链的侧链/支链可以继续有侧基和侧链/支链。其中，所述的“端基”，指的是同任意链相连接而位于链末端的化学基团。对于超支化和树枝状链及其相关的支化链结构，支链也可以视为主链，但通常最外围的支链仅视为支链。In the present invention, "skeleton" refers to a structure in the chain length direction of a polymer chain. For a crosslinked polymer, the "backbone" refers to any segment present on the backbone of the crosslinked network, including the backbone and crosslinks on the infinite three-dimensional network backbone; wherein the polymer The crosslinks between the chains can be one atom, one single bond, one group, one segment, one cluster, and the like. For a polymer of a non-crosslinked structure, the "backbone", unless otherwise specified, refers to the chain with the most links; wherein the "side chain" refers to the same polymer main The chain structure in which the chain skeletons are connected and distributed on the side of the skeleton; wherein the "branched" / "bifurcation chain" may be a side chain or other chain structure branched from any chain. Herein, the "side group" refers to a chemical group which is bonded to an arbitrary chain of the polymer and distributed on the side of the chain. For "side chains", "branched chains" and "side groups", it may have a multi-stage structure, ie the side chains/branches may continue to have side groups and side chains/branches, side chains/branched sides Chains/branches can continue to have side groups and side chains/branches. Wherein, the term "end group" refers to a chemical group attached to an arbitrary chain and located at the end of the chain. For hyperbranched and dendritic chains and their associated branched chain structures, the branch can also be considered a backbone, but usually the outermost branch is considered only a branch.
为了说明的简明性，在本发明的说明书中，利用连接词“和/或”来表示所述的术语可以包含选自连接词“和/或”之前所述的选项，或者选自连接词“和/或”之后所述的选项，或者同时选自连接词“和/或”之前和之后所述的选项这三种情况。For the sake of simplicity of the description, in the specification of the present invention, the term "and/or" is used to mean that the term may include an option selected from the conjunction "and/or" or may be selected from the conjunction " And/or the options described hereinafter, or both from the options described before and after the conjunction "and/or".
在本发明的实施方式中，所述的动态聚合物，其可以具有一个或多个玻璃化转变温度，也可以没有玻璃化转变温度。对于所述动态聚合物的玻璃化转变温度，其至少有一个低于0℃、或者处于0-25℃之间、或者处于25-100℃之间、或者高于100℃；其中，玻璃化转变温度低于0℃的动态聚合物具有较好的低温使用性能，方便作为密封胶、弹性体、凝胶等进行使用；玻璃化转变温度处于0-25℃之间的动态聚合物能够有利于在常温下进行使用，也能够方便将其作为弹性体、密封胶、凝胶、泡沫以及普通固体使用；玻璃化转变温度处于25-100℃之间的动态聚合物便于在室温以上获得普通固体、泡沫以及凝胶；玻璃化转变温度高于100℃的动态聚合物，其尺寸稳定性、力学强度、耐温性好，有利于作为应力承载材料、高抗冲材料进行使用。对于玻璃化转变温度低于25℃的动态聚合物，其能够体现出优良的动态性、自修复性、可回收性；对于玻璃化转变温度高于25℃的动态聚合物，其能够体现出良好的形状记忆能力、应力承载能力和抗冲击能力；此外，超分子氢键的存在，能够对动态聚合物的玻璃化转变温度进行进一步的调控，对动态聚合物的动态性、交联度、机械强度进行补充。对于本发明中的动态聚合物，优选至少有一个玻璃化转变温度不高于50℃，更进一步优选至少有一个玻璃化转变温度不高于25℃，最优选各个玻璃化转变温度均不高于25℃。各个玻璃化温度均不高于25℃的体系由于在日常使用温度下具有良好的柔性和可流动性/蠕变性，因此特别适合作为自修复材料、吸能材料进行使用。对于动态聚合物的玻璃化转变温度，其可通过DSC、DMA等本领域中所通用的玻璃化转变温度的测定方法进行测定。In an embodiment of the invention, the dynamic polymer may have one or more glass transition temperatures or may have no glass transition temperature. For 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. For 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. For 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.
在本发明的实施方式中，动态聚合物的各原料组分也可以具有一个或多个玻璃化转变温度，也可以没有玻璃化转变温度，其玻璃化转变温度，至少有一个低于0℃、或者处于0-25℃之间、或者处于25-100℃之间、或者高于100℃，其中，玻璃化转变温度低于0℃的化合物原料在制备动态聚合物时便于进行低温制备和加工；玻璃化转变温度处于0-25℃之间的化合物原料在常温下即可进行制备加工成型；玻璃化转变温度处于25-100℃之间的化合物原料利用常规加热设备即可成型，制造成本低；玻璃化转变温度高于100℃的化合物原料可用于制备 尺寸稳定性好、力学性能优良的耐高温材料。利用多种具有不同玻璃化转变温度的化合物原料制备动态聚合物，可以获得在不同范围内具有不同玻璃化转变温度的动态聚合物，其能够体现出多重的综合性能，兼具动态性和稳定性。In an embodiment of the present invention, 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. By using a variety of compound materials with different glass transition temperatures to prepare dynamic polymers, dynamic polymers with different glass transition temperatures can be obtained in different ranges, which can show multiple comprehensive properties, both dynamic and stable. .
在本发明的实施方式中，所述的无机硼酸硅酯键(B-O-Si)由无机硼化合物和含硅羟基和/或硅羟基前驱体的含硅化合物反应而成。In an embodiment of the invention, the inorganic boronic acid silicate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound containing a silicon hydroxy group and/or a silanol group precursor.
所述无机硼化合物，是指化合物中的硼原子不与碳原子通过硼碳键相连的含硼化合物。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.
所述无机硼化合物选自(包括但不限于)硼酸、硼酸酯、硼酸盐、硼酸酐、卤化硼。硼酸可以是原硼酸、偏硼酸、四硼酸。硼酸酯包括在水存在下水解成硼酸的烷基和烯丙基硼酸酯/三有机基硼酸酯，例如硼酸三甲酯、硼酸三乙酯、硼酸三苯酯、硼酸三苄酯、硼酸三环己酯、硼酸三(甲基甲硅烷酯)、硼酸三叔丁酯、三-正戊基硼酸酯、三仲丁基硼酸酯、DL-薄荷基硼酸酯、三(4-氯苯基)硼酸酯、2,6-二-叔-丁基-4-甲苯基二丁基原硼酸酯、三(2-甲氧基乙基)硼酸酯、苄基二氢硼酸酯、二苯基氢硼酸酯、异丙醇频哪醇硼酸酯、三乙醇胺硼酸酯等。合适的硼酸酐除包括通式为B 2O 3典型的氧化硼外，还包括但不仅限于三烷氧基环硼氧烷及其衍生物，例如三甲氧基环硼氧烷、三异丙氧基环硼氧烷、2,2′-氧双[4,4,6-三甲基-1,3,2-二氧杂硼氧烷等。合适的硼酸盐包括但不仅限于五硼酸二铵、十水合四硼酸钠(硼砂)、五硼酸钾、二硼酸镁、单硼酸钙、三硼酸钡、偏硼酸锌、三钾硼酸酯、原硼酸铁盐。合适的卤化硼包括但不仅限于三氟化硼、三氯化硼、三溴化硼、三碘化硼、四氯化二硼等。合适的无机硼化合物进一步包括前述硼酸酯的部分水解产物。典型地，无机硼化合物是通式为B 2O 3[CAS登记号#1303-86-2]的氧化硼或通式为H 3BO 3[CAS登记号#10043-35-3]的硼酸。作为例子，合适的无机硼化合物的化学结构式如下所示，但本发明不限于此： 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. 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. Typically, 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]. As an example, the chemical structural formula of a suitable inorganic boron compound is as follows, but the invention is not limited thereto:
Figure PCTCN2018072461-appb-000001
Figure PCTCN2018072461-appb-000001
所述含硅羟基和/或硅羟基前驱体的含硅化合物，是指化合物的端基和/或侧基含有硅羟基和/或硅羟基前驱体基团。在本发明中，所述含硅羟基和/或硅羟基前驱体的含硅化合物可以本 身含有连接L和/或连接基Y，或者可以通过合适的化学反应后生成连接基L和/或连接基Y。由于连接基L含有处于动态聚合物主链骨架上的碳原子，特别可以是含碳聚合物连接基，可以获得结构丰富、性能多样的动态聚合物主链骨架，特别是主链骨架碳的存在可以方便获得更高的动态聚合物力学性能、可印刷性。The silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor means that the terminal group and/or the pendant group of the compound contains a silyl group and/or a silanol precursor group. In the present invention, the silicon-containing compound containing a silicon hydroxy group and/or a silanol precursor may itself contain a linking group L and/or a linking group Y, or may form a linking group L and/or a linking group by a suitable chemical reaction. Y. Since the linking group L contains a carbon atom on the backbone of the dynamic polymer backbone, particularly a carbon-containing polymer linking group, a dynamic polymer backbone skeleton having rich structure and various properties can be obtained, in particular, the presence of the main chain skeleton carbon. It is convenient to obtain higher dynamic polymer mechanical properties and printability.
上述含有连接基Y或可以通过合适的化学反应生成含有连接基Y的含硅羟基和/或硅羟基前驱体的含硅化合物为(聚)硅氧烷化合物，是指化合物的末端含有硅羟基和/或硅羟基前驱体端基，且与所述端基相连的主链和/或侧链和/或其他链结构为任意合适的(聚)硅氧烷结构以及可以使得形成的无机硼酸硅酯键(B-O-Si)含有所述的连接基Y的化合物。The above silicon-containing compound containing a linker Y or a silicon-containing hydroxyl group and/or a silanol precursor containing a linker Y by a suitable chemical reaction is a (poly)siloxane compound, meaning that the terminal of the compound contains a silanol group and / or a silyl hydroxyl precursor end group, and the main chain and / or side chain and / or other chain structure connected to the end group is any suitable (poly) siloxane structure and inorganic boron silicate which can be formed The bond (BO-Si) contains the compound of the above-mentioned linker Y.
在本发明中，所述(聚)硅氧烷的主链或主体结构等由-(SiR 1R 2-O) n-单元组成，其中，n为硅氧烷单元(SiR 1R 2-O)的数量，为大于或等于1的整数，可以是固定值或平均值；R 1、R 2为连接在硅原子上的基团/链段，各自独立地选自H、卤素原子和其他任意合适的有机、无机基团/链段，包括羟基、以及其他反应性有机基团；优选为有机基团/链段，更优选为含碳有机基团/链段。所述含硅羟基和/或硅羟基前驱体的(聚)硅氧烷化合物选自小分子硅氧烷化合物和大分子聚硅氧烷化合物，可以是有机或者无机化合物，包括二氧化硅。所述(聚)硅氧烷化合物可以有任意合适的拓扑结构，包括但不限于线型、环状(包括但不限于单环、多环、桥环、嵌套环)、支化(包括但不限于梳型、H型、星型、树枝型、超支化型)、二维/三维团簇，及其组合的形式。 In the present invention, the main chain or main structure of the (poly)siloxane or the like is composed of -(SiR 1 R 2 -O) n - units, wherein n is a siloxane unit (SiR 1 R 2 -O) The number of ) is an integer greater than or equal to 1, and 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 the like. Suitable organic, inorganic groups/segments include hydroxyl groups, as well as other reactive organic groups; preferably organic groups/segments, more preferably carbon-containing organic groups/segments. 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, and combinations thereof.
本发明中所述的硅羟基，其指的是由硅原子以及与该硅原子相连的一个羟基所组成的结构基元(Si-OH)，其中，硅羟基可为有机硅羟基(即硅羟基中的硅原子至少与一个碳原子通过硅碳键相连，且至少有一个有机基团通过所述硅碳键连接到硅原子上)，也可为无机硅羟基(即硅羟基中的硅原子不与有机基团相连接)，优选为有机硅羟基。在本发明中，硅羟基中的一个羟基(-OH)即为一个官能团。一个(聚)硅氧烷可以含有多个硅羟基，多个Si原子可以含有羟基，同一个Si原子上也可以含有多个羟基。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. In the present invention, 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.
本发明中所述的硅羟基前驱体，其指的是由硅原子以及与该硅原子相连的一个可水解得到羟基的基团所组成的结构基元(Si-Z)，其中，Z为可水解得到羟基的基团，其可选自卤素、氰基、氧氰基、硫氰基、烷氧基、氨基、硫酸酯基、硼酸酯基、酰基、酰氧基、酰氨基、酮肟基、醇盐基等。合适的硅羟基前驱体举例如：Si-Cl，Si-CN，Si-CNS，Si-CNO，Si-SO 4CH 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-O-N＝C(CH 3) 2，Si-ONa。在本发明中，硅羟基前驱体中的一个可水解得到硅羟基的基团(Si-Z)即为一个官能团。一个(聚)硅氧烷可以含有多个硅羟基前驱体，多个Si原子可以含有Z基团，同一个Si原子上也可以含有多个Z基团。 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 silanol precursors are, for example, 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. In the present invention, one of the silanol precursors which can be hydrolyzed to give a siloxy 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.
为了说明本发明中所述含有含碳原子的连接基L的含硅化合物及其可生成所述含连接基L的含硅化合物，可以举例如下，但本发明不仅限于此，In order to explain the silicon-containing compound containing the carbon atom-containing linking group L in the present invention and the silicon-containing compound containing the linking group L, the following can be exemplified, but the present invention is not limited thereto.
Figure PCTCN2018072461-appb-000002
Figure PCTCN2018072461-appb-000002
Figure PCTCN2018072461-appb-000003
Figure PCTCN2018072461-appb-000003
Figure PCTCN2018072461-appb-000004
Figure PCTCN2018072461-appb-000004
其中m、n、x、y、z为重复单元的数量，可以是固定值或平均值。Where m, n, x, y, and z are the number of repeating units, and may be a fixed value or an average value.
对于聚硅氧烷，硅羟基可以在聚合物链的末端，也可以在聚合物链的侧基；同样地，对于含硅羟基前驱体的有机聚硅氧烷，硅羟基前驱体可以在聚合物链的末端，也可以在聚合物链的侧基。对于小分子硅氧烷，硅羟基/硅羟基躯体同样可以在端基或者侧基。For polysiloxanes, 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. For small molecule siloxanes, the silanol/silicon hydroxy body can also be at the end group or pendant group.
本发明中，所述含硅羟基和/或硅羟基前驱体的(聚)硅氧烷化合物，可以举例如下，本发明不仅限于此：In the present invention, 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:
Figure PCTCN2018072461-appb-000005
Figure PCTCN2018072461-appb-000005
其中m、n、x、y、z为重复单元的数量，可以是固定值或平均值。Where m, n, x, y, and z are the number of repeating units, and may be a fixed value or an average value.
在本发明中，可以采用任意合适的无机硼化合物和含硅羟基和/或硅羟基前驱体的化合物组合来生成无机硼酸硅酯键，优选采用无机硼酸与含硅羟基的大分子化合物、无机硼酸与含硅羟基前驱体的大分子化合物、无机硼酸酯(盐)与含硅羟基的大分子化合物来形成无机硼酸硅酯键，更优选采用无机硼酸与含硅羟基的大分子化合物、无机硼酸酯与含硅羟基的大分子化合物来形成无机硼酸硅酯键，更优选采用无机硼酸酯与含硅羟基的大分子化合物来形成无机硼酸硅酯键。In the present invention, any suitable inorganic boron compound and a compound containing a silicon hydroxy group and/or a silanol precursor may be used to form an inorganic boronic acid silicate bond, preferably an inorganic boric acid and a silanol group-containing macromolecular compound, inorganic boric acid. A macromolecular compound containing a silicon-containing hydroxy precursor, an inorganic borate (salt) and a silanol-containing macromolecular compound to form an inorganic boronic acid silicate bond, more preferably an inorganic boronic acid and a silicon-containing hydroxyl group-containing macromolecular compound, inorganic boron The acid ester and the silanol-containing macromolecular compound form an inorganic boronic acid silicate bond, and it is more preferred to use an inorganic boronic acid ester and a silicon-containing hydroxyl group-containing macromolecular compound to form an inorganic boronic acid silicate bond.
在本发明的实施方式中，可以通过生成无机硼酸硅酯键来得到所述的动态聚合物，也可以先制备含有所述无机硼酸硅酯键的化合物再聚合/交联以生成所述的动态聚合物。在本发明中，基于Si原子的多价性，所述的含硅化合物上一个参与形成B-O-Si的Si原子最多可以形成三个B-O-Si键，其共用一个Si原子；而且由于硼原子为三价结构，聚合过程生成所述的无机硼酸硅酯键可容易导致形成分叉并可以进而交联。In an embodiment of the present invention, the dynamic polymer may be obtained by forming an inorganic boronic acid silicate bond, or a compound containing the inorganic boronic acid silicate bond may be prepared to be repolymerized/crosslinked to generate the dynamic. polymer. In the present invention, based on the polyvalentity of Si atoms, a Si atom participating in the formation of BO-Si on the silicon-containing compound may form up to three BO-Si bonds, which share one Si atom; and since the boron atom is In the trivalent structure, the polymerization process produces the inorganic silicon silicate bond which can easily cause bifurcation and can be further crosslinked.
在本发明的一个实施方式中(第一种网络结构)，所述动态聚合物只有一个网络，该网络中同时含有普通共价交联和动态共价无机硼酸硅酯键交联，其中普通共价交联达到其凝胶点以上并且其交联网络骨架为碳链或碳杂链结构；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。该网络结构中，通过普通共价交联可以保持平衡结构，无机硼酸硅酯键可以提供额外的动态共价交联和动态共价性，所获得的动态聚合物不仅具有自支撑性能，还具有显著的胀流性而产生弹性增强，结构简单性能优异。In one embodiment of the invention (the first network structure), the dynamic polymer has only one network, and the network contains both common covalent crosslinks and dynamic covalent inorganic silicon borate linkages, wherein The valence crosslinks above its gel point and its crosslinked network backbone is a carbon chain or carbon heterochain structure; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is connected to three -O-, and Some of the Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and some Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group Y; The linker L, which contains a carbon atom on the backbone of the dynamic polymer backbone, the structure of the linker Y on the dynamic polymer backbone backbone contains only (poly)siloxane units. In the network structure, a balanced structure can be maintained by ordinary covalent cross-linking, and the inorganic boronic acid silicate bond can provide additional dynamic covalent cross-linking and dynamic covalentity, and the obtained dynamic polymer not only has self-supporting properties, but also has Significantly dilatant to produce elasticity, excellent structural simplicity.
在本发明的另一个实施方式中(第二种网络结构)，所述动态聚合物含有两个网络；第1网络中仅含普通共价交联，并且其共价交联网络骨架为碳链或碳杂链结构；第2网络中以动态共价无机硼酸硅酯键形成的交联达到其凝胶点以上，不含凝胶点以上的普通共价交联，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。该网络结构中，通过第1网络中的普通共价交联保持平衡结构，第2网络中的无机硼酸硅酯键提供动态共价性，两个网络互为正交，而且在制备上可以最小限度地受限于原料组成的互相干扰。In another embodiment of the invention (second network structure), the dynamic polymer contains two networks; the first network contains only ordinary covalent crosslinks, and the covalently crosslinked network backbone is a carbon chain Or a carbon heterocyclic structure; the crosslinking formed by the dynamic covalent inorganic boronic acid silicate bond in the second network reaches above the gel point, and does not contain ordinary covalent cross-linking above the gel point, wherein the dynamic covalent Any one of the B atoms of the inorganic boronic acid silicate bond is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on different B atoms. The different Si atoms in the BO-Si dynamic covalent bond are linked by a linker Y; the linker L, which contains a carbon atom on the backbone of the dynamic polymer backbone, which is in the dynamic state The structure on the backbone of the polymer backbone contains only (poly)siloxane units. In the network structure, the equilibrium structure is maintained by ordinary covalent cross-linking in the first network, and the inorganic boronic acid silicate bond in the second network provides dynamic covalentity, the two networks are orthogonal to each other, and can be minimized in preparation. Limit to the mutual interference of the composition of the raw materials.
在本发明的另一个实施方式中(第三种网络结构)，所述动态聚合物含有两个网络；第1网络如所述第一种网络结构；第2网络中仅含普通共价交联，不含所述动态共价无机硼酸硅酯键；其中，至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。该网络结构中，通过第1网络和第2网络中的普通共价交联保持平衡结构，第1网络中的无机硼酸硅酯键提供动态共价性，两个普通共价交联提供的双网络结构在力学性能上有突出的优势，再加上额外的动态共价交联，力学性能上可以得到升华。In another embodiment of the present invention (a third network structure), the dynamic polymer contains two networks; the first network is as described in the first network structure; and the second network contains only ordinary covalent cross-linking And not containing the dynamic covalent inorganic boronic acid borate bond; wherein at least one of the common covalent crosslinked network backbones is a carbon chain or a carbon heterochain structure; wherein any of the dynamic covalent inorganic boronic acid borate bonds A B atom is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and some are based on BO-Si dynamic covalent of different B atoms. The different Si atoms in the bond are connected by a linker Y; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, said linker Y being on the backbone of the dynamic polymer backbone The structure contains only (poly)siloxane units. In the network structure, the equilibrium structure is maintained by common covalent cross-linking in the first network and the second network, and the inorganic boronic acid silicate bond in the first network provides dynamic covalentity, and the two common covalent cross-linkings provide double The network structure has outstanding advantages in mechanical properties, coupled with additional dynamic covalent cross-linking, the mechanical properties can be sublimated.
在本发明的另一个实施方式中(第四种网络结构)，所述动态聚合物含有两个网络；第1网络和第2网络均为所述第一种网络结构，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构，但所述的第1和第2网络不同。这种不相同，可以举例如，聚合物链主体结 构不同、共价交联的交联密度不同、聚合物链侧基和/或侧链的组成不同等。该实施方式中，通过调节第1网络和/或第2网络的结构，可以达到精确控制动态聚合物性能的目的。In another embodiment of the present invention (fourth network structure), the dynamic polymer contains two networks; the first network and the second network are both the first network structure, and at least one of the ordinary The covalently crosslinked network backbone is a carbon chain or a carbon heterochain structure, but the first and second networks are different. Such a difference may be, for example, a difference in the structure of the polymer chain main body, a difference in the crosslinking density of the covalently crosslinked, a difference in the composition of the side chain of the polymer chain and/or the side chain, and the like. In this embodiment, by adjusting the structure of the first network and/or the second network, the purpose of accurately controlling the dynamic polymer performance can be achieved.
在本发明的另一个实施方式中(第五种网络结构)，所述动态聚合物含有至少一个网络，该些网络中仅含有普通共价交联，至少一个所述普通共价交联网络骨架为碳链或碳杂链结构，并且以动态共价无机硼酸硅酯键交联的聚合物以颗粒形式分散在所述网络中；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。该实施方式中，普通共价交联提供平衡结构，以无机硼酸硅酯键交联的动态聚合物以颗粒形式分散在普通共价交联网络中，其受力时可以提供局部胀流性引起的材料硬度和强度增加，达到有机调控能量分散的目的。In another embodiment of the invention (fifth network structure), the dynamic polymer contains at least one network containing only common covalent crosslinks, at least one of the common covalent crosslinked network backbones a polymer which is a carbon chain or a carbon hetero chain structure and crosslinked by a dynamic covalent inorganic boronic acid silicate bond is dispersed in the network in the form of particles; wherein any one of the dynamic covalent inorganic boron silicate bonds is B The atom is connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on the BO-Si dynamic covalent bond of different B atoms. The different Si atoms are connected by a linker Y; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the dynamic polymer backbone backbone, is only Contains (poly)siloxane units. In this embodiment, the common covalent cross-linking provides a balanced structure, and the dynamic polymer crosslinked by the inorganic boronic acid silicate bond is dispersed in the form of particles in a common covalent cross-linking network, which can provide local dilatancy when subjected to force. The hardness and strength of the material increase, achieving the purpose of organically regulating energy dispersion.
在本发明的另一个实施方式中(第六种网络结构)，所述动态聚合物仅含有一个网络，该网络中仅含有普通共价交联，所述普通共价交联网络骨架为碳链或碳杂链结构，并且含有动态共价无机硼酸硅酯键的非交联聚合物分散在所述网络中；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。该实施方式中，普通共价交联提供平衡结构，非交联的动态聚合物的胀流性可以在受力时提供完全的粘性损耗，起到强烈的吸能作用。In another embodiment of the present invention (sixth network structure), the dynamic polymer contains only one network, and the network only contains ordinary covalent crosslinks, and the common covalent crosslinked network skeleton is a carbon chain. Or a carbon heterochain structure, and a non-crosslinked polymer containing a dynamic covalent inorganic boronic acid silicate bond dispersed in the network; wherein the dynamic covalent inorganic boron silicate bond is any one of B atoms and three - O-linkage, and in which some Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected by a linker L, and partly based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms The linker Y is linked; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the backbone of the dynamic polymer backbone, contains only (poly)silicon Oxytomane unit. In this embodiment, the common covalent cross-linking provides a balanced structure, and the diverging property of the non-crosslinked dynamic polymer can provide a complete viscous loss when subjected to a force, and exerts a strong energy absorbing effect.
在本发明的另一个实施方式中(第七种网络结构)，所述动态聚合物含有两个网络，第1网络和第2网络中均仅含普通共价交联，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；第1网络和第2网络可以相同或者不同，优选不同；在其中至少一个网络中分散有含有动态共价无机硼酸硅酯键的非交联聚合物；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。在本实施方式中，两个普通共价交联网络作为双网络结构提供平衡结构和优异的力学性能，而分散其中的非交联动态聚合物的胀流性可以在受力时提供完全的粘性损耗，起到强烈的吸能作用。In another embodiment of the present invention (seventh network structure), the dynamic polymer contains two networks, and both the first network and the second network contain only ordinary covalent crosslinks, and at least one of the ordinary The covalently crosslinked network backbone is a carbon chain or a carbon heterochain structure; the first network and the second network may be the same or different, preferably different; in which at least one network is dispersed with a non-crossing containing a dynamic covalent inorganic boronic acid borate bond a bipolymer; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is linked to three -O-, and a part of which is based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms The linking group L is connected, and the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through a linking group Y; the linking group L, which contains a carbon atom on the backbone of the dynamic polymer backbone The linker Y, which is on the dynamic polymer backbone backbone, contains only (poly)siloxane units. In the present embodiment, two common covalent crosslinked networks provide a balanced structure and excellent mechanical properties as a dual network structure, and the dilatancy of the non-crosslinked dynamic polymer dispersed therein can provide complete viscosity when stressed. Loss, which plays a strong role in energy absorption.
除上述七种杂化交联网络结构的实施方式外，本发明还可以有其他多种多样的杂化交联网络结构实施方式，一个实施方式中可以包含三个或其以上相同或不相同的网络，同一个网络中可以包含不同的普通共价交联和/或不同的动态无机硼酸硅酯键交联，各个网络的化学结构、拓扑结构、交联度等均可以相同或不同，网络结构中可以分散/填充交联和/或非交联聚合物成分，各成分中还可以含有骨架氢键基团。无机硼酸硅酯键用于提供共价动态性能，包括但不限于可塑性和自修复性，可以利用其良好的动态性能，赋予聚合物应力/应变响应性、超韧性、自修复、形状记忆等性能。本领域的技术人员可以根据本发明的逻辑和脉络，合理有效地实现。In addition to the above embodiments of the seven hybrid cross-linking network structures, the present invention may have other various hybrid cross-linking network structure embodiments, and one embodiment may include three or more identical or different Network, the same network can contain different common covalent cross-linking and / or different dynamic inorganic boronic acid silicate bond cross-linking, the chemical structure, topology, cross-linking degree of each network can be the same or different, network structure The crosslinked and/or non-crosslinked polymer component may be dispersed/filled therein, and each component may further contain a skeleton hydrogen bond group. Inorganic boronic acid silicate bonds are used to provide covalent dynamic properties, including but not limited to plasticity and self-healing properties, which can be used to impart stress/strain responsiveness, super toughness, self-healing, shape memory, etc. . Those skilled in the art can implement the logic and the context of the present invention reasonably and effectively.
在本发明的实施方式中，提供一种吸能方法，其特征在于，提供一种具有杂化交联结构的动态聚合物并以其作为吸能材料进行吸能，其中，所述的动态聚合物包含至少一个普通共价交联网络，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；同时其中包含动态共价无机硼酸硅酯键，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连， 同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物骨架上的碳原子；所述的连接基Y，其处于动态聚合物骨架的结构仅含有(聚)硅氧烷单元。In an embodiment of the present invention, there is provided an energy absorbing method, characterized in that a dynamic polymer having a hybrid crosslinked structure is provided and energy absorption is performed as an energy absorbing material, wherein the dynamic polymerization And comprising at least one common covalent crosslinked network, and at least one of said common covalent crosslinked network backbones is a carbon chain or a carbon hetero chain structure; and wherein it comprises a dynamic covalent inorganic boronic acid borate linkage, wherein said dynamic Any one of the B inorganic silicon borate bonds is connected to three -O- groups, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and partly based on different B The different Si atoms in the BO-Si dynamic covalent bond of the atom are connected by a linker Y; the linker L, which contains a carbon atom on the dynamic polymer backbone; the linker Y, which is in a dynamic polymerization The structure of the skeleton contains only (poly)siloxane units.
在本发明的实施方式中，聚合物主链骨架上的氢键基团，即为“骨架氢键基团”，是指该基团中的至少部分原子直接参与构建连续的聚合物主链或交联网络骨架上的聚合物主链或交联链接。所述骨架氢键基团可以是在聚合物聚合/交联过程中生成，也即通过形成所述氢键基团而产生聚合/交联；也可以是预先生成再进行聚合/交联。In an embodiment of the present invention, a hydrogen bond group on a polymer backbone backbone, that is, a "backbone hydrogen bond group", means that at least a portion of the atoms in the group are directly involved in building a continuous polymer backbone or Crosslinking the polymer backbone or crosslinks on the backbone of the network. The skeleton hydrogen bond group may be formed during polymer polymerization/crosslinking, that is, by forming the hydrogen bond group to cause polymerization/crosslinking; or may be pre-formed and then polymerized/crosslinked.
在本发明的实施方式中，所述骨架氢键基团可以选自例如，酰胺基、氨基甲酸酯基、硫代氨基甲酸酯基、硅代氨基甲酸酯基、脲基以及基于以上基团的衍生物。优选氨基甲酸酯基、脲基以及它们的衍生物。作为例子，可以举出如下结构，但本发明不仅限于此：In an embodiment of the invention, the backbone hydrogen bonding group may be selected, for example, from an amide group, a urethane group, a thiourethane group, a silyl carbamate group, a urea group, and based on the above a derivative of a group. Preferred are carbamate groups, urea groups and derivatives thereof. As an example, the following structure can be mentioned, but the present invention is not limited to this:
Figure PCTCN2018072461-appb-000006
Figure PCTCN2018072461-appb-000006
在本发明的实施方式中，形成氢键作用的氢键基团既可以是不同氢键基团间的互补型组合，也可以是同种氢键基团间的自互补型组合，只要基团间能够形成合适的氢键作用即可。 一些氢键基团的组合可以举例如下，但本发明不仅限于此：In an embodiment of the present invention, 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:
Figure PCTCN2018072461-appb-000007
Figure PCTCN2018072461-appb-000007
在本发明中，同一种聚合物中可以含有超过一种的上述骨架氢键基团，同一个网络中也可以含有超过一种的上述骨架氢键基团。对可以导入所述骨架氢键基团的化合物并无特别限定，对应形成所述基团的反应类型和方式等亦无特别限定。In the present invention, more than one of the above-described skeleton hydrogen bond groups may be contained in the same polymer, and more than one of the above-described skeleton hydrogen bond groups may be contained in the same network. The compound into which the skeleton 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.
在本发明的实施方式中，所述具有杂化交联结构的动态聚合物组成的形态可以是普通固体、弹性体、凝胶(包括水凝胶、有机凝胶、齐聚物溶胀凝胶、增塑剂溶胀凝胶、离子液体 溶胀凝胶)、泡沫等。其中，动态聚合物普通固体的形状和体积比较固定，强度高，密度大，适合用于高强度的防爆墙体或器械外壳；弹性体具有普通固体的普遍性质，但更加柔软有弹性。动态聚合物凝胶质地柔软，有较好的吸能性和弹性，适用于制备高阻尼的吸能材料；动态聚合物泡沫材料在具有密度低、轻便、比强度高等一般泡沫塑料的优点时，其软泡材料还具有良好的弹性和吸能性。In an embodiment of the present invention, the dynamic polymer composition having a hybrid crosslinked structure may be in the form of a common solid, an elastomer, a gel (including a hydrogel, an organogel, an oligomer swollen gel, Plasticizer swollen gel, ionic liquid swollen gel), foam, and the like. Among them, the dynamic polymer ordinary solid has a fixed shape and volume, high strength and high density, and is suitable for use in a high-strength explosion-proof wall or an instrument casing; the elastomer has the general property of ordinary solids, but is softer and more elastic. The dynamic polymer gel has soft texture, good energy absorption and elasticity, and is suitable for preparing high damping energy absorbing materials. Dynamic polymer foam materials have the advantages of low density, light weight and high specific strength of general foam. Its soft foam material also has good elasticity and energy absorption.
在本发明的实施方式中，动态聚合物凝胶可以通过在溶胀剂(包括水、有机溶剂、齐聚物、增塑剂、离子液体中之一或其组合)中进行交联获得，也可以在动态聚合物制备完成后再利用溶胀剂进行溶胀获得。当然，本发明不仅限与此，本领域技术人员可以根据本发明的逻辑和脉络，合理有效地实现。In an embodiment of the present invention, 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. Of course, the present invention is not limited thereto, and those skilled in the art can implement the logic and the context of the present invention reasonably and effectively.
在动态聚合物发泡材料的制备过程中，主要采用机械发泡法、物理发泡法、化学发泡法三种方法对动态聚合物进行发泡。In the preparation process of dynamic polymer foaming materials, the dynamic polymer is mainly foamed by three methods: mechanical foaming method, physical foaming method and chemical foaming method.
其中，所述的机械发泡法，是在动态聚合物的制备过程中借助强烈搅拌把大量空气或其他气体引入聚合物的乳液、悬浮液或溶液中使之成为均匀的泡沫体，然后经过物理或化学变化使之胶凝、固化而成为泡沫材料。为缩短成型周期可通入空气和加入乳化剂或表面活性剂。Wherein, 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. To shorten the molding cycle, air can be introduced and an emulsifier or surfactant can be added.
其中，所述的物理发泡法，是在动态聚合物的制备过程中利用物理原理来实现聚合物的发泡，其一般包括以下五种方法：(1)惰性气体发泡法，即在加压情况下把惰性气体压入熔融聚合物或糊状物料中，然后减压升温，使溶解的气体膨胀而发泡；(2)利用低沸点液体蒸发气化发泡，即把低沸点液体压入聚合物中或在一定的压力、温度状况下，使液体溶入聚合物颗粒中，然后将聚合物加热软化，液体也随之蒸发气化而发泡；(3)溶出法，即用液体介质浸入聚合物中溶解掉事先所添加的固体物质，使聚合物中出现大量孔隙而呈发泡状，如将可溶性物质食盐、淀粉等先与聚合物混合，等到成型为制品后，再将制品放在水中反复处理，把可溶性物质溶出，即得到开孔型泡沫制品；(4)中空微球法，即在聚合物中加入中空微球后经固化而成为闭孔型泡沫；(5)冷冻干燥法，即先形成凝胶或者溶胀体，再进行冷冻干燥获得泡沫。其中，优选利用在聚合物中溶入惰性气体和低沸点液体的方法进行发泡。采用物理发泡法，具有操作中毒性较小，发泡原料成本较低，发泡剂无残留体等优点。Wherein, 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. with the polymer, and then forming the product into a product, and then the product Repeatedly treated in water to dissolve the soluble matter to obtain an open-cell foam product; (4) hollow microsphere method, that is, adding hollow microspheres to the polymer and solidifying to form a closed-cell foam; (5) freezing dry , I.e. to form a gel or a swellable material, then freeze-dried to obtain a foam. Among them, 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.
其中，所述的化学发泡法，是在动态聚合物发泡过程中伴随着化学反应，产生气体而发泡的方法，其一般包括以下两种方法：(1)热分解型发泡剂发泡法，即利用化学发泡剂加热后分解放出的气体进行发泡。(2)聚合物组分间相互作用产生气体的发泡法，即利用发泡体系中的两个或多个组分之间发生的化学反应，生成惰性气体(如二氧化碳或氮气)致使聚合物膨胀而发泡。发泡过程中为控制聚合反应和发泡反应平衡进行，为保证制品有较好的质量，一般加入少量催化剂和泡沫稳定剂(或表面活性剂)。其中，优选利用在聚合物中添加化学发泡剂的方法进行发泡。Wherein, 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. In order to control the balance between the polymerization reaction and the foaming reaction during the foaming process, in order to ensure a good quality of the product, a small amount of a catalyst and a foam stabilizer (or a surfactant) are generally added. Among them, it is preferred to carry out foaming by a method of adding a chemical foaming agent to the polymer.
在动态聚合物的制备过程中，主要采用模压发泡成型、注射发泡成型以及挤出发泡成型三种方法对动态聚合物泡沫材料进行成型。In the preparation process of dynamic polymers, dynamic polymer foam materials are mainly formed by three methods: compression foam molding, injection foam molding and extrusion foam molding.
其中，所述的模压发泡成型，其工艺过程较简单，容易控制，可以分为一步法和两步法两种。一步法成型是指将混合后的物料直接投入模腔进行发泡成型；两步法是指先将混合好的物料预发泡处理，然后放入模腔进行发泡成型。其中，由于一步法模压发泡成型比两步法操作方便且生产效率高，故优选一步法进行模压发泡成型。Among them, 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. Among them, since 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.
其中，所述的注射发泡成型，其工艺和设备与普通的注射成型类似，其气泡成核阶段在物料加入螺杆后，受加热和摩擦的使物料变为熔体状态，将发泡剂通过计量阀的控制以一定流速注入物料熔体内，然后通过螺杆头部的混合元件把发泡剂混合均匀，在成核剂的作用下形成气泡核。膨胀阶段和固化定型阶段都发生在充满模腔结束后，当型腔压力下降时，发生气泡核的膨胀过程，同时随着模具的降温而使泡体固化定型。Wherein, 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.
其中，所述的挤出发泡成型，其工艺和设备与普通的挤出成型类似，在挤出之前或挤出过程中将发泡剂加入挤出机中，熔体流经机头处压力下降，发泡剂挥发而形成要求的发泡结构。由于其不仅能够实现连续化生产，而且在成本上比注射发泡成型更具竞争性，因此是目前应用最广泛的发泡成型技术。Wherein, 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.
在动态聚合物的制备过程中，本领域的技术人员可根据实际制备情况以及目标聚合物性能选择合适的发泡方法以及泡沫材料成型方法对动态聚合物泡沫材料进行制备。In the preparation of the dynamic polymer, those skilled in the art can select a suitable foaming method and a foam molding method to prepare the dynamic polymer foam according to the actual preparation conditions and the target polymer properties.
在本发明的实施方式中，动态聚合物泡沫材料的结构涉及开孔结构、闭孔结构、半开半闭结构三种。开孔结构中，泡孔与泡孔之间互相连通，或完全连通，单维或三维都能通过气体或液体，泡孔径为0.01-3mm不等。闭孔结构，具有独立泡孔结构，内部泡孔与泡孔之间有壁膜隔开，绝大多数都不相互连通，泡孔径为0.01-3mm不等。所含有的泡孔既有相互连通又有互不连通的结构则为半开孔结构。对于已形成闭孔的泡沫结构，也可借助机械施压或化学方法使其成为开孔结构，本领域的技术人员可依据实际需要进行选择。In an embodiment of the invention, the structure of the dynamic polymer foam material involves three types of open-cell structures, closed-cell structures, and half-open half-close structures. In 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. For 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.
在本发明的实施方式中，动态聚合物泡沫材料按照其硬度分类，可分为软质、硬质和半硬质三类：(1)软质泡沫，在23℃和50％的相对湿度下，泡沫塑料的弹性模量小于70MPa；(2)硬质泡沫，在23℃和50％的相对湿度下，弹性模量大于700MPa；(3)半硬质(或半软质)泡沫，介于以上两类之间的泡沫体，其弹性模量介于70MPa和700MPa之间。In the embodiment of the present invention, 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; (2) the rigid foam has a modulus of elasticity greater than 700 MPa at 23 ° C and 50% relative humidity; (3) 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.
在本发明的实施方式中，动态聚合物泡沫材料按照其密度又可分为低发泡、中发泡和高发泡。低发泡的泡沫材料，其密度大于0.4g/cm 3，发泡倍率小于1.5；中发泡的泡沫材料，其密度为0.1～0.4g/cm 3，发泡倍率为1.5～9；而高发泡的泡沫材料，其密度小于0.1g/cm 3，发泡倍率大于9。 In the embodiment of the present invention, 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.
用于制备动态聚合物的原料配方组分，除所述的无机硼化合物和(聚)硅氧烷化合物之外，还包括可添加/使用的其他聚合物、助剂、填料，这些可添加/使用物可以以共混、参与化学反应的形式与无机硼化合物和含硅化合物的反应产物共同作为具有杂化交联结构的动态聚合物配方组分，或者在动态聚合物的制备过程中起到改善加工性能的作用。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 crosslinked structure, or in the preparation of a dynamic polymer. Improve the performance of processing.
所述的可添加的其他聚合物，其能够作为添加物在体系中起到改进材料性能、赋予材料新性能、提高材料使用与经济效益、达到材料综合利用的作用。可添加的其他聚合物，其可选自天然高分子化合物、合成树脂、合成橡胶、合成纤维。本发明对所添加的聚合物的性状以及所具有的分子量不做限定，根据分子量的不同，可以为低聚物，或者高聚物，根据聚合形态的不同，可以为均聚物，或者共聚物，在具体使用过程中应根据目标材料的性能以及实际制备过程的需要而进行选择。The other polymers that can be added 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 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.
当可添加的其他聚合物选自天然高分子化合物时，其可选自以下任一种或任几种天然高分子化合物：天然橡胶、壳聚糖、甲壳素、天然蛋白质等。When the other polymer that can be added is selected from natural polymer compounds, it may be selected from any one or any of the following natural polymer compounds: natural rubber, chitosan, chitin, natural protein, and the like.
当可添加的其他聚合物选自合成树脂时，其可选自以下任一种或任几种合成树脂：聚三氟氯乙烯、氯化聚乙烯、氯化聚氯乙烯、聚氯乙烯、聚偏氯乙烯、低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、超高分子量聚乙烯、三聚氰胺-甲醛树脂、聚酰胺、聚丙烯酸、聚丙烯酰胺、聚丙烯腈、聚苯并咪唑、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚碳酸酯、聚二甲基硅氧烷、聚乙二醇、聚酯、聚醚砜、聚芳砜、聚醚醚酮、四氟乙烯-全氟丙烷共聚物、聚酰亚胺、聚丙烯酸酯、聚丙烯腈、聚苯醚、聚丙烯、聚苯硫醚、聚苯砜、聚苯乙烯、高抗冲聚苯乙烯、聚砜、聚四氟乙烯、聚氨酯、聚脲、聚乙酸乙烯酯、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物、丙烯腈-丙烯酸酯-苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、氯乙烯-乙酸乙烯酯共聚物、聚乙烯吡咯烷酮、环氧树脂、酚醛树脂、脲醛树脂、不饱和聚酯等。When the other polymer that can be added 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, poly Vinylidene chloride, low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polybenzimidazole, poly Ethylene terephthalate, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene glycol, polyester, polyethersulfone, polyarylsulfone, polyether ether Ketone, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polyacrylate, polyacrylonitrile, polyphenylene ether, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high impact polyphenylene Ethylene, polysulfone, polytetrafluoroethylene, polyurethane, polyurea, polyvinyl acetate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-acrylate-styrene copolymer, acrylonitrile-butyl Alkene-styrene copolymer, vinyl chloride-vinyl acetate copolymer, polyethylene Pyrrolidone, epoxy resin, phenol resin, urea resin, unsaturated polyester.
当可添加的其他聚合物选自合成橡胶时，其可选自以下任一种或任几种合成橡胶：异戊橡胶、顺丁橡胶、丁苯橡胶、丁腈橡胶、氯丁橡胶、丁基橡胶、乙丙橡胶、硅橡胶、氟橡胶、聚丙烯酸酯橡胶、聚氨酯橡胶、氯醚橡胶、热塑性弹性体等。When the other polymer that can be added is selected from synthetic rubber, it may be selected from any one or any of the following synthetic rubbers: isoprene rubber, butadiene rubber, styrene butadiene rubber, nitrile rubber, neoprene, butyl Rubber, ethylene propylene rubber, silicone rubber, fluororubber, polyacrylate rubber, urethane rubber, chloroether rubber, thermoplastic elastomer, etc.
当可添加的其他聚合物选自合成纤维时，其可选自以下任一种或任几种合成纤维：黏胶纤维、铜氨纤维、二乙酯纤维、三乙酯纤维、聚酰胺纤维、聚酯纤维、聚氨酯纤维、聚丙烯腈纤维、聚氯乙烯纤维、聚烯烃纤维、含氟纤维等。When the other polymer that can be added 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.
在聚合物材料的制备过程中，可添加的其他聚合物优选天然橡胶、聚乙烯、聚丙烯、乙烯-乙酸乙烯酯共聚物、聚氨酯、聚氯乙烯、聚丙烯酸、聚丙烯酰胺、聚丙烯酸酯、环氧树脂、酚醛树脂、异戊橡胶、顺丁橡胶、丁苯橡胶、丁腈橡胶、氯丁橡胶、丁基橡胶、乙丙橡胶、硅橡胶、聚氨酯橡胶、热塑性弹性体。Other polymers that may be added during the preparation of the polymer material are preferably natural rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyurethane, polyvinyl chloride, polyacrylic acid, polyacrylamide, polyacrylate, 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.
所述的可添加/使用的助剂，其能够改善材料制备过程，提高产品质量和产量，降低产品成本或者赋予产品某种特有的应用性能。所述的可添加的助剂选自以下任一种或任几种助剂：合成助剂，包括催化剂、引发剂；稳定化助剂，包括抗氧剂、光稳定剂、热稳定剂；改善力学性能的助剂，包括交联剂、固化剂、扩链剂、增韧剂、偶联剂；提高加工性能的助剂，包括润滑剂、脱模剂；柔软化与轻质化的助剂，包括增塑剂、发泡剂、动态调节剂；改变表面性能的助剂，包括抗静电剂、乳化剂、分散剂；改变色光的助剂，包括着色剂、荧光增白剂、消光剂；难燃化与抑烟助剂，包括阻燃剂；其他助剂，包括成核剂、流变剂、增稠剂、流平剂。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 is selected from any one or any of the following auxiliary agents: a synthesis auxiliary agent, including a catalyst, an initiator, a stabilization aid, including an antioxidant, a light stabilizer, a heat stabilizer; Additives for mechanical properties, including crosslinkers, curing agents, chain extenders, toughening agents, coupling agents; additives to improve processing properties, including lubricants, mold release agents; softening and lightening additives , including plasticizers, foaming agents, dynamic regulators; 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 smoke suppressing additives, including flame retardants; other additives, including nucleating agents, rheological agents, thickeners, leveling agents.
所述的可添加/使用的助剂中的催化剂，其能够通过改变反应途径，降低反应活化能来加速反应物在反应过程中的反应速率。在本发明的实施方式中，所述的催化剂包括但不仅限于：(1)聚氨酯合成用催化剂：胺类催化剂，如三乙胺、三亚乙基二胺、双(二甲氨基乙基)醚、2-(2-二甲氨基-乙氧基)乙醇、三甲基羟乙基丙二胺、N,N-双(二甲胺丙基)异丙醇胺、N-(二甲氨基丙基)二异丙醇胺、N,N,N’-三甲基-N’-羟乙基双胺乙基醚、四甲基二亚丙基三胺、N,N-二甲基环己胺、N,N,N’,N’-四甲基亚烷基二胺、N,N,N’,N’,N’-五甲基二亚乙基三胺、N,N-二甲基乙醇胺、N-乙基吗啉、2,4,6-(二甲氨基甲基)苯酚、三甲基-N-2-羟丙基己酸、N,N-二甲基苄胺、N,N-二甲基十六胺等；有机金属类催化剂，如辛酸亚锡、二丁基锡二月桂酸酯、二辛基锡二月桂酸酯、异辛酸锌、异辛酸铅、油酸钾、环烷酸锌、环烷酸钴、乙酰丙酮铁、乙酸苯汞、丙酸苯汞、环烷酸铋、甲醇钠、辛酸钾、油酸钾、碳酸钙等。(2)聚烯烃合成用催化剂：如Ziegler-Natta催化剂、π-烯丙基镍、烷基锂催化剂、茂金属催化剂、一氯二乙基铝、四氯化钛、三氯化钛、三氟化硼乙醚络合物、氧化镁、二甲胺、氯化亚铜、三乙胺、四苯硼钠、三氧化二锑、倍半乙基氯化铝、三氯氧钒、三异丁基铝、环烷酸镍、环烷酸稀土等。(3)CuAAC反应的由一价铜化合物和胺配体共用协同催化。一价铜化合物可选自Cu(I)盐，如CuCl、CuBr、CuI、CuCN、CuOAc等；也可选自Cu(I)络合物，如[Cu(CH 3CN) 4]PF 6、[Cu(CH 3CN) 4]OTf、CuBr(PPh 3) 3等；还可以由单质铜和二价铜化合物(如CuSO 4、Cu(OAc) 2)在反应过程中原位生成；其中，Cu(I)盐优选CuBr和CuI，Cu(I)络合物优选CuBr(PPh 3) 3。胺配体可选自三[(1-苄基-1H-1,2,3-三唑-4-基)甲基]胺(TBTA)、三[(1-叔丁基-1H-1,2,3-三唑-4-基)甲基]胺(TTTA)、三(2-苯并咪唑甲基)胺(TBIA)、水合红菲绕啉二磺酸钠等；其中，胺配体优选TBTA和TTTA。(4)thiol-ene反应催化剂：光催化剂，如安息香二甲醚、2-羟基-2-甲基苯基丙酮、2,2-二甲氧基-2-苯基苯乙酮等；亲核试剂催化剂，如乙二胺、三乙醇胺、三乙胺、吡啶、4-二甲基氨基吡啶、咪唑、二异丙基乙基胺等。所用的催化剂用量没有特别限定，一般为0.01-2wt％。 The catalyst in the additive which can be added/used can accelerate the reaction rate of the reactant in the reaction process by changing the reaction route and reducing the activation energy of the reaction. In an embodiment of the present invention, 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, N,N,N',N',N'-pentamethyldiethylenetriamine, N,N-dimethyl Ethanolamine, N-ethylmorpholine, 2,4,6-(dimethylaminomethyl)phenol, trimethyl-N-2-hydroxypropylhexanoic acid, N,N-dimethylbenzylamine, N, N-dimethylhexadecylamine, etc.; organometallic catalysts such as stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctylate, lead isooctanoate, potassium oleate, zinc naphthenate , cobalt naphthenate, iron acetylacetonate, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octoate, potassium oleate, calcium carbonate, and the like. (2) Catalyst for polyolefin synthesis: such as Ziegler-Natta catalyst, π-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. (3) 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. (4) 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.
所述的可添加/使用的助剂中的引发剂，其能够在聚合反应过程中引起单体分子活化而产生游离基，提高反应速率，促进反应进行，包括但不仅限于以下任一种或任几种引发剂：有机过氧化物，如过氧化月桂酰、过氧化苯甲酰(BPO)、过氧化二碳酸二异丙酯、过氧化二碳酸二环己酯、过氧化二碳酸双(4-叔丁基环己基)酯、叔丁基过氧化苯甲酸酯、叔丁基过氧化特戊酸酯、二叔丁基过氧化物、过氧化氢二异丙苯；偶氮化合物，如偶氮二异丁腈(AIBN)、 偶氮二异庚腈；无机过氧化物，如过硫酸铵、过硫酸钾等；其中，引发剂优选过氧化月桂酰、过氧化苯甲酰、偶氮二异丁腈、过硫酸钾。所用的引发剂用量没有特别限定，一般为0.1-1wt％。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 lauroyl peroxide, benzoyl peroxide, azobis Nitrile and potassium persulfate. The amount of the initiator to be used is not particularly limited and is usually from 0.1 to 1% by weight.
所述的可添加/使用的助剂中的抗氧剂，其能够延缓聚合物样品的氧化过程，保证材料能够顺利地进行制备加工并延长其使用寿命，包括但不仅限于以下任一种或任几种抗氧剂：受阻酚类，如2,6-二叔丁基-4-甲基苯酚、1,1,3-三(2-甲基-4羟基-5-叔丁基苯基)丁烷、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)；含硫受阻酚类，如4,4’-硫代双-[3-甲基-6-叔丁基苯酚]、2,2’-硫代双-[4-甲基-6-叔丁基苯酚]；三嗪系受阻酚，如1,3,5-二[β-(3,5-二叔丁基-4-羟基苯基)丙酰]-六氢均三嗪；三聚异氰酸酯受阻酚类，如三(3,5-二叔丁基-4-羟基苄基)-三异氰酸酯；胺类，如N,N’-二(β-萘基)对苯二胺、N,N’-二苯基对苯二胺、N-苯基-N’-环己基对苯二胺；含硫类，如硫代二丙酸二月桂酯、2-巯基苯并咪唑、2-巯基苯并噻唑；亚磷酸酯类，如亚磷酸三苯酯、亚磷酸三壬基苯酯、三[2.4-二叔丁基苯基]亚磷酸酯等；其中，抗氧剂优选茶多酚(TP)、丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)、叔丁基对苯二酚(TBHQ)、三[2.4-二叔丁基苯基]亚磷酸酯(抗氧剂168)、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)。所用的抗氧剂用量没有特别限定，一般为0.01-1wt％。The 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[β-(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[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]-hexahydro-s-triazine; Isocyanate hindered phenols such as tris(3,5-di-tert-butyl-4-hydroxybenzyl)-triisocyanate; amines such as N,N'-bis(β-naphthyl)p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine; sulfur-containing, such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercapto Benzothiazole; phosphites such as phosphorous acid Phenyl ester, tridecyl phenyl phosphite, tris [2.4-di-tert-butylphenyl] phosphite, etc.; among them, the antioxidant is preferably tea polyphenol (TP), butylated hydroxyanisole (BHA), Butyl hydroxytoluene (BHT), tert-butyl hydroquinone (TBHQ), tris [2.4-di-tert-butylphenyl] phosphite (antioxidant 168), tetra [β-(3,5-di) Tert-butyl-4-hydroxyphenyl)propanoic acid]pentaerythritol ester (antioxidant 1010). The amount of the antioxidant to be used is not particularly limited and is usually from 0.01 to 1% by weight.
所述的可添加/使用的助剂中的光稳定剂，能够防止聚合物样品发生光老化，延长其使用寿命，其包括但不仅限于以下任一种或任几种光稳定剂：光屏蔽剂，如炭黑、二氧化钛、氧化锌、亚硫酸钙；紫外线吸收剂，如2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮、2-(2-羟基-3,5-二叔丁基苯基)-5-氯苯并三唑、2-(2-羟基-5-甲基苯基)苯并三唑、2,4,6-三(2-羟基-4-正丁氧基苯基)-1,3,5-均三嗪、2-氰基-3,3-二苯基丙烯酸2-乙基己酯；先驱型紫外线吸收剂，如水杨酸对-叔丁基苯酯、双水杨酸双酚A酯；紫外线猝灭剂，如双(3,5-二叔丁基-4-羟基苄基膦酸单乙酯)、2,2’-硫代双(4-特辛基酚氧基)镍；受阻胺光稳定剂，如癸二酸双(2,2,6,6-四甲基哌啶)酯、苯甲酸(2,2,6,6-四甲基哌啶)酯、三(1,2,2,6,6-五甲基哌啶基)亚磷酸酯；其他光稳定剂，如3,5-二叔丁基-4-羟基苯甲酸(2,4-二叔丁基苯)酯、烷基磷酸酰胺、N,N’-二正丁基二硫代氨基甲酸锌、N,N’-二正丁基二硫代氨基甲酸镍等；其中，光稳定剂优选炭黑、癸二酸双(2,2,6,6-四甲基哌啶)酯(光稳定剂770)。所用的光稳定剂用量没有特别限定，一般为0.01-0.5wt％。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-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) , 2,2'-thiobis(4-tertylphenoloxy) nickel; hindered amine light stabilizers, such as bis(2,2,6,6-tetramethylpiperidine) sebacate, benzene (2,2,6,6-tetramethylpiperidine) formate, tris(1,2,2,6,6-pentamethylpiperidinyl)phosphite; other light stabilizers such as 3,5 -di-tert-butyl-4-hydroxybenzoic acid (2,4-di-tert a base benzene) ester, an alkyl phosphate amide, a zinc N,N'-di-n-butyldithiocarbamate, a nickel N,N'-di-n-butyldithiocarbamate, etc.; wherein the light stabilizer is preferably carbon Black (2,2,6,6-tetramethylpiperidine) phthalate (light stabilizer 770). The amount of the photostabilizer to be used is not particularly limited and is generally from 0.01 to 0.5% by weight.
所述的可添加/使用的助剂中的热稳定剂，能够使得聚合物样品在加工或使用过程中不因受热而发生化学变化，或者延缓这些变化来达到延长使用寿命的目的，其包括但不仅限于以下任一种或任几种热稳定剂：铅盐类，如三盐基硫酸铅、二盐基亚磷酸铅、二盐基硬脂酸铅、二盐基苯二甲酸铅、三盐基马来酸铅、盐基性硅酸铅、硬脂酸铅、水杨酸铅、二盐基邻苯二甲酸铅、碱式碳酸铅、硅胶共沉淀硅酸铅；金属皂类：如硬脂酸镉、硬脂酸钡、硬脂酸钙、硬脂酸铅、硬脂酸锌；有机锡化合物类，如二月桂酸二正丁基锡、二月桂酸二正辛基锡、马来酸二(正)丁基锡、双马来酸单辛酯二正辛基锡，二巯基乙酸异辛酯二正辛基锡、京锡C-102、二巯基乙酸异辛脂二甲基锡、二硫醇二甲基锡及其复配物；锑稳定剂，如硫醇锑盐、巯基乙酸酯硫醇锑、巯基羧酸酯锑、羧酸酯锑；环氧化合物类，如环氧化油、环氧脂肪酸酯、环氧树脂；亚磷酸酯类，如亚磷酸三芳酯、亚磷酸三烷酯、亚磷酸三芳烷酯、烷芳混合酯、聚合型亚磷酸酯；多元醇类，如季戊四醇、木糖醇、甘露醇、山梨糖醇、三羟甲基丙烷；其中，热稳定剂优选硬脂酸钡，硬脂酸钙、二月桂酸二正丁基锡、马来酸二(正)丁基锡。所用的热稳定剂用量没有特别限定，一般为0.1-0.5wt％。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-n-octyltin, di-mercaptoacetic acid isooctyl di-n-octyl tin, jingxi C-102, di-mercaptoacetic acid isooctyl dimethyl tin, dithiol dimethyl tin and a compound; a hydrazine stabilizer such as a thiol sulfonium salt, a thioglycol thiol sulfonate, a decyl carboxylate hydrazine, Ethyl esters; epoxy compounds such as epoxidized oils, epoxidized fatty acid esters, epoxy resins; phosphites such as triaryl phosphite, trialkyl phosphite, triaryl phosphite, alkane Mixed esters, polymeric phosphites; polyhydric alcohols such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; wherein the heat stabilizer is preferably barium stearate, calcium stearate, Di-n-butyltin laurate, di(n-butyl)butylate. The amount of the heat stabilizer to be used is not particularly limited and is usually from 0.1 to 0.5% by weight.
所述的可添加的助剂中的交联剂，其配合在动态聚合物中需要进行交联的反应物组分进行使用，其能在线型的聚合物分子间起架桥作用，使多个线型分子相互键合交联成网状结构，能够进一步增加聚合物的交联密度和交联强度，提高聚合物的耐热性能及使用寿命，同时改善材料的机械性能及耐候性，其包括但不仅限于以下任一种或任几种交联剂：聚丙二醇缩水 甘油醚、氧化锌、氯化铝、硫酸铝、硝酸铬、正硅酸乙酯、正硅酸甲酯、对甲苯磺酸、对甲苯磺酰氯、二丙烯酸-1,4-丁二醇酯、二甲基丙烯酸乙二醇酯、丙烯酸丁酯、异丙醇铝、醋酸锌、乙酰丙酮钛、氮丙啶、异氰酸酯、酚醛树脂、六次甲基四胺、过氧化二异丙苯、过氧化月桂酰、过氧化硬酯酰、过氧化苯甲酰、过氧化环己酮、过氧化苯乙酮、过氧化二叔丁基、邻苯过氧二甲酸二叔丁酯、异丙苯过氧化氢、乙烯基三叔丁过氧基硅烷、二苯基-二叔丁过氧基硅烷、三甲基叔丁基过氧硅烷等。其中，交联剂优选过氧化二异丙苯(DCP)、过氧化苯甲酰(BPO)、过氧化2,4-二氯苯甲酰(DCBP)。所用的交联剂用量没有特别限定，一般为0.1-5wt％。The cross-linking agent in the additive which can be added, which is used in the dynamic polymer to be cross-linked, and which can bridge the polymer molecules in the on-line type, so that multiple The linear molecules are bonded to each other to form a network structure, which can further increase the crosslinking density and crosslinking strength of the polymer, improve the heat resistance and service life of the polymer, and improve the mechanical properties and weather resistance of the material, including However, it is not limited to any one or any of the following crosslinking agents: polypropylene glycol glycidyl ether, zinc oxide, aluminum chloride, aluminum sulfate, chromium nitrate, tetraethyl orthosilicate, methyl orthosilicate, p-toluenesulfonic acid , p-toluenesulfonyl chloride, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, butyl acrylate, aluminum isopropoxide, zinc acetate, titanium acetylacetonate, aziridine, isocyanate, phenolic Resin, hexamethylenetetramine, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, benzoyl peroxide, cyclohexanone peroxide, acetophenone peroxide, di-tert-butyl peroxide Base, di-tert-butyl phthalate, isopropyl Hydrogen peroxide, vinyl tri-tert-butylperoxy silane, diphenyl - di-t-butylperoxy silane, t-butyl peroxy trimethyl silane. Among them, the crosslinking agent is preferably dicumyl peroxide (DCP), benzoyl peroxide (BPO), or 2,4-dichlorobenzoyl peroxide (DCBP). The amount of the crosslinking agent to be used is not particularly limited and is usually from 0.1 to 5% by weight.
所述的可添加的助剂中的固化剂，其配合在动态聚合物中需要进行固化的反应物组分进行使用，能够增进或控制反应物组分在聚合过程中的固化反应，其包括但不仅限于以下任一种或任几种固化剂：胺类固化剂，如乙二胺、二乙烯三胺、三乙烯四胺、二甲氨基丙胺、六次甲基四胺、间苯二胺；酸酐类固化剂，如邻苯二甲酸酐、顺丁烯二酸酐、均苯四酸二酐；酰胺类固化剂，如低分子聚酰胺；咪唑类，如2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑；三氟化硼络合物等。其中，固化剂优选乙二胺(EDA)、二乙烯三胺(DETA)、邻苯二甲酸酐、顺丁烯二酸酐，所用的固化剂用量没有特别限定，一般为0.5-1wt％。The curing agent in the additive which can be added, which is used in combination with a reactant component which needs to be cured in a dynamic polymer, can enhance or control the curing reaction of the reactant component in the polymerization process, including but It is not limited to any one or any of the following curing agents: an amine curing agent such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, hexamethylenetetramine, m-phenylenediamine; An acid anhydride curing agent such as phthalic anhydride, maleic anhydride, pyromellitic dianhydride; an amide curing agent such as a low molecular polyamide; an imidazole such as 2-methylimidazole or 2-ethyl 4-methylimidazole, 2-phenylimidazole; boron trifluoride complex, and the like. Among them, the curing agent is preferably ethylenediamine (EDA), diethylenetriamine (DETA), phthalic anhydride or maleic anhydride, and the amount of the curing agent to be used is not particularly limited, and is usually from 0.5 to 1% by weight.
所述的可添加/使用的助剂中的扩链剂，能与反应物分子链上的反应性基团反应而使分子链扩展、分子量增大，通常用于制备可添加的聚氨酯/聚脲，其包括但不仅限于以下任一种或任几种扩链剂：多元醇类扩链剂，如乙二醇、丙二醇、一缩二乙二醇、甘油、三羟甲基丙烷、季戊四醇、1,4-丁二醇、1,6-己二醇、对苯二酚二羟乙基醚(HQEE)、间苯二酚双羟乙基醚(HER)、对双羟乙基双酚A；多元胺类扩链剂，如二氨基甲苯、二氨基二甲苯、四甲基亚二甲苯基二胺、四乙基二苯亚甲基二胺、四异丙基二苯亚基二胺、间苯二胺、三(二甲基氨基甲基)苯酚、二氨基二苯基甲烷、3,3’-二氯-4,4’-二苯基甲烷二胺(MOCA)、3,5-二甲硫基甲苯二胺(DMTDA)、3,5-二乙基甲苯二胺(DETDA)、1,3,5-三乙基-2,6-二氨基苯(TEMPDA)；醇胺类扩链剂，如三乙醇胺、三异丙醇胺、N,N’-双(2-羟丙基)苯胺。所用的扩链剂用量没有特别限定，一般为1-20wt％。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. , 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, tetraisopropyldiphenylidenediamine, Phenylenediamine, tris(dimethylaminomethyl)phenol, diaminodiphenylmethane, 3,3'-dichloro-4,4'-diphenylmethanediamine (MOCA), 3,5-di Methylthiotoluenediamine (DMTDA), 3,5-diethyltoluenediamine (DETDA), 1,3,5-triethyl-2,6-diaminobenzene (TEMPDA); alcohol amine chain extension Agents such as triethanolamine, triisopropanolamine, N,N'-bis(2-hydroxypropyl)aniline. The amount of the chain extender to be used is not particularly limited and is usually from 1 to 20% by weight.
所述的可添加/使用的助剂中的增韧剂，能够降低聚合物样品脆性，增大韧性，提高材料承载强度，其包括但不仅限于以下任一种或任几种增韧剂：甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物树脂、氯化聚乙烯树脂、乙烯-醋酸乙烯酯共聚物树脂及其改性物、丙烯腈-丁二烯-苯乙烯共聚物、丙烯腈-丁二烯共聚物、乙丙胶、三元乙丙胶、顺丁胶、丁苯胶、苯乙烯-丁二烯-苯乙烯嵌段共聚物等；其中，增韧剂优选乙丙胶、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物树脂(MBS)、氯化聚乙烯树脂(CPE)。所用的增韧剂用量没有特别限定，一般为5-10wt％。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. Nitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS), Chlorinated polyethylene resin (CPE). The amount of the toughening agent to be used is not particularly limited and is usually from 5 to 10% by weight.
所述的可添加/使用的助剂中的偶联剂，能够改善聚合物样品与无机填充剂或增强材料的界面性能，在塑料加工过程中降低材料熔体的粘度，改善填料的分散度以提高加工性能，进而使制品获得良好的表面质量及机械、热和电性能，其包括但不仅限于以下任一种或任几种偶联剂：有机酸铬络合物、硅烷偶联剂、钛酸酯偶联剂、磺酰叠氮偶联剂、铝酸酯偶联剂等；其中，偶联剂优选γ-氨丙基三乙氧基硅烷(硅烷偶联剂KH550)、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷(硅烷偶联剂KH560)。所用的偶联剂用量没有特别限定，一般为0.5-2wt％。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. Improve processing performance, and thus obtain good surface quality and mechanical, thermal and electrical properties of the product, including but not limited to 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 γ-aminopropyltriethoxysilane (silane coupling agent KH550), γ-(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.
所述的可添加/使用的助剂中的润滑剂，能够提高聚合物样品的润滑性、减少摩擦、降低界面粘附性能，其包括但不仅限于以下任一种或任几种润滑剂：饱和烃和卤代烃类，如固体石蜡、微晶石蜡、液体石蜡、低分子量聚乙烯、氧化聚乙烯蜡；脂肪酸类，如硬脂酸、羟基硬脂酸；脂肪酸酯类，如脂肪酸低级醇酯、脂肪酸多元醇酯、天然蜡、酯蜡和皂化蜡；脂肪族酰胺类，如硬脂酰胺或硬脂酸酰胺、油酰胺或油酸酰胺、芥酸酰胺、N,N’-乙撑双硬脂酰胺；脂肪醇和多元醇类，如硬脂醇、鲸蜡醇、季戊四醇；金属皂类，如硬脂酸铅、硬脂酸钙、硬 脂酸钡、硬脂酸镁、硬脂酸锌等；其中，润滑剂优选固体石蜡、液体石蜡、硬脂酸、低分子量聚乙烯。所用的润滑剂用量没有特别限定，一般为0.5-1wt％。The lubricant in the additive that can be added/used can improve the lubricity of the polymer sample, reduce friction, and reduce interfacial adhesion performance, including but not limited to any one or any of the following lubricants: saturation Hydrocarbons and halogenated hydrocarbons, such as paraffin wax, microcrystalline paraffin, liquid paraffin, low molecular weight polyethylene, oxidized polyethylene wax; fatty acids such as stearic acid, hydroxystearic acid; fatty acid esters, such as fatty acid lower alcohol esters , fatty acid polyol esters, natural waxes, ester waxes and saponified waxes; aliphatic amides such as stearic acid amide or stearic acid amide, oleamide or oleic acid amide, erucamide, N, N'-ethylene double hard Fatty acid amide; fatty alcohols and polyols such as stearyl alcohol, cetyl alcohol, pentaerythritol; metal soaps such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, etc. Among them, the lubricant is preferably paraffin wax, liquid paraffin, stearic acid, or low molecular weight polyethylene. The amount of the lubricant to be used is not particularly limited and is usually from 0.5 to 1% by weight.
所述的可添加/使用的助剂中的脱模剂，它可使聚合物样品易于脱模，表面光滑、洁净，其包括但不仅限于以下任一种或任几种脱模剂：石蜡烃、皂类、二甲基硅油、乙基硅油、甲基苯基硅油、蓖麻油、废机油、矿物油、二硫化钼、聚乙二醇、氯乙烯树脂、聚苯乙烯、硅橡胶等；其中，脱模剂优选二甲基硅油，聚乙二醇。所用的脱模剂用量没有特别限定，一般为0.5-2wt％。The release agent in the additive which can be added/used, which can make the polymer sample easy to demold, the surface is smooth and clean, including but not limited to any one or any of the following mold release agents: paraffin hydrocarbon , soap, dimethyl silicone oil, ethyl silicone oil, methyl phenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicone rubber, etc.; 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.
所述的可添加/使用的助剂中的增塑剂，其能够增加聚合物样品的塑性，使得聚合物的硬度、模量、软化温度和脆化温度下降，伸长率、曲挠性和柔韧性提高，其包括但不仅限于以下任一种或任几种增塑剂：苯二甲酸酯类：邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、邻苯二甲酸二异辛酯、邻苯二甲酸二庚酯、邻苯二甲酸二异癸酯、邻苯二甲酸二异壬酯、邻苯二甲酸丁苄酯、邻苯二甲酸丁酯乙醇酸丁酯、邻苯二甲酸二环己酯、邻苯二甲酸双(十三)酯、对苯二甲酸二(2-乙基)己酯；磷酸酯类，如磷酸三甲苯酯、磷酸(二苯-2-乙基)己酯；脂肪酸酯类，如己二酸二(2-乙基)己酯、癸二酸二(2-乙基)己酯；环氧化合物类，如环氧甘油酯类、环氧脂肪酸单酯类、环氧四氢邻苯二甲酸酯类、环氧大豆油、环氧硬脂酸(2-乙基)己酯、环氧大豆油酸2-乙基己酯、4,5-环氧四氢邻苯二甲酸二(2-乙基)己酯、黄杨乙酰蓖麻油酸甲酯；二元醇脂类，如C 5～9酸乙二醇酯、C 5～9酸二缩三乙二醇酯；含氯类，如绿化石蜡类、氯代脂肪酸酯；聚酯类，如乙二酸1,2-丙二醇系聚酯、癸二酸1,2-丙二醇聚酯、石油磺酸苯酯、偏苯三酸酯、柠檬酸酯和双季戊四醇酯等；其中，增塑剂优选邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异辛酯(DIOP)、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)、磷酸三甲苯酯(TCP)。所用的增塑剂用量没有特别限定，一般为5-20wt％。 a 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-ethyl)hexyl adipate, di(2-ethyl)hexyl sebacate; epoxy compounds such as epoxy glycerides, epoxidized fatty acids Monoesters, epoxy tetrahydrophthalate, epoxidized soybean oil, (2-ethylhexyl) epoxy stearate, 2-ethylhexyl epoxide, 4,5- Epoxy tetrahydroortylene Acid bis (2-ethylhexyl) ester, acetyl methyl ricinoleate boxwood; diol lipids, such as C 5 ~ 9 glycol acrylate, C 5 ~ 9 triethylene glycol diethyl ester; containing Chlorines, such as green paraffin, chlorinated fatty acid esters; polyesters, such as oxalic acid 1,2-propanediol polyester, azelaic acid 1,2-propanediol polyester, petroleum benzene sulfonate, benzene a triester, a citrate, a dipentaerythritol ester or the like; wherein the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate ( DIOP), diisodecyl phthalate (DINP), diisodecyl phthalate (DIDP), tricresyl phosphate (TCP). The amount of the plasticizer to be used is not particularly limited and is usually from 5 to 20% by weight.
所述的可添加/使用的助剂中的发泡剂，能使得聚合物样品发泡成孔，从而得到质轻、隔热、隔音、富有弹性的聚合物材料，其包括但不仅限于以下任一种或任几种发泡剂：物理发泡剂，如丙烷、甲醚、戊烷、新戊烷、己烷、异戊烷、庚烷、异庚烷、石油醚、丙酮、苯、甲苯、丁烷、乙醚、氯甲烷、二氯甲烷、二氯乙烯、二氯二氟甲烷、三氟氯甲烷；无机发泡剂，如碳酸氢钠、碳酸铵、碳酸氢铵；有机发泡剂，如N,N’-二硝基五次甲基四胺、N,N’-二甲基-N,N’-二亚硝基对苯二甲酰胺、偶氮二甲酰胺、偶氮二碳酸钡、偶氮二碳酸二异丙酯、偶氮甲酰胺甲酸钾、偶氮二异丁腈、4,4’-氧代双苯磺酰肼、苯磺酰肼、三肼基三嗪、对甲苯磺酰氨基脲、联苯-4,4’-二磺酰叠氮；发泡促进剂，如尿素、硬脂酸、月桂酸、水杨酸、三盐基性硫酸铅、二盐基亚磷酸铅、硬脂酸铅、硬脂酸镉、硬脂酸锌、氧化锌；发泡抑制剂，如马来酸、富马酸、硬脂酰氯、苯二甲酰氯、马来酸酐、苯二甲酸酐、对苯二酚、萘二酚、脂肪族胺、酰胺、肟、异氰酸酯、硫醇、硫酚、硫脲、硫化物、砜、环己酮、乙酰丙酮、六氯环戊二烯、二丁基马来酸锡等。其中，发泡剂优选碳酸氢钠、碳酸铵、偶氮二甲酰胺(发泡剂AC)、N,N’-二硝基五次甲基四胺(发泡剂H)、N,N’-二甲基-N,N’-二亚硝基对苯二甲酰胺(发泡剂NTA)，物理型微球发泡剂、所用的发泡剂用量没有特别限定，一般为0.1-30wt％。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, azodicarbonate Bismuth, diisopropyl azodicarbonate, potassium azoformate, azobisisobutyronitrile, 4,4'-oxobisbenzenesulfonylhydrazide, benzenesulfonylhydrazide, tridecyltriazine, pair Tosyl semicarbazide, biphenyl-4,4'-disulfonyl azide; foaming accelerators such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic amide Lead phosphate, Lead oleate, cadmium stearate, zinc stearate, zinc oxide; foaming inhibitors such as maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, Hydroquinone, naphthalenediol, aliphatic amine, amide, hydrazine, isocyanate, thiol, thiophenol, thiourea, sulfide, sulfone, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyl horse Come to tin and so on. Among them, 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. .
所述的可添加/使用的助剂中的动态调节剂，能够提升调节动态聚合物动态性，以便获得最优化的期望性能，其一般是带有自由羟基或者自由羧基，或者能够给出或接受电子对的化合物，包括但不仅限于水、氢氧化钠、醇(包括硅醇)、羧酸、路易斯酸、路易斯碱等。所用的动态调节剂用量没有特别限定，一般为0.1-10wt％。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.
所述的可添加/使用的助剂中的抗静电剂，可将聚合物样品中聚集的有害电荷引导或消除，使其不对生产和生活造成不便或危害，其包括但不仅限于以下任一种或任几种抗静电剂：阴离子型抗静电剂，如烷基磺酸盐、对壬基苯氧基丙烷磺酸钠、烷基磷酸酯二乙醇胺盐、对壬基二苯醚磺酸钾、磷酸酯衍生物、磷酸盐、磷酸聚环氧乙烷烷基醚醇酯、磷酸酯衍生物、 脂肪胺磺酸盐、丁酸酯磺酸钠；阳离子型抗静电剂，如脂肪铵盐酸盐、月桂基三甲基氯化铵、十二烷基三甲胺溴化物、烷基羟乙基二甲铵高氯酸盐；两性离子型抗静电剂，如烷基二羧甲基铵乙内盐、月桂基甜菜碱、N,N,N-三烷基铵乙酰(N’-烷基)胺乙内盐、N-月桂基-N,N-二聚氧化乙烯基-N-乙基膦酸钠、N-烷基氨基酸盐；非离子型抗静电剂，如脂肪醇环氧乙烷加成物、脂肪酸环氧乙烷加成物、烷基酚环氧乙烷加成物、磷酸三聚氧乙烯基醚酯、甘油单脂肪酸酯；高分子型抗静电剂，如乙二胺的环氧乙烷环氧丙烷加成物、聚烯丙酰胺N-季铵盐取代物、聚4-乙烯基-1-丙酮基吡啶磷酸-对丁基苯酯盐等；其中，抗静电剂优选月桂基三甲基氯化铵、十八烷基二甲基羟乙基季铵硝酸盐(抗静电剂SN)、烷基磷酸酯二乙醇胺盐(抗静电剂P)。所用的抗静电剂用量没有特别限定，一般为0.3-3wt％。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 ester 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, such as alkyl dicarboxymethyl ammonium ethyl beta salt , lauryl betaine, N,N,N-trialkylammonium acetyl (N'-alkyl)amine ethyl salt, N-lauryl-N,N-dipolyoxyethylene-N-ethylphosphonic acid Sodium, N-alkyl amino acid salt; nonionic antistatic agent, such as fatty alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, alkyl phenol ring Ethane adduct, tripolyoxyethylene ether phosphate, monoglyceride; polymer antistatic agent, such as ethylene oxide propylene oxide adduct of ethylenediamine, polyallylamide N- a quaternary ammonium salt substitute, a poly-4-vinyl-1-pyrimidinyl pyridine phosphate-p-butylphenyl ester salt or the like; wherein, the antistatic agent is preferably lauryl trimethyl ammonium chloride, octadecyl dimethyl hydroxy Ethyl quaternary ammonium nitrate (antistatic agent SN), alkyl phosphate diethanolamine salt (antistatic agent P). The amount of the antistatic agent to be used is not particularly limited and is usually from 0.3 to 3% by weight.
所述的可添加/使用的助剂中的乳化剂，能够改善包含助剂的聚合物混合液中各种构成相之间的表面张力，使之形成均匀稳定的分散体系或乳浊液，其优选用于进行乳液聚合/交联，其包括但不仅限于以下任一种或任几种乳化剂：阴离子型，如高级脂肪酸盐、烷基磺酸盐、烷基苯磺酸盐、烷基萘磺酸钠、琥珀酸酯磺酸盐、石油磺酸盐、脂肪醇硫酸盐、蓖麻油硫酸酯盐、硫酸化蓖麻酸丁酯盐、磷酸酯盐、脂肪酰-肽缩合物；阳离子型，如烷基铵盐、烷基季铵盐、烷基吡啶盐；两性离子型，如羧酸酯型、磺酸酯型、硫酸酯型、磷酸酯型；非离子型，如脂肪醇聚氧乙烯醚、烷基酚聚氧乙烯醚、脂肪酸聚氧乙烯酯、聚环氧丙烷-环氧乙烷加成物、甘油脂肪酸酯、季戊四醇脂肪酸酯、山梨醇及失水山梨醇脂肪酸酯、蔗糖脂肪酸酯、醇胺脂肪酰胺等；其中，乳化剂优选十二烷基苯磺酸钠、失水山梨醇脂肪酸酯、三乙醇胺硬脂酸酯(乳化剂FM)。所用的乳化剂用量没有特别限定，一般为1-5wt％。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, Preferably used for emulsion polymerization/crosslinking, 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 carboxylate type, sulfonate type, sulfate type, phosphate type; nonionic type, such as fatty alcohol polyoxygen Vinyl ether, alkylphenol ethoxylate, fatty acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester , sucrose fatty acid ester, alcohol amine fatty acid amide, etc.; among them, excellent emulsifier Sodium dodecyl benzene sulfonate, sorbitan fatty acid ester, triethanolamine stearate (emulsifier FM) are selected. The amount of the emulsifier used is not particularly limited and is usually from 1 to 5% by weight.
所述的可添加/使用的助剂中的分散剂，能够使得聚合物混合液中固体絮凝团分散为细小的粒子而悬浮于液体中，均一分散那些难于溶解于液体的固体及液体颗粒，同时也能防止颗粒的沉降和凝聚，形成安定悬浮液，其包括但不仅限于以下任一种或任几种分散剂：阴离子型，如烷基硫酸酯钠盐、烷基苯磺酸钠、石油磺酸钠；阳离子型；非离子型，如脂肪醇聚氧乙烯醚、山梨糖醇酐脂肪酸聚氧乙烯醚；无机型，如硅酸盐、缩合磷酸盐；其中，分散剂优选十二烷基苯磺酸钠、萘系亚甲基磺酸盐(分散剂N)、脂肪醇聚氧乙烯醚。所用的分散剂用量没有特别限定，一般为0.3-0.8wt％。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 limited and is usually from 0.3 to 0.8% by weight.
所述的可添加/使用的助剂中的着色剂，可以使聚合物产品呈现出所需要的颜色，增加表面色彩，其包括但不仅限于以下任一种或任几种着色剂：无机颜料，如钛白、铬黄、镉红、铁红、钼铬红、群青、铬绿、炭黑；有机颜料，如立索尔宝红BK、色淀红C、苝红、嘉基R红、酞菁红、永固洋红HF3C、塑料大红R和克洛莫红BR、永固橙HL、耐晒黄G、汽巴塑料黄R、永固黄3G、永固黄H 2G、酞青蓝B、酞青绿、塑料紫RL、苯胺黑；有机染料，如硫靛红、还原黄4GF、士林蓝RSN、盐基性玫瑰精、油溶黄等；其中，着色剂的选用根据样品颜色需求而定，不需要特别限定。所用的着色剂用量没有特别限定，一般为0.3-0.8wt％。 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 amount of the coloring agent to be used is not particularly limited and is usually from 0.3 to 0.8% by weight.
所述的可添加/使用的助剂中的荧光增白剂，能使所染物质获得类似荧石的闪闪发光的效应，其包括但不仅限于以下任一种或任几种荧光增白剂：二苯乙烯型、香豆素型、吡唑啉型、苯并氧氮型、苯二甲酰亚胺型等；其中，荧光增白剂优选二苯乙烯联苯二磺酸钠(荧光增白剂CBS)、4,4-双(5甲基-2-苯并噁唑基)二苯乙烯(荧光增白剂KSN)、2,2-(4,4’-二苯乙烯基)双苯并噁唑(荧光增白剂OB-1)。所用的荧光增白剂用量没有特别限定，一般为0.002-0.03wt％。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.
所述的可添加/使用的助剂中的消光剂，能够使得入射光到达聚合物表面时，发生漫反射，产生低光泽的亚光和消光外观，其包括但不仅限于以下任一种或任几种消光剂：沉降硫酸钡、二氧化硅、含水石膏粉、滑石粉、钛白粉、聚甲基脲树脂等；其中，消光剂优选二氧化硅。所用的消光剂用量没有特别限定，一般为2-5wt％。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.
所述的可添加/使用的助剂中的阻燃剂，能够增加材料的耐燃性，其包括但不仅限于以下任一种或任几种阻燃剂：磷系，如红磷、磷酸三甲酚酯、磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯二苯酯；含卤磷酸酯类，如三(2,3-二溴丙基)磷酸酯、磷酸三(2,3-二氯丙)酯；有机卤化物，如高含氯量氯化石蜡、1,1,2,2-四溴乙烷、十溴二苯醚、全氯环戊癸烷；无机阻燃剂，如三氧化二锑、氢氧化铝、氢氧化镁、硼酸锌；反应型阻燃剂，如氯桥酸酐、双(2,3-二溴丙基)反丁烯二酸酯、四溴双酚A、四溴邻苯二甲酸酐等；其中，阻燃剂优选十溴二苯醚、磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯二苯酯、三氧化二锑。所用的阻燃剂用量没有特别限定，一般为1-20wt％。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) fumarate, tetrabromobisphenol A, tetrabromo Phthalic anhydride or the like; among them, the flame retardant is preferably decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, toluene diphenyl phosphate or antimony trioxide. The amount of the flame retardant to be used is not particularly limited and is usually from 1 to 20% by weight.
所述的可添加/使用的助剂中的成核剂，能够通过改变聚合物的结晶行为，加快结晶速率、增加结晶密度和促使晶粒尺寸微细化，达到缩短材料成型周期，提高制品透明性、表面光泽、抗拉强度、刚性、热变形温度、抗冲击性、抗蠕变性等物理机械性能的目的，其包括但不仅限于以下任一种或任几种成核剂：苯甲酸、己二酸、苯甲酸钠、滑石粉、对苯酚磺酸钠、二氧化硅、二苄叉山梨糖醇及其衍生物、乙丙橡胶、三元乙丙橡胶等；其中，成核剂优选二氧化硅、二苄叉山梨糖醇(DBS)、三元乙丙橡胶。所用的成核剂用量没有特别限定，一般为0.1-1wt％。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.
所述的可添加/使用的助剂中的流变剂，能够保证聚合物在涂膜过程中具有良好的涂刷性和适当的涂膜厚度，防止贮存时固体颗粒的沉降，能够提高其再分散性，其包括但不仅限于以下任一种或任几种流变剂：无机类，如硫酸钡、氧化锌、碱土金属氧化物、碳酸钙、氯化锂、硫酸钠、硅酸镁、气相二氧化硅、水玻璃、胶态二氧化硅；有机金属化合物，如硬脂酸铝、烷醇铝、钛螯合物、铝螯合物；有机类，如有机膨润土、氢化蓖麻油/酰胺蜡、异氰酸酯衍生物、丙烯酸乳液、丙烯酸共聚物、聚乙烯蜡、纤维素酯等；其中，流变剂优选有机膨润土、聚乙烯蜡、疏水改性碱性可膨胀乳液(HASE)、碱性可膨胀乳液(ASE)。所用的流变剂用量没有特别限定，一般为0.1-1wt％。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 (HASE), alkaline swellable Emulsion (ASE). The amount of the rheology agent to be used is not particularly limited and is usually from 0.1 to 1% by weight.
所述的可添加/使用的助剂中的增稠剂，能够赋予聚合物混合液良好的触变性和适当的稠度，从而满足其在生产、贮存和使用过程中的稳定性能和应用性能等多方面的需求，其包括但不仅限于以下任一种或任几种增稠剂：低分子物质，如脂肪酸盐、烷基二甲胺氧化物、脂肪酸单乙醇酰胺、脂肪酸二乙醇酰胺、脂肪酸异丙酰胺、脱水山梨醇三羧酸酯、甘油三油酸酯、椰子酰胺丙基甜菜碱、钛酸酯偶联剂；高分子物质，如皂土、人工水辉石、微粉二氧化硅、胶体铝、动物蛋白、聚甲基丙烯酸盐、甲基丙烯酸共聚物、顺酐共聚物、巴豆酸共聚物、聚丙烯酰胺、聚乙烯吡咯酮、聚醚等；其中，增稠剂优选羟椰子油二乙醇酰胺、丙烯酸-甲基丙烯酸共聚物。所用的增稠剂用量没有特别限定，一般为0.1-1.5wt％。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 Ethanol amide, acrylic acid-methacrylic acid copolymer. The amount of the thickener to be used is not particularly limited and is usually from 0.1 to 1.5% by weight.
所述的可添加/使用的助剂中的流平剂，能够保证聚合物涂膜的平整光滑均匀，改善涂膜表面质量、提高装饰性，其包括但不仅限于以下任一种或任几种流平剂：聚二甲基硅氧烷、聚甲基苯基硅氧烷、聚丙烯酸酯类、有机硅树脂等；其中，流平剂优选聚二甲基硅氧烷、聚丙烯酸酯。所用的流平剂用量没有特别限定，一般为0.5-1.5wt％。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.
在动态聚合物的制备过程中，可添加的助剂优选催化剂、引发剂、抗氧剂、光稳定剂、热稳定剂、扩链剂、增韧剂、增塑剂、发泡剂、阻燃剂、动态调节剂。In the preparation of the dynamic polymer, additives which may be added are preferably catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, chain extenders, toughening agents, plasticizers, foaming agents, flame retardants Agent, dynamic regulator.
所述的可添加的填料，其在动态聚合物中主要起到以下作用：①降低成型制品的收缩率，提高制品的尺寸稳定性、表面光洁度、平滑性以及平光性或无光性等；②调节聚合物的粘度；③满足不同性能要求，如提高聚合物材料冲击强度及压缩强度、硬度、刚度和模量、提高耐磨性、提高热变形温度、改善导电性及导热性等；④提高颜料的着色效果；⑤赋予光稳定性和耐化学腐蚀性；⑥起到增容作用，可降低成本，提高产品在市场上的竞争能力。The additive which can be added 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; Adjust the viscosity of the polymer; 3 to meet different performance requirements, such as improving the impact strength and compressive strength, hardness, stiffness and modulus of the polymer material, improving wear resistance, improving heat distortion temperature, improving conductivity and thermal conductivity, etc.; The coloring effect of the pigment; 5 imparts light stability and chemical resistance; 6 acts as a compatibilizing agent, which can reduce the cost and improve the competitiveness of the product in the market.
所述的可添加的填料，选自以下任一种或任几种填料：无机非金属填料、金属填料、有机填料。The filler which can be added is selected from any one or any of the following fillers: an inorganic non-metallic filler, a metal filler, and an organic filler.
所述的无机非金属填料，包括但不限于以下任一种或任几种：碳酸钙、陶土、硫酸钡、硫酸钙和亚硫酸钙、滑石粉、白炭黑、石英、云母粉、粘土、石棉、石棉纤维、正长石、白垩、石灰石、重晶石粉、石膏、石墨、炭黑、石墨烯、氧化石墨烯、碳纳米管、二硫化钼、矿渣、烟道灰、木粉及壳粉、硅藻土、赤泥、硅灰石、硅铝炭黑、氢氧化铝、氢氧化镁、粉煤灰、油页岩粉、膨胀珍珠岩粉、氮化铝粉、氮化硼粉、蛭石、铁泥、白泥、碱泥、(中空)玻璃微珠、发泡微球、可发泡颗粒、玻璃粉、水泥、玻璃纤维、碳纤维、石英纤维、炭芯硼纤维、二硼化钛纤维、钛酸钙纤维、碳化硅纤维、陶瓷纤维、晶须等。在本发明的一个实施方式中，优选具有导电性的无机非金属填料，包括但不仅限于石墨、炭黑、石墨烯、碳纳米管、碳纤维，方便获得具有导电性和/或具有电热功能的复合材料。在本发明的另一个实施方式中，优选具有在红外和/或近红外光作用下具有发热功能的非金属填料，包括但不仅限于石墨烯、氧化石墨烯、碳纳米管，方便获得可利用红外和/或近红外光进行加热的复合材料。良好的发热性能，特别是遥控性的发热性能，有利于使得聚合物获得可控的形状记忆、自修复等性能。在本发明的另一个实施方式中，优选具有导热性的无机非金属填料，包括但不仅限于石墨、石墨烯、碳纳米管、氮化铝、氮化硼、碳化硅，方便获得导热功能的复合材料。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, carbon fiber, quartz fiber, carbon fiber boron fiber, titanium diboride Fiber, calcium titanate fiber, silicon carbide fiber, ceramic fiber, whisker, and the like. In one embodiment of the present invention, 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. In another embodiment of the present invention, it is preferred to have 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. Composite materials that are heated by and/or near-infrared light. Good heat generation performance, especially remote control heat generation, is beneficial to the polymer to obtain controllable shape memory, self-healing and other properties. In another embodiment of the present invention, 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.
所述的金属填料，包括金属化合物，包括但不仅限于以下任一种或任几种：金属粉末、纤维，其包括但不仅限于铜、银、镍、铁、金等及其合金的粉末、纤维；纳米金属颗粒，其包括但不仅限于纳米金颗粒、纳米银颗粒、纳米钯颗粒、纳米铁颗粒、纳米钴颗粒、纳米镍颗粒、纳米Fe 3O 4颗粒、纳米γ-Fe 2O 3颗粒、纳米MgFe 2O 4颗粒、纳米MnFe 2O 4颗粒、纳米CoFe 2O 4颗粒、纳米CoPt 3颗粒、纳米FePt颗粒、纳米FePd颗粒、镍铁双金属磁性纳米颗粒以及其他在红外、近红外、紫外、电磁至少一种作用下可以发热的纳米金属颗粒等；液态金属，其包括但不仅限于汞、镓、镓铟液态合金、镓铟锡液态合金、其它镓基液态金属合金；金属有机化合物分子、晶体以及其他在红外、近红外、紫外、电磁至少一种作用下可以发热的物质等。在本发明的一个实施方式中，优选可以进行电磁和/或近红外加热的填料，包括但不仅限于纳米金、纳米银、纳米钯、纳米Fe 3O 4，以便进行遥感加热。在本发明的另一个实施方式中，优选液态金属填料，方便获得具有良好导热性能、导电性能以及能够保持基材柔性和延展性的复合材料。在本发明的另一个实施方式中，优选在红外、近红外、紫外、电磁至少一种作用下可以发热的有机金属化合物分子、晶体，一方面方便复合，另一面提高诱导发热的效率和提升发热效果。 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 γ-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 and other substances that can generate heat under at least one of infrared, near-infrared, ultraviolet, and electromagnetic. In one embodiment of 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. In another embodiment of the present invention, 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. In another embodiment of the present invention, 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.
所述的有机填料，包括但不限于以下任一种或任几种：皮毛、天然橡胶、合成橡胶、合成纤维、合成树脂、棉花、棉绒、麻、黄麻、亚麻、石棉、纤维素、醋酸纤维素、虫胶、甲壳素、壳聚糖、木质素、淀粉、蛋白质、酶、激素、生漆、木粉、壳粉、糖原、木糖、蚕丝、人造丝、维尼纶、酚醛微珠、树脂微珠等。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.
其中，添加的填料类型不限定，主要根据所需求的材料性能而定，优选碳酸钙、硫酸钡、滑石粉、炭黑、石墨烯、(中空)玻璃微珠、发泡微球、玻璃纤维、碳纤维、金属粉、天然橡胶、壳聚糖、蛋白质、树脂微珠，所用的填料用量没有特别限定，一般为1-30wt％。Wherein, 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.
在动态聚合物的制备过程中，可通过本领域已知的任意合适的材料混合方式将一定配比的原料通过混合来制备动态聚合物，其可以是间歇、半连续或连续工艺形式的混合；同样地，也可选择间歇、半连续或连续工艺形式对动态聚合物进行成型。采用的混合方式包括但不仅限于溶液搅拌混合、熔融搅拌混合、捏合、密炼、开炼、熔融挤出、球磨等，其中优选溶液搅拌混合、熔融搅拌混合和熔融挤出。在物料混合过程中的能量提供形式包括但不仅限于加热、光照、辐射、微波、超声。采用的成型方式包括但不仅限于挤出成型、注射成型、模压成型、流延成型、压延成型、铸塑成型。In the preparation of the dynamic polymer, 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.
在动态聚合物的制备过程中，还可以添加/使用之前所述的其他聚合物、助剂、填料来共同组成动态聚合物复合体系，但这些添加/使用物并不都是必须的。In the preparation of dynamic polymers, other polymers, auxiliaries, and fillers previously described may also be added/used to form a dynamic polymer composite system, but these additions/uses are not all necessary.
利用溶液搅拌混合制备动态聚合物的具体方法，通常是将原料以溶解或分散的形式在各自的溶剂中或者共同的溶剂中在反应器中进行搅拌混合。通常，混合反应温度控制在0-200℃，优选25-120℃，更优选25-80℃，混合搅拌时间控制在0.5-12h，优选1-4h。可将混合搅拌后得到的产物浇注到合适的模具中，在0-150℃，优选25-80℃温度条件下，放置0-48h，得到聚合物样品。此过程中可根据需要选择保留溶剂制成以胶状等形式存在的聚合物样品，或者选择除去溶剂制成膜状、块状、泡沫状等形式存在的固态聚合物样品。以此方法制备动态聚合物时，通常还需要视情况在溶剂中加入引发剂以溶液聚合的方式来引发聚合得到动态聚合物，或者加入分散剂和油溶性引发剂配制成悬浮液以悬浮聚合或淤浆聚合的方式来引发聚合得到动态聚合物，或者加入引发剂和乳化剂配制成乳浊液以乳液聚合的方式来引发聚合得到动态聚合物。所采用的溶液聚合、悬浮聚合、淤浆聚合以及乳液聚合的方法，均为本领域的技术人员所熟知并广泛使用的聚合方法，可依据实际情况进行调整，这里不再详细展开。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. Usually, 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. In the process, a solvent sample may be selected as a gel or the like, or a solvent may be selected to remove the solvent to form a solid polymer sample in the form of a film, a block, a foam or the like. When preparing a dynamic polymer in this way, it is usually necessary to add an initiator in a solvent to initiate polymerization to obtain a dynamic polymer by solution polymerization, or to add a dispersing agent and an oil-soluble initiator to prepare a suspension for suspension polymerization or The slurry is polymerized to initiate polymerization to obtain a dynamic polymer, or an initiator and an emulsifier are added to prepare an emulsion to initiate polymerization by emulsion polymerization to obtain a dynamic polymer. The methods of solution polymerization, suspension polymerization, slurry polymerization, and emulsion polymerization employed are all known to those skilled in the art and widely used, and can be adjusted according to actual conditions, and will not be further developed here.
上述制备方法中所用到的溶剂，应根据反应物、产物及反应过程等实际情况进行选择，包括但不仅限于以下任一种溶剂或任几种溶剂的混合溶剂：去离子水、乙腈、丙酮、丁酮、苯、甲苯、二甲苯、乙酸乙酯、乙醚、甲基叔丁基醚、四氢呋喃、甲醇、乙醇、氯仿、二氯甲烷、1,2-二氯乙烷、二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、醋酸异丙酯、醋酸正丁酯、三氯乙烯、均三甲苯、二恶烷、Tris缓冲液、柠檬酸缓冲液、乙酸缓冲溶液、磷酸缓冲溶液、硼酸缓冲溶液等；优选去离子水、甲苯、氯仿、二氯甲烷、1,2-二氯乙烷、四氢呋喃、二甲基甲酰胺、磷酸缓冲溶液。此外，溶剂也可选自齐聚物、增塑剂、离子液体；所述的齐聚物包括但不仅限于聚乙二醇齐聚物、聚醋酸乙烯酯齐聚物、聚丙烯酸正丁酯齐聚物、液体石蜡等；所述的增塑剂可选自可添加的助剂中的增塑剂中所述类别，这里不再赘述；所述的离子液体一般由有机阳离子和无机阴离子组成，阳离子通常为烷基季铵离子、烷基季瞵离子、1,3-二烷基取代的咪唑离子、N-烷基取代的吡啶离子等；阴离子通常为卤素离子、四氟硼酸根离子、六氟磷酸根离子、也有CF 3SO 3 -、(CF3SO 2) 2N -、C 3F 7COO -、C 4F 9SO 3 -、CF 3COO -、(CF 3SO 2) 3C -、(C 2F 5SO 2) 3C -、(C 2F 5SO 2) 2N -、SbF 6 -、AsF 6 -等。其中，利用去离子水来制备动态聚合物并选择将其保留时，可以得到水凝胶；利用有机溶剂来制备动态聚合物并选择将其保留时，可以得到有机凝胶；利用齐聚物来制备动态聚合物并选择将其保留时，可以得到齐聚物溶胀凝胶；利用增塑剂来制备动态聚合物并选择将其保留时，可以得到增塑剂溶胀凝胶；利用离子液体来制备动态聚合物并选择将其保留时，可以得到离子液体溶胀凝胶。 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 water, toluene, chloroform, dichloromethane, 1,2-dichloroethane, tetrahydrofuran, dimethylformamide, phosphate buffer solution. In addition, 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. Wherein, 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.
上述制备方法中，所配置的化合物液体浓度根据所选反应物的结构、分子量、溶解度及所需的分散状态而定，没有特别限定，优选的化合物液体浓度为0.1～10mol/L，更优选为0.1～1mol/L。In the above production method, 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.
利用熔融搅拌混合制备动态聚合物的具体方法，通常是将原料在反应器中直接搅拌混合或加热熔融后搅拌混合反应，此种方式一般在原料为气体、液体或熔点较低的固体的情况下使用。通常，混合反应温度控制在0-200℃，优选25-120℃，更优选25-80℃，混合搅拌时间控制在0.5-12h，优选1-4h。可将混合搅拌后得到的产物浇注到合适的模具中，在0-150℃，优选25-80℃温度条件下，放置0-48h，得到聚合物样品。以此方法制备动态聚合物时，通常还需要视情况加入少量引发剂以熔融聚合或气相聚合的方式来引发聚合得到动态聚合物。其所采用的熔融聚合、气相聚合的方法，均为本领域的技术人员所熟知并广泛使用的聚合方法，可依据实际情况进行调整，这里不再详细展开。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. use. Usually, 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. When a dynamic polymer is prepared by this method, it is usually necessary to add a small amount of an initiator as a melt polymerization or a gas phase polymerization to initiate polymerization to obtain a dynamic polymer. The methods of melt polymerization and gas phase polymerization used 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.
利用熔融挤出混合制备动态聚合物的具体方法，通常是将原料加入到挤出机中进行挤出共混反应，挤出温度为0-280℃，优选50-150℃。反应产物可直接流延成型后裁成合适尺寸，或者将得到的挤出样品进行破碎后，利用注塑机或者模压机进行制样。注塑温度为0-280℃，优选50-150℃，注塑压力优选60-150MPa；模压温度为0-280℃，优选25-150℃，更优选 25-80℃，模压时间为0.5-60min，优选1-10min，模压压力优选4-15MPa。可将样条置于合适的模具中，在0-150℃，优选25-80℃温度条件下，放置0-48h，得到最终的聚合物样品。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.
在动态聚合物的制备过程中，所选用的无机硼化合物和(聚)硅氧烷化合物的摩尔当量比应处于适当的范围，优选0.1～10的范围，更优选0.3～3的范围，更优选0.8～1.2的范围。在实际制备过程中，本领域的技术人员可根据实际需要进行调整。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.
在动态聚合物的制备过程中，对动态聚合物各组分原料的添加量并未做特别的限定，本领域的技术人员可根据实际制备情况以及目标聚合物性能进行调整。In the preparation of the dynamic polymer, 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.
所述的动态聚合物性能大范围可调，具有广阔的应用前景，在军事航天设备、功能涂料及涂层、生物医药、生物医用材料、能源、建筑、仿生、智能材料等领域，都具有重要的应用。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.
通过利用动态聚合物所具有的胀流性、动态性，可将其应用于制作阻尼减震器，用于各种机动车辆、机械设备、桥梁、建筑的震动隔离，聚合物材料在受到振动时，可以耗散大量能量起到阻尼效果，从而有效地缓和震动；也可将其作为吸能缓冲材料，应用于缓冲包装材料、运动防护制品、冲击防护制品以及军警用防护材料等方面，从而减少物品或人体在外力作用下所受到的震动和冲击，包括噪音和爆炸产生的冲击波等。利用硼酸硅酯键的动态性，也可将其作为形状记忆材料进行使用，当外力去除时，材料在加载过程中产生的形变能够得以恢复；通过动态聚合物所具有的动态可逆性和应力速率依赖性，制备出应力敏感型的聚合物材料，一部分可以应用于制备具有应力/应变响应的魔幻玩具和健身材料，还可用于制备道路和桥梁的速度锁定器，还可以用于制作抗震剪切板或循环应力承载工具，或者用于制作应力监测传感器。By utilizing the dilatancy and dynamics of dynamic polymers, it can be applied to the production of damping dampers for vibration isolation of various motor vehicles, mechanical equipment, bridges, buildings, and when the polymer material is subjected to vibration. It can dissipate a large amount of energy to dampen the effect, thereby effectively alleviating the vibration; it can also be used as an energy absorbing cushioning material for cushioning packaging materials, sports protection products, impact protection products, and military and police protective materials, thereby Reduce the shock and impact of objects or the human body under external forces, including noise and shock waves generated by explosions. The dynamic properties of the silicon borate bond can also be used as a shape memory material. When the external force is removed, the deformation of the material during the loading process can be recovered; the dynamic reversibility and stress rate of the dynamic polymer Dependence, the preparation of stress-sensitive polymer materials, part of which can be used to prepare magic toys and fitness materials with stress/strain response, can also be used to prepare speed locks for roads and bridges, and can also be used for making seismic shears. Plate or cyclic stress bearing tool, or used to make stress monitoring sensors.
充分利用动态聚合物所具有动态性，可以制备出具有自修复功能的粘结剂，应用于各类材料的胶黏，也可作为防弹玻璃夹层胶；也可用于制备具有良好可塑性的聚合物封堵胶，可以设计制备出具有自修复功能的耐刮擦涂层，从而延长涂层的使用寿命，实现对基体材料的长效防腐保护。在军工、航天、电子、仿生等领域表现出巨大的应用潜力。Making full use of the dynamic properties of dynamic polymers, it can prepare adhesive with self-repairing function, can be applied to the adhesive of various materials, and can also be used as bulletproof glass interlayer adhesive. It can also be used to prepare polymer seals with good plasticity. Gluing 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.
将无机硼酸硅酯键作为可牺牲键进行使用时，可以吸收大量的能量而赋予聚合物材料以优异的韧性，从而可以获得韧性极佳的聚合物材料，广泛应用于军事、航天、运动、能源、建筑等领域。When the inorganic boronic acid silicate bond is used as a sacrificial bond, it can absorb a large amount of energy and impart excellent toughness to the polymer material, thereby obtaining a polymer material having excellent toughness, which is widely used in military, aerospace, sports, energy. , construction and other fields.
下面结合一些具体实施方式对本发明所述的动态聚合物做进一步描述。具体实施例为进一步详细说明本发明，非限定本发明的保护范围。The dynamic polymers of the present invention are further described below in conjunction with some specific embodiments. The specific embodiments are intended to describe the invention in further detail, without limiting the scope of the invention.
实施例1Example 1
将端羟基聚丁二烯(HTPB)和甲苯二异氰酸酯(2,4-TDI)充分混合，再加入少量丙三醇作为交联剂，控制反应中NCO：OH约为1.2:1，即2,4-TDI略过量，共价交联得到一种侧基含有双键的聚氨酯(分子量约18000)。The hydroxyl terminated polybutadiene (HTPB) and toluene diisocyanate (2,4-TDI) are thoroughly mixed, and a small amount of glycerol is added as a crosslinking agent to control the NCO:OH in the reaction is about 1.2:1, that is, 2, A slight excess of 4-TDI, covalently cross-linked to give a polyurethane with a double bond in the pendant group (molecular weight of about 18,000).
将12.8g上述侧基含有双键的聚氨酯(分子量约18000)、1.5g 6-巯丙基三甲氧基硅烷和0.7g 1,12-二巯基十二烷按照双键和两个巯基的化合物的摩尔比22:20:1混合，加入0.2wt％的光引发剂安息香双甲醚(DMPA)，搅拌充分后，放在紫外交联仪中紫外辐射4h，制备得到一种含有普通共价交联的聚氨酯。12.8 g of the above-mentioned pendant group containing a double bond polyurethane (molecular weight of about 18,000), 1.5 g of 6-mercaptopropyltrimethoxysilane and 0.7 g of 1,12-didecyldodecane according to a double bond and two mercapto compounds Mixing molar ratio of 22:20:1, adding 0.2wt% photoinitiator benzoin dimethyl ether (DMPA), stirring well, and then UV irradiation in UV cross-linking instrument for 4h, to prepare a common covalent cross-linking Polyurethane.
将35.1g上述含有普通共价交联的聚氨酯、12.0g端硅羟基聚二甲基硅油和4.8g硼酸三甲酯充分混合，再加入0.5g石墨烯粉，搅拌充分混合后，升温到80℃混合均匀后，加入4ml的去离子水，再滴加入少量的乙酸，在搅拌状态下进行聚合反应，制备得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。35.1 g of the above-mentioned common covalently crosslinked polyurethane, 12.0 g of silicic acid hydroxypolydimethylsiloxane oil and 4.8 g of trimethyl borate were thoroughly mixed, and 0.5 g of graphene powder was added thereto, and the mixture was thoroughly stirred and heated to 80 ° C. After mixing uniformly, 4 ml of deionized water was added, and a small amount of acetic acid was added dropwise thereto, and polymerization was carried out under stirring to prepare a dynamic polymer containing ordinary covalent crosslinks and silicic acid borate bonds.
该聚合物产品具有良好韧性，其导电性能够随压力和拉力变化而产生灵敏性的变化，具有力传感功能，可以作为力传感器使用。The polymer product has good toughness, its conductivity can change with sensitivity due to changes in pressure and tension, and has a force sensing function, which can be used as a force sensor.
实施例2Example 2
先将一定量的三羟甲基丙烷三(2-巯基乙酸酯)和1,6-己二烯按照巯基和双键的摩尔比为2:1混合，放在紫外交联仪中紫外辐射2h，得到一种含有轻度普通共价交联的聚合物以及残余一定量的三羟甲基丙烷三(2-巯基乙酸酯)，作为一种预聚物。First, a certain amount of trimethylolpropane tris(2-mercaptoacetate) and 1,6-hexadiene are mixed in a molar ratio of thiol and double bond of 2:1, and placed in an ultraviolet cross-linker for ultraviolet radiation. At 2 h, a polymer containing light ordinary covalent crosslinks and a residual amount of trimethylolpropane tris(2-mercaptoacetate) were obtained as a prepolymer.
将硼酸三甲酯和二甲基甲氧基-3-丁烯硅烷按照摩尔比1:3混合，加热到60℃通过搅拌进行溶解之后，加入少量水继续反应4h，得到一种含有硼酸硅酯键的三乙烯基化合物2a。Trimethyl borate and dimethylmethoxy-3-butene silane were mixed at a molar ratio of 1:3, heated to 60 ° C and dissolved by stirring, and then a small amount of water was added to continue the reaction for 4 h to obtain a silyl borate. The trivinyl compound 2a of the bond.
Figure PCTCN2018072461-appb-000008
Figure PCTCN2018072461-appb-000008
硅羟基封端且侧基带有末端烯烃基团的有机聚硅氧烷(分子量约2500)和2,6-二-叔-丁基-4-甲苯基二丁基原硼酸酯按照端基硅氧烷和硼酸酯的摩尔比1:1混合，升温到80℃混合均匀后，加入6ml的去离子水，在搅拌状态下进行聚合反应，制备得到一种含有硼酸硅酯键的有机聚硅氧烷。An organopolysiloxane having a silicon hydroxy end group and a terminal group having a terminal olefin group (molecular weight of about 2,500) and 2,6-di-tert-butyl-4-tolyldibutyl orthoboroate according to the terminal siloxane Mixing with the boric acid ester molar ratio of 1:1, heating to 80 ° C and mixing uniformly, adding 6 ml of deionized water, and carrying out polymerization under stirring to prepare an organopolysiloxane containing a silicon borate bond. .
将16.7g上述预聚物、1.4g化合物2a和9.8g上述含有硼酸硅酯键的有机聚硅氧烷充分混合，放在紫外交联仪中紫外辐射8h，得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。16.7 g of the above prepolymer, 1.4 g of the compound 2a and 9.8 g of the above-mentioned organopolysiloxane containing a silicon borate bond were thoroughly mixed and placed in an ultraviolet cross-linking apparatus for ultraviolet light for 8 hours to obtain a common covalent cross-linking. And a dynamic polymer of silicon borate bonds.
该聚合物产品可以作为具有一定自修复并且具有抗撕裂性能的片材或涂层使用。The polymer product can be used as a sheet or coating having some self-healing properties and tear resistance.
实施例3Example 3
(1)将3-氨丙基甲基二甲氧基硅烷和己二酰氯按照摩尔比2:1混合，以三乙胺作为催化剂，在无水二氯甲烷中反应，制备得到二硅氧烷化合物。(1) 3-Aminopropylmethyldimethoxysilane and adipyl chloride are mixed at a molar ratio of 2:1, and triethylamine is used as a catalyst to react in anhydrous dichloromethane to prepare a disiloxane compound. .
端硅羟基聚(二甲基-甲基苯基)硅氧烷、上述二硅氧烷化合物、异丙醇频哪醇硼酸酯按照Si-OH、Si-OCH 3基团和B-OR基团的摩尔比1:1:2混合，滴加入少量的20％乙酸水溶液，在50℃条件下搅拌均匀后，反应8h，制备得到一种含有硼酸硅酯键的动态聚合物，作为第1网络聚合物。 The terminal silylhydroxy poly(dimethyl-methylphenyl)siloxane, the above disiloxane compound, isopropanol pinacol borate according to Si-OH, Si-OCH 3 group and B-OR group The molar ratio of the group is 1:1:2, a small amount of 20% acetic acid aqueous solution is added dropwise, and the mixture is uniformly stirred at 50 ° C, and then reacted for 8 hours to prepare a dynamic polymer containing a silicon borate bond as the first network. polymer.
(2)N,N’-亚甲基双丙烯酰胺、卢丁二硫醇、三羟甲基丙烷三(3-巯基丙酸酯)按照摩尔比20:20:1混合，加入到120wt％增塑剂环氧乙酰蓖麻油酸甲酯中再加入0.2wt％的安息香双甲醚(DMPA)，再加入30mg石墨烯，溶胀于等质量的第1网络聚合物，超声分散，倒入夹有硅胶垫片的玻璃板模具中，放在紫外交联仪中紫外辐射8h，一种含有普通共价交联、骨架氢键基团与硼酸硅酯键的环氧乙酰蓖麻油酸甲酯溶胀的有机凝胶。(2) N, N'-methylenebisacrylamide, lutidine dithiol, trimethylolpropane tris(3-mercaptopropionate) are mixed according to a molar ratio of 20:20:1, and added to 120 wt%. Add 0.2wt% benzoin dimethyl ether (DMPA) to the plastic solvent epoxy acetyl ricinoleic acid methyl ester, add 30mg graphene, swell to the first network polymer of equal mass, ultrasonically disperse, pour into the silica gel In the glass plate mold of the gasket, it is placed in an ultraviolet cross-linking instrument for 8 hours of ultraviolet radiation, and an organic compound containing ordinary covalently crosslinked, skeleton hydrogen bond group and silicon silicate silicate sulphate is swollen. gel.
该实施例制备的环氧乙酰蓖麻油酸甲酯溶胀的有机凝胶的模量在22kPa，应变可以达到16倍，断裂应力在89kPa。这种有机凝胶可以用于制备空降和空投的抗冲击防护材料。The epoxy acetyl ricinoleic acid swelled organogel prepared in this example has a modulus of 22 kPa, a strain of 16 times, and a breaking stress of 89 kPa. This organogel can be used to prepare airborne and airborne impact resistant materials.
实施例4Example 4
(1)将乙烯基乙酸和2,6-二氨基吡啶按照摩尔比2:1反应，制得化合物4a。(1) A reaction of vinylacetic acid and 2,6-diaminopyridine at a molar ratio of 2:1 to obtain a compound 4a.
Figure PCTCN2018072461-appb-000009
Figure PCTCN2018072461-appb-000009
1,3-二苯基丙烷-2,2-二硫醇和化合物4a、三丙烯胺按照摩尔比9:6:2进行混合，放在紫外交联仪中紫外辐射8h，得到一种含有骨架氢键基团和普通共价交联的聚合物，作为第1网络聚合物。1,3-diphenylpropane-2,2-dithiol and compound 4a, tripropyleneamine are mixed according to a molar ratio of 9:6:2, and placed in an ultraviolet cross-linking instrument for ultraviolet light for 8 hours to obtain a skeleton-containing hydrogen. A bond group and a generally covalently crosslinked polymer are used as the first network polymer.
(2)将硼酸和丙烯基二甲基氯硅烷按照摩尔比1:3混合，以三乙胺为催化剂，在80℃下反应12h制备得到末端带有双键的硼酸硅酯化合物4b。(2) Boric acid and propenyldimethylchlorosilane are mixed at a molar ratio of 1:3, and triethylamine is used as a catalyst, and reacted at 80 ° C for 12 hours to prepare a silicon borate compound 4b having a double bond at the end.
Figure PCTCN2018072461-appb-000010
Figure PCTCN2018072461-appb-000010
在三口烧瓶中加入16g聚醚二硫醇，5.4g上述末端带有双键的硼酸硅酯化合物4b混合均匀，充分溶胀于第1网络聚合物中，再放在紫外交联仪中紫外辐射8h，得到一种含有普通共价交联和硼酸硅酯键的二元网络互穿动态聚合物。16 g of polyether dithiol was added to a three-necked flask, and 5.4 g of the above-mentioned siliconic acid borate compound 4b with a double bond was uniformly mixed, fully swelled in the first network polymer, and then placed in an ultraviolet cross-linker for 8 h of ultraviolet radiation. A binary network interpenetrating dynamic polymer containing common covalent crosslinks and silicon borate bonds is obtained.
(3)端硅羟基聚二甲基硅油、三仲丁基硼酸酯按照硅羟基和硼酸酯的摩尔比1:1混合，加入少量水、2g白炭黑、2g钛白粉、1.3g三氧化二铁，充分溶胀于上述二元互穿网络聚合物中，在50℃条件下搅拌均匀后，反应6h，制备得到一种含有普通共价交联和硼酸硅酯键的三元网络互穿动态聚合物。(3) The terminal silicic hydroxyl polydimethyl silicone oil and the tri-sec-butyl borate are mixed according to a molar ratio of silanol to boric acid ester, and a small amount of water, 2 g of white carbon black, 2 g of titanium dioxide, and 1.3 g of three are added. Ferric oxide is fully swelled in the above-mentioned binary interpenetrating network polymer, and stirred at 50 ° C for 6 h to prepare a ternary network interpenetrating medium containing common covalent crosslinks and silicic acid borate bonds. Dynamic polymer.
该聚合物产品可以用于制作抗震剪切板或循环应力承载工具。The polymer product can be used to make seismic shear plates or cyclic stress bearing tools.
实施例5Example 5
(1)从橙皮中提取的苎烯氧化物，与100psi二氧化碳，在β-二亚胺锌的催化作用下发生聚合反应，得到聚碳酸酯PLimC。(1) The terpene oxide extracted from the orange peel is polymerized with 100 psi of carbon dioxide under the catalysis of β-diimine zinc to obtain a polycarbonate PLimC.
Figure PCTCN2018072461-appb-000011
Figure PCTCN2018072461-appb-000011
将上述聚碳酸酯PLimC和N-[(2-巯基乙基)氨基甲酰]丙酰胺、二(2-巯基乙基)己二酸酯按照双键基团和巯基比例为10:9:1混合，加入0.6wt％的AIBN，通过点击反应制得含有普通共价交联和硅羟基前驱体的聚碳酸酯(分子量约10000)。The above polycarbonates PLimC and N-[(2-mercaptoethyl)carbamoyl]propionamide, bis(2-mercaptoethyl) adipate are 10:9:1 according to the ratio of the double bond group and the thiol group. Mixing, adding 0.6 wt% of AIBN, a polycarbonate containing a common covalent cross-linking and a silanol precursor (molecular weight of about 10,000) was obtained by a click reaction.
称取24g上述侧基硅羟基前驱体的聚碳酸酯、38g硅羟基封端的聚甲基三氟丙基-甲基硅氧烷(分子量8000)和5g三(2-甲氧基乙基)硼酸酯，充分搅拌混合均匀，升温到80℃后，加入10ml的去离子水，在搅拌状态下进行聚合反应，制备得到一种含有普通共价交联和硼酸硅酯键的动态聚合物，作为第1网络聚合物。Weigh 24 g of the above-mentioned pendant silyl hydroxyl precursor polycarbonate, 38 g of silyl-hydroxy terminated polymethyltrifluoropropyl-methylsiloxane (molecular weight 8000) and 5 g of tris(2-methoxyethyl)boron The acid ester is stirred and mixed well. After heating to 80 ° C, 10 ml of deionized water is added, and polymerization is carried out under stirring to prepare a dynamic polymer containing ordinary covalent cross-linking and silicic acid borate bond. The first network polymer.
Figure PCTCN2018072461-appb-000012
Figure PCTCN2018072461-appb-000012
(2)在三口烧瓶中加入15g聚醚二硫醇，2.0g三烯丙基胺，溶胀于第1网络聚合物中，加入3.2g三氧化二铁、0.2g碳纳米管，再放在紫外交联仪中紫外辐射8h，得到一种含有普通共价交联和硼酸硅酯键的二元网络互穿动态聚合物。(2) Add 15 g of polyether dithiol, 2.0 g of triallylamine, swell in the first network polymer, add 3.2 g of ferric oxide, 0.2 g of carbon nanotubes, and then place in a three-necked flask. Ultraviolet radiation in the diplomatic instrument for 8h gave a binary network interpenetrating dynamic polymer containing common covalent crosslinks and silicic acid silicide bonds.
该聚合物样品具有较大的粘性及非常良好的拉伸韧性，可进行较大程度的拉伸而不断裂(断裂伸长率可达600％)。在本实施例中，可将聚合物作为电子封装材料或胶黏剂使用，能够对出现的细小裂纹进行自修复，可避免材料的破坏和漏气。The polymer sample has a large viscosity and a very good tensile toughness, and can be stretched to a large extent without breaking (breaking elongation of up to 600%). In this embodiment, the polymer can be used as an electronic packaging material or an adhesive, which can self-repair the small cracks that occur, and can avoid material damage and gas leakage.
实施例6Example 6
(1)将3-异氰酸丙烯和3-羟基-1-丙烯等摩尔比反应，制得两端带乙烯基的氨基甲酸酯化合物6a。(1) An equimolar ratio of 3-isocyanic acid propylene and 3-hydroxy-1-propene is reacted to obtain a vinyl group-containing carbamate compound 6a at both ends.
Figure PCTCN2018072461-appb-000013
Figure PCTCN2018072461-appb-000013
以甲基丙烯酸叔丁酯和化合物6a为单体，控制两者的摩尔比为10:1，通过自由基聚合制得一种含有骨架氢键基团的普通共价交联聚合物(分子量约为7500)，作为第1网络聚合物。Using tert-butyl methacrylate and compound 6a as monomers, controlling the molar ratio of the two to 10:1, a common covalently crosslinked polymer containing a skeleton hydrogen bond group was prepared by radical polymerization (molecular weight It is 7500) as the first network polymer.
(2)以甲基丙烯酸3-(三甲氧基硅基)丙酯和二缩三(1,2-丙二醇)二丙烯酸酯为单体，控制两者的摩尔比为10:1，通过自由基聚合制得甲基丙烯酸3-(三甲氧基硅基)丙酯和二缩三(1,2-丙二醇)二丙烯酸酯的共聚物(分子量约为6000)。(2) using 3-(trimethoxysilyl)propyl methacrylate and tris(1,2-propanediol) diacrylate as monomers, controlling the molar ratio of the two to 10:1, through free radicals Polymerization A copolymer of 3-(trimethoxysilyl)propyl methacrylate and ditris(1,2-propanediol) diacrylate (molecular weight of about 6000) was obtained by polymerization.
将上述甲基丙烯酸3-(三甲氧基硅基)丙酯、端硅羟基聚二甲基硅油和二缩三(1,2-丙二醇)二丙烯酸酯共聚物、和硼酸三甲酯按照Si-OCH 3基团和B-OR基团的摩尔比1:1混合，充分溶胀于等质量的第1网络聚合物中，再加入5wt％粒径25nm的纳米二氧化硅，升温到80℃混合均匀后，加入10ml的去离子水，在搅拌状态下进行聚合反应，制备得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。 The above 3-(trimethoxysilyl)propyl methacrylate, the terminal silyl hydroxy polydimethylsiloxane oil and the tris(1,2-propanediol) diacrylate copolymer, and the trimethyl borate are in accordance with Si- molar ratio of OCH 3 group, and B-OR group 1: 1 mixture of a first polymer networks, and the like in the fully swollen mass, the particle diameter of 25nm was added 5wt% nanosilica, warmed to 80 deg.] C mixed Thereafter, 10 ml of deionized water was added, and polymerization was carried out under stirring to prepare a dynamic polymer containing ordinary covalent crosslinks and silicic acid borate bonds.
将该聚合物制备成薄膜，呈现出较为优良的综合性能，具有一定的拉伸强度和良好的抗撕裂性能，并可进行较大程度的拉伸。此类动态聚合物可应用于制备功能薄膜，或者可以作为汽车和家具的贴膜使用，也可作为拉伸包装薄膜进行使用，其十分耐刮擦。The polymer is prepared into a film, exhibits superior comprehensive properties, has a certain tensile strength and good tear resistance, and can be stretched to a greater extent. Such dynamic polymers can be used to make functional films, or can be used as films for automobiles and furniture, or as stretch wrap films, which are very scratch resistant.
实施例7Example 7
(1)以甲基丙烯酸3-(三甲氧基硅基)丙酯和三羟甲基丙烷三甲基丙烯酸酯为单体，控制两者的摩尔比为20:1，通过自由基聚合制得甲基丙烯酸3-(三甲氧基硅基)丙酯和三羟甲基丙烷三甲基丙烯酸酯的共聚物(分子量约为2500)。(1) using 3-(trimethoxysilyl)propyl methacrylate and trimethylolpropane trimethacrylate as monomers, controlling the molar ratio of the two to 20:1, by free radical polymerization Copolymer of 3-(trimethoxysilyl)propyl methacrylate and trimethylolpropane trimethacrylate (molecular weight of about 2,500).
将25g上述共聚物、16g硅羟基封端的聚甲基苯基-二甲基硅氧烷和2.7g硼酸三甲酯混合，升温到80℃混合均匀后，加入12ml的去离子水，在搅拌状态下进行聚合反应，制备得到一种含有普通共价交联和硼酸硅酯键的动态聚合物，作为第1网络聚合物。25 g of the above copolymer, 16 g of silyl-hydroxy terminated polymethylphenyl-dimethylsiloxane and 2.7 g of trimethyl borate were mixed, heated to 80 ° C and mixed uniformly, and then added with 12 ml of deionized water under stirring. The polymerization was carried out to prepare a dynamic polymer containing a common covalent crosslink and a silicic acid borate bond as the first network polymer.
(2)将硼酸和二甲基甲氧基-3-庚烯硅烷按照摩尔比1:3混合，加热到60℃通过搅拌进行溶解之后，加入少量水继续反应4h，得到一种含有硼酸硅酯键的三乙烯基化合物7a。(2) Boric acid and dimethylmethoxy-3-heptene silane are mixed at a molar ratio of 1:3, heated to 60 ° C and dissolved by stirring, and then a small amount of water is added to continue the reaction for 4 hours to obtain a silicon borate. The trivinyl compound 7a of the bond.
Figure PCTCN2018072461-appb-000014
Figure PCTCN2018072461-appb-000014
硅羟基封端且侧基带有末端烯烃基团的有机聚硅氧烷(分子量约2000)和2,6-二-叔-丁基-4-甲苯基二丁基原硼酸酯按照端基硅氧烷和硼酸酯的摩尔比1:1混合，升温到80℃混合均匀后，加入6ml的去离子水，在搅拌状态下进行聚合反应，制备得到一种含有硼酸硅酯键的有机聚硅氧烷。Silicone hydroxy-terminated and pendant olefinic group-containing organopolysiloxane (molecular weight of about 2000) and 2,6-di-tert-butyl-4-tolyldibutyl orthoboroate according to terminal siloxane Mixing with the boric acid ester molar ratio of 1:1, heating to 80 ° C and mixing uniformly, adding 6 ml of deionized water, and carrying out polymerization under stirring to prepare an organopolysiloxane containing a silicon borate bond. .
Figure PCTCN2018072461-appb-000015
Figure PCTCN2018072461-appb-000015
先将0.8g己二酸二烯丙酯和3.7g三羟甲基丙烷三(2-巯基乙酸酯)在紫外交联仪中紫外辐射8h进行预聚1h，然后再加入2.6g化合物7a和12g上述含有硼酸硅酯键的有机聚硅氧烷上述(分子量约25000)充分混合，并溶胀于第1网络聚合物中，放在紫外交联仪中紫外辐射8h，得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。First, 0.8g of diallyl adipate and 3.7g of trimethylolpropane tris(2-mercaptoacetate) were prepolymerized by UV irradiation for 8h in an ultraviolet cross-linker for 1h, then 2.6g of compound 7a and then 12g of the above organosilicone containing a boronic acid borate bond (the molecular weight of about 25000) is thoroughly mixed, and swelled in the first network polymer, and placed in an ultraviolet cross-linker for 8 hours of ultraviolet radiation to obtain a common covalent price. A dynamic polymer of cross-linking and silicic acid borate bonds.
该聚合物产品可以用于制备一种军警用防护材料。The polymer product can be used to prepare a military and police protective material.
实施例8Example 8
(1)将1,3,5-三(溴甲基)苯和叠氮化钠在DMF溶液中，搅拌2天，制得1,3,5-三(叠氮甲基)苯。(1) 1,3,5-tris(bromomethyl)benzene and sodium azide were stirred in a DMF solution for 2 days to obtain 1,3,5-tris(azidomethyl)benzene.
己二酸二炔丙基酯和1,3,5-三(叠氮甲基)苯按照摩尔比3:2混合，加入相对于单体0.1wt％的催化剂CuBr(PPh 3) 3和三[(1-苄基-1H-1,2,3-三唑-4-基)甲基]胺(TBTA)，搅拌充分混合后，60℃下反应4h，得到一种含有普通共价交联的聚合物，作为第1网络聚合物。 Dipropionyl adipate and 1,3,5-tris(azidomethyl)benzene are mixed at a molar ratio of 3:2, and 0.1 wt% of the catalyst CuBr(PPh 3 ) 3 and three are added relative to the monomer [ (1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (TBTA), stirred well and reacted at 60 ° C for 4 h to obtain a common covalent cross-linking The polymer acts as the first network polymer.
(2)50g羟基封端的甲基-3,3,3-三氟丙基聚硅氧烷、20g末端带有三甲氧基硅基团的四臂的PEG(分子量约为12000)和22g硼酸三甲酯混合，升温到80℃混合均匀后，再加入4ml的去离子水，在搅拌状态下进行聚合反应，制备得到一种含有硼酸硅酯键交联的动态聚合物。将此含有硼酸硅酯键交联的动态聚合物加入到小型挤出机中进行挤出共混，挤出温度为120℃，得到的挤出样条进行造粒之后，获得弹性小颗粒。(2) 50 g of hydroxy-terminated methyl-3,3,3-trifluoropropylpolysiloxane, 20 g of four-armed PEG having a trimethoxysilyl group at the end (molecular weight of about 12,000) and 22 g of boric acid The methyl ester was mixed, and the mixture was heated to 80 ° C to be uniformly mixed. Then, 4 ml of deionized water was added, and polymerization was carried out under stirring to obtain a dynamic polymer containing a boronic acid borate linkage. The dynamic polymer containing a silicon borate bond cross-linking was added to a small extruder for extrusion blending at an extrusion temperature of 120 ° C, and the obtained extruded spline was subjected to granulation to obtain elastic small particles.
Figure PCTCN2018072461-appb-000016
Figure PCTCN2018072461-appb-000016
将此弹性小颗粒在溶剂中分散于第1网络聚合物中，然后置于50℃烘箱中24h进行除溶剂，之后冷却到室温放置30min，得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。The elastic small particles were dispersed in the first network polymer in a solvent, and then placed in an oven at 50 ° C for 24 hours to remove the solvent, and then cooled to room temperature for 30 minutes to obtain a common covalent cross-linking and silicic acid borate bond. Dynamic polymer.
该聚合物产品表现出了良好的粘弹性，具有良好的隔离震动和应力缓冲效果，同时也表现出了优良的耐水解性。The polymer product exhibits good viscoelasticity, good isolation shock and stress buffering effect, and also exhibits excellent hydrolysis resistance.
实施例9Example 9
(1)将季戊四醇四巯基乙酸酯和己二酸二烯丙酯混合，控制三者摩尔数的比值为1:2，倒入夹有硅胶垫片的玻璃板模具中，放在紫外交联仪中紫外辐射4h，制得一种含有普通共价交联的聚合物，作为第1网络聚合物。(1) Mixing pentaerythritol tetradecyl acetate and diallyl adipate to control the molar ratio of the three is 1:2, pour into a glass plate mold with a silica gel gasket, and place it on the ultraviolet crosslinker. Medium ultraviolet radiation for 4 h, a polymer containing ordinary covalent crosslinks was prepared as the first network polymer.
(2)以BPO为引发剂，将甲基乙烯基二乙氧基硅烷与低密度聚乙烯进行接枝反应制得一种侧基含有二乙氧基硅烷基团的接枝聚乙烯。(2) Using BPO as an initiator, grafting reaction of methylvinyldiethoxysilane with low density polyethylene to obtain a grafted polyethylene containing pendant diethoxysilane groups.
Figure PCTCN2018072461-appb-000017
Figure PCTCN2018072461-appb-000017
1,11-二氯-1,1,3,3,5,5,7,7,9,9,11,11-十二甲基六硅氧烷、上述侧基含有二乙氧基硅烷基团的接枝聚乙烯和硼酸三甲酯按照Si-Cl、Si-OCH 2CH 3基团和B-OCH 3基团的摩尔比1:3:4混合，加入少量的水、2.3g白炭黑、4.1g钛白粉，在50℃条件下搅拌均匀后，反应6h，制备得到一种含有硼酸硅酯键交联的动态聚合物。 1,11-dichloro-1,1,3,3,5,5,7,7,9,9,11,11-dodecylhexasiloxane, the above pendant group contains a diethoxysilane group The grafted polyethylene and trimethyl borate are mixed according to the molar ratio of Si-Cl, Si-OCH 2 CH 3 group and B-OCH 3 group 1:3:4, and a small amount of water and 2.3 g of white carbon are added. Black, 4.1g titanium dioxide, after stirring at 50 ° C, the reaction was carried out for 6 h to prepare a dynamic polymer containing silyl borate linkage.
将上述含有硼酸硅酯键交联的动态聚合物加入到小型挤出机中进行挤出共混，挤出温度为120℃，得到的挤出样条进行造粒之后，获得弹性小颗粒。将此弹性小颗粒在溶剂中分散于第1网络聚合物中，然后置于50℃烘箱中24h进行除溶剂，之后冷却到室温放置30min，得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。The above dynamic polymer containing a silicon borate bond cross-linking was added to a small extruder for extrusion blending at an extrusion temperature of 120 ° C, and the obtained extruded spline was subjected to granulation to obtain elastic small particles. The elastic small particles were dispersed in the first network polymer in a solvent, and then placed in an oven at 50 ° C for 24 hours to remove the solvent, and then cooled to room temperature for 30 minutes to obtain a common covalent cross-linking and silicic acid borate bond. Dynamic polymer.
该动态聚合物力学性能强，抗冲击性能优异，可以制备一种抗冲击防护垫使用。The dynamic polymer has strong mechanical properties and excellent impact resistance, and can be used for preparing an impact resistant protective pad.
实施例10Example 10
(1)以甲基丙烯酸正丁酯和三羟甲基丙烷三甲基丙烯酸酯为单体，控制两者的摩尔比为60:1，加入3mol％的AIBN作为引发剂，通过自由基聚合制得甲基丙烯酸正丁酯和三羟甲基丙烷三甲基丙烯酸酯的共聚物(分子量约为8000)，即得到一种含有普通共价交联网络的聚合物。(1) using n-butyl methacrylate and trimethylolpropane trimethacrylate as monomers, controlling the molar ratio of the two to be 60:1, adding 3 mol% of AIBN as an initiator, and preparing by free radical polymerization. A copolymer of n-butyl methacrylate and trimethylolpropane trimethacrylate (molecular weight of about 8,000) was obtained, that is, a polymer containing a common covalent crosslinked network was obtained.
(2)将5-氯戊基二甲基甲氧基硅烷和三乙基硼酸酯按照等摩尔比混合，加热到60℃通过搅拌进行溶解之后，加入少量水反应3h，得到一种含有硼酸硅酯键的硼酸酯化合物。(2) 5-chloropentyldimethylmethoxysilane and triethylborate 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 boric acid. A boronate ester compound of a silicon ester bond.
Figure PCTCN2018072461-appb-000018
Figure PCTCN2018072461-appb-000018
将20g聚二甲基硅氧烷(分子量约4000)、15g两端为硅羟基封端的聚乙二醇(分子量约3000)和8g上述含有硼酸硅酯键的硼酸酯化合物混合，加入少量水和0.4g粒径为50nm的滑石粉，在80℃条件下搅拌均匀后，反应6h，制备得到一种含有硼酸硅酯键的非交联动态聚合物。将此含有硼酸硅酯键的非交联聚合物溶胀于含有普通共价交联的网络聚合物，得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。20 g of polydimethylsiloxane (molecular weight about 4000), 15 g of poly(ethylene glycol) terminated with silanol groups (molecular weight of about 3,000), and 8 g of the above boric acid ester compound containing a boronic acid borate bond, and a small amount of water was added. And 0.4 g of talc powder having a particle diameter of 50 nm, which was uniformly stirred at 80 ° C, and reacted for 6 hours to prepare a non-crosslinked dynamic polymer containing a silicon borate bond. The non-crosslinked polymer containing a silicon borate bond is swollen to a network polymer containing a common covalent crosslink to obtain a dynamic polymer containing a common covalent crosslink and a silicic acid borate bond.
该聚合物产品表现出了良好的粘弹性，具有良好的隔离震动和应力缓冲效果，可以作为一种弹性缓冲垫片进行使用。The polymer product exhibits good viscoelastic properties, good isolation shock and stress buffering, and can be used as an elastic cushioning gasket.
实施例11Example 11
(1)从橙皮中提取的苎烯氧化物，与100psi二氧化碳，在β-二亚胺锌的催化作用下发生聚合反应，得到聚碳酸酯PLimC。(1) The terpene oxide extracted from the orange peel is polymerized with 100 psi of carbon dioxide under the catalysis of β-diimine zinc to obtain a polycarbonate PLimC.
Figure PCTCN2018072461-appb-000019
Figure PCTCN2018072461-appb-000019
称取24g上述聚碳酸酯PLimC(分子量约6000)和1.6g二(2-巯基乙基)己二酸酯按照双键基团和巯基比例为20:1混合，加入0.6wt％的AIBN，通过点击反应制备得到一种含有普通共价交联的网络聚合物。24 g of the above polycarbonate PLimC (molecular weight about 6000) and 1.6 g of bis(2-mercaptoethyl) adipate were weighed and mixed in a ratio of a double bond group and a thiol group of 20:1, and 0.6 wt% of AIBN was added thereto. Click reaction to prepare a network polymer containing common covalent crosslinks.
(2)3-氯丙基二甲基甲氧基硅烷和硼酸按照等摩尔比混合，加热到60℃通过搅拌进行溶解之后，加入少量水反应3h，得到一种含有硼酸硅酯键的硼酸化合物。(2) 3-chloropropyldimethylmethoxysilane and boric acid 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 boric acid compound containing a silicon borate bond. .
Figure PCTCN2018072461-appb-000020
Figure PCTCN2018072461-appb-000020
将2.0g 4,4'-联硅苯醇、6.5g 1,11-二氯-1,1,3,3,5,5,7,7,9,9,11,11-十二甲基六硅氧烷和5.2g上述含有硼酸硅酯键的硼酸化合物混合，加热到80℃，然后加入少量水继续反应8h，得到 一种含有硼酸硅酯键的非交联动态聚合物。将此含有硼酸硅酯键的非交联聚合物溶胀于含有普通共价交联的网络聚合物，得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。2.0 g of 4,4'-biphenyl phenyl alcohol, 6.5 g of 1,11-dichloro-1,1,3,3,5,5,7,7,9,9,11,11-dodecylmethyl Hexasiloxane was mixed with 5.2 g of the above boric acid compound containing a boronic acid borate bond, heated to 80 ° C, and then a small amount of water was added to continue the reaction for 8 hours to obtain a non-crosslinked dynamic polymer containing a silicon borate bond. The non-crosslinked polymer containing a silicon borate bond is swollen to a network polymer containing a common covalent crosslink to obtain a dynamic polymer containing a common covalent crosslink and a silicic acid borate bond.
该聚合物产品可以用于制作抗震剪切板或循环应力承载工具。The polymer product can be used to make seismic shear plates or cyclic stress bearing tools.
实施例12Example 12
(1)在三口烧瓶中加入25g聚醚二硫醇、10g N,N’-亚甲基双丙烯酰胺、1.5g三烯丙基胺，放在紫外交联仪中紫外辐射8h，得到一种含有普通共价交联的聚合物，作为第1网络聚合物。(1) 25 g of polyether dithiol, 10 g of N, N'-methylenebisacrylamide, 1.5 g of triallylamine were placed in a three-necked flask, and placed in an ultraviolet cross-linker for 8 hours to obtain a kind of ultraviolet radiation. A polymer containing a common covalent crosslink is used as the first network polymer.
(2)将0.8g己二酸二烯丙酯和3.7g三羟甲基丙烷三(2-巯基乙酸酯)放在紫外交联仪中紫外辐射8h，得到一种含有普通共价交联的聚合物，作为第2网络聚合物。(2) 0.8 g of diallyl adipate and 3.7 g of trimethylolpropane tris(2-mercaptoacetate) were placed in an ultraviolet cross-linker for 8 h of ultraviolet radiation to obtain a common covalent cross-linking. The polymer acts as the second network polymer.
(3)将18-氯十八烷基二甲基甲氧基硅烷和硼酸三甲酯按照等摩尔比混合，加热到60℃通过搅拌进行溶解之后，加入少量水反应3h，得到一种含有硼酸硅酯键的硼酸酯化合物。(3) 18-chlorooctadecyldimethylmethoxysilane and trimethyl borate are mixed in an equimolar ratio, heated to 60 ° C, dissolved by stirring, and then added with a small amount of water for 3 h to obtain a boric acid. A boronate ester compound of a silicon ester bond.
Figure PCTCN2018072461-appb-000021
Figure PCTCN2018072461-appb-000021
将18g两端为硅羟基封端的聚硅氧烷嵌段聚乙二醇(分子量约12000)和5g上述含有硼酸硅酯键的硼酸酯化合物混合，加入少量水，在80℃条件下搅拌均匀后，反应6h，制备得到一种含有硼酸硅酯键的非交联动态聚合物。18 g of a polysiloxane block polyethylene glycol (having a molecular weight of about 12,000) having a silicon-hydroxyl-terminated end and 5 g of the above-mentioned boric acid ester compound containing a boronic acid borate bond were mixed, and a small amount of water was added thereto, and the mixture was uniformly stirred at 80 ° C. Thereafter, the reaction was carried out for 6 hours to prepare a non-crosslinked dynamic polymer containing a silicon borate bond.
将上述一种含有硼酸硅酯键的非交联动态聚合物和粒径25nm的纳米二氧化硅分散于第1网络聚合物和第2网络聚合物中，得到一种含有普通共价交联和硼酸硅酯键的动态聚合物。Disposing a non-crosslinked dynamic polymer containing a silicon borate bond and nano silica having a particle diameter of 25 nm in the first network polymer and the second network polymer to obtain a common covalent cross-linking and A dynamic polymer of a silicon borate bond.
该聚合物产品可用于制作阻尼减震器，应用于各种机动车辆、机械设备。The polymer product can be used to make damping dampers for a variety of motor vehicles and machinery.
以上所述仅为本发明的实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above is only the embodiment of the present invention, and is not intended to limit the scope of the invention, and the equivalent structure or equivalent process transformation made by using the content of the specification of the present invention, or directly or indirectly applied in other related technical fields, The same is included in the scope of patent protection of the present invention.

Claims (21)

  1. 具有杂化交联结构的动态聚合物，其特征在于，其中包含至少一个普通共价交联网络，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；同时其中包含动态共价无机硼酸硅酯键，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子；所述的连接基Y，其处于动态聚合物主链骨架的结构仅含有(聚)硅氧烷单元。A dynamic polymer having a hybrid crosslinked structure, characterized in that it comprises at least one common covalent crosslinked network, and at least one of said common covalently crosslinked network skeletons is a carbon chain or a carbon hetero chain structure; a dynamic covalent inorganic silicic acid silicate bond, wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is linked to three -O-, and a portion thereof is based on a BO-Si dynamic covalent bond of a different B atom The different Si atoms are connected by a linking group L, and at the same time, based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms, are connected via a linking group Y; the linking group L, which is contained in the dynamic polymer backbone The carbon atom on the backbone; the linker Y, which is in the structure of the dynamic polymer backbone backbone, contains only (poly)siloxane units.
  2. 根据权利要求1所述的具有杂化交联结构的动态聚合物，其特征在于，所述动态聚合物只有一个网络，该网络中同时含有普通共价交联和动态共价无机硼酸硅酯键交联，其中普通共价交联达到其凝胶点以上并且其交联网络骨架为碳链或碳杂链结构；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。The dynamic polymer having a hybrid crosslinked structure according to claim 1, wherein the dynamic polymer has only one network, and the network contains both common covalent crosslinks and dynamic covalent inorganic silicon borate bonds. Cross-linking, wherein common covalent cross-linking reaches above its gel point and its cross-linking network backbone is a carbon chain or a carbon hetero-chain structure; wherein any one of the dynamic covalent inorganic boronic acid silicate bond atoms and three -O-linkage, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected by a linker L, and are partially based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms. Linked by a linker Y; the linker L, which contains a carbon atom on the backbone of the dynamic polymer backbone, the linker Y, which is on the backbone of the dynamic polymer backbone, contains only (poly) A siloxane unit.
  3. 根据权利要求1所述的具有杂化交联结构的动态聚合物，其特征在于，所述动态聚合物含有两个网络；第1网络中仅含普通共价交联，普通共价交联达到其凝胶点以上并且其共价交联网络骨架为碳链或碳杂链结构；第2网络中以动态共价无机硼酸硅酯键形成的交联达到其凝胶点以上，不含凝胶点以上的普通共价交联，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。The dynamic polymer having a hybrid crosslinked structure according to claim 1, wherein the dynamic polymer contains two networks; the first network contains only ordinary covalent crosslinks, and ordinary covalent crosslinks are achieved. Above its gel point and its covalently crosslinked network backbone is a carbon chain or a carbon chain structure; in the second network, the crosslinking formed by the dynamic covalent inorganic boronic acid silicate bond reaches above its gel point, without gel Ordinary covalent cross-linking above the point, wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is connected to three -O-, and some of them are based on BO-Si dynamic covalent bonds of different B atoms The different Si atoms are connected by a linking group L, and at the same time, based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms, are connected via a linking group Y; the linking group L, which is contained in the dynamic polymer backbone The carbon atom on the backbone, the linker Y, which is on the dynamic polymer backbone backbone, contains only (poly)siloxane units.
  4. 根据权利要求1所述的具有杂化交联结构的动态聚合物，其特征在于，所述动态聚合物含有两个网络；第1网络中同时含有普通共价交联和动态共价无机硼酸硅酯键交联，其中普通共价交联达到其凝胶点以上并且其交联网络骨架为碳链或碳杂链结构；第2网络中仅含普通共价交联，不含所述动态共价无机硼酸硅酯键；其中，至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的 连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。The dynamic polymer having a hybrid crosslinked structure according to claim 1, wherein the dynamic polymer contains two networks; the first network contains both common covalent crosslinks and dynamic covalent inorganic silicon borate Ester bond cross-linking, wherein common covalent cross-linking reaches above its gel point and its cross-linked network backbone is carbon chain or carbon hetero-chain structure; the second network contains only ordinary covalent cross-linking, excluding the dynamic co- a valence inorganic silicic acid silicate bond; wherein at least one of said common covalent crosslinked network backbones is a carbon chain or a carbon heterochain structure; wherein said one of said dynamic covalent inorganic boronic silicate linkages has three B atoms and three O-linkage, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linker L, and are partially based on different Si atoms in the BO-Si dynamic covalent bond of different B atoms. The linker Y is linked; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the backbone of the dynamic polymer backbone, contains only (poly)silicon Oxytomane unit.
  5. 根据权利要求1所述的具有杂化交联结构的动态聚合物，其特征在于，所述动态聚合物含有两个网络；第1网络和第2网络均同时含有普通共价交联和动态共价无机硼酸硅酯键交联，其中普通共价交联达到其凝胶点以上，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构，但所述的第1和第2网络不同。其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。The dynamic polymer having a hybrid crosslinked structure according to claim 1, wherein the dynamic polymer contains two networks; the first network and the second network both contain common covalent crosslinks and dynamic totals. a valence inorganic silicon silicate bond cross-linking in which ordinary covalent cross-linking reaches above its gel point, and at least one of said common covalent cross-linking network backbones is a carbon chain or a carbon hetero chain structure, but said first sum The second network is different. Wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is connected to three -O-, and a part of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L. And at the same time, different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through a linking group Y; the linking group L, which contains carbon atoms on the backbone of the dynamic polymer backbone, The linker Y, which is on the backbone of the dynamic polymer backbone, contains only (poly)siloxane units.
  6. 根据权利要求1所述的具有杂化交联结构的动态聚合物，其特征在于，所述动态聚合物含有至少一个网络，该些网络中仅含有普通共价交联，至少一个所述普通共价交联网络骨架为碳链或碳杂链结构，并且以动态共价无机硼酸硅酯键交联的聚合物以颗粒形式分散在所述网络中；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。The dynamic polymer having a hybrid crosslinked structure according to claim 1, wherein the dynamic polymer contains at least one network, and the networks contain only ordinary covalent crosslinks, at least one of the common The crosslinked network backbone is a carbon chain or a carbon hetero chain structure, and a polymer crosslinked by a dynamic covalent inorganic boronic acid silicate bond is dispersed in the network in the form of particles; wherein the dynamic covalent inorganic boronic acid borate Any one of the B atoms is connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond of different B atoms are connected through the linking group L, and the BO-Si is partially based on different B atoms. The different Si atoms in the dynamic covalent bond are linked by a linker Y; the linker L, which contains a carbon atom on the backbone of the dynamic polymer backbone, said linker Y, which is in the dynamic polymer backbone The structure on the backbone contains only (poly)siloxane units.
  7. 根据权利要求1所述的具有杂化交联结构的动态聚合物，其特征在于，所述动态聚合物仅含有一个网络，该网络中仅含有普通共价交联，所述普通共价交联网络骨架为碳链或碳杂链结构，并且含有动态共价无机硼酸硅酯键的非交联聚合物分散在所述网络中；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。The dynamic polymer having a hybrid crosslinked structure according to claim 1, wherein the dynamic polymer contains only one network, and the network contains only ordinary covalent crosslinks, and the common covalent crosslinks. The network backbone is a carbon chain or a carbon hetero chain structure, and a non-crosslinked polymer containing a dynamic covalent inorganic boronic acid silicate bond is dispersed in the network; wherein any one of the dynamic covalent inorganic boron silicate linkages B The atom is connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linking group L, and are partially based on the BO-Si dynamic covalent bond of different B atoms. The different Si atoms are connected by a linker Y; the linker L contains a carbon atom on the backbone of the dynamic polymer backbone, and the linker Y, which is on the dynamic polymer backbone backbone, is only Contains (poly)siloxane units.
  8. 根据权利要求1所述的具有杂化交联结构的动态聚合物，其特征在于，所述动态聚合物含有两个网络，第1网络和第2网络中均仅含普通共价交联，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；第1网络和第2网络相同或者不同，优选不同；在其中至少一个网络中分散有含有动态共价无机硼酸硅酯键的非交联聚合物；其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，并且其中部分基于不同B原子的B-O-Si 动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物主链骨架上的碳原子，所述的连接基Y，其处于动态聚合物主链骨架上的结构仅含有(聚)硅氧烷单元。The dynamic polymer having a hybrid crosslinked structure according to claim 1, wherein the dynamic polymer contains two networks, and both the first network and the second network contain only ordinary covalent crosslinks, and At least one of the common covalent crosslinked network backbones is a carbon chain or a carbon hetero chain structure; the first network and the second network are the same or different, preferably different; and at least one of the networks is dispersed with a dynamic covalent inorganic boronic acid borate a non-crosslinked polymer of a bond; wherein any one of the B atoms of the dynamic covalent inorganic boronic silicate bond is linked to three -O-, and wherein the B-based dynamic covalent bond is partially based on a different B atom Different Si atoms are connected through a linking group L, and are partially connected via a linking group Y based on different Si atoms in a BO-Si dynamic covalent bond of different B atoms; the linking group L, which is contained in a dynamic polymer backbone skeleton The carbon atom, the linker Y, which is on the dynamic polymer backbone backbone, contains only (poly)siloxane units.
  9. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，所述连接基L和连接基Y均至少为二价，其聚合物链拓扑结构选自线型、环状、支化、团簇以及上述结构的组合形式。The dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, wherein the linking group L and the linking group Y are at least divalent, and the polymer chain topology is selected. From a linear form, a ring, a branch, a cluster, and a combination of the above structures.
  10. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，连接基L选自烃基、聚烯烃基、聚醚基、聚酯基、聚氨酯基、聚脲基、聚硫代胺酯基、聚丙烯酸酯基、聚丙烯酰胺基、聚碳酸酯基、聚醚砜基、聚芳砜基、聚醚醚酮基、聚酰亚胺基、聚酰胺基、聚胺基、聚苯醚基、聚苯硫醚基、聚苯砜基。The dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, wherein the linking group L is selected from the group consisting of a hydrocarbon group, a polyolefin group, a polyether group, a polyester group, a polyurethane group, Polyurea, polythiourethane, polyacrylate, polyacrylamide, polycarbonate, polyethersulfone, polyarylsulfonyl, polyetheretherketone, polyimide, polyamide Base, polyamine group, polyphenylene ether group, polyphenylene sulfide group, polyphenylsulfone group.
  11. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，所述的(聚)硅氧烷单元，其主链或主体结构由-(SiR 1R 2-O) n-单元组成，其中，n为硅氧烷单元(SiR 1R 2-O)的数量，为大于或等于1的整数；R 1、R 2为连接在硅原子上的基团或链段，其各自独立地选自氢原子、卤素原子、有机基团、无机基团、无机链段、有机链段。 The dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, wherein the (poly)siloxane unit has a main chain or a host structure of -(SiR 1 R 2 -O) n - unit composition, wherein n is the number of siloxane units (SiR 1 R 2 -O), an integer greater than or equal to 1; R 1 and R 2 are a group attached to a silicon atom The cluster or segment, each independently selected from the group consisting of a hydrogen atom, a halogen atom, an organic group, an inorganic group, an inorganic segment, and an organic segment.
  12. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，动态聚合物成分中还含有骨架氢键基团，该基团中的至少部分原子直接参与构建连续的聚合物主链或交联网络骨架上的聚合物主链或交联链接。The dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, wherein the dynamic polymer component further contains a skeleton hydrogen bond group, and at least a part of the atoms in the group are directly Participate in the construction of a continuous polymer backbone or a polymer backbone or cross-linking link on a crosslinked network backbone.
  13. 根据权利要求12所述的具有杂化交联结构的动态聚合物，所述的骨架氢键基团，其选自酰胺基、氨基甲酸酯基、硫代氨基甲酸酯基、硅代氨基甲酸酯基、脲基以及基于以上基团的衍生物。The dynamic polymer having a hybrid crosslinked structure according to claim 12, wherein said skeleton hydrogen bonding group is selected from the group consisting of an amide group, a urethane group, a thiocarbamate group, and a silylamino group. a formate group, a urea group, and a derivative based on the above group.
  14. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，所述动态聚合物及其原料组分具有一个或多个玻璃化转变温度，或者没有玻璃化转变温度；其中，所述动态聚合物及其原料组分的玻璃化转变温度，至少有一个低于0℃、或者处于0-25℃之间、或者处于25-100℃之间、或者高于100℃。A dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, wherein the dynamic polymer and its raw material components have one or more glass transition temperatures, or none a glass transition temperature; wherein the dynamic polymer and its raw material component have a glass transition temperature of at least one below 0 ° C, or between 0-25 ° C, or between 25-100 ° C, or Above 100 °C.
  15. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，其或含有其的组成具有以下任一种性状：凝胶、普通固体、弹性体、泡沫。The dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, characterized in that it or a composition containing the same has the following properties: gel, ordinary solid, elastomer, foam.
  16. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，所述的无机硼酸硅酯键由无机硼化合物和含硅化合物反应而成。The dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, wherein the inorganic boronic acid silicate bond is formed by reacting an inorganic boron compound with a silicon-containing compound.
  17. 根据权利要求16所述的具有杂化交联结构的动态聚合物，其特征在于，所述的无机硼化合物选自硼酸、硼酸酯、硼酸盐、硼酸酐、卤化硼。The dynamic polymer having a hybrid crosslinked structure according to claim 16, wherein the inorganic boron compound is selected from the group consisting of boric acid, boric acid ester, borate, boric anhydride, and boron halide.
  18. 根据权利要求16所述的具有杂化交联结构的动态聚合物，其特征在于，所述的含硅化合物，是指化合物的端基、侧基中的至少一处含有硅羟基、硅羟基前驱体基团中的至少一种；其中，所述的硅羟基，其指的是由硅原子以及与该硅原子相连的一个羟基所组成的结构基元；其中，所述的硅羟基前驱体，其指的是由硅原子以及与该硅原子相连的一个可水解得到羟基的基团所组成的结构基元，其中，可水解得到羟基的基团，其选自卤素、氰基、氧氰基、硫氰基、烷氧基、氨基、硫酸酯基、硼酸酯基、酰基、酰氧基、酰氨基、酮肟基、醇盐基。The dynamic polymer having a hybrid crosslinked structure according to claim 16, wherein the silicon-containing compound means that at least one of the terminal group and the side group of the compound contains a silanol group and a silanol precursor. At least one of a body group; wherein the silicon hydroxy group refers to a structural unit composed of a silicon atom and a hydroxyl group connected to the silicon atom; wherein the silanol precursor, It refers to a structural unit composed of a silicon atom and a group capable of hydrolyzing a hydroxyl group connected to the silicon atom, wherein a group which can be hydrolyzed to obtain a hydroxyl group is selected from the group consisting of halogen, cyano and oxycyano. , thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketoximino, alkoxide.
  19. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，其组成的配方组分还包括以下任一种或任几种可添加物或可使用物：其他聚合物、助剂、填料；The dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, wherein the constituent component of the composition further comprises any one or any of the following additives or can be used. Matter: other polymers, auxiliaries, fillers;
    其中，所述的其他聚合物选自以下任一种或任几种：天然高分子化合物、合成树脂、合成橡胶、合成纤维；Wherein, the other polymer is selected from any one or more of the following: a natural polymer compound, a synthetic resin, a synthetic rubber, a synthetic fiber;
    其中，所述的助剂选自以下任一种或任几种：催化剂、引发剂、抗氧剂、光稳定剂、热稳定剂、交联剂、固化剂、扩链剂、增韧剂、偶联剂、润滑剂、脱模剂、增塑剂、发泡剂、动态调节剂、抗静电剂、乳化剂、分散剂、着色剂、荧光增白剂、消光剂、阻燃剂、成核剂、流变剂、增稠剂、流平剂；Wherein, the auxiliary agent is selected from any one or more of the following: a catalyst, an initiator, an antioxidant, a light stabilizer, a heat stabilizer, a crosslinking agent, a curing agent, a chain extender, a toughening agent, Coupling agent, lubricant, mold release agent, plasticizer, foaming agent, dynamic regulator, antistatic agent, emulsifier, dispersant, colorant, fluorescent whitening agent, matting agent, flame retardant, nucleation Agent, rheological agent, thickener, leveling agent;
    其中，所述的填料选自以下任一种或任几种：无机非金属填料、金属填料、有机填料。Wherein, the filler is selected from any one or more of the following: an inorganic non-metallic filler, a metal filler, and an organic filler.
  20. 根据权利要求1-8中任一项所述的具有杂化交联结构的动态聚合物，其特征在于，其应用于以下制品：减震器、缓冲材料、抗冲击防护材料、运动防护制品、军警防护制品、自修复性涂层、自修复性板材、自修复性粘结剂、防弹玻璃夹层胶、储能器件材料、韧性材料、形状记忆材料、密封件、玩具、力传感器。The dynamic polymer having a hybrid crosslinked structure according to any one of claims 1 to 8, which is applied to the following articles: a shock absorber, a cushioning material, an impact resistant protective material, a sports protective article, Military and police protective products, self-healing coatings, self-healing sheets, self-healing adhesives, bulletproof glass interlayer adhesives, energy storage device materials, ductile materials, shape memory materials, seals, toys, force sensors.
  21. 一种吸能方法，其特征在于，提供具有杂化交联结构的动态聚合物并以其作为吸能材料进行吸能，其中，所述的动态聚合物包含至少一个普通共价交联网络，并且至少一个所述普通共价交联网络骨架为碳链或碳杂链结构；同时其中包含动态共价无机硼酸硅酯键，其中，所述动态共价无机硼酸硅酯键中任意一个B原子与三个-O-连接，且其中部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基L相连，同时部分基于不同B原子的B-O-Si动态共价键中的不同Si原子通过连接基Y相连；所述的连接基L，其含有处于动态聚合物骨架上的碳原子；所述的连接基Y，其处于动态聚合物骨架的结构仅含有(聚)硅氧烷单元。An energy absorbing method, characterized in that a dynamic polymer having a hybrid crosslinked structure is provided and energy is absorbed as an energy absorbing material, wherein the dynamic polymer comprises at least one common covalent crosslinked network, And at least one of the common covalent crosslinked network backbones is a carbon chain or a carbon heterochain structure; and at the same time comprises a dynamic covalent inorganic silicon borate linkage, wherein any one of the dynamic covalent inorganic boronic silicate linkages is B atoms Connected to three -O-, and some of the different Si atoms in the BO-Si dynamic covalent bond based on different B atoms are connected through the linker L, and partly based on the BO-Si dynamic covalent bond of different B atoms. The different Si atoms are connected by a linker Y; the linker L contains a carbon atom on the dynamic polymer backbone; the linker Y, which is in the structure of the dynamic polymer backbone, contains only (poly) siloxane Alkane unit.
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