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WO2018137508A1 - Polymère dynamique ayant une structure réticulée hybride, et application associée - Google Patents

Polymère dynamique ayant une structure réticulée hybride, et application associée Download PDF

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Publication number
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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Chinese (zh)
Inventor
徐晖
郭琼玉
张欢
梁愫
林淦
欧阳勇
翁文桂
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Weng Qiumei
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Weng Qiumei
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne un polymère dynamique ayant une structure réticulée hybride, comprenant un réseau de réticulation covalente usuel ayant au moins un squelette en chaîne carbonée ou en hétérochaîne carbonée, et simultanément comprenant une liaison ester covalente dynamique borate inorganique silicium. La réticulation covalente usuelle confère au polymère une certaine résistance mécanique et une certaine stabilité. La présence de la liaison ester borate inorganique silicium permet au polymère d'avoir une bonne réversibilité dynamique, en réalisant de ce fait des propriétés fonctionnelles telles qu'une sensibilité aux stimuli ; elle autorise aussi une bonne absorption de l'énergie par le polymère, et peut rendre le matériau tenace et l'amortir dans certaines configurations structurales. Le polymère dynamique peut être utilisé pour fabriquer des matériaux absorbant les chocs, des matériaux de protection contre les chocs, des matériaux autoréparables, des matériaux tenaces, des capteurs de force et analogues.
PCT/CN2018/072461 2017-01-25 2018-01-12 Polymère dynamique ayant une structure réticulée hybride, et application associée Ceased WO2018137508A1 (fr)

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