CN108341951B - Dynamic polymer with hybrid cross-linked structure and application thereof - Google Patents

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

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CN108341951B
CN108341951B CN201710056069.XA CN201710056069A CN108341951B CN 108341951 B CN108341951 B CN 108341951B CN 201710056069 A CN201710056069 A CN 201710056069A CN 108341951 B CN108341951 B CN 108341951B
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Abstract

The invention discloses a dynamic polymer with a hybrid crosslinking structure, which comprises common covalent crosslinking and supermolecule hydrogen bonding action participated by dynamic covalent inorganic silicon borate bonds and side hydrogen bonding groups, wherein the common covalent crosslinking reaches above the gel point. The dynamic polymer combines dynamic covalent inorganic silicon borate bonds with supermolecule hydrogen bonds, has good dynamic reversibility, and can show the functional characteristics of stimulus responsiveness, self-repairing property and the like; the common covalent crosslinking imparts a certain strength and stability to the polymer. In addition, the existence of inorganic silicon borate bonds and hydrogen bonds also enables the polymer to have good energy absorption effect, and the material is toughened and damped in a specific structure. The dynamic polymer can be used for manufacturing shock absorption buffer materials, shock resistance protection materials, self-repairing materials, toughness materials and the like.

Description

Dynamic polymer with hybrid cross-linked structure and application thereof
Technical Field
The invention relates to the field of intelligent polymers, in particular to a dynamic polymer with a hybrid cross-linked network and an application thereof, wherein the dynamic polymer consists of a common covalent bond, a dynamic covalent bond and a supermolecule hydrogen bond.
Background
The traditional three-dimensional network structure is generally formed by common covalent crosslinking, and the common covalent bonds have higher bond energy, so that the polymer is endowed with good stability and stress bearing capacity, and therefore, a larger proportion is occupied in the crosslinking of the polymer. However, when only ordinary covalent crosslinking is adopted, if the crosslinking density is low, the crosslinking effect is often not reflected, and particularly the mechanical property is poor; whereas if the crosslink density is high, the crosslinked polymer tends to be hard and brittle; moreover, general chemical crosslinking lacks the dynamic property that once chemical crosslinking is formed, the crosslinking itself cannot be changed and the properties of the polymer material are immobilized.
Therefore, there is a need to develop a new hybrid crosslinked dynamic polymer that allows the system to have both dimensional stability, good mechanical properties and excellent dynamic properties to solve the problems of the prior art.
Disclosure of Invention
Against the background of the above, the present invention provides a dynamic polymer having a hybrid crosslinked network structure, which comprises at least one covalent crosslinked network, wherein the common covalent crosslinks reach above the gel point; meanwhile, the method comprises the supermolecule hydrogen bonding action of a dynamic covalent inorganic silicon borate bond and a side hydrogen bonding group. The dynamic polymer has certain mechanical strength and good toughness, and simultaneously has excellent dynamic reversibility, and can show the functional characteristics of stimulus responsiveness, self-repairing property, self-adhesiveness and the like.
The invention is realized by the following technical scheme:
a dynamic polymer with a hybrid cross-linked structure, which at least comprises a covalent cross-linked network, wherein the degree of cross-linking of common covalent cross-links reaches above the gel point; meanwhile, the method comprises the supermolecule hydrogen bonding action of a dynamic covalent inorganic silicon borate bond and a side hydrogen bonding group.
In one embodiment of the invention, the dynamic polymer has only one network, and the network comprises common covalent crosslinking, dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, wherein the common covalent crosslinking reaches above the gel point, the dynamic covalent crosslinking is realized by inorganic silicon borate ester bonds, and the supermolecule hydrogen bond crosslinking comprises side hydrogen bond action.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network comprises a common covalent cross-linking and a dynamic covalent cross-linking, wherein the common covalent cross-linking reaches above the gel point of the common covalent cross-linking, the dynamic covalent cross-linking is realized by an inorganic silicon borate bond, and the side groups and the side chains of the dynamic covalent cross-linking do not contain the side hydrogen bond groups; the 2 nd network does not contain covalent bond cross-linking, but the polymer chain has the side hydrogen bond groups and participates in hydrogen bond cross-linking.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network comprises a common covalent cross-link and a supramolecular hydrogen bond cross-link, wherein the common covalent cross-link reaches above its gel point, and the supramolecular hydrogen bond cross-link is realized by participation of a lateral hydrogen bond group; the network 2 does not contain common covalent crosslinking, but contains dynamic covalent crosslinking of inorganic silicon borate bonds, which does not contain the side hydrogen bond groups.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network comprises a common covalent cross-link and a supramolecular hydrogen bond cross-link, wherein the common covalent cross-link reaches above its gel point, and the supramolecular hydrogen bond cross-link is realized by participation of the lateral hydrogen bond group; the 2 nd network comprises common covalent crosslinking and inorganic silicon borate bond dynamic covalent crosslinking, wherein the common covalent crosslinking reaches above the gel point of the inorganic silicon borate bond dynamic covalent crosslinking, and the inorganic silicon borate bond dynamic covalent crosslinking does not contain the side hydrogen bond groups.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network comprises both ordinary covalent crosslinking, dynamic covalent crosslinking and supramolecular hydrogen bonding crosslinking, wherein the ordinary covalent crosslinking reaches above its gel point, the dynamic covalent crosslinking is realized by inorganic silicon borate bonds, and the supramolecular hydrogen bonding crosslinking comprises the side hydrogen bonding; covalent bond crosslinks are absent from the 2 nd network, but the polymer chains have pendant hydrogen bond groups and participate in the formation of hydrogen bond crosslinks.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network comprises both ordinary covalent crosslinking, dynamic covalent crosslinking and supramolecular hydrogen bonding crosslinking, wherein the ordinary covalent crosslinking reaches above its gel point, the dynamic covalent crosslinking is realized by inorganic silicon borate bonds, and the supramolecular hydrogen bonding crosslinking comprises the side hydrogen bonding; the 2 nd network contains common covalent crosslinking and inorganic silicon borate bond dynamic covalent crosslinking, but does not contain the side hydrogen bond group.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network comprises both ordinary covalent crosslinking, dynamic covalent crosslinking and supramolecular hydrogen bonding crosslinking, wherein the ordinary covalent crosslinking reaches above its gel point, the dynamic covalent crosslinking is realized by inorganic silicon borate bonds, and the supramolecular hydrogen bonding crosslinking comprises the side hydrogen bonding; the 2 nd network contains inorganic silicon borate ester bond dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, and the supermolecule hydrogen bond crosslinking is realized by participation of the side hydrogen bond groups.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network comprises both ordinary covalent crosslinking, dynamic covalent crosslinking and supramolecular hydrogen bonding crosslinking, wherein the ordinary covalent crosslinking reaches above its gel point, the dynamic covalent crosslinking is realized by inorganic silicon borate bonds, and the supramolecular hydrogen bonding crosslinking comprises the side hydrogen bonding; the 2 nd network comprises common covalent crosslinking, dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, wherein the common covalent crosslinking reaches above the gel point of the network, the dynamic covalent crosslinking is realized by inorganic silicon borate bonds, and the supermolecule hydrogen bond crosslinking comprises the side hydrogen bond action; but the 1 st and 2 nd networks described above are not identical.
In another embodiment of the present invention, the dynamic polymer is composed of three networks, the 1 st network contains common covalent crosslinking and inorganic silicon borate bond dynamic covalent crosslinking, but does not contain the side hydrogen bond group; the 2 nd network does not contain covalent bond crosslinking, but the side hydrogen bond groups exist on the polymer chain, and hydrogen bond crosslinking participated by the side hydrogen bond groups is formed; the 3 rd network comprises common covalent crosslinking, dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, wherein the common covalent crosslinking reaches above the gel point, the dynamic covalent crosslinking is realized by inorganic silicon borate bonds, and the supermolecule hydrogen bond crosslinking comprises the side hydrogen bond function.
In another embodiment of the present invention, the dynamic polymer is composed of three networks, wherein the 1 st network contains inorganic silicon borate ester bond dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, and the supermolecule hydrogen bond crosslinking is realized by participation of the side hydrogen bond groups, but does not contain common covalent crosslinking; the 2 nd network does not contain covalent bond crosslinking, but the side hydrogen bond groups exist on the polymer chain, and hydrogen bond crosslinking participated by the side hydrogen bond groups is formed; the 3 rd network comprises common covalent crosslinking, dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, wherein the common covalent crosslinking reaches above the gel point, the dynamic covalent crosslinking is realized by inorganic silicon borate bonds, and the supermolecule hydrogen bond crosslinking comprises the side hydrogen bond function.
In another embodiment of the present invention, the dynamic polymer is composed of three networks, the 1 st network contains inorganic silicon borate ester bond dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, the supermolecule hydrogen bond crosslinking is realized by participation of the side hydrogen bond groups, but common covalent crosslinking does not exist; the 2 nd and 3 rd networks all comprise common covalent crosslinking, dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking at the same time, wherein the common covalent crosslinking reaches above the gel point of the supermolecule hydrogen bond crosslinking, the dynamic covalent crosslinking is realized by inorganic silicon borate ester bonds, the supermolecule hydrogen bond crosslinking comprises the side hydrogen bond action, but the 2 nd and 3 rd networks are different.
In another embodiment of the present invention, the dynamic polymer is composed of three networks, the 1 st network is a common covalent cross-linked network, and does not contain dynamic covalent bonds and hydrogen bonds; the 2 nd network is a dynamic covalent crosslinking network and does not contain hydrogen bond crosslinking; the 3 rd network is a hydrogen bond crosslinking network participated by the side hydrogen bond group, and does not contain dynamic covalent crosslinking and common covalent crosslinking.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network is a common covalent cross-linked network, and does not contain dynamic covalent bonds and hydrogen bonds; the 2 nd network is a hydrogen bond crosslinking network participated by the side hydrogen bond group, and does not contain dynamic covalent crosslinking and common covalent crosslinking; non-crosslinked dynamic covalent polymers containing dynamic covalent inorganic silicon borate linkages are dispersed in both networks.
In another embodiment of the present invention, the dynamic polymer is composed of two networks, the 1 st network is a common covalent cross-linked network, and does not contain dynamic covalent bonds and hydrogen bonds; the 2 nd network is a dynamic covalent crosslinking network and does not contain hydrogen bond crosslinking and common covalent crosslinking; non-crosslinked supramolecular polymers containing side hydrogen bonding are dispersed in both networks.
In another embodiment of the present invention, the dynamic polymer is composed of a network, and the crosslinked network is a common covalent crosslinked network, and does not contain dynamic covalent bond crosslinking and hydrogen bond crosslinking; non-crosslinked dynamic covalent polymers containing dynamic covalent inorganic silicon borate linkages and non-crosslinked dynamic supramolecular polymers containing pendant hydrogen bonds are dispersed in the network.
In another embodiment of the present invention, the dynamic polymer is composed of a network, and the crosslinked network is a common covalent crosslinked network, and does not contain dynamic covalent bond crosslinking and hydrogen bond crosslinking; non-crosslinked dynamic polymers containing both dynamic covalent inorganic silicon borate linkages and pendant hydrogen linkages are dispersed in the network.
In another embodiment of the present invention, the dynamic polymer is composed of a network, the crosslinked network is a common covalent crosslinked network, and optionally contains hydrogen bond crosslinks in which the side hydrogen bonds participate; the dynamic covalent polymer crosslinked with dynamic covalent inorganic silicon borate bonds is dispersed in the network in the form of particles containing hydrogen bond crosslinks optionally involving the side hydrogen bonds.
In addition to the seventeen embodiments of the hybrid cross-linked network structure described above, the present invention may also have other various hybrid cross-linked network structure embodiments, which may be reasonably and effectively implemented by those skilled in the art according to the logic and context of the present invention.
In an embodiment of the present invention, the inorganic silicon borate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound that contains a silicon hydroxyl group and/or a silicon hydroxyl group precursor.
The inorganic boron compound refers to a boron-containing compound in which boron atoms in the compound are not connected with carbon atoms through boron-carbon bonds.
The silicon-containing compound of the silicon-containing hydroxyl and/or silicon-hydroxyl precursor refers to any suitable compound of which the terminal end contains silicon hydroxyl and/or silicon-hydroxyl precursor. The silicon-containing compound is selected from small molecular silicon-containing compounds and large molecular silicon-containing compounds, which can be organic or inorganic compounds, including silica. The silicon-containing 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, star, dendritic, hyperbranched), two-dimensional/three-dimensional clusters, and combinations thereof.
In embodiments of the invention, the pendant hydrogen bond groups are pendant and/or hydrogen bond groups on the side chain backbone, which may be any suitable hydrogen bond groups. Preferably, there is both a hydrogen bond acceptor and a hydrogen bond donor within one of the pendant hydrogen bond groups; it is also possible that part of the side hydrogen bond groups contain hydrogen bond donors and the other part of the side hydrogen bond groups contain hydrogen bond acceptors; most preferably both acceptor and donor.
The acceptor of the side hydrogen bond group in the present invention preferably contains at least one of structures represented by the following general formula (1),
Figure SMS_1
wherein A is selected from oxygen atom and sulfur atom; d is selected from nitrogen atoms and C-R groups; x is a halogen atom;
Figure SMS_2
selected from any suitable atom, group, segment, cluster; wherein R is selected from hydrogen atom, substituent atom and substituent group.
The donor of the side hydrogen bond group in the present invention preferably contains at least one of structures represented by the following general formula (2),
Figure SMS_3
the structures represented by the general formulae (1) and (2) may be a side group, a terminal group, a linear structure, a branched structure containing a side group, a cyclic structure, or the like. The annular structure can be a single-ring structure, a multi-ring structure, a spiro structure, a condensed ring structure, a bridge ring structure, a nested ring structure and the like.
In an embodiment of the present invention, the side hydrogen bond group preferably contains both structures represented by the general formulae (1) and (2). According to the effect of the present invention, the side hydrogen bond group is preferably selected from the group consisting of amide group, carbamate group, thiocarbamate group, urea group, pyrazole, imidazole, imidazoline, triazole, purine, porphyrin, and derivatives thereof.
In an embodiment of the present invention, the dynamic polymer composition having the hybrid cross-linked structure may be in the form of a general solid, an elastomer, a gel (including hydrogel, organogel, oligomer-swollen gel, plasticizer-swollen gel, ionic liquid-swollen gel), foam, or the like.
In the embodiment of the invention, other polymers, auxiliary agents and fillers which can be added/used can be optionally added in the preparation process of the dynamic polymer with the hybrid cross-linked structure for blending to jointly form the dynamic polymer.
Wherein the other polymers that may be added/used are selected from any one or any several of the following: natural high molecular compound, synthetic resin, synthetic rubber and synthetic fiber;
wherein, the additive which can be added/used is selected from any one or any several of the following: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, cross-linking agents, curing agents, chain extenders, toughening agents, coupling agents, lubricants, mold release agents, plasticizers, foaming agents, dynamic regulators, antistatic agents, emulsifiers, dispersants, colorants, fluorescent whitening agents, matting agents, flame retardants, nucleating agents, rheology agents, thickening agents, leveling agents;
Wherein the filler which can be added/used is selected from any one or any several of the following: inorganic nonmetallic filler, metal filler and organic filler.
In the embodiment of the invention, the dynamic polymer with the hybrid cross-linked structure has adjustable performance in a large range and wide application prospect, and can be particularly applied to manufacturing shock absorbers, buffer materials, sound insulation materials, sound damping materials, anti-impact protection materials, sports protection products, military police protection products, self-repairing coatings, self-repairing plates, self-repairing adhesives, bulletproof glass sandwich adhesives, toughness materials, shape memory materials, toys, force sensors and other products.
Compared with the prior art, the invention has the following beneficial effects:
(1) The dynamic polymer with the hybrid crosslinking structure combines the advantages of common covalent crosslinking, dynamic covalent inorganic silicon borate ester bonds and supermolecule hydrogen bonds, and fully utilizes and combines the advantages of the bonding actions. Wherein, the common covalent crosslinking provides a strong and stable network structure for the dynamic polymer, and the polymer can maintain a balance structure, namely dimensional stability; and after the dynamic covalent inorganic silicon borate ester bond and the supermolecule hydrogen bond are introduced into the polymer, the dynamic property of the dynamic covalent bond and the hydrogen bond can endow the material with excellent dynamic properties, including but not limited to weak bond characteristics and dynamic bond characteristics, in particular dilatancy. Under the action of external force, the dynamic covalent bond and the hydrogen bond can be broken in a sacrificial bond mode, so that a large amount of energy is dissipated, enough toughness is provided for the crosslinked polymer, and the crosslinked polymer has excellent tensile toughness and tear resistance while having inherent mechanical strength and stability of a crosslinked structure; the dilatancy can provide excellent energy dispersion and absorption capacity for the material, and excellent damping, shock absorption, shock resistance and other performances are obtained. And the dynamic covalent bond and the hydrogen bond are mutually orthogonal, and coordinate and supplement to obtain the most ideal performance. This is not possible with only a single one of the bonds. Based on the difference of dynamic property, responsiveness and strength among different bonding, the dynamic change and response of orthogonality/sequence property and fracture/dissociation under stress can be obtained, thereby maximally obtaining multiple response, energy absorption, shape memory and other functions. This is not provided by the prior art.
(2) The dynamic polymer with the hybridized cross-linking structure has the advantages that the super molecular hydrogen bonding effect of the side hydrogen bonding groups is contained, the side hydrogen bonding is generally hung beside a main chain framework, the density, the distribution, the structure and the like of the dynamic polymer have flexible adjustability, the glass transition temperature of the polymer, particularly the glass transition temperature of the hydrogen bonding formed by the participation of the dynamic polymer, the dynamic property of the formed hydrogen bonding and the like can be conveniently regulated, and the dynamic polymer has outstanding advantages.
(3) In the dynamic polymer with the hybridized cross-linked structure, besides the side hydrogen bonds, other aspects are rich in structure and various in performance. By adjusting the number of functional groups, molecular structure and molecular weight in the raw material compound and/or introducing reactive groups, dynamic promoting groups, functional groups and/or adjusting parameters such as raw material composition in the raw material compound, dynamic polymers with different structures can be prepared, so that the dynamic polymers show various properties and the application requirements of different occasions are met.
(4) The dynamic polymer with the hybrid cross-linked structure has strong dynamic reactivity of dynamic reversible bonds and mild dynamic reaction conditions. Compared with other existing dynamic covalent systems, the invention fully utilizes the good thermal stability and high dynamic reversibility of the inorganic silicon borate ester bond, can realize the synthesis and dynamic reversibility of the dynamic polymer under the conditions of no need of catalyst, no need of high temperature, illumination or specific pH, improves the preparation efficiency, reduces the limitation of the use environment and expands the application range of the polymer. In addition, by selectively controlling other conditions (e.g., adding adjuvants, adjusting reaction temperature, etc.), the dynamic covalent chemical equilibrium can be accelerated or quenched in a desired state under appropriate circumstances, which is more difficult to achieve in existing supramolecular chemistry as well as dynamic covalent systems.
(5) In the present invention, a dynamic polymer having a hybrid cross-linked structure may exhibit functional characteristics. By adjusting the dynamic components in the dynamic polymer, the polymer can show stimulus response and dilatancy, and the polymer can respond to external stimulus such as external force, temperature, pH, illumination and the like to change the state of the polymer. After the dynamic reversible silicon borate ester bond and the supermolecule hydrogen bond are broken, the bonding can be carried out again by changing the external conditions, so that the material has the functional characteristics of plasticity, self-repairing property and the like, the service life of the polymer is prolonged, and the material can be applied to a plurality of special fields.
Detailed Description
The invention relates to a dynamic polymer with a hybridized crosslinking structure, which at least comprises a covalent crosslinking network, wherein the crosslinking degree of common covalent crosslinking reaches above the gel point; meanwhile, the method comprises the supermolecule hydrogen bonding action of a dynamic covalent inorganic silicon borate bond and a side hydrogen bonding group.
The term "polymerization" (reaction) as used herein is a chain growth process/action and includes processes in which reactants synthesize a product having a higher molecular weight by polycondensation, polyaddition, ring-opening polymerization, etc. reaction forms. The reactant is generally a compound such as a monomer, an oligomer, or a prepolymer having a polymerization ability (i.e., capable of spontaneously polymerizing or capable of polymerizing by an initiator or external energy). The product obtained by polymerizing one reactant is called a homopolymer. The products obtained by polymerizing two or more reactants are called copolymers. It is noted that "polymerization" as used herein includes a linear propagation process of reactant molecular chains, a branching process of reactant molecular chains, a cyclization process of reactant molecular chains, and a crosslinking process of reactant molecular chains.
The term "cross-linking" (reaction) as used herein refers to the process of chemical attachment of supramolecules by common covalent bonds or dynamic covalent bonds and/or hydrogen bonds between reactant molecules and/or within reactant molecules to form clusters having two-dimensional, three-dimensional clusters and thus to form three-dimensional infinite network products. In the crosslinking process, the polymer chains generally grow continuously in two-dimensional/three-dimensional directions, gradually form clusters (which can be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. Unless otherwise specified, the cross-linking in the present invention refers to a three-dimensional infinite network structure above (including, hereinafter, the same as) the gel point, and the non-cross-linking includes structures below the gel point such as linear, branched, cyclic, two-dimensional cluster structures, and three-dimensional cluster structures below the gel point.
The term "gel point" as used herein means the point of reaction at which the reactant begins to gel during crosslinking, i.e., the percolation threshold, when it reaches a three-dimensional infinite network for the first time, as the viscosity of the reactant increases suddenly. 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 loosely linked structure, does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can be formed as one whole across the entire polymer structure.
The term "ordinary covalent bond" as used herein means a covalent bond other than a dynamic covalent bond in the conventional sense, which is difficult to break at a normal temperature (generally not higher than 100 ℃) and a normal time (generally less than 1 day), and includes, but is not limited to, a normal carbon-carbon bond, a carbon-oxygen bond, a carbon-hydrogen bond, a carbon-nitrogen bond, a carbon-sulfur bond, a nitrogen-hydrogen bond, a nitrogen-oxygen bond, a hydrogen-oxygen bond, a nitrogen-nitrogen bond, and the like.
In embodiments of the present invention, the "dynamic covalent bond" refers to an inorganic silicon borate linkage. The inorganic silicon borate ester bond can be arranged at any suitable position on a polymer chain, namely on a polymer main chain framework, and can be arranged on a polymer side chain and/or a branched chain framework and/or a cross-linked chain. The present invention also does not exclude the inclusion of inorganic silicon borate linkages on the side groups and/or end groups of the polymer chain. Since the boron atom is trivalent, the formation of the inorganic silicon borate during polymerization can lead to the formation of branches and can be further crosslinked. The inorganic silicon borate linkage may be on a crosslinked polymer network, or on a non-crosslinked polymer, or not excluded from being on a small molecule.
In the present invention, "skeleton" refers to the structure in the chain length direction of a polymer chain. The term "backbone" refers to any segment present in the backbone of the crosslinked network for the crosslinked polymer; the term "non-crosslinked polymer" refers to the chain segment having the longest chain segment, unless otherwise specified. Wherein, the side chain refers to a chain structure which is connected with the main chain framework of the polymer and distributed beside the main chain framework; wherein, the "branched chain"/"furcation chain" can be a side chain or other chain structure which is furcated from any chain. Wherein, the "side group" refers to a chemical group which is connected with any chain of the polymer and distributed beside the chain. For "side chains", "branches" and "side groups", it may have a multi-stage structure, i.e., the side chains/branches may continue to bear side groups and side chains/branches, and the side chains/branches of the side chains/branches may continue to bear side groups and side chains/branches. Wherein, the term "terminal group" refers to a chemical group which is connected with any chain of the polymer and is positioned at the end of the chain. For hyperbranched and dendritic chains and their associated branched structures, the branches can also be considered the main chain, but in the present invention, the outermost branches are considered the branches, the remainder being considered the main chain. For simplicity, the branched/bifurcated chains are considered side chains in the present invention. In embodiments of the present invention, the term "pendant hydrogen bonding groups" refers to hydrogen bonding groups carried on the side groups and/or side backbones of the polymer chain, which may be on the crosslinked polymer network or on the non-crosslinked polymer. The side hydrogen bond groups can form hydrogen bond action with the side hydrogen bond groups, can also form hydrogen bond action with the hydrogen bond groups on the main chain framework of the polymer, can also form hydrogen bond action with the hydrogen bond groups on the surface of the organic/inorganic filler, and can also form hydrogen bond action with the hydrogen bond groups in the auxiliary agent/additive/solvent, but the invention is not limited to the side hydrogen bond action, and supermolecule hydrogen bond action participated by the side hydrogen bond groups can be generally called side hydrogen bond (action). The present invention may also include hydrogen bonding other than side-to-side hydrogen bonding, including, but not limited to, hydrogen bonding between backbone hydrogen bonding groups and backbone hydrogen bonding groups, and hydrogen bonding between backbone hydrogen bonding groups and end-group hydrogen bonding groups. Depending on the number, structure, distribution, etc., of hydrogen bonding groups, the hydrogen bonding may be polymerization, intra-chain cyclization, inter-chain crosslinking, grafting, side group functionalization, preferably polymerization, intra-chain cyclization, inter-chain crosslinking. The side hydrogen bond group has great flexibility in terms of structure and performance, so that the side hydrogen bond group can endow the dynamic polymer with performance which cannot be achieved by other hydrogen bonds.
According to an embodiment of the present invention, the dynamic polymer comprises at least one covalent cross-linked network, wherein the ordinary covalent cross-links reach above the gel point, i.e. the dynamic polymer comprises at least one ordinary covalent cross-linked network above the gel point; dynamic covalent crosslinking and/or supramolecular hydrogen bonding crosslinking may also be included in this covalently crosslinked network. The dynamic polymer may comprise one or more common covalent cross-linked networks and/or dynamic covalent cross-linked and/or supramolecular hydrogen-bonded networks in addition to the at least one common covalent cross-linked network. The dynamic covalent inorganic silicon borate bonds and/or supramolecular hydrogen bonds based on side hydrogen bonding groups may or may not be on the crosslinked network, i.e. the component containing the dynamic covalent inorganic silicon borate bonds and/or supramolecular hydrogen bonding based on side hydrogen bonding groups may be non-crosslinked (below the gel point) or may not be on the network of ordinary covalent crosslinks. Preferably dynamic covalent inorganic silicon borate bonds and/or supramolecular hydrogen bonding based on pendant hydrogen bonding groups participate in the crosslinking, more preferably on the same crosslinking network as common covalent crosslinking.
In the embodiment of the invention, one or more than one common covalent crosslinking in the same dynamic polymer system can be adopted, namely, any suitable common covalent crosslinking topological structure, chemical structure, reaction mode, combination thereof and the like can be adopted. In embodiments of the present invention, at least one of the crosslinked networks in a dynamic polymer system may be a single network, or may have multiple networks blended with each other, or may have multiple networks interpenetrating each other, or may have both blending and interpenetrating each other, etc.; wherein two or more networks may be the same or different; the present invention is not limited thereto, and the partial network may be a combination of only ordinary covalent crosslinks and partial network including only inorganic borate bonds and/or side hydrogen bonds, or a combination of only ordinary covalent crosslinks and partial inorganic borate bonds and/or side hydrogen bonds, or a combination of only inorganic borate bonds and/or side hydrogen bonds and partial inorganic borate bonds and/or side hydrogen bonds, or a combination of both ordinary covalent crosslinks and inorganic borate bonds and/or side hydrogen bonds, or both ordinary covalent crosslinks and inorganic borate bonds and/or side hydrogen bonds in each network. The crosslinks in a single network may be one or a combination of common covalent crosslinks, dynamic covalent crosslinks, hydrogen bond crosslinks. For the polymers of the invention, the usual covalent crosslinking reaches above the gel point in at least one network, which ensures that the polymer remains in equilibrium, i.e. can be (at least partially) insoluble and infusible solid in the usual state, even in the case of only one network. When multiple networks are present, there may be interactions, i.e., dynamic covalent and/or supramolecular interactions, between the different networks, or they may be independent of each other.
In one embodiment of the present invention, the hybrid crosslinked network dynamic polymer has only one network (first network structure), and is characterized in that the network contains both common covalent crosslinks, dynamic covalent crosslinks and supermolecular hydrogen bond crosslinks. Wherein the common covalent crosslinking is realized by a common covalent bond, and the common covalent crosslinking reaches above the gel point of the common covalent crosslinking; the dynamic covalent crosslinking is realized by inorganic silicon borate bonds; the supermolecular hydrogen bond cross-linking comprises side hydrogen bonding. The network structure is the simplest, but three different bonding modes can be fused in one network at the same time, so that the best orthogonal synergistic effect is realized.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of two networks (second network structure), characterized in that network 1 comprises a common covalent crosslink and a dynamic covalent crosslink, wherein said common covalent crosslink reaches above its gel point; the dynamic covalent crosslinking is realized by inorganic silicon borate bonds, and the side groups and the side chains of the dynamic covalent crosslinking do not contain the side hydrogen bond groups. The 2 nd network does not contain common covalent bonds and inorganic silicon borate ester bonds for crosslinking, but lateral hydrogen bond groups exist on lateral groups and/or lateral chain skeletons of polymer chains and participate in hydrogen bond crosslinking; in the network structure, the equilibrium structure is maintained through common covalent crosslinking in the 1 st network, and the inorganic silicon borate bonds in the equilibrium structure provide covalent dynamics, and the supermolecule dynamics are provided through side hydrogen bond crosslinking in the 2 nd network.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of two networks (third network structure), characterized in that network 1 comprises common covalent crosslinks and supramolecular hydrogen bond crosslinks, wherein the common covalent crosslinks reach above their gel point; the supermolecule hydrogen bond crosslinking is realized by participation of side hydrogen bond groups on a polymer chain side group and/or a side chain framework. The network 2 does not contain common covalent crosslinking, but contains dynamic covalent crosslinking formed by inorganic silicon borate bonds, and the side groups and the side chains of the network do not contain the side hydrogen bond groups. In the network structure, the equilibrium structure is maintained through common covalent crosslinking in the 1 st network, covalent dynamics is provided through inorganic silicon borate bonds in the 2 nd network, and supermolecular dynamics is provided through side hydrogen bond crosslinking in the 1 st network.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of two networks (fourth network structure), characterized in that network 1 comprises common covalent crosslinks and supramolecular hydrogen bond crosslinks, wherein the common covalent crosslinks reach above their gel point; the supermolecule hydrogen bond crosslinking is realized by participation of side hydrogen bond groups on a polymer chain side group and/or a side chain framework. The 2 nd network comprises common covalent crosslinking and inorganic silicon borate bond dynamic covalent crosslinking, wherein the common covalent crosslinking reaches above the gel point, and the side groups and side chains of the common covalent crosslinking do not contain the side hydrogen bond groups. In the network structure, the balance structure is maintained through common covalent crosslinking in the 1 st network and the 2 nd network, covalent dynamics is provided through inorganic silicon borate bonds in the 2 nd network, and supermolecular dynamics is provided through side hydrogen bond crosslinking in the 1 st network.
In another embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of two networks (a fifth network structure), characterized in that the 1 st network is the first network structure; covalent bond crosslinking is not contained in the 2 nd network, but lateral hydrogen bond groups exist on lateral groups and/or lateral chain skeletons of the polymer chains and participate in forming hydrogen bond crosslinking. In the network structure, the balance structure is maintained through covalent crosslinking in the 1 st network and the inorganic silicon borate bonds in the balance structure provide covalent dynamics; supermolecular dynamics are provided by side hydrogen bonding cross-linking in the 1 st and 2 nd networks.
In another embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of two networks (a sixth network structure), wherein the 1 st network is the first network structure; the 2 nd network contains common covalent crosslinking and inorganic silicon borate ester bond dynamic covalent crosslinking, but the side groups and the side chains do not contain the side hydrogen bond groups. In the network structure, the balance structure and the inorganic silicon borate bond in the balance structure are kept through common covalent crosslinking in the 1 st network and the 2 nd network to provide covalent dynamic property; supermolecular dynamics are provided by side hydrogen bonding cross-linking in network 1.
In another embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of two networks (seventh network structure), characterized in that the 1 st network is the first network structure; the 2 nd network contains inorganic silicon borate bond dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, wherein the supermolecule hydrogen bond crosslinking is realized by participation of side hydrogen bond groups existing on a polymer chain side group and/or a side chain framework. In the network structure, the balance structure and the inorganic silicon borate bond in the balance structure are kept through common covalent crosslinking in the 1 st network and the 2 nd network to provide covalent dynamic property; the supramolecular dynamics are provided by cross-linking of the side hydrogen bonds in network 1 and network 2.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of two networks (eighth network structure), wherein the 1 st network and the 2 nd network are both the structures described in the first network, but the 1 st and the 2 nd networks are not the same. Examples of such differences include differences in the main structure of the polymer chain, differences in the crosslinking density of covalent crosslinks, differences in the composition of the side groups and/or side chains of the polymer chain, differences in the hydrogen bonding groups on the side groups and/or side chains of the polymer chain, and the like. In this embodiment, the objective of precisely controlling the dynamic polymer properties can be achieved by adjusting the structure of the 1 st network and/or the 2 nd network.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of three networks (ninth network structure), wherein the 1 st network contains common covalent crosslinks and inorganic silicon borate bond dynamic covalent crosslinks, but the side groups and the side chains do not contain the side hydrogen bond groups; the 2 nd network does not contain common covalent crosslinking and dynamic covalent crosslinking, but side hydrogen bond groups exist on side groups and/or side chain skeletons of the polymer chains, and the side hydrogen bond groups participate in forming hydrogen bond crosslinking; the 3 rd network is the first network structure. In the network structure, the balance structure and the inorganic silicon borate ester bonds in the balance structure are maintained through common covalent crosslinking in the 1 st network and the 3 rd network, covalent dynamics are provided, and supermolecular dynamics are provided through side hydrogen bond crosslinking in the 2 nd network and the 3 rd network.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of three networks (tenth network structure), characterized in that the 1 st network contains inorganic silicon borate linkage dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, the supermolecule hydrogen bond crosslinking is realized by side hydrogen bond groups existing on polymer chain side groups and/or side chain skeletons, but does not contain common covalent crosslinking; the 2 nd network does not contain common covalent crosslinking and dynamic covalent crosslinking, but side hydrogen bond groups exist on side groups and/or side chains of the polymer chains, and the side hydrogen bond groups participate in forming hydrogen bond crosslinking; the 3 rd network is the first network structure. In the network structure, the equilibrium structure is maintained through common covalent crosslinking in the 3 rd network, covalent dynamics are provided through inorganic silicon borate bonds in the 1 st and 3 rd networks, and supermolecular dynamics are provided through side hydrogen bond crosslinking in the 1 st, 2 nd and 3 rd networks.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of three networks (tenth network structure), characterized in that network 1 contains inorganic silicon borate linkage dynamic covalent crosslinking and supermolecule hydrogen bond crosslinking, the supermolecule hydrogen bond crosslinking is realized by side hydrogen bond groups existing on polymer chain side groups and/or side chain skeletons, but common covalent crosslinking is not present; both networks 2 and 3 are the first network structure described, but networks 2 and 3 are different. In the network structure, the balance structure and the inorganic silicon borate bond in the balance structure are maintained through common covalent crosslinking in the 1 st, 2 nd and 3 rd networks to provide covalent dynamics, supermolecular dynamics are provided by side hydrogen bonding cross-linking in the 1 st and 3 rd networks.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of three networks (tenth network structure), wherein the 1 st network is a common covalent crosslinked network, and does not contain dynamic covalent bonds and hydrogen bonds; the 2 nd network is a dynamic covalent crosslinking network and does not contain hydrogen bond crosslinking; the 3 rd network is a hydrogen bond cross-linking network in which the side hydrogen bond groups participate, and does not contain dynamic covalent cross-linking and common covalent cross-linking. The three networks are independent and cooperate with each other.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of two networks (tenth three network structures), wherein the 1 st network is a common covalent crosslinked network, and does not contain dynamic covalent bonds and hydrogen bonds; the 2 nd network is a hydrogen bond crosslinking network which is formed by the participation of the side hydrogen bond groups, and does not contain dynamic covalent crosslinking and common covalent crosslinking; non-crosslinked dynamic covalent polymers containing dynamic covalent inorganic silicon borate linkages are dispersed in both networks. The 1 st network is used to provide an equilibrium structure, the 2 nd network is used to provide dynamic supramolecular cross-linking, and the non-cross-linked dynamic covalent polymer is used to provide additional viscosity.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of two networks (tenth network structure), characterized in that the 1 st network is a common covalent crosslinked network, and does not contain dynamic covalent bonds and hydrogen bonds; the 2 nd network is a dynamic covalent crosslinking network and does not contain hydrogen bond crosslinking and common covalent crosslinking; non-crosslinked supramolecular polymers containing side-hydrogen bonding are dispersed in both networks. The 1 st network is used to provide an equilibrium structure, the 2 nd network is used to provide dynamic covalent crosslinking, and the non-crosslinked dynamic supramolecular polymer is used to provide additional viscosity.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of one network (a tenth network structure), characterized in that the crosslinked network is a common covalent crosslinked network, and does not contain dynamic covalent crosslinking and hydrogen bonding crosslinking; non-crosslinked dynamic covalent polymers containing dynamic covalent inorganic silicon borate linkages and non-crosslinked dynamic supramolecular polymers containing pendant hydrogen bonds are dispersed in the network. Conventional covalent cross-linked networks are used to provide balanced structures and non-cross-linked dynamic covalent and supramolecular polymers are used to provide additional viscosity.
In another embodiment of the present invention, the hybrid crosslinked network dynamic polymer is composed of one network (tenth network structure), characterized in that the crosslinked network is a common covalent crosslinked network, and does not contain dynamic covalent crosslinking and hydrogen bonding crosslinking; non-crosslinked dynamic polymers containing both dynamic covalent inorganic silicon borate linkages and pendant hydrogen bonds are dispersed in the network. Conventional covalent cross-linked networks are used to provide balanced structures and non-cross-linked dynamic covalent and supramolecular polymers are used to provide additional viscosity.
In another embodiment of the present invention, the dynamic polymer of the hybrid crosslinked network is composed of one network (tenth network structure), characterized in that the crosslinked network is a common covalent crosslinked network and optionally contains hydrogen bond crosslinks with which the side hydrogen bonds are involved; the dynamic covalent polymer crosslinked by dynamic covalent inorganic silicon borate bonds is dispersed in the network in the form of particles, wherein the dynamic covalent polymer contains hydrogen bond crosslinking participated by the optional side hydrogen bonds. Conventional covalent cross-linked networks are used to provide an equilibrium structure, and the cross-linked dynamic covalent polymers are dispersed in the cross-linked network in the form of particles to provide additional viscosity and strength.
In addition to the seventeen hybrid crosslinked network structure embodiments described above, the present invention is capable of a wide variety of other hybrid crosslinked network structure embodiments, and in one embodiment may comprise three or more networks that are the same or different, and in the same network may comprise different common covalent crosslinks and/or different dynamic covalent crosslinks and/or different hydrogen bonds, and in the network structure may be dispersed/filled with non-crosslinked polymer components or crosslinked particles (including but not limited to fibers, flakes, and any suitable irregular shape) that contain dynamic covalent bonds and/or side hydrogen bonds. In special cases, the pendant hydrogen bonding groups within the covalently crosslinked network themselves cannot form hydrogen bonds with each other, and need to form hydrogen bonds with additional components added. Inorganic silicon borate linkages are used to provide covalent dynamic properties including, but not limited to, plasticity, self-healing, and dilatancy; the hydrogen bond action formed by the side hydrogen bond groups is used as reversible physical crosslinking to provide additional strength for the polymer, and on the one hand, the good dynamic performance of the polymer can be utilized to endow the polymer with the performances of stress/strain responsiveness, super toughness, self-repairing, shape memory and the like. Those skilled in the art may implement the logic and context of the present invention reasonably efficiently.
In the present invention, the number and distribution of the side hydrogen bond groups of the polymer are not limited. In particular, when the side hydrogen bond groups exist in the covalent cross-linked network, the number and the distribution of the side hydrogen bond groups on the polymer chain segment between two covalent cross-linked points are not limited, and the chain segment between any two covalent cross-linked points can contain the side hydrogen bond groups, or the chain segment between partial cross-linked points can contain the side hydrogen bond groups; on the segment between the covalent crosslinking points containing the pendant hydrogen bond groups, it is preferable that each segment contains not less than 2 of the pendant hydrogen bond groups, and it is more preferable that each segment contains not less than 5 of the pendant hydrogen bond groups; the number of the side hydrogen bond groups in the whole covalent cross-linked network is also not limited, and it is preferable that the average of the segments between the two covalent cross-linked points contains not less than 0.1 of the side hydrogen bond groups, more preferably not less than 1 of the side hydrogen bond groups.
Based on the dynamic and responsiveness of the dynamic covalent inorganic silicon borate bonds and hydrogen bonds, the dynamic polymers of the present invention may exhibit a wide variety of dynamic properties and responsiveness to external stimuli, including but not limited to self-healing, temperature responsiveness, stress/strain responsiveness, and in particular dilatant properties. When neither the inorganic silicon borate linkage nor the hydrogen bond co-acts with the common covalent cross-links and the co-action of the two does not produce cross-linked polymers, the dynamic polymer system does not contribute to elastic properties even when it is subject to dilatant behaviour under stress/strain, but only to increase the viscosity of the system, which phenomenon is beneficial for loss of mechanical energy through viscosity. When the crosslinking degree of any one of the inorganic silicon borate bond and the hydrogen bond reaches above the gel point, but the other one forms an independent non-crosslinked polymer, when the dynamic polymer system expands, the effect above the gel point is subjected to viscosity-elasticity conversion or elasticity enhancement, and the effect below the gel point is subjected to viscosity improvement, so that the damage to external force can be effectively reduced while the viscosity loss of external force occurs. When the crosslinking degree of the inorganic silicon borate ester bond and the hydrogen bond reaches above the gel point, the dynamic polymer system only generates viscosity-elasticity conversion or elasticity enhancement when expanding flow occurs, so that partial viscosity loss to external force can occur and the damage to external force can be reduced to the greatest extent. The different situations have features and advantages.
For simplicity of explanation, in the description of the present invention, the term "and/or" is used to indicate that the term may include three cases selected from the conjunction "and/or" previously described options, or from the conjunction "and/or" subsequently described options, or from the conjunction "and/or" previously and subsequently described options.
In an embodiment of the present invention, the inorganic silicon borate bond (B-O-Si) is formed by reacting an inorganic boron compound with a silicon-containing compound that contains a silicon hydroxyl group and/or a silicon hydroxyl group precursor.
The inorganic boron compound refers to a boron-containing compound in which boron atoms in the compound are not connected with carbon atoms through boron-carbon bonds.
The inorganic boron compound is selected from the group consisting of, but not limited to, boric acid esters, borates, boric anhydride, boron halides. The boric acid can be orthoboric acid, metaboric acid, tetraboric acid. The borate esters include alkyl and allyl borates/triorganoborates 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-t-butyl borate, tri-n-amyl borate, tri-sec-butyl borate, DL-menthyl borate, tris (4-chlorophenyl) borate, 2, 6-di-t-butyl-4-tolyldibutyl orthoborate, tris (2-methoxyethyl) borate, benzyl dihydroborate, diphenyl hydroborate, isopropyl pinacol borate, triethanolamine borate, and the like. Suitable boric anhydride units include those of the formula B 2 O 3 Typical boron oxides include, but are not limited to, trialkoxyboroxine and its derivatives, such as trimethoxyboroxine, triisopropoxyboroxine, 2' -oxybis [4, 6-trimethyl]-1,3, 2-dioxaboroxine and the like. Suitable borates include, but are not limited to, diammonium pentaborate, sodium tetraborate decahydrate (borax), potassium pentaborate, magnesium diborate, calcium monoborate, barium triborate, zinc metaborate, tripotassium borate, iron orthoborate salts. 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 hydrolysis products of the aforementioned borates. Typically, the inorganic boron compound is of the formula B 2 O 3 [ CAS registry #1303-86-2]Boron oxide of the formula H 3 BO 3 [ CAS registry #10043-35-3 ]]Is a boric acid of (2). As an example, a suitable inorganic boron compound has the chemical structural formula shown below, but the present invention is not limited thereto:
Figure SMS_4
the silicon-containing compound containing the silicon hydroxyl and/or the silicon hydroxyl precursor refers to any suitable compound containing the silicon hydroxyl and/or the silicon hydroxyl precursor in the structure of the compound. The silicon-containing compound is selected from small molecular silicon-containing compounds and large molecular silicon-containing compounds, which can be organic or inorganic compounds, including silica. The silicon-containing 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, star, dendritic, hyperbranched), two-dimensional/three-dimensional clusters, and combinations thereof. There may be a plurality of silicon-containing compounds in a dynamic covalent polymer, but the silicon-containing compounds of the present invention must satisfy at least some of the dynamic covalent polymers having hydrogen bonding groups thereon.
The silicon hydroxyl group refers to a structural element (Si-OH) consisting of a silicon atom and a hydroxyl group connected with the silicon atom, wherein the silicon hydroxyl group can be an organic silicon hydroxyl group (namely, the silicon atom in the silicon hydroxyl group is connected with at least one carbon atom through a silicon-carbon bond, and at least one organic group is connected with the silicon atom through the silicon-carbon bond), and can also be an inorganic silicon hydroxyl group (namely, the silicon atom in the silicon hydroxyl group is not connected with the organic group), and is preferably an organic silicon hydroxyl group. In the present invention, one hydroxyl (-OH) group in the silicon hydroxyl group is a functional group.
The silicon hydroxyl precursor in the invention refers to a structural element (Si-Z) consisting of a silicon atom and a group which is connected with the silicon atom and can be hydrolyzed to obtain hydroxyl, wherein Z is a group which can be hydrolyzed to obtain hydroxyl and can be selected from halogen, cyano, oxo-cyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide and the like. Suitable silicon hydroxyl precursors are, for example: si-Cl, si-CN, si-CNS, si-CNO, si-SO 4 CH 3 ， Si-OB(OCH 3 ) 2 ，Si-NH 2 ，Si-N(CH 3 ) 2 ，Si-OCH 3 ，Si-COCH 3 ，Si-OCOCH 3 ，Si-CONH 2 ， Si-O-N＝C(CH 3 ) 2 Si-ONa. In the present invention, one of the hydroxyl groups (-Z) of the silicon hydroxyl precursor that can be hydrolyzed to provide a hydroxyl group is a functional group.
In the present invention, the silicon-containing compound of the silicon-containing hydroxyl and/or silicon-hydroxyl precursor may be any suitable compound containing terminal and/or side groups of the silicon-hydroxyl and/or silicon-hydroxyl precursor, including small molecule and large molecule compounds, wherein the group or segment connecting the silicon-containing hydroxyl and/or silicon-hydroxyl precursor may be any suitable group or segment, including but not limited to carbon-based/carbon-chain structure, carbon-hetero-based/carbon-hetero-chain structure, carbon-elemental-based/carbon-elemental-chain structure, carbon-hetero-elemental-based/elemental-chain structure, hetero-elemental-based/hetero-elemental-chain structure. Wherein carbon group/carbon chain structure means that the group/chain backbone is composed of carbon atoms only; carbon heterogroup/carbon heterochain structure means that the group/chain backbone contains heteroatoms in addition to carbon atoms, wherein the heteroatoms include, but are not limited to, oxygen, nitrogen, sulfur; a carbon element group/carbon element chain structure refers to a group/chain backbone containing elemental atoms in addition to carbon atoms, wherein the elemental atoms include, but are not limited to P, si, se, ni, co, pt, ru, ti, al, ir; a carbon heteroatom group/carbon heteroatom chain structure refers to a group/chain backbone containing heteroatoms and elemental atoms in addition to carbon atoms; an elemental group/elemental chain structure refers to a group/chain backbone containing only elemental atoms; the hetero element group/element hetero chain structure means that the group/chain structure contains only an element atom and a hetero atom.
Suitable silicon-containing compounds of the silicon-hydroxyl-containing and/or silicon-hydroxyl-containing precursors can be exemplified as follows, the invention being not limited thereto:
Figure SMS_5
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Figure SMS_6
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Figure SMS_7
wherein m, n, x, y, z is the number of repeating units and may be a fixed value or an average value.
In the present invention, any suitable combination of an inorganic boron compound and a silicon-containing compound of a silicon-containing hydroxyl group and/or a silicon-containing hydroxyl group precursor may be used to form an inorganic silicon borate bond, and preferably, an inorganic boric acid and a silicon-containing macromolecular compound of a silicon-containing hydroxyl group precursor, an inorganic boric acid ester (salt) and a silicon-containing macromolecular compound are used to form an inorganic silicon borate bond, and more preferably, an inorganic boric acid and a silicon-containing macromolecular compound, an inorganic boric acid ester and a silicon-containing macromolecular compound are used to form an inorganic silicon borate bond, and even more preferably, an inorganic boric acid ester and a silicon-containing macromolecular compound are used to form an inorganic silicon borate bond.
In embodiments of the present invention, the dynamic polymer may be obtained by forming an inorganic silicon borate linkage, or a compound containing the inorganic silicon borate linkage may be prepared first and then polymerized/crosslinked/blended to form the dynamic polymer. In the present invention, based on the polyvalent nature of Si atoms, at most three B-O-Si atoms can be formed by one Si atom participating in the formation of B-O-Si on the silicon-containing compound containing a linking group, which shares one Si atom; moreover, since the boron atom is trivalent, the inorganic silicon borate generated in the polymerization process can easily cause branching and can be further crosslinked.
In the present invention, any polymer/segment of any other starting material, dynamic polymer composition, other than the silicon-containing compound, may have any suitable topology including, but not limited to, linear, cyclic (including, but not limited to, monocyclic, polycyclic, nested, bridged), branched (including, but not limited to, star-shaped, H-shaped, comb-shaped, dendritic, hyperbranched), two-dimensional/three-dimensional clusters, three-dimensional infinite network cross-linked structures, and combinations of the foregoing. The polymer chain has side group, side chain and branched chain, and the side group, side chain and branched chain can be continuously provided with side group, side chain and branched chain, i.e. can have a multi-stage structure.
In the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. If the number of teeth of the hydrogen bond is large, the strength is large, the dynamic property of the hydrogen bond crosslinking is weak, and the effects of promoting the dynamic polymer to keep a balance structure and improving the mechanical properties (modulus and strength) can be achieved. If the number of teeth of the hydrogen bond is small, the strength is low, the dynamic property of the hydrogen bond crosslinking is strong, and the dynamic property such as self-repairing property, energy absorption property and the like can be provided together with the dynamic covalent inorganic silicon borate bond. In embodiments of the invention, hydrogen bonds of no more than four teeth are preferred as crosslinks.
The number of teeth is the number of hydrogen bonds formed by the donor (D, i.e., hydrogen atom) of the pendant hydrogen bond group and (a, i.e., electronegative atom that accepts the hydrogen atom), each D-a combination is a single tooth (the hydrogen bond formation of the single, double and triple tooth hydrogen bond groups are exemplified by the following formulas).
Figure SMS_8
In embodiments of the present invention, the pendant hydrogen bond groups may be any suitable hydrogen bond groups. Preferably, there is both a hydrogen bond acceptor and a hydrogen bond donor within one of the pendant hydrogen bond groups; it is also possible that part of the side hydrogen bond groups contain hydrogen bond donors and the other part of the side hydrogen bond groups contain hydrogen bond acceptors; most preferably both acceptor and donor.
The acceptor of the side hydrogen bond group in the present invention preferably contains at least one of structures represented by the following general formula (1),
Figure SMS_9
wherein, the liquid crystal display device comprises a liquid crystal display device, A is selected from oxygen atom and sulfur atom; d is selected from nitrogen atoms and C-R groups; x is a halogen atom;
Figure SMS_10
selected from any suitable atom, group, segment, cluster; wherein R is selected from hydrogen atom, substituent atom and substituent group.
In the case of the substituent, the number of carbon atoms of R is not particularly limited, and is preferably 1 to 20, more preferably 1 to 10.
When used as a substituent, the structure of R is not particularly limited, including but not limited to a linear structure, a branched structure containing pendant groups, or a cyclic structure. The cyclic structure is not particularly limited, and may be selected from aliphatic rings, aromatic rings, sugar rings, and condensed rings, and aliphatic rings are preferable.
When used as a substituent, R may or may not contain a heteroatom.
R is selected from hydrogen atom, halogen atom, C 1-20 Hydrocarbon radicals, C 1-20 Heterohydrocarbyl, substituted C 1-20 Hydrocarbyl or substituted heterohydrocarbyl. The substituent atom or substituent in R is not particularly limited, and is selected from any one of a halogen atom, a hydrocarbon substituent, and a heteroatom-containing substituent.
R is more preferably a hydrogen atom, a halogen atom, or C 1-20 Alkyl, C 1-20 Alkenyl, aryl, aralkyl, C 1-20 Aliphatic, heteroaryl, heteroaromatic, C 1-20 Alkoxyacyl, aryloxyacyl, C 1-20 Any atom or group of an alkylthio acyl group, an arylthio acyl group, or a substituted version of any group.
Specifically, R may be selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, an allyl group, a propenyl group, a vinyl group, a phenyl group, a methylphenyl group, a butylphenyl group, a benzyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group, an ethylthiocarbonyl group, an ethylaminocarbonyl group, a benzylaminocarbonyl group, a methoxythiocarbonyl group, an ethoxythiocarbonyl group, a phenoxythiocarbonyl group, a benzylthiocarbonyl group, a substituted C 1-20 Alkyl, substituted C 1-20 Alkenyl, substituted aryl, substituted aromatic hydrocarbon base and substituted C 1-20 Aliphatic hetero hydrocarbon group, substituted heteroaryl group and substituted hetero aromatic hydrocarbonRadical, substituted C 1-20 Alkoxycarbonyl, substituted aryloxycarbonyl, substituted C 1-20 Alkylthiocarbonyl, substituted arylthiocarbonyl-substituted C 1-20 Alkoxythiocarbonyl, substituted aryloxycarbonyl, substituted C 1-20 Any one of an atom or group of alkylthio thiocarbonyl, substituted arylthio thiocarbonyl and the like. Wherein butyl includes, but is not limited to, n-butyl, t-butyl. Octyl groups include, but are not limited to, n-octyl, 2-ethylhexyl. Wherein the substituent atom or substituent is selected from any one of halogen atom, hydrocarbyl substituent and heteroatom-containing substituent.
The donor of the side hydrogen bond group in the present invention preferably contains at least one of structures represented by the following general formula (2),
Figure SMS_11
the structures represented by the general formulae (1) and (2) may be a side group, a terminal group, a linear structure, a branched structure containing a side group, a cyclic structure, or the like. The annular structure can be a single-ring structure, a multi-ring structure, a spiro structure, a condensed ring structure, a bridge ring structure, a nested ring structure and the like.
In an embodiment of the present invention, the side hydrogen bond group preferably contains both structures represented by the general formulae (1) and (2). According to the effect of the present invention, the side hydrogen bond group is preferably selected from the group consisting of amide group, carbamate group, thiocarbamate group, urea group, pyrazole, imidazole, imidazoline, triazole, purine, porphyrin, and derivatives thereof.
Suitable pendant and/or side-chain (including branched/bifurcated) skeletons include, for example, but the invention is not limited thereto:
Figure SMS_12
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Figure SMS_13
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Figure SMS_14
where m and n are the number of repeating units, which may be a fixed value or an average value, preferably less than 20, more preferably less than 5.
The terminal hydrogen bond groups may be identical to the pendant hydrogen bond groups. In addition, suitable backbone skeleton hydrogen bonding groups on both crosslinked and uncrosslinked backbone skeletons can be exemplified as, but the invention is not limited to, this:
Figure SMS_15
in the present invention, the same polymer may contain more than one of the above-mentioned side hydrogen bond groups, the same network may contain more than one of the above-mentioned side hydrogen bond groups, and other optional hydrogen bond groups. The compound into which the side hydrogen bond group and optionally other hydrogen bond groups can be introduced is not particularly limited, and the type and mode of reaction for forming the hydrogen bond groups are also not particularly limited. For example: formed by covalent reactions between carboxyl groups, acyl halide groups, anhydride groups, ester groups, amide groups, isocyanate groups and amino groups; formed by covalent reaction between isocyanate groups and hydroxyl, mercapto and carboxyl groups; formed by covalent reactions between succinimide groups and amino, hydroxyl, sulfhydryl groups.
In the present invention, the supramolecular hydrogen bonding crosslinks in the crosslinked network may have any suitable degree of crosslinking, either above or below its gel point. The supermolecule hydrogen bond crosslinking can be generated in the process of dynamic covalent crosslinking of the dynamic polymer; or the dynamic covalent crosslinking can be carried out after the supermolecule hydrogen bond crosslinking is generated in advance; the supramolecular hydrogen bonding crosslinks may also be generated during the subsequent shaping of the dynamic polymer after the dynamic covalent crosslinks are formed, but the invention is not limited thereto.
In an embodiment of the present invention, the dynamic polymer composition having the hybrid cross-linked structure may be in the form of a general solid, an elastomer, a gel (including hydrogel, organogel, oligomer-swollen gel, plasticizer-swollen gel, ionic liquid-swollen gel), a foam, or the like, wherein the content of the soluble small molecular weight component contained in the general solid and the solid foam is generally not higher than 10wt%, and the content of the small molecular weight component contained in the gel is generally not lower than 50wt%. The common solid has the advantage of high strength, is relatively fixed in shape and volume, has high density, and is suitable for high-strength explosion-proof walls or instrument shells; the elastomer has the general property of common solid, but has better elasticity, better softness and better energy absorption performances such as damping, shock absorption, sound insulation, noise elimination and the like; the gel has the advantage of softness, has better energy absorption and elasticity, and is suitable for preparing high-damping energy absorption materials; the foam has the advantages of low density, light weight, high specific strength and the like, and the soft foam material also has good elasticity and energy absorption.
In an embodiment of the present invention, the dynamic polymer gel may be obtained by crosslinking in a swelling agent (including one of water, an organic solvent, an oligomer, a plasticizer, an ionic liquid, or a combination thereof), or may be obtained by swelling with a swelling agent after the completion of the preparation of the dynamic polymer. Of course the number of the devices to be used, the present invention is not limited in this regard, those skilled in the art may implement the logic and context of the present invention, and the method is reasonably and effectively realized.
In the preparation process of the dynamic polymer foaming material, three methods of a mechanical foaming method, a physical foaming method and a chemical foaming method are mainly adopted to foam the dynamic polymer.
The mechanical foaming method is to introduce a large amount of air or other gases into emulsion, suspension or solution of the polymer by strong stirring in the preparation process of the dynamic polymer to form a uniform foam body, and then to gel and solidify the foam body by physical or chemical change to form the foam material. Air may be introduced and emulsifiers or surfactants may be added to shorten the molding cycle.
Wherein the physical foaming method realizes the foaming of the polymer by utilizing the physical principle in the preparation process of the dynamic polymer, it generally comprises the following five methods: (1) Inert gas foaming, namely, pressing inert gas into a molten polymer or pasty material under the condition of pressurization, and then reducing the pressure and heating to expand the dissolved gas for foaming; (2) Evaporating, gasifying and foaming by utilizing low-boiling point liquid, namely pressing the low-boiling point liquid into a polymer or dissolving the liquid into polymer particles under certain pressure and temperature conditions, and then heating and softening the polymer, so that the liquid is evaporated, gasified and foamed; (3) The dissolution method is to dissolve the solid substances added in advance by immersing the polymer in the liquid medium, so that a large number of pores appear in the polymer to form a foam shape, for example, soluble substances such as salt, starch and the like are firstly mixed with the polymer, after the soluble substances are molded into products, the products are placed in water for repeated treatment, and the soluble substances are dissolved out, thus obtaining the open-cell foam products; (4) Hollow microsphere method, namely adding hollow microspheres into polymer, and curing to form closed cell foam; (5) Freeze drying, i.e. forming gel or swelled body, and freeze drying to obtain foam. Among them, foaming is preferably carried out by a method of dissolving an inert gas and a low boiling point liquid in a polymer. The adoption of the physical foaming method has the advantages of low toxicity in operation, low cost of foaming raw materials, no residue of foaming agent and the like.
Wherein, the chemical foaming method is a foaming method which generates gas along with chemical reaction in the foaming process of dynamic polymer, and generally comprises the following two methods: (1) The thermal decomposition type foaming agent foaming method is to foam the gas decomposed and released after heating by using a chemical foaming agent. (2) Foaming processes in which interactions between polymer components produce a gas, i.e., the foaming of a polymer by the expansion of the polymer by the chemical reaction between two or more components in a foaming system to produce an inert gas, such as carbon dioxide or nitrogen. In the foaming process, in order to control the balance of polymerization reaction and foaming reaction, a small amount of catalyst and foam stabilizer (or surfactant) are generally added to ensure good quality of the product. Among them, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.
In the preparation process of the dynamic polymer, three methods of compression molding foaming molding, injection foaming molding and extrusion foaming molding are mainly adopted to mold the dynamic polymer foam material.
The compression molding foaming molding process is simple and easy to control, and can be divided into a one-step method and a two-step method. The one-step molding refers to that the mixed materials are directly put into a mold cavity for foam molding; the two-step method is to pre-foam the mixed materials, and then put the materials into a die cavity for foam molding. Among them, the one-step method is preferable because the one-step method is more convenient to operate and has higher production efficiency than the two-step method.
The process and the equipment are similar to those of the common injection molding, the material is heated and rubbed to be in a melt state after being added into a screw in the bubble nucleation stage, the foaming agent is injected into the melt of the material through a control valve of a metering valve at a certain flow rate, and then the foaming agent is uniformly mixed through a mixing element at the head of the screw, so that bubble nuclei are formed under the action of the nucleating agent. The expansion stage and the solidification and shaping stage both occur after the die cavity is filled, and when the pressure of the die cavity is reduced, the expansion process of the bubble nucleus occurs, and the bubble body is solidified and shaped along with the cooling of the die.
The extrusion foaming molding process and equipment are similar to those of the common extrusion molding, the foaming agent is added into an extruder before or during extrusion, the pressure of a melt flowing through a machine head is reduced, and the foaming agent volatilizes to form a required foaming structure. The foam molding technology is the most widely used foam molding technology at present, because the foam molding technology not only can realize continuous production, but also is more competitive in cost than injection foam molding.
In the preparation of the dynamic polymer, a person skilled in the art can select a proper foaming method and a foam molding method according to the actual preparation condition and the performance of the target polymer to prepare the dynamic polymer foam.
In an embodiment of the present invention, the structure of the dynamic polymer foam material relates to three of an open cell structure, a closed cell structure, and a half-open and half-closed structure. In the open pore structure, the cells are mutually communicated or completely communicated, and the single dimension or three dimensions can pass through gas or liquid, and the pore diameter of the cells is 0.01-3 mm. The closed cell structure has an independent cell structure, the inner cells are separated from the cells by wall membranes, most of the cells are not mutually communicated, and the pore diameters of the cells are 0.01-3 mm. The contained foam holes are of semi-open structures with structures which are not communicated with each other. For the foam structure which has formed closed cells, it can also be made into an open cell structure by mechanical pressure or chemical method, and the person skilled in the art can choose according to the actual need.
In embodiments of the present invention, dynamic polymer foams are classified by their hardness into three categories, soft, hard and semi-hard: (1) A flexible foam having an elastic modulus of less than 70MPa at 23 ℃ and 50% relative humidity; (2) Rigid foam having an elastic modulus greater than 700MPa at 23 ℃ and 50% relative humidity; (3) Semi-rigid (or semi-flexible) foams, foams between the two classes, have an elastic modulus between 70MPa and 700 MPa.
In embodiments of the present invention, dynamic polymer foams can be further classified into low foaming, medium foaming and high foaming according to their density. Low foaming foam material having a density greater than 0.4g/cm 3 The foaming multiplying power is less than 1.5; a density of 0.1 to 0.4g/cm 3 The foaming multiplying power is 1.5-9; while the high foaming foam material has a density of less than 0.1g/cm 3 The foaming ratio is more than 9.
The raw material formula components for preparing the dynamic polymer comprise other polymers, auxiliary agents and fillers which can be added/used in addition to the inorganic boron compound and the silicon-containing compound, and the added/used substances can be used together with the reaction product of the inorganic boron compound and the silicon-containing compound in a blending and chemical reaction mode to serve as the dynamic polymer formula components with a hybrid cross-linking structure or play a role in improving the processing performance in the preparation process of the dynamic polymer.
The additive/usable other polymers can be used as additives to improve the material performance, endow the material with new performance, improve the material use and economic benefit and achieve the effect of comprehensive material utilization. Other polymers which may be added/used may be selected from natural high molecular compounds, synthetic resins, synthetic rubbers, synthetic fibers. The properties and the molecular weight of the added polymer are not limited, and can be oligomer or high polymer according to the different molecular weights, and can be homopolymer or copolymer according to the different polymerization forms, and the properties and the actual preparation process of the target material can be selected in the specific use process.
When the other polymers that can be added/used are selected from natural high molecular compounds, it can be selected from any one or more of the following natural high molecular compounds: natural rubber, chitosan, chitin, natural protein, etc.
When the other polymer that can be added/used is selected from synthetic resins, it may be selected from any one or any several of the following synthetic resins: polytrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, polyvinylidene chloride, low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polybenzimidazole, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene glycol, polyester, polyethersulfone, polyarylsulfone, polyetheretherketone, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polyacrylate, polyacrylonitrile, polyphenylene oxide, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, high impact polystyrene, polysulfone, polytetrafluoroethylene, polyurethane, polyurea, polyvinyl acetate, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-acrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl chloride-vinyl acetate copolymer, polyvinylpyrrolidone, epoxy resin, phenolic resin, urea resin, unsaturated polyester, and the like.
When the other polymer that can be added/used is selected from synthetic rubbers, it may be selected from any one or any of the following synthetic rubbers: isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, fluoro rubber, polyacrylate rubber, polyurethane rubber, epichlorohydrin rubber, thermoplastic elastomer, and the like.
When the other polymer that can be added/used is selected from synthetic fibers, it can be selected from any one or any several of the following synthetic fibers: viscose fibers, cuprammonium fibers, diethyl fibers, triethyl fibers, polyamide fibers, polyester fibers, polyurethane fibers, polyacrylonitriles fibers, polyvinyl chloride fibers, polyolefin fibers, fluorine-containing fibers, and the like.
Other polymers that may be added/used in the preparation of the polymeric 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, polyurethane rubber, thermoplastic elastomer.
The additive can improve the material preparation process, improve the product quality and yield, reduce the product cost or endow the product with a certain specific application property. The additive/usable auxiliary agent is selected from any one or more of the following auxiliary agents: synthesis aids including catalysts, initiators; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; auxiliary agents for improving mechanical properties, including chain extenders, toughening agents and coupling agents; auxiliary agents for improving processability, including lubricants and release agents; the softening and light auxiliary agent comprises a plasticizer, a foaming agent and a dynamic regulator; adjuvants for modifying surface properties, including antistatic agents, emulsifiers, dispersants; auxiliary agents for changing the color light, including colorants, fluorescent whitening agents, matting agents; flame retardant and smoke suppressant additives, including flame retardants; other auxiliary agents, including nucleating agents, rheology agents, thickeners, leveling agents.
The catalyst in the auxiliary agent can be used for preparing the catalyst by changing the reaction path,the reaction activation energy is reduced to accelerate the reaction rate of the reactants during the reaction. In an embodiment of the invention, the catalyst includes, but is not limited to: (1) catalyst for polyurethane synthesis: amine catalysts such as triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethyl-propylenediamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N, N, N ' -trimethyl-N ' -hydroxyethyl-diamine-ethyl ether, tetramethyl-dipropylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N ' -tetramethyl-alkylenediamine, N, N, N ', N ', N ' -pentamethyldiethylenetriamine, N, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hydroxypropyl hexanoic acid, N, N-dimethylbenzylamine, N, N-dimethylhexadecylamine, and the like; organometallic catalysts such as stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, zinc isooctanoate, lead isooctanoate, potassium oleate, zinc naphthenate, cobalt naphthenate, iron acetylacetonate, phenylmercuric acetate, phenylmercuric propionate, bismuth naphthenate, sodium methoxide, potassium octoate, potassium oleate, calcium carbonate, and the like. (2) catalyst for polyolefin synthesis: such as Ziegler-Natta catalysts, pi-allylnickel, alkyllithium catalysts, metallocene catalysts, diethylaluminum monochloride, titanium tetrachloride, titanium trichloride, boron trifluoride etherate, magnesium oxide, dimethylamine, cuprous chloride, triethylamine, sodium tetraphenylborate, antimony trioxide, aluminum sesquichloride, vanadium oxychloride, triisobutylaluminum, nickel naphthenate, rare earth naphthenate, and the like. (3) The CuAAC reaction is co-catalyzed by monovalent copper compounds and amine ligands. The monovalent copper compound may be selected from Cu (I) salts, such as CuCl, cuBr, cuI, cuCN, cuOAc, etc.; or Cu (I) complexes, e.g. [ Cu (CH) 3 CN) 4 ]PF 6 、[Cu(CH 3 CN) 4 ]OTf、CuBr(PPh 3 ) 3 Etc.; it is also possible to use elemental copper and divalent copper compounds (such as CuSO 4 、Cu(OAc) 2 ) Generated in situ during the reaction process; wherein Cu (I) salt is preferably CuBr and CuI, and Cu (I) complex is preferably CuBr (PPh) 3 ) 3 . The amine ligand may be selected from the group consisting of tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tri[ (1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium hydrophosphate, etc.; among them, preferred amine ligands are TBTA and TTTA. (4) thio-ene reaction catalyst: photocatalysts such as benzoin dimethyl ether, 2-hydroxy-2-methylphenylacetone, 2-dimethoxy-2-phenylacetophenone, and the like; nucleophilic reagent catalysts such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine, and the like. The amount of the catalyst used is not particularly limited and is generally 0.01 to 2wt%.
The initiator in the additive/additive agent can be used for inducing the activation of monomer molecules to generate free radicals during the polymerization reaction, improving the reaction rate and promoting the reaction, including but not limited to any one or any several of the following initiators: organic peroxides such as lauroyl peroxide, benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butylperoxide, dicumyl hydroperoxide; azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; among them, preferred are lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile and potassium persulfate. The amount of the initiator used is not particularly limited, but is generally 0.1 to 1% by weight.
The antioxidant in the additive/the additive can delay the oxidation process of a polymer sample, ensure that the material can be successfully prepared and processed and the service life of the material is prolonged, and comprises any one or more antioxidants as follows: blocked phenols such as 2, 6-di-tert-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 2' -methylenebis (4-methyl-6-tert-butylphenol); sulfur-containing hindered phenols such as 4,4 '-thiobis- [ 3-methyl-6-t-butylphenol ], 2' -thiobis- [ 4-methyl-6-t-butylphenol ]; triazine-based hindered phenols such as 1,3, 5-bis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] -hexahydro s-triazine; blocked phenols of the trimeric isocyanate type, such as tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -triisocyanate; amines such as N, N ' -di (β -naphthyl) p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine; sulfur-containing compounds such as dilauryl thiodipropionate, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole; phosphites such as triphenyl phosphite, trisnonylphenyl phosphite, tris [ 2.4-di-t-butylphenyl ] phosphite, and the like; among them, preferred antioxidants include Tea Polyphenol (TP), butyl Hydroxy Anisole (BHA), dibutyl hydroxy toluene (BHT), tert-butyl hydroquinone (TBHQ), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168), and tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester (antioxidant 1010). The amount of the antioxidant used is not particularly limited, but is generally 0.01 to 1wt%.
The light stabilizer in the additive/usable auxiliary agent can prevent the polymer sample from photo-aging and prolong the service life of the polymer sample, and comprises any one or any several light stabilizers as follows: light-shielding agents such as carbon black, titanium dioxide, zinc oxide, and calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3, 5-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4, 6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3, 5-s-triazine, 2-cyano-3, 3-diphenylacrylic acid 2-ethylhexyl ester; precursor ultraviolet ray absorbers such as p-tert-butylphenyl salicylate, bisphenol A bis-salicylate; ultraviolet quenchers such as monoethyl bis (3, 5-di-t-butyl-4-hydroxybenzylphosphonate), 2' -thiobis (4-t-octylphenoloxy) nickel; a hindered amine light stabilizer is used in the preparation of a light stabilizer, such as bis (2, 6-tetramethylpiperidine) sebacate, 2, 6-tetramethylpiperidine benzoate tris (1, 2, 6-pentamethylpiperidinyl) phosphite; other light stabilizers such as (2, 4-di-t-butylphenyl) 3, 5-di-t-butyl-4-hydroxybenzoate, alkylphosphamide, zinc N, N '-di-N-butyldithiocarbamate, nickel N, N' -di-N-butyldithiocarbamate, etc.; among them, carbon black and bis (2, 6-tetramethylpiperidine) sebacate (light stabilizer 770) are preferable as the light stabilizer. The amount of the light stabilizer used is not particularly limited, but is generally 0.01 to 0.5wt%.
The heat stabilizer in the additive/the additive can prevent the polymer sample from being chemically changed due to heat in the processing or using process or delay the change to achieve the purpose of prolonging the service life, and the heat stabilizer comprises any one or any several of the following heat stabilizers: lead salts such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead phthalate, tribasic lead maleate, basic lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, and silica gel coprecipitated lead silicate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, and zinc stearate; organotin compounds such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di-n-butyltin maleate, di-n-octyltin mono-n-octyltin dimaleate, isooctyl di-n-octyltin dimercaptoacetate, genins-C-102, isooctyl dimercaptoacetate, dimethyl tin dithiol and their complexes; antimony stabilizers, such as antimony mercaptides, antimony mercaptoacetates, antimony mercaptocarboxylates, antimony carboxylates; epoxy compounds such as epoxidized oils, epoxidized fatty acid esters, and epoxy resins; phosphites, such as triaryl phosphites, trialkyl phosphites, triaryl alkyl phosphites, alkylaryl mixed esters, polymeric phosphites; polyols such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; among them, barium stearate, calcium stearate, di-n-butyltin dilaurate, and di-n-butyltin maleate are preferable as the heat stabilizer. The amount of the heat stabilizer used is not particularly limited, but is generally 0.1 to 0.5wt%.
The cross-linking agent in the auxiliary agent is matched with a reactant component which needs to be cross-linked in the dynamic polymer for use, can play a role of bridging among linear polymer molecules, enables a plurality of linear molecules to be mutually bonded and cross-linked into a network structure, can further increase the cross-linking density and the cross-linking strength of the polymer, improves the heat resistance and the service life of the polymer, and simultaneously improves the mechanical property and the weather resistance of the material, and comprises any one or any several cross-linking agents as follows: polypropylene glycol glycidyl ether, zinc oxide, aluminum chloride, aluminum sulfate, chromium nitrate, ethyl orthosilicate, methyl orthosilicate, p-toluenesulfonic acid, p-toluenesulfonyl chloride, 1, 4-butanediol diacrylate, ethylene glycol dimethacrylate, butyl acrylate, aluminum isopropoxide, zinc acetate, titanium acetylacetonate, aziridine, isocyanate, phenolic resin, hexamethylenetetramine, dicumyl peroxide, lauroyl peroxide, stearoyl peroxide, benzoyl peroxide, cyclohexanone peroxide, acetophenone peroxide, di-t-butyl phthalate, cumene hydroperoxide, vinyl tri-t-butylperoxy silane, diphenyl-di-t-butylperoxy silane, trimethyl t-butylperoxy silane, and the like. Among them, dicumyl peroxide (DCP), benzoyl Peroxide (BPO), and 2, 4-dichlorobenzoyl peroxide (DCBP) are preferable as the crosslinking agent. The amount of the crosslinking agent used is not particularly limited and is generally 0.1 to 5% by weight.
The curing agent in the auxiliary agent is used by being matched with a reactant component which needs to be cured in the dynamic polymer, can promote or control the curing reaction of the reactant component in the polymerization process, and comprises any one or any several curing agents of the following: amine curing agents such as ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminopropylamine, hexamethylenetetramine, m-phenylenediamine; anhydride-based curing agents such as phthalic anhydride, maleic anhydride, pyromellitic dianhydride; amide-based curing agents, such as low molecular polyamides; imidazoles, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole; boron trifluoride complex, and the like. Among them, ethylenediamine (EDA), diethylenetriamine (DETA), phthalic anhydride and maleic anhydride are preferable, and the amount of the curing agent used is not particularly limited, and is generally 0.5 to 1% by weight.
The chain extender of the additive/utilizable auxiliary agent can react with the reactive groups on the reactant molecular chain to expand the molecular chain and increase the molecular weight, and is generally used for preparing the additive polyurethane/polyurea, and comprises any one or any several of the following chain extenders: polyhydric alcohol chain extenders such as ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, 1, 4-butanediol, 1, 6-hexanediol, hydroquinone dihydroxyethyl ether (HQEE), resorcinol bishydroxyethyl ether (HER), p-bishydroxyethyl bisphenol a; polyamine chain extenders such as diaminotoluene, diaminoxylene, tetramethylxylylenediamine, tetraethyldiphenylenediamine, tetraisopropyldiphenylenediamine, m-phenylenediamine, tris (dimethylaminomethyl) phenol, diaminodiphenylmethane, 3 '-dichloro-4, 4' -diphenylmethanediamine (MOCA), 3, 5-dimethylthiotolylenediamine (DMTDA), 3, 5-diethyltoluenediamine (DETDA), 1,3, 5-triethyl-2, 6-diaminobenzene (TEMPDA); alcoholic amine chain extenders such as triethanolamine, triisopropanolamine, N' -bis (2-hydroxypropyl) aniline. The amount of the chain extender used is not particularly limited and is generally 1 to 20% by weight.
The toughening agent in the additive/usable auxiliary agent can reduce brittleness of the polymer sample, increase toughness and improve material bearing strength, and comprises any one or any several toughening agents including but not limited to: methyl methacrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin, and modified products thereof, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene rubber, ethylene-propylene-diene rubber, cis-butadiene rubber, styrene-butadiene-styrene block copolymer, and the like; among them, ethylene-propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS), chlorinated polyethylene resin (CPE) are preferable as the toughening agent. The amount of the toughening agent used is not particularly limited and is generally 5 to 10wt%.
The coupling agent in the additive/usable auxiliary agent can improve the interface performance of a polymer sample and an inorganic filler or a reinforcing material, reduce the viscosity of a material melt in the plastic processing process, improve the dispersity of the filler so as to improve the processing performance, and further enable the product to obtain good surface quality and mechanical, thermal and electrical properties, and comprises any one or more of the following coupling agents: organic acid chromium complexes, silane coupling agents, titanate coupling agents, sulfonyl azide coupling agents, aluminate coupling agents, and the like; among them, preferred are γ -aminopropyl triethoxysilane (silane coupling agent KH 550) and γ - (2, 3-glycidoxy) propyltrimethoxysilane (silane coupling agent KH 560). The amount of the coupling agent used is not particularly limited, and is generally 0.5 to 2wt%.
The lubricant in the additive/usable auxiliary agent can improve the lubricity of the polymer sample, reduce friction and reduce interfacial adhesion, and comprises any one or any several of the following lubricants: saturated hydrocarbons and halogenated hydrocarbons such as paraffin wax, microcrystalline wax, liquid paraffin wax, 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 stearamide or stearamide, oleamide or oleamide, erucamide, N' -ethylenebisstearamide; fatty alcohols and polyols, such as stearyl alcohol, cetyl alcohol, pentaerythritol; metal soaps such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, and the like; among them, the lubricant is preferably paraffin wax, liquid paraffin, stearic acid, and low molecular weight polyethylene. The amount of the lubricant used is not particularly limited and is generally 0.5 to 1wt%.
The release agent in the additive/the additive can be used for facilitating the release of the polymer sample, has smooth and clean surface and comprises any one or any several of the following release agents: paraffin, soaps, simethicone, ethyl silicone oil, tolyl silicone oil, castor oil, used engine oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicone rubber, and the like; wherein, the release agent is preferably dimethyl silicone oil or polyethylene glycol. The amount of the release agent used is not particularly limited, but is generally 0.5 to 2wt%.
The plasticizer in the additive/usable auxiliary agent can increase the plasticity of the polymer sample, so that the rigidity, modulus, softening temperature and embrittlement temperature of the polymer are reduced, and the polymer is elongatedIncreased rate, flexibility and pliability, including but not limited to any one or any of the following plasticizers: phthalates: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butyl benzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphates such as tricresyl phosphate, 2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds such as epoxyglycerides, epoxyfatty acid monoesters, epoxytetrahydrophthalate, epoxysoybean oil, epoxystearic acid (2-ethyl) hexyl ester, epoxysoybean oleic acid 2-ethylhexyl ester, 4, 5-epoxytetrahydrophthalate di (2-ethyl) hexyl ester, and cycloxaprine acetyl ricinoleic acid methyl ester; glycol lipids, e.g. C 5～9 Glycol acid ester, C 5～9 Triethylene glycol acid diacetate; chlorine-containing compounds such as greening paraffins and chlorinated fatty acid esters; polyesters such as 1, 2-propanediol-based polyester oxalate, 1, 2-propanediol polyester sebacate, phenyl petroleum sulfonate, trimellitate, citrate, dipentaerythritol ester and the like; among them, dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), tricresyl phosphate (TCP) are preferable as the plasticizer. The amount of plasticizer used is not particularly limited, and is generally 5 to 20wt%.
The foaming agent in the additive/additive can foam the polymer sample into pores, so as to obtain a light, heat-insulating, sound-insulating and elastic polymer material, which comprises any one or any several foaming agents of the following: physical blowing agents such as propane, methyl ether, pentane, neopentane, hexane, isopentane, heptane, isoheptane, petroleum ether, acetone, benzene, toluene, butane, diethyl ether, methyl chloride, methylene chloride, ethylene dichloride, dichlorodifluoromethane, trifluorochloromethane; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate; organic blowing agents, such as N, N ' -dinitropentamethylene tetramine, N ' -dimethyl-N, N ' -dinitroso terephthalamide, azodicarbonamide, barium azodicarbonate, diisopropyl azodicarbonate, potassium azodicarbonamide formate, azodiisobutyronitrile, 4' -oxybis-benzenesulfonyl hydrazide, trihydrazinotriazine, p-toluenesulfonyl semicarbazide, biphenyl-4, 4' -disulfonyl azide; foaming accelerators such as urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc oxide; foaming inhibitors such as maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalene diphenol, aliphatic amines, amides, oximes, isocyanates, thiols, thiophenols, thioureas, sulfides, sulfones, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, and the like. Among them, sodium hydrogencarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N ' -dinitropentamethylene tetramine (foaming agent H), N ' -dimethyl-N, N ' -dinitroso terephthalamide (foaming agent NTA) are preferable as the foaming agent, and the amount of the physical microsphere foaming agent and the foaming agent used is not particularly limited, and is generally 0.1 to 30% by weight.
The dynamic modifier in the additive/workable adjuvant is capable of enhancing the dynamic properties of the modified dynamic polymer to achieve optimal desired properties, typically compounds with free hydroxyl or free carboxyl groups, or capable of donating or accepting electron pairs, including but not limited to water, sodium hydroxide, alcohols (including silanol), carboxylic acids, lewis bases, and the like. The amount of the dynamic regulator used is not particularly limited and is generally 0.1 to 10% by weight.
The antistatic agent in the additive/additive can guide or eliminate the accumulated harmful charges in the polymer sample, so that the harmful charges are not inconvenient or harmful to production and living, and the antistatic agent comprises any one or any several of the following antistatic agents: anionic antistatic agents such as alkyl sulfonate, sodium p-nonylphenoxy propane sulfonate, alkyl phosphate diethanolamine salt, potassium p-nonyldiphenyl ether sulfonate, phosphate derivatives, phosphate salts, polyoxyethylene alkyl ether alcohol phosphate, phosphate derivatives, fatty amine sulfonate, sodium butyrate sulfonate; cationic antistatic agents such as fatty ammonium hydrochloride, lauryl trimethylammonium chloride, dodecyl trimethylammonium bromide, alkyl hydroxyethyl dimethylammonium perchlorate; zwitterionic antistatic agents, such as alkyl dicarboxymethylammonium acetate, lauryl betaine, N, N, N-trialkylammonium acetyl (N' -alkyl) amine acetate, sodium N-lauryl-N, N-polyoxyethylene-N-ethyl phosphonate, N-alkylamino salts; nonionic antistatic agents such as fatty alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, trioxyvinyl ether phosphate, glycerol monofatty acid esters; macromolecular antistatic agents such as ethylene oxide propylene oxide adducts of ethylenediamine, polyallylamine N-quaternary ammonium salt substituents, poly 4-vinyl-1-acetonyl pyridine phosphate-p-butylphenyl ester salts, and the like; among them, preferred are lauryl trimethyl ammonium chloride, stearyl dimethyl hydroxyethyl quaternary ammonium nitrate (antistatic agent SN) and alkyl phosphate diethanolamine salt (antistatic agent P). The amount of antistatic agent used is not particularly limited, but is generally 0.3 to 3% by weight.
The emulsifiers in the additive/utilizable adjuvant are capable of improving the surface tension between the various constituent phases in the polymer blend containing the adjuvant to form a uniform and stable dispersion or emulsion, which is preferably used to effect emulsion polymerization/crosslinking, including but not limited to any one or any of the following emulsifiers: anionic, such as higher fatty acid salts, alkyl sulfonates, alkylbenzene sulfonates, sodium alkyl naphthalene sulfonates, succinate sulfonates, petroleum sulfonates, fatty alcohol sulfates, castor oil sulfate, sulfated butyl ricinoleate, phosphate esters, fatty acyl-peptide condensates; cationic, such as alkyl ammonium salts, alkyl quaternary ammonium salts, alkyl pyridinium salts; zwitterionic, such as carboxylate, sulfonate, sulfate, phosphate; nonionic, such as fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polypropylene oxide-ethylene oxide adduct, glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbitol and sorbitan fatty acid ester, sucrose fatty acid ester, alcohol fatty acid amide, etc.; among them, sodium dodecylbenzenesulfonate, sorbitan fatty acid ester, triethanolamine stearate (emulsifier FM) are preferable as the emulsifier. The amount of the emulsifier used is not particularly limited and is generally 1 to 5% by weight.
The dispersing agent in the additive/the additive can disperse the solid flocculating groups in the polymer mixed liquid into fine particles to suspend in the liquid, uniformly disperse the solid and liquid particles which are difficult to dissolve in the liquid, and prevent the sedimentation and agglomeration of the particles to form stable suspension, and comprises any one or any several dispersing agents including but not limited to: anionic, such as sodium alkyl sulfate, sodium alkylbenzenesulfonate, sodium petroleum sulfonate; a cation type; nonionic, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic types such as silicate, condensed phosphate; among them, sodium dodecylbenzenesulfonate, naphthalene-based methylene sulfonate (dispersant N) and fatty alcohol polyoxyethylene ether are preferable as the dispersant. The amount of the dispersant used is not particularly limited, but is generally 0.3 to 0.8wt%.
The colorants in the additive/optional adjuvants described herein can impart a desired color to the polymer product to increase the surface color, including but not limited to any one or more of the following: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, e.g. Lixol red BK, lake red C, perylene red, jia-base R red, phthalocyanine red, permanent magenta HF3C, plastic scarlet R and Kelol Mo Gong BR, permanent orange HL, fast yellow G, sa Bao Plastic yellow R, permanent yellow 3G, permanent yellow H 2 G. Phthalocyanine blue B, phthalocyanine green, plastic violet RL and aniline black; organic dyes such as thioindirubin, vat yellow 4GF, vaseline blue RSN, basic rose essence, oil soluble yellow, etc.; the choice of the coloring agent is determined according to the color requirement of the sample, and is not particularly limited. The amount of the colorant used is not particularly limited, and is generally 0.3 to 0.8wt%.
The fluorescent whitening agent in the additive/the additive can be used for enabling the dyed substances to obtain the effect of the flash luminescence similar to fluorite, and the fluorescent whitening agent comprises any one or any several of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazepine type, phthalimide type, etc.; among them, sodium distyrene diphenyl disulfonate (fluorescent whitening agent CBS), 4-bis (5-methyl-2-benzoxazolyl) distyrene (fluorescent whitening agent KSN), 2- (4, 4' -distyrenyl) bisbenzoxazole (fluorescent whitening agent OB-1) are preferable. The amount of fluorescent whitening agent used is not particularly limited, but is generally 0.002 to 0.03. 0.03 wt%.
The matting agent in the additive/additive agent can cause diffuse reflection of incident light when reaching the polymer surface, and can generate low-gloss matt and matting appearance, and the matting agent comprises any one or any several of the following matting agents: settling barium sulfate, silicon dioxide, water-containing gypsum powder, talcum powder, titanium dioxide, polymethyl urea resin and the like; among them, silica is preferable as the matting agent. The amount of matting agent used is not particularly limited and is generally 2 to 5% by weight.
The flame retardant in the additive/usable auxiliary agent can increase the flame resistance of the material, and comprises any one or any several of the following flame retardants: phosphorus systems such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate; halogen-containing phosphates, such as tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dichloropropyl) phosphate; organic halides such as chlorinated paraffin with high chlorine content, 1, 2-tetrabromoethane, decabromodiphenyl ether, and perchlorocyclopentadecane; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants such as chlorobridge anhydride, bis (2, 3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, and the like; among them, decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate and antimony trioxide are preferable as the flame retardant. The amount of the flame retardant used is not particularly limited, but is generally 1 to 20wt%.
The nucleating agent in the additive/the additive can be added/used, and can accelerate the crystallization rate, increase the crystallization density and promote the grain size to be micronized by changing the crystallization behavior of the polymer, so as to achieve the purposes of shortening the material forming period and improving the physical and mechanical properties of the product such as transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, impact resistance, creep resistance and the like, and the nucleating agent comprises any one or more of the following nucleating agents: benzoic acid, adipic acid, sodium benzoate, talcum powder, sodium p-phenolsulfonate, silicon dioxide, dibenzylidene sorbitol and derivatives thereof, ethylene propylene rubber, ethylene propylene diene monomer rubber and the like; among them, silicon dioxide, dibenzylidene sorbitol (DBS) and ethylene propylene diene monomer are preferable as the nucleating agent. The amount of the nucleating agent used is not particularly limited, and is generally 0.1 to 1wt%.
The rheology agent in the additive/the additive can ensure that the polymer has good brushing property and proper coating thickness in the coating process, prevent sedimentation of solid particles during storage and improve redispersibility, and comprises any one or any several of the following rheology agents: inorganic substances such as barium sulfate, zinc oxide, alkaline earth metal oxides, calcium carbonate, lithium chloride, sodium sulfate, magnesium silicate, fumed silica, water glass, colloidal silica; organometallic compounds such as aluminum stearate, aluminum alkoxides, titanium chelates, aluminum chelates; organic, such as organobentonite, hydrogenated castor oil/amide wax, isocyanate derivative, acrylic emulsion, acrylic copolymer, polyethylene wax, cellulose ester, etc.; among them, the rheology agent is preferably organic bentonite, polyethylene wax, hydrophobically modified alkali-expandable emulsion (HASE), alkali-expandable emulsion (ASE). The amount of the rheological agent used is not particularly limited and is generally 0.1 to 1wt%.
The thickening agent in the additive/usable auxiliary agent can endow the polymer mixed solution with good thixotropic property and proper thickening property so as to meet the various requirements of stability, application performance and the like in the production, storage and use processes, and the thickening agent comprises any one or any several of the following thickening agents: low molecular substances such as fatty acid salts, alkyl dimethylamine oxides, fatty acid monoethanolamides, fatty acid diethanolamides, fatty acid isopropylamides, sorbitan tricarboxylic acid esters, glycerol trioleate, cocoamidopropyl betaine, titanate coupling agents; macromolecular substances such as bentonite, artificial hectorite, micro-powder silica, colloidal aluminum, animal protein, polymethacrylate, methacrylic acid copolymer, maleic anhydride copolymer, crotonic acid copolymer, polyacrylamide, polyvinylpyrrolidone, polyether, etc.; among them, the thickener is preferably hydroxycodeoxycholamide and acrylic acid-methacrylic acid copolymer. The amount of the thickener used is not particularly limited, and is generally 0.1 to 1.5% by weight.
The leveling agent in the additive/the additive can ensure the smoothness and uniformity of the polymer coating film, improve the surface quality of the coating film and improve the decoration, and comprises any one or any several of the following leveling agents: polydimethyl siloxane, polymethylphenyl siloxane, polyacrylates, silicone resins, and the like; among them, the leveling agent is preferably polydimethylsiloxane or polyacrylate. The amount of the leveling agent used is not particularly limited, but is generally 0.5 to 1.5wt%.
In the preparation process of the dynamic polymer, additives which can be added/used are preferably catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, chain extenders, toughening agents, plasticizers, foaming agents, flame retardants and dynamic regulators.
The filler mainly plays the following roles in the dynamic polymer: (1) the shrinkage rate of the formed product is reduced, and the dimensional stability, the surface smoothness, the flatness or the matt property and the like of the product are improved; (2) adjusting the viscosity of the polymer; (3) meets the requirements of different properties, such as improving the impact strength and the compression strength, the hardness, the rigidity and the modulus of the polymer material, improving the wear resistance, improving the heat deformation temperature, improving the electrical conductivity and the thermal conductivity and the like; (4) the coloring effect of the pigment is improved; (5) imparting photostability and chemical resistance; (6) plays a role in capacity increase, can reduce cost and improve the competitive capacity of products in the market.
The filler is selected from any one or more of the following fillers: inorganic nonmetallic filler, metal filler and organic filler.
The inorganic nonmetallic fillers include, but are not limited to, any one or any several of the following: calcium carbonate, clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon black, quartz, mica powder, clay, asbestos fibers, orthoclate, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene, carbon nanotubes, molybdenum disulfide, slag, flue dust, wood flour, shell powder, diatomaceous earth, red mud, wollastonite, silica-alumina carbon black, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, conductive carbon black, vermiculite, iron mud, white mud, alkali mud, boron mud, (hollow) glass beads, foamed microspheres, glass powder, cement, glass fibers, carbon fibers, quartz fibers, carbon core boron fibers, titanium diboride fibers, calcium titanate fibers, carbon silicon fibers, ceramic fibers, whiskers, and the like.
The metal filler includes, but is not limited to, any one or any several of the following: copper, silver, nickel, iron, gold, and the like, and their alloyed powders, nanoparticles, and fibers. The organic filler includes, but is not limited to, any one or any several of the following: fur, natural rubber, asbestos, shellac, chitin, chitosan, protein, raw lacquer, shell powder, silk, rayon, phenolic microbeads, resin microbeads, and the like.
The type of filler to be added is not limited, and is preferably calcium carbonate, barium sulfate, talc, carbon black, graphene, (hollow) glass beads, foam beads, glass fibers, carbon fibers, metal powder, natural rubber, chitosan, protein, and resin beads, depending on the desired material properties, and the amount of filler to be used is not particularly limited, but is generally 1 to 30wt%.
In the preparation of the dynamic polymer, the dynamic polymer may be prepared by mixing the raw materials in a certain ratio by any suitable material mixing means known in the art, which may be a batch, semi-continuous or continuous process type of mixing; likewise, the dynamic polymer may be molded in a batch, semi-continuous or continuous process. The mixing means used include, but are not limited to, solution stirring and mixing, melt stirring and mixing, kneading, banburying, open mill, melt extrusion, ball milling, etc., among which solution stirring and mixing, melt stirring and mixing, and melt extrusion are preferable. The energy supply forms in the material mixing process include but are not limited to heating, illumination, radiation, microwaves and ultrasound. The molding mode includes, but is not limited to, extrusion molding, injection molding, compression molding, casting molding, calendaring molding and casting molding.
Other polymers, additives, and fillers that may be added/used, and may be added/used, as previously described, to form a dynamic polymer composite system during the preparation of the dynamic polymer, although these additives are not required.
The method for producing a dynamic polymer by stirring and mixing a solution is generally to stir and mix a raw material in a dissolved or dispersed form in each solvent or in a common solvent in a reactor. In general, the mixing reaction temperature is controlled to be 0 to 200 ℃, preferably 25 to 120 ℃, more preferably 25 to 80 ℃, and the mixing stirring time is controlled to be 0.5 to 12 hours, preferably 1 to 4 hours. The product obtained after mixing and stirring can be poured into a proper mold and placed for 0-48 hours at the temperature of 0-150 ℃, preferably 25-80 ℃ to obtain a polymer sample. In the process, the solvent can be selectively reserved according to the requirement to prepare polymer samples in the forms of paste, colloid and the like, or the solvent can be selectively removed to prepare solid polymer samples in the forms of film, block, foam and the like. When preparing a dynamic polymer by this method, it is generally necessary to add an initiator to a solvent to initiate polymerization in a solution polymerization manner to obtain a dynamic polymer, or to add a dispersing agent and an oil-soluble initiator to prepare a suspension to initiate polymerization in a suspension polymerization manner or a slurry polymerization manner to obtain a dynamic polymer, or to add an initiator and an emulsifier to prepare an emulsion to initiate polymerization in an emulsion polymerization manner to obtain a dynamic polymer. The methods of solution polymerization, suspension polymerization, slurry polymerization and emulsion polymerization employed are all well known and widely used polymerization methods by those skilled in the art and can be adapted according to the actual circumstances and are not developed in detail herein.
The solvent used in the preparation method is selected according to the actual conditions of reactants, products, reaction process and the like, and comprises, but is not limited to, any one or more solventsMixed solvent of the agents: deionized water, acetonitrile, acetone, butanone, benzene, toluene, xylene, ethyl acetate, diethyl ether, methyl tertiary butyl ether, tetrahydrofuran, methanol, ethanol, chloroform, methylene chloride, 1, 2-dichloroethane, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, isopropyl acetate, N-butyl acetate, trichloroethylene, mesitylene, dioxane, tris buffer, citric acid buffer, acetic acid buffer, phosphoric acid buffer, boric acid buffer, and the like; deionized water, toluene, chloroform, methylene chloride, 1, 2-dichloroethane, tetrahydrofuran, dimethylformamide, and a phosphoric acid buffer solution are preferable. In addition, the solvent can be selected from oligomer, plasticizer and ionic liquid; the oligomer includes, but is not limited to, polyethylene glycol oligomer, polyvinyl acetate oligomer, n-butyl polyacrylate oligomer, liquid paraffin and the like; the plasticizer may be selected from the classes of plasticizers in the additizable auxiliaries, which are not described in detail herein; the ionic liquid is generally composed of organic cations and inorganic anions, wherein the cations are generally alkyl quaternary ammonium ions, alkyl Ji ions, 1, 3-dialkyl substituted imidazole ions, N-alkyl substituted pyridine ions and the like; the anions are typically halogen ions, tetrafluoroborate ions, hexafluorophosphate ions, and 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 - Etc. Wherein, when deionized water is utilized to prepare dynamic polymer and the dynamic polymer is selected to be reserved, hydrogel can be obtained; organogels can be obtained when dynamic polymers are prepared with organic solvents and selectively retained; when the oligomer is used for preparing dynamic polymer and selecting to keep the dynamic polymer, the oligomer swelling gel can be obtained; preparation of dynamic polymers Using plasticizers and selection of the desired polymer to be usedWhen it remains, a plasticizer swelling gel can be obtained; when ionic liquids are used to prepare dynamic polymers and optionally retain them, ionic liquid swelling gels can be obtained.
In the above production method, the concentration of the compound liquid to be prepared is not particularly limited, and is preferably 0.1 to 10mol/L, more preferably 0.1 to 1 mol/L, depending on the structure, molecular weight, solubility and desired dispersion state of the selected reactant.
In a specific method for preparing a dynamic polymer by melt stirring and mixing, the raw materials are directly stirred and mixed in a reactor or heated and melted and then stirred and mixed for reaction, and the method is generally used under the condition that the raw materials are gas, liquid or solid with a lower melting point. In general, the mixing reaction temperature is controlled to be 0 to 200 ℃, preferably 25 to 120 ℃, more preferably 25 to 80 ℃, and the mixing stirring time is controlled to be 0.5 to 12 hours, preferably 1 to 4 hours. The product obtained after mixing and stirring can be poured into a proper mold and placed for 0-48 hours at a temperature of 0-150 ℃, preferably 25-80 ℃ to obtain a polymer sample. In the preparation of dynamic polymers by this process, it is generally also necessary to add small amounts of initiator, if appropriate, to initiate the polymerization in the melt or gas phase, to give dynamic polymers. The methods of melt polymerization and gas phase polymerization used are well known and widely used by those skilled in the art, and can be adjusted according to the actual situation, and are not developed in detail here.
The specific method for preparing the dynamic polymer by melt extrusion mixing is to add the raw materials into an extruder for extrusion blending reaction, wherein the extrusion temperature is 0-280 ℃, preferably 50-150 ℃. The reaction product can be directly cast and formed and then cut into a proper size, or the obtained extruded sample is crushed and then is prepared by an injection molding machine or a molding press. The injection molding temperature is 0-280 ℃, preferably 50-150 ℃, and the injection molding pressure is preferably 60-150MPa; the molding temperature is 0-280 ℃, preferably 25-150 ℃, more preferably 25-80 ℃, the molding time is 0.5-60min, preferably 1-10min, and the molding pressure is preferably 4-15MPa. The bars may be placed in a suitable mold and left for 0-48 hours at a temperature of 0-150 c, preferably 25-80 c, to give the final polymer sample.
The molar equivalent ratio of the inorganic boron compound and the (poly) siloxane compound to be used in the dynamic polymer production process should be in a proper range, preferably in a range of 0.1 to 10, more preferably in a range of 0.3 to 3, and still more preferably in a range of 0.8 to 1.2. In the actual preparation process, the person skilled in the art can adjust the preparation process according to actual needs.
In the preparation of the dynamic polymer, the addition amount of each component raw material of the dynamic polymer is not particularly limited, and one skilled in the art can adjust according to the actual preparation and the target polymer properties.
The dynamic polymer has adjustable performance in a large range, has wide application prospect, and has important application in the fields of military aerospace equipment, functional paint and coating, biological medicine, biomedical materials, energy sources, buildings, bionics, intelligent materials and the like.
Based on the dilatancy and the dynamic property of the dynamic polymer, the dynamic polymer has excellent energy absorption performance, can absorb and reduce mechanical energy including vibration, impact, explosion, sound wave and the like, so the dynamic polymer can be used as an effective energy absorption method by taking the dynamic polymer as an energy absorption material, can be applied to manufacturing damping shock absorbers and used for vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings, and can dissipate a large amount of energy to play a damping effect when the polymer material is subjected to vibration, thereby effectively relieving the vibration; the material can also be used as an energy absorption buffer material and applied to the aspects of buffer packaging materials, sports protection products, impact protection products, army and police protection materials and the like, so that the vibration and impact of articles or human bodies under the action of external force, including noise, shock waves generated by explosion and the like, are reduced; as the energy absorbing material, sound insulation, noise elimination, and the like can also be performed. The bond energy intensity and dynamic difference of dynamic covalent bond and hydrogen bond are utilized, and the material can be used as a shape memory material, and when external force is removed, deformation generated in the loading process of the material can be recovered.
The stress-sensitive polymer material is prepared through the dynamic reversibility and stress rate dependence of the dynamic polymer, and part of the polymer material can be applied to preparing magic toys and body-building materials with stress/strain response, can also be used for preparing speed locks of roads and bridges, can also be used for manufacturing anti-seismic shear plates or circulating stress bearing tools, or can be used for manufacturing stress monitoring sensors.
The dynamic property of the dynamic polymer is fully utilized, so that the adhesive with a self-repairing function can be prepared, and the adhesive can be applied to the adhesion of various materials and also can be used as bulletproof glass interlayer adhesive; the polymer plugging adhesive can also be used for preparing polymer plugging adhesive with good plasticity, and can be designed and prepared into a scratch-resistant coating with partial self-repairing function, so that the service life of the coating is prolonged, and the long-acting anti-corrosion protection of a matrix material is realized. The method has great application potential in the fields of military industry, aerospace, electronics, bionics and the like.
When the inorganic silicon borate ester bond and the hydrogen bond are used as the sacrificial bond, the inorganic silicon borate ester bond and the hydrogen bond can be sequentially broken under the action of external force, and the inorganic silicon borate ester bond is broken after the ordinary hydrogen bond is broken, so that a great amount of energy is absorbed to endow the polymer material with excellent toughness, thereby obtaining the polymer material with excellent toughness, and being widely applied to the fields of military, aerospace, sports, energy sources, buildings and the like.
The dynamic polymers of the present invention are described further below in connection with some embodiments. The present invention will be further described in detail with reference to specific examples, which are not intended to limit the scope of the invention.
Example 1
Trimethyl borate and dimethylmethoxy-3-butene silane are mixed according to a molar ratio of 1:3, heated to 60 ℃ and dissolved by stirring, and then a small amount of water is added for continuous reaction for 4 hours, so as to obtain the trivinyl compound 1a containing a silicon borate ester bond.
Mixing 1, 5-hexadiene-3-alcohol and ethyl isocyanate according to an equimolar ratio, and reacting in dichloromethane by taking triethylamine as a catalyst to obtain a compound 1b with a carbamate group at a side band.
Mixing a compound 1a, a compound 1b and trimethylolpropane tri (2-mercaptoacetate) according to a molar ratio of 1:1:2, adding 1wt% of organic bentonite and 1wt% of bentonite, shaking and uniformly mixing, and placing the mixture in an ultraviolet cross-linking instrument for ultraviolet radiation for 8 hours to obtain the dynamic polymer containing common covalent cross-linking, silicon borate bonds and side hydrogen bond groups.
The polymer product can be used as a sheet or coating having certain energy absorbing properties and tear resistance.
Example 2
The organopolysiloxane with terminal olefin group at the side band (molecular weight about 8000), 5-mercaptomethyl uracil, 3-mercaptopropyl trimethoxy silane and 1, 12-dimercaptodecyl are mixed according to the mol ratio of double bond to each mercapto compound of 22:10:10:1, 0.2wt% of photoinitiator benzoin dimethyl ether (DMPA) is added, and after stirring is completed, the mixture is put into ultraviolet radiation for 4 hours in an ultraviolet crosslinking instrument, so that the organopolysiloxane containing common covalent crosslinking and side hydrogen bond groups is obtained.
The organopolysiloxane containing side hydrogen bond groups and trimethyl borate are prepared according to Si-OCH 3 Mixing the groups and the B-OR groups in a molar ratio of 1:1, heating to 80 ℃ to mix uniformly, adding 4ml of deionized water, dropwise adding a small amount of acetic acid, adding 5wt% of graphene powder, vibrating and mixing uniformly, and performing polymerization reaction in a stirring state to prepare the dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds.
The polymer product can be deformed greatly under the action of small pressure or stretching force, but can show high elasticity when being stretched or beaten quickly, and the conductivity of the polymer product can be changed obviously along with the change of the pressure or the stretching force and can be used as a force sensor.
Example 3
(1) The preparation method comprises the steps of mixing polydimethyl hydrogen-containing silicone oil (molecular weight 6000), 5-hexenyl trimethoxy silane and diallyl adipate, controlling the ratio of the mole number of active hydrogen atoms (hydrogen atoms directly connected with Si) to the mole number of double bonds in the polydimethyl hydrogen-containing silicone oil in the reaction to be about 10:9:1, and carrying out addition reaction by using chloroplatinic acid as a catalyst to prepare the organopolysiloxane with common covalent crosslinking and trimethoxy groups on side groups.
The organopolysiloxane and boric acid prepared above are prepared according to Si-OCH 3 The molar ratio of the groups to the B-OH groups is 1:1, and the mixture is heated to 60 ℃ and stirred to react for 16 hours to obtain a dynamic polymer containing common covalent crosslinking and a silicon borate bond, which is used as a 1 st network polymer.
(2) Mixing N-allyl-1H-benzimidazole-2-amine and 5-butane-2-yl-5-prop-2-alkenyl-1, 3-diazinon-2, 4, 6-trione according to the mol ratio of 10:10:3, swelling in a 1 st network polymer, adding 5wt% of carbon nano tubes, carrying out ultrasonic treatment for 5min, adding 5mol% of AIBN as an initiator, heating to 80 ℃ for reaction for 8H, and obtaining the dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds through free radical polymerization.
The polymer product has good toughness and can be prepared into polymer plugging glue and interlayer glue.
Example 4
(1) 3-aminopropyl methyl dimethoxy silane and adipoyl chloride are mixed according to a molar ratio of 2:1, triethylamine is used as a catalyst, and the mixture is reacted in anhydrous dichloromethane to prepare the disiloxane compound.
The disiloxane compound and boric acid are prepared according to Si-OCH 3 The molar ratio of the groups to the B-OR groups is 1:1, and the mixture is heated to 60 ℃ and stirred to react for 8 hours to obtain a dynamic polymer containing a silicon borate bond, which is used as a 1 st network polymer.
(2) Allyl hydroxyethyl ether and 5-chloromethyl-2-oxazolidone are dissolved in toluene according to a molar ratio of 1:1, potassium carbonate is used as a catalyst, tetrabutylammonium bromide is used as a phase transfer agent, and the olefin monomer 4a containing oxazolidone groups is obtained.
Under the anhydrous and anaerobic condition, allyl mercaptan and 2-thiophene isocyanate are dissolved in methylene dichloride according to the mol ratio of 1:1, and the olefin monomer 4b containing the thiocarbamate group is obtained under the catalysis of triethylamine.
The olefin monomer 4a, the olefin monomer 4b and the diallyl thioether are fully mixed according to the mol ratio of 50:50:3, 80 parts of epoxidized soybean oil is added, the mixture is fully mixed and is swelled in the 1 st network polymer, then 5mol percent of AIBN is added, and the dynamic polymer organogel swelled by the epoxidized soybean oil containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds is prepared through free radical polymerization.
The dynamic polymer organic gel swelled by the epoxidized soybean oil has soft elasticity, can be used for manufacturing an energy-absorbing material, and is applied to impact resistance protection.
Example 5
(1) 1, 11-dichloro-1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane and boric acid are mixed according to the mol ratio of silicon hydroxyl and boric acid ester of 3:2, a small amount of 20% acetic acid aqueous solution is dripped, and after being stirred uniformly at 50 ℃, the mixture is reacted for 6 hours, so that a dynamic polymer containing a silicon borate ester bond is prepared and is used as a 1 st network polymer.
(2) 5-vinyl-2-pyrrolidone, trimethylolpropane ethoxyester triacrylate, and 1-butyl-3-methylimidazole hexafluorophosphate ([ C ] dissolved therein at a molar ratio of 20:1 4 MIM]PF 6 ) Adding 5mol% of AIBN as an initiator into the ionic liquid to fully swell the AIBN in the 1 st network polymer, stirring and fully mixing the AIBN, pouring the AIBN into a glass plate die with a silica gel gasket, and placing the glass plate die into an ultraviolet crosslinking instrument to radiate for 10 hours to obtain the dynamic polymer ionic liquid gel containing side hydrogen bond groups and silicon borate bonds.
And replacing the ionic liquid by deionized water, and replacing the deionized water once every 12 hours for 4 times to obtain the dynamic polymer hydrogel containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds.
The hydrogel prepared in this example has a modulus of 13kPa, a strain of 15 times and a breaking stress of 69kPa. The hydrogel can be used for cushioning packaging materials of fragile objects.
Example 6
(1) The preparation method comprises the steps of mixing silicon hydroxyl-terminated poly (dimethyl-methylphenyl) siloxane and isopropanol pinacol borate according to a molar ratio of 1:1, dropwise adding a small amount of 20% acetic acid aqueous solution, uniformly stirring at 50 ℃, and reacting for 8 hours to prepare a dynamic polymer containing a silicon borate bond, wherein the dynamic polymer is used as a 1 st network polymer.
(2) Diallyl amino methoxy acetanilide, lu Dinger mercaptan and trimethylolpropane tri (3-mercaptopropionate) are mixed according to the mol ratio of 20:20:1, added into 120wt% plasticizer epoxy acetyl ricinoleic acid methyl ester, added with 0.2wt% benzoin dimethyl ether (DMPA), stirred and fully mixed, 50g of the mixture is taken to be swelled in 50g of the 1 st network polymer, and then 1.6g of surface modified Fe is added 3 O 4 Mixing the particles with 1.0g bentonite, and ultrasonic treating for 5min to obtain Fe 3 O 4 The particles are uniformly dispersed in the gel, then the gel is poured into a glass plate mold with a silica gel gasket, and the gel is put into an ultraviolet crosslinking instrument to radiate for 8 hours, so that the epoxy acetyl ricinoleic acid methyl ester swelling organogel containing common covalent crosslinking, hydrogen bond groups and silicon borate bonds is obtained.
The modulus of the epoxy acetyl ricinoleic acid methyl ester swelled organogel prepared in the example is 20kPa, the strain can reach 15 times, and the breaking stress is 100kPa. The organic gel can be used for preparing impact-resistant protective materials for air drop and air drop.
Example 7
(1) The preparation method comprises the steps of mixing end silicon hydroxyl poly (dimethyl-methylphenyl) siloxane and tri (4-chlorophenyl) borate according to a molar ratio of 1:2 of silicon hydroxyl to borate, dropwise adding a small amount of 20% acetic acid aqueous solution, uniformly stirring at 50 ℃, and reacting for 8 hours to prepare a dynamic polymer containing a silicon borate bond, wherein the dynamic polymer is used as a 1 st network polymer.
(2) Limonene oxide extracted from orange peel is polymerized with 100psi carbon dioxide under the catalysis of beta-diimine zinc to obtain polycarbonate PLimC.
Figure SMS_16
The polycarbonate PLimC, 2-aminoethanethiol and 2-tert-butyloxycarbonyl aminoethanethiol are mixed according to the proportion of double bond groups and mercapto groups of 10:5:5, 0.3wt% of AIBN is added, and the polycarbonate with amino groups and carbamate groups on side groups is obtained through polymerization.
Adding 0.2wt% of dibutyl tin dilaurate, 0.2wt% of triethylenediamine, 4wt% of polymer foaming microsphere and 80wt% of 1 st network polymer into the polycarbonate with the amino groups and the carbamate groups on the side groups, fully and uniformly stirring, finally adding 20wt% of hexamethylene diisocyanate, quickly stirring to generate bubbles by professional equipment, quickly injecting into a mold, curing for 30min at room temperature, and curing for 4h at 80 ℃ to obtain the binary interpenetrating network composite foam material with common covalent crosslinking, side hydrogen bond groups and silicon borate bonds.
The foam material has good chemical resistance, can be used as a glass product substitute, a rigid packaging box and a decorative plate material, has toughness and durability, and has good biodegradability.
Example 8
(1) 2-aminoethyl acrylate and equimolar equivalent of acetyl bromide were dissolved in methylene chloride to give an amide bond containing olefin monomer 8a under triethylamine catalysis.
1.0g of 4-amino-3, 5-difluorophenethyl ester, 8.5g of potassium permanganate and 8.6g of ferrous sulfate heptahydrate are dissolved in 30mLDCM and refluxed overnight to obtain an azobenzene product. 0.81g of the azobenzene product, 4.8g of 1, 6-hexanediol and 0.03g of K 2 CO 3 Dissolving in 14mLDMSO, and reacting at 60 ℃ for 9 hours to obtain azobenzene with hydroxyl at the tail end. 0.72g of azobenzene with hydroxyl at the tail end is added with 1.84mL of triethylamine and 3mgDMAP to be dissolved in 5mL of anhydrous DCM, and then 0.6mL of methacryloyl chloride is added to react overnight to obtain azobenzene 8b of diene.
Polymethylhydrosiloxane (PHMS, molecular weight 8000) is mixed with the amide bond-containing olefin monomer 8a and the diene azobenzene 8b, the ratio of the mole number of active hydrogen atoms (hydrogen atoms directly connected with Si) in polydimethyl hydrogen-containing silicone oil to the mole number of double bonds in 8a and 8b is controlled to be about 10:9:1, chloroplatinic acid is used as a catalyst for an addition reaction, and organopolysiloxane with hydrogen bond groups on side groups is prepared as a 1 st network polymer.
(2) The organopolysiloxane with terminal olefin group at the side band (molecular weight about 6000) is mixed with 1, 4-dimercaptobutane and 3-mercaptopropyl trimethoxysilane according to the mol ratio of double bond and two mercapto compounds of 20:2:16, 0.2wt% of photoinitiator benzoin dimethyl ether (DMPA) is added, and after stirring fully, the mixture is put into ultraviolet radiation for 4 hours in an ultraviolet cross-linking instrument to prepare the organopolysiloxane containing common covalent cross-linking and side hydrogen bond groups.
The organopolysiloxane and boric acid are prepared according to Si-OCH 3 The molar ratio of the groups to the B-OH groups is 1:1, the mixture is heated to 80 ℃ and mixed uniformly, and 100mL of 1-butyl-3-methylimidazole hexafluorophosphate ([ C ] is added 4 MIM]PF 6 ) The ionic liquid is fully swelled in the 1 st network, a small amount of 20% acetic acid solution is added dropwise, and polymerization reaction is carried out under the stirring state, so that the high-strength ionic liquid dynamic polymer gel containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds is prepared.
The ionic liquid gel has a modulus of 36kPa, a strain of 32 times and a breaking stress of 200kPa. The product can be used as a stress bearing material in a fine die, plays a role in bearing stress, has certain deformability and plays a role in buffering.
Example 9
(1) The organopolysiloxane with terminal alkene group on the side band (molecular weight about 3000) is mixed with 4' 4-dimercaptodiphenyl sulfide and 3-mercaptopropyl trimethoxy silane according to the mol ratio of double bond and two mercapto compounds of 2:1:1, 0.2wt% of light initiator benzoin dimethyl ether (DMPA) relative to 2-tert-butyloxycarbonyl amino ethane mercaptan is added, after stirring fully, the mixture is put into ultraviolet radiation for 4 hours in an ultraviolet cross-linking instrument, and the organopolysiloxane containing common covalent cross-linking is prepared.
The general covalent cross-linking organopolysiloxane and 2, 6-di-tert-butyl-4-toluyl dibutyl orthoborate are mixed according to the mol ratio of terminal siloxane to borate of 1:1, after the temperature is raised to 80 ℃, 4ml of deionized water is added after the mixture is uniformly mixed, a small amount of acetic acid is added dropwise, and polymerization reaction is carried out under the stirring state, so that the dynamic polymer containing side hydrogen bond groups and silicon borate bonds is prepared and used as the 1 st network polymer.
(2) 4, 5-dihydro-2-vinyl-1H-imidazole, 1- (3-pyrrolidinyl) -2-propylene-1-ketone and hexa-1, 5-diene-3, 4-dione are mixed according to the mol ratio of 10:10:1, swelled in a 1 st network polymer, 1 mol equivalent AIBN is added as an initiator, 5wt% titanium alloy powder, 5wt% ceramic powder and 10wt% calcium sulfate are added for fully blending, and the mixture is heated to 80 ℃ for reaction for 8 hours, so that a dynamic polymer containing common covalent crosslinking, multiple side hydrogen bond groups and silicon borate bonds is prepared through free radical polymerization.
The polymer product can be used as an impact-resistant material.
Example 10
(1) The organopolysiloxane with terminal olefin group at the side band (molecular weight about 3000) is mixed with 5-mercapto methyl uracil and pentaerythritol tetramercapto acetate according to the mol ratio of double bond to mercapto of 100:96:1, 0.2wt% of photoinitiator benzoin dimethyl ether (DMPA) is added, and after stirring fully, the mixture is put into ultraviolet radiation for 4 hours in an ultraviolet cross-linking instrument, so as to obtain the organopolysiloxane containing the side hydrogen bond group.
The organopolysiloxane containing side hydrogen bond groups and 2, 6-di-tert-butyl-4-tolyldibutyl orthoborate are mixed according to the mol ratio of terminal siloxane to borate of 1:1, after the temperature is raised to 80 ℃, 4ml of deionized water is added for uniform mixing, and polymerization reaction is carried out under the stirring state, so that the dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds is prepared and used as the 1 st network polymer.
(2) Mixing 4, 5-dihydro-2-vinyl-1H-imidazole and 1- (3-pyrrolidinyl) -2-propylene-1-ketone according to a molar ratio of 10:10, swelling in a 1 st network polymer, adding 1.0g montmorillonite, 1.2g carbon black and 0.35g ferric oxide, adding 1 molar equivalent AIBN as an initiator, heating to 80 ℃ for reacting for 8 hours, and preparing a dynamic polymer containing common covalent crosslinking, various side hydrogen bond groups and silicon borate bonds through free radical polymerization.
The product exhibits good viscoelasticity, good vibration isolation and stress buffering effects, and excellent hydrolysis resistance.
Example 11
(1) Limonene oxide extracted from orange peel is polymerized with 100psi carbon dioxide under the catalysis of beta-diimine zinc to obtain polycarbonate PLimC.
Figure SMS_17
The polycarbonate PLimC, gamma-mercaptopropyl methyl dimethoxy silane, N- [ (2-mercaptoethyl) carbamoyl ] propionyl amine and bis (2-mercaptoethyl) adipate are mixed according to the double bond group and mercapto group ratio of 20:10:8:2, and 0.6wt% of AIBN is added, and the polycarbonate containing common covalent crosslinking, side hydrogen bond groups and silicon hydroxyl precursor is prepared through click reaction.
24g of polycarbonate with the side groups containing hydrogen bond groups and silicon hydroxyl precursors and 5g of tri (2-methoxyethyl) borate are weighed, fully stirred and mixed uniformly, 10ml of deionized water is added after the temperature is raised to 80 ℃, and polymerization reaction is carried out in a stirring state, so that a dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds is prepared and used as a network 1 polymer.
(2) Boric acid and propenyl dimethyl chlorosilane are mixed according to a molar ratio of 1:3, triethylamine is used as a catalyst, and the mixture is reacted for 12 hours at 80 ℃ to prepare the silicon borate compound 11a with double bonds at the tail end.
16g of polyether dithiol, 5.4g of silicon borate compound 11a with double bonds at the tail end and 2.0 g of triallylamine are added into a three-neck flask, the mixture is swelled in a 1 st network polymer, then 6wt% of cellulose nanocrystalline and 0.3wt% of sodium dodecyl benzene sulfonate are added, the mixture is subjected to ultrasonic treatment for 20min, and then the mixture is put into an ultraviolet cross-linking instrument for ultraviolet irradiation for 8h, so that a binary network interpenetrating dynamic polymer containing common covalent cross-linking, lateral hydrogen bond groups and silicon borate bonds is obtained.
The polymer is prepared into a film, has relatively good comprehensive performance, certain tensile strength and good tear resistance, and can be stretched to a relatively large extent. The dynamic polymer can be applied to preparing functional films, or can be used as a film for automobiles and furniture, and can also be used as a stretch packaging film, and is quite scratch-resistant.
Example 12
(1) Hydroxyethyl acrylate is used as a monomer, and is prepared by free radical polymerization (the molecular weight is about 1000).
The oligomeric polyhydroxyethyl acrylate, hexamethylene diisocyanate and 3-isocyanatopropyl trimethoxy silane are mixed (the molar ratio of hydroxyl to isocyanate is 2:1.1:1.1, namely, the isocyanate is controlled to be slightly excessive), triethylamine is used as a catalyst, and the reaction is carried out in methylene dichloride, so that the polyacrylate with trimethoxy silane groups on side groups is prepared.
The polyacrylate and boric acid with trimethoxy silicon group on the side group are prepared according to Si-OCH 3 Mixing the groups and the B-OH groups in a molar ratio of 1:1, heating to 80 ℃ to mix uniformly, and carrying out polymerization reaction for 8 hours in a stirring state to obtain a dynamic polymer containing a silicon borate bond, wherein the dynamic polymer is used as a 1 st network polymer.
(2) Trimethyl borate and dimethyl methoxy-3-butynosilane are mixed according to a molar ratio of 1:3, heated to 60 ℃ and dissolved by stirring, and then a small amount of water is added for continuous reaction for 4 hours, so as to obtain the trivinyl compound 12a containing a silicon borate ester bond.
1, 4-diacetylene-3-alcohol and methyl isocyanate are mixed according to an equal molar ratio, triethylamine is used as a catalyst, and the mixture reacts in dichloromethane to obtain the compound 12b with a carbamate group at a side band.
Compound 12a, compound 12b and 1, 8-diazido-3, 5-dioxaoctane are mixed according to a molar ratio of 1:1:2, swelled in a 1 st network, added into dioctyl phthalate as plasticizer, and then added with 0.1wt% of catalyst CuBr (PPh 3 ) 3 And tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), stirring and fully mixing, and reacting for 12 hours at normal temperature A dioctyl phthalate swollen organogel is obtained.
The modulus of the dioctyl phthalate swelling organogel prepared in this example was 22kPa, the strain was 18 times, and the breaking stress was 100kPa. The organic gel can be used for preparing impact-resistant protective materials for air drop and air drop.
Example 13
(1) Polybutadiene, 2-tert-butyloxycarbonyl amino ethanethiol, mercaptomethyl diethoxysilane and 1, 4-butanedithiol are mixed according to the proportion of double bonds to mercapto of 100:50:40:10, DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and polybutadiene containing common covalent crosslinking and side groups containing side hydrogen bond groups and siloxane groups is prepared through click reaction.
26g of the polybutadiene prepared as described above and 3.2g of tris (4-chlorophenyl) borate were weighed, heated to 60℃and dissolved by stirring, and then a small amount of 20% aqueous acetic acid solution was added to continue the reaction for 4 hours, to obtain a dynamic polymer containing ordinary covalent crosslinks, pendant hydrogen bond groups and a silicon borate bond as the 1 st network polymer.
(2) 2, 3-dimercaptopropionic acid and aniline react according to the equimolar ratio, and then a condensing agent Dicyclohexylcarbodiimide (DCC) and an activator 4-N, N-lutidine (DMAP) are added, and stirred for 24 hours at room temperature, so that the compound 13a can be prepared.
Mixing methyl phenyl vinyl polysiloxane (molecular weight 10000), mercaptoethyl trimethoxy silane and a compound 13a according to the proportion of double bonds and mercapto groups of 100:80:20, adding 3g of white carbon black, 4g of titanium dioxide and 1.3g of ferric oxide, swelling in a 1 st network polymer, adding 0.4wt% of a photoinitiator benzoin dimethyl ether (DMPA), stirring thoroughly, and placing in an ultraviolet cross-linking instrument to ultraviolet radiate for 4h to obtain the binary network interpenetrating dynamic polymer containing common covalent cross-linking, lateral hydrogen bond groups and silicon borate bonds.
The polymer samples have greater tackiness and very good tensile toughness, and can be stretched to a greater extent without breaking (elongation at break up to 600%). In this embodiment, the polymer may be used as an electronic packaging material or an adhesive to prevent damage and air leakage.
Example 14
(1) The copolymer (molecular weight is about 2800) of 3- (trimethoxy silicon based) propyl methacrylate and trimethylol propane trimethacrylate is prepared by free radical polymerization by taking 3- (trimethoxy silicon based) propyl methacrylate and trimethylol propane trimethacrylate as monomers and controlling the mol ratio of the two to be 10:1.
The copolymer and trimethyl borate are prepared according to Si-OCH 3 Mixing the groups and the B-OR groups in a molar ratio of 1:1, heating to 80 ℃ to mix uniformly, adding 4ml of deionized water, and carrying out polymerization reaction in a stirring state to prepare a dynamic polymer containing common covalent crosslinking and a silicon borate bond as a 1 st network polymer.
(2) Mixing methacrylic acid 2-anilinoethyl ester and tert-butyl acrylate according to a molar ratio of 10:5, adding 1 molar equivalent of AIBN as an initiator, heating to 80 ℃ for reaction for 8 hours, and polymerizing by free radicals to obtain a dynamic polymer containing side hydrogen bond groups, wherein the dynamic polymer is used as a 2 nd network polymer.
(3) Mixing 4-allyl-1, 6-heptadiene-4-alcohol and methyl isocyanate according to an equimolar ratio, and reacting in methylene dichloride by using triethylamine as a catalyst to obtain a compound 14a with a carbamate group at a side band.
Boric acid and dimethylmethoxy-3-heptylene silane are mixed according to a molar ratio of 1:3, heated to 60 ℃ and dissolved by stirring, and then a small amount of water is added for continuous reaction for 4 hours, so as to obtain the trivinyl compound 14b containing a silicon borate ester bond.
1, 3-diphenylpropane-2, 2-dithiol and a compound 14a and a compound 14b are mixed according to a molar ratio of 1:1:3, then the mixture is dissolved and expanded in a 1 st network polymer and a 2 nd network polymer, and the mixture is placed in an ultraviolet crosslinking instrument for ultraviolet radiation for 8 hours, so that a dynamic polymer containing common covalent crosslinking, lateral hydrogen bond groups and silicon borate bonds is obtained.
The polymer product can be used for preparing a protective material for military and police.
Example 15
(1) The copolymer (molecular weight is about 4000) of 3- (trimethoxy silicon based) propyl methacrylate and 2-anilinoethyl methacrylate is prepared by free radical polymerization with 3- (trimethoxy silicon based) propyl methacrylate and 2-anilinoethyl methacrylate as monomers and with a molar ratio of 10:6.
The copolymer and triethyl borate are prepared according to Si-OCH 3 Mixing the groups and the B-OR groups in a molar ratio of 1:1, heating to 80 ℃ to mix uniformly, adding 4ml of deionized water, and carrying out polymerization reaction in a stirring state to prepare a dynamic polymer containing side hydrogen bond groups and silicon borate bonds as a 1 st network polymer.
(2) Mixing a certain amount of 5-cyclooctene-1, 2-diol and 2-imidazolidone-4-carboxylic acid, controlling the ratio of the two mole numbers to be about 1:2, and obtaining the monomer 15a containing hydrogen bond groups by taking dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalysts and methylene dichloride as a solvent.
Mixing a certain amount of monomer 15a containing hydrogen bond groups and cyclooctene, controlling the molar ratio of the monomer 15a containing hydrogen bond groups and the cyclooctene to be about 1:2, using Grubbs second generation catalyst as catalyst and using methylene dichloride as solvent, and obtaining the polycyclooctene-based polymer containing the hydrogen bond groups on the side groups.
And (2) fully mixing 100 parts by mass of the polymer with 6 parts by mass of dicumyl peroxide in methylene dichloride, removing a solvent, placing the mixture in a mould, heating to 150 ℃ for 2 hours, and cooling to obtain the dynamic polymer based on polycyclooctene with the side groups containing hydrogen bond groups as the 2 nd network polymer.
(3) The copolymer (molecular weight is about 6600) of 3- (trimethoxy silyl) propyl methacrylate, 2- (1H-imidazol-4-yl) ethyl methacrylate and tri (1, 2-propylene glycol) diacrylate is prepared by free radical polymerization with 3- (trimethoxy silyl) propyl methacrylate, 2- (1H-imidazol-4-yl) ethyl methacrylate and tri (1, 2-propylene glycol) diacrylate as monomers, wherein the molar ratio of the three monomers is controlled to be 10:4:1.
The copolymer and trimethyl borate are prepared according to Si-OCH 3 The molar ratio of the groups to the B-OR groups being 1:1And adding 1.0g of expanded graphite and 1.0g of ammonium polyphosphate, fully swelling in the 1 st network polymer and the 2 nd network polymer, heating to 80 ℃ to mix uniformly, adding 10ml of deionized water, and carrying out polymerization reaction in a stirring state to prepare the dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds.
The polymer product can be used for vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings, and when the polymer material is subjected to vibration, a large amount of energy can be dissipated to play a damping effect, so that the vibration is effectively alleviated.
Example 16
(1) The copolymer of 1-methyl-2- (trimethoxysilyl) ethyl methyl acrylate and 1- (3-pyrrolidinyl) -2-propen-1-one (molecular weight about 2800) was prepared by free radical polymerization using 1-methyl-2- (trimethoxysilyl) ethyl methacrylate and 1- (3-pyrrolidinyl) -2-propen-1-one as monomers, with a molar ratio of 10:5.
The copolymer and boric acid are prepared according to Si-OCH 3 Mixing the groups and the B-OH groups in a molar ratio of 1:1, heating to 80 ℃ to mix uniformly, adding 6ml of deionized water, and carrying out polymerization reaction in a stirring state to prepare a dynamic polymer containing side hydrogen bond groups and silicon borate bonds as a 1 st network polymer.
(2) The organopolysiloxane with terminal olefin group at the side band (molecular weight about 3000) is mixed with 2-mercaptoimidazole, 1, 9-nonyldithiol according to the mol ratio of double bond to mercapto of 100:90:5, 0.2wt% of photoinitiator benzoin dimethyl ether (DMPA) is added, and after stirring fully, the mixture is put into ultraviolet radiation for 4 hours in an ultraviolet cross-linking instrument, and the organic polysiloxane containing the side hydrogen bond group is obtained.
The organopolysiloxane containing side hydrogen bond groups and the 2, 6-di-tert-butyl-4-tolyldibutyl orthoborate Si-OR groups and B-OR groups are mixed according to a molar ratio of 1:1, heated to 80 ℃ and mixed uniformly, 4ml of deionized water is added, and polymerization reaction is carried out under a stirring state, so that a dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and borate bonds is prepared and used as a 2 nd network polymer.
(3) The copolymer (molecular weight is about 5000) of 3- (trimethoxy silicon based) propyl methacrylate, 3-allyl-2-pyrrolidone and N, N ' -methylenebisacrylamide is prepared by taking 3- (trimethoxy silicon based) propyl methacrylate, 3-allyl-2-pyrrolidone and N, N ' -methylenebisacrylamide as monomers and controlling the mol ratio of the 3- (trimethoxy silicon based) propyl methacrylate to the N, N ' -methylenebisacrylamide to be 10:5:1 through free radical polymerization.
The copolymer and trimethyl borate are prepared according to Si-OCH 3 The molar ratio of the group to the B-OR group is 1:1, the mixture is fully dissolved in the 1 st network polymer and the 2 nd network polymer, after the temperature is raised to 80 ℃, 10ml of deionized water is added for uniform mixing, and polymerization reaction is carried out under the stirring state, so that the dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds is prepared.
The polymer product can be used as an energy absorption buffer material and applied to a buffer packaging material.
Example 17
(1) The 3-isocyanatopropene and 3-hydroxy-1-propene were reacted in an equimolar ratio to obtain a urethane compound 17a having vinyl groups at both ends.
1, 3-diphenylpropane-2, 2-dithiol, compound 17a and tripropylamine are mixed according to a mol ratio of 9:6:2, and are put into an ultraviolet cross-linking instrument to ultraviolet radiate for 8 hours, so that a polymer containing common covalent cross-linking is obtained and is used as a 1 st network polymer.
(2) 20g of four-arm PEG (molecular weight: about 12000) with trimethoxy silicon group at the end and 3.2g of diphenyl hydrogen borate are mixed, heated to 80 ℃ and stirred uniformly, 4ml of deionized water is added, and polymerization reaction is carried out in a stirring state, so as to prepare a dynamic polymer containing a silicon borate bond as a 2 nd network polymer.
(3) Mixing N-allyl-1H-imidazole-1-formamide and 1- (3-buten-1-yl) -1H-1,2, 4-triazole according to a molar ratio of 50:30:60:1, adding 25mg of nano silicon dioxide with a particle size of 25nm, fully swelling the mixture in a 1 st network polymer and a 2 nd network polymer, adding 5mol% of AIBN as an initiator, and preparing the dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds through free radical polymerization.
The polymer product can be used for preparing magic toys and fitness materials with stress response.
Example 18
(1) Pentaerythritol tetrathioglycolate and diallyl adipate are mixed, the mole ratio of the pentaerythritol tetrathioglycolate to the diallyl adipate is controlled to be 1:2, the mixture is poured into a glass plate mold with a silica gel gasket, and the glass plate mold is placed into an ultraviolet crosslinking instrument to radiate the ultraviolet radiation for 4 hours, so that a polymer containing common covalent crosslinking is prepared and used as a 1 st network polymer.
(2) 2-aminoethyl acrylate and equimolar equivalents of acetyl bromide were dissolved in methylene chloride to give amide bond containing olefin monomer 18a under triethylamine catalysis.
The olefin monomer 18a and tert-butyl acrylate are fully mixed according to the mol ratio of 50:50, and then 5mol percent of AIBN is added, and the dynamic polymer containing side hydrogen bond groups is prepared by free radical polymerization and used as the 2 nd network polymer.
(3) The di (3-methoxy diethyl silane propyl) (Z) -but-2-enedioic acid ester and ethoxyboric acid are mixed according to the mol ratio of 1:1, 10ml of deionized water is added after the temperature is raised to 80 ℃, and the polymerization reaction is carried out under the stirring state, so as to prepare the non-crosslinked dynamic polymer containing the silicon borate ester bond. Dispersing the non-crosslinked dynamic polymer in the 1 st network polymer and the 2 nd network polymer to obtain the dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds.
The polymer product can be used for preparing speed lockers for roads and bridges.
Example 19
(1) The copolymer (molecular weight about 8000) of tert-butyl methacrylate and trimethylolpropane trimethacrylate is prepared by free radical polymerization by taking tert-butyl methacrylate and trimethylolpropane trimethacrylate as monomers, controlling the molar ratio of the tert-butyl methacrylate to the trimethylolpropane trimethacrylate to be 50:1, adding 3mol% of AIBN as an initiator, and taking the copolymer as a 1 st network polymer.
(2) Mixing methylallyl dichlorosilane and 1, 10-decanedithiol according to a molar ratio of 2:1, taking AIBN as an initiator and triethylamine as a catalyst, and preparing the silicon-containing compound of the silicon hydroxyl precursor through a thio-ene click reaction.
Mixing the silicon-containing compound of the silicon hydroxyl precursor and boric acid according to a molar ratio of 3:4, fully stirring and uniformly mixing, heating to 80 ℃, adding 4ml of deionized water, and carrying out polymerization reaction for 8 hours in a stirring state to prepare a dynamic polymer containing a silicon borate bond, wherein the dynamic polymer is used as a 2 nd network polymer.
(3) Ethyl methacrylate and 2- (1H-imidazol-4-yl) ethyl methacrylate are added with 3mol% of AIBN as an initiator according to the mol ratio of 200:1, a non-crosslinked supramolecular polymer (with the molecular weight of about 3000) containing side hydrogen bonds is prepared through free radical polymerization, and the non-crosslinked polymer containing the side hydrogen bonds is swelled in a 1 st network polymer and a 2 nd network polymer to obtain a dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds.
The polymer product can be used to make shock resistant shear plates or cyclic stress bearing tools.
Example 20
(1) 1,3, 5-tris (bromomethyl) benzene and sodium azide were stirred in DMF for 2 days to give 1,3, 5-tris (azidomethyl) benzene.
Dipropargyl adipate and 1,3, 5-tris (azidomethyl) benzene were mixed in a molar ratio of 3:2 and 0.1wt% of catalyst CuBr (PPh) relative to the monomer was added 3 ) 3 And tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), after stirring thoroughly, was reacted at 60℃for 4 hours to give a polymer containing ordinary covalent crosslinks as network 1 polymer.
(2) 3-chloropropyl dimethyl methoxy silane and boric acid are mixed according to the equimolar ratio, heated to 60 ℃ and dissolved by stirring, and then a small amount of water is added for reaction for 3 hours, so as to obtain the boric acid compound containing the silicon borate bond.
Mixing the silicon hydroxyl-terminated polyethylene glycol (molecular weight is about 5000) with the boric acid compound containing the silicon borate ester bond according to the molar ratio of the siloxane to the boric acid ester of about 1:1, adding a small amount of water, uniformly stirring at 80 ℃, and reacting for 6 hours to prepare the non-crosslinked dynamic polymer containing the silicon borate ester bond, wherein the non-crosslinked dynamic polymer is used as the 2 nd network polymer.
(3) Bis (2-mercaptoethyl) adipic acid, diallyl adipate and diallylaminomethoxyacetanilide are mixed according to a ratio of 51:50:1, 0.4g of talcum powder with a particle size of 50nm is added, 0.5wt% of AIBN is added, a non-crosslinked supramolecular polymer containing side hydrogen bonding is prepared through click reaction, and the non-crosslinked polymer containing side hydrogen bonding is swelled in a 1 st network polymer and a 2 nd network polymer to obtain a dynamic polymer containing common covalent crosslinking, side hydrogen bonding groups and silicon borate bonds.
The polymer product can be used for manufacturing damping shock absorbers and is applied to various motor vehicles and mechanical equipment.
Example 21
(1) Adipoyl chloride and polyoxypropylene triol are reacted in a molar ratio of acyl chloride to hydroxyl of about 1:1 to give a polymer containing conventional covalent cross-links.
(2) Mixing methoxy-terminated polydimethyl-phenyl hydrogen-containing siloxane (PHMS, molecular weight 10000) with a certain amount of tert-butyl acrylate and 2- (2-oxygen-1-imidazolidinyl) ethyl methacrylic acid, controlling the ratio of the mole number of active hydrogen atoms (directly connected with Si) in the polydiethyl hydrogen-containing silicone oil to the mole number of double bonds in the tert-butyl acrylate and 2- (2-oxygen-1-imidazolidinyl) ethyl methacrylic acid to be about 100:99:1, and taking chloroplatinic acid as a catalyst to carry out addition reaction to prepare the organopolysiloxane containing side hydrogen bond groups.
Mixing 5-aminopentyl dimethyl methoxy silane and tri-n-amyl borate according to an equimolar ratio, heating to 60 ℃ to dissolve the mixture by stirring, and then adding a small amount of water to react for 3 hours to obtain the borate compound containing a silicon borate bond.
The organopolysiloxane containing a side hydrogen bond group and the borate compound containing a borate ester bond are prepared according to Si-OCH 3 The molar ratio of the groups to the B-OR groups is 1:1, and the dripping amount is smallAdding 20% acetic acid aqueous solution in an amount of 5% by weight of graphene powder, stirring uniformly at 50 ℃, continuing to react for 4 hours to prepare a non-crosslinked dynamic polymer containing side hydrogen bond groups and silicon borate bonds, and swelling the non-crosslinked dynamic polymer containing the side hydrogen bond groups and the silicon borate bonds in a 1 st network polymer to obtain a dynamic polymer containing common covalent crosslinking, the side hydrogen bond groups and the silicon borate bonds.
The polymer product has good viscoelasticity and good vibration isolation and stress buffering effects, and can be used as an elastic buffer gasket.
Example 22
(1) The preparation method comprises the steps of taking brominated butyl rubber and mercaptopropyl methyl dimethoxy silane as raw materials, taking DMPA as a photoinitiator, and preparing siloxane grafted modified butyl rubber through thiol-olefin click addition reaction under the condition of ultraviolet irradiation. Adding the siloxane grafting modified butyl rubber, trimethyl borate and a proper amount of di-n-butyltin dilaurate, an antioxidant 168 and an antioxidant 1010 into a small internal mixer according to the mass ratio of 10:1, mixing, taking out the mixed materials, cooling, pressing into slices in a double-roller machine, cooling at room temperature, cutting the slices, immersing in 90 ℃ alkaline water for pre-crosslinking, placing in a vacuum drying oven at 80 ℃ for 4 hours for further reaction and drying, and crushing the 1 st network polymer into small particles.
(2) And (3) adding a proper amount of 1 st network polymer small particles and brominated butyl rubber (the mass ratio of the 1 st network polymer small particles to the brominated butyl rubber is controlled to be 1:5), adding a proper amount of 1, 6-hexanedithiol, N- [ (2-mercaptoethyl) carbamoyl ] propionamide and benzoin dimethyl ether (DMPA), 2wt% of white carbon black, 2wt% of titanium dioxide and 0.5wt% of stearic acid into a small internal mixer, continuously mixing for 20min, taking out the mixed materials, cooling, pressing into a sheet in a double-roller machine, cooling at room temperature, and cutting into sheets. And placing the film in a proper mold, and irradiating the film for 10min under normal temperature and normal pressure by utilizing ultraviolet light to prepare the dynamic polymer containing common covalent crosslinking, side hydrogen bond groups and silicon borate bonds.
The obtained rubber-based dynamic polymer material has good rebound resilience, and can be used as a rubber buffer material in the field of sports goods.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present invention.

Claims (1)

1. A dynamic polymer with a hybridized crosslinking structure is characterized by at least comprising a covalent crosslinking network, wherein the crosslinking degree of common covalent crosslinking reaches above the gel point; simultaneously comprises a dynamic covalent inorganic silicon borate bond and a supermolecule hydrogen bond function participated by a side hydrogen bond group;
Wherein the inorganic silicon borate bond is formed by reacting boric acid and trimethoxy silicon groups;
wherein the pendant hydrogen bond groups are selected from urethane groups;
wherein the inorganic silicon borate ester bond and the hydrogen bond are broken in a sacrificial bond mode under the action of external force;
wherein, the dynamic polymer with the hybridized cross-linking structure is in the form of organogel;
wherein, the dynamic polymer organogel with the hybridized crosslinking structure is prepared by the following method:
(1) Hydroxyethyl acrylate is taken as a monomer, and is prepared by free radical polymerization, and the molecular weight of the hydroxyethyl acrylate is 1000; mixing the polyhydroxyethyl acrylate, hexamethylene diisocyanate and 3-isocyanatopropyl trimethoxy silane, wherein the molar ratio of hydroxyl to isocyanate is controlled to be 2:1.1:1.1, and triethylamine is used as a catalyst to react in methylene dichloride to prepare polyacrylate with a side group containing trimethoxy silane groups; the polyacrylate and boric acid with trimethoxy silicon group on the side group are prepared according to Si-OCH 3 Mixing the groups and the B-OH groups in a molar ratio of 1:1, heating to 80 ℃ and uniformly mixing, and carrying out polymerization reaction for 8 hours in a stirring state to obtain the catalyst containing the B-OH groups A dynamic polymer having a silicon borate bond as the 1 st network polymer;
(2) Mixing trimethyl borate and dimethyl methoxy-3-butynosilane according to a molar ratio of 1:3, heating to 60 ℃, dissolving by stirring, and then adding water for continuous reaction for 4 hours to obtain a compound 12a; mixing 1, 4-diacetylene-3-alcohol and methyl isocyanate according to an equimolar ratio, and reacting in dichloromethane by taking triethylamine as a catalyst to obtain a compound 12b; mixing a compound 12a, a compound 12b and 1, 8-diaza-3, 5-dioxaoctane according to a molar ratio of 1:1:2, swelling in a 1 st network, adding into a plasticizer dioctyl phthalate, and adding a catalyst CuBr (PPh 3 ) 3 And tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]And (3) after the amine is fully mixed by stirring, reacting for 12 hours at normal temperature to obtain the dioctyl phthalate swelling organogel.
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