CN109666158B - Hybrid dynamic polymer and application thereof - Google Patents
Hybrid dynamic polymer and application thereof Download PDFInfo
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- CN109666158B CN109666158B CN201710966111.1A CN201710966111A CN109666158B CN 109666158 B CN109666158 B CN 109666158B CN 201710966111 A CN201710966111 A CN 201710966111A CN 109666158 B CN109666158 B CN 109666158B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a hybrid dynamic polymer, which simultaneously contains exchangeable covalent bonds based on alkyl triazolium, halogenated alkyl groups capable of carrying out exchange reaction with the alkyl triazolium and supermolecule hydrogen bonds, and at least one cross-linked network. In the hybrid dynamic polymer, the supermolecular hydrogen bond endows the material with stimulation responsiveness and self-repairability; the dynamic covalent bond endows the covalent cross-linked polymer with structural stability and mechanical strength under the non-catalytic reaction condition on one hand, and endows the covalent cross-linked polymer with structural stability and mechanical strength under the specific reaction condition on the other hand due to the dynamic reversibility of the covalent cross-linked polymer under the specific reaction condition; the two act together, so that the hybrid dynamic polymer has the characteristics of self-repairability, recyclability, repeatable processability and the like. The hybrid dynamic polymer can be widely applied to the aspects of self-repairing materials, tough elastomers and the like.
Description
Technical Field
The invention relates to the field of polymers, in particular to a hybrid dynamic polymer and application thereof.
Background
Crosslinking is a general method for forming a three-dimensional network structure by a polymer so as to achieve the effects of improving the stability, mechanical properties and the like of a polymer material. The cross-linking may be chemical (covalent) cross-linking or physical (non-covalent/supramolecular) cross-linking. Chemical crosslinking is a large proportion of polymer crosslinking because it is especially helpful to improve the stability and mechanical properties of polymer materials. However, when only chemical crosslinking is employed, if the crosslinking density is low, i.e., the chains between crosslinking points are long or the functionality of the crosslinking points is low, the crosslinked polymer tends to be softer, lack dimensional stability, and have poor mechanical properties; whereas, if the crosslink density is higher, i.e., the chains between crosslinks are shorter or the functionality of the crosslinks is higher, it tends to result in crosslinked polymers that are hard and brittle and that are susceptible to fragmentation failure; furthermore, general chemical crosslinking lacks dynamic properties, and once chemical crosslinking is formed, the crosslinking itself cannot be changed, so that not only the properties of the polymer material are immobilized, but also recycling is difficult.
Therefore, it is necessary to develop a novel crosslinked polymer, which can provide a system with good stability and mechanical properties, and excellent dynamic properties and can be recycled, so as to solve the problems in the prior art.
Disclosure of Invention
Against the background, the invention provides a hybrid dynamic polymer in order to obtain good stability and mechanical properties, and also have dynamic property and reusability. For this reason, we introduce dynamic covalent bonds and supramolecular hydrogen bonds into the polymer to replace traditional chemical covalent crosslinks with dynamic covalent crosslinks and supramolecular crosslinks to form a hybrid crosslinked network. The dynamic covalent crosslinking can maintain the structure and mechanical properties of the polymer, and the supermolecular hydrogen bond crosslinking can further improve the crosslinking density and enhance the stability and mechanical properties of the polymer; meanwhile, the dynamic property is provided by the supermolecule hydrogen bond, and the dynamic property lacking in chemical crosslinking is compensated by the fracture and reformation of the dynamic covalent bond under certain conditions, so that the polymer has self-repairability and recoverable reworkability.
The invention is realized by the following technical scheme:
a hybrid dynamic polymer, characterized in that, the hybrid dynamic polymer contains at least one cross-linking network, and contains exchangeable covalent bond based on alkyl triazolium, halogenated alkyl group capable of exchanging reaction with alkyl triazolium and hydrogen bonding group capable of forming supermolecular hydrogen bonding; wherein the alkyl triazolium-based exchangeable covalent bond has a structure represented by the following formula (1):
wherein X — Is negative ion selected from bromide ion and iodide ion;
represents a link to a polymer chain or any other suitable group/atom;
wherein the haloalkyl group which can undergo an exchange reaction with an exchangeable covalent bond based on alkyltriazolium has a structure represented by the following formula (2):
wherein X is a halogen atom selected from a bromine atom and an iodine atom; wherein the content of the first and second substances,
refers to a linkage to a polymer chain or any other suitable group or atom.
In one embodiment of the present invention, the hybrid dynamic polymer has only one cross-linked network, and the cross-linked network contains both dynamic covalent cross-links and supramolecular cross-links, wherein the degree of cross-linking of the dynamic covalent cross-links is above its gel point, and the degree of cross-linking of the supramolecular cross-links is above or below its gel point.
In one embodiment of the present invention, the hybrid dynamic polymer has only one cross-linked network, and the cross-linked network contains both dynamic covalent cross-links and supramolecular cross-links, wherein the degree of cross-linking of the dynamic covalent cross-links is below the gel point, and the degree of cross-linking of the supramolecular cross-links is above the gel point.
In one embodiment of the present invention, the hybrid dynamic polymer has only one crosslinked network, and the crosslinked network contains both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is below the gel point, and the degree of crosslinking of the supramolecular crosslinks is below the gel point, but the sum of the degrees of crosslinking of the supramolecular crosslinks and the gel point is above the gel point.
In one embodiment of the invention, the hybrid dynamic polymer contains two networks; the No. 1 network only contains dynamic covalent cross-linking, and the cross-linking degree is above the gel point; the No. 2 network only contains supramolecular cross-links, and the cross-linking degree is higher than the gel point.
In one embodiment of the invention, the hybrid dynamic polymer comprises two networks; the network 1 contains dynamic covalent cross-linking and supramolecular cross-linking, and the cross-linking network contains both dynamic covalent cross-linking and supramolecular cross-linking, wherein the cross-linking degree of the dynamic covalent cross-linking is above the gel point, and the cross-linking degree of the supramolecular cross-linking is above or below the gel point; the 2 nd network contains only supramolecular crosslinks, the degree of which is above its gel point.
In one embodiment of the present invention, the hybrid dynamic polymer comprises a network containing only dynamic covalent crosslinks above the gel point, and the supramolecular polymer having a degree of supramolecular crosslinking below its gel point is dispersed in the network of dynamic covalent crosslinks.
In one embodiment of the present invention, the hybrid dynamic polymer comprises a network, and the crosslinked network comprises both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular crosslinks is above or below its gel point; supramolecular polymers with a degree of supramolecular cross-linking below their gel point are dispersed in a dynamic covalent cross-linked network.
In one embodiment of the present invention, the hybrid dynamic polymer comprises a network, wherein only the dynamic covalent crosslinks above the gel point are contained, and the supramolecular polymer with the supramolecular crosslinking degree above the gel point is dispersed in the dynamic covalent crosslinked network in a particle state.
In one embodiment of the present invention, the hybrid dynamic polymer comprises a network, and the crosslinked network comprises both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular crosslinks is above or below its gel point; supramolecular polymers with a degree of supramolecular cross-linking above their gel point are dispersed in the dynamic covalent cross-linked network in the particulate state.
In one embodiment of the present invention, wherein said hybrid dynamic polymer has at least one glass transition temperature of not higher than 25 ℃.
In one embodiment of the present invention, wherein said hybrid dynamic polymer has at least one glass transition temperature of not higher than 0 ℃.
In one embodiment of the present invention, all of the glass transition temperatures of the hybrid dynamic polymers described therein are not greater than 25 ℃.
In one embodiment of the present invention, all of the glass transition temperatures of the hybrid dynamic polymers described therein are not greater than 0 ℃.
In one embodiment of the present invention, wherein said hybrid dynamic polymer has at least one glass transition temperature higher than 25 ℃ and lower than 40 ℃.
In one embodiment of the present invention, wherein said hybrid dynamic polymer has at least one glass transition temperature not lower than 40 ℃ and not higher than the dissociation temperature of the dynamic covalent bond.
In one embodiment of the present invention, all of the glass transition temperatures of the hybrid dynamic polymers are not lower than 40 ℃ and not higher than the dissociation temperature of the dynamic covalent bonds.
In one embodiment of the present invention, at least one of the hydrogen bonding groups is located in a side group or a side chain or both of the hybrid dynamic polymer.
In one embodiment of the present invention, at least one of the hydrogen bonding groups comprises both a hydrogen bonding donor and a hydrogen bonding acceptor, wherein the hydrogen bonding group comprising both a hydrogen bonding donor and a hydrogen bonding acceptor preferably comprises at least one secondary amino group, and more preferably comprises at least one of the following structural components:
wherein, the first and the second end of the pipe are connected with each other,
refers to a linkage to a polymer chain or any other suitable group/atom (including hydrogen atoms),
and/or>
May or may not be looped between.
In one embodiment of the present invention, the hydrogen bonding group is selected from a carbamate group, a urea group, a thiocarbamate group, derivatives thereof, and the like.
In one embodiment of the invention, the hybrid dynamic polymer contains at least one hydrogen bonding group that is not more than tetradentate.
In one embodiment of the invention, the hybrid dynamic polymer contains two or more hydrogen bonding groups.
In one embodiment of the present invention, wherein X in formula (1) — Is bromide ion; wherein X in the formula (2) is a bromine atom.
In one embodiment of the present invention, at least one of the polymer chain segments for connecting the dynamic covalent bond and the dynamic covalent bond, the dynamic covalent bond and the hydrogen bonding group, the hydrogen bonding group and the hydrogen bonding group is a polymer chain segment whose main chain is a carbon chain structure or a carbon-hetero chain structure.
In one embodiment of the present invention, at least one of the polymer chain segments for connecting the dynamic covalent bond and the dynamic covalent bond, the dynamic covalent bond and the hydrogen bonding group, the hydrogen bonding group and the hydrogen bonding group is a polymer chain segment whose main chain is an element hetero chain structure.
In one embodiment of the present invention, wherein at least one of the polymer segments linking the dynamic covalent bond and the dynamic covalent bond, the dynamic covalent bond and the hydrogen bonding group, the hydrogen bonding group and the hydrogen bonding group is a polymer segment having a glass transition temperature of not higher than 25 ℃.
In one embodiment of the present invention, wherein at least one of the polymer segments for linking dynamic covalent bonds and dynamic covalent bonds, dynamic covalent bonds and hydrogen bonding groups, hydrogen bonding groups and hydrogen bonding groups is a polymer segment having a glass transition temperature of not higher than 0 ℃.
In one embodiment of the present invention, wherein at least one of the polymer segments linking dynamic covalent bonds and dynamic covalent bonds, dynamic covalent bonds and hydrogen bonding groups, or hydrogen bonding groups and hydrogen bonding groups is a polymer segment having a glass transition temperature above 25 ℃ and below 40 ℃.
In one embodiment of the present invention, at least one of the polymer segments for linking the dynamic covalent bond and the dynamic covalent bond, the dynamic covalent bond and the hydrogen bonding group, or the hydrogen bonding group and the hydrogen bonding group is a polymer segment having a glass transition temperature of not less than 40 ℃ and less than a dissociation temperature of the dynamic covalent bond.
In one embodiment of the present invention, the hybrid dynamic polymer has any one of the following properties: common solids, elastomers, gels, foams.
In one embodiment of the present invention, the formulation components constituting the hybrid dynamic polymer further comprise any one or more of the following additives or utilizable substances: other polymers, auxiliaries, fillers, swelling agents. Wherein, the other polymer is preferably selected from any one or any several of the following: natural polymer compounds and synthetic polymer compounds; the auxiliary agent is preferably selected from any one or more of the following components: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants, toughening agents, coupling agents, solvents, lubricants, mold release agents, plasticizers, thickeners, thixotropic agents, leveling agents, colorants, optical brighteners, delustering agents, antistatic agents, dehydrating agents, fungicidal agents, foaming agents, co-foaming agents, nucleating agents, rheological agents; the filler is preferably selected from any one or more of the following: inorganic non-metallic fillers, organic fillers; the swelling agent is preferably selected from any one or any several of the following: water, organic solvent, ionic liquid, oligomer and plasticizer.
In one embodiment of the invention, the hybrid dynamic polymer is applied to the following materials or articles: self-repairing coating, self-repairing plate, self-repairing sealing material, self-repairing plugging glue, self-repairing conductive glue, tough material, tough elastomer material, heat insulation material, shape memory material, energy storage device material, toy and toy filler.
Compared with the prior art, the invention has the following beneficial effects:
(1) The hybrid dynamic polymers of the present invention comprise both dynamic covalent and hydrogen bonding crosslinks. Wherein, the dynamic covalent cross-linking is used for providing a balanced structure of the material on the one hand and realizing the dynamic property under specific conditions on the other hand, thereby endowing the material with self-repairability and reworkability; on one hand, the supermolecule hydrogen bond crosslinking is used for performing crosslinking supplementation on dynamic covalent crosslinking to enhance the stability and mechanical property of the dynamic covalent crosslinking, and on the other hand, the supermolecule hydrogen bond crosslinking is used for providing specific properties based on the dynamic property of the dynamic covalent crosslinking to endow the material with good toughness, self-repairability and reusability. This is not possible with existing polymer systems.
(2) The network structure of the hybrid dynamic polymers of the present invention can be varied. The supermolecule cross-linking can form a cross-linking network in the same network together with dynamic covalent cross-linking, can also independently form a dynamic cross-linking network, can also independently form dynamic cross-linking particles, and can also be dispersed in the dynamic covalent cross-linking network in a non-cross-linking polymer form. In different polymer structures, the supramolecular hydrogen bonds can exert dynamic properties, particularly strain responsiveness. Moreover, different structures have characteristics respectively, and respective advantages can be fully exerted. For example, when the supramolecular cross-linking and the dynamic covalent cross-linking form two networks which are interpenetrating or semi-interpenetrating respectively, the comprehensive efficiency can be better exerted; as another example, when both networks contain supramolecular crosslinks, the supramolecular crosslinks in both networks may be employed to provide synergistic or orthogonal dynamics.
(3) The dynamic covalent bond in the hybrid dynamic polymer is based on alkyl triazolium, and the hybrid dynamic polymer has the advantages of easily obtained raw materials, simple and easy synthesis and suitability for industrialization. The exchange reaction with the halogenated alkyl can be carried out only by heating without a catalyst, and the exchange rate of the exchange reaction can be regulated and controlled by the heating temperature.
(4) The hybrid dynamic polymer of the invention has good controllability. By controlling parameters such as molecular structure, molecular weight and the like of raw materials, hybrid dynamic polymers with different apparent characteristics, adjustable performance and wide application can be prepared; by controlling the position, the type and the number of hydrogen bond groups, hybrid dynamic polymers with different dynamic reversibility can be prepared; by controlling the proportion of the dynamic covalent crosslinking and different supermolecule hydrogen bond crosslinking, the hybrid dynamic polymer composition with diversity of mechanical properties, self-repairability, shape memory, multiple responses and the like can be prepared.
(5) The method and the way for preparing the hybrid dynamic polymer provided by the invention are various, and other additives can be added to modify the hybrid dynamic polymer material according to actual needs in the preparation process, so that the application performance of the material is expanded.
These and other features and advantages of the present invention will become apparent with reference to the following description of embodiments, examples and appended claims.
Detailed Description
The invention relates to a hybrid dynamic polymer, which simultaneously contains exchangeable covalent bonds based on alkyl triazolium, halogenated alkyl groups capable of carrying out exchange reaction with the alkyl triazolium and hydrogen bonding groups capable of forming supermolecular hydrogen bonding, and at least one cross-linking network.
For simplicity of description, 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 options described before the conjunction "and/or," or selected from the options described after the conjunction "and/or," or selected from the options described before and after the conjunction "and/or.
The "polymerization" reaction/action referred to in the present invention is a chain extension process/action, i.e., a polymer forming a linear, branched, cyclic, two-dimensional/three-dimensional cluster, three-dimensional infinite network structure through intermolecular reactions/actions (including covalent chemical reactions and supramolecular hydrogen bonding).
The term "crosslinking" reaction/action as used in the present invention refers to the process of intermolecular and/or intramolecular formation of a product having a three-dimensional infinite network type by covalent bond and/or supramolecular hydrogen bonding. During crosslinking, the polymer chains generally grow continuously in two/three dimensions, forming clusters (which may be two-dimensional or three-dimensional), and then evolve into a three-dimensional infinite network. Thus, crosslinking can be considered a special form of polymerization. The degree of crosslinking, just before a three-dimensional infinite network is reached during crosslinking, is called the gel point, also called the percolation threshold. A crosslinked product above the gel point (inclusive, the same applies hereinafter) having a three-dimensional infinite network structure, the crosslinked network constituting one entity and spanning the entire polymer structure; the crosslinked product below the gel point is only an open inter-chain linking structure, does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can be integrated across the entire polymer structure. Unless otherwise specified, the crosslinked structure in the present invention is a three-dimensional infinite network structure above the gel point, and the non-crosslinked structure includes linear and nonlinear structures with a degree of crosslinking of zero and a two-dimensional/three-dimensional cluster structure below the gel point.
In the present invention, "backbone" refers to a structure in the chain length direction of a polymer chain. For crosslinked polymers, the term "backbone" refers to any segment present in the backbone of the crosslinked network. For polymers of non-crosslinked structure, the "backbone", unless otherwise specified, refers to the chain with the most mer. Wherein, the side chain refers to a chain structure which is connected with the main chain of the polymer and distributed at the side of the main chain; the "branched chain"/"branched chain" may have a side chain or other chain structure branched from any chain. Wherein, the "side group" refers to a chemical group which is connected with any chain of the polymer and is arranged beside the chain. Wherein, the "terminal group" refers to a chemical group attached to any chain of the polymer and located at the end of the chain. Unless otherwise specified, a pendant group refers specifically to groups and subgroups thereof having a molecular weight of not more than 1000Da attached to the side of the backbone of the polymer chain. When the molecular weight of a side chain, branch, or branched chain does not exceed 1000Da, itself and the groups thereon are considered pendant. For simplicity, unless otherwise specified, side chains, branches, and branched chains are collectively referred to as "side chains". The "side chain" and "side group" may have a multi-stage structure, that is, the side chain/side group may be continued to have a side chain/side group, and the side chain/side group of the side chain/side group may be continued to have a side chain/side group. In the present invention, for hyperbranched and dendritic chains and their related chain structures, the outermost polymer chain segment can be regarded as a side chain, and the rest as a main chain.
The dynamic covalent cross-linked network refers to a polymer network still having a structure above a gel point when common covalent bonds and dynamic covalent bonds are left when supramolecular functions in the covalent cross-linked network are all broken; when the dynamic covalent bonds are also broken, the original polymer crosslinking network is dissociated and decomposed into any one or more of the following secondary units: monomers, polymer chain fragments, polymer clusters, polymer particles above the gel point, and the like.
The supermolecule crosslinked network in the invention refers to a polymer network still having a structure above a gel point when dynamic covalent bonds in the crosslinked network are all broken and only common covalent bonds and supermolecule hydrogen bonds are left; when the hydrogen bonds of the supermolecule are disconnected, the original polymer crosslinking network is dissociated and decomposed into any one or more of the following secondary units: monomers, polymer chain fragments, polymer clusters, polymer particles above the gel point, and the like.
The term "common covalent bond" as used herein refers to a covalent bond in the conventional sense other than dynamic covalent bond, which is difficult to break at normal temperature (generally not higher than 100 ℃) and normal time (generally less than 1 day), and includes, but is not limited to, normal carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen bond, carbon-nitrogen bond, carbon-sulfur bond, nitrogen-hydrogen bond, nitrogen-oxygen bond, hydrogen-oxygen bond, nitrogen-nitrogen bond, etc.
The term "dynamic covalent bond" as used herein refers to an exchangeable covalent bond based on alkyltriazolium which is capable of undergoing an exchange reaction under certain conditions. The "exchange reaction" refers to the formation of new covalent bonds and the dissociation of old covalent bonds, thereby resulting in exchange of chains and a change in polymer topology. For the purposes of the present invention, the crosslink density of the polymer network is essentially unchanged during this exchange process due to the particularity of the exchange reaction. Wherein the "certain conditions" refer to the presence of a haloalkyl group capable of undergoing an exchange reaction with an exchangeable alkyltriazolium and a solvent, and suitable conditions of temperature, humidity, pressure, and the like.
The term "supramolecular interaction" as used herein refers to a supramolecular hydrogen bonding, referred to as "hydrogen bonding" or "hydrogen bonding".
In embodiments of the present invention, the dynamic polymer may not have a glass transition temperature, and may have one or more glass transition temperatures. Among them, a preferred embodiment is that at least one glass transition temperature of the dynamic polymer is not higher than 25 ℃, more preferably not higher than 0 ℃, more preferably all glass transition temperatures are not higher than 25 ℃ when a plurality of glass transition temperatures exist, and most preferably all glass transition temperatures are not higher than 0 ℃, which is helpful for embodying the dynamic property and self-repairability of supramolecular hydrogen bonds in room temperature and low temperature use, and is convenient for obtaining materials or products such as adhesives, elastomers, gels, etc.; another preferred embodiment is that at least one glass transition temperature of the dynamic polymer is higher than 25 ℃ but lower than 40 ℃, which is beneficial to obtain elastomers, foams, ordinary solids and the like with stable size, moderate dynamic property and high temperature sensitivity; another preferred embodiment is that at least one glass transition temperature of the dynamic polymer composition component a is not lower than 40 ℃ and lower than the dissociation temperature of the dynamic covalent bonds (about 98 ℃), preferably none of the glass transition temperatures is lower than 40 ℃ and lower than the dissociation temperature of the dynamic covalent bonds, which helps to embody the characteristics of high-temperature dimensional stability, shape memory, hardness at low temperature and normal temperature of the material, and facilitates obtaining materials or products with special properties such as gel, foam, ordinary solid, etc.
In the embodiment of the invention, at least one crosslinking network contained in the hybrid dynamic polymer can be a single network, or a plurality of networks which are blended with each other, or a plurality of networks which are interpenetrating, or blending and interpenetrating simultaneously, etc.; it may employ any suitable cross-linking topology, chemical structure, reaction scheme, combinations thereof, and the like. Wherein, when the number of crosslinked networks contained in the hybrid dynamic polymer is two or more, these networks may be the same or different; it is possible that part of the network comprises only dynamic covalent cross-links and part of the network comprises only supramolecular cross-links, or part of the network comprises only dynamic covalent cross-links and part of the network comprises both dynamic covalent cross-links and supramolecular cross-links, or part of the network comprises only supramolecular cross-links and part of the network comprises both dynamic covalent cross-links and supramolecular cross-links, or both dynamic covalent cross-links and supramolecular cross-links are included in each network, but the invention is not limited thereto. Since the crosslinked network of the hybrid dynamic polymer of the present invention includes both dynamic covalent crosslinks and supramolecular crosslinks, the polymer network is referred to as a "hybrid crosslinked network".
In a preferred embodiment of the present invention (first network structure), the hybrid dynamic polymer has only one crosslinked network, and the crosslinked network contains both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular crosslinks is above or below its gel point. The network structure is simple, a balanced structure can be kept through dynamic covalent crosslinking, and dynamic property is provided by supermolecular crosslinking; dynamic covalent crosslinking may also provide covalent dynamics under certain conditions.
In another preferred embodiment of the present invention (second network structure), the hybrid dynamic polymer has only one crosslinked network, and the crosslinked network contains both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is below the gel point and the degree of crosslinking of the supramolecular crosslinks is above the gel point. The network structure has good dynamic property, in particular to the strain responsiveness based on supramolecular crosslinking; dynamic covalent crosslinking does not directly maintain an equilibrium structure, but under certain conditions dynamic covalent crosslinking may also provide additional covalent dynamic properties to serve as a tuning property.
In another preferred embodiment of the present invention (third network structure), the hybrid dynamic polymer has only one crosslinked network, and the crosslinked network contains both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is below the gel point, and the degree of crosslinking of the supramolecular crosslinks is below the gel point, but the sum of the degrees of crosslinking of the two is above the gel point. The degree of crosslinking of dynamic covalent crosslinking and supramolecular crosslinking in the network structure is low, the overall degree of crosslinking of the network structure is not high, and the dynamic covalent crosslinking and the supramolecular crosslinking are both important for providing the function of balancing the structure and adjusting the performance.
In another preferred embodiment of the present invention (fourth network structure), the hybrid dynamic polymer contains two networks; the 1 st network contains only dynamic covalent crosslinks, the degree of which is above its gel point; the 2 nd network contains only supramolecular crosslinks, the degree of which is above its gel point. In the network structure, the 2 nd network has good dynamic property, the 1 st network provides a balanced structure, and comprehensive efficiency can be better exerted through combination modes such as interpenetrating or semi-interpenetrating of the two networks; dynamic covalent crosslinking may also provide additional covalent dynamic properties to serve to tune performance under specific conditions.
In another preferred embodiment of the present invention (fifth network structure), the hybrid dynamic polymer contains two networks; the network 1 contains dynamic covalent cross-linking and supramolecular cross-linking, and the cross-linking network contains both dynamic covalent cross-linking and supramolecular cross-linking, wherein the cross-linking degree of the dynamic covalent cross-linking is above the gel point, and the cross-linking degree of the supramolecular cross-linking is above or below the gel point; the 2 nd network contains only supramolecular covalent crosslinks, the degree of crosslinking being above its gel point. In the network structure, the comprehensive efficiency can be better exerted through the combination modes of interpenetrating two networks and the like; and can provide synergistic or orthogonal dynamics with supramolecular cross-linking in both networks.
In another preferred embodiment of the present invention (sixth network structure), the hybrid dynamic polymer comprises a network, wherein only dynamic covalent crosslinks above the gel point are contained, and the supramolecular polymer having a degree of supramolecular crosslinking below its gel point is dispersed in the dynamic covalent crosslinked network. In the network structure, dynamic covalent crosslinking can keep a balanced structure, and can also provide covalent dynamics under specific conditions; the supramolecular polymer dispersed therein provides dynamic, in particular strain-responsive properties.
In another preferred embodiment (seventh network structure) of the present invention, the hybrid dynamic polymer comprises a network, and the crosslinked network comprises both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is above its gel point, and the degree of crosslinking of the supramolecular crosslinks is above or below its gel point; supramolecular polymers with a degree of supramolecular cross-linking below their gel point are dispersed in the dynamic covalent cross-linked network. In the network structure, dynamic covalent crosslinking can keep a balanced structure, and can also provide covalent dynamics under specific conditions; supramolecular cross-linking provides dynamic properties, and supramolecular polymers dispersed therein provide complementary dynamic properties, particularly strain-responsiveness.
In another preferred embodiment (eighth network structure) of the present invention, the hybrid dynamic polymer comprises a network containing only dynamic covalent crosslinks above the gel point, and the supramolecular polymer with a degree of supramolecular crosslinking above its gel point is dispersed in the dynamic covalent crosslinked network in the form of particles. In the network structure, dynamic covalent crosslinking can keep a balanced structure, and can also provide covalent dynamics under specific conditions; the supramolecular polymer particles provide packing and dynamic properties, allowing local viscosity and strength increase in the strain response.
In another preferred embodiment (ninth network structure) of the present invention, the hybrid dynamic polymer comprises a network, and the crosslinked network comprises both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is above its gel point, and the degree of crosslinking of the supramolecular crosslinks is above or below its gel point; supramolecular polymers with a degree of supramolecular cross-linking above their gel point are dispersed in the dynamic covalent cross-linked network in the particulate state. In the network structure, dynamic covalent crosslinking can keep a balanced structure, and can also provide covalent dynamics under specific conditions; supramolecular cross-linking provides dynamic properties, supramolecular polymer particles provide packing and complementary dynamic properties, and local viscosity and strength increases can be obtained in strain response.
Various other embodiments are also possible in the present invention. Those skilled in the art can implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.
In the embodiment of the present invention, the type of the exchangeable covalent bond based on alkyltriazolium is not particularly limited, and the position thereof is also not particularly limited, and it is preferable that at least a part of the dynamic covalent bond is located in the chain skeleton of the polymer network to exhibit the dynamic property; the alkyl triazolium-based exchangeable covalent bond has a structure represented by the following formula (1):
wherein, X — Is negative ion selected from bromide ion and iodide ionPreferably, bromide ion.
Refers to a linkage to a polymer chain or any other suitable group/atom (including a hydrogen atom). Such a device which appears again in the context>
The above definitions and ranges are used, and no repeated explanation is given unless otherwise specified.
In the embodiment of the present invention, the position of the halogenated alkyl group which can exchange with the exchangeable covalent bond based on alkyltriazolium is not particularly limited, and the halogenated alkyl group can exist in any suitable terminal group, side group and/or side chain in the hybrid dynamic polymer or in any suitable form in other components such as small molecules, oligomers and the like; the haloalkyl group which can undergo an exchange reaction with an exchangeable covalent bond based on alkyltriazolium has a structure represented by the following formula (2):
wherein, X is a halogen atom selected from a bromine atom and an iodine atom, and is preferably a bromine atom.
In the present invention, the hydrogen bonding groups capable of forming hydrogen bonding include hydrogen bonding groups present in the backbone of the polymer chain (including the backbone/side chains/branches/branched chains backbone) (hereinafter referred to as "backbone hydrogen bonding groups") as well as hydrogen bonding groups present in side groups of the polymer chain (hereinafter referred to as "side group hydrogen bonding groups") and hydrogen bonding groups present at the terminal ends of the polymer chain and other compounds (hereinafter referred to as "terminal hydrogen bonding groups"). The skeleton hydrogen bond group refers to a skeleton in which at least one atom directly participates in the construction of the polymer chain skeleton, including a polymer main chain, a side chain, a branched chain and a branched chain; the side group hydrogen bond group means that all atoms on the group are on the side group of the polymer chain; the terminal hydrogen bonding group, unless otherwise specified, means that all atoms in the group are at the end of the polymer chain.
In embodiments of the invention, the hydrogen bonding groups may be present in the hybrid dynamic polymer in any one or combination of more of the form of backbone hydrogen bonding groups, side group hydrogen bonding groups, end group hydrogen bonding groups, and the like. Because partial hydrogen bonds have no directionality and selectivity, under specific conditions, hydrogen bonding action can be formed between hydrogen bonding groups at different positions, hydrogen bonding groups at the same or different positions in the same or different polymer molecules can form hydrogen bonding action with each other, and hydrogen bonding action can be formed between hydrogen bonding groups contained in other components in the polymer, such as optional other polymer molecules, fillers, small molecules and the like. By way of example, hydrogen bonding in the present invention includes, but is not limited to, such as: the side chain and/or the hydrogen bond group in the side group form inter-chain hydrogen bond crosslinking among different molecules; inter-chain hydrogen bond crosslinking is formed between the side chain and/or the hydrogen bond group in the side group and the hydrogen bond group in the main chain skeleton; a part of the side chains and/or hydrogen bonding groups in the side groups independently form an intrachain ring through hydrogen bonding; hydrogen bonds are independently formed among hydrogen bonding groups in part of the main chain skeleton to form an intrachain ring; part of the side chains and/or hydrogen bonding groups in the side groups act together to form intrachain rings, etc. with hydrogen bonds. It is to be noted that, in the present invention, it is not excluded that some of the formed intra-chain hydrogen bonding effects form neither inter-chain nor intra-chain rings, and only effects including, but not limited to, grafting, etc. are formed.
In the embodiment of the invention, because the general number of the main chain skeleton hydrogen bond groups is limited and is not easy to control, the side chain/side group hydrogen bond groups can be generated before, after or in the process of polymerization/crosslinking, the number generated before or after can be freely controlled, the degree of freedom of the side chain/side group hydrogen bond is higher, and the dynamic property is easier to generate, the linking structure, the length and the structure of the side chain/side group hydrogen bond group and the skeleton chain can be variously adjusted, and therefore, the supramolecular hydrogen bond group in the invention preferably at least comprises one side chain/side group hydrogen bond group, so that the hydrogen bond strength, the steric hindrance, the thermal stability, the glass transition temperature and the like are controlled, the dynamic property is further adjusted, and different performances such as super toughness, self-repairing, strain responsiveness, shape memory and the like are endowed to the polymer.
In an embodiment of the invention, the hydrogen bonding in the supramolecular interaction is formed by the interaction of a donor (H, i.e. a hydrogen atom) and an acceptor (Y, i.e. an electronegative atom that accepts a hydrogen atom) of a hydrogen bonding group, which may be of any number of teeth. Wherein, the tooth number refers to the number of hydrogen bonds formed by a donor and an acceptor of the hydrogen bond group, and each H \8230andY combination is one tooth. In the following formula, the bonding of the monodentate, bidentate and tridentate hydrogen bonds is schematically illustrated, respectively.
The bonding of the monodentate, bidentate and tridentate hydrogen bonds can be specifically exemplified as follows:
in the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. The more the number of teeth of the hydrogen bond, the greater the synergistic effect and the greater the strength of the hydrogen bond. If the number of teeth of the formed hydrogen bonds is large, the strength is high, the dynamic property of the hydrogen bond action is weak, and the hydrogen bonds can be used as structural hydrogen bonds to play roles in promoting the hybrid dynamic polymer to keep an equilibrium structure and improving the mechanical properties (modulus and strength). If the number of the formed hydrogen bonds is small, the strength is low and the dynamics of the hydrogen bonding is strong. In the present invention, a preferred embodiment provides dynamics for the selection of hydrogen bonds of no more than four teeth; another preferred embodiment is to select two or more hydrogen bonding groups to form hydrogen bonds with different dynamics, so as to provide multilayer dynamics.
In an embodiment of the present invention, the hydrogen bonding may be caused by non-covalent interactions between any suitable hydrogen bonding groups, which may comprise only hydrogen bonding donors, or only hydrogen bonding acceptors, or both hydrogen bonding donors and acceptors, preferably both hydrogen bonding groups so that they can independently form hydrogen bonding, and the hydrogen bonding groups comprising both hydrogen bonding donors and acceptors preferably comprise at least one secondary amino group, more preferably at least one of the following structural components:
wherein the content of the first and second substances,
represents a linkage to a polymer chain or any other suitable group/atom (including a hydrogen atom);
and/or>
May or may not be looped between.
Wherein, by
The attached group or atom is designated as G. The structure of G is not particularly limited, and each independently includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure. Among them, the cyclic structure is not particularly limited, and may be selected from an aliphatic ring, an aromatic ring, a sugar ring, and a condensed ring, and an aliphatic ring is preferable.
The structures of G are each independently preferably a linear structure.
G may or may not contain a heteroatom.
The number of carbon atoms of G is not particularly limited, but each is independently preferably 1 to 20, and each is independently more preferably 1 to 10.
G is independently selected from hydrogen atom, halogen atom, C 1-20 Hydrocarbyl radical, C 1-20 Heterohydrocarbyl, substituted C 1-20 Hydrocarbyl or substituted heterohydrocarbyl. Wherein the substituent atom in G isThe substituents are not particularly limited, and each is independently selected from a halogen atom, a hydrocarbon group substituent, and a heteroatom-containing substituent.
G is each independently more preferably a hydrogen atom, a halogen atom, C 1-20 Alkyl radical, C 1-20 Unsaturated aliphatic, aryl, C 1-20 Heterohydrocarbyl radical, C 1-20 Hydrocarbyloxyacyl group, C 1-20 Hydrocarbyl thioacyl groups and substituted forms of any of them.
G is each independently more preferably a hydrogen atom, a halogen atom, C 1-20 Alkyl radical, C 1-20 Alkenyl, aryl, arylalkyl, C 1-20 Aliphatic heterocarbyl, heteroaryl, heteroaromatic hydrocarbyl, C 1-20 Alkoxyacyl, aryloxyacyl, C 1-20 Alkylsulfanyl acyl, arylsulfanyl acyl, and substituted forms of any of them.
G is each independently more preferably a hydrogen atom, a halogen atom, C 1-20 Alkyl radical, C 1-20 Alkenyl, aryl, arylalkyl, C 1-20 Aliphatic heteroalkyl, heteroaryl, heteroarylalkyl, C 1-20 Alkoxycarbonyl, aryloxycarbonyl, C 1-20 Alkylthio carbonyl, arylthio carbonyl, C 1-20 Alkoxythiocarbonyl, aryloxylthiocarbonyl, C 1-20 Alkylthio thiocarbonyl, arylthio thiocarbonyl and substituted forms of any thereof.
Specifically, each G is independently selected from the group consisting of, but not limited to, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, an 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 benzyloxycarbonyl group, a methylthiocarbonyl group, an ethylthiocarbonyl group, a phenylthiocarbonyl group, a benzylthiocarbonyl group, an ethylaminocarbonyl group, a benzylamino carbonyl group, a methoxythiocarbonyl group, an ethoxythiocarbonyl group, a phenoxythiocarbonyl group, a benzyloxythiocarbonyl group, a methylthio group, a methoxythiocarbonyl group, aThiocarbonyl, ethylthiocarbonyl, phenylthiocarbonyl, benzylthiocarbonyl, substituted C 1-20 Alkyl, substituted C 1-20 Alkenyl, substituted aryl, substituted arylalkyl, substituted C 1-20 Aliphatic heterocarbyl, substituted heteroaryl, substituted heteroarylalkyl, substituted C 1-20 Alkoxycarbonyl, substituted aryloxycarbonyl, substituted C 1-20 Alkylthio carbonyl, substituted arylthio carbonyl, substituted C 1-20 Alkoxythiocarbonyl, substituted aryloxythiocarbonyl, substituted C 1-20 Alkylthio thiocarbonyl, substituted arylthio thiocarbonyl. Wherein, butyl includes but is not limited to n-butyl and t-butyl. Octyl includes, but is not limited to, n-octyl, 2-ethylhexyl. Wherein the substituent atom or substituent group is selected from halogen atom, alkyl substituent group and substituent group containing hetero atom.
<xnotran> G , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,2- , , ,2- , , , , , , , , , , , , , , , , , , , , , , , C </xnotran> 1-10 Halogenated hydrocarbyl, trifluoroacetyl, halogenated phenyl, halogenated benzyl, nitrophenyl, nitrobenzyl, and substituted versions of any of these. Among them, the substituent atom or the substituent is preferably a fluorine atom, an alkoxy group or a nitro group.
G is each independently more preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, benzyl group, trityl group, phenyl group, benzyl group, methylbenzyl group, tert-butylthio group, benzylthio group, 2-pyridylthio group, 2-pyridylcarbonyl group, tert-butyloxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, tert-butyloxythiocarbonyl group, phenoxythiocarbonyl group, benzyloxythiocarbonyl group, tert-butylthiothiocarbonyl group, phenylthiothiocarbonyl group, benzylthiocarbonyl group, trifluoroacetyl group.
G is each independently more preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, benzyl group, trityl group, phenyl group, benzyl group, methylbenzyl group, tert-butylthio group, benzylthio group, 2-pyridylthio group.
Each G is independently most preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.
In another preferred embodiment of the present invention, the hydrogen bonding group is preferably selected from carbamate, urea, thiocarbamate, derivatives thereof, and the like, and is suitable for industrial production due to its abundant raw materials and simple synthesis.
Examples of the hydrogen bonding group include the following side groups and/or terminal groups, but the present invention is not limited thereto.
Wherein m, n and x are the number of repeating groups, and can be fixed values or average values. m and n are integers with the value range of 0 and more than or equal to 1; the value range of x is an integer greater than or equal to 1.
Examples thereof include hydrogen bonding groups on the main chain and/or side chain skeleton as described below, but the present invention is not limited thereto.
In the embodiment of the present invention, the hydrogen bonding group forming the hydrogen bonding action may be a complementary type combination between different hydrogen bonding groups, or a self-complementary type combination between the same type of hydrogen bonding group, as long as a suitable hydrogen bonding action can be formed between the groups. Some combinations of hydrogen bonding groups may be exemplified as follows, but the invention is not limited thereto:
in the present invention, the supramolecular hydrogen bonding may be generated during the dynamic supramolecular cross-linking/polymerization of the hybrid dynamic polymer; or the dynamic supermolecule cross-linking/polymerization is carried out after the supermolecule hydrogen bond is generated in advance; it is also possible to generate supramolecular hydrogen bonding during the subsequent shaping of the hybrid dynamic polymer after the dynamic supramolecular cross-linking/polymerization has been formed, but the invention is not limited thereto.
In the embodiment of the present invention, in addition to the formation of hydrogen bonding by hydrogen bonding between hydrogen bonding groups present in the polymer, hydrogen bonding may be formed by the hydrogen bonding groups with hydrogen bonding groups on other components introduced as additives. Such other components that can participate in hydrogen bonding include, but are not limited to, small molecules, inorganic materials, metallic materials, and the hydrogen bonding groups contained therein can be any groups that can form hydrogen bonds with the hydrogen bonding groups. Hydrogen bonds may also be formed between such other components.
In an embodiment of the present invention, said alkyl triazolium-based exchangeable covalent bond is preferably formed by reaction of a triazolyl-containing derivative and a haloalkyl compound, which may be carried out before or during the formation of the dynamic covalent cross-linking.
Wherein the introduction of the group or segment containing an exchangeable covalent bond based on alkyltriazolium, the derivative containing a triazolyl group and the haloalkyl group may be carried out by any suitable reaction, including but not limited to the following types: the reaction of isocyanate with amino, hydroxyl, sulfydryl, carboxyl and epoxy, the reaction of carboxylic acid, acyl halide, acid anhydride and active ester with amino, hydroxyl and sulfydryl, the free radical reaction of acrylate, the free radical reaction of acrylamide, the free radical reaction of double bonds, the reaction of epoxy with amino, hydroxyl and sulfydryl, the phenolic reaction, the azide-alkyne click reaction, the tetrazine-norbornene reaction and the silicon hydroxyl condensation reaction; preferably, the reaction of isocyanate with amino, hydroxyl and sulfhydryl, the reaction of acyl halide and anhydride with amino, hydroxyl and sulfhydryl, the reaction of acrylate free radical, the reaction of acrylamide free radical, the reaction of double bond free radical and the reaction of epoxy with amino, hydroxyl and sulfhydryl.
Wherein, the triazolyl derivative can be selected from commercially available raw materials, such as but not limited to 1-phenyl-4-carbinol-1H-1, 2, 3-triazole, [1- (phenylmethyl) -1,2, 3-triazol-4-yl ] methanol, 1H-1,2, 3-triazol-1-acetic acid, 1-benzyl-1, 2, 3-triazol-4, 5-dicarboxylic acid, 5-iodo-1-methyl- [1,2,3] triazole, 5-ethyl-1-phenyl-1H- [1,2,3] triazol-4-carboxylic acid, 4- [1,2,3] triazol-1-yl-piperidine, 1-phenyl-1H- [1,2,3] triazol-4-carboxylic acid methyl ester, 4,5,6, 7-tetrahydro-1, 2, 3-triazolo [1,5-A ] pyrazine hydrochloride, 4- ([ 1,2,3] triazol-1-yl) benzaldehyde, 1-methyl-1-amino-1, 3-triazole-4-methyl-1, 3-triazol-1, 3-triazole-4-amino-1, 2, 3-triazole-4-1, 3-triazole-4-methyl formamide, etc.
The triazolyl derivative can also be obtained by any suitable reaction, wherein the triazolyl derivative is preferably obtained by reaction of alkyne and azide, and is more preferably obtained by reaction of alkyne-containing small molecule/oligomer, azide-containing small molecule/oligomer and/or alkyne-and azide-containing small molecule/oligomer by directly heating in the absence of solvent and catalyst.
The halogenated alkyl compound can be directly selected from commercial raw materials, can also be obtained by any suitable reaction, and preferably is directly selected from commercial raw materials. By way of example, commercially available haloalkyl compounds that may be used include, but are not limited to, the following: dibromoalkanes such as 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 3-dibromo-2-methylpropane, 1, 3-dibromo-2, 2-dimethylpropane, 1, 3-dibromo-2, 2-diethylpropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 5-dibromo-3-methylpentane, 1, 6-dibromohexane, 1, 7-dibromoheptane, 1, 8-dibromooctane, 1, 9-dibromononane, 1, 10-dibromodecane, 1, 12-dibromododecane, 1, 15-dibromopentadecane, 1, 18-dibromooctadecane, etc.; tribromoalkanes such as 1,2, 3-tribromopropane, 1,2, 4-tribromobutane, 1,3, 5-tris (bromomethyl) benzene, 1,3, 5-tribromomethyl-2, 4, 6-trimethylbenzene, etc.; bromoalkyl alcohols such as 2-bromoethanol, 2, 3-dibromo-1-propanol, 1, 3-dibromo-2-propanol, 3-bromo-1-propanol, 4-bromo-1-butanol, 5-bromo-1-pentanol, 6-bromo-1-hexanol, 7-bromo-1-heptanol, 8-bromo-1-octanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 11-bromo-1-undecanol, 12-bromo-1-dodecanol, 14-bromo-1-tetradecanol, 16-bromo-1-hexadecanol, dibromoneopentyl glycol, 1, 4-dibromo-2, 3-butanediol, 1, 4-dibromo-2-butanol, 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propanediol, dibromomannitol, tribromoneopentanol, 2, 6-bis (bromomethyl) -4-methylphenol, and the like; bromoalkyl acids such as bromoacetic acid, 3-bromopropionic acid, 2, 3-dibromopropionic acid, 4-bromobutyric acid, 5-bromovaleric acid, 11-bromoundecanoic acid, 16-bromohexadecanoic acid, and the like; other bromine-containing compounds such as bromopropene, 6-bromo-1-hexene, 3-bromopropyne, 4-bromo-n-butyne, 5-bromo-n-pentyne, bromo-oligo (ethylene glycol) -bromo, (2-bromomethyl) benzoyl chloride, 4-bromobutyryl chloride, 6-bromohexanoyl chloride, 3-bromo-1-propanethiol, 6-bromohexylamine, etc.; diiodoalkyl compounds such as 1, 2-diiodoethane, 1, 3-diiodopropane, 1, 3-diiodo-2-methylpropane, 1, 3-diiodo-2, 2-dimethylpropane, 1, 4-diiodobutane, 1, 5-diiodopentane, 1, 6-diiodohexane, 1, 6-diiodo-3, 4-tetrafluorohexane, 1, 7-diiodoheptane, 1, 8-diiodooctane, 1, 9-diiodononane, 1, 10-diiododecane, 1, 12-diiodododecane and the like; iodoalkyl alcohols such as 2-iodoethanol, 3-iodopropanol, 1, 3-diiodo-2-propanol, 4-iodo-1-butanol, 5-iodo-1-pentanol, 6-iodo-1-hexanol, 7-iodo-1-heptanol, 8-iodo-1-octanol, 9-iodo-1-nonanol, 10-iodo-1-decanol, 11-iodo-1-undecanol, 12-iodo-1-dodecanol and the like; iodoalkyl acids such as iodoacetic acid, 4-iodobutyric acid, and the like; other iodine-containing compounds such as 3-iodopropene, 5-iodo-1-pentene, ethyl 5-iodovalerate, 2, 5-di (iodomethyl) -1, 4-dioxane, iodo-oligo (ethylene glycol) -iodo, etc.
In embodiments of the present invention, the generation and/or introduction of hydrogen bonding groups may be performed before, after or during the generation of the dynamic covalent crosslinks, and any suitable reaction may be employed, including but not limited to the following types: reaction of isocyanate with amino, hydroxyl, mercapto, carboxyl, acrylate radical reaction, double bond cyclization reaction, reaction of epoxy with amino, hydroxyl, mercapto, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, tetrazine-norbornene reaction, reaction of active ester with amino, hydroxyl, mercapto, silicon hydroxyl condensation reaction; preferably, the reaction of isocyanate with amino, hydroxyl, mercapto, urea-amine, amidation, reaction of active ester with amino, hydroxyl, mercapto. The formation and/or introduction of hydrogen bonding groups may have one or more of reaction type, reaction means and structure.
In embodiments of the invention, the components used to link dynamic covalent bonds and dynamic covalent bonds, dynamic covalent bonds and hydrogen bonding groups, hydrogen bonding groups and hydrogen bonding groups may be small molecules and/or polymer segments. The polymer chain segment includes, but is not limited to, a polymer chain segment whose main chain is a carbon chain structure, a carbon-hetero chain structure, a carbon element chain structure, an element-hetero chain structure, or a carbon-hetero element chain structure. The carbon chain structure is a structure of which the main chain skeleton only contains carbon atoms; the carbon heterochain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms and any one or more heteroatoms, wherein the heteroatoms comprise but are not limited to sulfur, oxygen and nitrogen; the carbon element chain structure is a structure that a main chain skeleton simultaneously contains carbon atoms and any one or more element atoms, wherein the element atoms comprise but are not limited to silicon, boron and aluminum; the element chain structure is a structure that a main chain skeleton only contains element atoms; the element heterochain structure is a structure which has a main chain skeleton and only contains at least one heteroatom and at least one element atom; the carbon-heteroatom chain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms, heteroatoms and element atoms. In one embodiment of the present invention, the polymer segment is preferably a polymer segment whose main chain has a carbon chain structure or a carbon hetero chain structure, because of its abundant structure and excellent performance. By way of example, preferred carbon and carbon heterochain polymer segments include, but are not limited to, homopolymers, copolymers, modifications, derivatives, and the like, such as acrylate polymers, saturated olefin polymers, unsaturated olefin polymers, polystyrene polymers, halogen-containing olefin polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, poly (2-oxazoline) polymers, polyether polymers, polyester polymers, bio-polyester polymers, polycarbonate polymers, polyurethane polymers, polyurea polymers, polyamide polymers, polyamine polymers, liquid crystal polymers, epoxy polymers, polythioether polymers, and the like. In another embodiment of the present invention, the polymer segment is preferably of an elemental heterochain structure, such as, for example, various types of polyorganosiloxane polymers. In another embodiment of the present invention, the glass transition temperature of the polymer chain segment is preferably not higher than 25 ℃, more preferably not higher than 0 ℃, and the polymer chain segment is flexible at room temperature before the reaction, so that the subsequent processing and preparation of the product can be conveniently performed at room temperature, the flexible and viscous product can be conveniently obtained, and the hardness of the material matrix can be conveniently adjusted by increasing the crosslinking density or using other additives, and the material matrix can be used as a matrix to be beneficial to embodying the dynamics of the supramolecular hydrogen bond. In another embodiment of the present invention, it is preferred that the glass transition temperature of the polymer segment is higher than 25 ℃ but lower than 40 ℃ to facilitate the introduction of temperature sensitivity, moderate elasticity and dynamic properties. In another embodiment of the present invention, the glass transition temperature of the polymer segment is preferably not lower than 40 ℃ and not higher than the dissociation temperature of the dynamic covalent bond (about 98 ℃), which is advantageous for introducing the characteristics of shape memory, high-temperature dimensional stability, low-temperature and room-temperature hardness, and the like. Preferable polymer segments include, for example, but are not limited to, homopolymers, copolymers, modifications, derivatives, and the like of acrylic polymers, saturated olefin polymers, unsaturated olefin polymers, halogen-containing olefin polymers, poly (2-oxazoline) polymers, polyether polymers, polyester polymers, biopolyester polymers, polyurethane polymers, polyurea polymers, polythioether polymers, silicone polymers, and the like. Specifically, preferred polymer segments of the present invention include, by way of example only, homopolymers, copolymers, modifications, derivatives, and the like of polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyethylene, polypropylene, polystyrene, polyisobutylene, polybutadiene, polycyclooctene, polynorbornene, polyisoprene, polyvinyl chloride, poly (2-oxazoline), polyethylene glycol, polypropylene glycol, polycaprolactone, poly (limonene carbonate), poly (beta-hydroxybutyrate), polycarbonate, polyurethane, polyurea, polyamide, polythioether, polysiloxane, and the like.
In embodiments of the present invention, the small molecules and/or polymer segments used to link dynamic covalent bonds and dynamic covalent bonds, dynamic covalent bonds and hydrogen bonding groups, hydrogen bonding groups and hydrogen bonding groups, and/or hybrid dynamic polymers may have any suitable topology, including but not limited to linear structures, branched structures (including but not limited to star, H, dendritic, comb, hyperbranched), cyclic structures (including but not limited to single ring, multiple ring, bridge, grommet, wheel ring), two-dimensional/three-dimensional cluster structures, and combinations of two or any of them; among them, a linear structure which facilitates synthesis and control of the structure, a branched structure which is abundant in the structure, and a two-dimensional/three-dimensional cluster structure which can be locally reinforced are preferable, and a linear structure and a branched structure are more preferable. In the present invention, it is not even excluded to use the crosslinked polymer particles for further polymerization/crosslinking etc. reactions and linkages.
The various polymers and chain segments thereof selected in the invention, namely the polymers and chain segments thereof containing both dynamic covalent bonds and hydrogen bond groups, the polymers and chain segments thereof containing neither dynamic covalent bonds nor hydrogen bond groups, the polymers and chain segments thereof containing only dynamic covalent bonds and no hydrogen bond groups, and the polymers and chain segments thereof containing only hydrogen bond groups and no dynamic covalent bonds can be directly selected from commercialized raw materials and can also be polymerized by self. Polymerization methods include, but are not limited to, polycondensation, polyaddition, and ring opening polymerization, depending on the type of polymer selected; wherein, addition polymerization includes, but is not limited to, radical polymerization, living radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, and the like. The polymerization process may be carried out in a solvent or may be carried out by bulk polymerization without a solvent. Specifically, by way of example, alternative aggregation methods of the present invention include, but are not limited to: thermal initiation general radical polymerization of styrene, (meth) acrylate monomers, photo initiation radical polymerization of styrene, (meth) acrylate monomers, initiation transfer terminator method radical polymerization of vinyl chloride monomers, atom Transfer Radical Polymerization (ATRP) of styrene, (meth) acrylate monomers, reversible addition-fragmentation transfer radical polymerization (RAFT) of styrene, (meth) acrylate, acrylonitrile monomers, nitroxide stable radical polymerization (NMP), ethylene, propylene coordination polymerization, anionic polymerization of styrene monomers, lactone ring-opening polymerization, lactam ring-opening polymerization, epoxy ring-opening polymerization, polycondensation between dibasic acid and dibasic alcohol, polycondensation between dibasic acid and diamine, click reaction polymerization between dibasic thiol and dibasic alkene/alkyne, click reaction polymerization between dibasic azide and dibasic alkyne, ring-opening polymerization of 2-oxazoline derivatives, polyurethane/polyurea reactions, and the like. In particular embodiments, the compound starting materials may be carried out by any suitable polymerization process commonly used in the art using any of the polymerization methods described above to obtain the hybrid dynamic polymers of the present invention.
The crosslinking mechanism for the polymer may be addition crosslinking or condensation crosslinking. Herein, addition crosslinking refers to a crosslinking polymerization reaction by an addition form, and generally forms a crosslinked product from a molecular chain containing a multifunctional group by an addition reaction of an intermolecular functional group, without generating a by-product. Condensation crosslinking refers to a crosslinking reaction by a form of condensation, and generally forms a crosslinked product from a molecular chain containing a polyfunctional group by an intermolecular functional group condensation reaction, with a by-product being generated.
In embodiments of the present invention, crosslinking may employ any suitable physical and chemical crosslinking process. Physical crosslinking processes include, but are not limited to, thermally induced crosslinking, photo-induced crosslinking, radiation induced crosslinking, plasma induced crosslinking, microwave induced crosslinking, and the like; chemical crosslinking processes include, but are not limited to, peroxide crosslinking, nucleophile-substituted crosslinking, isocyanate-reactive crosslinking, epoxy-reactive crosslinking, acrylate-reactive crosslinking, and the like. The crosslinking process may be carried out in bulk, solution, emulsion, etc. When the solid product is in a bulk form, the solid end product can be conveniently and directly obtained; when the solution form is adopted, the gel is conveniently and directly obtained; when an emulsion is used, it is convenient to obtain dispersed but self-adhering particles. It is to be noted that any cross-linking must ensure that complete or incomplete dissociation of the dynamic covalent bonds can lead to the disassembly of the covalently cross-linked network.
The polymerization method, the crosslinking method, and the initiator, catalyst, crosslinking agent, other auxiliaries, and reaction conditions required for the polymerization and crosslinking processes are well known conventional techniques (e.g. from "polymer chemistry" (enhanced), as written by spidernut "), and can be selected and combined as needed by those skilled in the art.
The following is an example of an embodiment of a partial preparation method of the network structure of the present invention.
For example, the first network structure of the present invention can be prepared by the following method: will have hydrogen bonding groups (denoted as R in the following structural formula) H ) The monomer (A) and the halogenated alkyl compound with at least two halogen atoms X are mixed and heated to react, and then the monomer (A) and the halogenated alkyl compound can be polymerized/crosslinked to form a first network structure in the invention. By controlling the formula proportion of the raw materials and the molecular weight of the monomers, the content and proportion of the dynamic covalent bonds in the network and each hydrogen bond group on different positions can be adjusted, so that the covalent crosslinking in the network is more than the covalent gel point.
As another example, a first network structure of the present invention can be prepared by: will bear a pendant hydrogen bonding group R H And an alkyl triazolium-based exchangeable covalent bond (denoted as V in the following structural formula) m ) The trihydroxy monomers of (a) can be polymerized/crosslinked to form the first network structure of the present invention. By controlling the formula proportion of the raw materials and the molecular weight of the monomers, the content and proportion of the dynamic covalent bonds in the network and each hydrogen bond group on different positions can be adjusted, so that the covalent crosslinking in the network is more than the covalent gel point.
As another example, the first network structure of the present invention can also be achieved by reacting a polymer having triazole groups pendant from the polymer and hydrogen bonding groups pendant from the polymer with a difunctional haloalkyl compound: will carry a pendant hydrogen bonding group R H And at least two triazolyl groups T r The first network structure of the present invention can be obtained by reacting the polymer of (a) with a haloalkyl compound having at least two halogen atoms X. By controlling the proportion of the formula of the monomer containing the hydrogen bond group and the monomer without the hydrogen bond group, the proportion of the dynamic covalent bond and the hydrogen bond group in the network can be adjusted, so that the supermolecule crosslinking in the network reaches above the gel point.
Other embodiments of the network structure of the present invention are similar to those of the present invention, and those skilled in the art can select an appropriate preparation method to achieve the desired purpose according to the understanding of the present invention.
In the present invention, the constituent interpenetrating networks can be classified into two categories, semi-interpenetrating and fully interpenetrating, depending on the crosslinking of the polymer components in the network. Only one component is covalently cross-linked in the semi-interpenetrating, and the other component is intercrossed and entangled in the covalently cross-linked component in the form of non-covalently cross-linked molecular chains.
Conventional interpenetrating network polymer preparation methods typically include one-step interpenetration and two-step interpenetration. All the components are added in one step, and then polymerization/crosslinking is carried out to prepare the target network. The two-step process is to prepare the 1 st network polymer, then soak it in the 2 nd network forming monomer/prepolymer solution, then initiate polymerization/crosslinking to obtain the target hybrid network. The hybrid dynamic polymer can be prepared by adopting one-step interpenetrating and two-step interpenetrating, and three or more steps are required under specific conditions.
The following is an illustration of an embodiment of a partial method of making the interpenetrating network polymer of the present invention. The following examples are given by way of illustration only and are not intended to limit the scope of the present invention, which is not limited to the following examples.
For example, in the fourth network structure of the present invention, the hybrid dynamic polymer is composed of two networks. First, a dynamic covalent crosslinked network of polymers is prepared in which no hydrogen bonding groups are present, but alkyl triazolium-based exchangeable covalent bonds are present in the backbone of the polymer chains. Then, the obtained dynamic covalent network is swelled, and is uniformly mixed with monomers or prepolymers of a supramolecular cross-linked network, a cross-linking agent and the like to carry out supramolecular cross-linking, so that a full interpenetrating network polymer is obtained, namely the supramolecular network is dispersed and penetrated in the dynamic covalent cross-linking. Or, the monomer or prepolymer of the dynamic covalent crosslinking network, the crosslinking agent, the monomer or prepolymer of the supramolecular crosslinking network, the crosslinking agent and the like are uniformly mixed, and dynamic covalent crosslinking and supramolecular crosslinking are simultaneously carried out, so as to obtain the fourth network structure of the invention.
As another example, in the seventh network structure of the present invention, first, the aforementioned method is rationally selected to prepare a hybrid cross-linked network having the first network structure that contains both dynamic covalent cross-links and supramolecular cross-links. And then, fully blending the obtained hybrid cross-linked network with the supramolecular polymer to obtain the semi-interpenetrating network polymer. Or, the monomer or prepolymer of the hybrid cross-linked network with the first network structure, the cross-linking agent and the supramolecular polymer are uniformly mixed and subjected to dynamic covalent cross-linking, so that the seventh network structure is obtained.
In the present invention, the form of the hybrid dynamic polymer and the composition containing the same may be a common solid, an elastomer, a gel, a foam, or the like. Wherein the content of soluble low molecular weight components contained in common solid and foam materials is generally not higher than 10wt%, and the content of low molecular weight components contained in gel is generally not lower than 50wt%. The common solid has good mechanical property, the elastomer has moderate mechanical property but has flexibility which is not possessed by the common solid, and the preparation method is the simplest and most convenient, so the preparation method is more preferable. Foams are also preferred because of their light weight, adjustable hardness and flexibility, and wide range of uses. In embodiments of the invention, a swelling agent may be incorporated into the hybrid dynamic polymer to produce a hybrid dynamic polymer gel. The gel product has good softness and bendability, and can have certain toughness through structure and formula adjustment, because the swelling agent exists, the gel product can be blended into beneficial composition components which are not available in materials with other forms, and has special application. The swelling agent can include but is not limited to organic solvent, ionic liquid, oligomer, plasticizer and water, and hybrid dynamic polymer organic solvent gel, ionic liquid gel, oligomer swelling gel, plasticizer swelling gel and hydrogel are obtained correspondingly. Among them, ionic liquid gels and plasticizer-swollen gels are preferable.
A preferred method for preparing the hybrid dynamic polymer swelling agent swollen gel of the present invention includes, but is not limited to, the following steps: adding the raw materials for preparing the hybrid dynamic polymer and other raw materials into a swelling agent and an optional solvent to ensure that the sum of the mass fractions of the raw materials for preparing the hybrid dynamic polymer is 0.5-70%, carrying out polymerization, coupling, crosslinking or other types of chemical reactions by the proper means, and removing the solvent according to the requirements after the reaction is finished to prepare the swelling gel of the hybrid dynamic polymer swelling agent. A preferred method for preparing another hybrid dynamic polymer swelling agent swollen gel of the present invention includes, but is not limited to, the following steps: swelling the hybrid dynamic polymer and other raw materials in a swelling agent and an optional solvent to ensure that the mass fraction of the hybrid dynamic polymer is 0.5-70%, and removing the solvent according to needs after full swelling to prepare the swelling gel of the hybrid dynamic polymer swelling agent.
In embodiments of the invention, the hybrid dynamic polymer can be prepared into a foamed material. Wherein the foam comprises a flexible foam, or is a semi-flexible, semi-rigid, microcellular, or rigid foam.
In the embodiment of the invention, the structure of the hybrid dynamic polymer foam material relates to an open-cell structure, a closed-cell structure, a semi-open semi-closed structure and the like. In the open pore structure, the cells are communicated with each other or completely communicated with each other, the single dimension or the three dimension can pass through gas or liquid, and the cell diameter is different from 0.01 to 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 inner cells are not communicated with each other, and the cell diameters are different from 0.01 to 3 mm. The contained cells have a structure which is not communicated with each other, and the structure is a semi-open cell structure.
In the embodiment of the present invention, the foaming method is a general method, and can be classified into a physical foaming method and a chemical foaming method according to the difference of the foaming agent used. The foam may be prepared in the presence or absence of water, and may be mechanically foamed or non-mechanically foamed. Further, the foam may be prepared using auxiliary non-reactive blowing agents known in the art.
The invention discloses a preparation method of a preferable hybrid dynamic polymer foam, which comprises the following steps: when preparing the single-network hybrid dynamic polymer foam, two-component reaction materials are prepared first. The reaction material comprises all small molecular monomers, chain extenders, cross-linking agents and other required auxiliaries for generating the hybrid dynamic polymer; the reaction material contains foaming agent, foam stabilizer, catalyst for catalyzing foaming and/or polymerization crosslinking reaction and other required assistants. Then mixing the two components of reaction materials according to a certain proportion, stirring, and controlling the temperature according to the requirement to obtain the foamed single-network hybrid dynamic polymer. The hybrid dynamic polymer for the hybrid dynamic polymer foam prepared according to this preparation process is preferably a polyurethane, polyurea based polymer.
Another preferred method for preparing the hybrid dynamic polymer foam of the present invention is a freeze-drying method, comprising the steps of: the hybrid dynamic polymer, swollen in a volatile solvent, is frozen and then escapes the solvent in a sublimating manner under near vacuum conditions. During and after the solvent has escaped, the polymer can maintain its shape before freezing, and a porous sponge-like foam is obtained.
In the method for preparing hybrid dynamic polymer foam of the present invention, when the foam contains a plurality of polymer networks, the plurality of networks may be generated simultaneously or separately.
The hybrid dynamic polymer foam material provided by the invention also relates to: converting the hybrid dynamic polymer foam material into any desired shape, such as tubes, rods, sheaths, containers, spheres, sheets, rolls and tapes, by welding, gluing, cutting, routing, perforating, embossing, laminating and thermoforming; combining the hybrid dynamic polymeric foam material with sheets, films, foams, fabrics, reinforcements, and other materials known to those skilled in the art into a complex sandwich structure by lamination, adhesion, fusion, and other joining techniques; use of the hybrid dynamic polymer foam in a gasket or seal; use of the hybrid dynamic polymer foam in packaging materials or in containers. With respect to the hybrid dynamic polymers of the present invention, the foamable hybrid dynamic polymers are of a type such that they can be deformed by extrusion, injection molding, compression molding or other forming techniques known to those skilled in the art.
The foaming material provided by the invention is different from a common foaming material, once the three-dimensional structure prepared by the common foaming material is shaped, the structure can not be changed any more, the repairing is difficult, and the damaged foaming material can not be recycled. Although the foaming material provided by the invention is a covalent cross-linked polymer network, the foaming material can be repaired after being broken under certain conditions or can be used for other purposes through reshaping or recycling, and the reason is that hydrogen bond action and dynamic covalent bonds exist in the network structure at the same time. The foaming material provided by the invention solves the difficult problems of remolding, controllable repair and recycling regeneration of common foaming materials.
The hybrid dynamic polymer material of the present invention can be prepared by optionally adding or using other polymers, additives, fillers, swelling agents as formulation components of the hybrid dynamic polymer, within the range not interfering with the object of the present invention, which can improve the processability of the material, increase the quality and yield of the product, reduce the cost of the product or give the product a specific application property, but these additives or agents are not essential.
The other polymers can be used as additives to improve the performance of materials, endow the materials with new performance, improve the use and economic benefits of the materials and achieve the comprehensive utilization of the materials in a system. Other polymers can be added, which can be selected from natural high molecular compounds and synthetic high molecular compounds. The invention does not limit the property and molecular weight of the added polymer, and can be oligomer or high polymer according to the difference of the molecular weight, and can be homopolymer or copolymer according to the difference of the polymerization form, and the polymer is selected according to the performance of the target material and the requirement of the actual preparation process in the specific using process.
When the other polymer is selected from natural high molecular compounds, it can be selected from any one or several of the following natural high molecular compounds: natural rubber, chitosan, chitin, natural protein, polysaccharide, etc.
When the other polymer is selected from synthetic macromolecular compounds, it can be selected from any one or several of the following: <xnotran> , , , , , , , , , - , , , , , , , , , , , , , , , - , , , , , , , , , , , , , , , - , - , - - , - - , - , , , , , , , , - , - , (2- -1,3- ), - , - -1,4- , - - , - - , , , , , </xnotran> Polymethyl vinyl trifluoropropyl siloxane, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, polyepichlorohydrin, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide-propylene oxide copolymer, and the like.
Wherein, the type of other polymers used is not limited, and is mainly determined according to the required material performance; the amount of the other polymer to be used is not particularly limited, but is generally 1 to 50% by weight.
The auxiliary agent can include, but is not limited to, one or a combination of several of the following, such as a synthesis auxiliary agent, including a catalyst and an initiator; stabilizing aids including antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants; the auxiliary agent for improving the mechanical property comprises a toughening agent and a coupling agent; the auxiliary agents for improving the processing performance comprise a solvent, a lubricant, a release agent, a plasticizer, a thickening agent, a thixotropic agent and a flatting agent; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; other auxiliary agents include antistatic agents, sterilization and mildew proofing agents, foaming agents, foam stabilizers, nucleating agents, rheological agents and the like.
The catalyst in the auxiliary agent can accelerate the reaction rate of reactants in the reaction process by changing the reaction path and reducing the reaction activation energy. It includes, but is not limited to, any one or any of the following catalysts: (1) catalyst for polyurethane Synthesis: amine catalysts such as triethylamine, triethylenediamine, bis (dimethylaminoethyl) ether, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethylpropylenediamine, N, N-bis (dimethylaminopropyl) isopropanolamine, N- (dimethylaminopropyl) diisopropanolamine, N, N, N ' -trimethyl-N ' -hydroxyethylbisaminoethyl ether, tetramethyldipropylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N ' -tetramethylalkylenediamine, N, N, N ', N ', N ' -pentamethyldiethylenetriamine, N, N-dimethylethanolamine, N-ethylmorpholine, 2,4,6- (dimethylaminomethyl) phenol, trimethyl-N-2-hydroxypropylhexanoic 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, etc.; (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 sesquiethylate, vanadium oxychloride, triisobutylaluminum, nickel naphthenate, rare earth naphthenate, etc.; (3) CuAAC reaction catalyst: co-concerted catalysis by a monovalent copper compound and an amine ligand; the monovalent copper compound may be selected from Cu (I) salts such as CuCl, cuBr, cuI, cuCN, cuOAc, etc.; can also be selected from Cu (I) complexes, such as [ Cu (CH) 3 CN) 4 ]PF 6 、[Cu(CH 3 CN) 4 ]OTf、CuBr(PPh 3 ) 3 Etc.; the amine ligand may be selected from the group consisting of tris [ (1-benzyl-1H-1, 2, 3-triazol-4-yl) methyl]Amine (TBTA), tris [ alpha ](1-tert-butyl-1H-1, 2, 3-triazol-4-yl) methyl]Amines (TTTA), tris (2-benzimidazolemethyl) amine (TBIA), sodium bathophenanthroline disulfonate hydrate, and the like; (4) thiol-ene reaction catalyst: photocatalysts such as benzoin dimethyl ether, 2-hydroxy-2-methylphenyl acetone, 2-dimethoxy-2-phenylacetophenone and the like; nucleophilic reagent catalysts such as ethylenediamine, triethanolamine, triethylamine, pyridine, 4-dimethylaminopyridine, imidazole, diisopropylethylamine, etc. The amount of the catalyst to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.
The initiator in the auxiliary agent can cause the monomer molecules to be activated to generate free radicals in the polymerization reaction process, so as to improve the reaction rate and promote the reaction to proceed, and the initiator comprises any one or more of the following initiators: (1) initiator for radical polymerization: organic peroxides such as lauroyl peroxide, benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxypivalate, di-t-butyl peroxide, diisopropylbenzene hydroperoxide; azo compounds, such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, and the like; (2) initiator for living polymerization: such as 2,2,6,6-tetramethyl-1-oxypiperidine, 1-chloro-1-phenylethane/cuprous chloride/bipyridine triad systems, and the like; (3) initiator for ionic polymerization: such as butyl lithium, sodium/naphthalene systems, boron trifluoride/water systems, tin tetrachloride/alkyl halide systems, and the like; (4) initiator for coordination polymerization: such as titanium tetrachloride/triethylaluminum systems, zirconocene dichloride/methylaluminoxane systems, and the like; (5) initiator for ring-opening polymerization: such as sodium methoxide, potassium methoxide, ethylenediamine, 1, 6-hexamethylene diisocyanate, stannous octoate, and the like. Among them, the initiator is preferably lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile, or potassium persulfate. The amount of the initiator to be used is not particularly limited, but is usually 0.1 to 1% by weight.
The antioxidant in the additive can delay the oxidation process of a polymer sample, ensure that the material can be processed smoothly and prolong the service life of the polymer sample, and comprises but is not limited to any one or more of the following antioxidants: hindered phenols such as 2, 6-di-t-butyl-4-methylphenol, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, pentaerythrityl tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], 2' -methylenebis (4-methyl-6-t-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-tert-butyl-4-hydroxyphenyl) propionyl ] -hexahydro-s-triazine; trimeric isocyanate hindered phenols 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 species, 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 as the antioxidant are Tea Polyphenol (TP), butylhydroxyanisole (BHA), dibutylhydroxytoluene (BHT), t-butylhydroquinone (TBHQ), tris [2, 4-di-t-butylphenyl ] phosphite (antioxidant 168), and pentaerythrityl tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate (antioxidant 1010). The amount of the antioxidant to be used is not particularly limited, but is usually 0.01 to 1% by weight.
The light stabilizer in the assistant can prevent the polymer sample from photo-aging and prolong the service life of the polymer sample, and the assistant comprises any one or more than one of the following light stabilizers: light-shielding agents such as carbon black, titanium dioxide, zinc oxide, calcium sulfite; ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2,4, 6-tris (2-hydroxy-4-n-butoxyphenyl) -1,3, 5-s-triazine, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate; precursor type ultraviolet absorbers such as p-tert-butyl benzoate salicylate, bisphenol A disalicylate; ultraviolet ray quenchers, such as bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester), 2' -thiobis (4-tert-octylphenoloxy) nickel; a hindered amine light stabilizer which is a light stabilizer, such as bis (2, 6-tetramethylpiperidine) sebacate, 2, 6-tetramethylpiperidine benzoate tris (1, 2, 6-pentamethylpiperidyl) phosphite; other light stabilizers, such as 2, 4-di-tert-butyl-4-hydroxybenzoic acid (2, 4-di-tert-butyl-phenyl) ester, alkylphosphoric acid amide, zinc N, N '-di-N-butyl dithiocarbamate, nickel N, N' -di-N-butyl-N-butyldithiocarbamate, etc.; among these, carbon black and bis (2, 6-tetramethylpiperidine) sebacate (light stabilizer 770) are preferable as the light stabilizer. The amount of the light stabilizer to be used is not particularly limited, but is usually 0.01 to 0.5% by weight.
The heat stabilizer in the assistant can prevent the polymer sample from being chemically changed due to heating in the processing or using process, or delay the change to achieve the purpose of prolonging the service life, and the heat stabilizer includes but is not limited to any one or more of the following heat stabilizers: lead salts, such as tribasic lead sulfate, dibasic lead phosphite, dibasic lead stearate, dibasic lead benzoate, tribasic lead maleate, basic lead silicate, lead stearate, lead salicylate, dibasic lead phthalate, basic lead carbonate, silica gel coprecipitated lead silicate; metal soaps: such as cadmium stearate, barium stearate, calcium stearate, lead stearate, zinc stearate; organotin compounds, such as di-n-butyltin dilaurate, di-n-octyltin dilaurate, di (n) -butyltin maleate, mono-octyl di-n-octyltin dimaleate, di-n-octyltin isooctyl dimercaptoacetate, tin C-102, isooctyl dimethyltin dimercaptoacetate, dimethyltin dimercaptolate, and combinations thereof; antimony stabilizers such as antimony mercaptide, antimony thioglycolate, antimony mercaptocarboxylate, antimony carboxylate; epoxy compounds, such as epoxidized oils, epoxidized fatty acid esters, epoxy resins; phosphites, such as triaryl phosphites, trialkyl phosphites, triarylalkyl phosphites, alkyl-aryl mixed esters, polymeric phosphites; polyols, such as pentaerythritol, xylitol, mannitol, sorbitol, trimethylolpropane; composite heat stabilizers such as coprecipitated metal soaps, liquid metal soap composite stabilizers, organic tin composite stabilizers and the like; 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 to be used is not particularly limited, but is usually 0.1 to 0.5% by weight.
The dispersing agent in the auxiliary agent can disperse solid flocculation in the polymer mixed solution into fine particles to suspend in the liquid, uniformly disperse solid and liquid particles which are difficult to dissolve in the liquid, and simultaneously can prevent the particles from settling and coagulating to form stable suspension, and the dispersing agent comprises any one or more of the following dispersing agents: anionic type, such as sodium alkyl sulfate, sodium alkyl benzene sulfonate, sodium petroleum sulfonate; a cationic type; nonionic types, such as fatty alcohol polyoxyethylene ether, sorbitan fatty acid polyoxyethylene ether; inorganic types such as silicates, condensed phosphates; polymer type, such as starch, gelatin, water soluble gum, lecithin, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, lignosulfonate, polyvinyl alcohol, etc. Among them, the dispersant is preferably sodium dodecylbenzene sulfonate, naphthalene methylene sulfonate (dispersant N) and fatty alcohol-polyoxyethylene ether, and the amount of the dispersant used is not particularly limited, and is generally 0.3 to 0.8wt%.
The emulsifier in the adjuvant can improve the surface tension between various constituent phases in the polymer mixed solution containing the adjuvant to form a uniform and stable dispersion system or emulsion, and the emulsifier includes but is not limited to any one or more of the following emulsifiers: anionic type, such as higher fatty acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, sodium alkylnaphthalenesulfonate, succinic acid ester sulfonates, petroleum sulfonates, fatty alcohol sulfates, castor oil sulfate ester salts, sulfated ricinoleate ester salts, phosphoric acid ester salts, 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 type, 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 amine fatty acid amide, etc. Among them, sodium dodecylbenzenesulfonate, sorbitan fatty acid ester, triethanolamine stearate (emulsifier FM) are preferable, and the amount of the emulsifier used is not particularly limited, but is generally 1 to 5wt%.
The flame retardant in the auxiliary agent can increase the flame resistance of the material, and includes but is not limited to any one or any several of the following flame retardants: phosphorus series such as red phosphorus, tricresyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate; halogen-containing phosphates such as tris (2, 3-dibromopropyl) phosphate, tris (2, 3-dichloropropyl) phosphate; organic halides such as high chlorine content chlorinated paraffins, 1, 2-tetrabromoethane, decabromodiphenyl ether, perchlorocyclopentadecane; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate; reactive flame retardants such as chlorendic anhydride, bis (2, 3-dibromopropyl) fumarate, tetrabromobisphenol A, tetrabromophthalic anhydride, and the like; among them, decabromodiphenyl ether, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and antimony trioxide are preferable as the flame retardant. The amount of the flame retardant to be used is not particularly limited, but is generally 1 to 20% by weight.
The toughening agent in the auxiliary agent can reduce the brittleness of a polymer sample, increase the toughness and improve the bearing strength of the material, and the toughening agent comprises any one or more of the following toughening agents: methyl methacrylate-butadiene-styrene copolymer resin, chlorinated polyethylene resin, ethylene-vinyl acetate copolymer resin and its modified product, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene rubber, ethylene-propylene-diene monomer rubber, butadiene rubber, styrene-butadiene-styrene block copolymer, etc.; among them, the toughening agent is preferably ethylene-propylene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene-styrene block copolymer (SBS), methyl methacrylate-butadiene-styrene copolymer resin (MBS) or chlorinated polyethylene resin (CPE). The amount of the toughening agent to be used is not particularly limited, but is generally 5 to 10% by weight.
The coupling agent in the additive 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 dispersion degree of the filler to improve the processing performance, and further ensure that a product obtains good surface quality and mechanical, thermal and electrical properties, wherein the coupling agent comprises any one or more of the following coupling agents: organic acid chromium complex, silane coupling agent, titanate coupling agent, sulfonyl azide coupling agent, aluminate coupling agent and the like; among them, the coupling agent is preferably γ -aminopropyltriethoxysilane (silane coupling agent KH 550) or γ - (2, 3-glycidoxy) propyltrimethoxysilane (silane coupling agent KH 560). The amount of the coupling agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.
The solvent in the auxiliary agent can adjust the viscosity, is convenient for process operation, and is used in the preparation process or preparation of products. It includes, but is not limited to, any one or any combination of the following: hydrocarbons (e.g., cyclohexane, heptane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, tetrachloromethane), aromatic hydrocarbons (e.g., toluene, xylene), ketones (e.g., acetone, methyl ethyl ketone), ethers (e.g., diethyl ether, tetrahydrofuran, dioxane), esters (e.g., ethyl acetate, butyl acetate), glycol ether esters (e.g., ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate), dimethylformamide (DMF), N-methylpyrrolidone (NMP), and the like. The amount of the solvent used is not particularly limited, but is generally 1 to 200% by weight.
The lubricant in the additive can improve the lubricity, reduce the friction and reduce the interfacial adhesion performance of a polymer sample, and comprises but is not limited to any one or any several of the following lubricants: saturated 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' -ethylene bis stearamide; fatty alcohols and polyols, such as stearyl alcohol, cetyl alcohol, pentaerythritol; metal soaps such as lead stearate, calcium stearate, barium stearate, magnesium stearate, zinc stearate, etc.; among them, the lubricant is preferably paraffin wax, liquid paraffin wax, stearic acid, low molecular weight polyethylene. The amount of the lubricant used is not particularly limited, but is generally 0.5 to 1% by weight.
The release agent in the auxiliary agent can make a polymer sample easy to release, smooth and clean in surface, and includes but is not limited to any one or more of the following release agents: paraffin, soaps, dimethyl silicone oil, ethyl silicone oil, methylphenyl silicone oil, castor oil, waste engine oil, mineral oil, molybdenum disulfide, polyethylene glycol, vinyl chloride resin, polystyrene, silicone rubber, polyvinyl alcohol and the like; among them, the release agent is preferably dimethyl silicone oil or polyethylene glycol. The amount of the release agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.
The plasticizer in the auxiliary agent can increase the plasticity of a polymer sample, so that the hardness, modulus, softening temperature and brittle temperature of the polymer are reduced, and the elongation, flexibility and flexibility of the polymer are improved, and the auxiliary agent comprises any one or more of the following plasticizers: phthalic acid esters: dibutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diheptyl phthalate, diisodecyl phthalate, diisononyl phthalate, butylbenzyl phthalate, butyl glycolate phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, bis (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate, diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, such as epoxy glycerides, epoxy fatty acid monoesters, epoxy tetrahydrophthalic acid esters, epoxy soybean oil, epoxy stearic acid (2-ethyl) hexyl ester, epoxy soybean oleic acid 2-ethylhexyl ester, 4, 5-epoxy tetrahydrophthalic acid di (2-ethyl) hexyl ester, methyl chrysene acetyl ricinoleate, and dihydric alcohol esters, such as C5-9 acid ethylene glycol ester, C5-9 acid triethylene glycol ester; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol ethanedioic acid polyester, 1, 2-propanediol sebacic acid polyester; phenyl petroleum sulfonate, trimellitate, citrate, pentaerythritol, dipentaerythritol, and the like; among them, the plasticizer is preferably dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), or tricresyl phosphate (TCP). The amount of the plasticizer to be used is not particularly limited, but is generally 5 to 20% by weight.
The thickening agent in the additive can endow the polymer mixed solution with good thixotropy and proper consistency, and is generally used in the production and semi-finished product storage processes of the invention, and the thickening agent comprises any one or more of the following thickening agents: low molecular substances such as fatty acid salts, fatty alcohol-polyoxyethylene ether sulfates, alkyldimethylamine oxides, fatty acid monoethanolamides, fatty acid diethanolamides, fatty acid isopropylamides, sorbitan tricarboxylates, glycerol trioleate, cocamidopropyl betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline, titanate coupling agents; high molecular substances such as bentonite, artificial hectorite, fine silica, colloidal aluminum, plant polysaccharides, microbial polysaccharides, animal proteins, celluloses, starches, alginic acids, polymethacrylates, methacrylic acid copolymers, maleic anhydride copolymers, crotonic acid copolymers, polyacrylamides, polyvinylpyrrolidone, polyvinyl alcohol, polyether, polyvinylmethylether urethane polymers, and the like; among them, preferred as the thickener are hydroxyethyl cellulose, coconut diethanolamide, and acrylic acid-methacrylic acid copolymer. The amount of the thickener to be used is not particularly limited, but is usually 0.1 to 1.5% by weight.
The thixotropic agent in the auxiliary agent is added into a polymer system to increase the thixotropy of the polymer system. Including but not limited to any one or any of the following: fumed silica, hydrogenated castor oil, bentonite, silicic anhydride, silicic acid derivatives, urea derivatives, and the like. The amount of the thixotropic agent used is not particularly limited, and is generally 0.5 to 2% by weight.
The leveling agent in the auxiliary agent can ensure the smoothness and the evenness of a polymer coating, improve the surface quality of the coating and improve the decoration, and the auxiliary agent comprises any one or more of the following leveling agents: polydimethylsiloxane, polymethylphenylsiloxane, cellulose acetate butyrate, polyacrylates, silicone resins, and the like; among them, polydimethylsiloxane and polyacrylate are preferable as the leveling agent. The amount of the leveling agent to be used is not particularly limited, but is usually 0.5 to 1.5% by weight.
The colorant in the additive can make the polymer product present the required color and increase the surface color, and the colorant comprises any one or more of the following colorants: inorganic pigments such as titanium white, chrome yellow, cadmium red, iron red, molybdenum chrome red, ultramarine, chrome green, carbon black; organic pigments, such as lithol rubine BK, lake red C, perylene red, galyl R red, phthalocyanine red, permanent carmine HF3C, plastic scarlet R and cromo red BR, permanent orange HL, fast yellow G, sparkle plastic yellow R, permanent yellow 3G, permanent yellow H2G, phthalocyanine blue B, phthalocyanine green, plastic violet RL, aniline black; organic dyes such as thioindigo red, vat yellow 4GF, vaseline blue RSN, basic rose essence, oil-soluble yellow, etc.; the selection of the colorant is determined according to the color requirement of the sample, and does not need to be particularly limited. The amount of the colorant to be used is not particularly limited, but is generally 0.3 to 0.8% by weight.
The fluorescent whitening agent in the auxiliary agent can enable the dyed substances to obtain the fluorite-like glittering effect, and the fluorescent whitening agent comprises any one or more of the following fluorescent whitening agents: stilbene type, coumarin type, pyrazoline type, benzoxazine type, phthalimide type, and the like; among them, the fluorescent whitening agent is preferably sodium distyrylbiphenyldisulfonate (fluorescent whitening agent CBS), 4-bis (5 methyl-2-benzoxazolyl) stilbene (fluorescent whitening agent KSN), 2- (4, 4' -distyryl) bisbenzoxazole (fluorescent whitening agent OB-1). The amount of the fluorescent whitening agent to be used is not particularly limited, but is generally 0.002 to 0.03% by weight.
The matting agent in the auxiliary agent can diffuse and reflect incident light to generate low-gloss matte and matte appearance when the incident light reaches the surface of the polymer, and the matting agent comprises any one or more of the following matting agents: settling barium sulfate, silicon dioxide, hydrous gypsum powder, talcum powder, titanium dioxide, polymethyl urea resin and the like; among them, the matting agent is preferably silica. The amount of the matting agent to be used is not particularly limited, but is generally 2 to 5% by weight.
The antistatic agent in the additive can guide or eliminate harmful charges accumulated in a polymer sample, so that the polymer sample does not cause inconvenience or harm to production and life, and the antistatic agent comprises any one or more of the following antistatic agents: anionic antistatic agents, such as alkylsulfonates, sodium p-nonylphenoxypropane sulfonate, alkyl phosphate ester diethanolamine salts, alkylphenol polyoxyethylene ether sulfonic acid triethanolamine, potassium p-nonylphenyl ether sulfonate, alkyl polyoxyethylene ether sulfonic acid triethanolamine, phosphate ester derivatives, phosphates, phosphoric acid polyethylene oxide alkyl ether alcohol esters, alkyl bis [ di (2-hydroxyethylamine) ] phosphate esters, phosphate ester derivatives, fatty amine sulfonates, sodium butyrate sulfonates; cationic antistatic agents, such as fatty ammonium hydrochloride, lauryl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, N-cetyl-ethylmorpholine ethyl sulfate, stearamidopropyl (2-hydroxyethyl) dimethylammonium nitrate, alkyl hydroxyethyl dimethylammonium perchlorate, 2-alkyl-3, 3-dihydroxyethyl imidazoline perchlorate, 2-heptadecyl-3-hydroxyethyl-4-carboxymethylimidazoline, N-bis (. Alpha. -hydroxyethyl) -N-3 (dodecyloxy-2-hydroxypropyl) methylammonium methyl sulfate; zwitterionic antistatic agents, such as alkyl dicarboxymethylammonium ethoxide, lauryl betaine, N, N, N-trialkylammonium acetyl (N' -alkyl) amine ethoxide, N-lauryl-N, N-dipolyoxyethylene-N-ethylphosphonate, alkyldi (polyoxyethylene) ammonium ethoxide hydroxide, 2-alkyl-3 hydroxyethyl-acetate-based imidazoline quaternary ammonium base, N-alkyl amino acid salts; nonionic antistatic agents, such as fatty alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, alkylphenol ethylene oxide adducts, polyoxyethylene phosphoric acid ether esters, glycerin monofatty acid esters, polyethylene oxide adducts of sorbitan monolaurate; high molecular antistatic agents, such as ethylene oxide propylene oxide adduct of ethylenediamine, polyethylene glycol-terephthalate-3, 5-dibenzoate sodium sulfonate copolymer, polyallylamine N-quaternary ammonium salt substitute, poly-4-vinyl-1-acetonylpyridinophosphate-p-butylbenzene ester salt, etc.; among them, preferred antistatic agents are lauryl trimethyl ammonium chloride, octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate (antistatic agent SN), and alkyl phosphate diethanol amine salt (antistatic agent P). The amount of the antistatic agent to be used is not particularly limited, but is generally 0.3 to 3% by weight.
The dehydrating agent in the auxiliary agent can remove moisture in a system, and the dehydrating agent comprises any one or more of the following components: oxazolidine compounds (e.g., 3-ethyl-2-methyl-2- (3-methylbutyl) -1, 3-oxazolidine), p-toluenesulfonyl isocyanate, triethyl orthoformate, vinylsilane, calcium oxide, and the like. The amount of the dehydrating solvent to be used is not particularly limited, but is usually 0.1 to 2% by weight.
The sterilization mildew preventive in the auxiliary agent can inhibit the growth of bacteria, keep the neat appearance of the product and prolong the service life; or protect the user, promote the health of the user, such as reducing beriberi and the like. It includes organic and inorganic substances, including but not limited to any one or more of the following: isothiazolinone derivatives such as 5-chloro-2-methyl-4-isothiazolin-3-one, N-N-butyl-1, 2-benzisothiazolin-3-one, octylisothiazolinone, 2, 4-trichloro-2-hydroxy-diphenyl ether, 2- (4-thiazolyl) benzimidazole, 8-hydroxyquinolinecarboxylic acid copper or bis (8-hydroxyquinolinyl) copper; organotin compounds such as tributyltin fumarate, tributyltin acetate, bis (tributyltin) sulfide, bis (tributyltin) oxide; n, N-dimethyl-N' -phenyl (fluorodichloromethylthio) sulfonamide; inorganic compounds or compounds, such as nano silver, nano titanium dioxide, nano silicon dioxide, nano zinc oxide, superfine copper powder, inorganic antibacterial agent YY-Z50, XT inorganic antibacterial agent, and composite antibacterial agent KHFS-ZN. The amount of the fungicidal agent to be used is not particularly limited, but is generally 0.5 to 2% by weight.
The foaming agent in the auxiliary agent can enable a polymer sample to be foamed into pores, so that a light polymer material is obtained, and the foaming agent comprises any one or more of the following foaming agents: physical blowing agents such as carbon dioxide, nitrogen, argon, methane, ethane, propane, butane, isobutane, pentane, neopentane, hexane, isopentane, heptane, isoheptane, acetone, benzene, toluene, methyl ether, diethyl ether, petroleum ether, methyl chloride, dichloromethane, dichloroethylene, dichlorodifluoromethane, chlorotrifluoromethane, hydrochlorofluorocarbon-22, hydrochlorofluorocarbon-142 b, hydrofluorocarbon-134 a, hydrofluorocarbon-152 a, chlorofluorocarbon-11, chlorofluorocarbon-12, chlorofluorocarbon-114; inorganic foaming agents such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium ammonium carbonate, azide compounds, borohydride compounds, and the like; organic blowing agents, such as N, N '-dinitrosopentamethylenetetramine, N' -dimethyl-N, N '-dinitrosoterephthalamide, azodicarbonamide, barium azodicarbonate, diisopropyl azodicarbonate, potassium azoformamide formate, azobisisobutyronitrile, 4' -oxybis-benzenesulfonyl hydrazide, 3 '-disulfonyl hydrazide diphenylsulfone, 1, 3-benzenedihuanyl hydrazide, benzenesulfonyl hydrazide, trihydrazinyltriazine, p-toluenesulfonyl semicarbazide, biphenyl-4, 4' -disulfonyl azide, diazoaminobenzene; physical microsphere/particle blowing agents such as expandable microspheres from Acksonobel, et al. Among them, the foaming agent is preferably environmentally friendly and harmless carbon dioxide, nitrogen, argon, sodium bicarbonate, ammonium carbonate, azodicarbonamide (foaming agent AC), N ' -dinitropentamethylenetetramine (foaming agent H), N ' -dimethyl-N, N ' -dinitrosoterephthalamide (foaming agent NTA), or physical microsphere foaming agent. The amount of the blowing agent to be used is not particularly limited, but is usually 0.1 to 30% by weight.
The auxiliary foaming agent in the auxiliary agent includes, but is not limited to, a foaming promoter, a foaming inhibitor, a foam stabilizer, and the like. The foaming promoter includes, but is not limited to, any one or any several of the following: urea, stearic acid, lauric acid, salicylic acid, tribasic lead sulfate, dibasic lead phosphite, lead stearate, cadmium stearate, zinc oxide, ZB-530, KZ-110 and MS-1; the foaming inhibitor comprises any one or more of the following components: maleic acid, fumaric acid, stearoyl chloride, phthaloyl chloride, maleic anhydride, phthalic anhydride, hydroquinone, naphthalenediol, aliphatic amines, amides, oximes, isocyanates, mercaptans, thiophenols, thioureas, sulfides, sulfones, cyclohexanone, acetylacetone, hexachlorocyclopentadiene, dibutyltin maleate, etc.; the foam stabilizer comprises any one or more of the following components in percentage by weight: : silicone oils, sulfonated fatty alcohols, sulfonated fatty acids, sodium lauryl sulfate, dodecyl dimethyl amine oxide, alkylolamides, polyethylene oxides, alkylaryl polyvinyl alcohol oxides, tridecyl ethers, polyethylene oxide sorbitan glyceryl laurate, block copolymers of silicone-ethylene oxides, and the like. The amount of the co-blowing agent to be used is not particularly limited, but is usually 0.05 to 10% by weight.
The nucleating agent in the additive can accelerate crystallization rate, increase crystallization density and promote grain size refinement by changing the crystallization behavior of the polymer, so as to achieve the purposes of shortening the molding cycle of the material and improving the physical and mechanical properties of the product, such as transparency, surface gloss, tensile strength, rigidity, heat distortion temperature, 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 and the like; among them, the nucleating agent is preferably silica, dibenzylidene sorbitol (DBS), ethylene propylene diene monomer. The amount of the nucleating agent used is not particularly limited, but is generally 0.1 to 1% by weight.
The rheological agent in the additive can ensure that the polymer has good brushing property and proper coating thickness in the coating process, prevents the solid particles from settling during storage, and can improve the redispersibility, and the rheological agent comprises any one or more of the following rheological agents: inorganic species 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 compounds such as organobentonite, hydrogenated castor oil/amide wax, isocyanate derivatives, acrylic emulsion, acrylic copolymer, polyethylene wax, cellulose ester, etc.; among them, the rheological agent is preferably organic bentonite, polyethylene wax, hydrophobically modified alkaline expandable emulsion (HASE), or alkaline expandable emulsion (ASE). The amount of the rheology agent used is not particularly limited, but is generally 0.1 to 1% by weight.
The filler described, which in the polymer sample, performs essentially the following functions: (1) the shrinkage rate of a molded 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 material; (3) different performance requirements are met, such as improvement of impact strength and compression strength, hardness, rigidity and modulus of the material, improvement of wear resistance, improvement of heat deformation temperature, improvement of electrical conductivity and thermal conductivity and the like; (4) the coloring effect of the pigment is improved; (5) imparting light stability and chemical resistance; (6) has the function of capacity increase, can reduce the cost and improve the competitive capacity of the product in the market.
The filler is selected from any one or any several of the following fillers: inorganic non-metallic filler, organic filler.
The inorganic non-metal filler comprises any one or more of the following components in percentage by weight: calcium carbonate, china clay, barium sulfate, calcium sulfate and calcium sulfite, talc, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene oxide, fullerene, carbon nanotube, molybdenum disulfide, slag, flue dust, wood powder and shell powder, diatomaceous earth, red mud, wollastonite, silicon aluminum black, aluminum hydroxide, magnesium hydroxide, fly ash, oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass microbeads, resin microbeads, glass powder, cement, glass fiber, carbon fiber, quartz fiber, carbon core boron fiber, titanium diboride fiber, calcium titanate fiber, silicon carbide fiber, ceramic fiber, whisker and the like. In one embodiment of the present invention, inorganic non-metallic fillers having electrical conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, are preferred, which facilitate obtaining a composite material having electrical conductivity and/or electrothermal function. In another embodiment of the present invention, the non-metallic filler having the heat generating function under the action of infrared and/or near infrared light is preferably selected, including but not limited to graphene, graphene oxide, and carbon nanotubes, so as to obtain a composite material that can be heated by infrared and/or near infrared light. Good heating performance, especially remote control heating performance, and is beneficial to obtaining controllable shape memory, self-repairing performance and the like. In another embodiment of the present invention, inorganic non-metallic fillers with thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, are preferred, which facilitate obtaining composite materials with thermal conductivity.
The metal filler comprises metal compounds, including but not limited to any one or any several of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano metal particles including, but not limited to, nano gold particles, nano silver particles, nano palladium particles, nano iron particles, nano cobalt particles, nano nickel particles, nano Fe 3 O 4 Granular, nano gamma-Fe 2 O 3 Particulate, nano MgFe 2 O 4 Particulate, nano-MnFe 2 O 4 Granular, nano CoFe 2 O 4 Granular, nano-CoPt 3 Particles, nano FePt particles, nano FePd particles, nickel-iron bimetal magnetic nanoparticles and other nano metal particles capable of heating under at least one of infrared, near infrared, ultraviolet and electromagnetic action; liquid metals including, but not limited to, mercury, gallium indium liquid alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys; the metal organic compound molecules, crystals and other substances which can generate heat under the action of at least one of infrared, near infrared, ultraviolet and electromagnetism, and the like. In one embodiment of the present invention, the filler capable of performing electromagnetic and/or near infrared heating is preferably selected, and includes, but is not limited to, nano gold, nano silver, nano palladium, nano Fe 3 O 4 For remote heating. In another embodiment of the present invention, liquid metal fillers are preferred, which can enhance the thermal and electrical conductivity of the flexible substrate while maintaining the flexibility and ductility of the substrate. In another embodiment of the present invention, organometallic compound molecules and crystals that can generate heat under at least one of infrared, near infrared, ultraviolet and electromagnetic are preferred, which facilitates the combination on the one hand, and improves the efficiency of induced heat generation and the heat generation effect on the other hand.
The organic filler includes, but is not limited to, any one or any several of the following: (1) natural organic fillers such as natural rubber, cotton, linter, hemp, jute, flax, asbestos, cellulose acetate, lignin, starch, wood flour, and the like; (2) synthetic resin fillers such as acrylonitrile-acrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, cellulose acetate, polychlorotrifluoroethylene, chlorinated polyethylene, chlorinated polyvinyl chloride, epoxy resin, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, high-density polyethylene, high-impact polystyrene, low-density polyethylene, medium-density polyethylene, melamine-formaldehyde resin, polyamide, polyacrylic acid, polyacrylamide, polyacrylonitrile, polyarylsulfone, polybenzimidazole, polybutylene terephthalate, polycarbonate, polydimethylsiloxane, polyethylene glycol, polyester, polysulfone, polyethersulfone, polyethylene terephthalate, phenol resin, tetrafluoroethylene-perfluoropropane copolymer, polyimide, polymethyl acrylate, polymethacrylonitrile, polymethyl methacrylate, polyphenylene ether, polypropylene, polyphenylene sulfide, polyphenylsulfone, polystyrene, polytetrafluoroethylene, polyurethane, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, polyvinyl formal, polyvinyl pyrrolidone, resin, ultra-high-molecular weight polyethylene, unsaturated polyester, polyether ether and the like; (3) synthetic rubber fillers such as isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber, silicone rubber, fluororubber, polyacrylate rubber, urethane rubber, epichlorohydrin rubber, thermoplastic elastomer, and the like; (4) synthetic fibrous fillers such as viscose, cuprammonium, diethyl ester, triethyl ester, polyamide, polycarbonate, polyvinyl alcohol, polyester, polyurethane, polyacrylonitrile, polyvinyl acetal, polyvinyl chloride, polyolefin, fluorine, polytetrafluoroethylene, aramid, or aramid fibers, etc.; (5) expanded polymer particles and expandable polymer particles.
Wherein, the type of the filler is not limited and is mainly determined according to the required material performance; the amount of the filler used is not particularly limited, but is generally 1 to 30% by weight.
The swelling agent may include, but is not limited to, water, organic solvents, ionic liquids, oligomers, and plasticizers. The oligomers can also be regarded as plasticizers.
The organic solvent in the swelling agent is selected from any one or any several of the following by way of example and not limitation: hydrocarbons (e.g., cyclohexane, heptane), halogenated hydrocarbons (e.g., dichloromethane, chloroform, tetrachloromethane), aromatic hydrocarbons (e.g., toluene, xylene), ketones (e.g., acetone, methyl ethyl ketone), ethers (e.g., diethyl ether, tetrahydrofuran, dioxane), esters (e.g., ethyl acetate, butyl acetate), glycol ether esters (e.g., ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate), dimethylformamide (DMF), N-methylpyrrolidone (NMP), and the like.
The ionic liquid in the swelling agent is generally composed of an organic cation and an inorganic anion, and the cation is selected from, by way of example, including but not limited to, alkyl quaternary ammonium ions, alkyl quaternary phosphine ions, 1,3-dialkyl-substituted imidazolium ions, N-alkyl-substituted pyridinium ions, and the like; the anion is selected from the group including but not limited to halogen, tetrafluoroborate, hexafluorophosphate, and CF 3 SO 3 - 、(CF3SO 2 ) 2 N - 、C 3 F 7 COO - 、C 4 F 9 SO 3 - 、CF 3 COO - 、(CF 3 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 2 N - 、SbF 6 - 、AsF 6 - And the like. In the ionic liquid used in the present invention, the cation is preferably an imidazolium cation, and the anion is preferably a hexafluorophosphate ion or a tetrafluoroborate ion.
The oligomer in the swelling agent is selected from any one or more of the following substances by way of example and not limitation: polyethylene glycol oligomer, polyvinyl alcohol oligomer, polyvinyl acetate oligomer, poly (n-butyl acrylate) oligomer, liquid paraffin and the like.
The plasticizer in the swelling agent is selected from any one or any several of the following by way of example and not limitation: phthalic acidEsters: dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), diheptyl phthalate (DIOP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), butylbenzyl phthalate, butylpeglycol butyl phthalate, dicyclohexyl phthalate, bis (tridecyl) phthalate, di (2-ethyl) hexyl terephthalate; phosphoric acid esters such as tricresyl phosphate (TCP), diphenyl-2-ethyl hexyl phosphate; fatty acid esters such as di (2-ethyl) hexyl adipate, di (2-ethyl) hexyl sebacate; epoxy compounds, e.g. epoxyglycerides, epoxyfatty acid monoesters, epoxytetrahydrophthalates, epoxidized soybean oil, 2-ethylhexyl epoxystearate, 2-ethylhexyl epoxysoyate, di (2-ethyl) 4, 5-epoxytetrahydrophthalate, methyl chrysoacetylricinoleate, glycols, e.g. C 5～9 Acid ethylene glycol ester, C 5～9 Triethylene glycol diacetate; chlorine-containing compounds such as greening paraffin, chlorinated fatty acid ester; polyesters such as 1, 2-propanediol ethanedioic acid polyester, 1, 2-propanediol sebacic acid polyester; phenyl petroleum sulfonate, trimellitate, citrate, pentaerythritol, dipentaerythritol, and the like. Among them, DBP, DOP, DIOP, DIDP, DINP, TCP, epoxidized soybean oil are preferable as the plasticizer. The epoxidized soybean oil is an environment-friendly plastic plasticizer with excellent performance, is prepared by performing epoxidation reaction on refined soybean oil and peroxide, is resistant to volatilization, difficult to migrate and difficult to dissipate in a polymer product, and is very beneficial to keeping the light and heat stability of the product and prolonging the service life. Epoxidized soybean oil, which is extremely low in toxicity and is approved by many countries for use in food and pharmaceutical packaging materials, is the only epoxy plasticizer approved by the U.S. food and drug administration for use in food packaging materials and is therefore more preferred.
In the preparation process of the hybrid dynamic polymer, the amount of each component raw material of the hybrid dynamic polymer is not particularly limited, and can be adjusted by those skilled in the art according to the actual preparation situation and the target polymer performance.
The hybrid dynamic polymer provided by the invention has adjustable performance in a large range, can be applied to various fields, has wide application prospect, is particularly reflected in the fields of military aerospace equipment, functional coatings and coatings, biomedicine, biomedical materials, energy, construction, bionics and the like, and has remarkable application effect. For example, through proper component selection and formulation design, a polymer plugging gel which has good plasticity and can be recycled can be prepared; for example, the self-repairing function is introduced into the polymer material, so that the material can be automatically repaired after damage is generated inside the material, and the structural material with longer service life, more reliable performance and more economical efficiency is facilitated. For example, in microelectronic polymer devices and adhesive applications, performance loss due to microcracks generated by thermal and mechanical fatigue is a long-standing problem, and the introduction of self-healing functions into these materials can greatly improve the reliability and service life of microelectronic products. The plug is widely applied to the fields of electronic appliances, foods, medicines and the like as a self-repairable plug, a sealing ring and the like, and for example, the plug is used as a plug at a charger interface, a data line interface and the like of a mobile phone, a tablet personal computer, a notebook, a camera and the like, and is used for repairing a hole generated in the process of plugging and unplugging a connector so as to achieve the purposes of preventing water and the like. The material with bionic effect can be obtained as a self-repairing material, has wide application prospect in the field of biological medical treatment, and can obtain more durable human body joints. The material as a self-repairing material is also helpful for developing materials for special purposes, such as materials capable of recovering the properties of interface, electric conduction, heat conduction and the like under certain conditions, for example, as a binder of a battery/supercapacitor electrode, a diaphragm can reduce the breakage of the electrode and prolong the service life of the electrode material. When the polymer contains two or more dynamic covalent bonds which can be dissociated at different temperatures, a multiple shape memory material can be obtained and has self-repairability. In addition, the supermolecule hydrogen bond can further enhance the toughness of the polymer, can be prepared into a film, a fiber or a plate with excellent performance, and can be widely applied to the fields of military affairs, aerospace, sports, energy, buildings and the like. In addition, by utilizing the dynamic reversibility and the strain responsiveness, the method can also be applied to preparing toys with viscous-elastic magic conversion effects.
The hybrid dynamic polymers of the present invention are further described below in conjunction with certain embodiments. The specific examples are intended to illustrate the invention in further detail, and are not intended to limit the scope of the invention.
Example 1
A hybrid dynamic polymer plasticizer swelling gel based on polynorbornene is prepared, wherein the supramolecular effect is based on cyanuric acid derivative side groups.
Cyanuric acid and 6-chloro-1-hexene are dissolved in anhydrous dimethyl sulfoxide in a molar ratio of 4, and are stirred and reacted for 15 hours at 80 ℃ under the catalysis of potassium carbonate to obtain the olefin monomer 1a containing hydrogen bond groups. Adding the compound 1a into toluene, cooling the reaction vessel to 5 ℃, dropwise adding cyclopentadiene while stirring at low temperature, and keeping the molar ratio of the compound 1a to cyclopentadiene at 10. After the dropwise addition, the temperature is raised to the reflux temperature, and the stirring reaction is continued to obtain the norbornene derivative 1b containing the hydrogen bond group. The above procedure was repeated, and allyl alcohol was used in place of the compound 1a, to give a hydroxyl-containing norbornene derivative 1c. And (3) reacting the 1c with an equivalent molar weight of 11-bromoundecanoic acid under the catalysis of DCC and DMAP to obtain the norbornene derivative 1d containing bromine atoms. 30 molar equivalents of norbornene derivative containing hydrogen bond groups 1b, 55 molar equivalents of norbornene and 15 molar equivalents of 1d are reacted in dichloromethane under the catalysis of Grubbs second generation catalyst to obtain linear polynorbornene containing side hydrogen bond groups and bromine atoms.
Taking a certain amount of the obtained copolymer, 1, 10-undecadiyne and azidobenzene, keeping the molar ratio of bromine atoms to 1, 10-undecadiyne to azidobenzene in the copolymer to be 5. The product has good strength, toughness and self-repairability, has good rebound resilience and small permanent deformability, can be stretched in a large range, and can be used for preparing conveyor belts, parts and the like.
Example 2
A hybrid dynamic polymer foam based on polyurethane is prepared, in which the supramolecular action is based on pendant urea groups and skeletal carbamate groups.
2-amino-1, 3-propanediol is reacted with an equivalent molar amount of ethyl isocyanate to provide diol 2a containing pendant urea groups.
The obtained diol 2a, 2, 4-Hexamethylene Diisocyanate (HDI), the oligoethylene glycol having one hydroxyl group and one azido group, the oligoethylene glycol having one hydroxyl group and one alkynyl group, and 1, 12-diiodododecane were mixed in a molar ratio of 16. Then, 50 parts by mass of montmorillonite, 0.2 part by mass of silicone oil, 1.5 parts by mass of foamable polymer microspheres, 0.1 part by mass of dibutyltin dilaurate (DBTDL) and 0.1 part by mass of triethylenediamine were added and mixed uniformly, and cured for 30 minutes at room temperature. Then curing for 4 hours at 80 ℃ and then keeping the temperature for 24 hours at 110 ℃ to obtain the hybrid dynamic polymer foam material containing the skeleton carbamate group and the lateral carbamido group. The product has excellent toughness and good self-repairing property, and can be used for manufacturing heat-insulating materials and insulating materials.
Example 3
A hybrid dynamic polymer based on polyesters is prepared as a normal solid, wherein the supramolecular action is based on pendant carbamate groups.
Dissolving 2-chlorocyclohexanone in dichloromethane, adding m-chloroperoxybenzoic acid, keeping the molar ratio of the 2-chlorocyclohexanone to the m-chloroperoxybenzoic acid at 10. Under anhydrous condition, 1 molar equivalent of ethanol is used as an initiator, stannous octoate is used as a catalyst, 40 molar equivalent of epsilon-caprolactone and 10 molar equivalent of compound 3a are dissolved in toluene to carry out ring opening polymerization of cyclic ester, and the polyester with the side group containing chlorine atoms is obtained. The resulting polymer having a chlorine atom-containing pendant group was dissolved in Dimethylformamide (DMF), and 2 molar equivalents of sodium azide to the chlorine atom was added to convert the chlorine atom pendant group into an azide group. And dissolving the polymer with the azido group as the side group and 2-propargyl-N-butyl carbamate in tetrahydrofuran, keeping the molar ratio of the two to be 1, and reacting at 35 ℃ under the catalysis of cuprous iodide and pyridine to obtain the polyester with the triazolyl group and the carbamate group as the side group. Blending the obtained polyester with a certain amount of 1, 8-dibromooctane, keeping the molar ratio of triazolyl to bromine atoms as 4. The hybrid dynamic polymer has good toughness and self-repairing property, and can be used as films, plates, pipes, profiles and the like with self-repairing and shape memory functions.
Example 4
A hybrid dynamic polymer flexible foam based on polyurea is prepared, wherein the supramolecular action is based on pendant carbamate groups.
The 1-methyl-4-amino-1, 2, 3-triazole and 6-bromohexylamine in equal molar equivalents are fully reacted at 110 ℃ to obtain the diamine containing dynamic covalent bonds. Under the protection of nitrogen, 10 molar equivalents of ethylene glycol monoallyl ether (average molecular weight about 500) and 1 molar equivalent of potassium methoxide are blended, and 70 molar equivalents of epoxypropanol is slowly added dropwise at 95 ℃ to obtain the olefin monomer 4a with a branched structure and a hydroxyl end group. Under the protection of nitrogen, an olefin monomer 4a with a branched structure and a hydroxyl end group and ethyl isocyanate with a hydroxyl molar equivalent react in dichloromethane under the catalysis of DBTDL to obtain an olefin monomer 4b. And (3) fully blending the olefin monomer 4b and 2, 4-diamino-6-mercaptopyrimidine in equivalent molar weight, adding 1wt% of photoinitiator 2, 2-dimethoxy-2-phenylacetophenone, and illuminating for 30 minutes under a 300W ultraviolet lamp to obtain diamine with a branched polyether side group, wherein the tail end of the branched side group contains a carbamate group.
X = a direct bond, and X = a direct bond,
5 molar equivalents of the diamine compound with the hydrogen bond group, 5 molar equivalents of polyether diamine, 9 molar equivalents of diamine containing a dynamic covalent bond, 20 molar equivalents of toluene diisocyanate and 2 molar equivalents of 6-bromohexylamine are blended to obtain 100 parts by mass, 1 part by mass of water-soluble organic silicone oil, 2 parts by mass of water, 0.2 part by mass of DBTDL and 0.1 part by mass of triethylene diamine are added, the mixture is uniformly mixed and rapidly stirred until bubbles are generated, the mixture is cured for 15 minutes at room temperature and then cured for 2 hours at 60 ℃, and the hybrid dynamic polymer foam product is obtained. The soft polyurea foam obtained in the example has good flexibility, can repair cracks, has long service life, and can be used as a filler of toys.
Example 5
A hybrid dynamic polymer based on polyethers is prepared as a normal solid, wherein the supramolecular interactions are based on pendant piperidinyl, pyrazinyl and imidazolyl groups.
The equivalent molar weight of 11-bromoundecanoic acid is fully reacted with 5-ethyl-1-phenyl-1H- [1,2,3] triazole-4-carboxylic acid at 110 ℃ to obtain diacid with dynamic covalent bond in the skeleton. The resulting diacid and polyethylene glycol diepoxyethylene methyl ether are mixed in a molar ratio of 5. And (3) fully blending the obtained polymer, 4-piperidinecarboxylic acid, 2-pyrazine formate, imidazole-4-acetic acid and side hydroxyl, 4-piperidinecarboxylic acid, 2-pyrazine formate, imidazole-4-acetic acid and 4-bromobutyric acid in a molar ratio of 7.
And (3) fully mixing and molding 100 parts by mass of the obtained hybrid dynamic polymer and 5 parts by mass of cellulose nanocrystalline to obtain a corresponding hybrid dynamic polymer product. The hybrid dynamic polymer obtained in the embodiment has good toughness and elasticity, can be pressed into products with different shapes and sizes according to the requirements, and can be recycled to be made into new products for use after damaged or no longer needed samples.
Example 6
A hybrid dynamic polymer ionic liquid gel based on polyether is prepared, wherein the supramolecular function is based on lateral carbamido.
2-amino-3-mercapto-1-propanol and an equivalent molar equivalent of ethyl isocyanate were reacted to convert the amino group to a ureido group. The obtained compound reacts with 4-bromo-1-butene with equal molar equivalent under ultraviolet irradiation in the presence of a photoinitiator BDK, and then reacts with 1 molar equivalent of azide-decapolyethylene glycol-acyl chloride under the catalysis of triethylamine to obtain the modified polyether with one end being a bromine atom and the other end being an azide side group and the carbamido side group. And reacting the obtained modified polyether with propine at 35 ℃ under the catalysis of cuprous iodide and pyridine to obtain the modified polyether with one triazole group end and one bromine atom end and containing one lateral carbamido group. 1 molar equivalent of 1, 6-dibromohexane, 1,3, 5-tri (bromomethyl) benzene and 50 molar equivalents of the obtained modified polyether are blended and fully reacted at 110 ℃ to obtain the hybrid dynamic polymer. And (3) fully mixing 100 parts by mass of the obtained hybrid dynamic polymer with 100 parts by mass of ionic liquid 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt ([ bmim ] NTf 2) to obtain the hybrid dynamic polymer ionic liquid gel. The ionic liquid gel prepared in the embodiment has good stability, and can be applied to the fields of dye solar cells, brakes, supercapacitors, artificial muscles, electrochromic devices and the like. In this example, after the surface of the polymer material was scratched by a blade, the polymer material was placed in a vacuum oven at 110 ℃ for 6 hours, and then the scratch disappeared, and the sample was able to perform self-repair.
Example 7
A hybrid dynamic polymer foam based on polyester is prepared, wherein the supramolecular interaction is based on terminal amide groups.
Under the anhydrous condition, 1 molar equivalent of cyclodextrin is used as an initiator, stannous octoate is used as a catalyst, 210 molar equivalent of epsilon-caprolactone is dissolved in toluene to carry out ring-opening polymerization of cyclic ester, and the hydroxyl-terminated twenty-one-arm polyester is obtained. Reacting 21 molar equivalents of 4-bromobutyryl chloride with the obtained polyester under the catalysis of triethylamine to obtain the twenty-one-arm polyester terminated by bromine atoms.
Under anhydrous condition, N-acetylethanolamine is used as an initiator, stannous octoate is used as a catalyst, 10 molar equivalent of epsilon-caprolactone is dissolved in toluene to carry out ring opening polymerization of cyclic ester, and thus, the oligoester with one hydroxyl end and one amido end is obtained. And reacting the obtained oligoester with 5-hexynoyl chloride with equal molar equivalent under the catalysis of triethylamine to obtain the oligoester with one alkynyl end and one amido end. 15 molar equivalents of the resulting oligoester, 15 molar equivalents of ethyl azidoacetate and 1 molar equivalent of a heneicosyl polyester end capped with a bromine atom were blended and heated to 110 ℃ and incubated for 48 hours before swelling in 1, 4-dioxane solvent. The blend containing the solvent is placed in a mould to be completely frozen at minus 80 ℃, an air pump is started at minus 50 ℃, the dry air pressure is maintained to be less than 50 mu atm for 24 hours, and then the blend is dried in a vacuum drying oven at 20 ℃ to extract all the solvent, so that the hybrid dynamic polymer foam material is obtained. The foam material has good toughness and self-repairing property, and can be used as a filter material or a carrier due to high aperture ratio.
Example 8
A hybrid dynamic polymer based on polyethers is prepared, wherein the supramolecular action is based on diaminotriazinyl-terminated and thymidinyl-terminated groups.
BDK is used as a photoinitiator, 1 molar equivalent of 3-bromine-1-propyl mercaptan and 1 molar equivalent of 2-vinyl-4, 6-diamino-1, 3, 5-triazine react under ultraviolet illumination to obtain a compound with one end being a hydrogen bond group and the other end being a bromine atom. BDK is used as a photoinitiator, 1 molar equivalent of polyethylene glycol with one sulfhydryl end and one azido group reacts with 1 molar equivalent of 2-vinyl-4, 6-diamino-1, 3, 5-triazine under ultraviolet illumination to obtain polyethylene glycol with one hydrogen bond group and one azido group. Heating and reacting 1 molar equivalent of the obtained polyethylene glycol with equivalent molar equivalent of 4-ethynyl anisole to obtain polyethylene glycol with one end being a hydrogen bond group and the other end containing triazole group. And reacting 1 molar equivalent of sulfhydryl-terminated four-arm polyethylene glycol with 4 molar equivalents of 1- (4-vinyl benzyl) thymine under ultraviolet irradiation by taking BDK as a photoinitiator to obtain thymine-terminated four-arm polyethylene glycol. Fully blending 10 molar equivalents of a compound with one end being a hydrogen bond group and the other end being a bromine atom, 8 molar equivalents of polyethylene glycol with one end being a hydrogen bond group and the other end containing triazole group, 9 molar equivalents of thymine terminated four-arm polyethylene glycol and 5% of graphene by mass, and fully reacting at 110 ℃ to obtain the hybrid dynamic polymer. The hybrid dynamic polymer shows obvious dynamic characteristics, can be applied to textiles or in foams for use, can be used as a functional coating, and can be used for preparing films with thermal and electric sensing functions.
Example 9
A hybrid dynamic polymer ionic liquid gel based on polyacrylate and polyacrylonitrile is prepared, wherein the supermolecular action is based on lateral carbamate group and lateral carbamide group.
1 molar equivalent of acrylonitrile (average molecular weight is about 10000), 3 molar equivalents of 2-azidoethylammonia, 20 molar equivalents of 2, 5-dehydration-1-azido-1-deoxy-D-glucitol and 100 molar equivalents of zinc chloride are dissolved in dimethylformamide, and the components are fully mixed by ultrasonic for 5 minutes at room temperature and then heated to 125 ℃ for stirring reaction to obtain the modified polyacrylonitrile containing hydroxyl and amino on the side group. And (3) reacting the obtained modified polyacrylonitrile with ethyl isocyanate with the same molar equivalent as the sum of the contained hydroxyl amino groups in dimethyl sulfoxide to obtain the modified polyacrylonitrile with the side groups containing carbamate and carbamido.
1-phenyl-4-carbinol-1H-1, 2, 3-triazole and acryloyl chloride react under the catalysis of triethylamine to obtain the acrylate monomer with the triazolyl. 1, 3-dibromo-2-propanol and acryloyl chloride react under the catalysis of triethylamine to obtain an acrylate monomer with a bromine atom. And (2) fully reacting 50 molar equivalents of butyl acrylate, 20 molar equivalents of acrylate monomer with triazolyl, 15 molar equivalents of acrylate monomer with bromine atom and 1 molar equivalent of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone under an ultraviolet lamp to obtain the polyacrylate with the triazole side group and the bromine atom.
Fully mixing 100 parts by mass of the obtained modified polyacrylonitrile with the side group containing urethane and urea bonds, 100 parts by mass of the obtained polyacrylate, 200 parts by mass of 1-butyl-2, 3-dimethyl imidazole tetrafluoroborate, 20 parts by mass of carbon nanotubes and a proper amount of dimethylformamide solvent, heating at 110 ℃ for full reaction, and then removing the solvent to obtain the corresponding hybrid dynamic polymer ionic liquid gel. The ionic liquid gel prepared by the embodiment has good stability, not only has good conductivity and mechanical strength, but also can be stable in a wide temperature range and an electrochemical window, can be manufactured into an ideal electrolyte material, and has good heating effect under near infrared light.
Example 10
A hybrid dynamic polymer plasticizer swelling gel based on polyvinyl chloride is prepared, wherein the supramolecular interaction is based on pendant urea groups.
Branched polyvinyl chloride (average molecular weight of about 50000) and 4- (2-pyrrolidinyl) thiophenol were dissolved in cyclohexane and reacted at 60 ℃ for 12 hours while maintaining the molar ratio of the pendant chlorine atom to the 4- (2-pyrrolidinyl) thiophenol at about 3. Reacting polyvinyl chloride containing a secondary amino group in a side group with methyl isocyanate in dichloromethane, and keeping the molar ratio of the secondary amino group to the methyl isocyanate to be about 1.
The branched polyvinyl chloride and sodium azide react in cyclohexane at 60 ℃ to convert partial side group chlorine atoms into azide groups. The compound 10a is obtained by reacting 1, 4-dibromo-2-butanol and 5-hexynoyl chloride with equal molar equivalent under the catalysis of triethylamine.
Taking a certain amount of polyvinyl chloride with partial side groups being azido, a compound 10a and 5-bromo-n-pentyne, keeping the molar ratio of azido to the compound 10a to 5-bromo-n-pentyne to be 5. The material has good toughness, and can be used as a plate, a pipe, a film, a sealing material and the like with a self-repairing function.
Example 11
A hybrid dynamic polymer ionic liquid gel based on polyacrylate and polyethyleneimine is prepared, wherein the supramolecular interaction is based on pendant thiocarbamate groups and terminal urea groups.
Reacting [1- (phenylmethyl) -1,2, 3-triazol-4-yl ] methanol with acryloyl chloride under the catalysis of triethylamine to obtain the acrylate monomer with triazolyl. Reacting 3-iodopropanol with acryloyl chloride under the catalysis of triethylamine to obtain an acrylate monomer with an iodine atom. Under the anhydrous and oxygen-free conditions, reacting ethanol and isocyanate ethyl acrylate with equal molar equivalent in dichloromethane under the catalysis of triethylamine to obtain the acrylate monomer containing the thiocarbamate group.
Under anhydrous and anaerobic conditions, keeping the molar ratio of the initiator methyl 2-bromopropionate to the acrylate monomer containing the thiocarbamate group at 1. 1 molar equivalent of the resulting polyacrylate and 25 molar equivalents of 5-amino-1-pentanol were dissolved in DMSO and reacted at 40 ℃ for 30 minutes. The reaction solution was dropped into methylene chloride, washed with hydrochloric acid, a sodium bicarbonate solution and water, and dried over anhydrous magnesium sulfate to obtain a polymer having a hydroxyl group at one end. And reacting the obtained polymer with acryloyl chloride under the catalysis of triethylamine to obtain the acrylate macromonomer containing hydrogen bond groups.
Dissolving isophorone diisocyanate and n-propylamine with equal molar equivalent weight in DMF, adding a certain amount of branched polyethyleneimine (the average molecular weight is about 20000) after the reaction is completed, and keeping the terminal amino group in a polyethyleneimine chain segment and the isocyanate group in the solution to be 3. Taking 100 parts by mass of 30 molar equivalents of n-butyl acrylate, 10 molar equivalents of acrylate monomer with triazolyl, 20 molar equivalents of acrylate monomer with iodine atoms and 5 molar equivalents of acrylate macromonomer containing hydrogen bond groups, and fully mixing the components with 1 molar equivalent of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, 50 parts by mass of modified branched polyethyleneimine and 150 parts by mass of ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate, wherein the mass of the ionic liquid is 50% of the total weight of the mixture. And (3) after the reaction is performed for 4 hours under the illumination of an ultraviolet lamp, stopping illumination, heating to 110 ℃ and performing full reaction to obtain the hybrid dynamic polymer ionic liquid gel. The hybrid dynamic polymer ionic liquid gel obtained by the embodiment has good toughness and self-repairability, and can be used as a tearing-resistant adhesive and a plugging adhesive.
Example 12
A hybrid dynamic polymer foam based on ethylene-butadiene random copolymer and polyethylene is prepared in which the supramolecular interaction is based on triazolinedione-ene adduct side groups and pendant ureidopyrimidinone groups.
Under anhydrous conditions, a 2L reactor was charged with ethylene and maintained at 1 atmosphere, with 14% by volume of toluene and 0.95% by volume of butadiene in toluene (9 wt%) added to the reactor. Adding catalyst containing scandium and Al at 40 deg.C i Bu 3 And [ Ph 3 C][B(C 6 F 5 ) 4 ]20 ml of the catalyst solution, and at the same time, 6 ml of a 6% by volume butadiene toluene solution (9 wt%) was dropped into the reactor at a rate of 6 ml per minute. After the butadiene solution was completely added dropwise, 20 ml of acidified methanol was rapidly added, and the product was precipitated in ethanol to obtain an ethylene-butadiene random copolymer. And (2) reacting the obtained copolymer with a certain amount of thioglycolic acid at 60 ℃ under the initiation of azodiisobutyronitrile, and keeping the molar ratio of alkenyl groups to the thioglycolic acid in the copolymer to be 10. The resulting copolymer was reacted with an amount of 1, 3-diiodo-2-propanol and 1-phenyl-4-methanoyl-1H-1, 2, 3-triazole under DCC and DMAP catalysis, maintaining the molar ratio of the pendant carboxyl groups, 1, 3-diiodo-2-propanol and 1-phenyl-4-methanoyl-1H-1, 2, 3-triazole in the copolymer at 5. Dissolving the obtained copolymer and a certain amount of 4-methyl-1, 2, 4-triazoline-3, 5-diketone in tetrahydrofuran, keeping the molar ratio of double bonds to the 4-methyl-1, 2, 4-triazoline-3, 5-diketone to be 5, stirring, and then fully reacting to obtain modified ethylene with the side group containing hydrogen bond groups and bromine atoms-butadiene random copolymers.
Heating and dissolving low-density branched polyethylene (with average molecular weight of about 20000) in xylene, adding 100 molar equivalents of maleic anhydride, adding dicumyl peroxide as an initiator dissolved in xylene when the temperature of the solution rises to 130 ℃, and reacting at constant temperature for 1-3 hours to obtain the polyethylene grafted maleic anhydride. Under the protection of inert gas, dissolving the UPy derivative 12a and the obtained polyethylene grafted maleic anhydride in xylene, keeping the molar ratio of the compound 12a to the maleic anhydride side group as 1, adding a catalyst sodium p-toluenesulfonate under stirring, and stirring at 105 ℃ for reaction. And hydrolyzing the obtained product with a dichloromethane solution of trifluoroacetic acid to obtain the modified polyethylene containing the UPy side group hydrogen bond group.
Fully blending 100 parts by mass of the obtained modified ethylene-butadiene random copolymer, 50 parts by mass of the obtained modified polyethylene, 30 parts by mass of sodium stearate, 20 parts by mass of calcium carbonate, 0.2 part by mass of antioxidant 754, 8 parts by mass of sodium bicarbonate and 0.2 part by mass of vaseline oil, extruding and molding to obtain a corresponding foam product, and fully curing at 110 ℃ to obtain the hybrid dynamic polymer foam.
The foam has good abrasion resistance and certain strength and compressibility, and can be stretched within a certain range.
Example 13
Hybrid dynamic polymer elastomers based on polysiloxanes and polyethylene glycols are prepared, wherein the supramolecular interaction is based on a terminal cytosine group and a terminal guanine group.
Reacting cytosine with polyethylene glycol with succinimide succinate groups at two ends under the catalysis of triethylamine to obtain polyethylene glycol with cytosine groups at two ends. Guanine and polyethylene glycol with succinimide succinate groups at two ends react under the catalysis of triethylamine to obtain the polyethylene glycol with guanine groups at two ends.
6-bromine-1-hexene reacts with excessive sodium azide to obtain 6-azido-1-hexene. Reacting polysiloxane containing 3 molar equivalents of silicon hydrogen with 2 molar equivalents of 6-bromo-1-hexene and 1 molar equivalent of 6-azido-1-hexene in cyclohexanone at 90 ℃ for 3 hours by taking chloroplatinic acid as a catalyst to obtain the crosslinked polysiloxane containing the dynamic covalent bond.
Fully blending 100 parts by mass of the obtained polysiloxane, 50 parts by mass of each of the two obtained polyethylene glycols and a certain amount of tetrapolyethylene glycol with one end being alkynyl, keeping the molar ratio of azido to alkynyl in the mixture as 1. The polymer is prepared into a film, has relatively excellent comprehensive performance, certain tensile strength and good tear resistance, and can be stretched to a relatively large extent. After the polymer film is cut off, the section is placed in a mold at 130 ℃ and attached for 6 hours, cracks on the section disappear, and the sample is formed into a film again, so that the self-repairing function is realized. The hybrid dynamic polymer can be applied to preparing functional films, or can be used as a film for sticking automobiles and furniture, and can also be used as a stretch packaging film, and can be recycled and reused.
Example 14
A hybrid dynamic polymer foam elastomer based on styrene-butadiene random copolymer rubber and polyisobutylene is prepared in which the supramolecular interaction is based on terminal carbamate groups and terminal urea groups.
And (2) fully reacting polyisobutylene with one end of amino-terminated with 2, 4-toluene diisocyanate with the same molar equivalent, adding ethanol with the same molar equivalent, and continuously reacting under the catalysis of TDBDL to obtain modified polyisobutylene with one end containing a terminal hydrogen bond group.
Reacting a certain amount of linear styrene-butadiene random copolymer, 3-bromo-1-propanethiol and mercapto-tetraethylene glycol-azide under ultraviolet light by taking BDK as a photoinitiator, and keeping the molar ratio of double bonds, 3-bromo-1-propanethiol and mercapto-tetraethylene glycol-azide in the copolymer to be 15. And (3) reacting the obtained copolymer with 4-tolylacetylene at 35 ℃ under the catalysis of cuprous iodide and pyridine to obtain the copolymer with the side group containing bromine atoms and triazole groups.
Melting 40 parts by mass of the modified polyisobutylene containing the terminal hydrogen bond group, 25 parts by mass of polystyrene and 8 parts by mass of polyvinyl acetate, 100 parts by mass of the styrene-butadiene random copolymer containing the bromine atom and the triazolyl in the side group at 110-120 ℃, fully blending and reacting, when the temperature is reduced to 60 ℃, preserving the heat for 1 hour, filling the mixture into a mold, placing the mold in a pressure reaction kettle, introducing supersaturated carbon dioxide, heating to 90 ℃, controlling the pressure to be 7-14MPa, and reducing the pressure at the speed of 1MPa per second after 4 hours, rapidly cooling the product in ice water, and demolding to obtain the hybrid dynamic polymer composition foam product. The foam product obtained by the embodiment has good self-repairing property and can be used as a light heat-insulating material.
Example 15
A hybrid dynamic polymer hydrogel based on a polyvinyl acetate-polyvinyl alcohol random copolymer and polyethylene glycol is prepared, wherein the supramolecular effect is based on a lateral oxathiazolyl group, a terminal diamido naphthyridinyl group and a terminal ureidopyrimidinonyl group.
Dissolving a certain amount of polyvinyl acetate-polyvinyl alcohol random copolymer (with average molecular weight of about 10000 and alcoholysis degree of about 20 percent), 5-bromovaleric acid, 5-ethyl-1-phenyl-1H- [1,2,3] triazole-4-carboxylic acid and propylcysteine in tetrahydrofuran, maintaining the molar ratio of hydroxyl, 5-bromovaleric acid, 5-ethyl-1-phenyl-1H- [1,2,3] triazole-4-carboxylic acid and propylcysteine in the copolymer to be 10, and reacting under the catalysis of dicycloethyl carbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) to obtain the modified polyvinyl acetate containing a side group bromine atom, a side triazolyl group and a side oxysulfazolyl group.
Using dichloromethane as a solvent, and reacting the polyethylene glycol with two end acyl chloride end groups as end caps with ammonium hydroxide to obtain the polyethylene glycol with two end groups as acylamino. Lead acetate, 4, 5-bis (diphenylphosphino) -9, 9-dimethyl xanthene and potassium carbonate are used as catalysts, 10 molar equivalents of 2, 7-dichloro-1, 8-naphthyridine and 9 molar equivalents of 2-ethylcaproamide react in chloroform to obtain a naphthyridine intermediate with one end connected with the 2-ethylcaproyl amino. Reacting the naphthyridine intermediate obtained by 2 molar equivalents with polyethylene glycol with two end groups as amido groups under the catalysis of lead acetate, 4, 5-bis (diphenylphosphine) -9, 9-dimethyl xanthene and potassium carbonate to obtain polycyclooctene with two end groups containing 2, 7-amido-1, 8-naphthyridine end groups. 1 molar equivalent of the compound 15a and 1 molar equivalent of 2, 6-diisopropylphenyl isocyanate were dissolved in tetrahydrofuran under anhydrous conditions and reacted at room temperature for 16 hours to give a UPy derivative 15b having one terminal alkenyl group. And (3) respectively reacting the obtained UPy derivative 15b with mercaptoethanol with the same molar equivalent under the combined action of BDK and ultraviolet light to convert alkenyl into hydroxyl, so as to obtain the UPy derivative 15c with one end being hydroxyl. Reacting 2 molar equivalents of UPy derivative 15c with one end being hydroxyl and 1 molar equivalent of polyethylene glycol with two end groups being carboxyl under the catalysis of DCC and DMAP to obtain polyethylene glycol with two end groups containing UPy derivative groups.
Fully mixing 100 parts by mass of modified polyvinyl acetate containing side group bromine atoms, side triazolyl and side oxathiazolyl, 20 parts by mass of polyethylene glycol containing 2, 7-amido-1, 8-naphthyridine end groups at two ends and 30 parts by mass of polyethylene glycol containing UPy derivative groups at two ends, fully reacting at 110 ℃, and swelling in water to obtain the hybrid dynamic polymer hydrogel. The hydrogel can be used as magic toy.
Example 16
A hybrid dynamic polymer elastomer based on polysiloxanes and poly-beta-hydroxybutyrate is prepared in which the supramolecular interactions are based on pendant imidazolinonyl groups, backbone amido groups and terminal ureidopyrimidonyl groups.
1 molar equivalent of high molecular weight poly-beta-hydroxybutyrate (PHB, average molecular weight about 300000) was dissolved in dichloromethane, and a mixed solution containing 1000 molar equivalents of p-toluenesulfonic acid and 10000 molar equivalents of 1, 4-butanediol was dropped. The reaction was carried out at room temperature, and the product was precipitated and washed with methanol to give a low molecular weight poly-beta-hydroxybutyrate having hydroxyl groups at both ends (average molecular weight about 3000). The UPy derivative 18c with one end as alkenyl reacts with mercaptoacetic acid with the same molar equivalent under the combined action of BDK and ultraviolet light to convert the alkenyl into carboxyl. Reacting PHB with hydroxyl at two ends obtained by 1 molar equivalent and UPy derivative with carboxyl end capping by 2 molar equivalents under the catalysis of DCC and DMAP to obtain PHB with UPy derivative at two ends.
Under the protection of nitrogen, adding urea into aminated dimethyl siloxane 16a, keeping the molar ratio of urea to side amino groups at 9, slowly heating to 160 ℃ under stirring, preserving the temperature for about 1 hour, and then cooling to room temperature to obtain modified polydimethylsiloxane 16b containing side imidazolinone groups and side amino groups.
A certain amount of modified polydimethylsiloxane 16b was blended with 5-bromovaleric acid, 5-ethyl-1-phenyl-1H- [1,2,3] triazole-4-carboxylic acid, the molar ratio of the pendant amino groups in the polydimethylsiloxane to 5-bromovaleric acid, 5-ethyl-1-phenyl-1H- [1,2,3] triazole-4-carboxylic acid was maintained at 5. 100 parts by mass of the obtained modified polydimethylsiloxane and 100 parts by mass of the obtained PHB with UPy derivatives at two ends are blended and fully reacted at 110 ℃ to obtain the hybrid dynamic polymer. The hybrid dynamic polymer shows good viscoelasticity and excellent hydrolysis resistance. When the surface of the plug is damaged, the plug can be healed and reshaped at the damaged part by heating, self-repairing and recycling of materials are realized, the plug can be used for preparing plugs at charger interfaces, data line interfaces and the like of mobile phones, tablet computers, notebooks, cameras and the like, and open holes generated in the process of plugging and unplugging the connectors are repaired, so that the purposes of water resistance and the like are achieved.
Example 17
A hybrid dynamic polymer elastomer based on polyisobutylene and polyacrylate is prepared, in which the supramolecular action is based on pendant urea groups.
2-aminoethyl acrylate and 4-biphenyl isocyanate were reacted in the solvent dichloromethane, maintaining the molar ratio of amino and isocyanate at 1. The isocyanate ethyl acrylate and n-propylamine were reacted in the solvent dichloromethane while maintaining the molar ratio of amino group to isocyanate at 1. Reacting isocyanate ethyl acrylate and tetrahydropyrrole in solvent dichloromethane, and keeping the molar ratio of isocyanate to amino as 1. The modified poly (meth) acrylate containing different pendant urea groups was obtained by thoroughly blending 1 molar equivalent of photoinitiator, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 10 molar equivalents of 17a, 30 molar equivalents of 17b, 10 molar equivalents of 17c, and 10 molar equivalents of ethyl methacrylate and polymerizing the blend under light. Reacting 4 molar equivalents of polyisobutene terminated by hydroxyl at two ends with 3 molar equivalents of 1-benzyl-1, 2, 3-triazole-4, 5-dicarboxylic acid under the catalysis of DCC and DMAP, adding excessive n-butyric acid after the carboxylic acid is completely reacted, and continuing the reaction to obtain polyisobutene containing triazolyl.
The hybrid dynamic polymer elastomer of the present invention was obtained by crushing 30 parts by mass of the obtained modified poly (meth) acrylate into particles, sufficiently reacting 100 parts by mass of the obtained polyisobutylene with a certain amount of 1, 6-diiodohexane at 110 ℃ while maintaining the molar ratio of the triazole group to the iodine atom in the polyisobutylene at 3. In the embodiment, the obtained elastomer can show good toughness and elasticity, and can be pressed into products with different shapes and sizes according to needs, and damaged or no longer needed samples can be recycled to be made into new products for use.
Example 18
A polyether-based hybrid dynamic polymer oligomer swelling gel is prepared, wherein the supramolecular function is based on terminal carbamate groups.
Under the protection of nitrogen, 5 molar equivalent pentaerythritol and 2 molar equivalent potassium methoxide are blended, and 300 molar equivalent epoxypropanol is slowly dripped at 95 ℃ to obtain the polyether with hyperbranched structure and hydroxyl as the terminal group. And (3) reacting the obtained polyether with excessive ethyl isocyanate under the catalysis of DBTDL, and obtaining the polyether with the hyperbranched structure and the terminal group of carbamate after the reaction is completed.
Fully blending 3 molar equivalents of azide-triethylene glycol-propargyl and 4 molar equivalents of bromo-hepta-polyethylene glycol-bromo, weighing the obtained mixture to 100 parts by mass, adding 50 parts by mass of the obtained hyperbranched polyether and 100 parts by mass of alkyl terminated polyethylene glycol oligomer, and reacting and molding at 110 ℃ to obtain the hybrid dynamic polymer oligomer swelling gel product.
The hybrid dynamic polymer oligomer swelling gel not only embodies excellent tensile toughness, but also has good plasticity and rebound resilience, and can be prepared into products with different shapes according to the size of a mould. When the surface of the material is damaged, the material can be remolded by heating, so that the material can be recycled.
Example 19
A hybrid dynamic polymer elastomer based on poly (2-oxazolidine) and polythioethers is prepared, in which the supramolecular interaction is based on pendant benzimidazoles, backbone amido groups and pendant oxazolidone groups.
Equimolar amounts of 1, 4-pentadien-3-ol and 5-chloromethyl-2-oxazolidinone were dissolved in toluene, and the diene containing a pendant oxazolidone group was obtained using potassium carbonate as the catalyst and tetrabutylammonium bromide as the phase transfer agent. Equal molar equivalent of 1, 4-butanedithiol, 4 molar equivalent of diene containing side oxazolidone group and a proper amount of benzoin dimethyl ether photoinitiator are mixed and react under the illumination of an ultraviolet lamp to obtain polythioether containing side hydrogen bond groups.
The cationic ring-opening polymerization of 20 molar equivalents of 2- (3-ethylheptyl) -2-oxazoline was carried out using 1 molar equivalent of propynyl p-toluenesulfonate as an initiator and 1 molar equivalent of hexynoic acid as a terminator to give poly (2-oxazoline) whose both ends were terminated with alkynyl groups. Equimolar 1, 4-pentadiyne-3-alcohol and benzimidazole-5-formic acid react under the catalysis of DCC and DMAP to obtain the diyne containing the side benzimidazolyl. 6-heptynoic acid and propargylamine are subjected to acylation reaction in the presence of a condensing agent 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline to obtain the diyne containing skeleton amide groups.
Poly (2-oxazoline) with 35 molar equivalents of both ends capped by alkynyl groups, diyne with 10 molar equivalents containing lateral benzimidazolyl, diyne with 5 molar equivalents containing skeleton amide groups, 1, 11-diazido-3, 6, 9-trioxaundecane with 49 molar equivalents and 1, 8-diiodooctane with 35 molar equivalents are blended to be 100 parts by mass, then 30 parts by mass of polythioether containing lateral hydrogen bonding groups are added to be fully blended and fully reacted at 110 ℃, and the hybrid dynamic polymer elastomer of the invention is obtained. The hybrid dynamic polymer elastomer obtained in the embodiment can be used for preparing a sealing member or other parts with self-repairing function.
Example 20
A hybrid dynamic polymer foam based on poly (limonene carbonate) and poly (beta-hydroxybutyrate) is prepared in which the supramolecular action is based on pendant ureidopyrimidinone and pendant carbamate groups.
Under the condition of anhydrous and air-free temperature of 90 ℃, dissolving limonene oxide and a catalyst 20a in toluene, keeping the molar ratio of the limonene oxide to the catalyst as 100. Dissolving a certain amount of the obtained poly-limonene carbonate 20b in chloroform, adding excessive 2-mercaptoacetic acid, n-butyl 3-mercaptopropionate and azodiisobutyronitrile, keeping the molar ratio of the 2-mercaptoacetic acid to the n-butyl 3-mercaptopropionate to the initiator at 3, and reacting at 60 ℃ to obtain part of the poly-limonene carbonate with side groups of carboxyl. Blending part of the obtained poly-limonene carbonate with side carboxyl groups, a UPy derivative 15c with one end being hydroxyl, 6-iodo-1-hexanol and 1-phenyl-4-carbinol-1H-1, 2, 3-triazole, keeping the molar ratio of the side carboxyl groups, the UPy derivative with one end being hydroxyl, 6-iodo-1-hexanol and 1-phenyl-4-carbinol-1H-1, 2, 3-triazole in the poly-limonene carbonate to be 10.
Reacting 6-amino-1-hexanol with methyl chloroformate in dichloromethane, and controlling the molar ratio of amino to methyl chloroformate to be 10 by using anhydrous sodium bicarbonate as a catalyst to obtain a compound 20c. Poly-beta-hydroxybutyrate (average molecular weight about 20000) and maleic anhydride were dissolved in chlorobenzene to give an initial mass volume concentration of 3% maleic anhydride. Adding benzoyl peroxide at 130 ℃ to make the initial concentration of the benzoyl peroxide be 0.2%, and keeping the temperature for reacting for 6 hours to obtain the poly beta-hydroxybutyrate grafted maleic anhydride. Under the protection of inert gas, dissolving the poly beta-hydroxybutyrate grafted maleic anhydride and the compound 20c in xylene, and keeping the molar ratio of the maleic anhydride side group to the compound segment 20c to be 1. Adding catalyst sodium p-toluenesulfonate under stirring, and stirring at 105 deg.C to obtain modified poly beta-hydroxybutyrate with pendant group containing urethane bond.
Fully mixing 100 parts by mass of the obtained cross-linked modified poly-limonene carbonate, 50 parts by mass of modified poly-beta-hydroxybutyrate containing a urethane bond, 50 parts by mass of polyester hollow microspheres and 15 parts by mass of polyvinylpyrrolidone microspheres, and fully reacting at 110 ℃ to obtain the hybrid dynamic polymer foam.
The hybrid dynamic polymer foam obtained in this example has a certain strength, rigidity and hygroscopicity. After being crushed, the mixture is placed in a mold at 130 ℃ for 8 hours, and then the sample can be pressed and molded again.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are also included in the scope of the present invention.
Claims (35)
1. A hybrid dynamic polymer, characterized in that, the hybrid dynamic polymer contains at least one cross-linking network, and contains exchangeable covalent bond based on alkyl triazolium, halogenated alkyl group capable of exchanging reaction with alkyl triazolium and hydrogen bonding group capable of forming supermolecular hydrogen bonding; wherein the alkyl triazolium-based exchangeable covalent bond has a structure represented by the following formula (1):
wherein, X — Is negative ion selected from bromide ion and iodide ion;
represents a linkage to a polymer chain;
wherein the haloalkyl group which can undergo an exchange reaction with an exchangeable covalent bond based on alkyltriazolium has a structure represented by the following formula (2):
wherein X is a halogen atom selected from a bromine atom and an iodine atom; wherein the content of the first and second substances,
represents a linkage to a polymer chain;
wherein said hydrogen bonding groups are selected from at least:
wherein the content of the first and second substances,
represents a linkage to a polymer chain; m, n, x are the number of repeating groups, which are fixed values or average values; the value ranges of m and n are 0 and integers more than or equal to 1; the value range of x is an integer greater than or equal to 1.
2. A hybrid dynamic polymer according to claim 1, wherein the hybrid dynamic polymer has only one cross-linked network, and the cross-linked network contains both dynamic covalent cross-links and supramolecular cross-links, wherein the degree of cross-linking of the dynamic covalent cross-links is above its gel point and the degree of cross-linking of the supramolecular cross-links is above or below its gel point.
3. A hybrid dynamic polymer according to claim 1, wherein the hybrid dynamic polymer has only one cross-linked network containing both dynamic covalent cross-links and supramolecular cross-links, wherein the degree of cross-linking of the dynamic covalent cross-links is below the gel point and the degree of cross-linking of the supramolecular cross-links is above the gel point.
4. A hybrid dynamic polymer according to claim 1, wherein the hybrid dynamic polymer has only one cross-linked network containing both dynamic covalent cross-links and supramolecular cross-links, wherein the degree of cross-linking of the dynamic covalent cross-links is below the gel point, the degree of cross-linking of the supramolecular cross-links is below the gel point, but the sum of the degrees of cross-linking is above the gel point.
5. A hybrid dynamic polymer according to claim 1, wherein said hybrid dynamic polymer comprises two networks; the No. 1 network only contains dynamic covalent cross-linking, and the cross-linking degree is above the gel point; the 2 nd network contains only supramolecular crosslinks, the degree of which is above its gel point.
6. A hybrid dynamic polymer according to claim 1, wherein said hybrid dynamic polymer comprises two networks; the first network contains dynamic covalent crosslinking and supramolecular crosslinking, and the crosslinked network contains the dynamic covalent crosslinking and the supramolecular crosslinking simultaneously, wherein the crosslinking degree of the dynamic covalent crosslinking is higher than the gel point of the supramolecular crosslinking, and the crosslinking degree of the supramolecular crosslinking is higher than or lower than the gel point of the supramolecular crosslinking; the 2 nd network contains only supramolecular crosslinks, the degree of which is above its gel point.
7. A hybrid dynamic polymer according to claim 1, comprising a network containing only dynamic covalent crosslinks above the gel point, the supramolecular polymer having a degree of supramolecular crosslinking below its gel point being dispersed in the network of dynamic covalent crosslinks.
8. A hybrid dynamic polymer according to claim 1, wherein the hybrid dynamic polymer comprises a network containing both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular crosslinks is above or below its gel point; supramolecular polymers with a degree of supramolecular cross-linking below their gel point are dispersed in the dynamic covalent cross-linked network.
9. A hybrid dynamic polymer according to claim 1, wherein the hybrid dynamic polymer comprises a network containing only dynamic covalent crosslinks above the gel point, and the supramolecular polymer with a degree of supramolecular crosslinking above its gel point is dispersed in the dynamic covalent crosslinked network in the form of particles.
10. The hybrid dynamic polymer of claim 1, wherein the hybrid dynamic polymer comprises a network containing both dynamic covalent crosslinks and supramolecular crosslinks, wherein the degree of crosslinking of the dynamic covalent crosslinks is above its gel point and the degree of crosslinking of the supramolecular crosslinks is above or below its gel point; supramolecular polymers with a degree of supramolecular cross-linking above their gel point are dispersed in the dynamic covalent cross-linked network in the particulate state.
11. A hybrid dynamic polymer according to claim 1, wherein at least one glass transition temperature of the hybrid dynamic polymer is not higher than 25 ℃.
12. A hybrid dynamic polymer according to claim 1, wherein at least one glass transition temperature of the hybrid dynamic polymer is not higher than 0 ℃.
13. A hybrid dynamic polymer according to claim 1, wherein all of the glass transition temperatures of the hybrid dynamic polymer are not higher than 25 ℃.
14. A hybrid dynamic polymer according to claim 1, wherein all of the glass transition temperatures of the hybrid dynamic polymer are not higher than 0 ℃.
15. A hybrid dynamic polymer according to claim 1, wherein at least one glass transition temperature of the hybrid dynamic polymer is above 25 ℃ and below 40 ℃.
16. A hybrid dynamic polymer according to claim 1, wherein at least one glass transition temperature of the hybrid dynamic polymer is not lower than 40 ℃ and not higher than the dissociation temperature of dynamic covalent bonds.
17. A hybrid dynamic polymer according to claim 1, wherein all the glass transition temperatures of the hybrid dynamic polymer are not lower than 40 ℃ and not higher than the dissociation temperature of the dynamic covalent bond.
18. A hybrid dynamic polymer according to claim 1, wherein at least one of said hydrogen bonding groups is located in a side group or a side chain or both of said hybrid dynamic polymer.
19. A hybrid dynamic polymer according to claim 1 wherein at least one of said hydrogen bonding groups comprises both a hydrogen bonding donor and a hydrogen bonding acceptor.
20. A hybrid dynamic polymer according to claim 19, wherein said hydrogen bonding groups containing both hydrogen bonding donor and hydrogen bonding acceptor comprise at least one secondary amino group.
21. The hybrid dynamic polymer of claim 19, wherein the hydrogen bonding groups comprising both hydrogen bonding donors and hydrogen bonding acceptors comprise at least one of the following structural elements:
wherein the content of the first and second substances,
denotes a linkage to a polymer chain or a group, atom>
And/or>
With or without loops in between.
22. A hybrid dynamic polymer according to claim 1, wherein the hydrogen bonding groups are selected from the group consisting of carbamate groups, urea groups, thiocarbamate groups, and derivatives thereof.
23. A hybrid dynamic polymer according to claim 1 wherein the hybrid dynamic polymer contains at least one hydrogen bonding group that is not more than tetradentate.
24. A hybrid dynamic polymer according to claim 1, wherein said hybrid dynamic polymer contains two or more hydrogen bonding groups.
25. A hybrid dynamic polymer according to claim 1, wherein X in formula (1) — Is bromide ion; wherein X in the formula (2) is a bromine atom.
26. The hybrid dynamic polymer of claim 1, wherein at least one of the polymer segments linking the dynamic covalent bond and the dynamic covalent bond, the dynamic covalent bond and the hydrogen bonding group, the hydrogen bonding group and the hydrogen bonding group is a polymer segment having a main chain of a carbon chain structure or a carbon-hetero chain structure.
27. A hybrid dynamic polymer according to claim 1, wherein at least one of the polymer chain segments for linking the dynamic covalent bond and the dynamic covalent bond, the dynamic covalent bond and the hydrogen bonding group, the hydrogen bonding group and the hydrogen bonding group is a polymer chain segment whose main chain is an elemental heterochain structure.
28. A hybrid dynamic polymer according to claim 1, wherein at least one of the polymer segments linking the dynamic covalent bonds and the dynamic covalent bonds, the dynamic covalent bonds and the hydrogen bonding groups, the hydrogen bonding groups and the hydrogen bonding groups is a polymer segment having a glass transition temperature of not higher than 25 ℃.
29. A hybrid dynamic polymer according to claim 1, wherein at least one of the polymer chain segments for linking the dynamic covalent bond and the dynamic covalent bond, the dynamic covalent bond and the hydrogen bonding group, the hydrogen bonding group and the hydrogen bonding group is a polymer chain segment having a glass transition temperature of not higher than 0 ℃.
30. A hybrid dynamic polymer according to claim 1, wherein at least one of the polymer segments linking dynamic covalent bonds and dynamic covalent bonds, dynamic covalent bonds and hydrogen bonding groups, or hydrogen bonding groups and hydrogen bonding groups is a polymer segment having a glass transition temperature of greater than 25 ℃ and less than 40 ℃.
31. The hybrid dynamic polymer according to claim 1, wherein at least one of the polymer segments for linking the dynamic covalent bond and the dynamic covalent bond, the dynamic covalent bond and the hydrogen bonding group, or the hydrogen bonding group and the hydrogen bonding group is a polymer segment having a glass transition temperature of not less than 40 ℃ and lower than a dissociation temperature of the dynamic covalent bond.
32. A hybrid dynamic polymer according to any one of claims 1 to 31, wherein the hybrid dynamic polymer has any one of the following properties: common solids, elastomers, gels, foams.
33. A hybrid dynamic polymer according to any one of claims 1 to 31 wherein the formulation components comprising the hybrid dynamic polymer further comprise any one or more of the following additives or utilizable agents: other polymers, auxiliaries, fillers, swelling agents.
34. A hybrid dynamic polymer according to claim 33 wherein said other polymer is selected from any one or more of the following: natural polymer compounds and synthetic polymer compounds; the auxiliary agent is selected from any one or any several of the following components: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants, toughening agents, coupling agents, solvents, lubricants, mold release agents, plasticizers, thickeners, thixotropic agents, leveling agents, colorants, optical brighteners, delustering agents, antistatic agents, dehydrating agents, sterilization and mold inhibitors, foaming agents, co-foaming agents, nucleating agents, and rheological agents; the filler is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers; the swelling agent is selected from any one or more of the following components: water, organic solvent, ionic liquid, oligomer and plasticizer.
35. A hybrid dynamic polymer according to any one of claims 1-31, 34, wherein said hybrid dynamic polymer is used in the following materials or articles: self-repairing coating, self-repairing plate, self-repairing sealing material, self-repairing plugging glue, self-repairing conductive glue, tough material, tough elastomer material, heat insulation material, shape memory material, energy storage device material, toy and toy filler.
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