CN111378165A - Combined hybrid cross-linked dynamic polymer and application thereof - Google Patents

Combined hybrid cross-linked dynamic polymer and application thereof Download PDF

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CN111378165A
CN111378165A CN201910000082.2A CN201910000082A CN111378165A CN 111378165 A CN111378165 A CN 111378165A CN 201910000082 A CN201910000082 A CN 201910000082A CN 111378165 A CN111378165 A CN 111378165A
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不公告发明人
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Xiamen Xiaoyang Sports Technology Co ltd
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Weng Qiumei
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C08J3/00—Processes of treating or compounding macromolecular substances
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    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
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    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
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    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The invention discloses a combined hybrid cross-linked dynamic polymer, which contains at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and an optional hydrogen bond; it contains at least one dynamic covalent cross-linked network, wherein the cross-linking degree of other dynamic covalent bond cross-links reaches above the gel point. The combined hybrid crosslinked dynamic polymer can be used for preparing dynamic polymer materials with wide controllable range, rich structure and various performances by introducing boron-containing dynamic covalent bonds with different dynamic properties, other dynamic covalent bonds and optional hydrogen bonds. The boron-containing dynamic covalent bonds, other dynamic covalent bonds and the differences among hydrogen bonds in the dynamic polymer enable the polymer to show the dynamic reversible effect with orthogonality and cooperativity under different conditions, thereby showing good self-repairing property and abundant stimulation responsiveness. The dynamic polymer can be widely applied as a self-repairing material, a tough material, a sealing material, an interlayer adhesive and the like.

Description

Combined hybrid cross-linked dynamic polymer and application thereof
Technical Field
The invention relates to the field of intelligent materials, in particular to a combined hybrid crosslinked dynamic polymer formed by boron-containing dynamic covalent bonds, other dynamic covalent bonds and optional hydrogen bonds.
Background
The development and the transition of the human society are greatly promoted by the progress of the material science and technology, and the rapid development of the material science is greatly promoted by a high-tech group formed by an information technology, a genetic engineering technology, a new energy technology, an aerospace technology, a nanotechnology and the like since the new century. The traditional single structural material or functional material can not meet the requirements of the rapidly-developed high-technology fields, and various multifunctional and intelligent materials are produced.
In the traditional polymer synthesis concept, new molecules are designed and synthesized mainly through common covalent bonds, and the common covalent bonds have high bond energy, so that the polymers have good stability and stress bearing capacity, but correspondingly, the polymer is difficult to reflect the responsiveness and the dynamic property to the outside, and the development requirement of materials under a new situation is difficult to meet. The dynamic covalent bond can be reversibly broken and formed under a proper condition, side reactions are few in the process, compared with a common covalent bond, the dynamic reversibility in supermolecule chemistry can be embodied, the dynamic reversibility can be used for designing and constructing a stimulus-responsive intelligent material, and compared with supermolecule acting force, the dynamic covalent bond has the advantages of strong bond energy, small influence of thermodynamics and stable property; the reversibility of the acting force of the supermolecule and the stability of the common covalent bond are combined by the dynamic covalent bond, so that the supermolecule dynamic covalent bond has a wide application prospect. The incorporation of dynamic covalent bonds into polymers is a viable approach to the formation of novel intelligent polymers.
With the further expansion and deepening of research, the variety of dynamic covalent bonds is more and more abundant, but the current research on dynamic polymers still stays in a single dynamic covalent bond system, because the dynamic effect and the dynamic regulation capability of a single dynamic covalent bond are limited, the comprehensive performance of synergetic orthogonality is difficult to have, and in order to obtain the dynamic polymers with diversity and synergetic orthogonality dynamics, a novel combined hybrid crosslinked dynamic polymer needs to be developed to solve the problem.
Disclosure of Invention
The present invention addresses the above background by providing a combinatorial hybrid crosslinked dynamic polymer comprising at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally a hydrogen bond; the dynamic polymer contains at least one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-links in at least one dynamic covalent cross-linked network reaches above a gel point. The combined hybrid crosslinked dynamic polymer has orthogonal and differential dynamic reversible effects, and can show self-repairability, recoverability, stimulus responsiveness and bionic mechanical properties under different conditions.
The invention is realized by the following technical scheme:
the invention provides a combined hybrid cross-linked dynamic polymer, which is characterized by comprising at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and a hydrogen bond; the dynamic polymer contains at least one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-links in the at least one dynamic covalent cross-linked network reaches above a gel point; wherein, the existence of the boron-containing dynamic covalent bond, other dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining a polymer structure.
The invention also provides a composite hybrid crosslinked dynamic polymer, characterized in that it contains at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and optionally hydrogen bonds; the dynamic polymer only contains one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-linked networks reaches above a gel point; wherein the presence of said boron-containing dynamic covalent bonds, other dynamic covalent bonds, optionally hydrogen bonds, are a necessary condition for forming or maintaining a polymer structure.
In the present invention, the boron-containing dynamic covalent bond includes, but is not limited to, an organoboron bond, an inorganic boranhydride bond, an organic-inorganic boranhydride bond, a saturated five-membered ring organic boronic acid ester bond, an unsaturated five-membered ring organic boronic acid ester bond, a saturated six-membered ring organic boronic acid ester bond, an unsaturated six-membered ring organic boronic acid ester bond, a saturated five-membered ring inorganic boronic acid ester bond, an unsaturated five-membered ring inorganic boronic acid ester bond, a saturated six-membered ring inorganic boronic acid ester bond, an unsaturated six-membered ring inorganic boronic acid ester bond, an organoboronic acid monoester bond, an inorganic boronic acid monoester bond, an organoboronic acid silicone bond, and an inorganic boronic acid silicone.
In the present invention, the other dynamic covalent bonds include, but are not limited to, dynamic sulfide bonds, dynamic diselenide bonds, dynamic selenazine bonds, dynamic acetal bonds, dynamic imine bonds, dynamic oxime bonds, dynamic hydrazone bonds, dynamic covalent bonds based on reversible radicals, combinable exchangeable acyl bonds, dynamic covalent bonds induced based on steric effects, reversible addition-fragmentation chain transfer dynamic covalent bonds, dynamic siloxane bonds, dynamic silicon ether bonds, exchangeable dynamic covalent bonds based on alkyltriazolium, unsaturated carbon-carbon double bonds capable of olefin cross-metathesis, unsaturated carbon-carbon triple bonds capable of alkyne cross-metathesis, dynamic covalent bonds of [2+2] cycloaddition, [4+2] cycloaddition, dynamic covalent bonds of [4+4] cycloaddition, dynamic covalent bonds of mercapto-michael, dynamic covalent bonds of aminoalkene-michael addition, dynamic covalent bonds of [4+4] cycloaddition, dynamic covalent bonds of mercapto-michael addition, and, A dynamic covalent bond based on triazolinedione-indole, a dynamic covalent bond based on diazacarbene, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinking network, and the crosslinking network comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and hydrogen bond crosslinking, and the crosslinking degree of the other dynamic covalent bond crosslinking is above the gel point. In this embodiment, the crosslinking degree of boron-containing dynamic covalent bond crosslinking and the crosslinking degree of hydrogen bond crosslinking may be at least the gel point thereof or at most the gel point thereof.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising at least one boron-containing dynamic covalent crosslinking and having a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; and further comprising hydrogen bonding crosslinks in at least one of the dynamic covalently crosslinked networks. In this embodiment, the degree of crosslinking in hydrogen bonding may be not less than the gel point thereof, or may be not more than the gel point thereof.
According to a preferred embodiment of the above invention, the combined hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink, and the crosslinking degree of the other dynamic covalent bond crosslink is above the gel point; the other crosslinking network is a hydrogen bonding crosslinking network, wherein the crosslinking degree of the hydrogen bonding crosslinking is above the gel point of the crosslinking network. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof.
According to a preferred embodiment of the invention, the combined hybrid crosslinked dynamic polymer comprises three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network which comprises at least one boron-containing dynamic covalent crosslinking and has a crosslinking degree above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinked network is a hydrogen-bonded crosslinked network, wherein the degree of crosslinking of the hydrogen-bonded crosslinks is above its gel point.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinked network, and at least one other dynamic covalent crosslinking and hydrogen bonding crosslinking are contained in the crosslinked network, and the crosslinking degree of the other dynamic covalent crosslinking is above the gel point, and a non-crosslinked dynamic polymer comprising at least one boron-containing dynamic covalent bond is dispersed in the crosslinked network.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinking network, and at least one other dynamic covalent crosslinking and hydrogen bonding crosslinking are contained in the crosslinking network, and the crosslinking degree of the other dynamic covalent crosslinking is above the gel point, and the dynamic polymer particles containing at least one boron-containing dynamic covalent bonding are dispersed in the crosslinking network.
In the above-described embodiments of the invention, the following combinations of boron-containing dynamic covalent bonds and other dynamic covalent bonds are preferred, respectively:
combination 1: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicone bond; at least one of a dynamic linkage, a dynamic diselenide linkage, a dynamic covalent linkage based on reversible radicals, a binding exchangeable acyl linkage, a dynamic covalent linkage based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent linkage, a dynamic silicon ether linkage, an exchangeable dynamic covalent linkage based on alkyltriazolium, a [2+2] cycloaddition dynamic covalent linkage, a [2+4] cycloaddition dynamic covalent linkage, a [4+4] cycloaddition dynamic covalent linkage, a mercapto-michael addition dynamic covalent linkage, a dynamic covalent linkage based on triazolinedione-indole, an aminoalkene-michael addition dynamic covalent linkage, a dynamic covalent linkage based on diazacarbene, a dynamic exchangeable trialkylsulfonium linkage combination;
and (3) combination 2: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one of a dynamic selenium-nitrogen bond, an acetal dynamic covalent bond, a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond, a hexahydrotriazine dynamic covalent bond, and an amine alkene-Michael addition dynamic covalent bond combination;
and (3) combination: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond combination;
and (4) combination: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one of a dynamic linkage, a dynamic diselenide linkage, a dynamic covalent linkage based on reversible radicals, a binding exchangeable acyl linkage, a dynamic covalent linkage based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent linkage, a dynamic silicon ether linkage, an exchangeable dynamic covalent linkage based on alkyltriazolium, a [2+2] cycloaddition dynamic covalent linkage, a [2+4] cycloaddition dynamic covalent linkage, a [4+4] cycloaddition dynamic covalent linkage, a mercapto-michael addition dynamic covalent linkage, a dynamic covalent linkage based on triazolinedione-indole, an aminoalkene-michael addition dynamic covalent linkage, a dynamic covalent linkage based on diazacarbene, a dynamic exchangeable trialkylsulfonium linkage combination;
and (3) combination 5: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one of a dynamic selenium-nitrogen bond, an acetal dynamic covalent bond, a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond, a hexahydrotriazine dynamic covalent bond, and an amine alkene-Michael addition dynamic covalent bond combination;
and (4) combination 6: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one member selected from the group consisting of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, and a triazolinedione-indole-based dynamic covalent bond.
Combinations of boron-containing dynamic covalent bonds and other dynamic covalent bonds included in the combined hybrid crosslinked dynamic polymers provided in the present invention include, but are not limited to, the preferences set forth above, and can be reasonably combined and selected by one skilled in the art according to specific practical needs.
The invention also provides a combined hybrid cross-linked dynamic polymer, which is characterized by comprising at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond; the dynamic polymer contains at least one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-links in the at least one dynamic covalent cross-linked network reaches above a gel point; wherein the other dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, a dynamic acetal bond, a dynamic imine bond, a dynamic hydrazone bond, a dynamic covalent bond based on a reversible radical, an associative exchangeable acyl bond, a dynamic covalent bond induced based on steric hindrance, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-Michael addition dynamic covalent bond, a, A dynamic covalent bond based on triazolinedione-indole, a dynamic covalent bond based on diazacarbene, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the presence of said boron-containing dynamic covalent bond, or other dynamic covalent bond, is a requirement for forming or maintaining a polymer structure.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinked network, and comprises at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond crosslink in the crosslinked network, and the crosslinking degree of the other dynamic covalent bond crosslink is above the gel point. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising at least one boron-containing dynamic covalent crosslinking and having a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network is more than the gel point.
According to a preferred embodiment of the invention, the combined hybrid crosslinked dynamic polymer comprises three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network which comprises at least one boron-containing dynamic covalent crosslinking and has a crosslinking degree above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinked network is a dynamic covalent crosslinked network which contains at least one other dynamic covalent bond crosslink and the crosslinking degree of the crosslinked network reaches above the gel point.
According to a preferred embodiment of the above invention, the combined hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising both at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network is more than the gel point. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinked network, and at least one other dynamic covalent crosslinking is contained in the crosslinked network, and the degree of crosslinking of the other dynamic covalent crosslinking is above the gel point, and a non-crosslinked dynamic polymer comprising at least one boron-containing dynamic covalent crosslinking is dispersed in the crosslinked network.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinking network, and at least one other dynamic covalent crosslinking is contained in the crosslinking network, and the degree of crosslinking of the other dynamic covalent crosslinking is above the gel point, and particles of the dynamic polymer comprising at least one boron-containing dynamic covalent linkage are dispersed in the crosslinking network.
In embodiments of the invention, the hydrogen bonding may be generated by non-covalent interactions that exist between any suitable hydrogen bonding groups. The hydrogen bond group may contain only a hydrogen bond donor, only a hydrogen bond acceptor, or both a hydrogen bond donor and a hydrogen bond acceptor, preferably both a hydrogen bond donor and a hydrogen bond acceptor.
In an embodiment of the present invention, the hydrogen bond is formed by hydrogen bond groups existing at any one or more of a combined hybrid cross-linked dynamic polymer chain skeleton (including a main chain and a side chain/branch/branched chain skeleton), a side group and an end group. Wherein said hydrogen bonding groups may also be present in said composite hybrid cross-linked dynamic polymer composition, such as a small molecule compound or filler.
In embodiments of the present invention, the linking group for linking the boron-containing dynamic covalent bond, the other dynamic covalent bond and/or the hydrogen bonding group may be selected from any one or more of a heteroatom linking group, a divalent or multivalent small molecule hydrocarbon group, a divalent or multivalent polymer chain residue, a divalent or multivalent inorganic small molecule chain residue, and a divalent or multivalent inorganic large molecule chain residue.
In embodiments of the invention, the combination hybrid crosslinked dynamic polymer may or may not have one or more glass transition temperatures. At least one of them is below 0 ℃, or between 0 and 25 ℃, or between 25 and 100 ℃, or above 100 ℃ for the glass transition temperature of the combined hybrid crosslinked dynamic polymer.
In the embodiment of the invention, the form of the combined hybrid cross-linked dynamic polymer can be common solid, elastomer, gel (including hydrogel, organic gel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), foam material and the like.
During the preparation process of the combined hybrid cross-linked dynamic polymer, certain solvent, other auxiliary agent/additive and filler which can be added/used can be added or used to jointly form the dynamic polymer material.
In an embodiment of the invention, the said combinatorial hybrid crosslinked dynamic polymers can be applied to the following materials or articles: self-repairing coating, self-repairing sheet material, self-repairing binder, sealing material, toughness material, energy storage device material, interlayer adhesive, toy and shape memory material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the combined hybrid crosslinked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and optional hydrogen bonds, fully utilizes the dynamic differences among the boron-containing dynamic covalent bond, the other dynamic covalent bonds and the hydrogen bonds, exerts orthogonality and cooperativity effects in the dynamic polymer, and has good regulation and control capability. The boron-containing dynamic covalent bond contained in the dynamic polymer has stronger dynamic property and mild dynamic reaction conditions, can synthesize the dynamic polymer without a catalyst, high temperature and non-illumination conditions, and shows dynamic reversibility. Other dynamic covalent bonds contained in the dynamic polymer can be kept stable under specific conditions, so that the aim of providing a balanced structure and mechanical strength is fulfilled, and dynamic reversibility can be realized under other specific conditions, so that the material can be subjected to complete self-repairing, recycling and plastic deformation; meanwhile, due to the existence of different boron-containing dynamic covalent bonds and other dynamic covalent bonds, the polymer can show different response effects on external stimuli such as heat, light, pH, oxidation reduction and the like. By combining the two types of dynamic covalent bonds, the combined hybrid crosslinked dynamic polymer with good regulation and control performance, rich dynamic performance and multiple response effects can be prepared, so that the dynamic reversible balance can be partially promoted or partially slowed down in a proper environment to be in a required state, the sensitivity of the dynamic regulation and control is greatly increased, and meanwhile, the performance of the material can be variously regulated and controlled by the structural design and the use condition of the material, which is difficult to realize in the existing supermolecular chemistry and dynamic covalent system. In addition, by controlling parameters such as molecular structure, functional group number, molecular weight and the like of the compound serving as a raw material, a dynamic polymer with adjustable performance and wide application can be prepared.
(2) The existence of boron-containing dynamic covalent bonds, other dynamic covalent bonds and optional hydrogen bonds in the combined hybrid crosslinked dynamic polymer enables the polymer to provide dynamic properties only through the boron-containing dynamic covalent bonds and the hydrogen bonds under specific conditions, and can also show complete self-repairability, recyclability and reuse characteristics under other specific conditions, the material has certain stability and mechanical strength, and can be processed, molded and recycled, which is one point ahead of the existing polymer system; meanwhile, as the polymer does not have common covalent cross-linking above gel points, the self-repairing, shaping, recycling and reprocessing of the polymer can be realized to a greater extent, and the application field of the polymer material is expanded.
(3) After the boron-containing dynamic covalent bond, other dynamic covalent bonds and optional hydrogen bonds contained in the combined hybrid crosslinked dynamic polymer are dissociated under a specific condition, the boron-containing dynamic covalent bond, other dynamic covalent bonds and optional hydrogen bonds can be bonded again under another specific condition for self-repairing and recycling, and the boron-containing dynamic covalent bond, other dynamic covalent bonds and optional hydrogen bonds have good durability and reusability, which are effects which are difficult to achieve by other polymer materials. The existence of different dynamic covalent bonds and hydrogen bonds with different strengths and dynamics enables the combined hybrid crosslinked dynamic polymer in the invention to embody multiple dynamics and responsiveness.
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 provides a combined hybrid cross-linked dynamic polymer, which is characterized by comprising at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and a hydrogen bond; the dynamic polymer contains at least one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-links in the at least one dynamic covalent cross-linked network reaches above a gel point; wherein, the existence of the boron-containing dynamic covalent bond, other dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining a polymer structure. In the invention, once the boron-containing dynamic covalent bond, other dynamic covalent bonds and hydrogen bonds contained in the dynamic covalent cross-linked network are dissociated, the cross-linked network is degraded, and the polymer system can be decomposed into any one or more of the following secondary units: non-crosslinked units such as monomers, polymer chain fragments, polymer clusters, and the like, and even units such as crosslinked polymer fragments and the like; meanwhile, the mutual transformation and dynamic reversibility of the dynamic covalent crosslinked network and the units can be realized through the bonding and dissociation of boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds.
In the present invention, the three-dimensional infinite network containing common covalent bond crosslinks is not present in the combined hybrid crosslinked dynamic polymer, but a common covalent bond crosslinked polymer component dispersedly filled in a particle form (particles which can be in any form, including but not limited to spheres, sheets, fibers, and irregular shapes) can be present.
The term "ordinary 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 ordinary temperature (generally not higher than 100 ℃) and ordinary time (generally less than 1 day), and includes, but is not limited to, ordinary 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. In the present invention, the dynamic covalent cross-linked network generally comprises common covalent bonds in addition to dynamic covalent bonds, wherein the dynamic covalent bonds are a necessary condition for the existence of the cross-linked network, and once the dynamic covalent bonds are dissociated, the cross-linked network is disintegrated. Since the existence of dynamic covalent bonds is a precondition for forming or maintaining the crosslinked network structure of the present invention, it is called "dynamic covalent crosslinked network", thereby distinguishing from the "ordinary covalent crosslinked network" formed simply by ordinary covalent bonds in the conventional sense.
The term "polymerization (reaction/action)" used in the present invention refers to a process/action of chain extension, that is, a process of forming a product having a higher molecular weight from a reactant having a lower molecular weight by a reaction form of polycondensation, polyaddition, ring-opening polymerization, etc. The reactant may be a monomer, oligomer, prepolymer, or other compound having a polymerization ability (i.e., capable of polymerizing spontaneously or under the action of an initiator or an external energy). The product resulting from the polymerization of one reactant is called a homopolymer. The product resulting from the polymerization of two or more reactants is referred to as a copolymer. It is to be noted that "polymerization" referred to in the present invention includes a linear growth process of a reactant molecular chain, a branching process of a reactant molecular chain, a ring formation process of a reactant molecular chain, but does not include a crosslinking process of a reactant molecular chain; in embodiments of the invention, "polymerization" comprises a chain growth process resulting from non-covalent interactions of boron-containing dynamic covalent bonds, bonding of other dynamic covalent bonds and common covalent bonds, and hydrogen bonds.
The term "crosslinking (reaction/action)" as used in the present invention refers to the process of generating a three-dimensional infinite network type product by chemical and/or supramolecular chemical linkage between and/or within reactant molecules through the formation of dynamic covalent bonds and/or common covalent bonds and/or hydrogen bonds. During the crosslinking process, the polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which may be two-dimensional or three-dimensional), and then develop into a three-dimensional infinite network. During the cross-linking of the reactants, the viscosity increases suddenly and gelation begins, the reaction point at which a three-dimensional infinite network is first reached, called the gel point, also called the percolation threshold. A crosslinked reaction product above the gel point (including the gel point, and the degree of crosslinking occurring elsewhere in the present invention includes the gel point in the description above its gel point) having a three-dimensional infinite network structure with the crosslinked network forming a unitary body and spanning the entire polymer structure; the crosslinked reaction products, which are below the gel point, do not form a three-dimensional infinite network structure and do not belong to a crosslinked network that can be integrated across the entire polymer structure. Unless otherwise specified, the term "crosslinked (topological structure) in the present invention includes only a three-dimensional infinite network (structure) having a crosslinking degree of not less than the gel point (including the gel point), and the term" uncrosslinked (structure) refers to a linear, cyclic, branched, etc. structure having a crosslinking degree of not more than the gel point, as well as a two-dimensional or three-dimensional cluster structure.
In embodiments of the invention, the combination hybrid crosslinked dynamic polymer may or may not have one or more glass transition temperatures. At least one of the glass transition temperatures of the hybrid crosslinked dynamic polymer is lower than 0 ℃, or between 0 and 25 ℃, or between 25 and 100 ℃, or higher than 100 ℃; wherein, the dynamic polymer with the glass transition temperature lower than 0 ℃ has better low-temperature service performance and is convenient to be used as a sealant, an elastomer, a gel and the like; the dynamic polymer with the glass transition temperature of 0-25 ℃ can be used at normal temperature and can be conveniently used as an elastomer, a sealant, gel, foam and a common solid; the dynamic polymer with the glass transition temperature of 25-100 ℃ has stronger mechanical property, and is convenient to obtain common solid, foam and gel at room temperature; the dynamic polymer with the glass transition temperature higher than 100 ℃ has good dimensional stability, mechanical strength and temperature resistance, and is favorable for being used as a stress bearing material. The dynamic polymer with the glass transition temperature lower than 25 ℃ can show excellent dynamic property, self-repairing property and recyclability; for the dynamic polymer with the glass transition temperature higher than 25 ℃, the polymer can show good shape memory capacity and stress bearing capacity; in addition, the optional supermolecule hydrogen bond can further regulate and control the glass transition temperature of the dynamic polymer, and supplement the dynamic property, the crosslinking degree and the mechanical strength of the dynamic polymer. For the dynamic polymers of the present invention, it is preferred that at least one glass transition temperature is not greater than 50 deg.C, more preferably at least one glass transition temperature is not greater than 25 deg.C, and most preferably no glass transition temperature is greater than 25 deg.C. Systems that do not have a glass transition temperature above 25 c are particularly suitable for use as self-healing materials due to their good flexibility and flowability/creep at the temperatures of daily use. The glass transition temperature of the dynamic polymer can be measured by a glass transition temperature measurement method commonly used in the art, such as DSC and DMA. In embodiments of the invention, the polymer glass transition temperature may be altered by chemical means.
In embodiments of the present invention, each raw material component of the combined hybrid crosslinked dynamic polymer may have one or more glass transition temperatures, or may have no glass transition temperature, and at least one of the glass transition temperatures is lower than 0 ℃, or between 0 ℃ and 25 ℃, or between 25 ℃ and 100 ℃, or higher than 100 ℃, wherein the raw material of the compound with the glass transition temperature lower than 0 ℃ is convenient for low-temperature preparation and processing during the preparation of the dynamic polymer; the compound raw material with the glass transition temperature of 0-25 ℃ can be prepared, processed and molded at normal temperature; the compound raw material with the glass transition temperature of 25-100 ℃ can be molded by conventional heating equipment, and the manufacturing cost is low; the compound raw material with the glass transition temperature higher than 100 ℃ can be used for preparing high-temperature resistant materials with good dimensional stability and excellent mechanical properties. The dynamic polymer is prepared by utilizing a plurality of compound raw materials with different glass transition temperatures, so that the dynamic polymer with different glass transition temperatures in different ranges can be obtained, multiple comprehensive properties can be embodied, and the dynamic polymer has dynamic property and stability.
In an embodiment of the present invention, the composite hybrid crosslinked dynamic polymer may be formed by one or more crosslinked networks, wherein at least one crosslinked network is a dynamic covalent crosslinked network, and the crosslinking degree of the crosslinking of other dynamic covalent bonds in at least one dynamic covalent crosslinked network is above the gel point, preferably the crosslinking degree of the crosslinking of at least one other dynamic covalent bond in at least one dynamic covalent crosslinked network is above the gel point. When the dynamic polymer is composed of only one crosslinked network, it is preferable to include both boron-containing dynamic covalent bond crosslinks and other dynamic covalent bond crosslinks in the crosslinked network structure. When the dynamic polymer is composed of two or more crosslinked networks, it may be composed of two or more crosslinked networks blended with each other, two or more crosslinked networks interpenetrating with each other, two or more crosslinked networks partially interpenetrating with each other, or a combination of the above three, but the present invention is not limited thereto. Wherein two or more crosslinked networks may be the same or different; wherein part of the covalently crosslinked network can form dynamic covalent crosslinks only by other dynamic covalent bonds, and part of the covalently crosslinked network can form dynamic covalent crosslinks only by boron-containing dynamic covalent bonds; wherein part or all of the covalently cross-linked networks may contain both boron-containing dynamic covalent bond crosslinks and other dynamic covalent bond crosslinks; wherein part of the cross-linked network can form dynamic covalent cross-linking only by dynamic covalent bonds, and part of the cross-linked network can also form hydrogen bond cross-linking only by hydrogen bonds; in this case, the degree of crosslinking of the hydrogen bonding crosslinking may be above the gel point or below the gel point. When two or more crosslinked networks are present, the different crosslinked networks may have interactions (e.g., hydrogen bonding) with each other or may be independent of each other. In the embodiment of the present invention, the crosslinked network structure of the hybrid crosslinked dynamic polymer may be blended and/or interpenetrated with one or more other non-crosslinked polymers, and the polymer chains may include dynamic covalent bonds and/or hydrogen bonds, or may be composed of only ordinary covalent bonds, and may have a linear, cyclic, branched, or two-dimensional or three-dimensional cluster structure below the gel point. In the combined hybrid crosslinked dynamic polymer, at least one dynamic covalent crosslink in a crosslinking network is formed by participation of other dynamic covalent bonds, and the crosslinking degree reaches above a gel point, so that when the other dynamic covalent bonds are kept stable under a specific condition, the dynamic polymer can keep a balanced structure under the specific condition and only embodies dynamics through the boron-containing dynamic covalent bonds and optional hydrogen bonds; under other specific conditions, other dynamic covalent bonds exhibit dynamic behavior, while boron-containing dynamic covalent bonds and optional hydrogen bonds remain stable; in more particular cases, other dynamic covalent bonds, boron-containing dynamic covalent bonds, and optionally hydrogen bonds may all exhibit dynamics; the invention is not limited thereto. Through the control of the material structure design and the use condition, the performance of the material can be variously regulated and controlled, orthogonal and/or synergistic dynamic performance and other functionalities can be obtained, and convenient processing, complete self-repairing and recycling can be carried out, and the effects cannot be reflected by the current dynamic polymer.
It should be noted that, in the present invention, the terms "species", "class" and "series" used for describing different structures are used in a range of series, which is larger than the class, that is, a series can have a plurality of classes, and a class can have a plurality of kinds. Even if the dynamic covalent bonds have the same basic structure, differences in properties may occur due to differences in the linking groups, substituents, isomers, and the like. In the present invention, dynamic covalent bonds having the same basic structure are generally regarded as the same structure, but they are regarded as different structures if the difference in properties is caused by the difference in a linker, a substituent, an isomer, or the like. The invention can be reasonably designed, selected and regulated according to the needs to obtain the best performance, which is also the advantage of the invention. In the present invention, different types of structures are preferably used, and more preferably different series of structures are used, in order to better regulate orthogonality.
The term "orthogonality" as used herein refers to the fact that different boron-containing dynamic covalent bonds, different other dynamic covalent bonds, and different hydrogen bonds can exhibit different dynamic reactivity and dynamic reversibility under different external conditions due to differences in dynamics, stability, dynamic reaction conditions, etc., so that the dynamic polymer can exhibit dynamic reversible effects of different dynamic covalent bonds and hydrogen bonds under different environmental conditions. Specifically, other dynamic covalent bonds do not generally exhibit dynamic reversibility at room temperature, and dynamic adjustment in the dynamic polymer system can be achieved only by boron-containing dynamic covalent bonds and optional hydrogen bonds; after the system is heated, illuminated, added with an oxidation-reduction agent, added with a catalyst, added with an initiator, illuminated, radiated, microwave and plasma, and the pH is adjusted, the dynamics of other corresponding dynamic covalent bonds under corresponding conditions can be triggered, and different environmental stimuli have different dynamic response capabilities among other different types of dynamic covalent bonds, such as dynamic acetal bonds, dynamic imine bonds, dynamic hydrazone bonds, hexahydrotriazine dynamic covalent bonds, amine alkene-Michael addition dynamic covalent bonds sensitive to the change of the pH value, dynamic siloxane bonds, unsaturated carbon-carbon double bonds capable of generating olefin cross metathesis reaction, unsaturated carbon-carbon triple bonds capable of generating alkyne cross metathesis reaction, and unsaturated carbon-carbon triple bonds capable of generating alkyne cross metathesis reaction, the dynamic equilibrium reaction is generally required to be carried out in the presence of a catalyst, and the difference of reaction conditions is utilized, when one function is played, other functions are not triggered, and therefore orthogonality regulation is achieved.
The term "synergy" as used herein means that different boron-containing dynamic covalent bonds, different other dynamic covalent bonds, and different hydrogen bonds can exhibit a dynamic reactivity and a dynamic reversibility which are compatible with each other and synergistic with each other under certain specific external conditions, so that the dynamic polymer can exhibit a dynamic reversible effect which is superior to the original single effect under specific environmental conditions. By selecting dynamic covalent bonds or optional hydrogen bonds that are capable of dynamic behavior under the same external stimulus conditions of heating, addition of redox agents, addition of catalysts, illumination, radiation, microwaves, plasma effects, pH, etc., one effect is effective while the other effect or effects are also capable of dynamic behavior under corresponding environmental conditions, producing a synergistic effect greater than the linear superposition of the two effects. For example, boron-containing dynamic covalent bonds, dynamic sulfide bonds, dynamic diselenide bonds, dynamic covalent bonds based on reversible radicals, associative exchangeable acyl bonds, dynamic covalent bonds based on steric effect induction, reversible addition fragmentation chain transfer dynamic covalent bonds, dynamic silicon ether bonds, exchangeable dynamic covalent bonds based on alkyltriazolium, 2+2 cycloaddition dynamic covalent bonds, [2+4] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, mercapto-michael addition dynamic covalent bonds, triazolinedione-indole-based dynamic covalent bonds, aminoalkene-michael addition dynamic covalent bonds, dinitrohetero carbene-based dynamic covalent bonds, and dynamically exchangeable trialkylsulfonium bonds may exhibit different dynamics with respect to changes in temperature, and may act synergistically under the action of heat; the dynamic acetal bond, the dynamic imine bond, the dynamic hydrazone bond, the hexahydrotriazine dynamic covalent bond and the amine alkene-Michael addition dynamic covalent bond are sensitive to the change of pH value and can synergistically play a role through the adjustment of acidity and alkalinity; the dynamic siloxane bonds, unsaturated carbon-carbon double bonds that can undergo olefin cross metathesis, and unsaturated carbon-carbon triple bonds that can undergo alkyne cross metathesis generally act synergistically by introducing a catalyst; by selecting proper reaction conditions and proper dynamic action, the cooperative regulation and control of the dynamic polymer can be realized.
In a preferred embodiment of the present invention, the combined hybrid crosslinked dynamic polymer, which may contain the boron-containing dynamic covalent bond, other dynamic covalent bonds at any suitable position of the polymer, is crosslinked to a degree above its gel point for other dynamic covalent bonds in at least one dynamic covalent crosslinked network of the combined hybrid crosslinked dynamic polymer; the dynamic covalent bonds and the hydrogen bonds in the dynamic polymer may function both independently and synergistically. For non-crosslinked dynamic covalent polymers, the polymer may contain dynamic covalent bonds on the backbone of the polymer backbone, or on the side chains/branches/branched chains of the polymer backbone; for the cross-linked network, the dynamic covalent bond can be contained on the cross-linked network chain skeleton, and the dynamic covalent bond can also be contained on the side chain/branched chain skeleton of the cross-linked network chain skeleton; the invention also does not exclude the inclusion of dynamic covalent bonds in the side and/or end groups of the polymer chain, other constituents of the polymer such as small molecules, fillers, etc. In embodiments of the present invention, the dynamic covalent bonds are preferably located on the backbone of the polymer backbone (for non-crosslinked structures) and on the backbone of the polymer crosslinked network chains (for crosslinked structures). The hydrogen bond, which may be formed between hydrogen bonding groups present at any one or more of any of the components in the composite hybrid dynamic polymer; wherein, the hydrogen bond group can be present on a dynamic polymer cross-linked network chain skeleton, can also be present on a side chain/branched chain skeleton of the cross-linked network chain skeleton, and can also be present on a side group and an end group of the cross-linked polymer; or can be present on the main chain skeleton, side chain/branched chain skeleton, side group and end group of the non-crosslinked polymer; may also be present in the combined hybrid crosslinked dynamic polymer composition (e.g., small molecule compound or filler). The dynamic covalent bond and the hydrogen bond can be reversibly dissociated and regenerated under a specific condition; under appropriate conditions, dynamic covalent and hydrogen bonds at any position in the dynamic polymer can participate in dynamic reversible exchange.
The "backbone" as used herein refers to the chain length direction of the polymer chain. The "crosslinked network chain skeleton" refers to any chain segment constituting the crosslinked network skeleton. The term "main chain" as used herein, unless otherwise specified, refers to the chain having the highest number of links in the polymer structure. The side chain refers to a chain structure which is connected with a polymer main chain skeleton or a crosslinking network chain skeleton in a polymer structure and is distributed beside the chain skeleton, and the molecular weight of the chain structure is more than 1000 Da; wherein the branched or branched chain refers to a chain structure with a molecular weight of more than 1000Da branched from a polymer main chain skeleton or a cross-linked network chain skeleton or any other chain; in the present invention, for the sake of simplicity, the side chain, the branched chain, and the branched chain are collectively referred to as a side chain unless otherwise specified. Wherein, the side group refers to a chemical group with molecular weight not higher than 1000Da and a short side chain with molecular weight not higher than 1000Da which are connected with the polymer chain skeleton and distributed beside the chain skeleton in the polymer structure. For the side chain and the side group, the side chain and the side group can have a multi-stage structure, that is, the side chain can be continuously provided with the side group and the side chain, the side chain of the side chain can be continuously provided with the side group and the side chain, and the side chain also comprises chain structures such as branched chain and branched chain. The "terminal group" refers to a chemical group which is linked to the polymer chain skeleton in the polymer structure and is located at the end of the chain skeleton; in the present invention, the side groups may have terminal groups in specific cases. For hyperbranched and dendritic chains and their related chain structures, the polymer chains therein can be regarded as main chains, but in the present invention, the outermost chains are regarded as side chains and the remaining chains as main chains, unless otherwise specified. In the present invention, the "side chain", "side group" and "end group" also apply to small molecular monomers and large molecular monomers that undergo supramolecular polymerization by hydrogen bonding. For non-crosslinked structures, the polymer chain skeleton comprises a polymer main chain skeleton and chain skeletons such as polymer side chains, branched chains and the like; for the crosslinked structure, the polymer chain skeleton includes a skeleton of an arbitrary segment present in the crosslinked network (i.e., crosslinked network chain skeleton) and chain skeletons thereof such as side chains, branched chains, and branched chains.
The boron-containing dynamic covalent bond described in the present invention contains a boron atom in its dynamic structural composition, which includes, but is not limited to, organoboron bonds, inorganic boranhydride bonds, organic-inorganic boranhydride bonds, saturated five-membered ring organoboronate bonds, unsaturated five-membered ring organoboronate bonds, saturated six-membered ring organoboronate bonds, unsaturated six-membered ring organoboronate bonds, saturated five-membered ring inorganic boronic acid bonds, unsaturated five-membered ring inorganic boronic acid bonds, saturated six-membered ring inorganic boronic acid bonds, unsaturated six-membered ring inorganic boronic acid bonds, organoboronate mono-bonds, inorganic boronic acid mono-bonds, organoboronate silicone bonds, inorganic boronic acid silicone bonds; wherein, each boron-containing dynamic covalent bond can comprise a plurality of boron-containing dynamic covalent bond structures. When two or more boron-containing dynamic covalent bonds are selected, the boron-containing dynamic covalent bonds can be selected from different structures in the same type of boron-containing dynamic covalent bonds, and also can be selected from different structures in different types of boron-containing dynamic covalent bonds, wherein, in order to achieve orthogonal and/or synergistic dynamic performance, the boron-containing dynamic covalent bonds are preferably selected from different structures in different types of boron-containing dynamic covalent bonds.
The organoboron anhydride linkages described herein are selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000081
wherein each boron atom in the organoboron anhydride linkage is connected to at least one carbon atom by a boron-carbon bond, and at least one organic group is connected to the boron atom by said boron-carbon bond;
Figure BDA0001933286640000085
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference in the same boron atom
Figure BDA0001933286640000083
Can be linked to form a ring, on different boron atoms
Figure BDA0001933286640000084
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical organoboronic anhydride bond structures may be exemplified by:
Figure BDA0001933286640000082
in the embodiment of the present invention, the organoboron anhydride linkages contained in the dynamic polymer may be formed by reacting organoboronic acid moieties contained in the compound raw materials with organoboronic acid moieties, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between the reactive groups contained in the organoboron anhydride linkages-containing compound raw materials.
The inorganic boron anhydride linkages described in this invention are selected from, but not limited to, the following structures:
Figure BDA0001933286640000091
wherein, Y1、Y2、Y3、Y4Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, Y3、Y4At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA0001933286640000096
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b, c, d denote each independently of Y1、Y2、Y3、Y4The number of connected connections; when Y is1、Y2、Y3、Y4When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b, c and d are 0; when Y is1、Y2、Y3、Y4When each is independently selected from oxygen atom and sulfur atom, a, b, c and d are 1; when Y is1、Y2、Y3、Y4When each is independently selected from nitrogen atom and boron atom, a, b, c and d are 2; when Y is1、Y2、Y3、Y4When each is independently selected from silicon atoms, a, b, c and d are 3; difference on the same atom
Figure BDA0001933286640000097
Can be linked to form a ring, on different atoms
Figure BDA0001933286640000098
Or may be linked to form a ring, including but not limited to an aliphatic ring,Aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic boron anhydride bond structures are exemplified by:
Figure BDA0001933286640000092
in the embodiment of the present invention, the inorganic boron anhydride bond contained in the dynamic polymer may be formed by the reaction of an inorganic boric acid moiety contained in the compound raw material with an inorganic boric acid moiety, or the dynamic polymer may be introduced by the polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an inorganic boron anhydride bond.
The organic-inorganic boron anhydride linkage described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000093
wherein, Y1、Y2Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein, the boron atom in the structure is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA0001933286640000099
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b denote independently from Y1、Y2The number of connected connections; when Y is1、Y2When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a and b are 0; when Y is1、Y2When each is independently selected from oxygen atom and sulfur atom, a and b are 1; when Y is1、Y2When each is independently selected from nitrogen atom and boron atom, a and b are 2; when Y is1、Y2When each is independently selected from silicon atoms, a, b is 3; difference on the same atom
Figure BDA00019332866400000910
Can be linked to form a ring, on different atoms
Figure BDA00019332866400000911
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical organic-inorganic boron anhydride bond structures may be exemplified by:
Figure BDA0001933286640000094
in embodiments of the present invention, the organic-inorganic boron anhydride linkages contained in the dynamic polymer may be formed by reaction of organic boronic acid moieties contained in the compound starting materials with inorganic boronic acid moieties, or may be introduced into the dynamic polymer by polymerization/crosslinking reactions between the reactive groups contained in the compound starting materials containing organic-inorganic boron anhydride linkages.
The saturated five-membered ring organic boric acid ester bond is selected from but not limited to the following structures:
Figure BDA0001933286640000095
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA00019332866400000912
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different on the same carbon atom
Figure BDA00019332866400000913
Can be linked to form a ring, on different carbon atoms
Figure BDA00019332866400000914
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring organoborate bond structures may be exemplified by:
Figure BDA0001933286640000101
in the embodiment of the present invention, the saturated five-membered ring organic boronic acid ester bond contained in the dynamic polymer may be formed by reacting a 1, 2-diol moiety contained in the compound raw material with an organic boronic acid moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the saturated five-membered ring organic boronic acid ester bond.
The unsaturated five-membered ring organic boric acid ester bond in the invention is selected from but not limited to the following structures:
Figure BDA0001933286640000102
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA0001933286640000107
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
Figure BDA0001933286640000108
an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated five-membered ring organoboronate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or may not be substituted. Typical unsaturated five-membered ring organoborate bond structures may be exemplified by:
Figure BDA0001933286640000103
in the embodiment of the present invention, the unsaturated five-membered ring organic borate bond contained in the dynamic polymer may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an organic borate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the unsaturated five-membered ring organic borate bond.
The saturated six-membered ring organic boric acid ester bond in the invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000104
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA0001933286640000109
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different on the same carbon atom
Figure BDA00019332866400001010
Can be linked to form a ring, on different carbon atoms
Figure BDA00019332866400001011
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring organoboronate bond structures may be exemplified by:
Figure BDA0001933286640000105
in the embodiment of the present invention, the saturated six-membered ring organoboronate bond contained in the dynamic polymer may be formed by reacting a 1, 3-diol moiety contained in the compound raw material with an organoboronate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated six-membered ring organoboronate bond.
The unsaturated six-membered ring organic boric acid ester bond in the invention is selected from but not limited to the following structures:
Figure BDA0001933286640000106
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA00019332866400001012
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
Figure BDA00019332866400001013
an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring organoboronate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom
Figure BDA00019332866400001014
Can be linked to form a ring, on different carbon atoms
Figure BDA0001933286640000117
Or can be connected into a ring. Typical unsaturated six-membered ring organoboronate bond structures may be exemplified by:
Figure BDA0001933286640000111
in the embodiment of the present invention, the unsaturated six-membered ring organoboronic acid ester bond contained in the dynamic polymer may be formed by reacting a 2-hydroxymethylphenol moiety contained in the compound raw material with an organoboronic acid moiety, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated six-membered ring organoboronic acid ester bond.
In the invention, the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond are preferably selected from boron atoms and aminomethyl benzene groups in the structure (B)
Figure BDA0001933286640000112
Indicates the position to which the boron atom is attached); the organic boric acid units for forming the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond are preferably aminomethyl phenylboronic acid (ester) units.
As the aminomethyl phenylboronic acid (ester) element has higher reaction activity when reacting with the 1, 2-diol element and/or the catechol element and/or the 1, 3-diol element and/or the 2-hydroxymethylphenol element, the formed boron-containing dynamic covalent bond has stronger dynamic reversibility, can perform dynamic reversible reaction under milder neutral conditions, can show a sensitive dynamic response effect, and has greater advantages when being used as a dynamic polymer material.
Typical structures of such boron-containing dynamic covalent bonds are exemplified by:
Figure BDA0001933286640000113
the saturated five-membered ring inorganic borate ester bond in the invention is selected from but not limited to at least one of the following structures:
Figure BDA0001933286640000114
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA0001933286640000118
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3; different on the same carbon atom
Figure BDA0001933286640000119
Can be linked to form a ring, on different carbon atoms
Figure BDA00019332866400001110
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated five-membered ring inorganic borate bond structures are exemplified by:
Figure BDA0001933286640000115
in the embodiment of the present invention, the saturated five-membered ring inorganic borate bond contained in the dynamic polymer may be formed by reacting a 1, 2-diol moiety contained in the compound raw material with an inorganic borate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a saturated five-membered ring inorganic borate bond.
The unsaturated five-membered ring inorganic borate bond in the invention is selected from but not limited to at least one of the following structures:
Figure BDA0001933286640000116
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA00019332866400001111
represents a polymer chain,A cross-linked network chain or any other suitable group/atom linkage, wherein a represents a linkage with Y1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3;
Figure BDA00019332866400001112
an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated five-membered ring inorganic borate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or may not be substituted. Typical unsaturated five-membered ring inorganic borate bond structures may be exemplified by:
Figure BDA0001933286640000121
in the embodiment of the present invention, the unsaturated five-membered ring inorganic borate bond contained in the dynamic polymer may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an inorganic borate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated five-membered ring inorganic borate bond.
The saturated six-membered ring inorganic borate bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000122
wherein, Y1Selected from oxygen atoms, sulphur atoms, nitrogen atoms, boron atoms, silicon atoms, preferably oxygen atoms;
Figure BDA0001933286640000127
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3; different on the same carbon atom
Figure BDA0001933286640000128
Can be linked to form a ring, on different carbon atoms
Figure BDA0001933286640000129
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring inorganic borate bond structures may be exemplified by:
Figure BDA0001933286640000123
in the embodiment of the present invention, the saturated six-membered ring inorganic borate bond contained in the dynamic polymer can be formed by reacting the 1, 3-diol moiety contained in the compound raw material with the inorganic borate moiety, or the dynamic polymer can be introduced by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the saturated six-membered ring inorganic borate bond.
The unsaturated six-membered ring inorganic borate bond in the invention is selected from but not limited to at least one of the following structures:
Figure BDA0001933286640000124
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA00019332866400001210
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a represents a linkage to Y1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3;
Figure BDA00019332866400001211
an aromatic ring of any number of members, preferably from a six-membered ring, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring inorganic borate bond; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom
Figure BDA00019332866400001212
Can be linked to form a ring, on different carbon atoms
Figure BDA00019332866400001213
Or can be connected into a ring. Typical unsaturated six-membered ring inorganic borate bond structures are exemplified by:
Figure BDA0001933286640000125
in the embodiment of the present invention, the unsaturated six-membered ring inorganic borate bond contained in the dynamic polymer may be formed by reacting a 2-hydroxymethylphenol moiety contained in the compound raw material with an inorganic borate moiety, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated six-membered ring inorganic borate bond.
The organoboronic acid monoester bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000126
wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond; i is1Selected from divalent linking groups; i is2Selected from the group consisting of a double bond directly attached to two carbon atoms, a trivalent carbene group directly attached to two carbon atoms
Figure BDA0001933286640000133
A divalent non-carbon atom, a linking group containing at least two backbone atoms;
Figure BDA0001933286640000134
an aromatic ring of any number of members, preferably selected from six-membered rings; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not;
Figure BDA0001933286640000135
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different in the same carbon atom, boron atom
Figure BDA0001933286640000136
Can be connected into a ring, on different carbon atoms and boron atoms
Figure BDA0001933286640000137
Can also be connected into a ring or can be connected with I1、I2The substituent atoms (substituents) in the (A) form a ring together, the ring comprises but is not limited to an aliphatic ring, an ether ring, a condensation ring and a combination thereof, wherein the organic boric acid single ester bond formed after the 6 and 7 structures form the ring is not the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond which are described in the previous description. Typical organic boronic acid monoester bond structures are exemplified by:
Figure BDA0001933286640000131
in the embodiment of the present invention, the organic boronic acid monoester bond contained in the dynamic polymer may be formed by the reaction of a monool moiety contained in the compound raw material with an organic boronic acid moiety, or the dynamic polymer may be introduced by the polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the organic boronic acid monoester bond.
The inorganic boric acid monoester bond in the invention is selected from at least one of the following structures:
Figure BDA0001933286640000132
wherein, Y1～Y13Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y1、Y2；Y3、Y4；Y5、Y6、Y7、Y8；Y9、Y10、Y11、Y12At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; y is14Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; i is1Selected from divalent linking groups; i is2Selected from the group consisting of a double bond directly attached to two carbon atoms, a trivalent carbene group directly attached to two carbon atoms
Figure BDA00019332866400001311
A divalent non-carbon atom, a linking group containing at least two backbone atoms;
Figure BDA0001933286640000139
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a to n each represent a linkage to Y1～Y14The number of connected connections; when Y is1～Y13When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a-m is 0; when Y is1～Y14When each is independently selected from oxygen atom and sulfur atom, a to n are 1; when Y is1～Y14When each is independently selected from nitrogen atom and boron atom, a to n are 2; when Y is1～Y14Each independently selected from silicon atoms, a to n is 3;
Figure BDA00019332866400001310
an aromatic ring of any number of members, preferably selected from six-membered rings; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom
Figure BDA00019332866400001312
Can be linked to form a ring, on different carbon atoms
Figure BDA00019332866400001313
Can also be connected into a ring or can be connected with I1、I2The substituted atoms (substituents) in the (A) form a ring together, the ring comprises but is not limited to aliphatic ring, ether ring, condensed ring and combination thereof, wherein the inorganic boric acid monoester bond formed after the 5, 6, 7 and 8 structures form the ring is not the saturated five-membered ring inorganic boric acid ester bond, the unsaturated five-membered ring inorganic boric acid ester bond, the saturated six-membered ring inorganic boric acid ester bond and the unsaturated six-membered ring inorganic boric acid ester bond which are described before. Typical inorganic boronic acid monoester bond structures are exemplified by:
Figure BDA0001933286640000141
in the embodiment of the present invention, the inorganic boronic acid monoester bond contained in the dynamic polymer may be formed by the reaction of a monool moiety contained in the compound raw material with an inorganic boronic acid moiety, or the dynamic polymer may be introduced by the polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing an inorganic boronic acid monoester bond.
The organic borate silicone bond in the invention is selected from but not limited to at least one of the following structures:
Figure BDA0001933286640000142
wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond;
Figure BDA0001933286640000146
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0001933286640000147
Can be linked to form a ring, on different atoms
Figure BDA0001933286640000148
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical silicon organoborate bond structures may be exemplified by:
Figure BDA0001933286640000143
in the embodiment of the present invention, the organoboronate silicone bond contained in the dynamic polymer may be formed by reacting a silanol group contained in the compound raw material with an organoboronic acid group, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between the reactive groups contained in the organoboronate silicone bond-containing compound raw material.
The inorganic borate silicone bond in the invention is selected from but not limited to at least one of the following structures:
Figure BDA0001933286640000144
wherein, Y1、Y2、Y3Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and Y1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;
Figure BDA0001933286640000149
denotes crosslinking with polymer chainsA network chain or any other suitable group/atom linkage, wherein a, b, c each independently represent a linkage with Y1、Y2、Y3The number of connected connections; when Y is1、Y2、Y3When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b and c are 0; when Y is1、Y2、Y3When each is independently selected from oxygen atom and sulfur atom, a, b and c are 1; when Y is1、Y2、Y3When each is independently selected from nitrogen atoms and boron atoms, a, b and c are 2; when Y is1、Y2、Y3When each is independently selected from silicon atoms, a, b and c are 3; difference on the same atom
Figure BDA00019332866400001410
Can be linked to form a ring, on different atoms
Figure BDA00019332866400001411
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic silicon borate ester bond structures include, for example:
Figure BDA0001933286640000145
in the embodiment of the present invention, the inorganic borate silicone bond contained in the dynamic polymer may be formed by the reaction of a silanol group contained in the compound raw material with an inorganic borate group, or the dynamic polymer may be introduced by the polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing an inorganic borate silicone bond.
The organic boronic acid moiety in the embodiments of the present invention is selected from, but not limited to, any of the following structures:
Figure BDA0001933286640000151
wherein, K1、K2、K3Is a monovalent organic group or a monovalent organosilicon group directly bonded to an oxygen atom through a carbon atom or a silicon atom, selected from any of the following structures: small molecule hydrocarbyl, small molecule silyl, polymer chain residues; k4Is a divalent organic or divalent organosilicon group directly attached to two oxygen atoms, directly attached to the oxygen atoms through a carbon or silicon atom, selected from any of the following structures: a divalent small molecule hydrocarbon group, a divalent small molecule silane group, a divalent polymer chain residue; m1 +、M2 +、M3 +Is a monovalent cation, preferably Na+、K+、NH4 +；M4 2+Is a divalent cation, preferably Mg2+、Ca2+、Zn2+、Ba2+；X1、X2、X3Is a halogen atom, preferably selected from chlorine and bromine atoms; d1、D2Is a group bound to a boron atom, D1、D2Are different and are each independently selected from hydroxyl (-OH), ester (-OK)1) Salt group (-O)-M1 +) Halogen atom (-X)1) Wherein, K is1、M1 +、X1The definitions of (A) and (B) are consistent with those described above, and are not described herein again; wherein, the boron atom in the structure is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure BDA0001933286640000157
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference in the same boron atom
Figure BDA0001933286640000158
May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.
The inorganic boronic acid moiety described in the embodiments of the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000152
wherein, W1、W2、W3Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably from an oxygen atom, and W1、W2、W3At least one selected from the group consisting of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom;
Figure BDA0001933286640000159
represents a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein x, y, z each represent a linkage to W1、W2、W3The number of connected connections; when W is1、W2、W3X, y, z is 0 when each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom; when W is1、W2、W3When each is independently selected from oxygen atom and sulfur atom, x, y and z are 1; when W is1、W2、W3When each is independently selected from nitrogen atom and boron atom, x, y and z are 2; when W is1、W2、W3Each independently selected from the group consisting of silicon atom, x, y, z ═ 3; difference on the same atom
Figure BDA00019332866400001510
Can be linked to form a ring, on different atoms
Figure BDA00019332866400001511
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.
The inorganic boric acid moiety described in the embodiment of the present invention is preferably introduced by using inorganic borane, inorganic boric acid, inorganic boric anhydride, inorganic borate ester, inorganic boron halide as a raw material.
The 1, 2-diol moiety described in the embodiments of the present invention is ethylene glycol
Figure BDA0001933286640000153
And substituted forms thereof which have been deprived of at least one non-hydroxyl hydrogen atom;
the 1, 3-diol moiety described in the embodiments of the present invention is 1, 3-propanediol
Figure BDA0001933286640000154
And substituted forms thereof which have been deprived of at least one non-hydroxyl hydrogen atom;
for the 1, 2-diol moiety and the 1, 3-diol moiety, they may be linear structures or cyclic group structures.
For linear 1, 2-diol motif structures, it may be selected from any one or several of the B-like structures and isomeric forms thereof:
class B:
Figure BDA0001933286640000155
for linear 1, 3-diol motif structures, it may be selected from any one or several of the C-like structures and isomeric forms thereof:
class C:
Figure BDA0001933286640000156
wherein R is1～R3Is a monovalent group attached to the 1, 2-diol moiety; r4～R8Is a monovalent group attached to the 1, 3-diol moiety;
Figure BDA0001933286640000169
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein R is1～R8Each independently selected from any one of the following structures: hydrogen atom, heteroatom group, small molecule hydrocarbon group and polymer chain residue.
Wherein, the isomeric forms of B1-B4 and C1-C6 are respectively and independently selected from any one of position isomerism, conformational isomerism and chiral isomerism.
For a cyclic 1, 2-diol elementary structure, two carbon atoms in an ethylene glycol molecule are connected through the same group; wherein, the cyclic group structure is 3-200 rings, preferably 3-10 rings, more preferably 3-6 rings, the number of the cyclic group structure is 1,2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic rings, ether rings, condensed rings, and combinations thereof; suitable cyclic group structures are exemplified by:
Figure BDA0001933286640000161
for cyclic 1, 3-diol motif structures, it can be formed by linking two carbon atoms in the 1, 3-propanediol molecule through the same group; wherein, the cyclic group structure is 3-200 rings, preferably 3-10 rings, more preferably 3-6 rings, the number of the cyclic group structure is 1,2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic rings, ether rings, condensed rings, and combinations thereof; suitable cyclic group structures are exemplified by:
Figure BDA0001933286640000162
the catechol moiety in the present invention is a catechol
Figure BDA0001933286640000163
And substituted forms thereof, hybridized forms thereof, and combinations thereof, having lost at least one non-hydroxyl hydrogen atom, suitable catechol motif structures being exemplified by:
Figure BDA0001933286640000164
the 2-hydroxymethylphenol moiety described in the present invention is a 2-hydroxymethylphenol
Figure BDA0001933286640000165
And substituted forms thereof and hybridized forms thereof and combinations thereof, with suitable 2-hydroxymethylphenol motifs such as:
Figure BDA0001933286640000166
the monool moiety in the embodiment of the present invention refers to a structural moiety consisting of a hydroxyl group and a carbon atom directly bonded to the hydroxyl group (
Figure BDA0001933286640000167
Wherein, the carbon atom can be a non-aromatic carbon atom, and can also be an aromatic carbon atom), and in the case that the 1, 2-diol unit, the catechol unit, the 1, 3-diol unit and the 2-hydroxymethylphenol unit form an unsaturated/saturated five-membered ring organic borate bond, an unsaturated/saturated six-membered ring organic borate bond, an unsaturated/saturated five-membered ring inorganic borate bond and an unsaturated/saturated six-membered ring inorganic borate bond, the monoalcohol unit is not the hydroxyl group in the 1, 2-diol unit, the catechol unit, the 1, 3-diol unit and the 2-hydroxymethylphenol unit, and besides this, the monoalcohol unit can also be selected from any suitable dihydric (polybasic) alcohol compound and/or any hydroxyl group in the group. Suitable structures containing monoalcohol moieties may be mentioned, for example:
Figure BDA0001933286640000168
the silanol moiety in the embodiment of the present invention refers to a structural moiety consisting of a silicon atom and a hydroxyl group or a group hydrolyzable to the silicon atom to obtain a hydroxyl group (
Figure BDA0001933286640000171
Or
Figure BDA0001933286640000172
Wherein Z may be selected from halogenCyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketoxime, alkoxide and the like, preferably halogen, alkoxy).
The boron-containing dynamic covalent bond selected by the invention has strong dynamic property and mild dynamic reaction condition, can realize the synthesis and dynamic reversible effect of the dynamic polymer under the conditions of no need of a catalyst, no need of high temperature, illumination or specific pH, can further improve the preparation efficiency, reduce the limitation of the use environment and expand the application range of the polymer.
Other dynamic covalent bonds described in the present invention, which do not contain a boron atom in their dynamic structural composition, include, but are not limited to, dynamic sulfide bonds, dynamic diselenide bonds, dynamic selenazone bonds, dynamic acetal-like bonds, dynamic imine bonds, dynamic hydrazone bonds, dynamic covalent bonds based on reversible radicals, associative exchangeable acyl bonds, dynamic covalent bonds induced based on steric effects, reversible addition fragmentation chain transfer dynamic covalent bonds, dynamic siloxane bonds, dynamic silicon ether bonds, exchangeable dynamic covalent bonds based on alkyltriazolium, unsaturated carbon-carbon double bonds that can undergo olefin cross-metathesis, unsaturated carbon-carbon triple bonds that can undergo alkyne cross-metathesis, 2+2 cycloaddition dynamic covalent bonds, [4+2] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, mercapto-michael addition dynamic covalent bonds, and combinations thereof, An amine alkene-Michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond, a diazacarbene-based dynamic covalent bond, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkylsulfonium bond; wherein, each series of other dynamic covalent bonds may comprise a plurality of types of other dynamic covalent bond structures. When two or more than two kinds of the other dynamic covalent bonds are selected, the other dynamic covalent bonds can be selected from different structures in the same kind of dynamic covalent bonds in the same series of other dynamic covalent bonds, can also be selected from different structures in different kinds of dynamic covalent bonds in the same series of other dynamic covalent bonds, and can also be selected from different structures in different series of other dynamic covalent bonds, wherein, in order to achieve orthogonal and/or synergistic dynamic performance, the other dynamic covalent bonds are preferably selected from different structures in different series of other dynamic covalent bonds.
The dynamic sulfur-connecting bond comprises a dynamic disulfide bond and a dynamic polysulfide bond, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic; the dynamic sulfur linkage described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000173
wherein x is the number of S atoms, x is more than or equal to 2,
Figure BDA0001933286640000175
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic sulfur linkage structures may be exemplified by:
Figure BDA0001933286640000174
in the embodiment of the invention, the dynamic reversible 'certain conditions' for activating dynamic sulfur-connecting bond includes, but is not limited to, temperature adjustment, addition of oxidation-reduction agent, addition of catalyst, addition of initiator, light irradiation, radiation, microwave, plasma action, pH adjustment and the like, for example, the dynamic sulfur-connecting bond can be broken to form sulfur radical by heating, so that the dynamic sulfur-connecting bond is dissociated and exchanged, the dynamic sulfur-connecting bond is reformed and stabilized after cooling, so that the polymer can obtain self-repairability and reworkability, light irradiation can also lead the dynamic sulfur-connecting bond to be broken to form sulfur radical, so that the dissociation and exchange reaction of disulfide bond can be carried out, the dynamic sulfur-connecting bond is reformed after removing the light irradiation, so that the polymer can obtain self-repairability and reworkability, radiation, microwave and plasma can generate radical in the system to act with the dynamic sulfur-connecting bond, so that the self-repairability and reworkability can be obtained, so that the dynamic sulfur-connecting bond can be formed and exchanged, so that the process is accelerated and the self-repairability can be obtained, wherein the dynamic reversible catalyst includes, the dynamic hydrogen peroxide-oxidizing agent can be obtained by adding the hydrogen peroxide-oxidizing agent, the hydrogen peroxide-oxidizing agent can also include, the hydrogen peroxide-oxidizing agent can be obtained by heating, the hydrogen peroxide-oxidizing agent includes, the hydrogen peroxide-oxidizing agent includes, the hydrogen peroxide-bis-2-bis-phenyl-bis-phenyl-2-bis-phenyl-thiobenzone-2-bis (2-ethyl-bis (2-phenyl-bis-phenyl-ethyl-phenyl-ethyl-ketone-ethyl-2-bis (2-phenyl-bis-phenyl-bis (2-phenyl-bis (2-phenyl-ethyl-phenyl-ethyl-ketone), the hydrogen peroxide-ketone-bis (2-phenyl-ethyl-phenyl-2-phenyl-ketone), the hydrogen peroxide-bis (2-ethyl-phenyl-bis (2) initiator, 2-bis (2-phenyl) initiator, 2-bis (2) initiator, 2-phenyl-bis (2-phenyl) initiator, 2-bis (2) initiator, 2-bis (4) initiator, 2-bis (2) initiator, 2-bis (2.
In the embodiment of the present invention, the dynamic sulfur linkage contained in the dynamic polymer may be formed by a bond formation reaction of a sulfur radical by an oxidative coupling reaction of a mercapto group contained in a compound raw material, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a disulfide linkage. Among these, the compound raw material containing a disulfide bond is not particularly limited, and a polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, ester, amide, sulfur, and mercapto compound containing a disulfide bond are preferable, and a polyol, isocyanate, epoxy compound, alkene, and alkyne containing a disulfide bond are more preferable.
The dynamic double selenium bond can be activated under certain conditions, and dissociation, bonding and exchange reaction of the bond are carried out, so that the dynamic reversible characteristic is embodied; the dynamic diselenide bond described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000181
wherein the content of the first and second substances,
Figure BDA0001933286640000182
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic double selenium bond structures may be mentioned for example:
Figure BDA0001933286640000183
in the embodiment of the invention, the dynamic reversible 'certain conditions' for activating the dynamic bis-seleno bond includes but is not limited to temperature adjustment, addition of redox agent, addition of catalyst, addition of initiator, irradiation, radiation, microwave, plasma action and the like, so that the dynamic polymer shows good self-repairing property, recycling property, stimulation responsiveness and the like, for example, heating can lead the dynamic bis-seleno bond to be broken to form selenium free radical, so that dissociation and exchange reaction of the bis-seleno bond can be generated, the dynamic bis-seleno bond is reformed and stabilized after cooling, self-repairing property and reprocessing property can be displayed, the polymer containing the bis-seleno bond can obtain good self-repairing property by laser irradiation, free radical can be generated in the system by irradiation, microwave and plasma, and the dynamic repairing bis-seleno bond can be generated in the system to act with the dynamic repairing bis-seleno bond so that self-repairing property and reprocessing property can be obtained, the dynamic polymer can also be recycled by adding the redox agent in the system, wherein the dynamic bis-seleno bond can be promoted to be dissociated into alcohol, so that the polymer is dissociated, the dynamic initiator can be formed into bis-seleno-peroxide, the peroxide system can also include but is not limited to be generated, the peroxide-2-peroxide-2-ethyl-bis-benzoyl peroxide-ketone-2-disulfide (such as 2-ethyl-2-thiobenzone-2-bis-oxobenzene-2-bis-oxoacetone-bis-oxobenzene-oxoketone, bis-oxoketone-bis-oxoketone, bis-oxoketone, bis-oxoethyl-oxoketone, 2-oxoketone-bis-oxoketone, bis-oxoketone, bis-oxoketone, bis-oxoketone.
In the embodiment of the present invention, the dynamic diselenide bond contained in the dynamic polymer may be formed by an oxidative coupling reaction of selenol contained in the compound raw material or a bond-forming reaction of a selenium radical, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the diselenide bond. Among these, the compound having a diselenide bond is not particularly limited as a raw material, and a polyol, isocyanate, epoxy compound, alkene, alkyne, carboxylic acid, diselenide (e.g., sodium diselenide, dichlorodiselenide) having a diselenide bond is preferable, and a polyol, isocyanate, epoxy compound, alkene, alkyne having a diselenide bond is more preferable.
In the invention, the dynamic selenium-nitrogen bond can be activated under a certain condition, and dissociation, bonding and exchange reaction of the bond occur, thus showing the dynamic reversible characteristic; the dynamic seleno-nitrogen bond described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000191
wherein X is selected from halogen ions, preferably chloride ions and bromide ions,
Figure BDA0001933286640000192
denotes a chain linked to a polymer chain or a crosslinked networkOr any other suitable group/atom linkage. Typical dynamic selenium nitrogen bond structures can be exemplified by:
Figure BDA0001933286640000193
in the embodiment of the present invention, the "certain condition" for activating the dynamic reversibility of the dynamic diselenide bond includes, but is not limited to, temperature regulation, addition of an acid-base catalyst, and the like, so that the dynamic polymer exhibits good self-repairing property, recycling property, stimulus responsiveness, and the like. Wherein, the acid-base catalyst can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, and cobalt carbonate. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf))3) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.
In an embodiment of the invention, the dynamic selenazonium bond contained in the dynamic polymer can be formed by reacting a phenyl seleno halide contained in the compound starting material with a pyridine derivative.
The dynamic acetal-like bond comprises a dynamic ketal bond, a dynamic acetal bond, a dynamic thioketal bond and a dynamic thioaldehyde bond, can be activated under a certain condition, and generates bond dissociation, ketal reaction and exchange reaction, thereby reflecting the dynamic reversible characteristic; the "certain condition" for activating the dynamic reversibility of the dynamic acetal-like bond is heating, an appropriate acidic aqueous condition, or the like. The dynamic acetal-like linkage described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000194
wherein, X1、X2、X3、X4Each independently selected from oxygen atom, sulfur atom, nitrogen atom, preferably from oxygen atom, sulfur atom; r1、R2Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; r3、R4Each independently selected from the group consisting of a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group, a divalent or polyvalent polymer chain residue;
Figure BDA0001933286640000201
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein
Figure BDA0001933286640000202
May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical dynamic acetal-like bond structures may be mentioned, for example:
Figure BDA0001933286640000203
in the embodiment of the present invention, the dynamic acetal bond can be dissociated in an acidic aqueous solution and formed under anhydrous acidic conditions, and has good pH stimulus responsiveness, so that dynamic reversibility can be obtained by adjustment of an acidic environment.
In embodiments of the present invention, acids that may be used in the dynamic ketal reaction include, but are not limited to, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid, oxalic acid, carbonic acid, propionic acid, nonanoic acid, silicic acid, acetic acid, nitric acid, chromic acid, phosphoric acid, 4-chloro-benzenesulfinic acid, p-methoxybenzoic acid, 1, 4-phthalic acid, 4, 5-difluoro-2-nitrophenylacetic acid, 2-bromo-5-fluorophenylpropionic acid, bromoacetic acid, chloroacetic acid, phenylacetic acid, adipic acid, and the like. The acid used in the present invention may be in the form of a simple acid, an organic acid solution, an aqueous acid solution, or a vapor of an acid, without limitation. The invention can also use different states of the acid in a combined mode, such as promoting the formation of dynamic covalent bonds by using an organic solution of p-toluenesulfonic acid, and dissociating the dynamic covalent bonds by using an aqueous solution of hydrochloric acid to obtain recycling property and the like.
In the embodiment of the present invention, the dynamic acetal bond contained in the dynamic polymer may be formed by condensation reaction of a ketone group, an aldehyde group, a hydroxyl group, and a mercapto group contained in a compound raw material, may be formed by exchange reaction of a dynamic acetal bond with an alcohol, a thiol, an aldehyde, and a ketone, or may be introduced into a dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in a compound raw material containing a dynamic acetal bond. Among these, the raw material of the compound having a dynamic acetal linkage is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic acetal linkage are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic acetal linkage are more preferable.
The dynamic imine bond can be activated under a certain condition, and dissociation, condensation and exchange reaction of the imine bond are carried out, so that the dynamic reversible characteristic is embodied; wherein, the "exchange reaction of dynamic imine bond" means that a new imine bond is formed elsewhere with dissociation of the old imine bond, thereby generating exchange of chain and change of polymer topology; the "certain condition" for activating the dynamic reversibility of the dynamic imine bond means an appropriate pH aqueous condition, an appropriate catalyst-existing condition, a heating condition, a pressurizing condition, or the like. The dynamic imine bond described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000204
wherein R is1Is a divalent or polyvalent small molecule hydrocarbon group;
Figure BDA0001933286640000205
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic imine bond structures may be mentioned, for example:
Figure BDA0001933286640000206
in the embodiment of the present invention, the suitable pH aqueous condition for promoting the dissociation and condensation reaction of the dynamic imine bond refers to that the dynamic polymer is swelled in an aqueous solution with a certain pH value or the surface thereof is wetted with an aqueous solution with a certain pH value, so that the dynamic imine bond in the dynamic polymer has dynamic reversibility. The aqueous solution can be all aqueous solution, or organic solution containing water, oligomer, plasticizer and ionic liquid. The pH of the aqueous solution selected varies depending on the type of dynamic imine bond selected, for example, for dynamic phenylimidine bonds, an acidic solution with a pH of less than or equal to 6.5 may be selected to effect hydrolysis.
In the embodiment of the present invention, the dynamic imine bond contained in the dynamic polymer may be formed by a condensation reaction of a ketone group, an aldehyde group, an acyl group and an amino group contained in a compound raw material, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic imine bond. Among these, the raw material of the compound having a dynamic imine bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, or a carboxylic acid having a dynamic imine bond is preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, or an alkyne having a dynamic imine bond is more preferable.
The dynamic oxime bond can be activated under certain conditions, and dissociation, condensation and exchange reaction of the oxime bond are carried out, so that the dynamic reversible characteristic is embodied; wherein, the "exchange reaction of dynamic oxime bonds" means that new oxime bonds are formed elsewhere with the dissociation of old oxime bonds, thereby generating exchange of chains and change of polymer topology; the "certain condition" for activating the dynamic reversibility of the dynamic oxime bond is, for example, an appropriate pH aqueous condition, an appropriate catalyst-existing condition, a heating condition, or a pressurizing condition. The dynamic oxime bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000211
wherein the content of the first and second substances,
Figure BDA0001933286640000212
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical dynamic oxime-like bond structures may be mentioned, for example:
Figure BDA0001933286640000213
in the embodiment of the present invention, the suitable pH aqueous condition for promoting the dissociation and condensation reaction of the dynamic oxime bond refers to swelling the dynamic polymer in an aqueous solution with a certain pH value or wetting the surface with an aqueous solution with a certain pH value, so that the dynamic oxime bond in the dynamic polymer has dynamic reversibility. The aqueous solution can be all aqueous solution, or organic solution containing water, oligomer, plasticizer and ionic liquid. The pH of the aqueous solution selected will vary depending on the type of dynamic oxime linkage selected.
In the embodiment of the present invention, the dynamic oxime bond contained in the dynamic polymer may be formed by condensation reaction of a ketone group, an aldehyde group, an acyl group and a hydroxylamine group contained in a compound raw material, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic oxime bond. Among these, the raw material of the compound having a dynamic oxime bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic oxime bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic oxime bond are more preferable.
The dynamic hydrazone bond can be activated under certain conditions, and dissociation, condensation and exchange reactions of the hydrazone bond are carried out, so that the dynamic reversible characteristic is embodied; wherein, the exchange reaction of the dynamic hydrazone bond means that a new hydrazone bond is formed elsewhere and is accompanied by the dissociation of an old hydrazone bond, thereby generating the exchange of chains and the change of the topological structure of the polymer; the "certain condition" for activating the dynamic reversibility of a dynamic hydrazone bond means an appropriate pH aqueous condition, an appropriate catalyst-existing condition, a heating condition, a pressurizing condition, or the like. The dynamic hydrazone bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000214
wherein the content of the first and second substances,
Figure BDA0001933286640000215
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Exemplary dynamic hydrazone-like bond structures are, for example:
Figure BDA0001933286640000216
in an embodiment of the present invention, the suitable pH aqueous condition for promoting the dissociation and condensation reaction of the dynamic hydrazone bond refers to swelling the dynamic polymer in an aqueous solution with a certain pH value or wetting the surface thereof with an aqueous solution with a certain pH value, so that the dynamic hydrazone bond in the dynamic polymer has dynamic reversibility. The aqueous solution can be all aqueous solution, or organic solution containing water, oligomer, plasticizer and ionic liquid. The pH of the aqueous solution is varied according to the type of the hydrazone linkage, for example, an acidic solution having a pH of 4 or less may be used to hydrolyze the hydrazone linkage.
In an embodiment of the present invention, the dynamic hydrazone bond contained in the dynamic polymer may be formed by a condensation reaction of a ketone group, an aldehyde group, an acyl group with a hydrazine group, and a hydrazide group contained in a compound raw material, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic hydrazone bond. Among these, the starting materials of the compounds having a dynamic hydrazone bond are not particularly limited, and polyols, polythiols, polyamines, isocyanates, epoxy compounds, alkenes, alkynes, and carboxylic acids having a dynamic hydrazone bond are preferable, and polyols, polyamines, isocyanates, epoxy compounds, alkenes, alkynes having a dynamic hydrazone bond are more preferable.
The acid-base catalyst used for the dissociation, condensation and exchange reactions of the dynamic imine bond, the dynamic oxime bond and the dynamic hydrazone bond in the present invention may be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, and cobalt carbonate. (3) Group IIA alkali metals and compounds thereof are exemplifiedSuch as calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide, and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf))3) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferable.
The dynamic covalent bond based on the reversible free radical can be activated under certain conditions to form a reversible oxygen/sulfur/carbon/nitrogen free radical, and generates bonding or exchange reaction of the bond, so that the dynamic reversible characteristic is embodied; the "exchange reaction of dynamic covalent bonds based on reversible free radicals" refers to that intermediate reversible free radicals formed after the dissociation of old dynamic covalent bonds in the polymer form new dynamic covalent bonds elsewhere, so that the exchange of chains and the change of the topological structure of the polymer are generated. The dynamic covalent bond based on reversible free radicals in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000221
wherein, X1、X2Is a sterically hindered divalent or polyvalent radical directly bonded to the nitrogen atom, each of which is independently selected from divalent or polyvalent C3-20Alkyl, divalent or polyvalent cyclic C3-20Alkyl, phenyl, benzyl, aromatic hydrocarbon, carbonyl, sulfone, phosphate and unsaturated forms, substituted forms, hybridized forms and combinations thereofMore preferably from the group consisting of isopropylidene, isobutylene, isoamylidene, isohexylidene, cyclohexylidene, phenylene, benzylidene, carbonyl, sulfone, phosphate; r' is a group directly linked to a carbon atom, each independently selected from a hydrogen atom, C3-20Alkyl, ring C3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated, substituted, hybridized forms of the above groups and combinations thereof, R 'is preferably selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl, methylbenzyl, R' is more preferably selected from the group consisting of methyl, ethyl, isopropyl, phenyl, benzyl; wherein each W is independently selected from an oxygen atom, a sulfur atom; w1Each independently selected from ether groups, thioether groups, secondary amine groups and substituents thereof, preferably from ether groups; w2Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups and substituents thereof, carbonyl groups, thiocarbonyl groups, divalent methyl groups and substituents thereof, preferably from the group consisting of thioether groups, secondary amine groups and substituents thereof, carbonyl groups; w3Each independently selected from ether groups, thioether groups; w4Each independently selected from the group consisting of a direct bond, an ether group, a thioether group, a secondary amine group and substituents thereof, a carbonyl group, a thiocarbonyl group, a divalent methyl group and substituents thereof, preferably from the group consisting of a direct bond, an ether group, a thioether group; w, W at different locations1、W2、W3、W4The structures of the two groups can be the same or different; wherein R is1Each independently selected from hydrogen atom, halogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residue, R1Preferably selected from hydrogen atom, hydroxy group, cyano group, carboxy group, C1-20Alkyl radical, C1-20Aryl radical, C1-20Heteroaryl, substituted C1-20Alkyl, substituted hetero C1-20Alkyl radical, R1More preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group, and R at different positions1May be the same or different; wherein R is2Each independently selected from a hydrogen atom,Cyano, hydroxy, phenyl, phenoxy, C1-10Alkyl radical, C1-10Alkoxy radical, C1-10Alkoxyacyl group, C1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group; wherein L 'is a divalent linking group selected from the group consisting of a single bond, a heteroatom linking group, and a divalent small hydrocarbon group, L' is preferably selected from the group consisting of acyl, acyloxy, acylthio, amido, oxyacyl, sulfuryl, phenylene, divalent C1-20Alkyl, substituted divalent C1-20Alkyl, substituted divalent C1-20The heteroalkyl group, L 'is more preferably selected from acyl, oxyacyl, aminoacyl, phenylene, and L' at different positions may be the same or different; wherein V, V ' are independently selected from carbon atom and nitrogen atom, V, V ' at different positions can be the same or different, and when V, V ' is selected from nitrogen atom, it is connected with V, V
Figure BDA0001933286640000222
Is absent; wherein the content of the first and second substances,
Figure BDA0001933286640000223
the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted;
Figure BDA0001933286640000231
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; wherein, X1And X2On
Figure BDA0001933286640000232
Can be connected into a ring, and can form the following structure:
Figure BDA0001933286640000233
wherein, the ring is nitrogen-containing aliphatic ring, nitrogen-containing aromatic ring or their combination with any number of elements, at least one ring atom is nitrogen atom, the hydrogen atom on the ring atom can be substituted by any substituent or not, the ring is preferably nitrogen-containing five-membered ring or nitrogen-containing six-membered ring, and is optimally selected from 2,2,6, 6-tetramethyl-piperidine, 4,5, 5-tetramethyl-imidazole, 2,5, 5-tetramethyl pyrrole, maleimide, succinimide and triazone. Typical dynamic covalent bond structures based on reversible free radicals may be mentioned, for example:
Figure BDA0001933286640000234
in an embodiment of the present invention, the "certain conditions" for activating dynamic reversibility of dynamic covalent bond based on reversible free radical include, but are not limited to, temperature adjustment, addition of initiator, light irradiation, radiation, microwave, plasma action, etc., for example, the dynamic covalent bond may be cleaved by heating to form nitroxide radical/thioaza radical/carbon radical, thereby causing dissociation and exchange reaction of dynamic covalent bond, and the dynamic covalent bond may be reformed and stabilized after cooling, thereby allowing the polymer to obtain self-repairability and reworkability, the light irradiation may also cause the dynamic covalent bond to be cleaved to form nitroxide radical/thioaza radical/carbon radical, thereby causing dissociation and exchange reaction of dynamic covalent bond, and the dynamic covalent bond may be reformed after removing light irradiation, microwave and the like, thereby obtaining self-repairability and reworkability, the initiator may generate free radical, thereby promoting dissociation or exchange of dynamic covalent bond, thereby obtaining self-repairability or recycling of repairability, wherein the initiator includes any one of the following initiators, such as photoinitiator, including, bis (2-tert-butyl) benzoyloxybenzoyl-2-bis (2-butyl-2-p-2-butyl-2-oxoethyl-2-bis (p-2-propyl-2-bis (4-butyl-oxoethyl-2-bis (p-propyl-2-propyl-p-2-propyl-2-bis (preferably-2-bis (di-tert-butyl-propyl-butyl-2-propyl-p-propyl-2-butyl-2-p-2-propyl-p-2-propyl-peroxybenzoylperoxy-2-butyl-2-propyl-2-peroxy-2-propyl-peroxy.
In an embodiment of the present invention, the dynamic covalent bond based on the reversible radical contained in the dynamic polymer may be formed by a bonding reaction of a nitroxide radical, a nitrogen-sulfur radical, a carbon radical, a nitrogen radical contained in a compound raw material, or other suitable coupling reaction; it can be generated in situ in the polymer or can be introduced into the dynamic polymer by polymerization/crosslinking reactions between the reactive groups it contains using a compound starting material containing a dynamic covalent bond based on a reversible free radical. Among these, the raw material of the compound having a dynamic covalent bond based on a reversible radical is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having a dynamic covalent bond based on a reversible radical are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond based on a reversible radical are more preferable.
The combinable exchangeable acyl bond can be activated under certain conditions, and can perform combinable acyl exchange reaction (such as combinable ester exchange reaction, combinable amide exchange reaction, combinable carbamate exchange reaction, combinable vinyl-inserting amide or vinyl-inserting carbamate exchange reaction and the like) with a nucleophilic group, so that the dynamic reversible characteristic is shown; wherein, the 'associative acyl exchange reaction' means that the associative exchangeable acyl bonds are firstly combined with nucleophilic groups to form an intermediate structure, and then the acyl exchange reaction is carried out to form a new dynamic covalent bond, thereby generating exchange of chains and change of a topological structure of the polymer, wherein the crosslinking degree of the polymer can be kept unchanged; wherein the "certain conditions" for activating the dynamic reversibility of the binding exchangeable acyl bond means suitable catalyst existence conditions, heating conditions, pressurizing conditions, etc.; the "nucleophilic group" refers to a reactive group such as hydroxyl, sulfhydryl and amino group, which is present in a polymer system for a binding acyl exchange reaction, and the nucleophilic group may be on the same polymer network/chain as the binding exchangeable acyl bond, may be on a different polymer network/chain, or may be introduced through a small molecule or a polymer containing the nucleophilic group. The binding exchangeable acyl bond as described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000241
wherein, X1、X2Selected from carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; y is selected from the group consisting of an oxygen atom, a sulfur atom and a secondary amine group; z1、Z2Selected from oxygen atom, sulfur atom; r5Selected from the group consisting of hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein, when X1、X2When it is an oxygen atom or a sulfur atom, R1、R2、R3、R4Is absent; when X is present1、X2When it is a nitrogen atom, R1、R3Exist, R2、R4Is absent, and R1、R3Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present1、X2When it is a carbon atom or a silicon atom, R1、R2、R3、R4Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues;
Figure BDA0001933286640000242
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Wherein the binding exchangeable acyl bond is preferably selected from the group consisting of a binding exchangeable ester bond, a binding exchangeable thioester bond, a binding exchangeable amide bond, a binding exchangeable urethane bond, a binding exchangeable thiocarbamate bond, a binding exchangeable urea bond, a binding exchangeable vinyl amide bond, and a binding exchangeable vinyl carbamate bond. Typical binding exchangeable acyl bond structures may be exemplified by:
Figure BDA0001933286640000243
among them, the acyl bond having an exchangeable binding property to a nucleophilic group is more preferable, and typical structures thereof are, for example:
Figure BDA0001933286640000244
in the present invention, some of the bonded acyl exchange reactions need to be carried out under catalytic conditions, and the catalysts include catalysts for transesterification (including esters, thioesters, carbamates, thiocarbamates, etc.) and amine exchange (including amides, carbamates, thiocarbamates, ureas, vinylogous amides, vinylogous carbamates, etc.). By adding the catalyst, the occurrence of the combined acyl exchange reaction can be promoted, so that the dynamic polymer shows good dynamic characteristics.
Wherein the catalyst for the transesterification reaction may be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof. Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and its compound include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium carbonate, and cobalt carbonate. (3) The alkali metal of group IIA and its compounds are exemplified by calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, and magnesium ethoxide. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, and an aluminum alkoxide-based compound can be cited. (5) Tin compounds include inorganic tin compounds and organic tin compounds. Examples of the inorganic tin include tin oxide, tin sulfate, stannous oxide, and stannous chloride. Examples of the organotin include dibutyltin oxide, dibutyltin dilaurate, dibutyltin dichloride, tin tributylacetate, tributyltin chloride and trimethyltin chloride. (6) Examples of the group IVB element compound include titanium dioxide, tetramethyl titanate, isopropyl titanate, isobutyl titanate, tetrabutyl titanate, zirconium oxide, zirconium sulfate, zirconium tungstate, and tetramethyl zirconate. (7) Anionic layered column compounds, the main component of which is generally composed of hydroxides of two metals, called double metal hydroxides LDH, and the calcined product of which is LDO, such as hydrotalcite { Mg }6(CO3)[Al(OH)6]2(OH)4·4H2O }. (8) Supported solid catalysts, which may be mentioned by way of example KF/CaO, K2CO3/CaO、KF/γ-Al2O3、K2CO3/γ-Al2O3、KF/Mg-La、K2O/activated carbon, K2CO3Coal ash powder, KOH/NaX, KF/MMT (montmorillonite) and other compounds. (9) Examples of the organozinc compound include zinc acetate and zinc acetylacetonate. (10) Examples of the organic compound include 1,5, 7-triazabicyclo [4.4.0]Dec-5-ene (TBD), 2-methylimidazole (2-MI), triphenylphosphine, and the like. Among them, preferred are organotin compounds, titanate compounds, organozinc compounds, supported solid catalysts, TBD, 2-MI; more preferably, TBD and zinc acetate are mixed and used for concerted catalysis, and 2-MI and zinc acetylacetonate are mixed and used for concerted catalysis.
Among them, the catalyst for amine exchange reaction can be selected from: nitric acid, hydrochloric acid, aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylHydroxylamine, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf)3) Montmorillonite KSF, hafnium tetrachloride (HfCl)4)、Hf4Cl5O24H24、HfCl4KSF-polyDMAP, transglutaminase (TGase); divalent copper compounds, such as copper acetate; examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, copper acetate is preferable; sc (OTf)3And HfCl4Mixing and sharing synergistic catalysis; HfCl4KSF-polyDMAP; the glycerol, the boric acid and the ferric nitrate hydrate are mixed to share the synergistic catalysis.
In the present embodiment, some of the coupling acyl exchange reactions may be performed by microwave irradiation or heating. For example, common urethane bonds, thiourethane bonds and urea bonds can be heated to 160-180 ℃ under the pressure of 4MPa to perform acyl exchange reaction; the vinylogous amide bond and the vinylogous carbamate bond can generate acyl exchange reaction through Michael addition when being heated to more than 100 ℃;
Figure BDA0001933286640000251
the urethane bond of the structure can be heated to more than 90 ℃ to carry out acyl exchange reaction with the molecular chain containing the phenolic hydroxyl or the benzyl hydroxyl structure. The present invention preferably performs the reversible reaction under normal temperature and normal pressure conditions by adding a catalyst that can be used for the binding acyl exchange reaction.
In the embodiment of the present invention, the exchangeable acyl bond for binding contained in the dynamic polymer may be formed by condensation reaction of acyl group, thioacyl group, aldehyde group, carboxyl group, acid halide, acid anhydride, active ester, isocyanate group contained in the compound raw material with hydroxyl group, amino group, mercapto group, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between the reactive groups contained in the compound raw material containing the exchangeable acyl bond for binding. Among these, the starting material of the compound having the exchangeable acyl bond is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, and a carboxylic acid having the exchangeable acyl bond are preferable, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, and an alkyne having the exchangeable acyl bond are more preferable.
The dynamic covalent bond based on steric effect induction can be activated at room temperature or under a certain condition due to the fact that the dynamic covalent bond contains the large group with the steric effect, and the dissociation, bonding and exchange reaction of bonds occur, so that the dynamic reversible characteristic is embodied. The steric effect induced dynamic covalent bond is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000252
wherein, X1、X2Selected from carbon atoms, silicon atoms and nitrogen atoms, preferably carbon atoms, nitrogen atoms; z1、Z2Selected from oxygen atoms and sulfur atoms, preferably oxygen atoms; when X is present1、X2When it is a nitrogen atom, R1、R3Exist, R2、R4Is absent, and R1、R3Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present1、X2When it is a carbon atom or a silicon atom, R1、R2、R3、R4Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein R isbIs a bulky group with steric hindrance directly bonded to the nitrogen atom, and is selected from C3-20Alkyl, ring C3-20Alkyl, phenyl, benzyl, aralkyl and unsaturated forms, substituted forms, hybridized forms of the above groups and combinations thereof, more preferably from isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, octadecyl, nonadecyl, and combinations thereofA radical, benzyl, methylbenzyl, most preferably selected from the group consisting of tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, methylbenzyl;
Figure BDA0001933286640000253
a nitrogen-containing ring having an arbitrary number of atoms, which may be an aliphatic ring or an aromatic ring, which may be an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, or a combination thereof, wherein the ring-forming atoms are each independently selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or another hetero atom, and the hydrogen atom on the ring-forming atom may or may not be substituted with any substituent, and the ring formed is preferably a pyrrole ring, an imidazole ring, a piperidine ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring; n represents the number of linkages to the ring-forming atoms of the cyclic group structure. Typical steric effect-based induced dynamic covalent bond structures may be exemplified by:
Figure BDA0001933286640000261
the large group with steric hindrance effect in the invention is directly connected with a nitrogen atom or forms a ring structure with the nitrogen atom, and can weaken the chemical bond strength between a carbon atom in carbonyl and thiocarbonyl and an adjacent nitrogen atom, so that the carbon-nitrogen bond shows the property of a dynamic covalent bond, and the dynamic reversible reaction can be carried out at room temperature or under certain conditions. It is to be noted that the larger the steric effect in the "bulky group having steric effect" is, the better, the moderate size is, and the appropriate dynamic reversibility of the carbon-nitrogen bond is imparted. The 'certain condition' for activating dynamic covalent bond dynamic reversibility induced by steric effect comprises but is not limited to action modes of heating, pressurizing, lighting, radiation, microwave, plasma action and the like, so that the dynamic polymer has good self-repairability, recycling property, stimulus responsiveness and the like. For example,
Figure BDA0001933286640000262
the dynamic covalent bond of the structure can carry out dynamic exchange reaction at 60 ℃, and shows dynamic characteristics.
In the present invention, the steric effect induced dynamic covalent bond is preferably selected from steric effect induced amide bond, steric effect induced urethane bond, steric effect induced thiourethane bond, and steric effect induced urea bond.
In an embodiment of the present invention, the steric effect induced dynamic covalent bond contained in the dynamic polymer may be formed by condensation reaction of an acyl group, a thioacyl group, an aldehyde group, a carboxyl group, an acid halide, an acid anhydride, an active ester, and an isocyanate group contained in a compound raw material with an amino group having a bulky group having steric effect attached thereto, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between reactive groups contained therein using a compound raw material containing the steric effect induced dynamic covalent bond. Among these, the raw material of the compound having a dynamic covalent bond induced by steric hindrance is not particularly limited, and a polyol, a polythiol, a polyamine, an isocyanate, an epoxy compound, an alkene, an alkyne, or a carboxylic acid having a dynamic covalent bond induced by steric hindrance is preferably contained, and a polyol, a polyamine, an isocyanate, an epoxy compound, an alkene, or an alkyne having a dynamic covalent bond induced by steric hindrance is more preferably contained.
The reversible addition fragmentation chain transfer dynamic covalent bond can be activated in the presence of an initiator, and a reversible addition fragmentation chain transfer reaction is carried out, so that the dynamic reversible characteristic is embodied. The reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000263
wherein R is1～R10Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; x1、X2、X3Each independently selected fromSingly-bound, divalent or polyvalent small-molecule hydrocarbon radicals, preferably from divalent C1-20Alkyl groups and substituted forms thereof, hybridized forms thereof, and combinations thereof, more preferably selected from the group consisting of divalent isopropyl groups, divalent cumyl groups, divalent isopropyl ester groups, divalent isopropylcarboxyl groups, divalent isopropyl nitrile groups, divalent nitrile cumyl groups, divalent acrylic acid group n-mers, divalent acrylic ester group n-mers, divalent styrene group n-mers and substituted forms thereof, hybridized forms thereof, and combinations thereof, wherein n is greater than or equal to 2; z1、Z2、Z3Each independently selected from a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbyl group, preferably from a heteroatom linking group having or associated with a group having an electro-absorption effect, a divalent or polyvalent small molecule hydrocarbyl group having or associated with a group having an electro-absorption effect; wherein as Z2、Z3Preferably, it can be selected from the group consisting of ether group, sulfide group, selenium group, divalent silicon group, divalent amine group, divalent phosphoric acid group, divalent phenyl group, methylene group, ethylene group, divalent styrene group, divalent isopropyl group, divalent cumyl group, divalent isopropyl ester group, divalent isopropylcarboxyl group, divalent isopropylnitrile group, divalent nitrile cumyl group; wherein, the group having the electric absorption effect includes, but is not limited to, carbonyl group, aldehyde group, nitro group, ester group, sulfonic group, amido group, sulfone group, trifluoromethyl group, aryl group, cyano group, halogen atom, alkene, alkyne and combination thereof;
Figure BDA0001933286640000271
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.
The reversible addition fragmentation chain transfer dynamic covalent bonds described herein are preferably polyacrylic and ester groups, polymethacrylic and ester groups, polystyrene, polymethylstyrene, allyl sulfide groups, dithioester groups, diseleno groups, trithiocarbonate groups, triselenocarbonate groups, diseleno thiocarbonate groups, dithioselenocarbonate groups, bisthioester groups, bisseleno groups, bistrothiocarbonate groups, bistriselenocarbonate groups, dithiocarbamato groups, diseleno carbamate groups, dithiocarbonate groups, diseleno carbonate groups, and derivatives thereof.
Typical reversible addition fragmentation chain transfer dynamic covalent bond structures may be exemplified by:
Figure BDA0001933286640000272
wherein n is the number of the repeating units, can be a fixed value or an average value, and n is more than or equal to 1.
The "reversible addition fragmentation chain transfer reaction" described in the present invention means that when a reactive radical reacts with the reversible addition fragmentation chain transfer dynamic covalent bond described in the present invention to form an intermediate, the intermediate can be fragmented to form a new reactive radical and a new reversible addition fragmentation chain transfer dynamic covalent bond, and this process is a reversible process. This process is similar to, but not exactly identical to, the reversible addition fragmentation chain transfer process in reversible addition fragmentation chain transfer polymerization. Firstly, reversible addition fragmentation chain transfer polymerization is a solution polymerization process, and the reversible addition fragmentation chain transfer reaction can be carried out in solution or solid; in addition, in the reversible addition fragmentation chain transfer reaction, a proper amount of a substance capable of generating an active free radical can be added to generate the active free radical under a certain condition, so that the reversible addition fragmentation chain transfer dynamic covalent bond has good dynamic reversibility, and the progress of the reversible addition fragmentation chain transfer reaction is promoted.
Wherein, the initiator optionally used in the reversible addition-fragmentation chain transfer exchange reaction includes, but is not limited to, any one or any of photoinitiators such as 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropiophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone and α -ketoglutaric acid, organic peroxides such as lauroyl peroxide, Benzoyl Peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, tert-butylperoxybenzoate, tert-butylperoxypivalate, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, azo compounds such as Azobisisobutyronitrile (AIBN), azobisisoheptonitrile, inorganic peroxides such as dimethoxyacetophenone, potassium peroxydisulfate, etc., preferably, 2-dimethoxybenzoyl peroxybenzoate, ammonium persulfate, and azobenzoperoxydisulfonitrile.
In an embodiment of the present invention, the reversible addition fragmentation chain transfer dynamic covalent bond contained in the dynamic polymer may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between the reactive groups contained therein using a compound starting material containing the reversible addition fragmentation chain transfer dynamic covalent bond.
The dynamic siloxane bond can be activated under the condition of catalyst or heating, and siloxane exchange reaction is carried out, so that the dynamic reversible property is embodied; the term "siloxane exchange reaction" refers to the formation of new siloxane bonds elsewhere with concomitant dissociation of old siloxane bonds, resulting in exchange of chains and a change in polymer topology. The dynamic siloxane bond described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000281
wherein the content of the first and second substances,
Figure BDA0001933286640000282
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
Figure BDA0001933286640000283
can form a ring or notLooping.
In the present invention, the siloxane reaction is carried out in the presence of a catalyst or under heating, wherein the dynamic siloxane bond is preferably subjected to a siloxane bond exchange reaction in the presence of a catalyst. The catalyst can promote the siloxane equilibrium reaction, so that the dynamic polymer has good dynamic characteristics. Among them, the catalyst for the siloxane equilibrium reaction can be selected from: (1) examples of the alkali metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, and calcium hydroxide. (2) Examples of the alkali metal alkoxide and the alkali metal polyalcohol salt include potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium propoxide, potassium n-butoxide, potassium isobutoxide, sodium t-butoxide, potassium t-butoxide, lithium pentoxide, potassium ethylene glycol, sodium glycerol, potassium 1, 4-butanediol, sodium 1, 3-propanediol, lithium pentaerythritol, and sodium cyclohexanolate. (3) Examples of the silicon alkoxide include potassium triphenylsilanolate, sodium dimethylphenylsilicolate, lithium tri-tert-butoxysilicolate, potassium trimethylsilolate, sodium triethylsilanolate, lithium (4-methoxyphenyl) dimethylsilolate, tri-tert-pentoxysilicolate, potassium diphenylsilanediol, and potassium benzyltrimethylammonium bis (catechol) phenylsilicolate. (4) Examples of the quaternary ammonium base include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), trimethylbenzylammonium hydroxide, tetrabutylammonium hydroxide, (1-hexadecyl) trimethylammonium hydroxide, methyltriethylammonium hydroxide, phenyltrimethylammonium hydroxide, tetra-N-hexylammonium hydroxide, tetrapropylammonium hydroxide, tetraoctylammonium hydroxide, triethylbenzylammonium hydroxide, choline, [3- (methacrylamido) propyl ] dimethyl (3-thiopropyl) ammonium hydroxide inner salt, phenyltriethylammonium hydroxide, N, N, N-trimethyl-3- (trifluoromethyl) aniline hydroxide, N-ethyl-N, N-dimethyl-ethylammonium hydroxide, tetradecylammonium hydroxide, tetrapentylammonium hydroxide, N, N, N-trimethyl-1-adamantylammonium hydroxide, N-ethylbutylammonium hydroxide, N-dodecylammonium hydroxide, tetrapentylammonium hydroxide, N, N, N-trimethyl-1-adamantylammonium hydroxide, and mixtures thereof, Forty-eight alkyl ammonium hydroxide, N-dimethyl-N- [3- (sulfo-oxo) propyl ] -1-nonane ammonium hydroxide inner salt, (methoxycarbonyl sulfamoyl) triethyl ammonium hydroxide, 3-sulfopropyl dodecyl dimethyl betaine, 3- (N, N-dimethyl palmityl amino) propane sulfonate, methacryloyl ethyl sulfobetaine, N-dimethyl-N- (3-sulfopropyl) -1-octadecane ammonium inner salt, tributyl methyl ammonium hydroxide, tris (2-hydroxyethyl) methyl ammonium hydroxide, tetradecyl sulfobetaine, etc. In the present invention, the catalyst used for the siloxane equilibrium reaction is preferably a catalyst of quaternary ammonium base, silanol type, or alkali metal hydroxide type, and more preferably a catalyst of lithium hydroxide, potassium trimethylsilanolate, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), or the like.
In the embodiment of the present invention, the dynamic siloxane bond contained in the dynamic polymer may be formed by a condensation reaction between a silicon hydroxyl group contained in the compound raw material and a silicon hydroxyl group precursor, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing the dynamic siloxane bond. Among these, the raw material of the compound having a dynamic siloxane bond is not particularly limited, and a polyol, a polyamine, an isocyanate, a siloxane compound, a hydrosiloxane compound, an epoxy compound, an alkene, and an alkyne having a dynamic siloxane bond are preferable, and a polyol, an isocyanate, a siloxane compound, a hydrosiloxane compound, and an alkene having a dynamic siloxane bond are more preferable. Wherein the silicon hydroxyl precursor refers to a structural unit (Si-X) consisting of a silicon atom and a group which can be hydrolyzed to obtain a hydroxyl group and is connected with the silicon atom1) Wherein X is1Groups which are hydrolyzable to give hydroxyl groups may be selected from the group consisting of halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide groups. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO4CH3，Si-OB(OCH3)2，Si-NH2，Si-N(CH3)2，Si-OCH3，Si-COCH3，Si-OCOCH3，Si-CONH2，Si-O-N＝C(CH3)2，Si-ONa。
The dynamic silicon ether bond can be activated under the heating condition, and generates a silicon ether bond exchange reaction, so that the dynamic reversible characteristic is embodied; the "exchange reaction of the silyl ether bond" refers to the formation of a new silyl ether bond elsewhere with concomitant dissociation of the old silyl ether bond, resulting in exchange of the chains and a change in the topology of the polymer. The dynamic silicon ether linkage described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000284
wherein the content of the first and second substances,
Figure BDA0001933286640000285
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;
Figure BDA0001933286640000286
may be looped or not looped. Among them, the dynamic silicon ether bond is more preferably selected from the following structures:
Figure BDA0001933286640000291
in the embodiment of the present invention, the dynamic silicon ether bond contained in the dynamic polymer may be formed by condensation reaction of a silicon hydroxyl group contained in a compound raw material, a silicon hydroxyl group precursor and a hydroxyl group in the system, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction of a reactive group contained in a compound raw material containing a dynamic silicon ether bond. Among these, the raw material of the compound having a dynamic silicon ether bond is not particularly limited, and a polyol, a polyamine, an isocyanate, a siloxane compound, a hydrosilation compound, an epoxy compound, an alkene, and an alkyne having a dynamic silicon ether bond are preferable, and a polyol, an isocyanate, a siloxane compound, a hydrosilation compound, and an alkene having a dynamic silicon ether bond are more preferable. Wherein the silicon hydroxyl precursor refers to a precursor obtained by hydrolyzing a silicon atom and one bonded to the silicon atomStructural element (Si-X) consisting of a hydroxyl radical1) Wherein X is1Groups which are hydrolyzable to give hydroxyl groups may be selected from the group consisting of halogen, cyano, oxacyano, thiocyano, alkoxy, amino, sulfate, borate, acyl, acyloxy, amido, ketoxime, alkoxide groups. Examples of suitable silicon hydroxyl precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO4CH3，Si-OB(OCH3)2，Si-NH2，Si-N(CH3)2，Si-OCH3，Si-COCH3，Si-OCOCH3，Si-CONH2，Si-O-N＝C(CH3)2，Si-ONa。
The exchangeable dynamic covalent bond based on the alkyl triazolium can be activated under certain conditions, and can perform dynamic exchange reaction with the halogenated alkyl, so that the exchangeable dynamic covalent bond based on the alkyl triazolium shows dynamic reversible characteristics. The alkyl triazolium-based exchangeable dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000292
wherein, X—Is negative ion selected from bromide ion and iodide ion, preferably bromide ion;
Figure BDA0001933286640000293
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical interchangeable dynamic covalent bond structures based on alkyltriazolium are exemplified by:
Figure BDA0001933286640000294
in the embodiment of the present invention, the haloalkyl group, which may be an aliphatic haloalkyl group or an aromatic haloalkyl group, may be present in any suitable terminal group, side group and/or side chain in the dynamic polymer, or may be present in any suitable form in other components such as small molecules, oligomers, etc., and may be on the same polymer network/chain with exchangeable dynamic covalent bonds based on alkyltriazolium, or on different polymer networks/chains, or may be introduced through small molecules or polymers containing haloalkyl groups.
In the present embodiment, the "certain conditions" for activating the dynamic reversibility of exchangeable dynamic covalent bonds based on alkyltriazolium means in the presence of a halogenated alkyl group and a solvent and under suitable conditions of temperature, humidity and the like.
In the embodiment of the present invention, the raw material compound containing the alkyl triazolium-based exchangeable dynamic covalent bond is not particularly limited, but preferably contains an alkyl triazolium-based exchangeable dynamic covalent bond, an epoxy-based compound, an alkyl vinyl chloride, a vinyl chloride.
The unsaturated carbon-carbon double bond capable of generating the olefin cross-metathesis double decomposition reaction can be activated in the presence of a catalyst, and generates the olefin cross-metathesis double decomposition reaction, so that the dynamic reversible characteristic is embodied; wherein, the olefin cross metathesis double decomposition reaction refers to the carbon skeleton rearrangement reaction between unsaturated carbon-carbon double bonds catalyzed by metal catalyst; wherein, the rearrangement reaction refers to the generation of new carbon-carbon double bonds at other places and the dissociation of old carbon-carbon double bonds, thereby generating the exchange of chains and the change of polymer topological structure. The structure of the unsaturated carbon-carbon double bond capable of undergoing olefin cross metathesis reaction in the present invention is not particularly limited, and is preferably selected from the following structures having low steric hindrance and high reactivity:
Figure BDA0001933286640000301
in embodiments of the present invention, the catalyst for catalyzing olefin cross metathesis reaction includes, but is not limited to, metal catalysts based on ruthenium, molybdenum, tungsten, titanium, palladium, nickel, etc.; among them, the catalyst is preferably a catalyst based on ruthenium, molybdenum, tungsten, more preferably a ruthenium catalyst having higher catalytic efficiency and being insensitive to air and water, particularly a catalyst which has been commercialized such as Grubbs 'first generation, second generation, third generation catalysts, Hoveyda-Grubbs' first generation, second generation catalysts, etc. Among these, examples of catalysts useful in the present invention for catalyzing olefin cross metathesis reactions include, but are not limited to, the following:
Figure BDA0001933286640000302
Figure BDA0001933286640000311
wherein Py is3Is composed of
Figure BDA0001933286640000312
Mes is
Figure BDA0001933286640000313
Ph is phenyl, Et is ethyl, i-Pr is isopropyl, t-Bu is tert-butyl, and PEG is polyethylene glycol.
The unsaturated carbon-carbon triple bond capable of generating alkyne cross-metathesis reaction can be activated in the presence of a catalyst, and generates alkyne cross-metathesis reaction, thereby showing dynamic reversible property; wherein, the alkyne cross metathesis double decomposition reaction refers to the carbon skeleton rearrangement reaction between unsaturated carbon-carbon triple bonds catalyzed by a metal catalyst; the rearrangement reaction refers to the formation of new triple bonds between carbon and the dissociation of old triple bonds between carbon and carbon, resulting in exchange of chains and change of polymer topology. The structure of the unsaturated carbon-carbon triple bond in which the alkyne cross metathesis reaction can occur in the present invention is not particularly limited, and is preferably selected from the structures shown below which are small in steric hindrance and high in reactivity:
Figure BDA0001933286640000314
in embodiments of the present invention, the catalyst for catalyzing alkyne cross-metathesis reaction includes, but is not limited to, metal catalysts based on molybdenum, tungsten, and the like; among them, the catalyst is preferably a catalyst having compatibility with the functional group, such as catalysts 15 to 20 in the exemplified structure, etc.; the catalyst is also preferably a catalyst having higher catalytic efficiency and being insensitive to air, such as catalysts 1, 18-20, etc. in the exemplified structure; the catalyst is also preferably a catalyst which can function catalytically at ambient temperature or in the ambient temperature range, such as catalyst 11 in the illustrated construction. Examples of catalysts useful in the present invention for catalyzing alkyne cross metathesis reactions include, but are not limited to, the following:
Figure BDA0001933286640000315
wherein Py is3Is composed of
Figure BDA0001933286640000316
Ph is phenyl and t-Bu is tert-butyl.
In the embodiment of the present invention, the unsaturated carbon-carbon double bond capable of undergoing olefin cross metathesis reaction and the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross metathesis reaction contained in the dynamic polymer may be derived from a selected polymer precursor already containing the unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond, or may be generated or introduced on the basis of a polymer precursor not containing the unsaturated carbon-carbon double bond/unsaturated carbon-carbon triple bond. However, since the reaction conditions for forming the carbon-carbon double bond/carbon-carbon triple bond are generally harsh, it is preferable to use a polymer precursor having carbon-carbon double bond/carbon-carbon triple bond to carry out the reaction, thereby achieving the purpose of introducing carbon-carbon double bond/carbon-carbon triple bond.
Among them, polymer precursors which already contain unsaturated carbon-carbon double bonds/unsaturated carbon-carbon triple bonds include, by way of example and not limitation, butadiene rubber, 1, 2-butadiene rubber, isoprene rubber, polynorbornene, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, polychloroprene, brominated polybutadiene, ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), unsaturated polyester, unsaturated polyether and its copolymer, 1, 4-butylene glycol, 1, 5-di-p-hydroxyphenyl-1, 4-pentadien-3-one, unsaturated carbon-carbon triple bonds, Glyceryl monoricinoleate, maleic acid, fumaric acid, trans-methylbutenedioic acid (mesaconic acid), cis-methylbutenedioic acid (citraconic acid), chloromaleic acid, 2-methylenesuccinic acid (itaconic acid), 4' -diphenylenedicarboxylic acid, 1, 5-di-p-hydroxyphenyl-1, 4-pentadien-3-one, fumaroyl chloride, 1, 4-phenylenediacryloyl chloride, citraconic anhydride, maleic anhydride, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, dimethyl citraconate, 1, 4-dichloro-2-butene, 1, 4-dibromo-2-butene, etc., and oligomers having a carbon-carbon double bond/carbon-carbon triple bond in the terminal-functionalized chain skeleton may also be used.
The [2+2] cycloaddition dynamic covalent bond is formed based on the [2+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic; wherein, the [2+2] cycloaddition reaction refers to a reaction that one unsaturated double bond and another unsaturated double bond or unsaturated triple bond respectively provide 2 pi electrons to react and add with each other to form a quaternary ring structure. The [2+2] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000321
wherein D is1～D6Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, preferably from carbon atom, D1、D2At least one of them is selected from carbon atoms or nitrogen atoms; a is1～a6Respectively represent with D1～D6The number of connected connections; when D is present1～D6Each independently selected from an oxygen atom and a sulfur atom1～a60; when D is present1～D6Each independently selected from nitrogen atoms, a1～a61 is ═ 1; when D is present1～D6Each independently selected from carbon atoms, a1～a6＝2；Q1～Q6Each independently selected from carbon atoms, oxygen atoms; b1～b6Respectively represent and Q1～Q6The number of connected connections; when Q is1～Q6Each independently selected from oxygen atoms, b1～b60; when Q is1～Q6Each independently selected from carbon atoms, b1～b6＝2；
Figure BDA0001933286640000322
Represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0001933286640000323
Can be linked to form a ring, on different atoms
Figure BDA0001933286640000324
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typically [2+2]]CycloadditionExamples of dynamic covalent bond structures are:
Figure BDA0001933286640000325
Figure BDA0001933286640000331
in an embodiment of the present invention, the unsaturated double bond for performing the [2+2] cycloaddition reaction may be selected from a carbon-carbon double bond, a carbon-oxygen double bond, a carbon-sulfur double bond, a carbon-nitrogen double bond, a nitrogen-nitrogen double bond; unsaturated triple bonds, which may be selected from carbon-carbon triple bonds, for forming said [2+2] cycloaddition dynamic covalent bond; wherein, the unsaturated double bond and the unsaturated triple bond are preferably directly connected with an electroabsorption effect group or an electrosupply effect group, and the electroabsorption effect group comprises but is not limited to carbonyl, aldehyde group, nitro, ester group, sulfonic group, acylamino, sulfonyl, trifluoromethyl, aryl, cyano, halogen atom, alkene, alkyne and combination thereof; the electron donating effector groups include, but are not limited to, hydroxyl, p-methoxyphenyl, thioether, amino, secondary amine, tertiary amine, methyl, ethyl, isopropyl, isobutyl, and combinations thereof.
In the embodiment of the present invention, the [2+2] cycloaddition dynamic covalent bond contained in the dynamic polymer may be formed by [2+2] cycloaddition reaction between unsaturated carbon-carbon double bonds, azo groups, carbonyl groups, aldehyde groups, thiocarbonyl groups, imino groups, cumulative diene groups, ketene groups contained in compound raw materials, or between the unsaturated carbon-carbon triple bonds and the compound raw materials, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in compound raw materials containing [2+2] cycloaddition dynamic covalent bonds, wherein the compound raw materials containing unsaturated carbon-carbon double bonds are preferably ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, butenedicarboxylic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α -unsaturated nitro compounds, cyclooctene, norbornene, maleic anhydride, p-propargyl dicarboxylic acid, butynedicarboxylic acid, azodicarboxylate, bisthioester, maleimide, fullerene, and derivatives of the above compounds, and the like, and wherein the raw materials containing [2+2] cycloaddition dynamic covalent bond, the compound containing [2+2] cycloaddition, alkyne, isocyanate, the compound containing no limitation is particularly preferred.
The [4+2] cycloaddition dynamic covalent bond is formed based on the [4+2] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic; wherein the [4+2] cycloaddition reaction refers to a reaction in which 4 pi electrons are provided by a diene group and 2 pi electrons are provided by a dienophile group to form a cyclic group structure by addition. The [4+2] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000332
wherein, K1、K2、K5～K10Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K1、K2Or K5、K6Or K7、K8Or K9、K10At least one atom selected from carbon atom or nitrogen atom; c. C1～c10Respectively represent and K1～K10The number of connected connections; when K is1、K2、K5～K10Each independently selected from an oxygen atom and a sulfur atom, c1、c2、c5～c100; when K is1、K2、K5～K10Each independently selected from nitrogen atoms, c1、c2、c5～c101 is ═ 1; when K is1、K2、K5～K10Each is independentWhen the earth is selected from carbon atoms, c1、c2、c5～c10＝2；K3、K4Each independently selected from oxygen atom, sulfur atom, nitrogen atom; c. C3、c4Respectively represent and K3、K4The number of connected connections; when K is3、K4Each independently selected from an oxygen atom and a sulfur atom, c3、c40; when K is3、K4Each independently selected from nitrogen atoms, c3、c4＝1；I1、I2Each independently selected from the group consisting of an oxygen atom, a sulfur atom, a secondary amine group and substituted forms thereof, an amide group, an ester group, a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, a 1, 2-diethylene group, a 1, 2-vinylidene group, a 1,1' -vinyl group, substituted forms of a secondary amine group, an amide group, an ester group;
Figure BDA0001933286640000341
the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carry a positive charge; the structure of the cyclic group is preferably benzene ring, naphthalene ring, anthracene ring and substituted forms of the above groups; n represents the number of linkages to the ring-forming atoms of the cyclic group structure;
Figure BDA0001933286640000342
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0001933286640000343
Can be linked to form a ring, on different atoms
Figure BDA0001933286640000344
Can also be connected into a ring, the ringIncluding but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical [4+2]]Examples of cycloaddition dynamic covalent bond structures are:
Figure BDA0001933286640000345
Figure BDA0001933286640000351
wherein, the [4+2] cycloaddition dynamic covalent bond can be connected with the light-control locking element to form the light-control DA structure. The light-operated locking element can react with the dynamic covalent bond and/or the light-operated locking element under a specific illumination condition to change the structure of the dynamic covalent bond, thereby achieving the purpose of locking/unlocking DA reaction; wherein, when the dynamic covalent bond is locked, it is unable or more difficult to perform DA equilibrium reaction, and when the dynamic covalent bond is unlocked, it is able to perform DA equilibrium reaction, realizing dynamic characteristics.
In the invention, the light control locking element comprises the following structural units:
Figure BDA0001933286640000352
wherein the content of the first and second substances,
Figure BDA0001933286640000353
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0001933286640000354
Can be linked to form a ring, on different atoms
Figure BDA0001933286640000355
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof;
a photo-controlled [4+2] cycloaddition dynamic covalent bond attached to a photo-control locking motif, preferably selected from at least one of the following general structures:
Figure BDA0001933286640000356
wherein, K1、K2、K3、K4、K5、K6Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K1、K2Or K3、K4Or K5、K6At least one of them is selected from carbon atoms; a is1、a2、a3、a4、a5、a6Respectively represent and K1、K2、K3、K4、K5、K6The number of connected connections; when K is1、K2、K3、K4、K5、K6Each independently selected from an oxygen atom and a sulfur atom1、a2、a3、a4、a5、a60; when K is1、K2、K3、K4、K5、K6Each independently selected from nitrogen atoms, a1、a2、a3、a4、a5、a61 is ═ 1; when K is1、K2、K3、K4、K5、K6Each independently selected from carbon atoms, a1、a2、a3、a4、a5、a6＝2；I1、I2、I3Each independently absent or each independently selected from the group consisting of an oxygen atom, a 1,1 '-carbonyl group, a methylene group and substituted forms thereof, a 1, 2-ethylene group and substituted forms thereof, a 1,1' -vinyl group and substituted forms thereof; when I is1、I2、I3Each independently absent, b ═ 2; when I is1、I2、I3Independently from each other, an oxygen atom, a 1,1 '-carbonyl group, a methylene group and substituted forms thereof, a 1, 2-ethylene group and substituted forms thereof, and a 1,1' -vinyl group and substituted forms thereof,b is 1; m is selected from the group consisting of an oxygen atom, a nitrogen atom, a divalent alkoxy chain: (
Figure BDA0001933286640000357
n ═ 2, 3, 4), preferably an oxygen atom or a nitrogen atom; c represents the number of connections to M; when M is selected from an oxygen atom, a divalent alkoxy chain, c ═ 0; when M is selected from nitrogen atoms, c ═ 1; c1、C2、C3、C4、C5、C6Represent carbon atoms in different positions; difference on the same atom
Figure BDA0001933286640000361
Can be linked to form a ring, on different atoms
Figure BDA0001933286640000362
Can also be linked to form a ring, where K is preferred1And K2K to3And K4K to5And K6C to1And C2C to3And C4C to5And C6Forming a ring; the ring may be any number of rings, preferably five-membered and six-membered rings, which may be aliphatic, aromatic, ether, condensed, or combinations thereof, the ring-forming atoms are each independently selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, selenium atoms, or other heteroatoms, and the hydrogen atoms on the ring-forming atoms may be substituted with any substituent or not; wherein, K1And K2K to3And K4K to5And K6The ring formed between preferably has the following structure:
Figure BDA0001933286640000363
C1and C2C to3And C4The ring formed between preferably has the following structure:
Figure BDA0001933286640000364
C5and C6The ring formed between preferably has the following structure:
Figure BDA0001933286640000365
in the embodiment of the present invention, the diene group used for the [4+2] cycloaddition reaction may be any suitable group containing conjugated diene and its derivatives, such as butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and its derivatives, etc.; dienophile groups for forming the [4+2] cycloaddition dynamic covalent bonds containing any suitable unsaturated double or triple bonds, such as carbon-carbon double bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, carbon-sulfur double bonds, carbon-nitrogen double bonds, nitrogen-nitrogen double bonds, and the like; wherein, the diene group, unsaturated double bond or unsaturated triple bond in the dienophile group are preferably directly connected with the electric absorption effect group or the electric supply effect group, and the electric absorption effect group comprises but is not limited to carbonyl, aldehyde group, nitro group, ester group, sulfonic group, acylamino group, sulfonyl group, trifluoromethyl, aryl, cyano group, halogen atom, alkene, alkyne and combination thereof; the electron donating effector groups include, but are not limited to, hydroxyl, p-methoxyphenyl, thioether, amino, secondary amine, tertiary amine, methyl, ethyl, isopropyl, isobutyl, and combinations thereof.
In the embodiment of the present invention, the [4+2] cycloaddition dynamic covalent bond contained in the dynamic polymer may be formed by [4+2] cycloaddition reaction between a compound raw material containing a diene group and a compound raw material containing a dienophile group, or the dynamic polymer may be introduced by polymerization/crosslinking reaction between reactive groups contained in the compound raw material containing a [4+2] cycloaddition dynamic covalent bond, wherein the compound raw material containing a diene group may be selected from butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and derivatives thereof, and wherein the compound raw material containing a dienophile group may be selected from ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, butenedicarboxylic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α -unsaturated nitro compound, cyclooctene, norbornene, maleic acid, p-benzoquinone, butynedicarboxylic acid, azodicarboxylate, bisanhydride, maleimide, and compounds containing a cyclic addition of more preferably a compound containing a 4+ 2-epoxy group, a maleimide group, a compound containing a cycloaddition of a maleimide group, a more preferably a compound containing a fullerene group, a compound, a sulphur, a compound containing a mercapto group, and a compound containing a more preferably a cycloaddition of a 4+ 2-epoxy group, a compound.
The [4+4] cycloaddition dynamic covalent bond is formed based on the [4+4] cycloaddition reaction, can be activated under a certain condition, and generates bond dissociation, bonding and exchange reaction, thereby showing the dynamic reversible characteristic; wherein the [4+4] cycloaddition reaction refers to a reaction in which two conjugated diene groups each provide 4 pi electrons to form a cyclic group structure by addition. The [4+4] cycloaddition dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000371
wherein the content of the first and second substances,
Figure BDA0001933286640000372
the ring group structure is an aromatic ring or a hybrid aromatic ring, the ring atoms of the ring group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms, the ring group structure is preferably 6-50-membered rings, more preferably 6-12-membered rings; the hydrogen atoms on each ring-forming atom may be substituted or unsubstituted, wherein, when the ring-forming atoms are selected from nitrogen atoms, the nitrogen atoms may carryA positive charge; the structure of the cyclic group is preferably benzene ring, naphthalene ring, anthracene ring, aza benzene, aza naphthalene, aza anthracene and substituted forms of the above groups; i is6～I14Each independently selected from the group consisting of an oxygen atom, a sulfur atom, an amide group, an ester group, an imine group, and a divalent small hydrocarbon group, more preferably from the group consisting of an oxygen atom, a methylene group, 1, 2-diethylene, 1, 2-vinylidene, an amide group, an ester group, and an imine group;
Figure BDA0001933286640000373
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom
Figure BDA0001933286640000374
Can be linked to form a ring, on different atoms
Figure BDA0001933286640000375
And may be linked to form a ring, including but not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Typically [4+4]]Examples of cycloaddition dynamic covalent bond structures are:
Figure BDA0001933286640000376
Figure BDA0001933286640000381
in an embodiment of the present invention, the conjugated diene group used for the [4+4] cycloaddition reaction may be any suitable group containing conjugated diene and its derivatives, such as benzene, anthracene, naphthalene, furan, cyclopentadiene, cyclohexadiene, pyrone, pyridone and its derivatives, and the like.
In the embodiment of the present invention, the [4+4] cycloaddition dynamic covalent bond contained in the dynamic polymer may be formed by a [4+4] cycloaddition reaction between the compound raw materials containing the conjugated diene group, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between the reactive groups contained therein using the compound raw materials containing the [4+4] cycloaddition dynamic covalent bond.
In the embodiment of the present invention, the "certain condition" for activating the dynamic reversibility of the [2+2] cycloaddition dynamic covalent bond, [4+4] cycloaddition dynamic covalent bond includes, but is not limited to, the action modes of temperature regulation, catalyst addition, illumination, radiation, microwave, etc. For example, the [2+2] cycloaddition dynamic covalent bond can be dissociated by heating at a higher temperature, and then the [2+2] cycloaddition dynamic covalent bond is reformed by heating at a lower temperature; furan and maleimide can carry out a [4+2] cycloaddition reaction at room temperature or under a heating condition to form a dynamic covalent bond, the formed dynamic covalent bond can be dissociated at a temperature higher than 110 ℃, and the dynamic covalent bond can be reformed through cooling. For another example, the [2+2] cycloaddition dynamic covalent bond can be subjected to [2+2] cycloaddition reaction under the long-wavelength light irradiation condition to form a dynamic covalent bond, and then the dynamic covalent bond is dissociated under the short-wavelength light irradiation condition to obtain an unsaturated carbon-carbon double bond again; for example, the cinnamoyl unsaturated carbon-carbon double bond can be subjected to a [2+2] cycloaddition reaction under the ultraviolet irradiation condition that the lambda is more than 280nm to form a dynamic covalent bond, and the bond dissociation is carried out under the ultraviolet irradiation condition that the lambda is less than 280nm to obtain the cinnamoyl unsaturated carbon-carbon double bond again; the coumarin unsaturated carbon-carbon double bond can be subjected to [2+2] cycloaddition reaction under the condition that lambda is larger than 319nm ultraviolet irradiation to form a dynamic covalent bond, and the bond dissociation is carried out under the condition that lambda is smaller than 319nm ultraviolet irradiation to obtain the coumarin unsaturated carbon-carbon double bond again. For another example, anthracene and maleic anhydride can undergo a [4+2] cycloaddition reaction under ultraviolet irradiation at λ 250nm to form a dynamic covalent bond. For another example, anthracene can undergo a [4+4] cycloaddition reaction under uv irradiation at λ 365nm to form a dynamic covalent bond, and then undergo bond dissociation under uv irradiation at λ less than 300 nm. In addition, the [2+2], [4+4] cycloaddition reaction can be carried out under the catalytic condition of a catalyst to form a dynamic covalent bond, wherein the catalyst comprises but is not limited to Lewis acid, Lewis base and metal catalyst; the lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkylmetal compound, borane, boron trifluoride and its derivatives, arylboron difluoride, scandium trifluoroalkylsulfonate, and the like, preferably titanium tetrachloride, aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, iron tribromide, iron trichloride, tin tetrachloride, borane, boron trifluoride etherate, scandium trifluoromethanesulfonate; the Lewis bases, which include, but are not limited to, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), azacyclocarbene (NHC), quinidine, quinine, etc.; the metal catalyst includes, but is not limited to, catalysts based on iron, cobalt, palladium, ruthenium, nickel, copper, silver, gold, molybdenum, and examples of the metal catalyst used in the present invention for catalyzing the [2+2], [4+4] cycloaddition include, but are not limited to, the following:
Figure BDA0001933286640000382
Figure BDA0001933286640000391
the dynamic covalent bond of the mercapto-Michael addition can be activated under certain conditions, and bond dissociation, bonding and exchange reaction occur, so that the dynamic reversible characteristic is embodied; the dynamic covalent thiol-michael addition bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000392
wherein X is selected from ketone group, ester group, amide group, thiocarbonyl group and sulfone group; y is an electron withdrawing effect group including, but not limited to, aldehyde groups, carboxyl groups, nitro groups, phosphate groups, sulfonate groups, amide groups, sulfone groups, trifluoromethyl groups, cyano groups, halogen atoms, and combinations thereof;
Figure BDA0001933286640000393
expression and aggregationA polymer chain, a cross-linked network chain, or any other suitable group/atom linkage, wherein each is different on the same carbon atom
Figure BDA0001933286640000394
Can be linked to form a ring, on different carbon atoms
Figure BDA0001933286640000395
Or may be linked to form a ring, the carbon atom being attached to X
Figure BDA0001933286640000396
May be linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical mercapto-michael addition dynamic covalent bond structures may be exemplified by:
Figure BDA0001933286640000397
in the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the thiol-michael addition dynamic covalent bond include, but are not limited to, temperature adjustment, catalyst addition, pH adjustment, and the like. For example, the dissociated mercapto-michael addition dynamic covalent bonds can be regenerated by heating or exchanged to allow the polymer to achieve self-repairability and re-processability. For another example, for a thiol-michael addition dynamic covalent bond, it can be dissociated with a neutral or weakly alkaline solution to be in a dynamic reversible equilibrium. As another example, the presence of a catalyst that promotes the formation and exchange of dynamic covalent bonds, such mercapto-Michael addition reaction catalysts include, but are not limited to, Lewis acids, organophosphates, organo-base catalysts, nucleophilic catalysts, ionic liquid catalysts, and the like; the Lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkyl metal compound, borane, boron trifluoride and its derivative, aryl boron difluoride, scandium trifluoroalkyl sulfonate, etc.; the organic phosphide includes, but is not limited to potassium phosphate, tri-n-propyl phosphine, dimethyl phenyl phosphine, methyl diphenyl phosphine, triphenyl phosphine; organic base catalysts including, but not limited to, ethylenediamine, triethanolamine, triethylamine, pyridine, diisopropylethylamine, and the like; the nucleophilic catalyst comprises 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylguanidine, 1, 5-diazabicyclo [4,3,0] non-5-ene, 1, 8-diazabicyclo [5,4,0] -undec-7-ene, 1,5, 7-triazabicyclo [4,4,0] dec-5-ene, 1, 4-diazabicyclo [2,2,2] octane, imidazole and 1-methylimidazole; the ionic liquid catalyst includes but is not limited to 1-butyl-3-methylimidazolium hexafluorophosphate, 1- (4-sulfonic) butylpyridine, 1-butyl-3-methylimidazolium tetrahydroborate, 1-allyl-3-methylimidazolium chloride and the like.
In the embodiment of the present invention, the mercapto-michael addition dynamic covalent bond contained in the dynamic polymer may be formed by a mercapto-michael addition reaction using a mercapto group contained in a compound raw material with a conjugated olefin or a conjugated alkyne, or may be introduced into the dynamic polymer by a polymerization/crosslinking reaction between reactive groups contained therein using a compound raw material containing a mercapto-michael addition dynamic covalent bond. Wherein the compound material containing conjugated olefin or conjugated alkyne can be selected from acrolein, acrylic acid, acrylate, propiolate, methacrylate, acrylamide, methacrylamide, acrylonitrile, crotonate, butenedioate, butynedioate, itaconic acid, cinnamate, vinyl sulfone, maleic anhydride, maleimide and derivatives thereof; among these, the raw material of the compound having a dynamic covalent bond of mercapto-michael addition is not particularly limited, and a polyol, an isocyanate, an epoxy compound, an alkene, an alkyne, a carboxylic acid, an ester, and an amide having a dynamic covalent bond of mercapto-michael addition are preferable, and a polyol, an isocyanate, an epoxy compound, an alkene, and an alkyne having a dynamic covalent bond of mercapto-michael addition are more preferable.
The amine alkene-Michael addition dynamic covalent bond can be activated under a certain condition, and undergoes bond dissociation, bonding and exchange reaction, so that the dynamic reversible characteristic is embodied; the amine alkene-michael addition dynamic covalent bond described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000401
wherein the content of the first and second substances,
Figure BDA0001933286640000402
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.
In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the amine alkene-michael addition dynamic covalent bond include, but are not limited to, temperature adjustment, pH adjustment, and the like. For example, for amine alkene-Michael addition dynamic covalent bonds, a weakly acidic (pH 5.3) solution can be used to cause dissociation and thus dynamic reversible equilibrium. As another example, the dissociated amine alkene-Michael addition dynamic covalent bond can be regenerated by heating at 50-100 deg.C or exchanged to allow the polymer to achieve self-repairability and re-processability.
In an embodiment of the present invention, the amine alkene-michael addition dynamic covalent bond contained in the dynamic polymer may be formed by preparing an intermediate product from terephthalaldehyde, malonic acid, and malonic diester as raw materials, and reacting the intermediate product with an amino compound through amine alkene-michael addition.
The dynamic covalent bond based on triazoline diketone-indole can be activated under certain conditions, and bond dissociation, bonding and exchange reaction are carried out, so that the dynamic reversible characteristic is embodied; the dynamic covalent bond based on triazolinedione-indole described in the present invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000403
wherein the content of the first and second substances,
Figure BDA0001933286640000404
denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom
In the embodiment of the present invention, the "certain conditions" for activating the dynamic covalent bond dynamic reversibility based on triazolinedione-indole include, but are not limited to, temperature regulation, pressurization, addition of a catalyst, and the like. For example, the indole and the oxazoline diketone can generate a dynamic covalent bond based on triazoline diketone-indole at the temperature of 0 ℃, the bond dissociation is realized by heating, and the dynamic covalent bond is regenerated by cooling or the exchange of the dynamic covalent bond is carried out, so that the polymer can obtain self-repairability and reprocessing property. For another example, for dynamic covalent bonds based on triazolinedione-indole, they may optionally be dissociated in neutral or slightly alkaline solution to be in dynamic reversible equilibrium. As another example, the presence of a catalyst capable of promoting the formation and exchange of dynamic covalent bonds, said addition reaction catalyst being selected from Lewis acids; the lewis acid includes, but is not limited to, metal chloride, metal iodide, trifluoromethanesulfonate, alkyl metal compound, borane, boron trifluoride and its derivative, aryl boron difluoride, scandium trifluoroalkyl sulfonate, and the like.
In an embodiment of the present invention, the dynamic covalent bond based on triazolinedione-indole contained in the dynamic polymer may be formed by an alder-olefin addition reaction using a bisoxazolinedione group and derivatives thereof contained in a compound raw material and indole and derivatives thereof. Wherein the indole or its derivative is selected from indole-3-propionic acid, indole-3-butyric acid, indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carboxylic acid, 4- (aminomethyl) indole, 5- (aminomethyl) indole, 3- (2-hydroxyethyl) indole, indole-4-methanol, indole-5-methanol, 3-mercaptoindole, 3-acetylenoindole, 5-amino-2 phenylindole, 2-phenyl-1H-indol-6 amine, 2-phenyl-1H-indol-3-acetaldehyde, (2-phenyl-1H-indol-3-alkyl) carboxylic acid, 6-amino-2-phenyl-1H-indole-3-carboxylic acid ethyl ester Esters, 2- (2-aminophenyl) indole, 2-phenylindole-3-acetonitrile, 4, 6-diamidino-2-phenylindole dihydrochloride, and the like.
The dynamic covalent bond based on the dinitrogen heterocarbene can be activated under certain conditions, and the dissociation, bonding and exchange reaction of the bond are generated, so that the dynamic reversible characteristic is embodied; the dinitrogabine-based dynamic covalent bond described in the present invention is selected from, but not limited to, at least one of the following structures:
Figure BDA0001933286640000411
wherein the content of the first and second substances,
Figure BDA0001933286640000412
represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; in which, on different carbon atoms
Figure BDA0001933286640000413
May be linked to form a ring including, but not limited to, aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical bis-azacarbene based dynamic covalent bond structures may be exemplified by:
Figure BDA0001933286640000414
Figure BDA0001933286640000415
wherein Me represents a methyl group, Et represents an ethyl group, nBu represents an n-butyl group, Ph represents a phenyl group, and Mes represents a trimethylphenyl group.
In the embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the double-nitrogen heterocarbene-based dynamic covalent bond include, but are not limited to, temperature regulation, solvent addition and other action modes. For example, the polymer can obtain self-repairability and reworkability by heating the dynamic covalent bond based on the diazacarbone under the temperature condition of higher than 90 ℃ to dissociate the dynamic covalent bond into a diazacarbone structure, and then reducing the temperature to regenerate the dynamic covalent bond or exchange the dynamic covalent bond.
In an embodiment of the present invention, the dynamic covalent bond based on the diazacarbone contained in the dynamic polymer may be formed by using the diazacarbone group contained in the compound raw material itself or by reacting it with a thiocyano group.
The hexahydrotriazine dynamic covalent bond can be activated under certain conditions, and generates bond dissociation, bonding and exchange reaction, so as to embody the dynamic reversible characteristic; the "certain condition" for activating the dynamic reversibility of the hexahydrotriazine dynamic covalent bond refers to an appropriate pH condition, heating condition, or the like. The hexahydrotriazine dynamic covalent bond in the invention is selected from but not limited to at least one of the following structures:
Figure BDA0001933286640000421
wherein the content of the first and second substances,
Figure BDA0001933286640000422
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom. Typical hexahydrotriazine dynamic covalent bond structures may be mentioned, for example:
Figure BDA0001933286640000423
in the embodiment of the invention, the suitable pH condition for carrying out the hexahydrotriazine dynamic covalent bond dynamic reversible reaction refers to that the dynamic polymer is swelled in a solution with a certain pH value or the surface of the dynamic polymer is wetted by a solution with a certain pH value, so that the hexahydrotriazine dynamic covalent bond in the dynamic polymer shows dynamic reversibility. For example, hexahydrotriazine dynamic covalent bonds can be dissociated at a pH < 2 and reformed at neutral pH, allowing the polymer to be self-healing and re-processing. Wherein, the acid-base reagent for adjusting pH can be selected from: (1) inorganic acid, organic acid and acid salt catalyst thereof.Examples of the inorganic acid include sulfuric acid, hydrochloric acid, phosphoric acid, and the like; examples of the organic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and the like; examples of the salts include sulfate, hydrogen sulfate, and hydrogen phosphate. (2) Examples of the group IA alkali metal and compounds thereof include lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate, brilliant carbonate, and potassium tert-butoxide. (3) Examples of the group IIA alkali metal and compounds thereof include calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide and the like. (4) Aluminum metal and its compounds, for example, aluminum powder, alumina, sodium aluminate, a complex of hydrous alumina and sodium hydroxide, an aluminum alkoxide-based compound, and the like can be cited. (5) Examples of the organic compound include ammonium chloride, triethylamine hydrochloride, pyridine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N' -diphenylthiourea, scandium trifluoromethanesulfonate (Sc (OTf))3) And the like. (6) Examples of the divalent copper compound include copper acetate. (7) Examples of the trivalent iron compound include an aqueous ferric chloride solution, ferric sulfate hydrate, and ferric nitrate hydrate. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, copper acetate, and potassium tert-butoxide are preferable.
In the embodiment of the present invention, the hexahydrotriazine dynamic covalent bond contained in the dynamic polymer can be formed by performing a polycondensation reaction between an amino group and an aldehyde group contained in a compound raw material under a low temperature condition (e.g., 50 ℃) to form a hexahydrotriazine dynamic covalent bond of the (I) type, and then heating under a high temperature condition (e.g., 200 ℃) to form a hexahydrotriazine dynamic covalent bond of the (II) type; the starting compounds containing hexahydrotriazine dynamic covalent bonds can also be used to introduce dynamic polymers by polymerization/crosslinking reactions between the reactive groups they contain. Among these, the starting materials of the hexahydrotriazine compound having a dynamic covalent bond are not particularly limited, and polyols, isocyanates, epoxy compounds, alkenes, alkynes, carboxylic acids, esters, and amides having a dynamic covalent bond of hexahydrotriazine are preferable, and polyols, isocyanates, epoxy compounds, alkenes, alkynes having a dynamic covalent bond of hexahydrotriazine are more preferable.
The dynamic exchangeable trialkyl sulfonium bond can be activated under the heating condition, and performs alkyl exchange reaction, so that the dynamic exchangeable trialkyl sulfonium bond has dynamic reversible characteristics; wherein the "transalkylation reaction" refers to the formation of new trialkylsulfonium bonds elsewhere with concomitant dissociation of old trialkylsulfonium bonds, resulting in exchange of chains and changes in polymer topology. In the present invention, the transalkylation reaction is preferably carried out under the heating conditions of 130-160 ℃. The dynamically exchangeable trialkylsulfonium linkage described in this invention is selected from, but not limited to, the following structures:
Figure BDA0001933286640000431
wherein, X—Selected from sulfonates, preferably benzenesulfonates, more preferably p-bromobenzenesulfonates;
Figure BDA0001933286640000432
refers to a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom.
In an embodiment of the present invention, the dynamic exchangeable trialkylsulfonium bond contained in the dynamic polymer can be formed by a mercapto-michael addition reaction between a mercapto group contained in a compound raw material and an unsaturated carbon-carbon double bond, and a sulfonate is added as an alkylating agent.
Other dynamic covalent bonds in the invention can be kept stable under specific conditions, so as to achieve the purpose of providing a balanced structure and mechanical strength, and can also show dynamic reversibility under other specific conditions, so that the material can be completely self-repaired, recycled and plastically deformed; meanwhile, due to the existence of different types of other dynamic covalent bonds, the polymer can show different response effects to external stimuli such as heat, illumination, pH, oxidation reduction and the like, and dynamic reversible balance can be promoted or slowed down in a proper environment by selectively controlling external conditions, so that the dynamic polymer is in a required state.
In the embodiment of the present invention, in the process of introducing a dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in a raw material of a compound having a dynamic covalent bond, the type and mode of reaction for introducing a dynamic covalent bond are not particularly limited, and the following reaction is preferred: the reaction of isocyanate with amino, hydroxyl, mercapto, carboxyl and epoxy group, the reaction of carboxylic acid, acyl halide, acid anhydride and active ester with amino, hydroxyl and mercapto, the reaction of epoxy group with amino, hydroxyl and mercapto, thiol-ene click reaction, acrylate free radical reaction, acrylamide free radical reaction, double bond free radical reaction, Michael addition reaction of alkene-amine, azide-alkyne click reaction, tetrazole-alkene cycloaddition reaction and silicon hydroxyl condensation reaction; more preferably, the reaction can be carried out rapidly at a temperature of not higher than 100 ℃, including but not limited to the reaction of isocyanate group with amino group, hydroxyl group, mercapto group, carboxyl group, the reaction of acyl halide, acid anhydride with amino group, hydroxyl group, mercapto group, acrylate radical reaction, acrylamide radical reaction, and thiol-ene click reaction.
The reactive group in the embodiments of the present invention refers to a group capable of undergoing chemical reaction and/or physical action to form a common covalent bond and/or dynamic covalent bond and/or hydrogen bond spontaneously or under the conditions of an initiator or light, heating, irradiation, catalysis, etc., and suitable groups include, but are not limited to: hydroxyl, carboxyl, carbonyl, acyl, amide, acyloxy, amino, aldehyde, sulfonic, sulfonyl, thiol, alkenyl, alkynyl, cyano, oxazinyl, oxime, hydrazine, guanidino, halogen, isocyanate, anhydride, epoxy, hydrosilyl, acrylate, acrylamide, maleimide, succinimide, norbornene, azo, azide, heterocyclic, triazolinedione, carbon, oxygen, sulfur, selenium, hydrogen bonding, and the like; hydroxyl, amino, mercapto, alkenyl, isocyanate, epoxy, acrylate, acrylamide, oxygen radical, sulfur radical, hydrogen bonding group are preferred. The reactive group plays a role in a system, namely, derivatization reaction is carried out to prepare a hydrogen bond group, and common covalent bond and/or dynamic covalent bond and/or hydrogen bond are directly formed between the compound per se or between the compound and other compounds or between the compound and reaction products of the compound through the reaction of the reactive group, so that the molecular weight of the compound and/or the reaction products of the compound is increased/the functionality of the compound is increased, and polymerization or crosslinking is formed between the compound and/or the reaction products of the compound.
The other dynamic covalent bonds in the present invention are in dynamic reversible equilibrium, thereby having dynamic reversibility and exhibiting good dynamic reversible effect, which usually needs to be made dynamic reversible by means of temperature adjustment, adding redox agent, adding catalyst, illumination, radiation, microwave, plasma action, adjusting pH, etc. among them, the temperature adjustment means that can be used in the present invention includes, but is not limited to, water bath heating, oil bath heating, electric heating, microwave heating, laser heating, etc. the type of illumination used in the present invention is not limited, preferably Ultraviolet (UV), infrared light, visible light, laser, chemiluminescence, more preferably ultraviolet light, infrared light, visible light, etc. the radiation used in the present invention includes, but is not limited to, high energy ionizing rays such as α rays, β rays, gamma rays, x-rays, electron beams, etc. the plasma action used in the present invention refers to catalysis using ionized gas-like substances composed of positive and negative ions generated after part of atoms and atomic groups are ionized, the microwave used in the present invention refers to electromagnetic waves with a frequency of 300MHz to 300 GHz.
The hydrogen bond in the present invention is any suitable supramolecular interaction established by hydrogen bond, and is generally a hydrogen bond link between Z and Y through hydrogen atom covalently linked to atom Z with large electronegativity and atom Y with large electronegativity and small radius, which is mediated by hydrogen, to form Z-H … Y, wherein Z, Y is any suitable atom with large electronegativity and small radius, which may be the same kind of element or different kind of element, and is selected from atoms of F, N, O, C, S, Cl, P, Br, I, etc., more preferably from F, N, O atom, and more preferably from O, N atom. The hydrogen bond can exist as supramolecular polymerization and/or crosslinking and/or intrachain cyclization, namely the hydrogen bond can only play a role of connecting two or more chain segment units to increase the size of a polymer chain but not play a role of supramolecular crosslinking, or the hydrogen bond only plays a role of interchain supramolecular crosslinking, or only plays a role of intrachain cyclization, or the combination of any two or more of the three.
In embodiments of the present invention, the hydrogen bonds may be any number of teeth. Wherein the number of teeth refers to the number of hydrogen bonds formed by a donor (H, i.e., a hydrogen atom) and an acceptor (Y, i.e., an electronegative atom that accepts a hydrogen atom) of hydrogen bonding groups, each H … Y combining into one tooth. In the following formula, the hydrogen bonding of monodentate, bidentate and tridentate hydrogen bonding groups is schematically illustrated, respectively.
Figure BDA0001933286640000441
The more the number of teeth of the hydrogen bond, the greater the synergistic effect and the greater the strength of the hydrogen bond. In the embodiment of the present invention, the number of teeth of the hydrogen bond is not limited. If the number of teeth of the hydrogen bond is large, the strength is large, the dynamic property of the hydrogen bond action is weak, and the hydrogen bond can play a role in promoting the dynamic polymer to keep an equilibrium structure and improving the mechanical properties (modulus and strength). If the number of teeth of the hydrogen bond is small, the strength is low, the dynamic nature of the hydrogen bonding is strong, and dynamic properties can be provided together with dynamic covalent bonds. In embodiments of the invention, preferably no more than four teeth hydrogen bonding are involved.
In embodiments of the invention, the hydrogen bonding may be generated by non-covalent interactions that exist between any suitable hydrogen bonding groups. The hydrogen bond group may contain only a hydrogen bond donor, only a hydrogen bond acceptor, or both a hydrogen bond donor and a hydrogen bond acceptor, preferably both a hydrogen bond donor and a hydrogen bond acceptor.
The hydrogen bond donor in the present invention may be any suitable hydrogen atom-containing donor group, preferably containing at least one of the following structural elements:
Figure BDA0001933286640000442
more preferably contains
Figure BDA0001933286640000443
The hydrogen bond acceptor in the present invention may be an acceptor group containing any suitable electronegative atom (e.g., O, N, S, F, etc.), preferably containing at least one of the following structural components:
Figure BDA0001933286640000444
wherein A is selected from oxygen atom and sulfur atom; d is selected from nitrogen atom and mono-substituted alkyl; x is selected from halogen atoms.
The hydrogen bond group containing both a hydrogen bond donor and a hydrogen bond acceptor in the present invention may be any suitable hydrogen bond group containing a hydrogen bond donor and a hydrogen bond acceptor, and preferably contains at least one of the following structural components:
Figure BDA0001933286640000445
in the present invention, the hydrogen bonding groups may be present only on the polymer chain backbone (including the main chain and the side chain/branch chain backbone), referred to as backbone hydrogen bonding groups, wherein at least part of the atoms are part of the chain backbone; or may be present only on pendant groups of the polymer chain backbone (including the main chain and the side chain/branch/branched chain backbone), referred to as pendant hydrogen bonding groups, wherein pendant hydrogen bonding groups may also be present on the multilevel structure of pendant groups; or may be present only on the polymer chain backbone/end groups of the small molecule, referred to as end hydrogen bonding groups; or can be simultaneously present on at least two of the polymer chain skeleton, the side group and the end group; the hydrogen bonding groups may also be present in the combined hybrid crosslinked dynamic polymer composition, such as a small molecule compound or filler. When hydrogen bonding groups are present on at least two of the backbone, pendant group, and terminal group of the polymer chain at the same time, hydrogen bonding may occur between hydrogen bonding groups in different positions, for example, the backbone hydrogen bonding group may form hydrogen bonding with the pendant group hydrogen bonding group in a specific case.
In the embodiment of the present invention, the backbone hydrogen bond group preferably contains any one or more of the following structural components:
Figure BDA0001933286640000451
wherein W is selected from oxygen atom and sulfur atom; x is selected from oxygen atom, sulfur atom, nitrogen atom and carbon atom; wherein a is the number of D's attached to the X atom; when X is selected from an oxygen atom or a sulfur atom, a ═ 0, D is absent; when X is selected from nitrogen atoms, a ═ 1; when X is selected from carbon atoms, a ═ 2; d is selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues, preferably from hydrogen atoms;
Figure BDA0001933286640000452
refers to a linkage to a polymer backbone, a cross-linked network chain backbone, a side chain backbone (including multilevel structures thereof), a side group (including multilevel structures thereof), or any other suitable group/atom; the cyclic group structure is a non-aromatic or aromatic nitrogen heterocyclic group containing at least one N-H bond, at least two ring-forming atoms are nitrogen atoms, the cyclic group structure can be a micromolecular ring or a macromolecule ring, and the cyclic group structure is preferably a 3-50-membered ring, and more preferably a 3-10-membered ring; the ring-forming atoms of the cyclic group structure are each independently a carbon atom, a nitrogen atom or other hetero atom, and the hydrogen atoms on the respective ring-forming atoms may or may not be substituted. In embodiments of the present invention, the backbone hydrogen bonding group is preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazole groups, imidazole groups, imidazoline groups, triazole groups, purine groups, porphyrin groups and derivatives of the above groups.
Suitable backbone hydrogen bonding groups are exemplified by (but the invention is not limited to):
Figure BDA0001933286640000453
in the embodiment of the present invention, the pendant hydrogen bonding group/terminal hydrogen bonding group preferably contains any one or more of the following structural components:
Figure BDA0001933286640000454
wherein W is selected from oxygen atom and sulfur atom; x is selected from oxygen atom, sulfur atom, nitrogen atom and carbon atom; wherein a is the number of D's attached to the X atom; when X is selected from an oxygen atom or a sulfur atom, a ═ 0, D is absent; when X is selected from nitrogen atoms, a ═ 1; when X is selected from carbon atoms, a ═ 2; d is selected from hydrogen atom, heteroatom group, small molecule alkyl, preferably hydrogen atom; i is a divalent linking group selected from the group consisting of a single bond, a heteroatom linking group, and a divalent small molecule hydrocarbon group; q is a terminal group selected from a hydrogen atom, a heteroatom group, a small molecule hydrocarbon group;
Figure BDA0001933286640000455
refers to a linkage to a polymer backbone, a cross-linked network chain backbone, a side chain backbone (including multilevel structures thereof), a side group (including multilevel structures thereof), or any other suitable group/atom; i, D, Q wherein any two or more of them may be linked together to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof; the cyclic group structure is a non-aromatic or aromatic nitrogen heterocyclic group containing at least one N-H bond, at least two ring-forming atoms are nitrogen atoms, and the cyclic group structure is preferably selected from 3-50 membered rings, more preferably from 3-10 membered rings; the ring-forming atoms of the cyclic group structure are each independently a carbon atom, a nitrogen atom or other hetero atom, and the hydrogen atoms on the respective ring-forming atoms may or may not be substituted. In embodiments of the invention, the pendant/terminal hydrogen bonding groups are preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazoles, imidazolesOxazolines, triazoles, purines, porphyrins, and derivatives of the foregoing.
Suitable pendant/terminal hydrogen bonding groups may have the following exemplary structure (but the invention is not limited thereto) in addition to the above-described backbone hydrogen bonding group structure:
Figure BDA0001933286640000456
Figure BDA0001933286640000461
wherein m and n are the number of repeating units, and may be fixed values or average values, and are preferably less than 20, and more preferably less than 5.
In the embodiment of the present invention, the hydrogen bonding groups forming hydrogen bonding may be complementary combinations of different hydrogen bonding groups or self-complementary combinations of the same hydrogen bonding groups, as long as the groups can form proper hydrogen bonding. Some combinations of hydrogen bonding groups may be exemplified as follows, but the invention is not limited thereto:
Figure BDA0001933286640000462
Figure BDA0001933286640000471
the hydrogen bond groups on other optional components in the composition of the combined hybrid crosslinked dynamic polymer, such as small molecules, polymers and fillers, can refer to the skeleton hydrogen bond group, the side group hydrogen bond and the end group hydrogen bond group, and are not described again here.
In the embodiment of the present invention, it is preferable that the composite hybrid crosslinked dynamic polymer contains at least one of backbone hydrogen bonding groups, side hydrogen bonding groups, and end hydrogen bonding groups. By way of example, in a preferred embodiment of the invention, the dynamic polymer contains only backbone hydrogen bonding groups; in another preferred embodiment of the invention, the dynamic polymer contains only pendant hydrogen bonding groups; in another preferred embodiment of the invention, the dynamic polymer contains only terminal hydrogen bonding groups; in another preferred embodiment of the present invention, the dynamic polymer contains only backbone hydrogen bonding groups and pendant hydrogen bonding groups; in another preferred embodiment of the present invention, the dynamic polymer contains only backbone hydrogen bonding groups and terminal hydrogen bonding groups; in another preferred embodiment of the present invention, the dynamic polymer contains only pendant and terminal hydrogen bonding groups; in another preferred embodiment of the invention, the dynamic polymer contains skeleton hydrogen bond groups, side group hydrogen bond groups and end group hydrogen bond groups; the invention is not limited thereto.
In the embodiment of the present invention, since some hydrogen bonds have no directionality and selectivity, in a specific case, hydrogen bonding interactions can be formed between hydrogen bonding groups at different positions, hydrogen bonding interactions can be formed between hydrogen bonding groups at the same or different positions in the same or different polymer molecules, and hydrogen bonding interactions can also 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. In the present invention, intrachain rings may be formed in addition to interchain crosslinks. It is to be noted that the present invention does not exclude that some of the hydrogen bonding actions formed do not form interchain crosslinking actions nor intrachain rings, but only non-crosslinking polymerization, grafting, and the like. In embodiments of the present invention, it is preferred that at least one of the backbone hydrogen bonding groups, the side group hydrogen bonding groups, the end group hydrogen bonding groups form interchain crosslinks between the same respective hydrogen bonding groups and/or interchain crosslinks between at least two different types of hydrogen bonding groups. By way of example, in one embodiment of the present invention, it is preferred that interchain crosslinks be formed between backbone hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks be formed between pendant hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks be formed between terminal hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks are formed between backbone hydrogen bonding groups and pendant hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks are formed between backbone hydrogen bonding groups and terminal hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks are formed between the pendant and terminal hydrogen bonding groups; in another embodiment of the present invention, it is preferred that interchain crosslinks are formed between backbone hydrogen bonding groups, pendant hydrogen bonding groups and terminal hydrogen bonding groups; the invention is not limited thereto.
In the invention, the same combined hybrid cross-linked dynamic polymer can contain one or more than one hydrogen bonding group, and the same cross-linked network can also contain one or more than one hydrogen bonding group, that is, the dynamic polymer can contain one hydrogen bonding group or the combination of a plurality of hydrogen bonding groups. The hydrogen bonding groups may be formed by any suitable chemical reaction, for example: formed by covalent reaction between carboxyl groups, acid halide groups, acid anhydride groups, ester groups, amide groups, isocyanate groups and amino groups; formed by covalent reaction between isocyanate groups and hydroxyl, mercapto and carboxyl groups; formed by covalent reaction between the succinimide ester group and amino, hydroxyl, sulfhydryl groups.
In embodiments of the invention, hydrogen bonding groups may be introduced in any suitable composition and at any suitable time, including but not limited to from monomers, while forming a prepolymer, while forming a dynamic covalent crosslink, after forming a dynamic covalent crosslink. Preferably at the same time as the prepolymer is formed and the covalent crosslinking is dynamic. In order to avoid the influence of the formation of hydrogen bond crosslinking after the introduction of the hydrogen bond group on the operations of mixing, dissolving and the like, the hydrogen bond group can also be subjected to closed protection, and then the deprotection is carried out after a proper time (such as the formation of dynamic covalent crosslinking at the same time or after).
The invention fully utilizes the dynamic difference among boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds, exerts the orthogonality and the cooperativity effect, and obtains the dynamic polymer with the self-repairing, recoverable and reusable characteristics, because the strength and the dynamic property of different types of dynamic covalent bonds are different, the different hydrogen bond structures and the performances thereof are also different, and the strength, the dynamic property, the responsiveness and the like of the dynamic polymer can be adjusted in a large range on the basis of containing at least two types of dynamic covalent bonds and adding the hydrogen bonds; meanwhile, by regulating and controlling parameters such as molecular structure, functional group number, molecular weight and the like of a compound used as a raw material, the dynamic polymer with different structures and apparent characteristics, adjustable performance and wide application can be prepared, and the dynamic polymer with controllable dynamic property and glass transition temperature can be obtained by conveniently regulating and controlling the number of introduced boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds and the linking structure of the dynamic polymer with a polymer chain.
In embodiments of the present invention, the linking group for linking the boron-containing dynamic covalent bond, the other dynamic covalent bond and/or the hydrogen bonding group may be selected from any one or more of a heteroatom linking group, a divalent or multivalent small molecule hydrocarbon group, a divalent or multivalent polymer chain residue, a divalent or multivalent inorganic small molecule chain residue, and a divalent or multivalent inorganic large molecule chain residue.
The topology of the linking group for linking the boron-containing dynamic covalent bond, other dynamic covalent bond and/or hydrogen bond group is not particularly limited, and may be linear, branched, multi-armed, star, H, comb, dendrimer, monocyclic, polycyclic, spiro, fused ring, bridged ring, chain with cyclic structure, two-dimensional and three-dimensional cluster type and combinations thereof, and the topology of the linking group is preferably linear, branched, star, comb, dendrimer, two-dimensional and three-dimensional cluster type, more preferably linear or branched. For the linking group with straight chain type and branched chain type structures, the molecular chain motion energy barrier is low, the molecular chain motion capability is strong, the processing and forming are facilitated, the polymer can show quick self-repairing performance and sensitive stress/strain response capability, and the dynamic polymer with quick self-repairing performance, recyclable and reusable characteristics and good processing performance can be obtained. For the connecting base with two-dimensional and three-dimensional cluster structures, the topological structure is stable, and good mechanical property, thermal stability, solvent resistance and creep resistance can be provided for the dynamic polymer.
The invention also provides a composite hybrid crosslinked dynamic polymer, characterized in that it contains at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and optionally hydrogen bonds; the dynamic polymer only contains one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-linked networks reaches above a gel point; wherein the presence of said boron-containing dynamic covalent bonds, other dynamic covalent bonds, optionally hydrogen bonds, are a necessary condition for forming or maintaining a polymer structure.
In the above-described embodiments of the invention, the following combinations of boron-containing dynamic covalent bonds and other dynamic covalent bonds are preferred, respectively:
combination 1: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicone bond; dynamic linkage, dynamic diselenide linkage, dynamic covalent linkage based on reversible radicals, associative exchangeable acyl linkage, dynamic covalent linkage induced based on steric effects, reversible addition fragmentation chain transfer dynamic covalent linkage, dynamic silicon ether linkage, exchangeable dynamic covalent linkage based on alkyltriazolium, [2+2] cycloaddition dynamic covalent linkage, [2+4] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, mercapto-michael addition dynamic covalent linkage, dynamic covalent linkage based on triazolinedione-indole, aminoalkene-michael addition dynamic covalent linkage, dynamic covalent linkage based on diazacarbene, dynamic exchangeable trialkylsulfonium linkage. The boron-containing dynamic covalent bonds selected in the combination have good regulation and control performance and rich structure selectivity, and dynamic polymers with different topological structures and different dynamic properties can be prepared by controlling parameters such as the molecular structure, the number of functional groups, the molecular weight and the like of organic boric acid elements in the boron-containing dynamic covalent bonds; the selected other dynamic covalent bonds can realize the dynamic reversible balance of the dynamic covalent bonds by conventional means such as temperature regulation, illumination and the like, the operation is simple and convenient, the cost is low, and the dynamic reaction balance process of other dynamic covalent bonds can be controlled by regulating and controlling the temperature and the illumination frequency.
And (3) combination 2: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one of a dynamic selenium nitrogen bond, an acetal dynamic covalent bond, a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond, a hexahydrotriazine dynamic covalent bond, and an amine alkene-Michael addition dynamic covalent bond combination. The boron-containing dynamic covalent bonds selected in the combination have good regulation and control performance and rich structure selectivity, and dynamic polymers with different topological structures and different dynamic properties can be prepared by controlling parameters such as the molecular structure, the number of functional groups, the molecular weight and the like of organic boric acid elements in the boron-containing dynamic covalent bonds; the other selected dynamic covalent bonds can dynamically respond to the change of the pH value, are usually suitable for preparing gel materials, and can realize the control of dynamic equilibrium reaction and the gel-sol transformation of polymer materials by regulating and controlling the pH value of the swelling agent.
And (3) combination: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one member selected from the group consisting of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, and a triazolinedione-indole-based dynamic covalent bond. The boron-containing dynamic covalent bonds selected in the combination have good regulation and control performance and rich structure selectivity, and dynamic polymers with different topological structures and different dynamic properties can be prepared by controlling parameters such as the molecular structure, the number of functional groups, the molecular weight and the like of organic boric acid elements in the boron-containing dynamic covalent bonds; the other dynamic covalent bonds are required to perform dynamic equilibrium reaction of the dynamic covalent bonds under the condition of catalyst, and after the catalyst or the composite component containing the catalyst is added into the system, the other dynamic covalent bonds can show dynamic characteristics under mild conditions, so that the boron-containing dynamic covalent bonds are combined and matched to show the characteristics of self-repairing property, recyclability and the like.
And (4) combination: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; dynamic linkage, dynamic diselenide linkage, dynamic covalent linkage based on reversible radicals, associative exchangeable acyl linkage, dynamic covalent linkage induced based on steric effects, reversible addition fragmentation chain transfer dynamic covalent linkage, dynamic silicon ether linkage, exchangeable dynamic covalent linkage based on alkyltriazolium, [2+2] cycloaddition dynamic covalent linkage, [2+4] cycloaddition dynamic covalent linkage, [4+4] cycloaddition dynamic covalent linkage, mercapto-michael addition dynamic covalent linkage, dynamic covalent linkage based on triazolinedione-indole, aminoalkene-michael addition dynamic covalent linkage, dynamic covalent linkage based on diazacarbene, dynamic exchangeable trialkylsulfonium linkage. The boron-containing dynamic covalent bond selected in the combination has a simple and stable structure, and can show sensitive dynamic responsiveness under the action of an external force; the selected other dynamic covalent bonds can realize the dynamic reversible balance of the dynamic covalent bonds by conventional means such as temperature regulation, illumination and the like, the operation is simple and convenient, the cost is low, and the dynamic reaction balance process of other dynamic covalent bonds can be controlled by regulating and controlling the temperature and the illumination frequency.
And (3) combination 5: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one of a dynamic selenium nitrogen bond, an acetal dynamic covalent bond, a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond, a hexahydrotriazine dynamic covalent bond, and an amine alkene-Michael addition dynamic covalent bond combination. The boron-containing dynamic covalent bond selected in the combination has a simple and stable structure, and can show sensitive dynamic responsiveness under the action of an external force; the other selected dynamic covalent bonds can dynamically respond to the change of the pH value, are usually suitable for preparing gel materials, and can realize the control of dynamic equilibrium reaction and the gel-sol transformation of polymer materials by regulating and controlling the pH value of the swelling agent.
And (4) combination 6: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one member selected from the group consisting of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, and a triazolinedione-indole-based dynamic covalent bond. The boron-containing dynamic covalent bond selected in the combination has a simple and stable structure, and can show sensitive dynamic responsiveness under the action of an external force; the other dynamic covalent bonds are required to perform dynamic equilibrium reaction of the dynamic covalent bonds under the condition of catalyst, and after the catalyst or the composite component containing the catalyst is added into the system, the other dynamic covalent bonds can show dynamic characteristics under mild conditions, so that the boron-containing dynamic covalent bonds are combined and matched to show the characteristics of self-repairing property, recyclability and the like.
Combinations of boron-containing dynamic covalent bonds and other dynamic covalent bonds included in the combined hybrid crosslinked dynamic polymers provided in the present invention include, but are not limited to, the preferences set forth above, and can be reasonably combined and selected by one skilled in the art according to specific practical needs.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinking network, and the crosslinking network comprises at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and hydrogen bond crosslinking, and the crosslinking degree of the other dynamic covalent bond crosslinking is above the gel point. In this embodiment, the crosslinking degree of boron-containing dynamic covalent bond crosslinking and the crosslinking degree of hydrogen bond crosslinking may be at least the gel point thereof or at most the gel point thereof. In the embodiment, only one cross-linked network is contained, the structure is simple, the performance is excellent, and boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds can be used for providing dynamic reversible effects with abundant orthogonality and/or cooperativity.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising at least one boron-containing dynamic covalent crosslinking and having a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; and further comprising hydrogen bonding crosslinks in at least one of the dynamic covalently crosslinked networks. In this embodiment, the degree of crosslinking in hydrogen bonding may be not less than the gel point thereof, or may be not more than the gel point thereof. In the embodiment, by designing the structures of the two dynamic covalent cross-linked networks and controlling the use conditions, the performances of boron-containing dynamic covalent bonds, other dynamic covalent bonds and hydrogen bonds in different dynamic covalent cross-linked networks can be fully exerted, and outstanding orthogonality and cooperativity are obtained, so that better comprehensive performance is achieved. In addition, the boron-containing dynamic covalent bond crosslinking network and other dynamic covalent bond crosslinking networks are mutually blended and dispersed, and can respectively form discontinuous, partially continuous or bicontinuous dispersed phases in a system, thereby showing the self-repairing performance with difference.
According to a preferred embodiment of the above invention, the combined hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink, and the crosslinking degree of the other dynamic covalent bond crosslink is above the gel point; the other crosslinking network is a hydrogen bonding crosslinking network, wherein the crosslinking degree of the hydrogen bonding crosslinking is above the gel point of the crosslinking network. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof. In the embodiment, by additionally introducing the supermolecular crosslinked network, the polymer can show a hierarchical dynamic reversible effect.
According to a preferred embodiment of the invention, the combined hybrid crosslinked dynamic polymer comprises three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network which comprises at least one boron-containing dynamic covalent crosslinking and has a crosslinking degree above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinked network is a hydrogen-bonded crosslinked network, wherein the degree of crosslinking of the hydrogen-bonded crosslinks is above its gel point. In the embodiment, the dynamic covalent cross-linked network and the hydrogen bond cross-linked network exist independently, and the networks can also be mutually independent in raw material composition, so that the dynamic polymer shows different orthogonality and cooperativity by utilizing the difference of the dynamic property and the stability between different cross-linked networks, and the dynamic reversible effect with the orthogonality is achieved. In addition, the boron-containing dynamic covalent bond crosslinking network, other dynamic covalent bond crosslinking networks and the hydrogen bond crosslinking network are mutually blended and dispersed, and can respectively form discontinuous, partially continuous or bicontinuous dispersed phases in a system, thereby showing the self-repairing performance with difference.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinked network, and at least one other dynamic covalent crosslinking and hydrogen bonding crosslinking are contained in the crosslinked network, and the crosslinking degree of the other dynamic covalent crosslinking is above the gel point, and a non-crosslinked dynamic polymer comprising at least one boron-containing dynamic covalent bond is dispersed in the crosslinked network. In this embodiment, the non-crosslinked dynamic polymer is dispersed in the dynamic covalent crosslinked network, which can provide a dynamic complement to the crosslinked network, providing additional self-healing capabilities.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinking network, and at least one other dynamic covalent crosslinking and hydrogen bonding crosslinking are contained in the crosslinking network, and the crosslinking degree of the other dynamic covalent crosslinking is above the gel point, and the dynamic polymer particles containing at least one boron-containing dynamic covalent bonding are dispersed in the crosslinking network. In this embodiment, the dynamic polymer particles are dispersed in a dynamic covalent cross-linked network, which can provide a dynamic complement to the cross-linked network as well as a local increase in viscosity and strength.
Furthermore, according to a preferred embodiment of the present invention, a non-crosslinked polymer having a crosslinking degree below the gel point or polymer particles having a crosslinking degree above the gel point may be dispersed in the crosslinked network, and the non-crosslinked polymer or the polymer particles may contain one or more of boron-containing dynamic covalent bonds, other dynamic covalent bonds, and hydrogen bonding, or may be formed of only ordinary covalent bonds. The non-crosslinked polymer having a degree of crosslinking below its gel point dispersed therein may provide dynamic or entanglement properties to the crosslinked network; while polymer particles dispersed therein having a degree of crosslinking above their gel point may provide filling and dynamic properties, and may achieve localized viscosity and strength increases upon strain.
The invention also provides a combined hybrid cross-linked dynamic polymer, which is characterized by comprising at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond; the dynamic polymer contains at least one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-links in the at least one dynamic covalent cross-linked network reaches above a gel point; wherein the other dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, a dynamic acetal bond, a dynamic imine bond, a dynamic hydrazone bond, a dynamic covalent bond based on a reversible radical, an associative exchangeable acyl bond, a dynamic covalent bond induced based on steric hindrance, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-Michael addition dynamic covalent bond, a, A dynamic covalent bond based on triazolinedione-indole, a dynamic covalent bond based on diazacarbene, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the presence of said boron-containing dynamic covalent bond, or other dynamic covalent bond, is a requirement for forming or maintaining a polymer structure.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinked network, and comprises at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond crosslink in the crosslinked network, and the crosslinking degree of the other dynamic covalent bond crosslink is above the gel point. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof. In the embodiment, only one cross-linked network is contained, the structure is simple, the performance is excellent, and the boron-containing dynamic covalent bond and other dynamic covalent bonds can be used for providing a dynamic reversible effect with orthogonality and/or cooperativity.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising at least one boron-containing dynamic covalent crosslinking and having a degree of crosslinking above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network is more than the gel point. In the embodiment, the dissociation of one type of dynamic covalent bonds does not immediately cause the failure of the other type of dynamic covalent cross-linked network, and the structure and the performance of one dynamic covalent cross-linked network can be respectively regulated and controlled by designing the structures of the two dynamic covalent cross-linked networks and controlling the use conditions, so that the aim of reasonably regulating and controlling the performance of the dynamic polymer is fulfilled. In addition, by dispersing and blending the boron-containing dynamic covalent bond crosslinking network and other dynamic covalent bond crosslinking networks, discontinuous, partially continuous or bicontinuous dispersed phases can be respectively formed in a system, so that the dynamic characteristics of the boron-containing dynamic covalent bond crosslinking network and the other dynamic covalent bond crosslinking networks are respectively embodied, and the self-repairing performance with difference is embodied.
According to a preferred embodiment of the invention, the combined hybrid crosslinked dynamic polymer comprises three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network which comprises at least one boron-containing dynamic covalent crosslinking and has a crosslinking degree above the gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinked network is a dynamic covalent crosslinked network which contains at least one other dynamic covalent bond crosslink and the crosslinking degree of the crosslinked network reaches above the gel point. In the embodiment, three dynamic covalent cross-linked networks exist independently, and the networks can also be independent from each other in raw material composition, so that the dynamic polymer shows different orthogonality and cooperativity by utilizing the difference of dynamic property and stability between different cross-linked networks, and the dynamic reversible effect with orthogonality is achieved. In addition, the boron-containing dynamic covalent bond crosslinking network and other dynamic covalent bond crosslinking networks are mutually blended and dispersed, and can respectively form discontinuous, partially continuous or bicontinuous dispersed phases in a system, thereby showing the self-repairing performance with difference.
According to a preferred embodiment of the above invention, the combined hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network comprising both at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network is more than the gel point. In this embodiment, the degree of crosslinking of the boron-containing dynamic covalent bond crosslinks may be at least the gel point thereof or at most the gel point thereof. By designing the structures of the two dynamic covalent cross-linked networks and controlling the use conditions, the structure and the performance of one dynamic covalent cross-linked network can be respectively regulated and controlled, and the aim of reasonably regulating and controlling the performance of the dynamic polymer is fulfilled.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinked network, and at least one other dynamic covalent crosslinking is contained in the crosslinked network, and the degree of crosslinking of the other dynamic covalent crosslinking is above the gel point, and a non-crosslinked dynamic polymer comprising at least one boron-containing dynamic covalent crosslinking is dispersed in the crosslinked network. In this embodiment, the non-crosslinked dynamic polymer is dispersed in the dynamic covalent crosslinked network, which can provide a dynamic complement to the crosslinked network, providing additional self-healing capabilities.
According to a preferred embodiment of the above invention, the hybrid crosslinked dynamic polymer comprises only one dynamic covalent crosslinking network, and at least one other dynamic covalent crosslinking is contained in the crosslinking network, and the degree of crosslinking of the other dynamic covalent crosslinking is above the gel point, and particles of the dynamic polymer comprising at least one boron-containing dynamic covalent linkage are dispersed in the crosslinking network. In this embodiment, the dynamic polymer particles are dispersed in a dynamic covalent cross-linked network, which can provide a dynamic complement to the cross-linked network as well as a local increase in viscosity and strength.
Furthermore, according to a preferred embodiment of the present invention, a non-crosslinked polymer having a crosslinking degree below the gel point or polymer particles having a crosslinking degree above the gel point may be dispersed in the crosslinked network, and the non-crosslinked polymer or the polymer particles may contain one or more of boron-containing dynamic covalent bonds and other dynamic covalent bonds, or may be formed of only ordinary covalent bonds. The non-crosslinked polymer having a degree of crosslinking below its gel point dispersed therein may provide dynamic or entanglement properties to the crosslinked network; while polymer particles dispersed therein having a degree of crosslinking above their gel point may provide filling and dynamic properties, and may achieve localized viscosity and strength increases upon strain.
In addition, the invention can also have other various crosslinking network structure embodiments, one embodiment can comprise a plurality of same or different dynamic covalent crosslinking networks, and one dynamic covalent crosslinking network can contain one or more different boron-containing dynamic covalent bonds and also can contain one or more different other dynamic covalent bonds; optionally containing the same or different hydrogen bonds, wherein the hydrogen bonds may be in the same cross-linked network as the dynamic covalent crosslinks or in separate cross-linked networks or partly interact with the dynamic covalent cross-linked network, or may be dispersed in the dynamic covalent cross-linked network in the form of non-cross-linked supramolecular polymer chains and/or supramolecular cross-linked particles. The degree of crosslinking of any crosslink of any network in the dynamic polymer can also be reasonably controlled to achieve the purpose of regulating and controlling the balance structure and dynamic properties. The structure of the hybrid crosslinked dynamic polymer of the present invention includes, but is not limited to, the preferred embodiments given above, and those skilled in the art can reasonably realize the structure according to the logic and context of the present invention.
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. For example, the term "comprising dynamic covalent and hydrogen bonds at the side groups and/or end groups of the polymer chains" and/or "as used herein means comprising dynamic covalent and hydrogen bonds at the side groups of the polymer chains, or at the end groups of the polymer chains, or at the side groups and end groups of the polymer chains. The conjunction "and/or" appearing elsewhere in the specification of the invention is intended to be such meaning.
The combined hybrid crosslinked dynamic polymer simultaneously contains at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and optional hydrogen bonds, different types of dynamic covalent bonds and hydrogen bonds are different in the aspects of strength, structure, dynamics, responsiveness, formation conditions and the like, the responsiveness of the boron-containing dynamic covalent bonds and the other dynamic covalent bonds to different external conditions is also different, the synergistic and orthogonal dynamic effect and response effect can be achieved, and the structure and performance of the material are more adjustable. In addition, by selectively controlling other conditions (such as adding auxiliary agents, adjusting reaction temperature, performing illumination and the like), the dynamic covalent chemical equilibrium can be accelerated or quenched to be in a required state under a proper environment.
For the combined hybrid cross-linked dynamic polymer containing two or more cross-linked networks, a step method and a synchronous method can be adopted for preparation.
For example, for a dynamic polymer having a double-network structure, when the dynamic polymer is prepared by a step-by-step method, a first network may be prepared by using a monomer or a prepolymer, a catalyst, and an initiator, and then a second network prepared may be added and blended to obtain a cross-linked network blended with each other, wherein the second network may be swollen by a solvent and then blended with the first network; or preparing a first network, placing the crosslinked first network into a second network monomer or prepolymer melt or solution containing a catalyst, an initiator and the like to swell the first network, and then polymerizing and crosslinking the second network monomer or prepolymer in situ to form a second network to obtain a (partially) interpenetrating crosslinked network, wherein the crosslinking degree of the first network is preferably selected from slight crosslinking above a gel point so as to facilitate the interpenetrating effect of the second network; by analogy, for a dynamic polymer containing a multi-network structure, a plurality of mutually blended or mutually interpenetrated cross-linked networks can be obtained by adopting a similar fractional step method.
For example, for a dynamic polymer containing a double-network structure, when the dynamic polymer is prepared by a synchronous method, two prepared cross-linked networks can be placed in the same reactor to be blended to obtain a cross-linked network which is blended with each other, wherein the cross-linked networks can be swelled by means of a solvent and then blended; it is also possible to mix two or more monomers or prepolymers and react them in the same reactor according to the respective polymerization and crosslinking sequences to give (partially) interpenetrating crosslinked networks.
In the embodiment of the invention, the form of the composite hybrid crosslinked dynamic polymer can be common solid, elastomer, gel (including hydrogel, organogel, oligomer swelling gel, plasticizer swelling gel and ionic liquid swelling gel), foam material and the like, wherein the content of soluble small molecular weight components in the common solid and the foam material is generally not higher than 10 wt%, and the content of small molecular weight components in the gel is generally not lower than 50 wt%. Common solid, elastomeric, gel and foam materials have various features and advantages. The shape and volume of the common solid are fixed, the common solid has better mechanical strength and can not be restrained by an organic swelling agent or water. Elastomers have the general properties of ordinary solids, but at the same time have better elasticity and are softer, which is beneficial for providing good resilience and toughness. The gel has good flexibility and can show better variability and rebound resilience. The foam material has the advantages of low density and lightness, can overcome the problems of brittleness of partial common solid and low mechanical strength of gel, and has good elasticity and soft and comfortable characteristics. Materials of different morphologies may have suitable uses in different fields.
In the embodiment of the invention, the combined hybrid crosslinked dynamic polymer gel can be obtained by performing dynamic covalent crosslinking in a swelling agent (including one or a combination of water, an organic solvent, an oligomer, a plasticizer and an ionic liquid), or can be obtained by performing swelling by using the swelling agent after the preparation of the dynamic polymer is finished. Of course, the present invention is not limited to this, and those skilled in the art can implement the present invention reasonably and effectively according to the logic and context of the present invention.
In the preparation process of the dynamic polymer foam material, three methods, namely a mechanical foaming method, a physical foaming method and a chemical foaming method, are mainly adopted to foam the dynamic polymer.
The mechanical foaming method is that during the preparation of dynamic polymer, large amount of air or other gas is introduced into emulsion, suspension or solution of polymer via strong stirring to form homogeneous foam, which is then physically or chemically changed to form foam. Air can be introduced and an emulsifier or surfactant can be added to shorten the molding cycle.
Wherein, the physical foaming method is to realize the foaming of the polymer by using the physical principle in the preparation process of the dynamic polymer, and the method comprises the following steps: (1) inert gas foaming, i.e. by pressing inert gas into molten polymer or pasty material under pressure, then raising the temperature under reduced pressure to expand the dissolved gas and foam; (2) evaporating, gasifying and foaming low-boiling-point liquid, namely pressing the low-boiling-point liquid into the polymer or dissolving the liquid into the polymer (particles) under certain pressure and temperature conditions, heating and softening the polymer, and evaporating and gasifying the liquid to foam; (3) dissolving out method, i.e. soaking liquid medium into polymer to dissolve out solid matter added in advance to make polymer have lots of pores and be foamed, for example, mixing soluble matter salt with polymer, etc. first, after forming into product, placing the product in water to make repeated treatment, dissolving out soluble matter to obtain open-cell foamed product; (4) the hollow/foaming microsphere method is that hollow microspheres are added into the material and then compounded to form closed-cell foamed polymer; (5) a filling foamable particle method of mixing filled foamable particles first and then foaming the foamable particles in a molding or mixing process to obtain a foamed polymer material; (6) the freeze-drying method is that the dynamic polymer is swelled in a volatile solvent to be frozen, and then the solvent is escaped in a sublimation manner under the condition of approximate vacuum, thereby obtaining the porous sponge-like foam material. Among them, it is preferable to carry out foaming by a method of dissolving an inert gas and a low boiling point liquid in the polymer.
The chemical foaming method is a method for generating gas and foaming along with chemical reaction in the dynamic polymer foaming process, and includes, but is not limited to, the following methods: (1) the thermal decomposition type foaming method is a method of foaming by using a gas released by decomposition of a chemical foaming agent after heating. (2) The foaming process in which the polymer components interact to produce a gas utilizes a chemical reaction between two or more of the components in the foaming system to produce an inert gas (e.g., carbon dioxide or nitrogen) to cause the polymer to expand and foam. In order to control the polymerization reaction and the foaming reaction to be carried out in balance in the foaming process and ensure that the product has better quality, a small amount of catalyst and foam stabilizer (or surfactant) are generally added. Among these, foaming is preferably performed by a method of adding a chemical foaming agent to a polymer.
In an embodiment of the present invention, the structure of the dynamic polymer foam material relates to three structures, namely an open-cell structure, a closed-cell structure and a semi-open and semi-closed structure; dynamic polymer foams are classified according to their hardness into three categories, soft, hard and semi-hard; dynamic polymer foams can be further classified by their density into low-foaming, medium-foaming and high-foaming.
The initiator, catalyst and redox agent for activating/adjusting other dynamic covalent bond dynamic equilibrium reactions described in the foregoing of the present invention can be directly dispersed in the polymer component for use, or can be used in the form of a composite, for example, coated or loaded on an organic, inorganic or polymer carrier by a physical or chemical method, or coated in a microcapsule or a microcatheter together with other components having high fluidity under dynamic reaction conditions, etc. When the initiator, catalyst and redox agent are used alone, they are compatible with the polymer components and optionally various groups of the various auxiliary fillers. The reasonable selection of the carrier can enhance the dispersibility of the initiator, the catalyst, the redox agent or the compound component thereof in the polymer component and reduce the particle size of the cluster, thereby improving the reaction efficiency, reducing the use amount and lowering the cost. Proper selection of the coating material also avoids deactivation of the additive during the preparation or operation of the composition.
The organic carrier for coating the initiator, the catalyst and the redox agent is not particularly limited, and examples of the organic carrier can be selected from paraffin, polyethylene glycol and the like, the method for coating the additive in the organic carrier is a known and disclosed technical means, and a common preparation method is selected for the invention. For example, a preferred preparation method for coating with paraffin as the organic carrier is: fully blending the selected additive, paraffin and surfactant in a paraffin melting state, and pouring the blend into water which is stirred at a certain rotating speed and has the temperature higher than the melting point of the paraffin; stirring until the blending liquid reaches a stable state, and adding ice water to quickly cool the water to below the melting point of paraffin; stopping stirring, and filtering to obtain the paraffin-coated composite component.
The carrier for loading the initiator, the catalyst and the redox agent on the organic or inorganic carrier through physical adsorption or chemical reaction is not particularly limited, and can be selected from polystyrene resin particles, magnetic nanoparticles, silica gel particles, molecular sieves, other mesoporous materials and the like as examples, a method for loading the additive on the organic or inorganic carrier is a known and disclosed technical means, and a common preparation method is selected in the invention.
The present invention also allows for the encapsulation of initiators, catalysts, redox agents and other optional adjuvants in polymer-shell microcapsules. Among them, the polymer as the outer wall of the microcapsule is not particularly limited, and includes, but is not limited to, the following: natural polymers such as gum arabic, agar, etc., semisynthetic polymers such as cellulose derivatives, and synthetic polymers such as polyolefin, polyester, polyether, polyurethane, polyurea-aldehyde, polyamide, polyvinyl alcohol, polysiloxane, etc., and the usual preparation method is selected for the present invention.
In the preparation process of the combined hybrid cross-linked dynamic polymer, in addition to the initiator, the catalyst and the redox agent which are used for activating/adjusting other dynamic covalent bond dynamic equilibrium reactions, certain solvent, other auxiliary agents/additives and fillers which can be added/used can be added or used to jointly form the dynamic polymer material.
The other additive/additive which can be added/used can improve the material preparation process, improve the product quality and yield, reduce the product cost or endow the product with certain specific application performance. The auxiliary agent is selected from any one or any several of the following auxiliary agents: auxiliary agents for synthesis, including catalysts; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; an auxiliary agent for improving mechanical properties, comprising a toughening agent; the processing performance improving additives comprise a lubricant and a release agent; the auxiliary agents for softening and lightening comprise a plasticizer, a foaming agent and a dynamic regulator; the auxiliary agents for changing the surface performance comprise an antistatic agent, an emulsifier and a dispersant; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; flame retardant and smoke suppressant aids including flame retardants; other auxiliary agents include nucleating agents, rheological agents, thickening agents and leveling agents.
The fillers that can be added/used include, but are not limited to, inorganic non-metallic fillers, organic fillers, organometallic compound fillers.
The inorganic non-metal filler includes, but is not limited to, any one or more of the following: calcium carbonate, argil, barium sulfate, calcium sulfate and calcium sulfite, talcum powder, white carbon black, quartz, mica powder, clay, asbestos fiber, orthoclase, chalk, limestone, barite powder, gypsum, graphite, carbon black, graphene oxide, fullerene, carbon nano tube, molybdenum disulfide, silica, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, nano silica, nano Fe3O4Particulate, nano gamma-Fe2O3Particulate, nano MgFe2O4Particulate, nano-MnFe2O4Granular, nano CoFe2O4Particles, quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), upconversion crystal particles (including but not limited to NaYF)4:Er、CaF2:Er、Gd2(MoO4)3:Er、Y2O3:Er、Gd2O2S:Er、BaY2F8:Er、LiNbO3:Er,Yb,Ln、Gd2O2:Er,Yb、Y3Al5O12:Er,Yb、TiO2:Er,Yb、YF3:Er,Yb、Lu2O3:Yb,Tm、NaYF4:Er,Yb、LaCl3:Pr、NaGdF4:Yb,Tm@NaGdF4Core-shell nanostructure of Ln, NaYF4:Yb,Tm、Y2BaZnO5:Yb,Ho、NaYF4:Yb,Er@NaYF4Core-shell nanostructures of Yb, Tm, NaYF4:Yb,Tm@NaGdF4Core-shell nanostructure of Yb), oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass beads, resin beads, glass powder, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, silicon carbide fibers, ceramic fibers, whiskers 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 and/or electromagnetic is preferably selected from graphene, graphene oxide, carbon nanotube, nano-Fe3O4The composite material which can be heated by infrared and/or near infrared light is conveniently obtained. 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 includes 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-CoPt3Particles, 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 alloysGallium indium tin liquid alloy and other gallium base liquid metal alloys. In one embodiment of the present invention, fillers that can be heated electromagnetically and/or near-infrared, including but not limited to nanogold, nanosilver, and nanopalladium, are preferred 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.
The organic filler comprises any one or more of ① natural organic filler, ② synthetic resin filler, ③ synthetic rubber filler, ④ synthetic fiber filler, ⑤ foamable polymer particles, ⑥ conjugated polymer and ⑦ organic functional dye/pigment, and the organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal property and the like has important significance to the invention and can fully utilize the properties to obtain multifunctionality.
The organic metal compound filler contains a metal organic complex component, wherein a metal atom is directly connected with a carbon atom to form a bond (including a coordination bond, a sigma bond and the like), and the metal organic complex component can be a small molecule or a large molecule and can be in an amorphous or crystal structure. Metal organic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat, and the like.
Wherein, the type of the added filler is not limited, and is mainly determined according to the required material performance, and calcium carbonate, clay, carbon black, graphene, (hollow) glass microsphere and nano Fe are preferred3O4Particles, nano-silica, quantum dots, up-conversion metal particles, foamed microspheres, foamable particles, glass fibers, carbon fibers, metal powder, nano-metal particles, synthetic rubber, synthetic fibers, synthetic resin, resin microbeads, organometallic compounds, organic materials having photo-thermal properties. The amount of the filler used is not particularly limited, but is generally 1 to 30% by weight. In the embodiment of the invention, the filler can be selectively modified and then dispersed and compounded or directly connected into a polymer chain, so that the dispersibility, the compatibility, the filling amount and the like can be effectively improved, and particularly, the filler can be used for photo-thermal, electromagnetic heat and the likeHas important significance when in action.
In the preparation process of the hybrid crosslinked dynamic polymer, the addition amount of each component raw material of the dynamic polymer is not particularly limited, and can be adjusted by a person skilled in the art according to the actual preparation condition and the target polymer performance.
The combined hybrid crosslinked dynamic polymer contains different boron-containing dynamic covalent bonds, other dynamic covalent bonds and optional hydrogen bonds, and can embody the dynamic responsiveness with orthogonality and various dynamic reversible effects, thereby embodying unique performance; through proper component selection and formula design, the obtained polymer material can be widely applied to the fields of military aerospace equipment, functional coatings, biomedicine, biomedical materials, self-repairing materials, buildings, energy sources, bionics and the like.
For example, by utilizing the dynamic reversibility of dynamic covalent bonds and hydrogen bonds, the adhesive with the self-repairing function can be prepared, and can be applied to the adhesion of various materials, such as the adhesive for the electrode of a battery/super capacitor and the separator, so as to reduce the damage of the electrode and prolong the service life of the electrode material; the preparation method can also be used for preparing polymer plugging glue with good plasticity, recoverability and reusability, and sealing elements such as sealing plugs, sealing rings and the like, and can be widely applied to the aspects of electronic appliances, pipeline sealing and the like; the method can also be applied to the preparation of self-repairing and tear-resistant instrument equipment or kits; based on the dynamic reversibility of dynamic covalent bonds and hydrogen bonds, the scratch-resistant coating with the self-repairing function can be designed and prepared, so that the service life of the coating is prolonged, and long-acting anticorrosion protection on a substrate material is realized; through proper component selection and formula design, the polymer gasket or the polymer plate with the self-repairing function can be prepared, so that the principle of organism injury healing can be simulated, the material can carry out self-healing on internal or external injuries, hidden dangers are eliminated, the service life of the material is prolonged, the bionic effect is embodied, the recoverable characteristic and the recycling capability of the material are realized, and the material has great application potential in the fields of military industry, aerospace, electronics, bionics and the like.
For another example, by combining the differences in stimulus responsiveness of different types of other dynamic covalent bonds in the hybrid crosslinked dynamic polymer, a polymer material having different stimulus dependencies and dynamic response effects can be prepared, and a multiple response effect is exhibited by the coordination with the boron-containing dynamic covalent bond. For example, different other dynamic covalent bonds are selected, so that the dynamic polymer can show different response effects to stimulus conditions such as heat, illumination, pH, redox and the like, and can be applied to the manufacture of intelligent materials such as a thermal response type shape memory material, pH response type gel, a photochromic material, a drug controlled release system and the like.
For another example, various dynamic covalent bonds and hydrogen bonds are introduced, so that the polymer material can show excellent toughness under the action of external force, and a polymer film, a fiber or a plate with excellent toughness can be obtained; through dynamic equilibrium reaction in the polymer, internal defects of the material caused by internal stress can be effectively reduced, so that the obtained polymer material has better performance; the polymer material can also be applied to the preparation of coating materials with viscous flow property and high elasticity conversion, energy storage devices and the like, and the preparation of toys and body-building materials with viscous-elastic magic conversion effect.
In addition, the combined hybrid crosslinked dynamic polymer can be applied to other various suitable fields according to the embodied performance, and the technical personnel in the field can expand and implement the polymer according to the actual needs.
The dynamic polymer materials of the present invention are further described below in conjunction with certain embodiments. The specific examples are intended to illustrate the present invention in further detail, and are not intended to limit the scope of the present invention.
Example 1
And (2) taking dicumyl peroxide as an initiator, and grafting and modifying the low molecular weight polypropylene by using maleic anhydride through a melt grafting reaction to obtain the graft modified polypropylene, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 10.
An amino compound (a) is obtained by condensation reaction of equimolar amounts of 2-aminoethylaminoboronic acid and 2- (4-aminobutyl) propane-1, 3-diol as starting materials and tetrahydrofuran as a solvent at 50 ℃ and a pH of 8.
Weighing 25g of graft modified polypropylene and 20mg of BHT antioxidant, adding the weighed graft modified polypropylene and 20mg of BHT antioxidant into a dry clean three-neck flask, heating to 160 ℃ under the protection of nitrogen, stirring and melting, then adding 2.0g of diamino compound (a), 1.5g of bis (2-hydroxy) ethyl tetrasulfide (b), 1.8g of 2,2' -diselenide diethanol (c), 0.15g of p-toluenesulfonic acid, 2.0g of plasticizer DOP and 0.25g of dimethyl silicone oil, continuing to react for 3h under the condition of nitrogen, then pouring the mixture into a suitable mold, carrying out compression molding under the condition of 120 ℃, cooling to room temperature, and placing for 30min, finally obtaining a blocky polypropylene-based polymer sample, wherein the sample is prepared into a boron-containing dumbbell-type sample with the size of 80.850 mm 83.0 (2.0-4.0) mm, the sample is subjected to tensile test by using a tensile tester with the tensile rate of 50mm/min, the tensile strength of 6.0 mm, the sample can be self-repaired by heating under the condition of a dynamic light irradiation, and a self-repairing by using a dynamic light-heating environment, and a dynamic light-induced thermal sealing machine, so as a self-repairing method for a dynamic sealing material with the dynamic tensile test for achieving the dynamic tensile test of a.
Figure BDA0001933286640000561
Example 2
Using dicumyl peroxide as an initiator, and grafting and modifying low molecular weight polyethylene by maleic anhydride through a melt grafting reaction to obtain graft modified polyethylene, wherein the mass ratio of the dicumyl peroxide to the maleic anhydride is 1: 10; then, the boric acid graft modified polymer (a) is prepared by using 1-aminoethylboric acid through a melt grafting reaction by using p-toluenesulfonic acid as a catalyst.
Figure BDA0001933286640000562
The preparation method comprises the steps of uniformly mixing 20g of boric acid grafted modified polyethylene (a), 5g of ethylene-vinyl alcohol copolymer, 3g of dioctyl phthalate, 1.5g of N-aminoethyl-S-aminoethyl dithiocarbamate (b), 1.2g of stearic acid, 1.2g of tribasic basic lead sulfate, 0.5g of di-N-butyltin dilaurate, 0.1g of antioxidant 168, 0.2g of antioxidant 1010, 0.2g of photoinitiator DMPA and 0.25g of dimethyl silicone oil, adding the mixture into a small internal mixer, mixing for 10min, adding 5g of carbon fiber, continuously mixing, taking out the mixed materials, cooling, placing the mixed materials in a double-roll machine at 150 ℃ to prepare a sheet, cooling and cutting the sheet at room temperature, placing the sample in a flat vulcanizing machine, heating for 10min at 160 ℃, taking out, placing the sheet in a vacuum oven at 80 ℃ to perform 12h further reaction, finally obtaining the carbon fiber reinforced polyethylene polymer material, preparing the carbon fiber reinforced polyethylene polymer material into the field of 80.0 ×.0 field (2.0 mm ×), performing a tensile dumbbell test, using a tensile testing machine with the tensile strength of 20.0mm to obtain a tensile strength of a tensile testing machine, and the tensile strength of a tensile testing machine with the tensile strength of 20.52 mm, wherein the tensile strength of the tensile testing machine has the tensile strength of 20.50 MPa, and the tensile strength of a good tensile strength of a roll, and the tensile strength of.
Example 3
Dibenzoyl peroxide is used as an initiator, and maleic anhydride is used for grafting modification of ethylene propylene diene monomer through melt grafting reaction, wherein the mass ratio of dibenzoyl peroxide to maleic anhydride is 1: 10.
Adding 2mol of 1,1,1,3,3, 3-hexamethyldisilazane and 2mol of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine into a nitromethane solution, heating to 50 ℃, stirring for reaction, adding 2mol of sodium acetate and DMF under a nitrogen atmosphere to prepare an intermediate product, cooling the reaction solution to 0 ℃, dropwise adding 1mol of disulfide dichloride, continuously stirring for reaction for 15min, pouring into cold water, collecting the product, dissolving in n-hexane, and adding Na2SO4Drying, purifying, dissolving the product in methanol solvent, adding appropriate amount of K2CO3The mixture was stirred at room temperature for 4 hours, purified and recrystallized from methanol to obtain the dihydroxy compound (a).
1-aminoethylboronic acid and dopamine in equal molar amounts are used as raw materials, tetrahydrofuran is used as a solvent, and a diamino compound (b) is obtained through condensation reaction at the temperature of 60 ℃.
Weighing 12g of maleic anhydride graft modified ethylene propylene diene monomer, adding into a reaction bottle, adding 100ml of epoxidized soybean oil, 50ml of tricresyl phosphate, 1.5g of dihydroxy compound (a), 1.0g of diamino compound (b), 0.1g of p-toluenesulfonic acid, 2.0mg of BHT antioxidant, 2.0g of organobentonite, 1.2g of carbon black, 0.35g of nano Fe3O4Introducing nitrogen for protection, heating to 80 ℃, stirring for reaction for 2h, then placing the reaction solution in a proper mould, continuing the reaction for 6h in a vacuum oven at 80 ℃, then cooling to room temperature, standing for 30min, and taking out a sample from the mould to obtain the ethylene propylene diene monomer heat-conducting dynamic polymer material. The obtained polymer rubber can be slowly expanded under the action of external force stretching, has certain deformability, can be slowly restored after the external force is removed, has a shape memory function, can realize a synergistic dynamic effect of a dynamic covalent bond under the action of stress under a heating condition, or can realize an orthogonal dynamic effect of the dynamic covalent bond under the action of stress under an illumination condition, and shows different extensibility, self-repairability and heat conductivity.
Figure BDA0001933286640000563
Example 4
Mixing and dissolving equal molar amount of cyclooctadiene and m-chloroperoxybenzoic acid in a certain amount of acetonitrile solvent, dropwise adding a proper amount of H2SO4Stirring and reacting at room temperature to obtain 5-cyclooctene-1, 2-diol; the polyoctene polyol and cyclooctene are mixed in a molar ratio of 1:2, and under the action of a Grubbs second-generation catalyst (1, 3-bis (2,4, 6-trimethylphenyl) -2- (imidazolidinylidene) (dichlorobenzylidene) (tricyclohexylphosphine) ruthenium), the polyoctene polyol is prepared.
The modified polysilsesquioxane (a) is prepared by taking mercaptopropyl triethoxysilane as a raw material and ferric trichloride and HCl as catalysts, performing hydrolytic condensation to obtain mercapto-modified polysilsesquioxane, and then partially blocking by utilizing quantitative vinylcyclopropane.
Figure BDA0001933286640000571
Adding a certain amount of toluene solvent into a dry and clean three-neck flask, adding 0.03mol of boron trioxide into the toluene solvent, dropwise adding a proper amount of acetic acid aqueous solution, hydrolyzing for 30min, adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, adding 3mmol of polycyclooctene polyol and a proper amount of triethylamine, uniformly mixing, heating to 60 ℃, and continuing stirring and reacting. The viscosity of the solution continuously rises along with the stirring, and a first network is formed after the reaction is carried out for 2 hours; then 0.02mol of modified polysilsesquioxane (a), 5mmol of 1, 6-hexanedithiol, 5mmol of ethylene glycol diacrylate, 1 wt% of montmorillonite, 1 wt% of silicon dioxide and 0.2 wt% of photoinitiator DMPA are added and uniformly mixed, the mixture reacts for 15min under the irradiation of ultraviolet light to form a second network, then the reaction solution is poured into a proper mould and placed in a vacuum oven at 60 ℃ for 12h for further reaction and drying, and then the mixture is cooled to room temperature and placed for 30min to obtain a rubbery polymer sample. In the embodiment, the dynamically crosslinked polymer material has good extensibility and self-repairing performance, can achieve the capability of coordination and orthogonal regulation by utilizing the difference of dynamic covalent bond dynamics under the condition of heating or illumination, embodies the self-repairing effect and the tensile toughness of different degrees, and can be used as a functional sealant or a plugging adhesive.
Example 5
Adding 4-hydroxy-2, 2,6, 6-tetramethyl-1-oxypiperidine into a mixed solution of styrene and benzoyl peroxide, heating to 90 ℃ under the protection of nitrogen, and reacting for 20 hours to obtain a compound (a), wherein the molar ratio of the benzoyl peroxide to the 4-hydroxy-2, 2,6, 6-tetramethyl-1-oxypiperidine is 1: 2; adding an ethanol solution in which the compound (a) is dissolved into a KOH aqueous solution, carrying out reflux reaction for 16h under the protection of nitrogen to obtain a compound (b), dissolving the compound (b) and methacryloyl chloride in an anhydrous tetrahydrofuran solvent, and carrying out reaction for 10h under the protection of argon at room temperature to obtain a compound (c).
Figure BDA0001933286640000572
Taking AIBN as an initiator, and preparing a phenylboronic acid-styrene copolymer by carrying out free radical copolymerization on styrene and 3-acrylamide phenylboronic acid; the dopamine-styrene copolymer is prepared by taking AIBN as an initiator and utilizing styrene and 3-acrylamide dopamine through free radical copolymerization.
Adding a certain amount of toluene solvent into a dry and clean reaction bottle, introducing argon to remove water and oxygen for 1h, adding 8g of styrene, 1.6g of compound (c) and 0.8 wt% of benzoyl peroxide, heating to 80 ℃ under the protection of argon, and reacting for 24h to form a first network; adding 150ml of toluene solvent into another reaction bottle, adding 8mmol of dopamine-styrene copolymer into the reaction bottle, dissolving and stirring uniformly, adding a proper amount of triethylamine, dropwise adding 8mmol of phenylboronic acid-styrene copolymer under a stirring state, placing the mixture in a water bath kettle at 60 ℃ for reaction for 2 hours, adding 5g of first network polymer, continuing to react for 2 hours, placing the mixed solution in a proper mold, drying in a vacuum oven at 80 ℃ for 24 hours, and finally obtaining the hard polystyrene-based polymer material which has certain surface glossiness and surface hardness but relatively common toughness.
Example 6
The benzoyl peroxide is used as an initiator, and the styrene-phenylboronic acid copolymer (a) is prepared by the free radical copolymerization of styrene and 4-vinylphenylboronic acid. Taking benzoyl peroxide as an initiator, and carrying out free radical copolymerization on styrene and 2-methyl-2-propyl (2-oxo-3-butene-1-yl) carbamate to prepare the hydrogen bond group copolymerization modified styrene (b). Taking benzoyl peroxide as an initiator, and carrying out free radical copolymerization on styrene and 4-vinylpyridine to obtain the styrene-pyridine copolymer.
Figure BDA0001933286640000581
Adding 200ml of dichloromethane solvent into a dry clean reaction bottle, removing water and oxygen by argon gas for 1h, adding 15g of styrene-pyridine copolymer and 1.92g of phenyl selenium bromide, stirring and mixing for 1h to form a first network, adding 30g of styrene-phenylboronic acid copolymer (a), 2g of 1,2,5, 6-tetrahydroxyhexane and 10g of hydrogen bond group copolymerization modified styrene (b), pouring 50ml of n-hexane solvent, heating to 80 ℃, stirring and dissolving, dropwise adding a small amount of triethylamine, continuously reacting for 4h, adding 1 wt% of potassium tert-butoxide, uniformly mixing, placing the mixed solution into a suitable mould, drying for 24h in a vacuum oven at 60 ℃, and finally obtaining a polymer hard solid which has a smooth surface, a certain glossiness, a certain hardness and mechanical strength, preparing a dumbbell type sample with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0) mm, performing a tensile test by using a tensile testing machine, wherein the tensile rate is 10mm/min, the tensile strength is 7.0, the optical modulus is 7.85.85 MPa, and the dumbbell type sample can be made into a dumbbell type sample with the optical property of 18.77 +/-4.0 MPa and the optical property of a self-testing machine.
Example 7
Taking hydroxyl-terminated 1, 3-polybutadiene and dichlorodimethylsilane as raw materials, taking toluene as a solvent, and absorbing HCl generated by the reaction by triethylamine to prepare the chlorosilane-terminated polybutadiene (a). Methyl lithium, vinyl lithium and trimethyl borate are reacted to prepare methyl vinyl boric acid; the organic boron compound (b) is prepared by taking AIBN as an initiator and triethylamine as a catalyst and carrying out thiol-ene click reaction on methyl vinyl boric acid and 1, 6-hexanedithiol.
1, 6-hexanediol diacrylate and cyclopentadiene are used as raw materials, the molar ratio of the raw materials to the 1:2 is controlled, aluminum trichloride is used as a catalyst, and a norbornene compound (c) is prepared through a Diels-Alder reaction.
Figure BDA0001933286640000582
150ml of toluene solvent is added into a dry and clean reaction bottle, then 0.02mol of norbornene and 4mmol of norbornene compound (c) are added, metallocene catalyst/methylaluminoxane is taken as a catalytic system, and the crosslinked polynorbornene compound is prepared by addition polymerization reaction at the temperature of 70 ℃.
Adding 200ml of o-dichlorobenzene solvent into a dry and clean reaction bottle, adding 0.02mol of chlorosilane-terminated polybutadiene (a) and 0.02mol of organic boron compound (b), dropwise adding a proper amount of acetic acid aqueous solution for hydrolysis for 30min, adding a proper amount of triethylamine, stirring and mixing for 10min, heating to 80 ℃, stirring and reacting for 3h, adding 5mmol of crosslinked polynorbornene compound, 6 mol% of 2-methylimidazole and 5 mol% of copper acetate, stirring and mixing for 10min, adding 5 wt% of cellulose nanocrystal and 0.3 wt% of sodium dodecyl benzene sulfonate, reacting for 2h, and drying under reduced pressure to obtain a solid polymer sample. The polymer sample is placed into a mold for heating and pressing molding, so that the polymer material with certain flexibility and self-repairing capability can be obtained.
Example 8
Limonene oxide is extracted from orange peel, the limonene oxide and carbon dioxide are subjected to polymerization reaction under the catalysis of β -zinc diimine to obtain polycarbonate PLimC, and then the polycarbonate PLimC, quantitative mercaptomethyl methyl diethoxysilane and 3-mercaptoindole are subjected to thiol-ene click reaction to obtain the modified polycarbonate compound (a).
Figure BDA0001933286640000583
Pouring a certain amount of chloroform solvent into a dry clean flask, adding 0.03mol of tricresyl borate into the chloroform solvent, dropwise adding a proper amount of acetic acid aqueous solution for hydrolysis for 30min, then adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, then adding 3mmol of modified polycarbonate compound (a), stirring and mixing for 30min, heating to 60 ℃ for reaction for 3h, then introducing nitrogen to remove water and remove oxygen for 1h, then adding 4mg of BHT antioxidant, 0.04mol of triazolinedione compound (b), 2mmol of diphenyl carbonate, 0.01mol of zinc acetate, 5 wt% of glass microfiber and 0.3 wt% of sodium dodecyl benzene sulfonate, dropwise adding a small amount of triethylamine, reacting for 4h under an ice bath condition in a nitrogen scratch atmosphere, then placing the mixed solution into a proper mold, drying for 24h in a 50 ℃ vacuum oven, finally obtaining a bulk transparent polycarbonate sample, preparing the sample into a 80.0 × 10.0.0 (2.0-4.0) 10.0 × (2.0-4.0) mm-size tensile dumbbell, performing a tensile test for 24 min, placing the sample in a tensile testing machine, placing the sample into a self-tensile testing bottle with a tensile strength of a tensile bar, obtaining a sample with a high mechanical strength of a high tensile strength of a hard tensile strength of a sample, and a sample with a tensile strength of a tensile.
Example 9
Using tert-butyl hypochlorite as an oxidant, oxidizing the urea azole of the urea azole compound (a) into triazolinedione, and reacting the triazolinedione-indole with indole-5-methanol to obtain a triazolinedione-indole compound (b). Using triethylamine as a catalyst, and carrying out condensation reaction on equimolar [ (1E) -6-hydroxy-1-hexene-1-yl ] boric acid and 3- (2-hydroxyethoxy) propane-1, 2-diol at 50 ℃ to prepare the borate compound (c). The polyoxypropylene triol is capped with toluene diisocyanate to produce the isocyanate-terminated polyether.
200ml of dichloromethane solvent is measured in a dry and clean reaction bottle, 15g of isocyanate-terminated polyether is added and stirred to be dissolved, then 3.5g of triazolinedione-indole compound (b) and 1.0g of borate compound (c) are added and stirred to be mixed for 10min, the mixture is heated to 60 ℃ to react for 2h, then the reaction solution is poured into a proper mould and placed in a vacuum oven at 80 ℃ to react and dry for 24h, and the reaction solution is cooled to room temperature, so that a polymer sample similar to maltose is finally obtained, and the polymer sample is low in strength, but high in viscosity and good in ductility. In the embodiment, the polymer can be used as an electronic packaging material or an adhesive, and can be recycled in the using process, so that the polymer sample has a long service life.
Figure BDA0001933286640000591
Example 10
Brominated butyl rubber and 3-mercapto-1-propanol are used as raw materials, DMPA is used as a photoinitiator, and under the condition of ultraviolet irradiation, mercaptan-olefin click addition reaction is carried out to prepare the brominated butyl rubber (a) containing side hydroxyl.
Figure BDA0001933286640000592
200ml of toluene solvent is measured in a dry and clean reaction bottle, 15g of brominated butyl rubber (a) containing side hydroxyl is added, after complete dissolution and stirring, 0.91g of boric acid is added, a proper amount of triethylamine is added, after uniform stirring and mixing, the reaction is heated to 60 ℃ for 2h, then nitrogen is introduced to remove water and remove oxygen for 1h, 2.68g of terephthalaldehyde and a proper amount of p-toluenesulfonic acid are added, after stirring and mixing, the reaction is carried out for 3h at 65 ℃ under the protection of nitrogen, then 0.09g of ruthenium-based catalyst 2 is added, 0.06g of antioxidant 754 is continuously reacted for 24h at 65 ℃, then the reaction liquid is poured into a proper mould and placed in a vacuum oven at 80 ℃ for reaction and drying for 24h, finally, the cross-linked butyl rubber with good resilience is prepared, can be stretched and expanded in a large range under the action of external force, can be elastically restored after the external force is removed, after a polymer sample is cut off by a blade, and (3) heating at 50 ℃ for 3h, then the sample can be bonded again for stretching, and the obtained polymer material can be used as a polymer material with self-repairing property and shape memory property.
Example 11
Using DMPA as a photoinitiator and ultraviolet light as a light source, and carrying out thiol-ene click reaction on 4-mercaptophenylboronic acid and hydroxyl-terminated polyisoprene to obtain phenylboronic acid graft modified polyisoprene (a).
Figure BDA0001933286640000593
Adding 25g of phenylboronic acid graft modified polyisoprene (a) into a dry and clean reaction bottle, adding 2g of gallium-indium liquid alloy, 0.2g of talcum powder, 0.1g of dibutyltin dilaurate and 0.5g of anhydrous sodium sulfate, heating to 80 ℃, stirring for reaction for 2h, adding 3g of polymethylene polyphenyl polyisocyanate (the content of isocyanate is about 30%) for rapid mixing, adding 0.05g of ruthenium-based catalyst 1, pouring into a proper mold, placing at 80 ℃ for continuous reaction for 2h, cooling to room temperature, and placing for 30min, thereby finally obtaining the heat-conducting polyisoprene elastomer material which has good tensile toughness and flexibility.
Example 12
Mixing and dissolving equal molar amounts of cyclooctadiene and m-chloroperoxybenzoic acid in a certain amount of tetrahydrofuran/chloroform mixed solvent, stirring and reacting for 19h at room temperature to obtain a cyclooctene compound (a), dissolving the cyclooctene compound in dichloromethane solvent, cooling to 0 ℃, dropwise adding diisobutylaluminum hydride, stirring for 30min, heating to room temperature, stirring and reacting for 19h, cooling to 0 ℃, adding deionized water and NaOH, heating to room temperature, and stirring and reacting for 15min to obtain a cyclooctene compound (b); it is mixed with cyclooctene in a molar ratio of 1:2, and a polycyclooctene compound (c) is produced under the action of a ruthenium-based catalyst 2.
Figure BDA0001933286640000601
Adding 30g of polycyclooctene compound (c) into a dry and clean reaction bottle, adding 0.5g of boric acid, adding an appropriate amount of triethylamine, stirring and mixing uniformly, heating to 60 ℃ for reaction for 2 hours, introducing nitrogen to remove water and remove oxygen for 1 hour, adding 2.5g of toluene diisocyanate, stirring and mixing, reacting for 2 hours under the protection of nitrogen, adding 0.08g of ruthenium-based catalyst 2, 0.05g of antioxidant 754, and continuing to react for 24 hours at 65 ℃ to obtain the polycyclooctene elastomer with good ductility.
Example 13
Taking DMPA as a photoinitiator and ultraviolet light as a light source, and carrying out thiol-ene click reaction on 3-mercapto-1-propanol and terminal amino 1, 3-polybutadiene to obtain the hydroxyl graft modified polybutadiene.
1.8g of the hexafluorocyclopentene compound (a) was weighed and dissolved in 10ml of a toluene solvent, 0.96g of N- (2-hydroxyethyl) maleimide was added, and the mixture was stirred at 90 ℃ for 24 hours, washed with ethyl acetate and deionized water and purified to obtain the hexafluorocyclopentene compound (b).
Figure BDA0001933286640000602
Adding 200ml of xylene solvent into a dry and clean three-neck flask, adding 0.5g of tri-tert-butyl borate into the xylene solvent, dropwise adding an appropriate amount of acetic acid aqueous solution for hydrolysis for 30min, then adding an appropriate amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, then adding 9.5g of hydroxyl graft modified polybutadiene, heating to 80 ℃ for mixing reaction for 4h, then adding 2.8g of hexafluorocyclopentene compound (b), 0.5g of plant fiber, 0.1g of talcum powder, 0.05g of dibutyltin dilaurate and 0.2g of silicone oil foam stabilizer, stirring and mixing uniformly at a high speed, then adding 3.5g of diphenylmethane diisocyanate, mixing rapidly, stirring for 30s at a high speed, when the mixture foams white and bubbling, pouring into a suitable mold rapidly, molding and foaming for 12h at 80 ℃ to ensure complete reaction polymerization, finally obtaining a hard polyurethane foam material, preparing a 20.0. ×.0.0 mm-0.0.0-inch thermal insulation foam material, and obtaining a thermal insulation foam material with the characteristics of light compression strength, good thermal insulation effect measured by a refrigerator under the light compression test speed test, good compression strength or the light compression strength test under the synergistic effect of a refrigerator.
Example 14
The amino compound (a) is prepared by condensation reaction of 2-aminoethylaminoboronic acid and 1, 6-diaminohexane-3, 4-diol in equal molar weight as raw materials and tetrahydrofuran as solvent under the conditions of 50 ℃ and pH 8.
Figure BDA0001933286640000603
Adding 5.3g of toluene-2, 4, 6-triyl triisocyanate into a three-neck flask, carrying out vacuum dehydration for 2h at 120 ℃, cooling to 45 ℃, adding 12ml of DMF for dissolution and dilution, introducing argon for protection, dissolving 4.05g of 6-hydroxycoumarin and a small amount of ethyl butyl dilaurate solution in 40ml of DMF, and dropwise adding the solution into a reaction bottle at a constant speed. Heating to 70 ℃ for reaction for 3h, adding 10g of polyethylene glycol 400, and continuing the reaction for 6h at 70 ℃ to obtain the coumarin side group-containing polyurethane; adding 200ml of THF solvent into another flask, vacuumizing to remove water for 1h, adding 5g of polyethylene glycol 400, 3g of polyamino compound (a), 4.0g of trimethyl-1, 6-hexamethylene diisocyanate, heating to 60 ℃, reacting for 3h in nitrogen atmosphere, adding 15g of polyurethane containing coumarin side groups, 3.0g of microsphere foaming agent, 0.04g of diethanolamine, 0.25g of stannous octoate, 2.0g of expanded graphite and 2.0g of ammonium polyphosphate, rapidly stirring for 30s, uniformly mixing, pouring reactants into a proper mold, placing in a vacuum oven at 80 ℃, continuously reacting for 12h, cooling to room temperature, placing for 30min, irradiating and curing for 2h by ultraviolet light at 350nm, and carrying out foaming molding by using a flat plate vulcanizing machine, wherein the mold pressing temperature is 140 and 150 ℃, the mold pressing time is 10-15min, and the pressure is 10MPa, finally obtaining the polyurethane foam material. In this embodiment, the obtained polyurethane foam material can be used as a building board with a flame retardant effect, and can realize self-repairing of the material under heating or illumination conditions of specific frequency.
Example 15
Adding 15g of 2, 4-di-tert-butylphenol, 10g of 4-hydroxymandelic acid and 30ml of acetic acid into a reaction bottle, heating to 95 ℃, uniformly mixing, adding 0.09ml of methanesulfonic acid, continuing to react for 3h, cooling overnight, filtering and purifying to obtain an intermediate product 1, dissolving the intermediate product 1 in an NaOH aqueous solution, heating to 80 ℃ under the protection of nitrogen, adding a proper amount of 3-chloro-1, 2-propanediol, continuing to react for 3h, cooling to room temperature, adding a hydrochloric acid aqueous solution, heating to 80 ℃, continuing to react for 1h, purifying to obtain an intermediate product 2, uniformly mixing the intermediate product 2 with di-tert-butyl peroxide and benzene, irradiating by ultraviolet light at 30 ℃ for 90min, and purifying to obtain a compound (a).
Figure BDA0001933286640000611
The amino compound (b) is obtained by condensation reaction of equimolar 2-aminoethylaminoboronic acid and dopamine as raw materials and tetrahydrofuran as a solvent at 50 ℃ and pH 8.
Figure BDA0001933286640000612
Weighing 30g of polyethylene glycol 400 as a chain extender in a dry and clean flask, heating to 100 ℃, introducing nitrogen to remove water and oxygen for 1h, adding 15g of 1, 6-hexamethylene diisocyanate, reacting for 2h under the condition of nitrogen protection at 80 ℃, cooling to 60 ℃, adding 6.5g of a compound (a), 2.5g of an amino compound (b), 1.5g of triethylamine, 12g of acetone and 0.15g of stannous octoate, carrying out reflux reaction for 2h, then adding 1.5g of calcium carbonate, 1.5g of barium sulfate and 1.0g of talcum powder, carrying out ultrasonic treatment for 20min, after the reaction is finished, removing acetone in vacuum, cooling to room temperature, and finally obtaining the polyurethane-based elastomer which can be used as a polyurethane sealant with a self-repairing effect.
Example 16
Boric acid and dimethyl methoxy-3- (2-amino ethyl thio) propyl silane are used as raw materials, tetrahydrofuran is used as a solvent, and condensation reaction is carried out under the conditions of 50 ℃ and pH 8 to obtain the polyamino compound (a).
Figure BDA0001933286640000613
Adding 0.01mol of polyamino compound (a) and 0.02mol of polyetheramine with the molecular weight of 400 into a dry and clean reaction bottle, uniformly mixing, adding 0.04mol of trimethyl-1, 6-hexamethylene diisocyanate, reacting for 2 hours in a nitrogen atmosphere to obtain a first network polymer, and crushing the first network polymer into small particles; adding 0.01mol of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) ethylenediamine (b), 0.02mol of polycarbonate diol with the molecular weight of about 1,000, 2mmol of diphenyl carbonate and 1mmol of zinc acetate into another reaction bottle, dropwise adding a small amount of triethylamine, uniformly mixing, adding 0.03mol of hexamethylene diisocyanate trimer, reacting for 2 hours in a nitrogen atmosphere, adding a proper amount of first network polymer particles, continuously stirring and mixing for 2 hours, and finally obtaining a polymer colloid with a certain viscosity after the reaction is finished.
Example 17
The amino compound (a) is obtained by condensation reaction of equimolar amounts of 2-aminoethylaminoboronic acid and 2-amino-1, 3-propanediol as raw materials and tetrahydrofuran as a solvent at 50 ℃ and a pH of 8. 1, 6-hexamethylene diisocyanate and furfuryl alcohol are used as raw materials, dichloromethane is used as a solvent, stannous octoate is used as a catalyst, the molar ratio of the raw materials to the dichloromethane is controlled to be 1:2, the reaction is carried out for 2 hours at room temperature under the protection of nitrogen, and the reflux reaction is carried out for 2 hours to prepare a difuran compound (b).
Figure BDA0001933286640000621
Weighing 5mmol of polyetheramine D2000 in a dry clean flask, heating to 100 ℃, introducing nitrogen to remove water and remove oxygen for 1h, adding 0.02mol of diphenylmethane diisocyanate, reacting for 2h under the condition of 80 ℃ nitrogen protection, cooling to 60 ℃, adding 8mmol of N- (2, 3-dihydroxypropyl) maleimide, a proper amount of triethylamine and 0.5 wt% of stannous octoate, continuing to react for 4h, adding 5mmol of an amino compound (a), 8mmol of a furan compound (b), 5 wt% of plant fibers, 5 wt% of barium sulfate and 5 wt% of talcum powder, continuing to react for 1h, after the reaction is finished, placing a polymer sample in a suitable mold, drying for 24h in a vacuum oven, cooling to room temperature to finally obtain the polyurethane-based elastomer with high elasticity, preparing a dumbbell-type sample with the size of 80.0 × 10.0.0 (10.0 ×) (2.0-4.0) mm, performing tensile test by using a tensile testing machine, measuring the tensile rate of 50mm/min, measuring the tensile strength of the sample to be 7.21 +/-2.30 MPa, the tensile modulus of the sample to be × (2.0.0-4.0 mm), and showing different tensile elongation of polyurethane materials under the conditions of normal temperature and showing different elongation of normal temperature, and showing different elongation of the polyurethane materials in the normal temperature.
Example 18
Using triethylamine as a catalyst, and carrying out condensation reaction on equimolar [ (1E) -6-hydroxy-1-hexene-1-yl ] boric acid and 3- (2-hydroxyethoxy) propane-1, 2-diol at 50 ℃ to prepare the borate compound (a).
Figure BDA0001933286640000622
0.01mol of borate compound (a), 0.01mol of butynediol, 0.04mol of butynedioic acid, 0.01mol of polyoxypropylene triol having a molecular weight of about 3,000, 0.04mol of dicyclohexylcarbodiimide condensing agent, and 4mmol of catalyst 4-dimethylaminopyridine were weighed and dissolved in 80ml of dichloromethane solvent, and after stirring and mixing uniformly, the reaction was carried out for 4 hours under reflux conditions, and then ruthenium-based catalyst 10 was added, and the reaction was continued for 2 hours. After the reaction is finished, the generated dicyclohexylurea is filtered out under normal pressure, the solvent is removed by drying under reduced pressure to obtain a residue, and the residue is purified to obtain a colloidal dynamic polymer solid. The obtained dynamic polymer has soft surface and certain viscoelasticity, can be used for preparing a polymer sample into a sealant or a recyclable elastic member, can embody good toughness and elasticity, can be pressed into products with different shapes and sizes according to the requirements, and can be recycled to prepare a new product for use after a damaged or no longer needed sample.
Example 19
Taking propenyl boric acid and 1,3, 5-triazine-2, 4, 6-trithiol as raw materials, controlling the molar ratio of the propenyl boric acid to the 1,3, 5-triazine-2, 4, 6-trithiol to be 3:1, taking DMPA as a photoinitiator and ultraviolet light as a light source, and preparing the organic boron compound (a) through thiol-ene click reaction.
Adding a certain amount of anhydrous toluene into a reaction bottle, adding 5g of polyethylene glycol 800 and a proper amount of tert-butyl alcohol solution dissolved with potassium tert-butoxide, uniformly mixing, introducing nitrogen for 20min, dropwise adding 3ml of ethyl bromoacetate, stirring at room temperature for 24h, dissolving in a methanol solvent after purification, slowly adding a hydrazine hydrate methanol solution, stirring at room temperature for 24h, filtering and purifying to obtain the hydrazide-terminated polyethylene glycol.
Figure BDA0001933286640000623
Adding a certain amount of NMP solvent into a dry and clean reaction bottle, adding 0.03mol of hydrazide-terminated polyethylene glycol, heating to 60 ℃, introducing nitrogen to remove water and remove oxygen for 1h, then adding 0.02mol of 1,3, 5-benzenetricarboxylic aldehyde, and reacting for 24h under the protection of nitrogen to form a first network; adding 3mmol of polyethylene glycol 2000, stirring and dissolving completely, adding a proper amount of triethylamine, adding 1mmol of organic boron compound (a) under a stirring state, mixing uniformly, heating to 60 ℃ and reacting for 3 hours to form a second network; adding 4mmol of polyethylene glycol diamine with molecular weight of about 4,000 and 0.01mol of paraformaldehyde, heating to 50 ℃ under stirring for reaction for 30min to form a third network, finally obtaining the polyethylene glycol-based organic gel with a triple network structure, wherein the polymer gel has larger surface viscosity, after being cut by a blade, the surface of the polymer gel can be completely healed again by slightly heating, and the polymer gel has excellent self-repairing performance, can be degraded to different degrees under heating and acidic conditions, and has potential application in aspects of bioseparation, drug controlled release, sensors and the like by utilizing the self-repairing performance and the temperature/pH responsiveness of the network structure of the gel.
Example 20
Reacting 9-anthracenecarboxylic acid with thionyl chloride to prepare 9-anthraceneacyl chloride; trimethylolpropane and epoxypropane are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, hydroxyl-terminated three-arm polypropylene oxide is synthesized through cationic ring-opening polymerization, and then the hydroxyl-terminated three-arm polypropylene oxide reacts with 9-anthracene acyl chloride to prepare anthracene-terminated three-arm polypropylene oxide (a).
Trimethylolpropane and epoxypropane are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, hydroxyl-terminated three-arm polypropylene oxide is synthesized through cation ring-opening polymerization, then the hydroxyl-terminated three-arm polypropylene oxide is subjected to esterification reaction with equimolar amount of acrylic acid to obtain three-arm polypropylene oxide triacrylate, and the three-arm polypropylene oxide triacrylate is subjected to thiol-ene click reaction with equimolar amount of gamma-mercaptopropyl methyldimethoxysilane to obtain silane-terminated three-arm polypropylene oxide (b).
Weighing a certain amount of tetrahydrofuran solvent, adding 0.02mol of silane terminated three-arm polypropylene oxide (b) into the tetrahydrofuran solvent, stirring and dissolving the mixture completely, adding a small amount of 20% acetic acid aqueous solution, hydrolyzing the mixture for 30min, adding a proper amount of triethylamine and 0.03mol of p-phenylboronic acid, reacting the mixture for 3h at 50 ℃ to form a first network, then introducing nitrogen to remove water and remove oxygen for 1h, adding 0.02mol of anthracene terminated three-arm polypropylene oxide (a), 0.03mol of 1, 8-bis (maleimide) -3, 6-dioxaoctane, stirring and dissolving the mixture completely, adding a small amount of tin tetrachloride, refluxing the mixture under nitrogen protection for 12h to form a second network, pouring the reaction solution into a suitable mold, placing the mold in a vacuum oven at 60 ℃ for 24h for further reaction and drying, then cooling to room temperature for 30min, finally obtaining a colloidal polymer sample with certain elasticity, which can be expanded within a certain range to prepare a specimen of 80.0 × 10.0.0.0 mm 10.0 × (2.0.0.0.0.0.0 mm), and standing the colloidal polymer sample for 30min, and exhibiting good tensile strength change in a tensile strength test sample with a high elasticity of a tensile strength of 18 mm, and a tensile strength of a sample bar elongation test applied to a sample with a high elasticity of a tensile strength of 18MPa, wherein the sample, and a tensile strength test environment, and a tensile strength of a tensile test of a tensile strength of a tensile test of 18 mm, and a tensile strength of a sample of a.
Example 21
The method comprises the steps of taking glycerol and propylene oxide as raw materials, taking boron trifluoride diethyl etherate as a catalyst, synthesizing hydroxyl-terminated three-arm polypropylene oxide through cation ring-opening polymerization, carrying out esterification reaction on 1 molar amount of the hydroxyl-terminated three-arm polypropylene oxide and 3 molar amounts of acrylic acid to obtain three-arm polypropylene oxide triacrylate, and carrying out thiol-ene click reaction on the three-arm polypropylene oxide triacrylate and 3 molar amounts of 3-mercapto-1, 2-propylene glycol to obtain the 1, 2-glycol-terminated three-arm polypropylene oxide.
Adding 0.03mol of triethanolamine borate into a dry and clean reaction bottle, dropwise adding an appropriate amount of acetic acid aqueous solution, hydrolyzing for 30min, then adding an appropriate amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, then adding 0.02mol of 1, 2-diol terminated three-arm polypropylene oxide, uniformly mixing, and reacting for 6h at 60 ℃ to obtain a first network polymer; adding a certain amount of ethanol/chloroform mixed solvent into another reaction bottle, adding 0.03mol of polypropylene glycol 400 and 0.06mol of toluene diisocyanate, reacting for 2 hours at room temperature, heating to 60 ℃, introducing nitrogen to remove water and remove oxygen for 1 hour, adding 0.06mol of adipic acid dihydrazide and 0.02mol of 1,3, 5-benzenetricarboxylic acid to react for 24 hours under the protection of nitrogen, adding a proper amount of first network polymer, continuously stirring to react for 2 hours, cooling to room temperature after the reaction is finished, and finally obtaining a polymer elastomer with good resilience.
Example 22
The amino-terminated compound (a) is obtained by condensation reaction at 60 ℃ by using equimolar amounts of 2-aminomethyl phenylboronic acid and 2- (4-aminobutyl) propane-1, 3-diol as raw materials and tetrahydrofuran as a solvent.
Figure BDA0001933286640000641
Adding a certain amount of tetrahydrofuran solvent into a dry and clean reaction bottle, sealing, carrying out deoxygenation by bubbling with argon for 1h, adding 0.02mol of an amino-terminated compound (a), 0.03mol of N, N '-di-tert-butyl hexanediamine (b) and 0.02mol of N, N' -tri-tert-butyl-tri (3-aminoethyl) amine (c), stirring for dissolving, adding 2ml of triethylamine, mixing uniformly, dropwise adding 0.08mol of octanedioyl chloride, and continuously stirring, mixing and reacting for 6 h. After the reaction is finished, the polyamide-based dynamic cross-linked polymer colloid is obtained by decompression, drying, removing the solvent and purifying. In the embodiment, the self-repairing adhesive can be used as a metal edge seam adhesive with an excellent self-repairing function and a caulking material of plastic and automobile bodies, and can realize self-adhesion and self-repairing of the material under mild conditions.
Example 23
Pentaerythritol and 3-bromopropionic acid are used as raw materials, the molar ratio of the pentaerythritol to the 3-bromopropionic acid is controlled to be 1:4, pentaerythritol 3-bromopropionate is obtained through esterification, and then the pentaerythritol 3-bromopropionate reacts with sodium azide with the same molar amount to obtain pentaerythritol tetraazide (a).
Using dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalysts, and sequentially carrying out amidation and esterification on polyamide with the molecular weight of about 5,000 and 5-alkynyl caproic acid and propargyl alcohol with the equimolar weight to obtain alkynyl terminated polyamide (b).
Diethylene glycol diacrylate and 3-mercapto phenylboronic acid are used as raw materials, the molar ratio of the diethylene glycol diacrylate to the 3-mercapto phenylboronic acid is controlled to be 1:2, AIBN is used as an initiator, triethylamine is used as a catalyst, and the phenylboronic acid compound (c) is prepared through a mercapto-Michael addition reaction.
4-hydroxystyrene and formaldehyde are taken as raw materials, the raw materials and zinc nitrate hexahydrate are refluxed for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, methanol is taken as a solvent, AIBN is taken as an initiator, triethylamine is taken as a catalyst, and the polyhydric alcohol compound (d) is prepared by the mercaptan-olefin click addition reaction of the polyhydric alcohol compound and pentaerythritol tetramercapto acetic ester.
Figure BDA0001933286640000642
Adding a certain amount of tetrahydrofuran solvent into a dry and clean reaction bottle, sealing, carrying out bubbling deoxygenation for 1h by using argon, and then adding 0.01mol of tetraazide pentaerythritol ester (a), 0.02mol of alkynyl-terminated polyamide (b), 0.5ml of N, N-diisopropylethylamine and 35mg of catalyst Cu (PPh)3)3Br is added. The reaction flask was heated to 60 ℃ and reacted for 12h with stirring, and 6 mol% 2-methylimidazole and 5 mol% copper acetate were added to obtain a first network.
Adding 0.02mol of polyol compound (d) into the reaction bottle, stirring and dissolving completely, then sequentially adding a proper amount of pyridine and 0.04mol of phenylboronic acid compound (c), placing the mixture into a water bath kettle at 60 ℃, heating and reacting for 2 hours, adding 1 wt% of metal osmium heteroaromatic ring particles and 1 wt% of nano silver particles, shaking and mixing uniformly, and continuing to react for 2 hours to obtain the dynamic polymer with the double networks. And then pouring the reaction liquid into a proper mould, placing the mould in a vacuum oven at 60 ℃ for 24h for further reaction and drying, cooling to room temperature, and placing for 30min to obtain a block-shaped polymer sample with certain elasticity, wherein the block-shaped polymer sample has good processing formability and self-repairability and can generate heat under the action of infrared rays, and the obtained polymer sample can be used for manufacturing heat-conducting gaskets and is applied to the fields of automobile industry and various mechanical devices.
Example 24
Dissolving 0.028g of stannous octoate in 0.5ml of toluene solvent, pouring into a reaction bottle, adding 50g of lactide and 1.9g of pentaerythritol, uniformly mixing, heating to 160 ℃, reacting for 3 hours, dissolving the product in dichloromethane, precipitating by using ethanol, repeatedly washing for 10 times, and drying for 24 hours under nitrogen atmosphere to obtain the hydroxyl-terminated four-arm polylactide.
Weighing 100ml of dichloromethane solvent in a reaction bottle, adding 1mol of hydroxyl-terminated four-arm polylactide, 0.2mol of 4,4' -biphenyl diboronic acid and a proper amount of pyridine, heating to 60 ℃, stirring for reaction for 4 hours, adding 1.6mol of diphenylmethane diisocyanate, 0.35 wt% of tris (nonylphenyl) phosphite and 0.02mol of stannous octoate catalyst, after complete dissolution and stirring, adding 5 wt% of titanium alloy powder, 5 wt% of ceramic powder and 10 wt% of calcium sulfate, continuing to react for 1 hour at 60 ℃, pouring the polymer solution into a suitable mold, placing the mold in a vacuum oven at 60 ℃ for 24 hours for drying and further reaction, then cooling to room temperature and placing for 30 minutes, finally obtaining a milky white translucent polymer solid sample with glossiness, preparing a dumbbell type sample with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0) mm, performing tensile test by using a tensile testing machine, obtaining a sample with the tensile rate of 50mm/min, measuring the tensile strength of the sample as 7.59 +/-2.84 MPa, the tensile modulus of the sample, and realizing the self-repairing of the bionic fracture surface crack of the polymer under the temperature of the sample, and realizing the bionic crack growth rate of the bionic polymer under the bionic material under the temperature of the sample under the temperature of 60 ℃ of 140.
Example 25
Using 2-ethyl isocyanate acrylate and hydroxyethyl acrylate in equal molar amount as raw materials, using triethylamine as a catalyst, and reacting in a dichloromethane solvent to prepare the diolefin compound (a) containing carbamate groups in the chain.
1, 4-pentadiene-3-alcohol and cyclohexyl isocyanate in equal molar amount are taken as raw materials, 1 wt% of dibutyltin dilaurate is taken as a catalyst, and the raw materials react in a dichloromethane solvent to prepare the diolefin compound (b) with a carbamate group on a side group.
Figure BDA0001933286640000651
The tetraboric acid compound (c) is prepared by taking vinyl boric acid and pentaerythritol tetra-3-mercaptopropionate as raw materials, controlling the molar ratio of the vinyl boric acid to the pentaerythritol tetra-3-mercaptopropionate to be 4:1, taking AIBN as an initiator and triethylamine as a catalyst through a thiol-ene click reaction.
4-hydroxystyrene and formaldehyde are taken as raw materials, the raw materials and zinc nitrate hexahydrate are refluxed for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, methanol is taken as a solvent, AIBN is taken as an initiator, triethylamine is taken as a catalyst, and the obtained product and 1, 6-hexanedithiol are subjected to mercaptan-olefin click addition reaction to prepare the hydroxymethyl phenol compound (d).
Figure BDA0001933286640000652
The method comprises the steps of mixing a diolefin compound (a), a diolefin compound (b), di-2-allyl trithiocarbonate, 1, 6-hexanedithiol and pentaerythritol tetramercaptoacetate according to an equal molar amount, adding 0.2 wt% of benzoin dimethyl ether (DMPA) as a photoinitiator, adding 6 mol% of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD) and 5 mol% of zinc acetate, stirring, fully mixing, and placing in an ultraviolet crosslinking instrument for ultraviolet radiation for 4 hours to obtain a dynamic polymer crosslinking network containing a skeleton hydrogen bond and a side hydrogen bond. And (3) adding a tetraboric acid compound (c) and a hydroxymethyl phenol compound (d) into the reaction bottle, controlling the molar ratio of the tetraboric acid compound to the hydroxymethyl phenol compound to be 1:2, and adding a proper amount of triethylamine to react for 4 hours at the temperature of 60 ℃ to obtain the dynamic polymer material with the double networks, wherein the dynamic polymer material has good rebound resilience and certain tensile toughness. After the surface of the polymer material is scratched by a blade, the polymer material is placed in a vacuum oven at 60 ℃ for 3 hours, the scratch disappears, and the cut polymer sample can be bonded again after being placed in a vacuum oven at 120 ℃ for 4 hours. In the embodiment, the polymer sample can be prepared into a recyclable elastic ball for use, the recyclable elastic ball can show good toughness and elasticity, products with different shapes and sizes can be pressed according to needs, and the damaged or no longer needed sample can be recycled by heating to prepare a new product for use.
Example 26
Trimethylolpropane tri (3-mercaptopropionate) and diisopropyl propenyl borate are taken as raw materials, the molar ratio of the trimethylolpropane tri (3-mercaptopropionate) to the diisopropyl propenyl borate is controlled to be 1:3, AIBN is taken as an initiator, triethylamine is taken as a catalyst, and the triborate ester compound (a) is prepared through a thiol-ene click reaction. The method comprises the steps of taking vinyl boronic acid pinacol ester and 1, 10-decanedithiol as raw materials, controlling the molar ratio of the vinyl boronic acid pinacol ester to the 1, 10-decanedithiol to be 1:1, taking AIBN as an initiator and triethylamine as a catalyst, and carrying out thiol-ene click reaction to obtain a diboronate compound (b).
Figure BDA0001933286640000661
Adding 0.4mol of hexadecanedioic acid and 5 mol% of zinc acetate catalyst into a dry and clean reaction bottle, uniformly mixing, gradually heating the reactants to 180 ℃ under a vacuum condition, continuously reacting for 3 hours at the temperature, dissolving the catalyst in carboxylic acid, cooling to 130 ℃, adding 0.1mol of tetraglycidyl methyl diphenylamine epoxy resin, stirring and mixing for 4 hours, cooling to room temperature, adding 0.05mol of a tribolate compound (a), 0.1mol of a diboronate compound (b), 0.2mol of sodium borate, 4ml of deionized water and a small amount of acetic acid under a stirring state, stirring and mixing for 30 minutes, adding 2ml of triethylamine and a small amount of anhydrous magnesium sulfate, heating to 110 ℃ for heating reaction for 4 hours, pouring the polymer solution into a suitable mold, placing the polymer solution into a 120 ℃ vacuum oven for continuous reaction for 12 hours, then cooling to room temperature, placing for 30 minutes, finally obtaining a bulk polymer sample, preparing the bulk polymer sample into 80.0 ×.0 × (2.0.0-4.0.0.0) type dumbbell size, performing tensile test by using a tensile tester, obtaining a tensile strength test, obtaining a tensile strength sample with a tensile strength of 14.65 mm, and obtaining a tensile strength of a sample which can be measured by using a sample under a sample of an epoxy sample with a tensile test of an electrical appliance under a certain heating condition of 14.0.0.72 MPa, and a tensile strength of an epoxy sample, and a tensile strength of an extensible sample with a.
Example 27
Figure BDA0001933286640000662
The silane copolymerization modified acrylate (a) is obtained by emulsion polymerization by using potassium persulfate as an initiator and 3- (dimethoxymethylsilyl) propyl acrylate and methyl acrylate as raw materials.
Adding 15g of silane copolymerization modified acrylate (a) and 100ml of 1, 4-dioxane solvent into a three-neck flask, heating to 50 ℃, stirring and dissolving, then adding 2g of boric acid, adding a proper amount of triethylamine, heating to 100 ℃, reacting for 3 hours, then cooling to 30 ℃, adding 2.5g of polycaprolactone diol with the molecular weight of about 500 and 1.8g of N, N-bis (2-hydroxyethyl) cinnamamide (b), uniformly mixing, heating to 80 ℃ under the protection of nitrogen, adding 1.68g of hexamethylene diisocyanate, continuously stirring and reacting for 3 hours, removing the solvent through reduced pressure drying after the reaction is finished, obtaining white residue, purifying the white residue, placing the white residue into a proper mold, and irradiating for 30 minutes under 280nm ultraviolet light to obtain the hybrid crosslinked dynamic polymer. The prepared dynamic polymer can be made into an emulsion film with excellent adhesion, scrub resistance and self-repairing property, can realize self-repairing under the conditions of heating or ultraviolet irradiation with different frequencies, and has environmental responsiveness.
Example 28
Figure BDA0001933286640000663
The preparation method comprises the following steps of taking AIBN as an initiator, reacting 4-hydroxymethyl phenylboronic acid pinacol ester with acryloyl chloride to prepare a phenylboronic acid ester acrylate monomer, and carrying out free radical polymerization on the phenylboronic acid ester acrylate monomer, methyl methacrylate and mercapto methyl methacrylate to obtain an acrylate copolymer (a).
And (b) carrying out free radical polymerization on 2, 3-dihydroxypropyl acrylate, methyl methacrylate and mercaptomethyl methacrylate by using AIBN as an initiator to obtain the acrylate copolymer (b).
Using AIBN as an initiator, methyl methacrylate and N- (aminocarbonyl) methacrylamide are subjected to free radical polymerization to obtain an acrylate copolymer (c).
Adding a certain amount of toluene solvent into a dry and clean three-neck flask, adding 3mmol of acrylate copolymer (a), dropwise adding a proper amount of acetic acid aqueous solution, hydrolyzing for 30min, adding a proper amount of triethylamine, stirring and mixing for 10min, adding 3mmol of acrylate copolymer (b), and reacting for 2h under the condition of water bath at 60 ℃. And then heating the reaction liquid to 80 ℃, introducing nitrogen to remove water and oxygen for 1h, then adding a proper amount of triethylamine and manganese dioxide oxidant, continuing to stir for reaction for 3h, adding 3mmol of acrylate copolymer (c), 6 wt% of cellulose nanocrystal and 0.3 wt% of sodium dodecyl benzene sulfonate, performing ultrasonic treatment for 20min, heating to 80 ℃, and continuing to stir for reaction for 2 h. After the reaction is finished, the solvent is removed by drying under reduced pressure to obtain a white residue, the white residue is purified to obtain a dynamic polymer solid, the surface of the dynamic polymer solid is uniform, has certain glossiness and certain formability, can be pressed and heated to be formed into a required shape according to the shape of a die, and is reheated or irradiated after scratches are formed on the surface of the dynamic polymer solid, the scratches can be self-repaired, and the dynamic polymer solid can be made into an industrial art molding with good formability and self-repairing capability.
Example 29
Dissolving 2g of selenocysteine hydrochloride into 120mL of dichloromethane, adding 5g of triethylamine under a stirring state, cooling to 0-5 ℃, slowly adding 2.5g of acryloyl chloride, reacting under stirring at room temperature for 24 hours under the protection of nitrogen, and distilling under reduced pressure to obtain the N, N' -bis (acryloyl) selenocysteine.
4-hydroxystyrene and formaldehyde are taken as raw materials, and are refluxed with zinc nitrate hexahydrate for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, and potassium persulfate is taken as an initiator, so that the 2- (hydroxymethyl) -4-vinylphenol and acrylamide are subjected to free radical polymerization to obtain the acrylamide copolymer (a).
Figure BDA0001933286640000671
Taking a certain amount of ionic liquid 1-ethyl-3-methylimidazole tetrafluoroborate, adding 0.03mol of boric acid, stirring and dissolving completely, adding a proper amount of NaOH aqueous solution, adjusting the pH value of the solution to 7.5-8, continuously mixing for 10min, adding 4mmol of acrylamide copolymer (a), stirring and dissolving completely, adding a proper amount of pyridine, and placing in a 60 ℃ water bath kettle for heating and reacting for 2h to form a first dynamic cross-linked network; then adding 1mol of acrylamide, 0.01mol of N, N' -bis (acryloyl) selenocysteine and 0.6 mol% of initiator potassium persulfate, stirring and mixing uniformly, standing for 1h to remove bubbles, placing in a constant temperature water bath at 60 ℃ for reaction for 5h, and then adding 5 wt% of surface modified Fe3O4And (3) carrying out ultrasonic treatment on the particles, 5 wt% of nano metal magnetic powder and 1 wt% of bentonite for 1min to uniformly disperse the metal particles in the particles, placing the mixture in a constant-temperature water bath at the temperature of 60 ℃ to react for 2h, and obtaining the double-network ionic liquid gel dispersed with the magnetic particles after the reaction is finished. In the present embodiment, it is preferred that,the obtained polymer gel can show the shape memory capacity by utilizing electromagnetic wave heating control due to the fact that the polymer gel is wrapped with the magnetic particles, can show different deformation capacities under the heating or illumination condition due to the fact that the polymer gel contains different types of dynamic covalent bonds, has multiple magnetic response effects, and shows orthogonal and synergistic response effects.
Example 30
Dissolving a certain amount of trimethylolpropane in a hydrochloric acid solution, adding a proper amount of 3-hydroxy-2, 2-dimethylpropionaldehyde, stirring and reacting for 24 hours under the protection of argon at 90 ℃, wherein the molar ratio of the trimethylolpropane to the 3-hydroxy-2, 2-dimethylpropionaldehyde is 3:2, then uniformly mixing a proper amount of intermediate product with allyl bromide and NaOH powder, adding tetrabutylammonium bromide as a phase transfer catalyst, heating to 70 ℃, stirring and reacting for 24 hours, and preparing the diene compound (a).
4-hydroxystyrene and formaldehyde are taken as raw materials, and are refluxed with zinc nitrate hexahydrate for 24 hours to synthesize 2- (hydroxymethyl) -4-vinylphenol, and then methanol is taken as a solvent, AIBN is taken as an initiator, triethylamine is taken as a catalyst, and the mixture and pentaerythritol tetramercapto acetate are subjected to mercaptan-olefin click addition reaction to prepare the polyol compound (b).
Figure BDA0001933286640000672
Adding a certain amount of tetrahydrofuran solvent into a dry and clean reaction bottle, sealing, then carrying out deaeration for 1h by using argon bubbling, and then adding 0.01mol of diene compound (a), 0.01mol of pentaerythritol tetramercaptoacetate, 0.2 wt% of initiator AIBN and 5 wt% of triethylamine into the reaction bottle to be uniformly mixed. And heating the reaction bottle to 80 ℃, and reacting for 6h under the protection of nitrogen to obtain a first network.
Adding 0.02mol of boron tribromide into the reaction bottle, dropwise adding an appropriate amount of acetic acid aqueous solution, hydrolyzing for 30min, adding an appropriate amount of triethylamine, adjusting the pH value of the solution to 7.5-8, shaking and mixing for 10min, adding 0.01mol of polyol compound (c), shaking and mixing uniformly with 1 wt% of organic bentonite, reacting for 4h at 50 ℃ to obtain a dynamic polymer with a double network, pouring the reaction solution into an appropriate mold, placing in a vacuum oven at 60 ℃ for 24h for further reaction and drying, cooling to room temperature, and standing for 30min to obtain a blocky polymer sample with certain elasticity, wherein the blocky polymer sample is prepared into a dumbbell-shaped sample bar with the size of 80.0 × 10.0.0 10.0 × (2.0-4.0) mm, a tensile test is carried out by using a tensile testing machine, the tensile rate is 50mm/min, the tensile strength of the sample is 3.59 +/-1.15 MPa, the tensile modulus is 5.62 +/-1.73 MPa, the elongation at break is 150%, and the dynamic cross-linked polymer material can be recovered into sheets with good performance and can be processed into sheets.
Example 31
Using AIBN as an initiator, and carrying out free radical polymerization on 2, 3-dihydroxypropyl acrylate and vinyl pyrrolidone to obtain a 1, 2-diol-vinyl pyrrolidone copolymer; using AIBN as an initiator, and carrying out free radical polymerization on 4-acrylamide sodium phenylboronate and vinyl pyrrolidone to obtain a phenylboronic acid-vinyl pyrrolidone copolymer; taking AIBN as an initiator, and carrying out free radical polymerization on vinyl pyrrolidone, hydroxyethyl acrylate and 2-aminoethyl acrylate to obtain the vinyl pyrrolidone-hydroxyl-amino copolymer.
Weighing a certain amount of deionized water in a reaction bottle, adding 8mmol of vinyl pyrrolidone-hydroxyl-amino copolymer, 0.04mol of terephthalaldehyde and a proper amount of p-toluenesulfonic acid, stirring and dissolving completely, and carrying out reflux reaction at 65 ℃ for 6 hours under the protection of nitrogen to obtain a first network; and taking another reaction bottle, measuring a certain amount of deionized water, adding 5mmol of 1, 2-diol-vinyl pyrrolidone copolymer, stirring and dissolving completely, adding a proper amount of triethylamine, stirring and mixing uniformly, adding 5mmol of phenylboronic acid-vinyl pyrrolidone copolymer, heating to 50 ℃ for reaction for 1h, adding the obtained first network gel, swelling in the mixed solution, and continuing to react for 2h at 50 ℃. And after the reaction is finished, obtaining the hybrid cross-linked double-network hydrogel. In this example, the resulting polymeric hydrogel can be used as a liquid-absorbent liner material having both superabsorbent and pH-responsive properties, which can achieve self-healing and recycling of the gel under heat or different pH conditions.
Example 32
Adding a proper amount of 3,3 '-trithiocarbonate dipropionate and triphenylphosphine into a reaction bottle, adding an anhydrous tetrahydrofuran solution of hydroxyethyl acrylate under an anaerobic condition, then dropwise adding a toluene solution of ethyl azodicarboxylate, controlling the molar ratio of the 3, 3' -trithiocarbonate dipropionate to the hydroxyethyl acrylate to be 1:2, controlling the reaction temperature to be 10 ℃, and finishing the reaction after the dropwise addition is finished to obtain the diene compound (a) containing trithiocarbonate.
Figure BDA0001933286640000681
Taking potassium persulfate as an initiator, and carrying out free radical polymerization on N, N' -dimethylacrylamide and 2-acrylamide dopamine to obtain the acrylamide-dopamine copolymer.
Adding 200ml of deionized water into a dry and clean reaction bottle, adding 0.03mol of sodium borate, stirring and dissolving completely, adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, continuously mixing for 10min, adding 3mmol of acrylamide-dopamine copolymer, heating to 60 ℃, stirring and reacting for 3h to form a first network.
Weighing a certain amount of N, N '-dimethylacrylamide, dissolving the N, N' -dimethylacrylamide in deionized water to prepare a 1mol/L solution, adding 1 mol% of a cross-linking agent diene compound (a) and 0.6 mol% of an initiator potassium persulfate, stirring and mixing uniformly, standing for 1h to remove bubbles, placing in a constant-temperature water bath at 60 ℃ for reaction for 2h, swelling the obtained first network gel in the mixed solution, reacting at 80 ℃ for 3h, adding 5 wt% of graphene powder, performing ultrasonic treatment for 20min, continuing to react for 2h to obtain a graphene-dispersed double-network polymer sample, wherein the graphene-dispersed double-network polymer sample has good resilience, the graphene-dispersed double-network polymer sample is prepared into a block sample with the size of 20.0 × 20.0.0 20.0 × 20.0.0 mm, a compression performance test is performed by using a universal testing machine, the compression rate is 2mm/min, and the compression strength of the sample is measured to be 0.78 +/-0.25 MPa.
Example 33
1- (3-hydroxypropyl) -3, 6-dimethyl pyrimidine-2, 4-diketone and acryloyl chloride are used as raw materials to react to prepare the acrylic pyrimidone (a). And (b) carrying out free radical polymerization on the N-isopropyl acrylamide and the acrylic pyrimidone (a) by using AIBN as an initiator to obtain a pyrimidone-acrylamide copolymer (b). The silane-acrylamide copolymer (c) is obtained by radical polymerization of N-isopropylacrylamide and 3- (diethoxymethylsilyl) propyl-2-acrylate using AIBN as an initiator.
Figure BDA0001933286640000682
Weighing 5g of pyrimidone-acrylamide copolymer (b) in a dry and clean beaker, adding 40ml of deionized water, continuously stirring for dissolving at 50 ℃, adding 0.6g of ammonium metaborate after complete dissolution, adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, mixing for 10min, adding 3g of silane-acrylamide copolymer (c), continuously stirring for dissolving and mixing in the process, heating to 50 ℃ for reaction for 1h after complete dissolution, adding 5 wt% of nano-silver particles, 1 wt% of sodium dodecyl benzene sulfonate, performing ultrasonic treatment for 5min, continuously reacting for 2h at 50 ℃, continuously increasing the viscosity of the solution along with the reaction, heating for reaction for 2h to obtain a viscous polymer sample, and irradiating the viscous polymer sample for 2h under 300nm ultraviolet light. And after the reaction is finished, obtaining the double-network hydrogel polymer sample dispersed with the heat-conducting nano silver particles. In this embodiment, the polymer sample can be used as a composite heat conducting sheet, the heat conducting sheet can be pressed into products with different shapes and sizes according to the requirements, and can exhibit different heat conducting properties and self-repairing properties under different temperature and illumination frequency conditions, and the damaged or no longer needed sample can be recycled to be used as a new product.
Example 34
Using AIBN as an initiator, and using acrylic acid and 3-acrylamide phenylboronic acid to prepare an acrylic acid-phenylboronic acid copolymer through free radical copolymerization.
Adding 100ml of deionized water into a dry and clean reaction bottle, adding 2g of calcium borate and 12g of acrylic acid-phenylboronic acid copolymer, dropwise adding an appropriate amount of acetic acid for hydrolysis for 30min, then adding an appropriate amount of KOH aqueous solution, adjusting the pH value of the solution to 7.5-8, shaking and mixing for 10min, then adding 0.54g of pentaerythritol and 8g of polyvinyl alcohol, heating to 65 ℃, stirring and reacting for 4h, then introducing nitrogen for 1h, adding 4.5g of aldehyde-terminated polyethylene glycol and 0.02g of p-toluenesulfonic acid, stirring and mixing, reacting for 3h at 65 ℃ under the protection of nitrogen, adding 3g of carbon nanotube, 3g of active carbon and 0.03g of sodium dodecyl benzene sulfonate, shaking and mixing uniformly, continuing to react for 1h, then pouring the reaction solution into a suitable mold, placing in a vacuum oven at 60 ℃ for 24h for further reaction and drying, then cooling to room temperature and standing for 30min, the soft colloidal polymer material dispersed with the conductive filler is finally obtained, shows certain flexibility and good thermal stability, and can be self-repaired by heating.
Example 35
Hydroxyl-terminated methyl vinyl silicone oil with the molecular weight of about 3,000 and 3-mercapto-1-propanol are taken as raw materials, a proper amount of DMPA is added to be taken as a photoinitiator, and the modified silicone oil (a) is prepared through a thiol-ene click reaction under the condition of ultraviolet irradiation.
Figure BDA0001933286640000691
Adding 50ml of liquid paraffin, 20ml of modified silicone oil (a) and 0.03mol of tris (trimethylsilyl) borate into a dry and clean three-neck flask in sequence, dropwise adding a proper amount of acetic acid aqueous solution, hydrolyzing for 30min, then adding a proper amount of triethylamine and 0.12mol of siloxane compound (b), heating to 80 ℃, reacting for 4h, then adding, cooling to room temperature, and standing for 30min to finally obtain a polymer colloid with certain viscoelasticity. The polymer elastomer has low surface strength, good ductility and good moisture resistance. After the polymer sample is broken, stress is slightly applied to the section, the sample can be bonded by itself, and a good self-repairing effect is achieved. The obtained polymer colloid can be used as a recyclable electronic encapsulating material.
Example 36
Figure BDA0001933286640000692
Dissolving 10g of 9-anthracene methanol in 100ml of pyridine solvent, cooling in an ice bath under an inert atmosphere, adding 50ml of undecylenoyl chloride, and stirring at room temperature overnight to obtain an anthracene derivative (a); taking methyl mercapto silicone oil with molecular weight of about 60,000 and vinyl boric acid as raw materials, taking DMPA as a photoinitiator, and preparing boric acid grafted methyl mercapto silicone oil (b) through thiol-ene click reaction under the condition of ultraviolet irradiation; methyl mercapto silicone oil with molecular weight of about 60,000 and ethyl 5-hexene-1-yl carbamate are used as raw materials, DMPA is used as a photoinitiator, and under the condition of ultraviolet irradiation, through thiol-ene click reaction, methyl mercapto silicone oil (c) containing side hydrogen bond groups is prepared.
Adding 60ml of boric acid grafted methyl mercapto silicone oil (b) into a three-neck flask, heating to 80 ℃, uniformly stirring, adding 0.01 wt% of BHT antioxidant and a small amount of anhydrous sodium sulfate, heating to 80 ℃, reacting for 1h, then adding 30ml of methyl mercapto silicone oil (c) containing side hydrogen bond groups, continuously stirring and mixing for 1h, then adding 2g of anthracene derivative (a) and 0.2 wt% of photoinitiator DMPA, mixing and stirring for 1h, pouring the polymer into a proper mold, and irradiating for 30min by 365nm ultraviolet light under the nitrogen atmosphere to finally obtain a polymer sample with soft surface and certain viscosity. The polymer material has low surface strength, is easy to extend under the action of external force, shows good tensile toughness and can be stretched to a large extent without breaking. When the surface of the film has defects, the film is placed in a vacuum oven at 60 ℃ to be heated for 2-4h, and the defects disappear. In the embodiment, the dynamic bonds and hydrogen bonds in the dynamic polymer material can generate different dynamic response effects under the conditions of room temperature or ultraviolet irradiation, and the dynamic polymer material can be used as super hot melt adhesive or room temperature self-adhesive material with self-repairing property, and also can be used as a medium of a speed locker for bridge and road construction.
Example 37
The phenylboronic acid-diol graft modified silicone rubber is prepared by taking methyl vinyl silicone rubber, 3-mercapto-1, 2-propanediol and 4-mercaptophenylboronic acid pinacol as raw materials and DMPA as a photoinitiator through mercaptan-olefin click addition reaction under the ultraviolet irradiation condition.
Weighing 25g of phenylboronic acid-diol graft modified silicone rubber, 8g of white carbon black, 8g of titanium dioxide, 1.5g of ferric oxide, 0.15g of di-n-butyltin dilaurate and 0.03g of silicone oil, adding the mixture into a small internal mixer, mixing for 20min to ensure that an additive and a rubber material are fully mixed uniformly, taking out the mixed material, cooling, placing the mixture into a double-roller press to prepare a sheet, cooling at room temperature, cutting the sheet, soaking the sheet in 90 ℃ alkaline water for pre-crosslinking, placing the sheet in an 80 ℃ vacuum oven for 6h for further reaction and drying, remixing the dried mixed rubber, adding 1.0g of mercapto modified silicone oil, 0.03g of a photoinitiator DMPA, 0.75g of tetramethylammonium hydroxide, 0.25g of sodium trimethylsilanolate, 0.05g of an antioxidant 168 and 0.1g of an antioxidant 1010, continuously mixing for 20min at 120 ℃, carrying out heat treatment for 20min, forming under 10MPa, irradiating the obtained silicon rubber-based polymer material by using ultraviolet light at normal temperature for 10min to obtain a tensile rubber-based polymer material, preparing a tensile strength sample with a tensile strength of a tensile strength test sample of 354.854 mm, and heating the sample of the sample under normal pressure, wherein the tensile strength of the sample is measured by using an ultraviolet light, the tensile test sample is that the tensile strength of the sample is 20.7 mm, the tensile strength of the sample is measured by a tensile test sample under normal pressure is equal to the tensile test sample, and the tensile test sample, the tensile test sample is equal to be equal.
Example 38
Reacting 6-bromo-1-hexene with excessive sodium azide to obtain 6-azido-1-hexene; 1 molar equivalent of propargyl acrylate and 1 molar equivalent of 6-azido-1-hexene were reacted in cyclohexanone at 90 ℃ for 3 hours to obtain the diolefin compound (a).
Figure BDA0001933286640000701
Adding 20ml of methyl hydroxyl-terminated silicone oil and 0.03mol of ethylboric acid into a dry and clean three-neck flask, dropwise adding a proper amount of triethylamine, heating to 80 ℃ for reacting for 4h, then adding 50ml of methyl hydrogen-containing silicone oil (molecular weight is about 30,000), introducing nitrogen for 1h, then adding 5.8g of diene compound (a), 3g of 1, 11-dibromo-undecane and 2ml of 1% Pt (dvs) -xylene solution as a catalyst, heating to 80 ℃, continuing to react for 24h under the nitrogen protection condition, and then adding the obtained dynamic polymer colloid, wherein the surface of the obtained dynamic polymer colloid is soft and good in toughness, and can be slowly stretched and extended under the external stress. In this example, the dynamic polymer can maintain an elastic state for a long period of time, and the resulting polymer sample can be made into a toy with a magic viscous-elastic transition effect.
Example 39
Vinyl boric acid and hydrogen-terminated silicone oil with the viscosity of about 6,000mPa & s are used as raw materials, and hydrosilylation is carried out under the catalysis of a platinum-olefin complex Pt (dvs) to prepare the boric acid modified silicone oil.
And (2) putting dibenzoyl peroxide in a flask, drying in high vacuum for 15min, then uniformly mixing the dibenzoyl peroxide with octamethylcyclotetrasiloxane, heating to 120 ℃ to react for 2h, filtering the solution by using a neutral active aluminum sieve, and drying to obtain the dimeric cyclotetrasiloxane (a).
Figure BDA0001933286640000702
Adding 120ml of anhydrous toluene solvent into a dry and clean three-neck flask, adding 0.02mol of octamethylcyclotetrasiloxane and 2mmol of dicyclo-tetrasiloxane (a), heating to 110 ℃, rapidly adding a proper amount of tetramethylammonium hydroxide under a stirring state, and continuously reacting for 4 hours to obtain a first network. Adding 0.04mol of hydroxyl-terminated polysiloxane and a proper amount of triethylamine into a flask, stirring and mixing for 10min, adding 0.01mol of boric acid modified silicone oil, reacting for 4h under the protection of nitrogen at 80 ℃ to form a second network, pouring the obtained viscous cross-linked polymer into a proper mold, placing the mold in a vacuum oven at 60 ℃ for 12h for further reaction, cooling to room temperature, and placing for 30min to finally obtain the cross-linked polysiloxane elastomer with certain viscosity, wherein the cross-linked polysiloxane elastomer can be used for preparing polymer plugging rubber which has good plasticity and can be recycled and reused, and self-repairing of the surface can be realized at room temperature or under the condition of slight heating.
Example 40
Adding 0.1mol of diethanolamine and a certain amount of anhydrous methanol into a dry three-neck flask, uniformly stirring at room temperature, adding 0.2mol of methyl acrylate, stirring at 35 ℃ for 4h, vacuumizing to remove excessive methanol and methyl acrylate, reacting the mixture with trimethylolpropane in a dropwise manner at 115 ℃ under the catalysis of p-toluenesulfonic acid to obtain a primary intermediate product, reacting the primary intermediate product with 3- (bis (2-hydroxyethyl) amino) methyl propionate to obtain a secondary intermediate product, and blocking by using 3-propylene isocyanate to obtain the hyperbranched compound (a).
4-mercaptomethylbenzeneboronic acid and 3-mercapto-1, 2-propanediol in equimolar amount are used as raw materials, tetrahydrofuran is used as a solvent, and a dimercapto compound (b) containing a boronic ester bond is obtained through condensation reaction at the temperature of 60 ℃.
Figure BDA0001933286640000711
Adding 0.01mol of hyperbranched compound (a) into a dry and clean reaction bottle, adding 0.02mol of dimercapto compound (b), 0.01mol of 1, 8-octanedithiol, 0.02mol of trithiol compound (c) and 3mmol of 4-bromobenzenesulfonate (d), uniformly mixing, adding 0.2 wt% of photoinitiator DMPA, stirring and fully mixing, placing in an ultraviolet crosslinking instrument for 4 hours of ultraviolet radiation, placing the reactant in a proper mold, placing in a vacuum oven at 60 ℃ for 12 hours for further reaction and drying, cooling to room temperature, and placing for 30 minutes to finally obtain a dynamic polymer film, wherein the dynamic polymer film is prepared into a dumbbell type sample bar with the size of 80.0 × 10.0.0 10.0 × (0.08 +/-0.02) mm, and performing tensile test by using a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 4.13 +/-1.25 MPa, the tensile modulus is 7.68 +/-2.18 MPa, the elongation at break is 736 percent.
EXAMPLE 41
1-aminoethylboric acid and diethanol amine are used as raw materials, tetrahydrofuran is used as a solvent, the molar ratio of the raw materials to the tetrahydrofuran is controlled to be 1:2, and an amino-terminated compound (a) is obtained through condensation reaction at the temperature of 60 ℃.
1-aminoethylboric acid and 3-aminopropyldimethylmethoxysilane are used as raw materials, tetrahydrofuran is used as a solvent, the molar ratio of the raw materials to the tetrahydrofuran is controlled to be 1:2, and an amino-terminated compound (b) is obtained through condensation reaction at the temperature of 60 ℃.
Figure BDA0001933286640000712
Adding a certain amount of dichloroethane solvent into a dry and clean reaction bottle, adding 1, 10-bis (2-oxocyclohexyl) -1, 10-decanedione, 1, 4-butanediamine, 1,3, 5-tris (aminomethyl) -2,4, 6-triethylbenzene into the reaction bottle according to the molar ratio of 10:6:3, fully mixing, adding 6 mol% of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene and 5 mol% of zinc acetate as catalysts, heating to 100 ℃ for 24 hours, and reacting to obtain the 1 st network polymer. Then, 0.02mol of the amino-terminated compound (a), 0.02mol of the amino-terminated compound (b) and 0.05mol of 1, 8-octanediamine were added to the reaction flask, stirred and dissolved, then, 2ml of triethylamine was added to the mixture, and the mixture was uniformly mixed, 0.11mol of octanedioyl chloride was added dropwise, and further stirred and mixed to react for 6 hours. After the reaction is finished, the solvent is removed through reduced pressure drying, and then the polyamide-based polymer colloid is obtained through purification. The obtained polymer colloid not only shows excellent tensile toughness, but also has good plasticity and rebound resilience; the product of different shapes can be prepared according to the size of the mould, after the surface of the product is pressed, the concave part can be quickly recovered, and when the surface of the product is damaged, the product can be remolded through heating, so that the product can be recycled. The sealing strip can be used as a sealing strip and a sealing ring which can be self-repaired and recycled.
Example 42
The organic boric acid compound (a) is prepared by taking AIBN as an initiator and triethylamine as a catalyst and utilizing 4-pentenyl boric acid and 1, 6-hexanedithiol through a thiol-ene click reaction, wherein the molar ratio of the two is 2: 1.
Weighing 3g of terephthalaldehyde, dissolving in 50ml of absolute ethanol, adding 8.9g of diethyl malonate, 0.2g of piperidine and 0.2g of acetic acid, carrying out reflux reaction for 12 hours under the argon atmosphere, and then cooling and purifying to obtain a compound (b).
Figure BDA0001933286640000721
Weighing 5.0g of ethylene-vinyl alcohol copolymer and 1.0g of organic boric acid compound (a) in a reaction bottle, uniformly mixing, heating to 110 ℃ for reaction for 2h, then adding 2.0g of compound (b) and 1.6g of triethylenetetramine in the reaction bottle, uniformly stirring, cooling to room temperature, standing for 6h, heating to 50 ℃, and standing for 10h to finally obtain the crosslinked polymer film. The obtained polymer film has soft texture, certain strength and toughness, can be expanded within a certain range, and has certain tear resistance. The sample is recovered after being snapped, and is placed in a mold at 50 ℃ for attaching for 2-4h, so that the film can be formed again for repeated use, and the sample can be used as a recyclable packaging film by utilizing the property of the film.
Example 43
Figure BDA0001933286640000722
Trimethylolpropane and ethylene oxide are used as raw materials, boron trifluoride ethyl ether is used as a catalyst, and hydroxyl-terminated three-arm polyethylene oxide is synthesized through cationic ring-opening polymerization. Reacting quantitative diphenylmethane diisocyanate and polyoxypropylene glycol PPG-700 to prepare the isocyanate-terminated polyether.
Adding 0.04mol of hydroxyl-terminated three-arm polyethylene oxide into a dry and clean reaction bottle, heating to 80 ℃, vacuum dehydrating for 2h, adding 0.03mol of 1, 4-phenyl diboronic acid, adding a proper amount of triethylamine, stirring, mixing uniformly, heating to 80 ℃, reacting for 5h to form a first network, and crushing a product into small particles; and adding 0.01mol of bis-aza-carbene compound (a) and 0.04mol of isocyanate terminated polyether into another reaction bottle, heating to 60 ℃, reacting for 3 hours in a nitrogen atmosphere, adding 15g of first network polymer particles, 3g of foaming agent F141b, 0.24g of stearic acid, 0.06g of antioxidant 168 and 0.12g of antioxidant 1010, uniformly mixing, adding into a small internal mixer, and carrying out internal mixing and blending, wherein the mixing temperature is controlled to be below 40 ℃. After mixing, taking out the sample, putting the sample into a compression mold, closing the mold, pressurizing and heating, wherein the mold pressing temperature is 100-110 ℃, the mold pressing time is 15-20min, and the pressure is 10MPa, then taking out the sample, placing the sample in a vacuum oven at 80 ℃ for 6h for further reaction and drying, and finally obtaining the soft polyurethane foam material, wherein the foam pore diameter in the sample is uniform, the obtained polyurethane foam material can be used as a foam heat-insulating material to play a heat-insulating role for internal articles, and when cracks appear on the surface of the sample, the material can be placed under a heating condition to realize the self-repairing of the cracks.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (13)

1. A combination hybrid crosslinked dynamic polymer comprising at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and hydrogen bonds; the dynamic polymer contains at least one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-links in the at least one dynamic covalent cross-linked network reaches above a gel point; wherein, the existence of the boron-containing dynamic covalent bond, other dynamic covalent bonds and hydrogen bonds is a necessary condition for forming or maintaining a polymer structure.
2. The combined hybrid crosslinked dynamic polymer according to claim 1, wherein the combined hybrid crosslinked dynamic polymer has one of the following network structures:
the first method comprises the following steps: the combined hybrid crosslinked dynamic polymer only contains one dynamic covalent crosslinking network, and the crosslinking network simultaneously contains at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond and hydrogen bond crosslinking, and the crosslinking degree of the other dynamic covalent bond crosslinking is above the gel point;
and the second method comprises the following steps: the combined hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network which comprises at least one boron-containing dynamic covalent bond crosslink and the crosslinking degree of the boron-containing dynamic covalent bond crosslink reaches above a gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; and further comprising hydrogen bonding crosslinks in at least one of said dynamic covalent crosslink networks;
and the third is that: the combined hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network and simultaneously comprises at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink, and the crosslinking degree of the other dynamic covalent bond crosslinks is more than the gel point; the other crosslinking network is a hydrogen bond crosslinking network, wherein the crosslinking degree of the hydrogen bond crosslinking is above the gel point;
and fourthly: the combined hybrid crosslinked dynamic polymer contains three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network which contains at least one boron-containing dynamic covalent bond crosslink and the crosslinking degree of the boron-containing dynamic covalent bond crosslink reaches above a gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinking network is a hydrogen bond crosslinking network, wherein the crosslinking degree of the hydrogen bond crosslinking is above the gel point;
and a fifth mode: the combined hybrid crosslinked dynamic polymer only contains one dynamic covalent crosslinked network, and the crosslinked network contains at least one other dynamic covalent crosslinking and hydrogen bonding crosslinking, the crosslinking degree of the other dynamic covalent crosslinking is above the gel point, and the crosslinked network is dispersed with at least one non-crosslinked dynamic polymer containing boron-containing dynamic covalent bonding;
and a sixth mode: the combined hybrid crosslinked dynamic polymer only contains one dynamic covalent crosslinking network, and the crosslinking network contains at least one other dynamic covalent crosslinking and hydrogen bonding crosslinking, the crosslinking degree of the other dynamic covalent crosslinking is above the gel point, and dynamic polymer particles containing at least one boron-containing dynamic covalent bonding are dispersed in the crosslinking network.
3. A combination hybrid crosslinked dynamic polymer comprising at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond, and optionally hydrogen bonding; the dynamic polymer only contains one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-linked networks reaches above a gel point; wherein the presence of said boron-containing dynamic covalent bonds, other dynamic covalent bonds, optionally hydrogen bonds, are a necessary condition for forming or maintaining a polymer structure.
4. The combinatorial hybrid crosslinked dynamic polymer according to any of claims 1 to 3, wherein the boron-containing dynamic covalent bond is selected from the group consisting of organoborane bonds, inorganic boranhydride bonds, organic-inorganic boranhydride bonds, saturated five-membered ring organoboronate bonds, unsaturated five-membered ring organoboronate bonds, saturated six-membered ring organoboronate bonds, unsaturated six-membered ring organoboronate bonds, saturated five-membered ring inorganic boronic acid bonds, unsaturated five-membered ring inorganic boronic acid bonds, saturated six-membered ring inorganic boronic acid bonds, unsaturated six-membered ring inorganic boronic acid bonds, organoboronate mono-bonds, inorganic boronic acid mono-bonds, organoboronate silicone bonds, inorganic boronic acid silicone bonds.
5. The hybrid crosslinked dynamic polymer of claim 4, wherein the organoboron anhydride linkages are selected from at least one of the following structures:
Figure FDA0001933286630000021
wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond;
the inorganic boron anhydride linkage is selected from the following structures:
Figure FDA0001933286630000022
wherein, Y1、Y2、Y3、Y4Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, and Y1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, Y3、Y4At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a, b, c, d are each independently of Y1、Y2、Y3、Y4The number of connected connections; when Y is1、Y2、Y3、Y4When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b, c and d are 0; when Y is1、Y2、Y3、Y4When each is independently selected from oxygen atom and sulfur atom, a, b, c and d are 1; when Y is1、Y2、Y3、Y4When each is independently selected from nitrogen atom and boron atom, a, b, c and d are 2; when Y is1、Y2、Y3、Y4When each is independently selected from silicon atoms, a, b, c and d are 3;
the organic-inorganic boron anhydride linkage selected from the following structures:
Figure FDA0001933286630000023
wherein, Y1、Y2Each independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, oxygen atom, sulfur atom, nitrogen atom, boron atomA seed, a silicon atom, and Y1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a and b are each independently of Y1、Y2The number of connected connections; wherein, the boron atom in the structure is connected with at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; when Y is1、Y2When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a and b are 0; when Y is1、Y2When each is independently selected from oxygen atom and sulfur atom, a and b are 1; when Y is1、Y2When each is independently selected from nitrogen atom and boron atom, a and b are 2; when Y is5、Y6When each is independently selected from silicon atoms, a, b is 3;
the saturated five-membered ring organic boric acid ester bond is selected from the following structures:
Figure FDA0001933286630000031
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
the unsaturated five-membered ring organic boric acid ester bond is selected from the following structures:
Figure FDA0001933286630000032
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure FDA0001933286630000033
represents an aromatic ring with any number of elements, and the aromatic ring contains two adjacent carbon atoms which are positioned in an unsaturated five-membered ring organic borate bond;
the saturated six-membered ring organic boric acid ester bond is selected from the following structures:
Figure FDA0001933286630000034
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
the unsaturated six-membered ring organic boric acid ester bond is selected from the following structures:
Figure FDA0001933286630000035
wherein the boron atom is connected with a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond;
Figure FDA0001933286630000036
represents an aromatic ring of any number of elements, and the aromatic ring contains two adjacent carbon atoms, which are located in an unsaturated six-membered ring organoboronate bond;
the saturated five-membered ring inorganic borate ester bond is selected from at least one of the following structures:
Figure FDA0001933286630000037
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a represents a group represented by the formula1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3;
the unsaturated five-membered ring inorganic borate ester bond is selected from at least one of the following structures:
Figure FDA0001933286630000041
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a represents a group represented by the formula1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3;
Figure FDA0001933286630000042
represents an aromatic ring with any number of elements, and the aromatic ring contains two adjacent carbon atoms which are positioned in an unsaturated five-membered ring inorganic borate bond;
the saturated six-membered ring inorganic borate ester bond is selected from at least one of the following structures:
Figure FDA0001933286630000043
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a represents a group represented by the formula1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3;
the unsaturated six-membered ring inorganic borate ester bond is selected from at least one of the following structures:
Figure FDA0001933286630000044
wherein, Y1Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a represents a group represented by the formula1The number of connected connections; when Y is1When the atom is selected from oxygen atom and sulfur atom, a is 1; when Y is1When the atom is selected from nitrogen atom and boron atom, a is 2; when Y is1When selected from silicon atoms, a is 3;
Figure FDA0001933286630000045
aromatic of arbitrary numberA ring, and the aromatic ring contains two adjacent carbon atoms, which are located in an unsaturated six-membered ring inorganic borate bond;
the organic boric acid monoester bond is selected from at least one of the following structures:
Figure FDA0001933286630000046
wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond; i is1Selected from divalent linking groups; i is2Selected from the group consisting of a double bond directly to two carbon atoms, a trivalent carbene group directly to two carbon atoms, a divalent non-carbon atom, a linking group comprising at least two backbone atoms;
Figure FDA0001933286630000047
an aromatic ring having an arbitrary number of elements; wherein, the organic boric acid monoester bonds formed after the 6 and 7 structures are formed into rings are not the saturated five-membered ring organic boric acid ester bond, the unsaturated five-membered ring organic boric acid ester bond, the saturated six-membered ring organic boric acid ester bond and the unsaturated six-membered ring organic boric acid ester bond;
the inorganic boric acid monoester bond is selected from at least one of the following structures:
Figure FDA0001933286630000051
wherein, Y1～Y13Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, and Y1、Y2；Y3、Y4；Y5、Y6、Y7、Y8；Y9、Y10、Y11、Y12At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; y is14Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom,A silicon atom; i is1Selected from divalent linking groups; i is2Selected from the group consisting of a double bond directly to two carbon atoms, a trivalent carbene group directly to two carbon atoms, a divalent non-carbon atom, a linking group comprising at least two backbone atoms; wherein a to n each represents Y1～Y14The number of connected connections; when Y is1～Y13When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a-m is 0; when Y is1～Y14When each is independently selected from oxygen atom and sulfur atom, a to n are 1; when Y is1～Y14When each is independently selected from nitrogen atom and boron atom, a to n are 2; when Y is1～Y14Each independently selected from silicon atoms, a to n is 3;
Figure FDA0001933286630000052
an aromatic ring having an arbitrary number of elements; wherein, the inorganic boric acid monoester bonds formed after the structures of 5,6, 7 and 8 are cyclized are not the saturated five-membered ring inorganic boric acid ester bond, the unsaturated five-membered ring inorganic boric acid ester bond, the saturated six-membered ring inorganic boric acid ester bond and the unsaturated six-membered ring inorganic boric acid ester bond;
the organic borate silicone bond is selected from at least one of the following structures:
Figure FDA0001933286630000053
wherein the boron atom is linked to at least one carbon atom by a boron-carbon bond and at least one organic group is linked to the boron atom by said boron-carbon bond;
the inorganic borate silicon ester bond is selected from at least one of the following structures:
Figure FDA0001933286630000054
wherein, Y1、Y2、Y3Each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom,Oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom, and Y1、Y2At least one selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom; wherein a, b and c are each independently of Y1、Y2、Y3The number of connected connections; when Y is1、Y2、Y3When each is independently selected from hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom, a, b and c are 0; when Y is1、Y2、Y3When the atom is selected from oxygen atom and sulfur atom, a, b and c are 1; when Y is1、Y2、Y3When the atoms are selected from nitrogen atoms and boron atoms, a, b and c are 2; when Y is1、Y2、Y3When each is independently selected from silicon atoms, a, b and c are 3.
6. The combinatorial hybrid crosslinked dynamic polymer according to any of claims 1 to 3, wherein the other dynamic covalent bonds are selected from the group consisting of dynamic sulfide bonds, dynamic diselenide bonds, dynamic selenazone bonds, dynamic acetal-like bonds, dynamic imine bonds, dynamic oxime bonds, dynamic hydrazone bonds, dynamic covalent bonds based on reversible free radicals, exchangeable acyl bonds for bonding, dynamic covalent bonds induced based on steric effects, reversible addition fragmentation chain transfer dynamic covalent bonds, dynamic siloxane bonds, dynamic silicon ether bonds, exchangeable dynamic covalent bonds based on alkyltriazolium, unsaturated carbon-carbon double bonds capable of undergoing olefin cross metathesis reactions, unsaturated carbon-carbon triple bonds capable of undergoing cross alkyne metathesis reactions, [2+2] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, A mercapto-michael addition dynamic covalent bond, an amine alkene-michael addition dynamic covalent bond, a triazolinedione-indole based dynamic covalent bond, a diazacarbene based dynamic covalent bond, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkylsulfonium bond.
7. The hybrid crosslinked dynamic polymer according to claim 6, wherein the dynamic sulfur linkage is selected from the following structures:
Figure FDA0001933286630000061
wherein x is the number of S atoms and is more than or equal to 2;
the dynamic double selenium bond is selected from the following structures:
Figure FDA0001933286630000062
the dynamic selenium-nitrogen bond is selected from the following structures:
Figure FDA0001933286630000063
wherein X is selected from halide ions;
the dynamic acetal-like bond is selected from at least one of the following structures:
Figure FDA0001933286630000064
wherein, X1、X2、X3、X4Each independently selected from oxygen atom, sulfur atom, nitrogen atom; r1、R2Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; r3、R4Each independently selected from the group consisting of a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group, a divalent or polyvalent polymer chain residue;
the dynamic imine bond selected from the following structures:
Figure FDA0001933286630000065
wherein R is1Is a divalent or polyvalent small molecule hydrocarbon group;
the dynamic hydrazone bond is selected from at least one of the following structures:
Figure FDA0001933286630000071
the dynamic covalent bond based on the reversible free radical is selected from at least one of the following structures:
Figure FDA0001933286630000072
wherein, X1、X2Is a sterically hindered divalent or polyvalent radical directly bonded to the nitrogen atom, each of which is independently selected from divalent or polyvalent C3-20Alkyl, divalent or polyvalent cyclic C3-20Alkyl, phenyl, benzyl, aromatic, carbonyl, sulfone, phosphate, and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof; r' is a group directly linked to a carbon atom, each independently selected from a hydrogen atom, C3-20Alkyl, ring C3-20Alkyl, phenyl, benzyl, aromatic and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof; wherein each W is independently selected from an oxygen atom, a sulfur atom; w1Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups, and substituents thereof; w2Each independently selected from the group consisting of ether groups, thioether groups, secondary amine groups and substituents thereof, carbonyl groups, thiocarbonyl groups, divalent methyl groups and substituents thereof; w3Each independently selected from ether groups, thioether groups; w4Each independently selected from the group consisting of a direct bond, an ether group, a thioether group, a secondary amine group and substituents thereof, a carbonyl group, a thiocarbonyl group, a divalent methyl group and substituents thereof; w, W at different locations1、W2、W3、W4The structures of (A) are the same or different; wherein R is1Each independently selected from hydrogen atom, halogen atom, hetero atom group, small molecule hydrocarbon group, polymer chain residue, R at different positions1The same or different; wherein R is2Each independently selected from hydrogen atom, cyano group, hydroxy group, phenyl group, phenoxy group, C1-10Alkyl radical, C1-10Alkoxy radical, C1-10Alkoxyacyl group, C1-10An alkyl acyloxy group,Trimethylsiloxy, triethylsiloxy; wherein, L 'is a divalent linking group selected from a single bond, a heteroatom linking group and a divalent small molecule hydrocarbon group, and L' at different positions is the same or different; wherein V, V ' are each independently selected from carbon atom, nitrogen atom, V, V ' at different positions are the same or different, and when V, V ' is selected from nitrogen atom, it is connected to V, V
Figure FDA0001933286630000073
Is absent; wherein the content of the first and second substances,
Figure FDA0001933286630000074
the cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms;
the binding exchangeable acyl bond is selected from at least one of the following structures:
Figure FDA0001933286630000075
wherein, X1、X2Selected from carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms and silicon atoms; y is selected from the group consisting of an oxygen atom, a sulfur atom and a secondary amine group; z1、Z2Selected from oxygen atom, sulfur atom; r5Selected from the group consisting of hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein, when X1、X2When it is an oxygen atom or a sulfur atom, R1、R2、R3、R4Is absent; when X is present1、X2When it is a nitrogen atom, R1、R3Exist, R2、R4Is absent, and R1、R3Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present1、X2When it is a carbon atom or a silicon atom, R1、R2、R3、R4Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymersChain residues;
the dynamic covalent bond based on steric effect induction is selected from at least one of the following structures:
Figure FDA0001933286630000081
wherein, X1、X2Selected from carbon atoms, silicon atoms and nitrogen atoms; z1、Z2Selected from oxygen atoms and sulfur atoms; when X is present1、X2When it is a nitrogen atom, R1、R3Exist, R2、R4Is absent, and R1、R3Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X is present1、X2When it is a carbon atom or a silicon atom, R1、R2、R3、R4Are present and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; wherein R isbIs a bulky group with steric effect directly connected with nitrogen atom and selected from C3-20Alkyl, ring C3-20Alkyl, phenyl, benzyl, aromatic and unsaturated forms, substituted forms, hybridized forms of the above groups, and combinations thereof;
the reversible addition fragmentation chain transfer dynamic covalent bond is selected from at least one of the following structures:
Figure FDA0001933286630000082
wherein R is1～R10Each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; x1、X2、X3Each independently selected from single bond, divalent or polyvalent small molecule alkyl; z1、Z2、Z3Each independently selected from single bonds, heteroatom linking groups, divalent or polyvalent small molecule hydrocarbon groups;
the dynamic siloxane bond is selected from the following structures:
Figure FDA0001933286630000083
the dynamic silicon ether bond is selected from the following structures:
Figure FDA0001933286630000084
the alkyl triazolium-based exchangeable dynamic covalent bond is selected from the following structures:
Figure FDA0001933286630000085
wherein, X—Is negative ion selected from bromide ion and iodide ion;
the unsaturated carbon-carbon double bond capable of olefin cross metathesis reaction is selected from the following structures:
Figure FDA0001933286630000086
the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross metathesis reaction is selected from the following structures:
Figure FDA0001933286630000087
the [2+2] cycloaddition dynamic covalent bond is selected from at least one of the following structures:
Figure FDA0001933286630000091
wherein D is1～D6Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, D1、D2At least one of them is selected from carbon atoms or nitrogen atoms; a is1～a6Respectively represent with D1～D6Is connected withConnecting the number; when D is present1～D6Each independently selected from an oxygen atom and a sulfur atom1～a60; when D is present1～D6Each independently selected from nitrogen atoms, a1～a61 is ═ 1; when D is present1～D6Each independently selected from carbon atoms, a1～a6＝2；Q1～Q6Each independently selected from carbon atoms, oxygen atoms; b1～b6Respectively represent and Q1～Q6The number of connected connections; when Q is1～Q6Each independently selected from oxygen atoms, b1～b60; when Q is1～Q6Each independently selected from carbon atoms, b1～b6＝2；
The [4+2] cycloaddition dynamic covalent bond is selected from at least one of the following structures:
Figure FDA0001933286630000092
wherein, K1、K2、K5～K10Each independently selected from carbon atom, oxygen atom, sulfur atom, nitrogen atom, and at K1、K2Or K5、K6Or K7、K8Or K9、K10At least one atom selected from carbon atom or nitrogen atom; c. C1～c10Respectively represent and K1～K10The number of connected connections; when K is1、K2、K5～K10Each independently selected from an oxygen atom and a sulfur atom, c1、c2、c5～c100; when K is1、K2、K5～K10Each independently selected from nitrogen atoms, c1、c2、c5～c101 is ═ 1; when K is1、K2、K5～K10Each independently selected from carbon atoms, c1、c2、c5～c10＝2；K3、K4Each independently selected from the group consisting of pro-oxygensA sulfur atom, a nitrogen atom; c. C3、c4Respectively represent and K3、K4The number of connected connections; when K is3、K4Each independently selected from an oxygen atom and a sulfur atom, c3、c40; when K is3、K4Each independently selected from nitrogen atoms, c3、c4＝1；I1、I2Each independently selected from oxygen atom, sulfur atom, secondary amine group and substitution form thereof, amide group, ester group, divalent small molecule alkyl;
Figure FDA0001933286630000093
the cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms; n represents the number of linkages to the ring-forming atoms of the cyclic group structure;
the [4+4] cycloaddition dynamic covalent bond is selected from at least one of the following structures:
Figure FDA0001933286630000101
wherein the content of the first and second substances,
Figure FDA0001933286630000102
the cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are independently selected from carbon atoms, nitrogen atoms or other hetero atoms; i is6～I14Each independently selected from oxygen atom, sulfur atom, amido, ester group, imino, divalent small molecule alkyl;
the dynamic covalent bond of the mercapto-Michael addition is selected from at least one of the following structures:
Figure FDA0001933286630000103
wherein X is selected from ketone group, ester group, amide group, thiocarbonyl group and sulfone group; y is an electron withdrawing effect group selected from the group consisting of aldehyde groups, carboxyl groups, nitro groups, phosphate groups, sulfonic acid groups, amide groups, sulfone groups, trifluoromethyl groups, cyano groups, halogen atoms, and combinations thereof;
the amine alkene-Michael addition dynamic covalent bond is selected from the following structures:
Figure FDA0001933286630000104
the dynamic covalent bond based on triazolinedione-indole is selected from the following structures:
Figure FDA0001933286630000105
the dynamic covalent bond based on the diazacarbene is selected from at least one of the following structures:
Figure FDA0001933286630000106
the hexahydrotriazine dynamic covalent bond is selected from at least one of the following structures:
Figure FDA0001933286630000107
the dynamically exchangeable trialkylsulfonium linkage is selected from the following structures:
Figure FDA0001933286630000111
wherein, X—Selected from the group consisting of sulfonate salts.
8. The combined hybrid crosslinked dynamic polymer according to any of claims 1 to 3 wherein the boron-containing dynamic covalent bonds and other dynamic covalent bonds are selected from the group consisting of:
combination 1: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicone bond; at least one of a dynamic linkage, a dynamic diselenide linkage, a dynamic covalent linkage based on reversible radicals, a binding exchangeable acyl linkage, a dynamic covalent linkage based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent linkage, a dynamic silicon ether linkage, an exchangeable dynamic covalent linkage based on alkyltriazolium, a [2+2] cycloaddition dynamic covalent linkage, a [2+4] cycloaddition dynamic covalent linkage, a [4+4] cycloaddition dynamic covalent linkage, a mercapto-michael addition dynamic covalent linkage, a dynamic covalent linkage based on triazolinedione-indole, an aminoalkene-michael addition dynamic covalent linkage, a dynamic covalent linkage based on diazacarbene, a dynamic exchangeable trialkylsulfonium linkage combination;
and (3) combination 2: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one of a dynamic selenium-nitrogen bond, an acetal dynamic covalent bond, a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond, a hexahydrotriazine dynamic covalent bond, and an amine alkene-Michael addition dynamic covalent bond combination;
and (3) combination: at least one of saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond, organic boric acid monoester bond and organic boric acid silicon ester bond combination; at least one of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, a triazolinedione-indole-based dynamic covalent bond combination;
and (4) combination: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one of a dynamic linkage, a dynamic diselenide linkage, a dynamic covalent linkage based on reversible radicals, a binding exchangeable acyl linkage, a dynamic covalent linkage based on steric effect induction, a reversible addition fragmentation chain transfer dynamic covalent linkage, a dynamic silicon ether linkage, an exchangeable dynamic covalent linkage based on alkyltriazolium, a [2+2] cycloaddition dynamic covalent linkage, a [2+4] cycloaddition dynamic covalent linkage, a [4+4] cycloaddition dynamic covalent linkage, a mercapto-michael addition dynamic covalent linkage, a dynamic covalent linkage based on triazolinedione-indole, an aminoalkene-michael addition dynamic covalent linkage, a dynamic covalent linkage based on diazacarbene, a dynamic exchangeable trialkylsulfonium linkage combination;
and (3) combination 5: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one of a dynamic selenium-nitrogen bond, an acetal dynamic covalent bond, a dynamic imine bond, a dynamic oxime bond, a dynamic hydrazone bond, a hexahydrotriazine dynamic covalent bond, and an amine alkene-Michael addition dynamic covalent bond combination;
and (4) combination 6: at least one of the combination of inorganic boron anhydride bond, saturated five-membered ring inorganic borate bond, unsaturated five-membered ring inorganic borate bond, saturated six-membered ring inorganic borate bond, unsaturated six-membered ring inorganic borate bond, inorganic borate single-ester bond and inorganic borate silicon ester bond; at least one member selected from the group consisting of a dynamic siloxane bond, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [2+4] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-michael addition dynamic covalent bond, and a triazolinedione-indole-based dynamic covalent bond.
9. A composite hybrid crosslinked dynamic polymer comprising at least one boron-containing dynamic covalent bond, at least one other dynamic covalent bond; the dynamic polymer contains at least one dynamic covalent cross-linked network, and the cross-linking degree of other dynamic covalent cross-links in the at least one dynamic covalent cross-linked network reaches above a gel point; wherein the other dynamic covalent bond is selected from the group consisting of a dynamic sulfide bond, a dynamic diselenide bond, a dynamic selenazone bond, a dynamic acetal bond, a dynamic imine bond, a dynamic hydrazone bond, a dynamic covalent bond based on a reversible radical, an associative exchangeable acyl bond, a dynamic covalent bond induced based on steric hindrance, a reversible addition fragmentation chain transfer dynamic covalent bond, a dynamic siloxane bond, a dynamic silicon ether bond, an exchangeable dynamic covalent bond based on alkyltriazolium, an unsaturated carbon-carbon double bond capable of olefin cross-metathesis, an unsaturated carbon-carbon triple bond capable of alkyne cross-metathesis, a [2+2] cycloaddition dynamic covalent bond, a [4+4] cycloaddition dynamic covalent bond, a mercapto-Michael addition dynamic covalent bond, an aminoalkene-Michael addition dynamic covalent bond, a, A dynamic covalent bond based on triazolinedione-indole, a dynamic covalent bond based on diazacarbene, a hexahydrotriazine dynamic covalent bond, and a dynamic exchangeable trialkyl sulfonium bond; wherein the presence of said boron-containing dynamic covalent bond, or other dynamic covalent bond, is a requirement for forming or maintaining a polymer structure.
10. The combined hybrid crosslinked dynamic polymer according to claim 9, wherein the combined hybrid crosslinked dynamic polymer has one of the following network structures:
the first method comprises the following steps: the combined hybrid crosslinked dynamic polymer only contains one dynamic covalent crosslinking network, and the crosslinking network simultaneously contains at least one boron-containing dynamic covalent bond and at least one other dynamic covalent bond crosslinking, and the crosslinking degree of the other dynamic covalent bond crosslinking is above the gel point;
and the second method comprises the following steps: the combined hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network which comprises at least one boron-containing dynamic covalent bond crosslink and the crosslinking degree of the boron-containing dynamic covalent bond crosslink reaches above a gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point;
and the third is that: the combined hybrid crosslinked dynamic polymer contains three crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network which contains at least one boron-containing dynamic covalent bond crosslink and the crosslinking degree of the boron-containing dynamic covalent bond crosslink reaches above a gel point; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point; the last crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the last crosslinking network reaches above the gel point;
and fourthly: the combined hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network is a dynamic covalent crosslinked network and simultaneously comprises at least one boron-containing dynamic covalent bond crosslink and at least one other dynamic covalent bond crosslink; the other crosslinking network is a dynamic covalent crosslinking network which contains at least one other dynamic covalent crosslinking and the crosslinking degree of the other crosslinking network reaches above the gel point;
and a fifth mode: the combined hybrid crosslinked dynamic polymer only contains one dynamic covalent crosslinked network, and the crosslinked network contains at least one other dynamic covalent bond crosslink, the crosslinking degree of the other dynamic covalent bond crosslink is above the gel point, and the non-crosslinked dynamic polymer containing at least one boron-containing dynamic covalent bond is dispersed in the crosslinked network;
and a sixth mode: the combined hybrid crosslinked dynamic polymer only contains one dynamic covalent crosslinking network, and at least one other dynamic covalent crosslinking is contained in the crosslinking network, the crosslinking degree of the other dynamic covalent crosslinking is above the gel point, and dynamic polymer particles containing at least one boron-containing dynamic covalent crosslinking are dispersed in the crosslinking network.
11. The combined hybrid crosslinked dynamic polymer according to any one of claims 1,3 and 9, wherein the formulation components constituting the combined hybrid crosslinked dynamic polymer composition comprise any one or more of the following additives/additives: auxiliaries/additives, fillers;
wherein, the auxiliary agent/additive is selected from any one or more of the following components: catalysts, initiators, redox agents, antioxidants, light stabilizers, heat stabilizers, toughening agents, lubricants, mold release agents, plasticizers, foaming agents, dynamic modifiers, antistatic agents, emulsifiers, dispersants, colorants, fluorescent whitening agents, delustering agents, flame retardants, nucleating agents, rheological agents, thickeners, and leveling agents;
wherein, the filler is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers, organometallic compound fillers.
12. The combined hybrid crosslinked dynamic polymer according to any of claims 1,3, 9, characterized in that the morphology of the combined hybrid crosslinked dynamic polymer has any of the following: common solids, elastomers, gels, foams.
13. The hybrid cross-linked dynamic polymer according to any one of claims 1,3 and 9, wherein it is applied to self-healing coatings, self-healing sheet materials, self-healing adhesives, sealing materials, tough materials, energy storage device materials, interlayer adhesives, toys, shape memory materials.
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