CN111040203A

CN111040203A - Energy absorption method based on hybrid cross-linked dynamic polymer

Info

Publication number: CN111040203A
Application number: CN201910000075.2A
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Daimeng Sports Technology Co.,Ltd.
Priority date: 2019-01-01
Filing date: 2019-01-01
Publication date: 2020-04-21

Abstract

The invention discloses an energy absorption method based on a hybrid cross-linked dynamic polymer, wherein the hybrid cross-linked dynamic polymer contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect and common covalent cross-links formed by common covalent bonds, wherein the gel point of the common covalent cross-links in at least one cross-linking network is more than that of the common covalent cross-links. The dynamic polymer combines the respective advantages of boron-containing dynamic covalent bonds, supramolecular action and common covalent crosslinking, and has excellent energy dissipation, dispersion, absorption and other characteristics when the polymer is subjected to physical impact through regulating and controlling the structure of a reactant. The dynamic polymer is used as an energy absorption material for energy absorption, and can play roles in damping, buffering, impact resistance protection, shock absorption, noise elimination, sound insulation and the like.

Description

Energy absorption method based on hybrid cross-linked dynamic polymer

Technical Field

The invention relates to an energy absorption method, in particular to an energy absorption method based on a hybrid cross-linked dynamic polymer.

Background

In daily life and actual production processes, methods or means are often needed to avoid or mitigate the influence caused by physical impact in the forms of impact, vibration, shock, explosion, sound and the like, wherein the energy absorption material is widely applied to absorb energy, so that the physical impact is effectively protected. The materials for absorbing energy are mainly metals, polymers, composite materials and the like. The energy loss sources of the polymer material are mainly the following: 1. energy is absorbed by the phenomenon that polymers have a high dissipation factor near their glass transition temperature. In the method, because the material is near the glass-transition temperature, the mechanical property of the material is sensitive to the temperature change, and the mechanical property of the material is easy to change violently along with the change of the environmental temperature in the use process, which brings difficulty to the use; 2. the energy absorption is carried out by utilizing the processes of breaking chemical bonds such as covalent bonds and the like, generating cracks in the material and even breaking the whole material, and the like, in the processes, the breaking of the covalent bonds, the macroscopic cracks and the breaking can not be recovered, and the mechanical property of the material is reduced, and after one or a few times of energy absorption processes, the material must be replaced in time to maintain the original property; 3. the method generally needs the material to generate large deformation to generate obvious effect by utilizing the deformation, particularly the internal friction energy absorption between molecular chain segments caused by the large deformation of the rubber state or the viscoelastic state of the polymer, and after the material generates the deformation with high energy loss, the material can not be recovered to the original shape, can not be used continuously and needs to be replaced. The novel impact-resistant and energy-absorbing material is a novel material proposed in recent years, and the appearance of the novel impact-resistant and energy-absorbing material has important practical value for the selection of the material and the performance research thereof. The impact-resistant energy-absorbing material with different configurations has excellent mechanical, bearing, impact-resistant and energy-absorbing characteristics, and also has other functions of damping, vibration reduction, sound absorption and noise reduction, stimulus response and the like, so that the requirements of high and new technical fields such as aviation, precise instruments, automobile industry and the like on the material are met.

In the prior art, common structures of polymer materials used as energy absorption materials are polymer alloys, polymer interpenetrating networks, polymer elastomers and the like designed based on the various energy loss mechanisms. These structures for energy absorption are usually simple superposition of the above mechanisms, and compared with a single mechanism, although the energy absorption range is expanded to a certain extent and the energy absorption efficiency is improved, the defects thereof cannot be avoided. Therefore, there is a need to develop a new energy absorption method and material, especially a polymer with a new energy absorption and loss mechanism to solve the problems in the prior art.

Disclosure of Invention

The invention provides an energy absorption method based on a hybrid cross-linked dynamic polymer, aiming at the background, the hybrid cross-linked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect and common covalent cross-links formed by common covalent bonds, wherein the common covalent cross-links reach the gel point of the common covalent cross-links in at least one cross-linking network. The dynamic polymer has good mechanical strength and certain toughness, simultaneously shows good dynamic reversibility, and can show the functional characteristics of self-repairing property, plasticity, shock absorption, shock resistance and the like.

The invention is realized by the following technical scheme:

the invention relates to an energy absorption method based on a hybrid cross-linked dynamic polymer, which is characterized in that the hybrid cross-linked dynamic polymer is provided and used as an energy absorption material for energy absorption; wherein the hybrid cross-linked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction and common covalent cross-links formed by common covalent bonds, wherein the common covalent cross-links reach above the gel point of the common covalent cross-links in at least one cross-linked network.

The hybrid crosslinked dynamic polymer of the present invention optionally contains hydrogen bonding, wherein the hydrogen bonding may be intra-chain non-crosslinking and/or inter-chain crosslinking and/or non-crosslinking.

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.

Non-hydrogen bonded supramolecular interactions described in the present invention include, but are not limited to, metal-ligand interactions, ionic interactions, ion-dipole interactions, host-guest interactions, metallophilic interactions, dipole-dipole interactions, halogen-bond interactions, lewis acid-base pair interactions, cation-pi interactions, anion-pi interactions, benzene-fluorobenzene interactions, pi-pi stacking interactions, ionic hydrogen bonding interactions, radical cation dimerization interactions, phase separation interactions, crystallization interactions.

In embodiments of the invention, the optional hydrogen bond may be generated by the presence of a non-covalent interaction 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 optional hydrogen bond is formed by hydrogen bond groups present at any one or more of the dynamic polymer chain backbone (including main chain and side chain/branch/branched chain backbone), side group, and end group. Wherein said hydrogen bonding groups may also be present in said dynamic polymer composition, such as a small molecule compound or filler.

In embodiments of the invention, the hybrid crosslinked dynamic polymer may be comprised of one or more crosslinked networks. When the hybrid cross-linked dynamic polymer is composed of only one cross-linked network, it is preferable that both the boron-containing dynamic covalent bond and the non-hydrogen bond type supramolecular interaction are contained in the cross-linked network structure. When the hybrid crosslinked 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 crosslinked networks, but the present invention is not limited thereto.

According to a preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond and an unsaturated six-membered ring organic borate bond.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring inorganic borate bond, an unsaturated five-membered ring inorganic borate bond, a saturated six-membered ring inorganic borate bond and an unsaturated six-membered ring inorganic borate bond.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein, the boron-containing dynamic covalent bond is selected from organic boric acid monoester bond, organic boric acid silicon ester bond, inorganic boric acid monoester bond and inorganic boric acid silicon ester bond.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one metal-ligand action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one ionic action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one ion-dipole effect and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one host-guest action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one Lewis acid-base pair effect and common covalent cross-linking formed by the common covalent bond, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one pi-pi stacking function and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above a gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond, an unsaturated six-membered ring organic borate bond, an organic borate single-ester bond and an organic borate silicon ester bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, and pi-pi stacking interaction.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from 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 monoester bond and inorganic borate silicon bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, Lewis acid-base pair interaction, and pi-pi stacking interaction.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network only comprises common covalent cross-links formed by common covalent bonds, and the cross-linking degree of the common covalent cross-links is above the gel point, the other cross-linked network comprises dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond and supramolecular cross-links formed by at least one non-hydrogen bond type supramolecular interaction and optionally at least one hydrogen bond interaction, and the sum of the cross-linking degrees of the dynamic covalent cross-links and the supramolecular cross-links is above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is above the gel point, and the other cross-linked network comprises supramolecular cross-linking formed by at least one non-hydrogen bond type supramolecular interaction and optionally at least one hydrogen bond interaction, and the cross-linking degree of the supramolecular cross-linking is above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network simultaneously comprises at least one non-hydrogen bond type supermolecule effect and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is above the gel point, the other cross-linked network comprises dynamic covalent cross-linking formed by at least one boron-containing dynamic covalent bond, and the cross-linking degree of the dynamic covalent cross-linking is above the gel point, and at least one hydrogen bond effect is optionally contained in at least one cross-linked network.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent crosslinks formed by common covalent bonds with the degree of crosslinking of the common covalent crosslinks being above the gel point, the other crosslinked network simultaneously comprises at least one non-hydrogen bond type supramolecular interaction and common covalent crosslinks formed by common covalent bonds with the degree of crosslinking of the common covalent crosslinks being above the gel point, and optionally at least one hydrogen bond interaction in the at least one crosslinked network.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network only comprises common covalent cross-links formed by common covalent bonds and has a cross-linking degree of the common covalent cross-links above the gel point, the other cross-linked network comprises dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond and has a cross-linking degree of the dynamic covalent cross-links above the gel point, the last cross-linked network comprises supramolecular cross-links formed by at least one non-hydrogen bond type supermolecule interaction and has a cross-linking degree of the supramolecular cross-links above the gel point, and at least one hydrogen bond interaction is optionally contained in at least one cross-linked network.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network only comprises common covalent cross-links formed by common covalent bonds, and the cross-linking degree of the common covalent cross-links is above the gel point, the other cross-linked network comprises dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond, and the sum of the cross-linking degrees of the dynamic covalent cross-links and the supramolecular cross-links formed by at least one non-hydrogen bond type supramolecular action is above the gel point, and the last cross-linked network comprises supramolecular cross-links formed by at least one hydrogen bond action, and the cross-linking degree of the supramolecular cross-links is above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is higher than the gel point of the hybrid cross-linked dynamic polymer, the other cross-linked network comprises supramolecular cross-linking formed by at least one non-hydrogen bond type supramolecular interaction, and the cross-linking degree of the supramolecular cross-linking is higher than the gel point of the hybrid cross-linked dynamic polymer, and the last cross-linked network comprises supramolecular cross-linking formed by at least one hydrogen bond interaction, and the cross-linking degree of the supramolecul.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network simultaneously contains at least one non-hydrogen bond type supramolecular function and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is higher than the gel point of the cross-linked network, the other cross-linked network contains dynamic covalent cross-linking formed by at least one boron-containing dynamic covalent bond, and the cross-linking degree of the dynamic covalent cross-linking is higher than the gel point of the cross-linked network, and the last cross-linked network contains supramolecular cross-linking formed by at least one hydrogen bond function, and the cross-linking degree of the supramolecular cross-linking is higher than.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond and an unsaturated six-membered ring organic borate bond.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring inorganic borate bond, an unsaturated five-membered ring inorganic borate bond, a saturated six-membered ring inorganic borate bond and an unsaturated six-membered ring inorganic borate bond.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein, the boron-containing dynamic covalent bond is selected from organic boric acid monoester bond, organic boric acid silicon ester bond, inorganic boric acid monoester bond and inorganic boric acid silicon ester bond.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one metal-ligand action and common covalent cross-links formed by the common covalent bond, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one ionic action and common covalent cross-links formed by the common covalent bond, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid crosslinked dynamic polymer comprises two or more crosslinked networks, and at least one boron-containing dynamic covalent bond, at least one ion-dipole effect and common covalent crosslinks formed by the common covalent bonds in the crosslinked networks, wherein the degree of crosslinking of the common covalent crosslinks in at least one of the networks is above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one host-guest interaction and common covalent cross-links formed by the common covalent bond, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one Lewis acid-base pair effect and common covalent cross-links formed by the common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above a gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one pi-pi stacking function and common covalent cross-links formed by the common covalent bond, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond, an unsaturated six-membered ring organic borate bond, an organic borate single ester bond and an organic borate silicon ester bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, and pi-pi stacking interaction.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from 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 monoester bond and inorganic borate silicon bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, and pi-pi stacking interaction.

Furthermore, according to a preferred embodiment of the present invention, non-crosslinked polymers having a crosslinking degree below the gel point and/or polymer particles having a crosslinking degree above the gel point may be dispersed in the provided hybrid dynamic polymer crosslinked network, and the non-crosslinked polymers and/or polymer particles may contain one or any of boron-containing dynamic covalent bonds, supramolecular interactions, or may be formed by only ordinary covalent bonds.

The invention can also have other various hybrid network structure embodiments, one embodiment can comprise a plurality of identical or different cross-linked networks, and the same cross-linked network can contain different common covalent cross-links and/or different dynamic covalent cross-links and/or different supermolecular cross-links. The degree of crosslinking of any one crosslink of any one network can also be reasonably controlled to achieve the purpose of regulating and controlling the balance of structure and dynamic properties. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized in that the hybrid crosslinked dynamic polymer only contains a crosslinked network, and the crosslinked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect, at least one optional hydrogen bond effect and common covalent crosslinking formed by common covalent bonds, wherein the crosslinking degree of the common covalent crosslinking reaches above the gel point.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized in that the hybrid crosslinked dynamic polymer comprises two crosslinked networks, and the crosslinked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect, at least one optional hydrogen bond effect and common covalent crosslinks formed by common covalent bonds, wherein the crosslinking degree of the common covalent crosslinks in at least one network reaches above a gel point; wherein, the boron-containing dynamic covalent bond is selected from organic borate ester bonds.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized by comprising two crosslinked networks, wherein the crosslinked networks contain at least one boron-containing dynamic covalent bond, at least one metal-ligand action and common covalent crosslinks formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network reaches above the gel point; wherein, the boron-containing dynamic covalent bond is selected from inorganic borate ester bonds.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized by comprising two crosslinked networks, wherein the crosslinked networks comprise at least one boron-containing dynamic covalent bond, at least one metal-ligand action, a hydrogen bond action and common covalent crosslinks formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein the boron-containing dynamic covalent bond is selected from inorganic borate bonds.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer characterized in that it comprises two crosslinked networks and in the crosslinked networks at least one boron-containing dynamic covalent bond, at least one metal-ligand interaction, at least one supramolecular interaction selected from the group consisting of ionic interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bond interaction, lewis acid-base pair interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic hydrogen bonding interaction, radical cation dimerization, phase separation, crystallization, and common covalent crosslinks formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein the boron-containing dynamic covalent bond is selected from inorganic borate bonds.

The invention also provides an energy-absorbing hybrid cross-linked dynamic polymer, which is characterized by comprising two cross-linked networks, wherein the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein at least one network contains both common covalent crosslinks and boron-containing dynamic covalent bonds; wherein, the boron-containing dynamic covalent bond is selected from inorganic borate ester bonds.

The invention also provides an energy-absorbing hybrid cross-linked dynamic polymer, which is characterized by comprising two cross-linked networks, wherein the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein only boron-containing dynamic covalent bond crosslinks in at least one network; wherein, the boron-containing dynamic covalent bond is selected from inorganic borate ester bonds.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized in that the hybrid crosslinked dynamic polymer comprises two crosslinked networks, and the crosslinked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect, at least one optional hydrogen bond effect and common covalent crosslinks formed by common covalent bonds, wherein the crosslinking degree of the common covalent crosslinks in at least one network reaches above a gel point; wherein the non-hydrogen bonded supramolecular interaction is selected from ionic interaction, metallophilic interaction, dipole-dipole interaction, halogen bond interaction, lewis acid-base pair interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, ionic hydrogen bonding interaction, radical cation dimerization interaction, phase separation interaction, crystallization interaction.

The invention also provides an energy-absorbing hybrid cross-linked dynamic polymer, which is characterized by comprising two cross-linked networks, wherein the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein, the boron-containing dynamic covalent bond is selected from inorganic borate bond; the form of the hybrid cross-linked dynamic polymer is selected from organic gel, oligomer swelling gel, plasticizer swelling gel, ionic liquid swelling gel, common solid, foam and elastomer.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized by comprising at least three crosslinked networks, wherein the crosslinked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent crosslinks formed by common covalent bonds, and the crosslinking degree of the common covalent crosslinks in at least one network reaches above the gel point.

In embodiments of the present invention, the linking group for linking the boron-containing dynamic covalent bond and/or the supramolecular motif 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 present invention, the hybrid crosslinked dynamic polymer and its raw material components 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 hybrid crosslinked dynamic polymer.

In an embodiment of the present invention, the hybrid crosslinked dynamic polymer has a form selected from the group consisting of a common solid, an elastomer, a gel (including a hydrogel, an organogel, an oligomer-swollen gel, a plasticizer-swollen gel, an ionic liquid-swollen gel), a foam, and the like.

During the preparation process of the hybrid cross-linked dynamic polymer, certain other polymers, auxiliaries/additives and fillers which can be added/used can be added or used to jointly form the dynamic polymer material.

In an embodiment of the invention, the hybrid crosslinked dynamic polymer is applicable to the following materials or articles: the composite material comprises a damping material, a buffering material, an impact-resistant protective material, a damping material, a noise-reduction material, a sound-insulation material, a motion protective product, a military police protective product, a self-repairable coating, a self-repairable plate, a self-repairable binder, a bulletproof glass interlayer adhesive, a toughness material, a shape memory material, a sealing element and a toy.

Compared with the prior art, the invention has the following beneficial effects:

(1) in the energy absorption method provided by the invention, the used hybrid cross-linked dynamic polymer combines common covalent cross-linking, boron-containing dynamic covalent bonds, non-hydrogen bond type supermolecule action and optional hydrogen bond action in the structure, and fully utilizes and combines the advantages of each action. Wherein, common covalent crosslinking provides a strong and stable network structure for the dynamic polymer, and the polymer can keep a balanced structure, namely dimensional stability; the boron-containing dynamic covalent bond and the non-hydrogen bond type supermolecule effect provide a dynamic structure which can be reversibly changed spontaneously or under the external action for the dynamic polymer, so that the dynamic and static combination of the dynamic bond and the common covalent bond is realized, the synergistic action is shown in a polymer network, the energy absorption capacity with adjustable dynamic and performance effects can be obtained, and the energy absorption effects of orthogonality and cooperativity can be shown, so that the organic coordination of the mechanical property, the energy absorption performance and the effect is achieved, which is lacking in the prior art.

(2) Compared with the traditional common covalent cross-linked polymer, the boron-containing dynamic covalent bond and supermolecule action selected in the invention has strong dynamic property and mild dynamic reaction condition, and can realize the synthesis and dynamic reversible effect of the dynamic polymer under the conditions of no need of a catalyst, high temperature, illumination or specific pH; and the common covalent crosslinking in the system enables the polymer to have self-supporting property, so that the trouble that the polymer is wrapped by a bag but possibly leaked is avoided, and the system has excellent practicability. The invention maintains the characteristics of the traditional cross-linked polymer such as mechanical strength, stability and the like, changes the defects of low elongation at break and poor toughness of the traditional cross-linked polymer, and has certain dynamic reversibility which cannot be achieved by the prior art.

(3) The non-hydrogen bond type supermolecule function used in the hybrid cross-linked dynamic polymer can be reasonably selected and used for material design according to requirements, so that the hybrid cross-linked dynamic polymer can provide various performances: such as directionality of halogen bond action, cation-pi action, anion-pi action, controllable selectivity and controllable identification of small molecules/ions/groups in host-guest action, orderliness of benzene-fluorobenzene action, pi-pi stacking action, ionic action (positive and negative ion pair action), ion-dipole action, pH, concentration sensitivity of ion hydrogen bond action, conductivity, special photoelectricity of metallophilic interaction, radical cation dimerization, and the like. In addition, the application range of the compound can be expanded by reasonably selecting and designing non-hydrogen bond type supermolecule action combination, for example, the controllable selectivity and controllable identification of small molecules/ions/groups can be enhanced by combining the host-guest action with other supermolecule actions; the electric conductivity of the dynamic polymer can be enhanced by combining the supermolecule effects containing ionic groups; the mutually orthogonal supermolecule actions are combined to obtain dynamic polymers which respond to different external stimuli in different ways; the dynamic polymer with more stable mechanical property can be obtained by combining the synergistic supermolecule effect.

(4) In the energy absorption method provided by the invention, the hybrid cross-linked dynamic polymer for energy absorption has rich structure and various performances, and the common covalent component and the dynamic component contained in the hybrid cross-linked dynamic polymer have controllability. By controlling parameters such as molecular structure, functional group number, molecular weight and the like of the compound serving as the raw material, the dynamic polymer with different topological structures, apparent characteristics, adjustable performance and wide application can be prepared. In addition, the dynamic property of the polymer can be combined, matched and regulated in a wider range by selecting the boron-containing dynamic covalent bond, the supermolecule element and the hydrogen bond group in the system, and based on the difference of the boron-containing dynamic covalent bond and the non-hydrogen bond type supermolecule action dynamic property, the polymer material with richer structure, more diversified performance, more dynamic effect and more hierarchical energy absorption capability can be obtained, and the selective regulation and control on the energy absorption is lacked in the prior art system.

(5) According to the invention, on the basis of common covalent crosslinking, through selection and use of proper boron-containing dynamic covalent bonds and supermolecule effect, a hybrid crosslinked dynamic polymer with very rich dynamic performance can be constructed, besides the energy absorption performance, part of the structure can also show excellent shape memory performance, self-repairing performance, plastic deformation, bionic super toughness and the like, and the hybrid crosslinked dynamic polymer has incomparable excellent performance.

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 also provides an impact resistance method, which is characterized in that a hybrid cross-linked dynamic polymer is provided and is used as an impact resistance material for impact resistance; wherein the hybrid cross-linked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action and common covalent cross-links formed by common covalent bonds, wherein the common covalent cross-links reach the gel point of the common covalent cross-links in at least one cross-linking network.

The invention also provides a damping method, which is characterized in that a hybrid cross-linked dynamic polymer is provided and is used as a damping material for damping; wherein the hybrid cross-linked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction and common covalent cross-links formed by common covalent bonds, wherein the common covalent cross-links reach above the gel point of the common covalent cross-links in at least one cross-linked network.

The invention also provides a buffering method, which is characterized in that a hybrid cross-linked dynamic polymer is provided and is used as a buffering material for buffering; wherein the hybrid cross-linked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction and common covalent cross-links formed by common covalent bonds, wherein the common covalent cross-links reach above the gel point of the common covalent cross-links in at least one cross-linked network.

The invention also provides a sound insulation method, which is characterized in that a hybrid cross-linked dynamic polymer is provided and is used as a sound insulation material for sound insulation; wherein the hybrid cross-linked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction and common covalent cross-links formed by common covalent bonds, wherein the common covalent cross-links reach above the gel point of the common covalent cross-links in at least one cross-linked network.

The invention also provides a noise elimination method, which is characterized in that a hybrid cross-linked dynamic polymer is provided and is used as a noise elimination material for noise elimination; wherein the hybrid cross-linked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction and common covalent cross-links formed by common covalent bonds, wherein the common covalent cross-links reach above the gel point of the common covalent cross-links in at least one cross-linked network.

The term "energy absorption" as used herein refers to the absorption, dissipation, dispersion, etc. of energy generated by physical impact in the form of impact, vibration, shock, explosion, sound, etc.

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" encompasses chain growth processes resulting from non-covalent interactions of ordinary covalent bonds, boron-containing dynamic covalent bonds, and supramolecular interactions.

The term "cross-linking (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 ligation between and/or within reactant molecules through the formation of boron-containing dynamic covalent bonds and/or common covalent bonds and/or non-hydrogen bond type supramolecular interactions and/or hydrogen bonding interactions. 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 to occur, 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 an integral whole 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" non-crosslinked (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.

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 embodiments of the invention, the hybrid crosslinked dynamic polymer may be comprised of one or more crosslinked networks. When the hybrid cross-linked dynamic polymer is composed of only one cross-linked network, it is preferable that both the boron-containing dynamic covalent bond and the non-hydrogen bond type supramolecular interaction are contained in the cross-linked network structure. When the hybrid crosslinked 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 crosslinked networks, but the present invention is not limited thereto. Wherein, two or more cross-linked networks can be the same or different, the cross-linked network can only form common covalent cross-linking by common covalent bond, or can only form dynamic covalent cross-linked network by boron-containing dynamic covalent bond, or can only form supermolecule cross-linked network by non-hydrogen bond type supermolecule action, the cross-linked network can also be a proper combination of the above various bonds/actions, but the invention must have at least one common covalent cross-linking in the network above the gel point. It is to be noted that the boron-containing dynamic covalent bonds and/or supramolecular interactions described in the present invention may not participate in the crosslinking, preferably participate in the crosslinking.

For the hybrid crosslinked dynamic polymer of the present invention, the common covalent crosslinks reach above the gel point of the common covalent crosslinks in at least one crosslinked network, which ensures that even in the case of only one crosslinked network, the polymer can maintain an equilibrium structure, i.e., can be (at least partially) an insoluble and non-molten solid in the normal state, even when all boron-containing dynamic covalent bonds and non-hydrogen bonded supramolecules are dissociated. When two or more crosslinked networks are present, there may be interactions between different crosslinked networks (including the boron-containing dynamic covalent bonds and/or non-hydrogen bonding supramolecular interactions and/or hydrogen bonding interactions), or they may be independent of each other; in addition to the common covalent crosslinks of at least one crosslinked network having to be above the gel point of the common covalent crosslinks, other crosslinks (including common covalent crosslinks, dynamic covalent crosslinks, supramolecular crosslinks, and the sum thereof) may be above the gel point, or below the gel point, preferably above the gel point.

In the embodiment of the present invention, the cross-linked network structure of the hybrid cross-linked dynamic polymer may be blended and/or interpenetrated with one or more other non-cross-linked polymers, and the polymer chains may be linear, cyclic, branched, and two-dimensional or three-dimensional clusters below the gel point.

In embodiments of the invention, the 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, a gel, a 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. For the dynamic polymer with the glass transition temperature lower than 25 ℃, the dynamic polymer can embody better dynamic property and partial self-repairing capability; the polymer has a glass transition temperature higher than 25 ℃, and can show good shape memory capacity and stress bearing capacity. 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 hybrid cross-linked 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.

The hybrid cross-linked dynamic polymer may contain the boron-containing dynamic covalent bond, supramolecular motif and hydrogen bonding group at any suitable position of the polymer. For non-crosslinked dynamic polymers, the boron-containing dynamic covalent bond, the supramolecular element and the hydrogen bond group can be contained on a polymer main chain skeleton, and the boron-containing dynamic covalent bond, the supramolecular element and the hydrogen bond group can also be contained on a polymer side chain/branched chain skeleton; for the crosslinked dynamic polymer, the boron-containing dynamic covalent bond, the supramolecular element and the hydrogen bond group can be contained on a crosslinked network chain skeleton, and the boron-containing dynamic covalent bond, the supramolecular element and the hydrogen bond group can also be contained on a side chain/branched chain skeleton of the crosslinked network chain skeleton; the present invention also does not exclude the inclusion of boron-containing dynamic covalent bonds, supramolecular motifs and hydrogen bonding groups on the side and/or end groups of the polymer chain, on other constituents of the polymer such as small molecules, fillers, etc. In embodiments of the invention, the boron-containing dynamic covalent bonds, supramolecular motifs, and hydrogen bonding groups 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 boron-containing dynamic covalent bond, the non-hydrogen bond type supermolecule action and the hydrogen bond action can be subjected to reversible fragmentation and regeneration under a common condition; under appropriate conditions, boron-containing dynamic covalent bonds, non-hydrogen bond type supramolecular interactions and hydrogen bonding interactions 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 chain and the branched chain refer to chain structures which are branched from a polymer main chain skeleton or a crosslinking network chain skeleton or other arbitrary chains and have the molecular weight of more than 1000 Da; 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 linked 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 positioned 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 associated chain structures, the polymer chains therein can all 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" are also applicable to small molecular monomers and large molecular monomers which undergo supramolecular polymerization by non-hydrogen bond type supramolecular interaction or hydrogen bond interaction. 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 any chain 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 common covalent crosslinks contained in the hybrid cross-linked dynamic polymer are any suitable covalent cross-links established by common covalent bonds, including but not limited to covalent cross-links formed by carbon-carbon bonds, covalent cross-links formed by carbon-sulfur bonds, covalent cross-links formed by carbon-oxygen bonds, covalent cross-links formed by carbon-nitrogen bonds, covalent cross-links formed by silicon-carbon bonds, covalent cross-links formed by silicon-oxygen bonds. Common covalent crosslinks in any crosslinked network structure of a dynamic polymer may have at least one chemical structure, and at least one reaction type and reaction means.

The boron-containing dynamic covalent bond in the invention contains boron atoms in the dynamic structure composition, and comprises fifteen bonds of organic boron anhydride bonds, inorganic boron anhydride bonds, organic-inorganic boron anhydride bonds, saturated five-membered ring organic borate bonds, unsaturated five-membered ring organic borate bonds, saturated six-membered ring organic borate bonds, unsaturated six-membered ring organic borate bonds, saturated five-membered ring inorganic borate bonds, unsaturated five-membered ring inorganic borate bonds, saturated six-membered ring inorganic borate bonds, unsaturated six-membered ring inorganic borate bonds, organic borate monoester bonds, inorganic borate monoester bonds, organic borate silicone bonds and inorganic borate silicone bonds; wherein, each boron-containing dynamic covalent bond can comprise a plurality of boron-containing dynamic covalent bond structures. The organic boric acid ester bonds disclosed by the invention comprise but are not limited to organic boron anhydride bonds, saturated five-membered ring organic boric acid ester bonds, unsaturated five-membered ring organic boric acid ester bonds, saturated six-membered ring organic boric acid ester bonds, unsaturated six-membered ring organic boric acid ester bonds, organic boric acid monoester bonds and organic boric acid silicon ester bonds; the inorganic borate bond in the invention includes, but is not limited to, inorganic borate 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 monoester bond, and inorganic borate silicon bond. When the boron-containing dynamic covalent bonds are selected from two or more than two, 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 regulation effects, different structures in different types of boron-containing dynamic covalent bonds are preferred.

The organoboron anhydride linkages described herein are selected from, but not limited to, at least one of the following structures:

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;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference in the same boron atom

Can be linked to form a ring, on different boron atoms

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:

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:

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;

denotes a linkage to a polymer chain, a crosslinked 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 atom 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

Can be linked to form a ring, on different atoms

Or linked to form a ring, including but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof. Typical inorganic boron anhydride bond structures are exemplified by:

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:

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;

denotes a chain with a polymerA cross-linked network chain or any other suitable group/atom, wherein a, b each represent a bond to 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

Can be linked to form a ring, on different atoms

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:

in an embodiment of the present invention, the organic-inorganic boron anhydride linkages contained in the dynamic polymer may be formed by reaction of organic boric acid moieties contained in the compound starting material with inorganic boric acid moieties, or may be introduced into the dynamic polymer by polymerization/crosslinking reaction between reactive groups contained in the compound starting material 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:

wherein the boron atom is bonded to a carbon atom via a boron-carbon bond, and at least one organic group is bonded to the boron atom via said boron-carbon bondOn the seed;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; different on the same carbon atom

May be linked to form a ring, on different carbon atoms

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:

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:

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;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom;

an aromatic ring of any number of members, preferably 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 organoboronate bond structures can be exemplified by:

in an embodiment of the present invention, the unsaturated five-membered ring organoboronic acid ester bond contained in the dynamic polymer may be formed by reacting an ortho-diphenol moiety contained in the compound raw material with an organoboronic acid moiety, or the dynamic polymer may be introduced by polymerizing/crosslinking reaction between reactive groups contained in the compound raw material containing an unsaturated five-membered ring organoboronic acid ester bond.

The saturated six-membered ring organic boric acid ester bond in the invention is selected from, but not limited to, the following structures:

May be linked to form a ring, on different carbon atoms

Or may be joined to form a ring, including but not limited toIn aliphatic rings, ether rings, condensed rings, and combinations thereof. Typical saturated six-membered ring organoboronate bond structures may be exemplified by:

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:

an aromatic ring of any number of members, preferably six-membered, containing two adjacent carbon atoms in the aromatic ring, which is located in an unsaturated six-membered ring organoboronate linkage; the hydrogen atom on the aromatic ring-forming atom may be substituted with any substituent or not; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Or can be connected into a ring. Typical unsaturated six-membered ring organoboronate bond structures may be exemplified by:

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 therein using the compound raw material containing an unsaturated six-membered ring organoboronic acid ester bond.

In the invention, the boron atom in the saturated five-membered ring organic borate bond, the unsaturated five-membered ring organic borate bond, the saturated six-membered ring organic borate bond and the unsaturated six-membered ring organic borate bond in the structure is preferably selected from (A) an aminomethyl benzene group (B)

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 sensitive dynamic responsiveness and obvious energy absorption effect, and can embody greater advantages when being used as an energy absorption material.

Typical structures of such boron-containing dynamic covalent bonds are exemplified by:

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:

wherein, Y₁Selected from oxygen atom, sulfur atom, nitrogen atom, boron atom, silicon atom;

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

Can be linked to form a ring, on different carbon atoms

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:

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:

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;

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:

in an 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:

wherein, Y₁Selected from oxygen atoms, sulphur atoms, nitrogen atoms, boron atoms, silicon atoms, preferably oxygen atoms;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a denotes a linkage to Y₁The number of connected connections; when Y is₁When the compound 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

Can be linked to form a ring, on different carbon atoms

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:

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:

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 may not be substituted; different on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Or can be connected into a ring. Typical unsaturated six-membered ring inorganic borate bond structures are exemplified by:

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 therein using 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:

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

A divalent non-carbon atom, a linking group containing at least two backbone atoms;

an aromatic ring of any number of members, preferably selected from six-membered rings; the hydrogen atom on the ring-forming atom of the aromatic ring may be substituted with any substituent or may be unsubstituted;

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

Can be connected into a ring, on different carbon atoms and boron atoms

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 rings, ether rings, condensation rings and combinations thereof, wherein the organic boric acid monoester bonds formed after the 6 and 7 structures form the ring 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 which are described in the specification. Typical organicThe boric acid monoester bond structure may be exemplified by:

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:

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

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, whereina 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;

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; on the same carbon atom

Can be linked to form a ring, on different carbon atoms

Can also be connected into a ring or can be connected with I₁、I₂The substituted atoms (substituents) in (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 ring formation of 5, 6, 7 and 8 structures 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 above. Typical inorganic boronic acid monoester bond structures are exemplified by:

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:

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;

represents a linkage to a polymer chain, a cross-linked network chain, or any other suitable group/atom; difference on the same atom

Can be linked to form a ring, on different atoms

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:

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:

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;

denotes a linkage to a polymer chain, a cross-linked network chain or any other suitable group/atom, wherein a, b, c denote 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 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 atom and boron atom, 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

Can be linked to form a ring, on different atoms

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:

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:

wherein, K₁、K₂、K₃Is a monovalent organic group or a monovalent organosilicon group directly attached 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 bonded to two oxygen atoms, directly bonded 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-M)₁ ⁺) 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;

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:

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;

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

Can be linked to form a ring, on different atoms

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 preferably introduced by using an inorganic borane, an inorganic boronic acid, an inorganic boronic anhydride, an inorganic borate, an inorganic boronic ester, an inorganic boron halide as a raw material.

The 1, 2-diol moiety described in the embodiments of the present invention is ethylene glycol

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

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:

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:

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;

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, 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; examples of suitable cyclic group structures are:

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:

the catechol moiety described in the present inventionIs ortho-diphenol

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:

the 2-hydroxymethylphenol moiety described in the present invention is a 2-hydroxymethylphenol

And substituted forms thereof, hybridized forms thereof, and combinations thereof, having at least one non-hydroxo atom removed, suitable 2-hydroxymethylphenol motif structures being exemplified by:

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 (

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 (polyhydric) alcohol compound and/or any hydroxyl group in the group. Suitable structures containing monoalcohol moieties may be mentioned, for example:

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 (

Wherein Z can be selected from halogen, cyano, oxygen cyano, sulfur cyano, alkoxy, amino, sulfate ester group, borate ester group, acyl, acyloxy, acylamino, ketoxime group, alkoxide group and the like, and preferably halogen and alkoxy).

The boron-containing dynamic covalent bond 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.

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 compound raw material containing a boron-containing dynamic covalent bond, the type and mode of the reaction for introducing a boron-containing 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 boron-containing dynamic covalent bond and/or non-hydrogen bonding type supramolecular interaction and/or hydrogen bonding interaction spontaneously or under the conditions of 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, norbomene, azo, azide, heterocyclic, triazolinedione, supramolecular moieties, hydrogen bonding groups, and the like; hydroxyl, amino, mercapto, alkenyl, isocyanate, epoxy, acrylate, acrylamide, supramolecular moieties, hydrogen bonding groups are preferred.

In the present invention, the non-hydrogen bond type supramolecular interactions include, but are not limited to, metal-ligand interactions, ionic interactions, ion-dipole interactions, host-guest interactions, metallophilic interactions, dipole-dipole interactions, halogen bond interactions, lewis acid-base pair interactions, cation-pi interactions, anion-pi interactions, benzene-fluorobenzene interactions, pi-pi stacking interactions, ionic hydrogen bonding interactions, radical cation dimerization interactions, phase separation interactions, crystallization interactions.

Among them, the metal-ligand interaction described in the present invention refers to a supramolecular interaction established by a coordination bond formed by a ligand group (represented by L) and a metal center (represented by M). The ligand group is selected from cyclopentadiene or a structural unit containing at least one coordination atom or ion (represented by A). The metal center can be selected from metal ions, metal centers of metal chelates, metal centers of metal organic compounds and metal centers of metal inorganic compounds. Wherein, a coordinating atom or ion may form one or more coordination bonds with one or more metal centers, and a metal center may also form one or more coordination bonds with one or more coordinating atoms or ions. The number of coordination bonds a ligand group forms with the metal center is referred to as the number of teeth of the ligand group. In the embodiment of the present invention, in the same individual system, one metal center can form a metal-ligand effect with one or more of a bidentate ligand, a bidentate ligand and a tridentate ligand, and different ligands can also form a ring through the metal center connection, so that the present invention can effectively provide dynamic metal-ligand effects with sufficient variety, quantity and performance, and the structures shown in the following general formulas are some examples, but the present invention is not limited thereto:

wherein A is a coordinating atom or ion, M is a metal center, and an A-M bond formed by each ligand group and the same metal center is a tooth, wherein the A is connected by a single bond to represent that the coordinating atoms or ions belong to the same ligand group, when one ligand group contains two or more coordinating atoms or ions, A can be the same atom or different atoms, and is selected from the group consisting of but not limited to boron, nitrogen, oxygen, sulfur, phosphorus, silicon, arsenic, selenium and tellurium; preferably boron, nitrogen, oxygen, sulfur, phosphorus; more preferably nitrogen, oxygen; most preferably nitrogen. Incidentally, a sometimes exists in the form of negative ions;

is a cyclopentadiene ligand. In the present invention, it is preferable that one coordinating atom or ion form only one coordination bond with one metal center, and therefore the number of coordinating atoms or ions contained in a ligand group is the number of teeth of the ligand group. The ligand group and the metal centerThe metal-ligand interaction formed (as M-L)_xRepresenting the number of ligand groups interacting with the same metal center) is related to the kind and number of coordinating atoms or ions on the ligand groups, the kind and valence of the metal center, and the like.

In embodiments of the invention, where supramolecular interactions crosslinks above the gel point are formed, one metal center must be capable of forming a metal-ligand interaction with at least two of the ligand groups (i.e., M-L) in order to enable cross-linking based on the metal-ligand interaction₂Structure) or a metal-ligand interaction may be formed by multiple ligands with the same metal center, where two or more ligand groups may be the same or different. The number of coordination sites of one metal center is limited, the more the coordinating atoms or ions of the ligand groups are, the fewer the number of ligands which can be coordinated by one metal center is, and the lower the supramolecular crosslinking degree based on the metal-ligand effect is; however, since the more denticity each ligand forms with the metal center, the stronger the coordination, the lower the dynamic properties, and thus, in the present invention, it is preferable that the number of ligand groups not exceed tridentate.

In embodiments of the invention, only one ligand may be present in a polymer chain or in a dynamic polymer system, or any suitable combination of ligands may be present simultaneously. The ligand refers to a core ligand structure, and a skeleton ligand, a side group ligand and a terminal group ligand can have the same core ligand structure, and the difference is that the connecting points and/or positions of the core ligand structure connected to the polymer chain or the small molecule are different. Suitable ligand combinations can effectively produce dynamic polymers with specific properties, for example, to act synergistically and/or orthogonally to enhance the overall properties of the material. Suitable ligand groups (core ligand structures) may be exemplified by, but are not limited to:

examples of monodentate ligand groups are as follows:

bidentate ligand groups are exemplified as follows:

tridentate ligand groups are exemplified below:

tetradentate ligand groups are exemplified below:

the polydentate ligands are exemplified by:

in embodiments of the present invention, the metal center M may be a metal center of any suitable metal ion or compound/chelate or the like, which may be selected from any suitable ionic form, compound/chelate form and combinations thereof of any one of the metals of the periodic table of the elements.

The metal is preferably a metal of the first to seventh subgroups and group eight. The metals of the first to seventh subgroups and group VIII also include the lanthanides (i.e., La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and the actinides (i.e., Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr).

More preferably, the metal is a metal of the first subgroup (Cu, Ag, Au), a metal of the second subgroup (Zn, Cd), a metal of the eighth group (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), a metal of the lanthanide series (La, Eu, Tb, Ho, Tm, Lu), or a metal of the actinide series (Th). Further preference is given to Cu, Zn, Fe, Co, Ni, Pd, Ag, Pt, Au, La, Ce, Eu, Tb and Th to obtain stronger dynamic property.

In the embodiment of the present invention, the metal organic compound is not limited, and suitable examples include the following:

other suitable metal organic compounds capable of providing a metal center include, but are not limited to, metal-organic cages, metal-organic frameworks. Such metal organic compounds may be used alone or introduced into the polymer chain at suitable locations by means of suitable covalent chemical linkages. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.

In the embodiment of the present invention, the metal inorganic compound is preferably an oxide or sulfide particle of the above metal, particularly a nanoparticle.

In embodiments of the present invention, the metal chelate compound which can provide a suitable metal center is preferably a chelate compound having a vacancy in a coordination site, or a chelate compound in which a part of the ligand may be substituted with the skeletal ligand of the present invention.

In the embodiment of the present invention, the combination of the ligand group and the metal center is not particularly limited as long as the ligand can form a suitable metal-ligand action with the metal center. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

the ionic interaction in the present invention refers to a supramolecular interaction which contains at least one pair of positively and negatively charged ionic groups in a dynamic polymer structure and is formed by coulomb force between the positive ionic group and the negative ionic group. The positive ionA group refers to a group having a positive charge, and examples thereof include:

preference is given to

The anionic group refers to a group having a negative charge, and examples thereof include:

preference is given to

Wherein the anionic groups may also be present in clay minerals including, but not limited to, kaolinite, antigorite, pyrophyllite, talc, montmorillonite, saponite, stone, hydromicas, micas, chlorite, palygorskite, sepiolite. In special cases, the positive and negative ionic groups may be in the same compound structure, such as choline glycerophosphate, 2-methacryloyloxyethyl phosphorylcholine, l-carnitine, methacryloylethyl sulfobetaine, etc. The ionic action can be stably existed in the polymer, and the strength of the ionic action can be well controlled by changing the concentration and the kind of the ionic group.

In the embodiment of the present invention, the combination of the positive ion group and the negative ion group is not particularly limited as long as the positive ion group can form a suitable ionic action with the negative ion group. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

the ion-dipole effect in the present invention means that when two atoms having different electronegativities are bonded, the charge distribution is not uniform due to the induction of the atom having the larger electronegativity, resulting in the asymmetric distribution of electronsAn electric dipole is generated, which electric dipole interacts with the charged ionic groups to form supramolecular interactions. The ionic group may be any suitable charged group, such as the following, but the invention is not limited thereto:

preference is given to

The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-N, C ≡ N, C ≡ N, C ≡ O, C-O, C-S, C ≡ S, C-F, C-Cl, C-Br, C-I, H-O, H-S, H-N, preferably C ≡ N, C ≡ O, C-F, H-O. The ion-dipole effect can stably exist in an electrochemical environment, the acting force is easy to regulate and control, and the conditions of generating and dissociating the acting force are mild.

In the embodiment of the present invention, the combination of the ionic group and the electric dipole is not particularly limited as long as the ionic group can form a suitable ion-dipole action with the electric dipole. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

the host molecule (represented by G) is a compound (small molecule or ionic group) which can be recognized by the host and is embedded into the cavity of the host, one host molecule can recognize and bond a plurality of guest molecules, in the embodiment of the invention, one host molecule is preferably capable of recognizing at most two guest molecules, and the host molecule comprises but is not limited to ethers (including crown ethers, cryptates, spherules, hemispheres, pods, lassos, benzocrown, heteroacrown ethers, cryptates, mixed cryptates), cyclodextrins, cyclophanes, cucurbiturils, calixarenes, pillararomatics and suitable inorganic organic ionic frameworks, preferably crown ethers, β -cyclodextrin, calix [8] urea, calixarenes, pillaraffins [5] arenes, compounds of cycloparaffins, long-chain heteroaromatics, and long-chain heteroaromatics, which are capable of forming a long-chain heteroarene-chain-bridged aromatic hydrocarbon structure, and a long-chain heteroarene-bridged aromatic compound, which can be used for stabilizing the host molecule under moderate conditions, long-chain heteroarene, cycloarene, and long-chain heteroarene-chain bridged compound, and compound which can be used for stabilizing the host molecule.

Suitable host molecules may be exemplified by, but are not limited to:

Ni(PDC)(H₂O)₂skeleton, Zn₃(PTC)₂(H₂O)₈·4H₂An O skeleton;

suitable guest molecules may be exemplified by, but are not limited to:

in the embodiment of the present invention, the combination of the host molecule and the guest molecule is not particularly limited as long as the host can form a suitable host-guest interaction with the guest. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

wherein, the term "metallophilic" as used in the present invention means when the two outermost electronic structures are d¹⁰Or d⁸The metal ions of (a) are brought closer to less than the sum of their van der waals radii; wherein, the two metal ions which have the effect of the metallophilic can be the same or different. The outermost electronic structure is d¹⁰Metal ions of (2) include, but are not limited to, Cu⁺、Ag⁺、Au⁺、Zn²⁺、Hg²⁺、Cd²⁺Preferably of Au⁺、 Cd²⁺(ii) a The outermost electronic structure is d⁸Metal ions of (2) include, but are not limited to, Co⁺、Ir⁺、Rh⁺、Ni²⁺、Pt²⁺、Pb²⁺Preferably Pt²⁺、 Pb²⁺. The metallophilic action can exist stably in the polymer, has moderate action strength, certain directionality and no obvious saturation, can be aggregated to form a polynuclear complex, is less influenced by the external environment, and can ensure that the dynamic property of the prepared polymer is more sufficient.

In the embodiment of the present invention, the combination of forming the metallophilic action is not particularly limited as long as a suitable metallophilic action is formed between metal ions. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

Cu—Cu、Ag—Ag、Au—Au、Zn—Zn、Hg—Hg、Cd—Cd、Co—Co、Ir—Ir、Rh—Rh、Ni—Ni、Pt—Pt、 Pb—Pb、Cu—Ag、Cu—Au、Ag—Au、Cu—Zn、Cu—Co、Cu—Pt、Zn—Co、Zn—Pt、Co—Pt、Co—Rh、 Ni—Pb。

herein, the dipole-dipole effect in the present invention refers to a mutual interaction between two electric dipoles generated by asymmetric distribution of electrons and generation of the electric dipoles due to non-uniform charge distribution induced by atoms having greater electronegativity when two atoms having different electronegativities are bonded. The electric dipole may be generated by bonding any suitable two atoms with different electronegativities, such as the following, but the invention is not limited thereto: C-N, C ≡ N, C ≡ N, C ≡ O, C-O, C-S, C ≡ S, C-F, C-Cl, C-Br, C-l, H-O, H-S, H-N, preferably C ≡ N, C ≡ O, C-F, H-O, and more preferably C ≡ N. The dipole-dipole effect can stably exist in the polymer and is easy to regulate, and the pairing of the acting groups can generate a micro-domain, so that the interaction is more stable; at higher temperatures, the dipole-dipole effect is reduced or even eliminated, and thus polymers containing dipole-dipole effects may exhibit differences in dynamics depending on the temperature differences.

In the embodiment of the present invention, the combination between the electric dipoles is not particularly limited as long as an appropriate dipole-dipole action can be formed between the electric dipoles. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

among them, the halogen bond interaction in the present invention refers to a non-covalent interaction formed between a halogen atom and a neutral or negatively charged lewis base, and is essentially an interaction between a sigma-anti bond orbital of the halogen atom and an atom or pi-electron system having a lone electron pair. Halogen bond interactions can be represented by-X.Y-, wherein X can be selected from Cl, Br, I, preferably Br, I; y can be selected from F, Cl, Br, I, N, O, S, pi bond, preferably Br, I, N, O. The halogen bond has directional and linear inclined geometric characteristics; as the atomic number of halogen increases, the number of electron donors that can be bonded increases, and the strength of the halogen bond formed increases. Based on halogen bond effect, ordered and self-repairing dynamic polymer can be designed.

In the embodiment of the present invention, the combination of the atoms forming the halogen bond function is not limited as long as a stable halogen bond function can be formed in the dynamic polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

—Cl···Cl—、—Cl···F—、—Cl···Br—、—Cl···I—、—Cl···N—、—Cl···O—、—Cl···S—、—Cl···π—、 —Br···Br—、—Br···F—、—Br···I—、—Br···N—、—Br···O—、—Br···S—、—Br···π—、—I···I—、—I···F—、 —I···N—、—I···O—、—I···S—、—I···π—。

herein, the Lewis acid-base pair referred to in the present invention refers to a non-covalent interaction formed between a Lewis acid and a Lewis base. Wherein, the lewis acid refers to a substance (including molecules, ions or atomic groups) capable of accepting an electron pair, and can be selected from positive ion groups (such as alkyl positive ions, nitro positive ions, quaternary ammonium positive ions, imidazole positive ions and the like), metal ions (such as sodium ions, potassium ions, calcium ions, magnesium ions and the like), electron-deficient compounds (such as boron trifluoride, organoborane, aluminum chloride, ferric chloride, sulfur trioxide, dichlorocarbene, trifluoromethanesulfonate and the like), and the lewis acid is preferably alkyl positive ions, quaternary ammonium positive ions, imidazole positive ions, organoborane, and more preferably organoborane; the Lewis base refers to a substance (including a molecule, an ion or an atomic group) capable of giving an electron pair, and can be selected from a group consisting of an anionic group (such as a halide ion, an oxide ion, a sulfide ion, a hydroxide ion, a carbonate ion, a nitrate ion, a sulfate ion, a phosphate ion, an alkoxide ion, an olefin, an aromatic compound, etc.), a compound having a lone pair of electrons (such as ammonia, an amine, an imine, an azo compound, a nitroso compound, cyanogen, an isocyanate, an alcohol, an ether, a thiol, carbon monoxide, carbon dioxide, nitrogen monoxide, dinitrogen monoxide, sulfur dioxide, an organophosphine, a carbene, etc.), and the Lewis base is preferably an alkoxide ion, an olefin, an aromatic compound, an amine, an azo compound, a nitroso compound, an isocyanate, carbon dioxide, an organophosphine, more preferably an amineAzo compounds, nitroso compounds, organophosphanes. Wherein, the Lewis acid-base pair action is preferably 'hindered Lewis acid-base pair action', and the 'hindered Lewis acid-base pair action' refers to that at least one of Lewis acid and Lewis base in the Lewis acid-base pair action is required to be connected with a 'big group with steric hindrance effect'; said "bulky group with steric hindrance" may weaken the strength of the coordination bond between the Lewis acid and the Lewis base, thereby allowing the Lewis acid-base pair to exhibit the property of a strong dynamic supramolecule selected from the group consisting of C_3-20Alkyl, ring C_3-20Alkyl, 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, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl, most preferably from tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, trimethylphenyl, fluorophenyl, benzyl, methylbenzyl. Wherein the azo compound is preferably selected from azomethane, azotert-butane, N-methyl azomethylamine, N-methyl azoethylamine, N-ethyl azoethylamine, azodiacetic acid, azobenzene, azodiphenylamine, dichloroazobenzene, azodiisobutyronitrile, azodicarbonamide, dimethyl azodicarboxylate, diethyl azodicarboxylate, diisopropyl azodicarboxylate, and di-tert-butyl azodicarboxylate; the nitroso compound is preferably selected from the group consisting of nitrosomethane, nitrosotert-butane, N-nitromethyleneamine, nitrosobenzene, nitrosotoluene, nitrosochlorobenzene, nitrosonaphthalene, and N-nitrosourea. The Lewis acid-base pair has good dynamic reversibility and can be rapidly dissociated under the condition of slight heating or the existence of an organic solvent, thereby realizing self-repairing or reshaping.

In the embodiment of the present invention, the combination of the formation of the Lewis acid-base pair effect is not limited as long as a stable Lewis acid-base pair effect can be formed in the dynamic polymer. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

wherein, in the present invention, the cation-pi action refers to the non-covalent interaction formed between a cationic group and an aromatic pi system. There are three main classes of cation-pi action, the first group being simple inorganic cations or ionic groups (e.g. Na)⁺、K⁺、Mg²⁺、NH₄ ⁺、Ca²⁺) And aromatic pi systems; the second group is the interaction between organic cations (e.g., quaternary ammonium cations) and aromatic pi systems; the third type is the interaction between positively charged atoms in the dipolar bond (e.g., H atoms in an N-H bond) and aromatic π systems. The cation-pi effect has rich varieties and moderate intensity, can stably exist in various environments, and can prepare dynamic polymers with rich performance based on the cation-pi effect.

In the embodiment of the present invention, the kind of the cation-. pi.function is not particularly limited as long as it can form a stable cation-. pi.function in the dynamic polymer. Some suitable cationic groups may be exemplified by, but are not limited to:

Na⁺、K⁺、Li⁺、Mg²⁺、Ca²⁺、 Be²⁺、H-O、H-S、H-N。

wherein, in the present invention, anion-pi interaction refers to non-covalent interaction formed between an anionic group and an electron-deficient aromatic pi system. The anionic groups may be simple inorganic non-metallic ions or ionic groups (e.g. Cl)^-、Br^-、I^-、OH^-) (ii) a Or an organic anionic group (e.g., a benzenesulfonic acid group); it may also be a negatively charged atom in a dipole bond (e.g. a chlorine atom in a C-Cl bond). The electron-deficient aromatic pi system means that due to different electronegativities of ring-forming atoms, the density distribution of pi electron clouds of a ring is not uniform, and pi electrons mainly deviate to the direction of electronegativity high atoms, so that the density distribution of the pi electron clouds of the aromatic ring is reduced, such as pyridine, fluorobenzene and the like. The anion-pi action has reversibility and controllable identification, and can be used for constructing dynamic polymers with special properties.

In the embodiment of the present invention, the kind of the anion- π action is not particularly limited as long as it can form a stable anion- π action in the dynamic polymer. Some suitable anionic groups may be exemplified by, but are not limited to:

Cl^-、Br^-、I^-、OH^-、SCN^-；

some suitable electron deficient aromatic pi systems may be exemplified, but the invention is not limited thereto: pyridine, pyridazine, fluorobenzene, nitrobenzene, tetraoxacalix [2] arene [2] triazine and benzene tri-imide.

In the present invention, the benzene-fluorobenzene reaction refers to a non-covalent interaction consisting of the combination of an aromatic hydrocarbon and a polyfluorinated aromatic hydrocarbon by dispersion force and quadrupole moment. Because the ionization potential of fluorine atoms is very high and the atomic polarizability and atomic radius are both small, the fluorine atoms around the polyfluorinated aromatic hydrocarbon are negatively charged due to large electronegativity, and the skeleton of the central carbon ring is positively charged due to small electronegativity. Because the electronegativity of the carbon atom is greater than that of the hydrogen atom, the direction of the electric quadrupole moment of the aromatic hydrocarbon is opposite to that of the polyfluorinated aromatic hydrocarbon, and because the volume of the fluorine atom is very small, the volume of the polyfluorinated aromatic hydrocarbon is similar to that of the aromatic hydrocarbon, the aromatic hydrocarbon and the polyfluorinated aromatic hydrocarbon are stacked in an alternate face-to-face mode to form a columnar stacking structure, and the stacking mode is basically not influenced by the introduced functional group. The reversibility and stacking effect of the benzene-fluorobenzene action are utilized to prepare the dynamic polymer with special functions.

In the embodiment of the present invention, the kind of the benzene-fluorobenzene action is not limited as long as a stable benzene-fluorobenzene action can be formed in the dynamic polymer. Some suitable benzene-fluorobenzene reactions may be exemplified by, but the invention is not limited to:

wherein, the pi-pi stacking effect in the invention refers to the pi-pi stacking effect formed by the mutual overlapping of pi-bond electron clouds due to the fact that the dynamic polymer contains an aromatic pi system capable of providing the pi-bond electron clouds. Pi-pi stacking functions in three ways, including face-to-face stacking, offset stacking, and edge-to-face stacking. The surface accumulation means that the interactive ring surfaces are parallel to each other, the distance between the centers of the parallel ring surfaces is almost equal to the distance between the ring surfaces, the pi-pi action of the accumulation mode is electrostatic mutual exclusion and is relatively unstable, but when the electron-withdrawing property of a substituent group connected to the ring surfaces is relatively strong, the pi-pi action of the surface accumulation becomes relatively obvious; the offset accumulation means that the action ring surfaces are parallel to each other, but the center of the ring has certain offset, namely the distance of the center of the ring is larger than the distance between the ring surfaces, the accumulation mode relieves the mutual exclusion action between the two ring surfaces, correspondingly increases the attraction of sigma-pi, and is a common accumulation mode; stacking other than planar stacking and offset stacking is called edge-planar stacking, which has the smallest energy and the smallest intermolecular repulsion, and is often found between ring-conjugated molecules having smaller van der waals surfaces or between ring-conjugated molecules having flexible linkers.

Aromatic pi systems capable of providing pi-bonded electron clouds, including but not limited to most condensed ring compounds and some heterocyclic compounds in which pi-pi conjugation occurs, suitable aromatic pi systems may be exemplified by, but are not limited to, the following:

the pi-pi stacking effect has simple forming mode, can stably exist in the polymer, is less influenced by the external environment, and can be conveniently regulated and controlled by changing the conjugated compound and the content.

In the embodiment of the present invention, the combination of the aromatic pi systems providing the pi-bond electron cloud is not particularly limited as long as a suitable pi-pi stacking effect is formed between the aromatic pi systems. Some suitable combinations may be exemplified as follows, but the invention is not limited thereto:

the ionic hydrogen bonding in the invention is composed of a positive ionic group and a negative ionic group which can form hydrogen bonding, and simultaneously forms hydrogen bonding and coulomb interaction between positive ions and negative ions, or is composed of a positive/negative ionic group which can form hydrogen bonding and a neutral hydrogen bonding group, and simultaneously forms hydrogen bonding and ion-dipole interaction between positive ions and negative ions and the neutral group.

In the embodiments of the present invention, some suitable combinations of ionic hydrogen bonding can be exemplified as follows, but the present invention is not limited thereto:

herein, the radical cationic dimerization referred to in the present invention refers to a supramolecular interaction established by an interaction between radical cationic groups containing both a radical and a cation. By way of example, the radical cationic groups that can form radical cationic dimerization include, but are not limited to, the following:

in an embodiment of the present invention, some suitable combinations of free radical cationic dimerization may be exemplified as follows, but the present invention is not limited thereto:

herein, the phase separation effect in the present invention refers to an unstable tendency of separation between phases due to a change in a certain environmental condition in a multi-phase system, and includes phase separation caused during a supramolecular action such as coordination, recombination, assembly, combination, aggregation, etc., phase separation caused by an incompatible phase, phase separation caused by an incompatible block structure, etc.

In the embodiments of the present invention, the phase topology (phase morphology) formed by phase separation is not limited, and includes, but is not limited to, spherical, cylindrical, helical, lamellar, and combinations thereof. Any phase, including different phases, can be dispersed in another phase, can form interpenetrating double/multiple continuous phases with other phases, can be mutually independent continuous phases, and can also be in a mixed form. In the embodiment of the present invention, it is preferable that one phase is dispersed in the other phase in a spherical shape as phase-separated physical crosslinking, so that the polymer can more conveniently have better flexibility and elasticity and more suitably exert dynamic properties.

In the present invention, the crystallization refers to a process in which polymer chains are arranged and folded to form ordered domains, and includes crystallization caused by a supramolecular reaction process such as coordination, recombination, assembly, combination, aggregation, crystallization caused by an incompatible phase, crystallization caused by an incompatible block structure, crystallization caused by a regular easy-to-crystallize segment, crystallization caused by a liquid crystal, and the like. The liquid crystal chain segment is introduced, and crystallization caused by liquid crystal can be utilized to effectively regulate and control crystallization, so that dynamic reversible change can be realized under the stimulation conditions of heat, light, pH, chemical change and the like; wherein, the liquid crystal chain segment can be introduced by liquid crystal polymer (such as poly-p-benzamide, poly-p-phenylene terephthamide, poly-benzothiazole, poly-benzoxazole, and the like), liquid crystal group (such as azobenzene and derivatives thereof, biphenyl, diphenyl terephthalate, cholesteric derivatives, and the like), mesogen (such as 4, 4' -dimethoxy azobenzene oxide, vinyl terephthalic acid di-p-methoxyphenyl, mesogenic diacrylate, and the like), and the like.

In the present invention, the phase separation and crystallization may be independent of each other, or may be simultaneously carried out by the same unit structure. The phase separation and/or crystallization generated by the supermolecule effect not only has the functions of increasing the apparent molecular weight of the supermolecule and regulating the topological structure of the supermolecule and the microstructure of the polymer, but also has the self-reinforcing effect, and can improve the properties of the polymer, such as strength, modulus and the like.

In an embodiment of the present invention, the dynamic polymer having the phase separation/crystallization may be a segment based on the following polymer segments, groups, or any combination thereof, but is not limited thereto: amorphous polymer segments with high glass transition temperatures (i.e., glass transition temperatures above the upper limit of the material's operating temperature, typically above 40 ℃, preferably not less than 100 ℃), such as polystyrene, polymethylmethacrylate, polyvinylpyridine, hydrogenated polynorbornene, polyether, polyester, polyetheretherketone, polyaromatic carbonate, polysulfone, and the like; polymer segments, groups rich in hydrogen bonding groups, such as polyamides, polypeptides, segments rich in urea bonds, segments rich in urethane bonds, segments based on ureidopyrimidinone, and the like; polymer segments, groups rich in crystalline phases, such as crystalline polyethylene, crystalline polypropylene, crystalline polyester, crystalline polyether, liquid crystal polymer, liquid crystal groups, and the like; ionic polymer segments such as polyacrylate, polymethacrylate, polyacrylamide, polystyrene sulfonate, and the like; polymer chain segments rich in conjugated structures, such as polyacetylene, polyphenylacetylene, polyphenyl, polyfluorene, polythiophene and the like. Among them, amorphous polymer segments with high glass transition temperature, polymer segments/groups rich in hydrogen bonding groups, and polymer segments/groups rich in crystalline phases are preferred in order to design and control the molecular structure of the dynamic polymer to obtain the best performance.

In the embodiment of the present invention, the "supramolecular unit" refers to a group or molecule or a structural unit for forming non-hydrogen bond type supramolecules, which includes, but is not limited to, ligand group, metal center, ionic group, electric dipole, host molecule, guest molecule, metal ion, halogen atom, lewis base, lewis acid, aromatic pi system, aromatic hydrocarbon, polyfluorinated aromatic hydrocarbon, radical cationic group, phase-separable polymer segment, crystalline polymer segment, etc. The supramolecular motif may be located at any suitable position on the dynamic polymer, for example on the backbone of the non-crosslinked dynamic polymer, on the side chain/branch chain backbone of the non-crosslinked dynamic polymer, on the crosslinked network chain backbone of the crosslinked dynamic polymer, on the side chain/branch chain backbone of the crosslinked network chain backbone of the crosslinked dynamic polymer, on the side and/or end groups of the dynamic polymer, other constituents of the polymer such as small molecules, fillers, etc.

In an embodiment of the invention, said non-hydrogen bonded supramolecular interactions are preferably combined as follows:

the metal-ligand action and the ion action, and the ions and the metal in the two actions can greatly improve the conductivity of the dynamic polymer; the metal-ligand effect and the host-guest effect, and the function specificity of the dynamic polymer can be greatly improved by utilizing the recognition effect of the two effects; the metal-ligand action and the ion-dipole action, and the conductivity of the dynamic polymer can be greatly improved by utilizing ions and metals in the two actions; the metal-ligand action and the pi-pi stacking action, most ligand groups of the metal-ligand action can also form the pi-pi stacking action, so that the dynamic polymer combining the two supermolecule actions is easy to prepare and generally has better mechanical stability; the dynamic polymer has the advantages that the ionic effect, the ionic-dipole effect and the dipole-dipole effect are simple in acting groups of the three supramolecular effects, and the dynamic polymer can form a combination of the three supramolecular effects only by containing ions with opposite electric properties and a proper amount of dipole groups, so that the dynamic polymer not only has good conductivity, but also has good mechanical property and energy absorption characteristic; the dynamic polymer combined by the two supermolecular actions is easy to prepare, the metallophilic action is usually accompanied with the pi-pi stacking action, and the prepared dynamic polymer has stable mechanical property and good dynamic responsiveness and energy absorption effect.

The optional hydrogen bonding in the present invention is any suitable supramolecular interaction established by hydrogen bonding, which is generally linked by hydrogen atoms covalently linked to atom Z with large electronegativity and small radius, with hydrogen as medium between Z and Y, to generate hydrogen bond in the form of Z-H … Y, wherein Z, Y is any suitable atom with large electronegativity and small radius, which may be the same or different, and may be selected from atoms F, N, O, C, S, Cl, P, Br, I, etc., more preferably from atoms F, N, O, more preferably from atoms O, N.

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.

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 to 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 property of the hydrogen bond action is strong, and the dynamic property can be provided together with the dynamic covalent bond and the specific supermolecule action. 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. Wherein, the hydrogen bond group can only contain a hydrogen bond donor, only contain a hydrogen bond acceptor, or contain both the hydrogen bond donor and the hydrogen bond acceptor, preferably contain both the hydrogen bond donor and the 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:

more preferably contains

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:

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:

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 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:

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;

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, and at least two ring-forming atoms are nitrogen atoms,the cyclic group structure can be a micromolecular ring or a macromolecular ring, and is preferably a 3-50-membered ring, 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):

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:

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;

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; wherein I, D, Q any two or more of them can be connected into a ringIncluding 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 present invention, the pendant/terminal hydrogen bonding groups are preferably selected from amide groups, carbamate groups, urea groups, thiocarbamate groups, thiourea groups, pyrazoles, imidazoles, imidazolines, triazoles, purines, porphyrins, and derivatives of the above.

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:

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 mentioned, for example, but the invention is not limited thereto:

in the embodiment of the present invention, since some hydrogen bonds have no directionality and selectivity, under specific conditions, 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 should be noted that the hydrogen bonding effect formed by the non-excluded portion in the present invention forms neither interchain crosslinking effect nor intrachain ring, and only non-crosslinking polymerization, grafting, etc. In the embodiment of the present invention, it is preferable that at least one of the backbone hydrogen bonding groups, the side group hydrogen bonding groups, and the end group hydrogen bonding groups form interchain crosslinks between the same hydrogen bonding groups and/or at least two different kinds of hydrogen bonding groups.

In the embodiment of the present invention, the hybrid crosslinked dynamic polymer may contain one or more than one supramolecular moiety and/or hydrogen bond group, and the same crosslinked network may also contain one or more than one supramolecular moiety and/or hydrogen bond group, that is, the dynamic polymer may contain a combination of one or more than one supramolecular moiety and/or hydrogen bond group. The supramolecular moiety and/or hydrogen bonding group may be introduced by any suitable chemical reaction, for example: reaction of isocyanate with amino, hydroxyl, mercapto, carboxyl, electrophilic substitution of heterocycle, nucleophilic substitution of heterocycle, double bond free radical reaction, side chain reaction of heterocycle, azide-alkyne click reaction, mercapto-double bond/alkyne click reaction, urea-amine reaction, amidation reaction, tetrazine-norbornene reaction, reaction of active ester with amino; preferably, the reaction of isocyanate with amino, hydroxyl and sulfhydryl, the azide-alkyne click reaction, the urea-amine reaction, the amidation reaction, the reaction of active ester with amino, and the sulfhydryl-double bond/alkyne click reaction; more preferably isocyanate with amino, hydroxyl, thiol reaction, thiol-double bond/alkyne click reaction, azide-alkyne click reaction.

In embodiments of the invention, the supramolecular motif and hydrogen bonding group may be introduced in any suitable composition and at any suitable time, including but not limited to from the monomer, while forming the prepolymer, after forming the prepolymer, while forming the cross-link, after forming the cross-link. Preferably at the same time as the prepolymer is formed and crosslinked. In order to avoid the influence of supramolecular cross-linking formed after introduction of the supramolecular element and the hydrogen bond group on operations such as mixing, dissolving and the like, the supramolecular element and the hydrogen bond group can be subjected to closed protection, and then the deprotection is carried out after a proper time (such as the formation of cross-linking and the like).

According to a preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point. For this embodiment, which contains only one cross-linked network, ordinary covalent cross-linking is used to provide an equilibrium structure, dynamic covalent cross-linking, supramolecular cross-linking may be above or below its gel point, used to provide additional cross-linking to the cross-linked network beyond ordinary covalent cross-linking, and used to provide dynamicity, effectively achieving toughening; and the preparation is more convenient.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point. In the embodiment, by introducing hydrogen bond action into the single-network crosslinking structure, the boron-containing dynamic covalent bond and non-hydrogen bond type supermolecule action can be supplemented, so that the polymer can show a hierarchical dynamic reversible effect.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond and an unsaturated six-membered ring organic borate bond. In the embodiment, the selected boron-containing dynamic covalent bond has good regulation and control performance and rich structure selectivity, and the dynamic polymers with different topological structures and different energy absorption effects 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 bond.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring inorganic borate bond, an unsaturated five-membered ring inorganic borate bond, a saturated six-membered ring inorganic borate bond and an unsaturated six-membered ring inorganic borate bond. In the embodiment, the selected boron-containing dynamic covalent bond has a simple and stable structure and sensitive dynamic responsiveness.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein, the boron-containing dynamic covalent bond is selected from organic boric acid monoester bond, organic boric acid silicon ester bond, inorganic boric acid monoester bond and inorganic boric acid silicon ester bond. In the embodiment, the selected boron-containing dynamic covalent bond raw material has wide sources and simple preparation, and can show sensitive dynamic responsiveness and energy absorption effect.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one metal-ligand action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point. In the embodiment, by controlling parameters such as ligand groups, metal centers and the like in the metal-ligand action, the dynamic property of the polymer can be combined, matched and regulated in a larger range, so that the polymer material with rich structure, various performances and excellent energy absorption effect is obtained.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one ionic action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point. In this embodiment, the selected ionic action is stable in the polymer, and the strength of the ionic action can be well controlled by varying the concentration and type of ionic groups.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one ion-dipole effect and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point. In the embodiment, the selected ion-dipole effect can stably exist in an electrochemical environment, the conditions for generating and dissociating the acting force are mild, the acting force is easy to control, and the pH value, the concentration sensitivity and the conductivity are realized.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one host-guest action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point. In this embodiment, the selected host molecule and guest molecule can exist stably in the polymer, and the formed host and guest have moderate action strength and can interact or dissociate under mild conditions, so that the dynamic property and the energy absorption property of the dynamic polymer can be realized under mild conditions.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one Lewis acid-base pair effect and common covalent cross-linking formed by the common covalent bond, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point. In the embodiment, the selected Lewis acid-base pair has good dynamic reversibility and can be rapidly dissociated under the condition of slight heating or the existence of an organic solvent, so that the self-repairing or reshaping effect and the good energy absorption effect are realized.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one pi-pi stacking function and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above a gel point. In the embodiment, the selected pi-pi stacking effect is simple in forming mode, can stably exist in the polymer, is less influenced by the external environment, and can be conveniently regulated and controlled by changing the conjugated compound and the content.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond, an unsaturated six-membered ring organic borate bond, an organic borate single-ester bond and an organic borate silicon ester bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, and pi-pi stacking interaction. In the embodiment, the selected boron-containing dynamic covalent bonds have good controllability and rich structural 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 units in the boron-containing dynamic covalent bonds; the selected supramolecular function can stably exist in the polymer and has good dynamic reversible characteristic.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein, the cross-linking degree of the common covalent cross-linking reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from 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 monoester bond and inorganic borate silicon bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, Lewis acid-base pair interaction, and pi-pi stacking interaction. In the embodiment, the selected boron-containing dynamic covalent bond has a simple and stable structure, and can show sensitive dynamic responsiveness under the action of an external force; the selected supramolecular function can stably exist in the polymer and has good dynamic reversible characteristic.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network only comprises common covalent cross-links formed by common covalent bonds, and the cross-linking degree of the common covalent cross-links is above the gel point, the other cross-linked network comprises dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond and supramolecular cross-links formed by at least one non-hydrogen bond type supramolecular interaction and optionally at least one hydrogen bond interaction, and the sum of the cross-linking degrees of the dynamic covalent cross-links and the supramolecular cross-links is above the gel point. In the embodiment, the dynamic cross-linked network can exist independently of a common covalent cross-linked network, and the two networks can be mutually independent in raw material composition, so that the preparation has special advantages; meanwhile, the dynamic polymer can show different orthogonality and cooperativity by utilizing the difference between the dynamic property and the stability of the dynamic cross-linked network and the common covalent cross-linked network. In addition, through dispersing and blending the common covalent cross-linked network and the dynamic covalent cross-linked network, discontinuous, partially continuous or bicontinuous disperse phases can be respectively formed in a system, so that the respective functional characteristics are respectively reflected, the common covalent cross-linked network has good stability and creep resistance and is convenient to keep the shape, and the dynamic covalent cross-linked network can disperse, absorb and dissipate impact energy and has self-repairing performance.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is above the gel point, and the other cross-linked network comprises supramolecular cross-linking formed by at least one non-hydrogen bond type supramolecular interaction and optionally at least one hydrogen bond interaction, and the cross-linking degree of the supramolecular cross-linking is above the gel point. In the embodiment, the supramolecular cross-linked network exists independently of a common covalent cross-linked network and a dynamic covalent cross-linked network, and the aim of reasonably regulating and controlling the balance structure and the mechanical property of the dynamic polymer can be achieved by selecting the structures and the components of the supramolecular cross-linked network and the covalent cross-linked network; meanwhile, the dynamic polymer can show different orthogonality and cooperativity by utilizing the difference of the dynamic property and the stability between the supermolecule cross-linked network and the covalent cross-linked network. In addition, through dispersing and blending the covalent cross-linked network and the supramolecular cross-linked network, discontinuous, partially continuous or bicontinuous disperse phases can be respectively formed in a system, so that the respective functional characteristics are respectively embodied, the covalent cross-linked network can provide certain stability and mechanical property, and the supramolecular cross-linked network can embody good dynamic property and self-repairing property.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein, the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network simultaneously comprises at least one non-hydrogen bond type supermolecule effect and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is above the gel point, the other cross-linked network comprises dynamic covalent cross-linking formed by at least one boron-containing dynamic covalent bond, and the cross-linking degree of the dynamic covalent cross-linking is above the gel point, and at least one hydrogen bond effect is optionally contained in at least one cross-linked network. In the embodiment, a non-hydrogen bond type supermolecule effect is introduced into a common covalent cross-linking network, so that the dynamic polymer has certain dynamic reversibility, and the aim of reasonably regulating and controlling the balance structure and the mechanical property of the dynamic polymer can be achieved by the mutual matching between the dynamic polymer and the independent dynamic covalent cross-linking network.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent crosslinks formed by common covalent bonds with the degree of crosslinking of the common covalent crosslinks being above the gel point, the other crosslinked network simultaneously comprises at least one non-hydrogen bond type supramolecular interaction and common covalent crosslinks formed by common covalent bonds with the degree of crosslinking of the common covalent crosslinks being above the gel point, and optionally at least one hydrogen bond interaction in the at least one crosslinked network. In this embodiment, the purpose of reasonably regulating and controlling the equilibrium structure and mechanical properties of the dynamic polymer can be achieved by controlling the structure of the two common covalent cross-linked networks and the dynamic components contained therein.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network only comprises common covalent cross-links formed by common covalent bonds and has a cross-linking degree of the common covalent cross-links above the gel point, the other cross-linked network comprises dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond and has a cross-linking degree of the dynamic covalent cross-links above the gel point, the last cross-linked network comprises supramolecular cross-links formed by at least one non-hydrogen bond type supermolecule interaction and has a cross-linking degree of the supramolecular cross-links above the gel point, and at least one hydrogen bond interaction is optionally contained in at least one cross-linked network. In the embodiment, the common covalent cross-linked network, the dynamic covalent cross-linked network and the supermolecule cross-linked network exist independently, the dissociation of one cross-linked network does not immediately cause the failure of other cross-linked networks, and the networks can be independent from each other in raw material composition, so that the dynamic polymer can show different orthogonality and synergy by utilizing the difference of dynamic property and stability among different cross-linked networks. In addition, through dispersing and blending the common covalent cross-linked network, the dynamic covalent cross-linked network and the supramolecular cross-linked network, discontinuous, partially continuous or bicontinuous disperse phases can be respectively formed in a system, so that the respective functional characteristics are respectively embodied, the common covalent cross-linked network has good stability and creep resistance and is convenient to keep the shape, and the dynamic covalent cross-linked network and the supramolecular cross-linked network can disperse, absorb and dissipate impact energy and embody the self-repairing performance with difference.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network only comprises common covalent cross-links formed by common covalent bonds, and the cross-linking degree of the common covalent cross-links is above the gel point, the other cross-linked network comprises dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond, and the sum of the cross-linking degrees of the dynamic covalent cross-links and the supramolecular cross-links formed by at least one non-hydrogen bond type supramolecular action is above the gel point, and the last cross-linked network comprises supramolecular cross-links formed by at least one hydrogen bond action, and the cross-linking degree of the supramolecular cross-links is above the gel point. In the embodiment, two different dynamic crosslinking networks are introduced into the dynamic polymer system, and the two dynamic crosslinking networks and the common covalent crosslinking network can exert the regulation and control effects of orthogonality and cooperativity by regulating the structures and components of the two dynamic crosslinking networks.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is higher than the gel point of the hybrid cross-linked dynamic polymer, the other cross-linked network comprises supramolecular cross-linking formed by at least one non-hydrogen bond type supramolecular interaction, and the cross-linking degree of the supramolecular cross-linking is higher than the gel point of the hybrid cross-linked dynamic polymer, and the last cross-linked network comprises supramolecular cross-linking formed by at least one hydrogen bond interaction, and the cross-linking degree of the supramolecul. In the embodiment, the three cross-linked networks respectively contain dynamic components, and the introduced two supramolecular cross-linked networks can provide certain dynamic reversible property and self-repairing capability for the system.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network simultaneously contains at least one non-hydrogen bond type supramolecular function and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is higher than the gel point of the cross-linked network, the other cross-linked network contains dynamic covalent cross-linking formed by at least one boron-containing dynamic covalent bond, and the cross-linking degree of the dynamic covalent cross-linking is higher than the gel point of the cross-linked network, and the last cross-linked network contains supramolecular cross-linking formed by at least one hydrogen bond function, and the cross-linking degree of the supramolecular cross-linking is higher than. In the implementation mode, the three cross-linked networks contain dynamic components, and the introduced dynamic covalent cross-linked network and the introduced supramolecular cross-linked network can provide a certain dynamic reversible characteristic and self-repairing capability for the system.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond and an unsaturated six-membered ring organic borate bond. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in a different crosslinked network. In the embodiment, the selected boron-containing dynamic covalent bond has good regulation and control performance and rich structure selectivity, and the dynamic polymers with different topological structures and different energy absorption effects 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 units in the boron-containing dynamic covalent bond.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring inorganic borate bond, an unsaturated five-membered ring inorganic borate bond, a saturated six-membered ring inorganic borate bond and an unsaturated six-membered ring inorganic borate bond. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in a different crosslinked network. In the embodiment, the selected boron-containing dynamic covalent bond has a simple and stable structure and sensitive dynamic responsiveness.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein, the boron-containing dynamic covalent bond is selected from organic boric acid monoester bond, organic boric acid silicon ester bond, inorganic boric acid monoester bond and inorganic boric acid silicon ester bond. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In the embodiment, the selected boron-containing dynamic covalent bond raw material has wide sources and simple preparation, and can show sensitive dynamic responsiveness and energy absorption effect.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one metal-ligand action and common covalent cross-links formed by the common covalent bond, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In the embodiment, by controlling parameters such as ligand groups, metal centers and the like in the metal-ligand action, the dynamic property of the polymer can be combined, matched and regulated in a wider range, so that the polymer material with rich structure, various performances and excellent energy absorption effect is obtained.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one ionic action and common covalent cross-links formed by the common covalent bond, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In this embodiment, the selected ionic action is stable in the polymer, and the strength of the ionic action can be well controlled by varying the concentration and type of ionic groups.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid crosslinked dynamic polymer comprises two or more crosslinked networks, and at least one boron-containing dynamic covalent bond, at least one ion-dipole effect and common covalent crosslinks formed by the common covalent bonds in the crosslinked networks, wherein the degree of crosslinking of the common covalent crosslinks in at least one of the networks is above the gel point. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In the embodiment, the selected ion-dipole effect can stably exist in an electrochemical environment, the conditions of generating and dissociating the acting force are mild, the acting force is easy to control, and the pH, the concentration and the conductivity are realized.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one host-guest interaction and common covalent cross-links formed by the common covalent bond, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In this embodiment, the selected host molecule and guest molecule can exist stably in the polymer, and the formed host and guest have moderate action strength and can interact or dissociate under mild conditions, so that the dynamic property and energy absorption property of the dynamic polymer can be realized under mild conditions.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one Lewis acid-base pair effect and common covalent cross-links formed by the common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above a gel point. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In the embodiment, the selected Lewis acid base has good dynamic reversibility to the action and can be rapidly dissociated under the condition of slight heating or in the presence of an organic solvent, so that self-repairing or reshaping and a good energy absorption effect are realized.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one pi-pi stacking function and common covalent cross-links formed by the common covalent bond, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In the embodiment, the selected pi-pi stacking effect is simple in forming mode, can stably exist in the polymer, is less influenced by the external environment, and can be conveniently regulated and controlled by changing the conjugated compound and the content.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond, an unsaturated six-membered ring organic borate bond, an organic borate single ester bond and an organic borate silicon ester bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, and pi-pi stacking interaction. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In the embodiment, the selected boron-containing dynamic covalent bonds 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 units in the boron-containing dynamic covalent bonds; the selected supramolecular function can stably exist in the polymer and has good dynamic reversible characteristic.

According to another preferred embodiment of the invention, a hybrid cross-linked dynamic polymer is provided and used as an energy absorbing material for absorbing energy; wherein the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular action, optionally at least one hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from 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 monoester bond and inorganic borate silicon bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, and pi-pi stacking interaction. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In the embodiment, the selected boron-containing dynamic covalent bond has a simple and stable structure, and can show sensitive dynamic responsiveness under the action of an external force; the selected supramolecular function can stably exist in the polymer and has good dynamic reversible characteristic.

Furthermore, according to a preferred embodiment of the present invention, a non-crosslinked polymer having a crosslinking degree below the gel point and/or a polymer particle having a crosslinking degree above the gel point may be dispersed in the hybrid crosslinked dynamic polymer crosslinked network, and the non-crosslinked polymer and/or the polymer particle may contain one or more of boron-containing dynamic covalent bonds and supramolecular interactions, or may be formed by only common covalent bonds. Non-crosslinked polymers having a degree of crosslinking below their 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 hybrid network structure embodiments, one embodiment can comprise a plurality of identical or different cross-linked networks, and the same cross-linked network can comprise different common covalent cross-links and/or different dynamic covalent cross-links and/or different supermolecule cross-links. The degree of crosslinking of any one crosslink of any one network can also be reasonably controlled to achieve the purpose of regulating and controlling the balance structure and dynamic properties. Those skilled in the art may implement the present invention reasonably and effectively in light of the logic and spirit of the present invention.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized in that the hybrid crosslinked dynamic polymer only contains a crosslinked network, and the crosslinked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect, at least one optional hydrogen bond effect and common covalent crosslinking formed by common covalent bonds, wherein the crosslinking degree of the common covalent crosslinking reaches above the gel point. For this embodiment, which contains only one cross-linked network, ordinary covalent cross-linking is used to provide an equilibrium structure, dynamic covalent cross-linking, supramolecular cross-linking may be above or below its gel point, to provide additional cross-linking to the cross-linked network beyond ordinary covalent cross-linking, and to provide dynamic, effectively achieving toughening; and the preparation is more convenient.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized in that the hybrid crosslinked dynamic polymer comprises two crosslinked networks, and the crosslinked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect, at least one optional hydrogen bond effect and common covalent crosslinks formed by common covalent bonds, wherein the crosslinking degree of the common covalent crosslinks in at least one network reaches above a gel point; wherein, the boron-containing dynamic covalent bond is selected from organic borate ester bonds. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In the embodiment, the selected organic boric acid ester bond has good regulation and control performance and rich structure selectivity, and the dynamic polymer with different topological structures and different energy absorption effects can be prepared by controlling parameters such as the molecular structure, the number of functional groups, the molecular weight and the like of the organic boric acid element in the organic boric acid ester bond.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized in that the hybrid crosslinked dynamic polymer comprises two crosslinked networks, and the crosslinked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect, at least one optional hydrogen bond effect and common covalent crosslinks formed by common covalent bonds, wherein the crosslinking degree of the common covalent crosslinks in at least one network reaches above a gel point; wherein the non-hydrogen bonded supramolecular interaction is selected from ionic interaction, metallophilic interaction, dipole-dipole interaction, halogen bond interaction, lewis acid-base pair interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, ionic hydrogen bonding interaction, radical cation dimerization interaction, phase separation interaction, crystallization interaction. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In this embodiment, the selected supramolecular interaction is stable in the polymer and has good dynamic reversible properties.

The invention also provides an energy-absorbing hybrid crosslinked dynamic polymer, which is characterized by comprising at least three crosslinked networks, wherein the crosslinked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent crosslinks formed by common covalent bonds, and the crosslinking degree of the common covalent crosslinks in at least one network reaches above the gel point. In this embodiment, the boron-containing dynamic covalent bonds, supramolecular interactions, and common covalent crosslinks may be in the same crosslinked network or may each be in different crosslinked networks. In this embodiment, by incorporating multiple cross-linked networks into the dynamic polymer system, the structure and composition of each cross-linked network can be adjusted to exert both orthogonality and synergistic control effects.

In the invention, because the hybrid cross-linked dynamic polymer structure simultaneously contains common covalent cross-linking, boron-containing dynamic covalent bond, non-hydrogen bond type super molecular action and optional hydrogen bond action, the strength, the dynamic property, the responsiveness and the like of the dynamic polymer can be adjusted in a large range; meanwhile, 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, supramolecular elements and hydrogen bond groups and the linkage structure of the boron-containing dynamic covalent bonds, supramolecular elements and hydrogen bond groups and the polymer chain. The boron-containing dynamic covalent bond, the non-hydrogen bond type supermolecule effect and the hydrogen bond effect can provide good tensile toughness and tear resistance for the cross-linked polymer in a specific structure due to the dynamic characteristics of the boron-containing dynamic covalent bond, the non-hydrogen bond type supermolecule effect and the hydrogen bond effect; due to the difference of the intensity and the dynamic property between the boron-containing dynamic covalent bond, the non-hydrogen bond type supermolecule effect and the hydrogen bond effect, the sequential dynamic response effect can be generated, so that the dynamic polymer shows different orthogonality and cooperativity, and the common covalent crosslinking in the system provides a strong and stable network structure for the dynamic polymer.

The topology of the linking group for linking the boron-containing dynamic covalent bond and/or supramolecular motif and/or hydrogen bonding group is not particularly limited, and may be linear, branched, multi-armed, star, H, comb, dendrimer, monocyclic, polycyclic, spiro, fused, bridged, 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 molding are facilitated, the polymer can show rapid dynamic responsiveness, and the dynamic polymer with partial self-repairing and good processing performance can be obtained. For the connecting base with two-dimensional and three-dimensional cluster structures, the structure is stable, and good mechanical property, thermal stability, solvent resistance and creep resistance can be provided for the dynamic polymer.

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 "and/or" as used herein in the specification "may include different common covalent crosslinks and/or different dynamic covalent crosslinks" means that the crosslinked network may include different common covalent crosslinks, or the crosslinked network may include different dynamic covalent crosslinks, or both different common covalent crosslinks and different dynamic covalent crosslinks. The conjunction "and/or" appearing elsewhere in the specification of the invention is intended to be such meaning.

The hybrid cross-linked dynamic polymer contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the boron-containing dynamic covalent bonds, the non-hydrogen bond type supermolecule actions and the hydrogen bond actions of different types have different strengths, structures, dynamics, responsiveness, formation conditions and the like, so that the dynamic effect and the response effect of synergy and orthogonality can be achieved, and the structure and the performance of the material are more adjustable; the common covalent cross-linking in the system provides a strong and stable network structure for the dynamic polymer. 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 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, when a dynamic polymer having a double-network structure is prepared by a step method, a first network may be prepared by using a monomer or a prepolymer, a catalyst, an initiator, and a crosslinking agent, and then a second network prepared may be added and blended to obtain a mutually blended crosslinked network, 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, a crosslinking agent 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 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 an embodiment of the present invention, the hybrid crosslinked dynamic polymer has a form selected from the group consisting of normal solids, elastomers, gels (including hydrogels, organogels, oligomer-swollen gels, plasticizer-swollen gels, ionic liquid-swollen gels), foams, and the like, wherein the normal solids and foams generally contain no more than 10 wt% of soluble low molecular weight components, and the gels generally contain no less than 50 wt% of low molecular weight components. 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 advantageous for providing damping/energy absorbing capabilities. The gel has good flexibility, can embody better energy absorption characteristics and rebound resilience, and is suitable for preparing the energy absorption material with the damping effect. The foam material has the advantages of low density, lightness and high specific strength, can overcome the problems of brittleness of part of common solids and low mechanical strength of gel, and has good elasticity, energy absorption and soft and comfortable characteristics. Materials of different morphologies may have suitable uses in different fields.

In an embodiment of the present invention, the hybrid crosslinked dynamic polymer gel may be obtained by crosslinking in a swelling agent (including one or a combination of water, an organic solvent, an oligomer, a plasticizer, and an ionic liquid), or may be obtained by swelling with a swelling agent after the preparation of the dynamic polymer is completed. 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 a large amount of air or other gases are introduced into emulsion, suspension or solution of a polymer by means of strong stirring in the preparation process of a dynamic polymer to form a uniform foam body, and then the uniform foam body is formed into a foam material through physical or chemical change. 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 during molding or mixing 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 foam materials can be further classified by their density into low-foaming, medium-foaming and high-foaming.

The other polymer which can be added/used can form a crosslinking system together with the dynamic polymer to form a hybrid crosslinking dynamic polymer material, or can be used as an additive to play a role in improving material performance, endowing new performance to the material, improving material use and economic benefit and achieving comprehensive utilization of the material in the system. Other polymers may be added/used, which may be selected from natural high molecular compounds, synthetic resins, synthetic rubbers, synthetic fibers. The invention does not limit the character and molecular weight of the added polymer, and can be oligomer or high polymer according to the difference of molecular weight, and can be homopolymer or copolymer according to the difference of polymerization form, and the polymer is selected according to the performance of the target material and the requirement of the actual preparation process in the specific using process.

The 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: the synthesis auxiliary agent comprises a catalyst and an initiator; stabilizing aids including antioxidants, light stabilizers, heat stabilizers; the auxiliary agent for improving the mechanical property comprises a cross-linking agent, an auxiliary cross-linking agent, a curing agent, a chain extender, a toughening agent and a coupling 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 inventionIn the formula, the inorganic non-metallic filler with conductivity is preferred, and includes but not limited to graphite, carbon black, graphene, carbon nanotubes and carbon fibers, so that the composite material with conductivity and/or electrothermal function is conveniently obtained. 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 the heating performance of remote control, 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, and 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 alloys, gallium indium tin liquid alloys, other gallium based liquid metal alloys. In one embodiment of the present invention, fillers that can perform electromagnetic and/or near infrared heating, including but not limited to nanogold, nanosilver, and nano palladium, 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 ultraviolet absorption, fluorescence, luminescence, photo-thermal and other properties 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. Organometallic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic thermal, etc.

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 the filler has important significance particularly on the action of photo-thermal, electromagnetic heat and the like.

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 hybrid crosslinked dynamic polymer of the invention can show orthogonal dynamic responsiveness and various dynamic reversible effects due to the common covalent crosslinking, boron-containing dynamic covalent bonds and supermolecule effect, thereby having 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, buffer materials, buildings, energy sources, bionics, intelligent materials and the like.

For example, by utilizing the dilatancy of the hybrid cross-linked dynamic polymer, the hybrid cross-linked dynamic polymer can be applied to the preparation of damping materials for vibration isolation of various motor vehicles, mechanical equipment, bridges and buildings, and the polymer material can dissipate a large amount of energy to play a role in damping when being vibrated, thereby effectively mitigating the vibration of a vibrator; the swelling flow property of the hybrid cross-linked dynamic polymer can be utilized to generate the change of the cross-linking degree, the change of flexibility and strong elasticity is generated, and the effect of effectively dispersing impact force is achieved, so that the hybrid cross-linked dynamic polymer can be used as an energy-absorbing buffer material to be applied to the aspects of buffer packaging materials, sports protection products, impact protection products, military and police protection materials and the like, and the vibration and impact of articles or human bodies under the action of external force, including shock waves generated by explosion and the like, are reduced; because common covalent crosslinking exists, the material can also be used as a shape memory material, and when external force is removed, the deformation of the material generated by the dissociation of boron-containing dynamic covalent bonds and supermolecule action in the loading process can be recovered; the polymer material can also be applied to the preparation of magic effects toys and fitness materials with creep and high elastic conversion, or speed lockers for roads and bridges, and anti-seismic shear plates or cyclic stress carriers.

For another example, by utilizing the dynamic reversibility of boron-containing dynamic covalent bonds, non-hydrogen bond type supramolecular action and optional hydrogen bond action, the adhesive with partial self-repairing function can be prepared, and can be applied to the adhesion of various materials, such as the electrode adhesive of a battery/super capacitor and a diaphragm, so as to reduce the damage of an electrode and prolong the service life of the electrode material; the preparation method can also be used for preparing various sealing elements such as polymer plugging glue with certain wound self-healing property, sealing plugs, sealing rings and the like, and can be widely applied to the aspects of electronic appliances, pipeline sealing and the like; based on the dynamic reversibility of boron-containing dynamic covalent bonds and supermolecule action, the scratch-resistant coating with the scratch 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 matrix material is realized; through proper component selection and formula design, a polymer gasket or a polymer plate with a partial self-repairing function can be prepared, so that the principle of organism injury healing can be simulated, the material can perform self-healing on internal or external injuries, hidden dangers are eliminated, the service life of the material is prolonged, the bionic effect is embodied, and great application potential is shown in the fields of military industry, aerospace, electronics, bionics and the like.

For another example, the introduction of boron-containing dynamic covalent bond, non-hydrogen bond type supramolecular action and optional hydrogen bond action enables the cross-linked polymer material to show certain toughness under proper conditions, so that a polymer film, fiber or plate with super 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; because common covalent crosslinking exists, the material can also be used as a shape memory material, and when external force is removed, the deformation of the material generated by the dissociation of boron-containing dynamic covalent bonds and supermolecule action in the loading process can be recovered.

In addition, the hybrid crosslinked dynamic polymer can be applied to other various suitable fields according to the embodied performance, and the person skilled in the art can expand and implement the hybrid crosslinked dynamic 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

3-acrylamide dopamine is used as a raw material, AIBN is used as an initiator, and the 3-acrylamide dopamine and N, N-dimethylacrylamide are subjected to free radical polymerization to prepare the acrylamide-dopamine copolymer.

Weighing a certain amount of N, N-dimethylacrylamide, and dissolving the N, N-dimethylacrylamide in deionized waterPreparing a 1mol/L solution, adding 1 mol% of cross-linking agent N, N' -methylene bisacrylamide and 0.6 mol% of initiator potassium persulfate into the solution, stirring and mixing uniformly, standing for 1h to remove air bubbles, and placing in a constant-temperature water bath at 60 ℃ for reaction for 4h to obtain the polyacrylamide gel. Weighing a certain amount of acrylamide-dopamine copolymer, dissolving the acrylamide-dopamine copolymer in deionized water to prepare a 0.5mol/L solution, adding a proper amount of sodium borate, dropwise adding a small amount of NaOH solution, uniformly mixing, reacting for 2 hours, adding 0.05mol of sodium alginate, swelling the prepared polyacrylamide gel in the mixed solution, and dropwise adding 0.05mol/L CaCl₂Reacting the solution for 30min, and adding 1.2g of Fe subjected to surface modification by the silane coupling agent A151₃O₄Mixing the particles with bentonite 1.0g, and ultrasonic treating for 1min to obtain Fe₃O₄The particles are uniformly dispersed in the solution, then a small amount of 1mol/L NaOH solution is added dropwise, and the solution is placed in a thermostatic water bath at the temperature of 60 ℃ for reaction for 2 hours. After the reaction is finished, the IPN multi-network hydrogel dispersed with the magnetic particles is obtained. The polymer gel has good mechanical property and rebound resilience, and can be used as an intelligent buffer gel for absorbing and buffering external stress because the polymer gel contains magnetic particles and can control the shape memory capacity of the material by heating electromagnetic waves.

Example 2

Acrylamide and 3-acrylamidophenylboronic acid are used as raw materials, AIBN is used as an initiator, and the acrylamide-phenylboronic acid copolymer (a) is obtained through RAFT free radical polymerization.

Dissolving a certain amount of sodium alginate in deionized water to prepare a 0.1mol/L solution, adding 50ml of the solution into a dry and clean three-neck flask, dropwise adding 5ml of Ca-EDTA/GDL mixed solution, adding 15g of acrylamide-phenylboronic acid copolymer (a), 8g of polyvinyl alcohol and 200ml of deionized water, heating to 50 ℃, stirring and dissolving for 30min, adding 2ml of triethylamine, and continuously stirring and reacting for 2h at 50 ℃ to form a first network. Then adding 10g of polyacrylic acid, stirring to dissolve, then adding 0.84g of aziridine crosslinking agent (b), and continuing to react for 1h to obtain the hybrid crosslinked multi-network hydrogel after the reaction is finished. In this example, the resulting polymer hydrogel was used as a composite packaging material or a liquid-absorbent backing material having both high water absorption and cushioning properties.

Example 3

Reacting 1 molar equivalent of four-arm polyethylene glycol with 4 molar equivalents of chloroformyl isocyanate to prepare the hydrogen bond group-terminated polyethylene glycol.

Weighing a certain amount of vinyl pyrrolidone in a reaction bottle, dissolving the vinyl pyrrolidone in deionized water to prepare a 1mol/L solution, adding 1 mol% of neopentyl glycol dimethacrylate serving as a cross-linking agent and 0.6 mol% of potassium persulfate serving as an initiator into the solution, stirring and mixing uniformly, standing for 1h to remove bubbles, and placing the mixture in a constant-temperature water bath at 60 ℃ to react for 4h to obtain the polyvinyl pyrrolidone gel. Dissolving a certain amount of sodium alginate in a deionized water/acetone mixed solvent to prepare a 0.1mol/L solution, adding 50ml of the solution into the reaction bottle, and then adding 0.5g of borax and 5ml of 0.05mol/LCaCl₂Heating the solution and a proper amount of pyridine to 60 ℃ for reaction for 4h, adding 5g of hydrogen bond group-terminated polyethylene glycol, 0.5g of carbon nano tube, 0.1g of organic bentonite, 0.1g of dibutyltin dilaurate and 0.02g of sodium dodecyl benzene sulfonate, carrying out ultrasonic treatment for 20min, dropwise adding a small amount of 1mol/LNaOH solution, heating to 60 ℃ for continuous reaction for 3h, finally obtaining the multi-network hydrogel dispersed with the carbon nano tube, wherein the multi-network hydrogel has good resilience, is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, and is subjected to compression performance test by a universal testing machine, the compression rate is 2mm/min, and the compression strength of the sample is measured to be 0.64 +/-0.10 MPa. The conductive hydrogel in the embodiment can show different conductivities and buffering capabilities under the action of an external electric field, and can realize self-repairing of the scars under the heating condition.

Example 4

Octamethylcyclotetrasiloxane and tetra (dimethylsiloxy) silane are used as raw materials, concentrated sulfuric acid is used as a catalyst, and the tetra-hydrogen-terminated polysiloxane is prepared by a ring-opening polymerization method.

12g of [4- (2,2',6',2 '-terpyridin-4' -yl) phenyl ] methanol was dissolved in 100ml of a pyridine solvent, cooled in an ice bath under an inert atmosphere, and then 50ml of undecylenoyl chloride was added thereto, and the mixture was stirred at room temperature overnight to prepare a pyridine ligand compound. The modified methyl silicone oil (a) is prepared by taking methyl mercapto silicone oil with the molecular weight of about 60,000, a pyridine ligand compound and vinyl dimethyl borate as raw materials and DMPA as a photoinitiator through a thiol-ene click reaction under the condition of ultraviolet irradiation.

Adding 120ml of anhydrous toluene solvent, 12mmol of vinyl-terminated polydimethylsiloxane with the molecular weight of about 2,000 and 3mmol of hydrosilyl-terminated polysiloxane into a dry and clean three-neck flask in sequence, introducing nitrogen to remove water and oxygen for 20min, heating to 40 ℃, stirring and dissolving, then adding a platinum-olefin complex Pt (dvs) as a catalyst, and reacting for 30h under the protection of nitrogen to form a covalent cross-linked network; adding 0.01mol of modified methyl silicone oil (a) and 2mmol of pentaerythritol, heating to 80 ℃, adding a small amount of deionized water, dropwise adding 2ml of triethylamine, carrying out polymerization reaction for 3h under a stirring state, adding 2g of organic bentonite, 1g of metal osmium heteroaromatic ring particles, 0.5g of zinc trifluoromethanesulfonate and 0.3g of sodium dodecyl benzene sulfonate, continuously stirring and mixing for 1h, pouring the polymer into a proper mould, placing the mould in a vacuum oven at 80 ℃ for 12h for drying to obtain a rubbery polymer sample, wherein when the sample is quickly knocked, the sample can show temporary rigidity and carry out stress dissipation, and when stress is slowly exerted on the surface of the sample, the sample shows viscous deformable characteristic, and can be used as an impact-resistant protective pad with a heat conduction function for protection of a precision instrument.

Example 5

Taking tetraallyloxyethane and 3-mercapto-1, 2-propylene glycol as raw materials, and controlling the molar ratio of the tetraallyloxyethane to the 3-mercapto-1, 2-propylene glycol to be 1: and 4, preparing the polyol compound (a) by a mercaptan-olefin click addition reaction by using AIBN as an initiator and triethylamine as a catalyst.

Adding a certain amount of chloroform solvent into a dry and clean reaction bottle, adding 0.05mol of 4-vinylpyridine, 2mmol of silver nitrate and 1mmol of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, stirring and mixing uniformly, irradiating under 300W ultraviolet light for 20min for photopolymerization, adding 0.02mol polyethylene glycol 400, 0.02mol polyalcohol compound (a) and 0.04mol trimethyl borate, dripping appropriate amount of acetic acid water solution, hydrolyzing for 30min, adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, heating to 60 ℃ for reaction for 5 hours, removing unreacted raw materials after the reaction is finished, adding 4mmol of polyoxypropylene triol with the molecular weight of 2000, heating to 80 ℃, introducing nitrogen to remove water and remove oxygen for 1 hour, then 6mmol of 1, 6-hexamethylene diisocyanate is added for reaction for 1h at the temperature of 60 ℃. After the reaction is finished, pouring the reaction solution into a proper mould, placing the mould in a vacuum oven at 60 ℃ for 24h for drying, then cooling to room temperature and placing for 30min to finally obtain the soft colloidal polyurethane-based polymer material. In the embodiment, the prepared polymer material can be used as the interlayer adhesive of a multilayer board to be applied to explosion-proof buildings for absorbing and dissipating external impact energy.

Example 6

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 gamma-mercaptopropyldimethylmethoxysilane are used as raw materials, the molar ratio of the raw materials to the raw materials is controlled to be 1:2, and a trimercapto compound (b) is obtained through condensation reaction at the temperature of 60 ℃. 4-mercaptomethylbenzyl boronic acid and 2-mercaptoethanol are used as raw materials, the molar ratio of the raw materials to the raw materials is controlled to be 1:2, and a trimercapto compound (c) is obtained through condensation reaction at the temperature of 60 ℃. Equimolar heptafluoro-2-naphthol and thioglycolic acid are reacted under the catalysis of DCC and DMAP to obtain the mercaptofluoronaphthalene (d).

Adding 0.01mol of hyperbranched compound (a) into a dry and clean reaction bottle, adding a certain amount of chloroform solvent for dissolving, then introducing nitrogen to remove water and remove oxygen for 1h, adding 0.01 wt% of BHT antioxidant, 0.2 wt% of AIBN and 1.0 wt% of triethylamine, slowly adding 0.01mol of trimercapto compound (b), 0.01mol of trimercapto compound (c), 0.02mol of mercaptofluoronaphthalene (d), 0.02mol of 3-phenyl-1-propanethiol and 0.02mol of 1, 6-hexanedithiol, and continuously reacting for 6h under the condition of nitrogen protection at 60 ℃. And then pouring the polymer solution into a proper mould, and placing the mould in a vacuum oven at 50 ℃ for 12h for drying to finally obtain the dynamic polymer elastomer with good resilience. The polymer material is made into a dumbbell-shaped sample strip with the size of 80.0 multiplied by 10.0 multiplied by (2.0-4.0), a tensile testing machine is used for tensile testing, the tensile rate is 50mm/min, the tensile strength of the sample is 3.62 +/-0.84 MPa, the tensile modulus is 6.20 +/-1.73 MPa, the elongation at break is 1025 +/-280%, the stress-strain curve of the polymer sample shows a step-shaped change trend, and the supermolecule effect and the boron-containing dynamic covalent bond in the system are sequentially separated step by step under the action of external force, so that the gradual dissipation of energy is realized, the toughness of the material is improved, and the material can be used as an energy-absorbing buffer gasket for damping and silencing of precision instruments or electronic products.

Example 7

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 5mmol of polyetheramine D2000 in a dry clean flask, heating to 100 ℃, introducing nitrogen to remove water and remove oxygen for 1h, then adding 0.01mol of polymethylene polyphenyl polyisocyanate, reacting for 2h under the protection of 80 ℃ nitrogen, then cooling to 60 ℃, adding 4mmol of chain extender dimethylolpropionic acid, a proper amount of triethylamine and 0.5 wt% of stannous octoate, continuing to react for 2h, then adding 6mmol of amino compound (a), 4mmol of heptafluoro-2-naphthol, 4mmol of benzyl alcohol, 5 wt% of silicon dioxide and 4 wt% of silicone oil foam stabilizer, stirring at high speed and mixing uniformly, then adding 0.01mol of polymethylene polyphenyl polyisocyanate for rapid mixing, stirring at high speed for 30s, when the mixture is whitish and bubbling, rapidly pouring the mixture into a proper mold, molding and foaming at 80 ℃ for 12h to ensure complete reaction and polymerization, finally, the rigid polyurethane foam material can be obtained. The material is prepared into a block sample with the size of 20.0 multiplied by 20.0mm, a universal tester is utilized to carry out compression performance test, the compression rate is 2mm/min, and the compression strength of the sample is measured to be 0.80 plus or minus 0.33 MPa. The obtained polymer foam can be used as a stress buffering foam packaging material to buffer and absorb external impact force by utilizing the characteristics of light weight, high specific strength, good heat insulation and insulation, outstanding energy absorption effect and the like of the obtained polymer foam.

Example 8

AIBN is used as an initiator, 3- (2-hydroxyethyl) phenylboronic acid pinacol ester reacts with acryloyl chloride to prepare a phenylboronic acid ester acrylate monomer, and BPO is used as an initiator to polymerize with methyl methacrylate and 2-aminoethyl acrylate through free radicals to obtain the acrylate copolymer (a) containing a borate side group and a side amino group.

Performing ester exchange reaction on equimolar amounts of adamantane-1-ethyl formate and hydroxyethyl methacrylate to obtain an adamantane-containing methacrylate monomer, and polymerizing the monomer and methyl methacrylate by taking BPO as an initiator to obtain an acrylate copolymer (b) containing an adamantane side group, wherein β -cyclodextrin reacts with toluene-2, 4, 6-triyl triisocyanate to obtain the β -cyclodextrin polymer.

Adding a certain amount of toluene solvent into a dry and clean reaction bottle, adding 8mmol of acrylate copolymer (a) into the reaction bottle, stirring and dissolving completely, then dropwise adding a proper amount of acetic acid aqueous solution for hydrolysis for 30min, adding a proper amount of anhydrous sodium sulfate, introducing nitrogen, heating to 80 ℃, removing water and oxygen, reacting for 2h, then adding a proper amount of triethylamine and 0.04mol of polycaprolactone diol, continuing to stir for reaction for 3h, then adding 0.01mol of ethylene glycol diglycidyl ether, continuing to react for 3h, then adding 4mmol of acrylate copolymer (b), 0.1mol of β -cyclodextrin polymer, adding 5 wt% of titanium alloy powder, 5 wt% of ceramic powder and 10 wt% of calcium sulfate, stirring uniformly, continuing to react for 2h, pouring the polymer solution into a proper mold, placing in a vacuum oven at 80 ℃ for 24h to remove the solvent, then cooling to room temperature, and placing for 30min to finally obtain a milky polymer solid sample with gloss.

Example 9

Taking potassium persulfate as an initiator, and carrying out free radical polymerization on 4-acrylamido phenylboronic acid sodium salt, N-dimethylacrylamide and 2-aminoethyl acrylate to obtain a phenylboronic acid-acrylamide copolymer; taking potassium persulfate as an initiator, and carrying out free radical polymerization on 3-acrylamide dopamine, N-dimethylacrylamide and 2-aminoethyl acrylate to obtain the dopamine-acrylamide copolymer.

Adding 6-amino- β -cyclodextrin and sodium bicarbonate solution into a reactor, placing the reactor in an ice bath, adding acryloyl chloride, stirring for reaction for 4 hours, adding acetone for precipitation, centrifuging the precipitation solution, drying the collected product in a vacuum oven, and preparing acrylamide- β -cyclodextrin, adding 1-aminoadamantane and triethylamine into the reactor, dissolving the 1-aminoadamantane and the triethylamine in tetrahydrofuran in the ice bath, adding the acyl chloride, stirring for reaction, filtering after 4 hours, removing the precipitate, concentrating the supernatant under reduced pressure to obtain a crude product, recrystallizing the crude product with chloroform to obtain acrylamide-1-adamantane, and carrying out free radical polymerization on the acrylamide- β -cyclodextrin, the acrylamide-1-adamantane and the N, N-dimethylacrylamide by using potassium persulfate as an initiator and N, N' -methylenebisacrylamide as a crosslinking agent to obtain the acrylamide copolymer (a).

Taking a certain amount of ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate, adding 3mmol of dopamine-acrylamide copolymer and 5mmol of phenylboronic acid-acrylamide copolymer, stirring and dissolving completely, adding a proper amount of pyridine, placing in a water bath kettle at 60 ℃, heating for reaction for 2 hours, then adding 5mmol of acrylamide copolymer (a), and then adding 5 wt% of surface modified Fe₃O₄And (3) carrying out ultrasonic treatment on the particles, 5 wt% of metal magnetic powder and 1 wt% of bentonite for 1min to uniformly disperse the metal particles in the particles, then placing the particles in a constant-temperature water bath at 60 ℃ to react for 2h, and obtaining the ionic liquid gel dispersed with the magnetic particles after the reaction is finished. In the embodiment, the obtained polymer magnetic gel can be used as an intelligent buffer gel material with magnetic field responsiveness, so that the external impact energy is absorbed and dissipated.

Example 10

Hydroxyl-terminated methyl mercapto silicone oil with the molecular weight of about 2,000 and 3- (allyloxy) -1, 2-propylene glycol 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. 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, methyl mercapto silicone oil (b) containing side hydrogen bond groups is prepared through thiol-ene click reaction.

15ml of methyl hydrogen silicone oil having a molecular weight of about 20,000 was charged in a three-necked flask, and 0.02mol of 4-methyl-4-pentenoic acid, 0.01mol of 1, 6-hexadiene and 0.01mol of ZnCl were added₂Adding a platinum-olefin complex Pt (dvs) as a catalyst, heating to 80 ℃, and reacting for 30h under the protection of nitrogen to form a first network; adding 0.02mol triethyl borate into a three-neck flask, dropwise adding an appropriate amount of acetic acid aqueous solution, hydrolyzing for 30min, adding 20ml modified silicone oil (a) and 15ml methyl mercapto silicone oil (b), adding an appropriate amount of triethylamine, heating to 80 ℃, reacting for 5h, and polymerizingDuring the compounding process, the viscosity of the silicone oil is continuously increased, the silicone oil is poured into a proper mould and placed in a vacuum oven at 80 ℃ for continuous reaction for 12 hours, and then the silicone oil is cooled to room temperature and placed for 30 minutes, and finally a rubbery polymer sample with certain strength and surface elasticity is obtained. In the embodiment, the damping characteristic of the polymer material can be used as a high-damping shock-insulation rubber support to perform shock isolation on bridges and building buildings.

Example 11

Brominated butyl rubber (a) and 3-mercapto-1, 2-propylene glycol are used as raw materials, DMPA is used as a photoinitiator, and the 1, 2-diol graft modified butyl rubber is prepared by mercaptan-olefin click addition reaction under the condition of ultraviolet irradiation.

Brominated butyl rubber (a) and mercaptomethyl methyl diethoxy silane are used as raw materials, DMPA is used as a photoinitiator, and the silane grafted modified butyl rubber is prepared through mercaptan-olefin click addition reaction under the ultraviolet irradiation condition.

Weighing 3g of boric acid, 15g of 1, 2-diol modified graft modified butyl rubber, 15g of silane graft modified butyl rubber, 0.4g of dicumyl peroxide, 1.8g of 2, 7-dibromopyrene, 0.3g of di-n-butyltin dilaurate, 0.05g of antioxidant 168, 0.1g of antioxidant 1010 and 0.3g of dimethyl silicon oil, adding the materials into a small internal mixer, mixing for 20min, taking out the mixed materials, cooling, placing the materials in a double-roller press to prepare sheets, cooling at room temperature, cutting into pieces, soaking in 90 deg.C alkaline water for pre-crosslinking, taking out, placing in 80 deg.C vacuum oven for 5 hr for drying and further reaction, then placing the sample wafer in a proper mould, placing the mould on a flat vulcanizing machine, preheating for 10min at 160 ℃, and then pressurizing to 10MPa, and maintaining the pressure for 10min to finally obtain the butyl rubber-based dynamic polymer material. The polymer rubber can keep elasticity in a normal state, shows temporary rigidity when being impacted, returns to a normal elastic state after the impact, and can be made into a rubber-based buffer pad for use by utilizing the stress response characteristic of a sample, and the rubber-based buffer pad can buffer and absorb external stress.

Example 12

Adding a certain amount of tetrahydrofuran solvent into a dry and clean reaction bottle, adding 0.04mol of trimethyl borate, 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 0.02mol of decatetramethyl-1, 11-dichlorohexasiloxane and 0.02mol of four-arm polyethylene glycol (a) with the molecular weight of about 3,000, stirring and dissolving completely, heating to 60 ℃ for reaction for 5h, removing unreacted raw materials after the reaction is finished, then adding 2mmol of ethylenediamine polyether tetrol with the molecular weight of 300, 2mmol of 1, 4-dibromo-2, 3-butanediol, heating to 80 ℃, introducing nitrogen to remove water and remove oxygen for 1h, then adding 6mmol of 1, 6-hexamethylene diisocyanate, and reacting for 1h at the temperature of 60 ℃. After the reaction is finished, pouring the reaction solution into a proper mould, placing the mould in a vacuum oven at 60 ℃ for 24h for drying, then cooling to room temperature and placing for 30min to finally obtain the soft colloidal polyurethane-based polymer material. In this example, the prepared polymer material can be applied to explosion-proof buildings as an interlayer adhesive of a multi-layer board, thereby absorbing external impact energy.

Example 13

Polyetheramine D2000 was reacted with an equimolar amount of catalyst triethyl orthoacetate in the presence of phenol to give the amidino polyether.

Adding a certain amount of dichloromethane solvent into a three-neck flask, adding 5mmol of hydroxyl-terminated polydimethylsiloxane with the molecular weight of about 2,000, adding a proper amount of triethylamine, stirring and mixing uniformly, adding 0.01mol of hexamethoxydisilane and 0.01mol of sodium borate, dropwise adding a small amount of acetic acid aqueous solution, heating to 80 ℃ to react for 4 hours, adding 5mmol of polyacrylic acid, 2mmol of amidino polyether and 3mmol of aziridine crosslinking agent, continuing to react for 1 hour, adding 5 wt% of mixed powder of ground ultramarine, chrome yellow, phthalocyanine blue and soft carbon black, 3 wt% of organic swelling soil, 3 wt% of nano-silica, 5 wt% of hydroxyethyl cellulose, 2 wt% of dibutyltin dilaurate, trace fluorescent KSN and a light stabilizer 770, stirring and mixing uniformly, standing for 12 hours, coating the mixture on the surface of a substrate to obtain a coating with energy absorption property, thereby absorbing external impact energy.

Example 14

DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and 4-mercapto phenylboronic acid and terminal amino 1, 3-polybutadiene are subjected to thiol-ene click reaction to prepare phenylboronic acid graft modified polybutadiene. DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and 3-mercapto-1, 2-propanediol and amine-terminated 1, 3-polybutadiene are subjected to thiol-ene click reaction to prepare the 1, 2-diol graft modified polybutadiene. DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and 3-mercaptopropionic acid and 1, 3-polybutadiene are subjected to thiol-ene click reaction to prepare carboxyl graft modified polybutadiene. The amino graft modified polybutadiene is prepared by taking DMPA as a photoinitiator and ultraviolet light as a light source and carrying out thiol-ene click reaction on mercaptoethylamine and 1, 3-polybutadiene.

Adding 3mmol of 1, 2-diol graft modified polybutadiene and 3mmol of phenylboronic acid graft modified polybutadiene into a dry and clean reaction bottle, dissolving the materials in a certain amount of xylene solvent, adding a proper amount of acetic acid aqueous solution, stirring and mixing for 20min, adding a proper amount of triethylamine, heating to 80 ℃, mixing and reacting for 4h, adding 0.01mol of polymethylene polyphenyl polyisocyanate (the content of isocyanate is about 30%) for mixing and reacting for 30min to form a first network, adding 2mmol of carboxyl graft modified polybutadiene and 2mmol of amino graft modified polybutadiene, adding 5 wt% of gallium-indium liquid alloy, 2 wt% of talcum powder and 0.4 wt% of dibutyltin dilaurate, stirring and uniformly mixing, pouring the mixture into a proper mold, placing the mold in a vacuum oven at 80 ℃ for 12h for further reaction, and obtaining a dynamic polymer elastomer with good resilience after the reaction is finished, the heat-conducting buffer gasket can be used as a heat-conducting buffer gasket for damping and heat dissipation of precision instruments or electronic products.

Example 15

4-hydroxy-2, 6-bis (1-methylbenzimidazole-2-yl) pyridine and acryloyl chloride are reacted by equimolar amount to prepare acrylic ester-2, 6-bis (1-methylbenzimidazole-2-yl) pyridine.

Mixing 1 molar equivalent of acryloyloxyethyl trimethyl ammonium chloride, 1 molar equivalent of sodium allylsulfonate, 1 molar equivalent of acrylate-2, 6-bis (1-methylbenzimidazole-2-yl) pyridine and 10 molar equivalents of ethyl acrylate in a reaction bottle, dissolving in a proper amount of tetrahydrofuran solvent, adding 2 molar equivalents of polyvinyl alcohol, 0.2 molar equivalent of fatty alcohol polyoxyethylene ether sulfate and 0.05 molar equivalent of potassium persulfate, stirring and mixing uniformly, pre-emulsifying the raw materials in an emulsifier, transferring the pre-emulsion to another reaction bottle, removing water and oxygen for 1h, adding 0.02 molar equivalent of 1,2,7, 8-diepoxyoctane, stirring and reacting for 2h, adding deionized water and 0.05 molar equivalent of sodium borate, stirring uniformly, heating to 80 ℃, continuing to react for 4h, then cooling the product to below 40 ℃, and adjusting the pH of the product to 8-9 by using sodium bicarbonate to prepare a modified acrylate emulsion; and adding 31 parts by mass of water, 2 parts by mass of coconut oil diethanolamide, 1 part by mass of sodium dodecyl benzene sulfonate, 0.3 part by mass of mildew preventive Z and 1 part by mass of defoaming agent into another reaction bottle, stirring for 10min, adding 5 parts by mass of titanium dioxide, 3 parts by mass of lithopone, 11 parts by mass of light calcium carbonate and 1 part by mass of light stabilizer 770, dispersing for 30min at a high speed, adding 5 parts by mass of modified acrylate emulsion, stirring uniformly, and adjusting the viscosity by using water to obtain the dynamic polymer emulsion. The emulsion can be used as a coating with energy-absorbing property to resist impact and protect a base material.

Example 16

Glycerol 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.

Adding 50 parts by mass of ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate, 10 parts by mass of polyether polyol ED-28, 2 parts by mass of 2, 3-epoxypropyltrimethylammonium chloride, 1.6 parts by mass of potassium epoxyethane carboxylate, 1 part by mass of glycidyl ether and 0.05 part by mass of boron trifluoride diethyl etherate into a dry and clean reaction bottle, heating to 100 ℃, reacting for 4 hours, and then adding 10 parts by mass of boron trifluorideAdding a proper amount of triethylamine into hydroxyl-terminated three-arm polyethylene oxide and 2 parts of boric acid by mass, stirring and mixing uniformly, heating to 80 ℃, reacting for 4 hours, and then adding 5 parts of surface-modified Fe by mass₃O₄And (3) carrying out ultrasonic treatment on the particles, 5 parts by mass of metal magnetic powder and 1 part by mass of bentonite for 1min to uniformly disperse the metal particles in the particles, then continuing to react for 2h, and obtaining the ionic liquid gel dispersed with the magnetic particles after the reaction is finished. In the embodiment, the obtained polymer magnetic gel can be used as an intelligent buffer gel material with magnetic field responsiveness, and can absorb and dissipate energy.

Example 17

DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and 4-mercapto phenylboronic acid and terminal amino 1, 3-polybutadiene are subjected to thiol-ene click reaction to prepare phenylboronic acid graft modified polybutadiene. The silane grafted modified polybutadiene is prepared by taking DMPA as a photoinitiator and ultraviolet light as a light source and carrying out thiol-ene click reaction on mercaptomethyl dichlorosilane and amino-terminated 1, 3-polybutadiene. DMPA is used as a photoinitiator, ultraviolet light is used as a light source, and 3-mercapto-1, 2, 4-triazole and terminal amino 1, 3-polybutadiene are subjected to thiol-ene click reaction to prepare the azole grafted modified polybutadiene. Taking DMPA as a photoinitiator and ultraviolet light as a light source, and carrying out thiol-ene click reaction on 12-mercapto dodecyl phosphoric acid and terminal amino 1, 3-polybutadiene to obtain the phosphoric acid grafted modified polybutadiene.

Dissolving 4mmol of silane grafted and modified polybutadiene in 200ml of xylene solvent, adding a proper amount of acetic acid aqueous solution, stirring and mixing for 10min, adding 4mmol of phenylboronic acid grafted and modified polybutadiene, stirring and mixing uniformly, heating to 80 ℃, mixing and reacting for 2h, then adding 3mmol of triazole grafted and modified polybutadiene, reacting for 30min, adding 0.2g of talcum powder and 0.05g of dibutyltin dilaurate, stirring and mixing uniformly, adding 0.02mol of triphenylmethane triisocyanate, mixing rapidly to obtain a polyurea colloid with good resilience, stretching with a finger, performing large-scale extension under the action of external force, retracting slowly after the external force is removed, having shape memory property, and being used as a sandwich adhesive of a multilayer board for manufacturing an explosion-proof building, the energy is absorbed and dissipated.

Example 18

Vinyl boric acid and hydrogen-terminated silicone oil with the viscosity of about 3,000mPa & 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 end-capped silicone oil.

The amidino terminated silicone oil is obtained by taking amine terminated silicone oil with the viscosity of about 2,000 mPas as a raw material and reacting in the presence of triethyl orthoacetate serving as an equivalent molar catalyst.

Adding 120ml of anhydrous toluene solvent, 12mmol of vinyl-terminated polydimethylsiloxane with the molecular weight of about 2,000 and 3mmol of hydrosilyl-terminated polysiloxane into a dry and clean three-neck flask in sequence, introducing nitrogen to remove water and oxygen for 20min, heating to 40 ℃, stirring and dissolving, then adding a platinum-olefin complex Pt (dvs) as a catalyst, and reacting for 30h under the protection of nitrogen to form a covalent cross-linked network; then adding 0.02mol of boric acid end-capped silicone oil, 0.02mol of pentaerythritol, 0.02mol of amidino end-capped silicone oil, 0.02mol of 3- [ (2-carboxyethyl-dimethyl-silyl) oxy-dimethyl-silyl ] propionic acid, adding a proper amount of triethylamine, and continuing to react for 5 hours at the temperature of 80 ℃ to obtain a light yellow transparent viscous sample which can be used as a protective coating to be coated on the surface of a substrate to protect the substrate against impact.

Example 19

Dissolving 2 molar equivalents of 1,4,5, 8-naphthalene tetracarboxylic anhydride in KOH aqueous solution, adding 1 molar equivalent of 2,2' - (ethylene dioxy) bis (ethylamine) and stirring for 20min, adding phosphoric acid to adjust the pH value to 6.3, and reacting at 110 ℃ for 24h to obtain the tetranaphthaline carbodiimide compound. Under the protection of inert gas, 5 molar equivalents of tetranaphthalimide compound and 6 molar equivalents of aminodouble-terminated polyisobutylene are refluxed and reacted in a mixed solution of DMSO and toluene for 20h to obtain aminodouble-terminated polyisobutylene containing tetranaphthalimide. Carrying out acylation reaction on 2 molar equivalents of 1-pyrenebutyric acid and 1 molar equivalent of amino double-terminated polyisobutylene in the presence of a condensing agent 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline to obtain pyrene double-terminated polyisobutylene.

Polymerizing ethylene under the catalysis of Zr-FI catalyst to generate vinyl-terminated polyethylene, and then carrying out mercaptan-olefin click addition reaction on the vinyl-terminated polyethylene and 4-mercaptophenylboronic acid to obtain the organic boric acid compound (a). With a metallocene catalyst rac-CH₂(3-t-Bu-Ind)₂ZrCl₂) Catalyzing propylene and isoprene to copolymerize to obtain the propylene-isoprene copolymer whose side group contains vinylidene double bond. The modified polysilsesquioxane (b) 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 performing partial end capping by using quantitative vinylcyclopropane.

Dissolving 0.03mol of tetraboric acid and 8mmol of organic boric acid compound (a) in a certain amount of toluene solvent, adding a proper amount of calcium chloride dehydrating agent, heating to 80 ℃, and stirring for reaction for 5 hours to form a first network. Then adding 4mmol of amino double-terminated polyisobutylenes containing naphthalene tetracarbodiimide groups and 4mmol of pyrenyl double-terminated polyisobutylene, uniformly mixing, then adding 0.02mol of modified polysilsesquioxane (b), 4mmol of propylene-isoprene copolymer, 3 wt% of cellulose nanocrystal, 1 wt% of silicon dioxide, 0.3 wt% of sodium dodecyl benzene sulfonate and 0.2 wt% of photoinitiator DMPA, uniformly mixing, reacting for 20min under ultraviolet irradiation, then pouring the reaction solution into a proper mould, placing in a vacuum oven at 60 ℃ for 12h for further reaction and drying, then cooling to room temperature and placing for 30min to obtain a rubbery polyolefin sample. The sample is made into a dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by (2.0-4.0) mm, and a tensile test is carried out by a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 4.52 +/-1.73 MPa, the tensile modulus is 7.26 +/-2.50 MPa, and the elongation at break is 628 +/-233%. The obtained polymer sample can be used for manufacturing an energy absorption protective tool for sports protection or military police protection, and the impact energy is absorbed and dissipated.

Example 20

The amino-terminated compound (a) is obtained by condensation reaction of 2-aminomethyl phenylboronic acid and 2- (4-aminobutyl) propane-1, 3-diol which are equal molar amounts as raw materials and tetrahydrofuran as a solvent at the temperature of 60 ℃.

Weighing 0.02mol of polybutadiene epoxy resin (b) with the molecular weight of about 2,000, adding the polybutadiene epoxy resin (b) into a three-neck flask, heating to 80 ℃, introducing nitrogen for 1h, adding a proper amount of triethylamine, adding 0.08mol of amino-terminated compound (a), 0.04mol of 8-hydroxybenzo [ a ] pyrene, 0.02mol of ethyl- (3-hydroxypropyl) -dimethylammonium and 0.08mol of 1, 6-hexanediamine under a stirring state, and continuously heating for reaction for 2h to finally obtain the epoxy resin elastomer with toughness and high elongation, wherein the epoxy resin elastomer has good electric insulation property, weather resistance and impact toughness. The sample is made into a dumbbell-shaped sample bar with the size of 80.0 multiplied by 10.0 multiplied by (2.0-4.0) mm, and a tensile test is carried out by a tensile testing machine, wherein the tensile rate is 50mm/min, the tensile strength of the sample is 3.58 +/-1.05 MPa, the tensile modulus is 7.10 +/-2.05 MPa, and the elongation at break is 1045 +/-360%. In this embodiment, the obtained epoxy resin material can be applied to the field of electronic and electrical appliances as an insulating damping and buffering material to absorb and dissipate external impact force.

Example 21

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 compound (a) is obtained through condensation reaction at the temperature of 60 ℃.

Equimolar toluene-2, 4, 6-triyl triisocyanate and 6-hydroxymethyl anthanthrene (b) are reacted to prepare the anthracene structure modified diisocyanate.

30 parts by mass of polyetheramine D2000, 3 parts by mass of polyamino compound (a), 5 parts by mass of triethanolamine, 1 part by mass of ethylenediamine, 0.2 part by mass of dibutyltin dilaurate, 0.5 part by mass of organic silicone oil, 8 parts by mass of hexamethylene diisocyanate trimer and 6 parts by mass of anthracene structure modified diisocyanate are added into a reactor and uniformly mixed, the temperature is increased to 80 ℃, after 2 hours of reaction, 4 parts by mass of graphene powder and 0.5 part by mass of sodium dodecyl benzene sulfonate are added, the mixture is continuously stirred and reacted for 3 hours, and after cooling, the polyurea-based dynamic polymer elastomer is prepared and can be used as a conductive buffer material.

Example 22

The acrylate copolymer (a) was obtained by radical polymerization of 2, 3-dihydroxypropyl acrylate and methyl methacrylate using AIBN as an initiator.

Reacting acryloyl chloride and 3-iodine-1-propanol with equal molar equivalent under the catalysis of triethylamine, blending the obtained product and 1-butylimidazole with equal molar equivalent at 40 ℃ for 2 days, and adding a small amount of sodium fluoborate to obtain the acrylate monomer containing imidazolium groups. Using AIBN as an initiator, and carrying out free radical polymerization on an acrylate monomer containing imidazolium groups, methyl methacrylate and 2-aminoethyl acrylate to obtain an acrylate copolymer (b).

Dissolving 1 molar equivalent of 4- (chloromethyl) benzoyl chloride in a mixed solution of diethyl ether/normal hexane with the same volume ratio, slowly dripping an aqueous solution containing 1.3 molar equivalents of lithium peroxide at 0 ℃, and reacting for 6 hours at 0 ℃ to obtain the peroxide bifunctional initiator. Acetonitrile is used as a solvent, and the obtained bifunctional initiator initiates the free radical copolymerization of vinylidene fluoride and hexafluoropropylene at 90 ℃ to obtain the fluorine-containing copolymer (c).

Adding 0.02mol of boron tribromide into a dry and clean reaction bottle, dropwise adding a proper amount of acetic acid aqueous solution, hydrolyzing for 30min, then adding a proper amount of triethylamine, adjusting the pH value of the solution to 7.5-8, shaking and mixing for 10min, then adding 3mmol of acrylate copolymer (a), shaking and mixing uniformly, and reacting for 4h under the condition of a water bath at 60 ℃. And then heating the reaction liquid to 80 ℃, introducing nitrogen to remove water and remove oxygen for 1h, adding 3mmol of acrylate copolymer (b), 1mmol of fluorine-containing copolymer (c) and 0.01mol of 1,2,7, 8-diepoxyoctane, continuing to react for 30min, adding 6 wt% of cellulose nanocrystal and 0.3 wt% of sodium dodecyl benzene sulfonate, and continuing to react for 2h after ultrasonic treatment for 20 min. After the reaction is finished, pouring the polymer solution into a proper mould, placing the mould in a vacuum oven at 80 ℃ for 24h to remove the solvent, then cooling to room temperature and placing for 30min to finally obtain a hard solid polymer polyester sample. The sample was prepared into a dumbbell-shaped specimen having a size of 80.0X 10.0X (2.0 to 4.0) mm, and a tensile test was carried out using a tensile testing machine at a tensile rate of 10mm/min to obtain a specimen having a tensile strength of 10.34. + -. 2.98MPa and a tensile modulus of 18.23. + -. 4.16 MPa. In the embodiment, the polymer material can be used as an anti-seismic shearing material or a cyclic stress bearing material with an efficient damping effect to absorb and dissipate energy.

Example 23

1 molar equivalent of boron trifluoride diethyl etherate is used as an initiator, epichlorohydrin is used as an accelerator, ring-opening copolymerization of tetrahydrofuran and 2- (tetrahydrofuran-3-yl) acetonitrile is initiated, and water is used as a terminator to obtain hydroxyl terminated polytetrahydrofuran containing side nitrile groups.

The tetraboric acid compound is prepared by taking vinyl boric acid and pentaerythritol tetramercaptoacetate as raw materials, controlling the molar ratio of the vinyl boric acid to the pentaerythritol tetramercaptoacetate to be 4:1, taking AIBN as an initiator and triethylamine as a catalyst through mercaptan-olefin click addition reaction.

Using glycerol and propylene oxide as raw materials, using boron trifluoride diethyl etherate as a catalyst, synthesizing hydroxyl-terminated three-arm polypropylene oxide through cation ring-opening polymerization, performing esterification reaction on the hydroxyl-terminated three-arm polypropylene oxide and equimolar acrylic acid to obtain three-arm polypropylene oxide triacrylate, and performing thiol-ene click reaction on the three-arm polypropylene oxide triacrylate and equimolar 3-mercapto-1, 2-propanediol respectively to obtain the 1, 2-diol-terminated three-arm polypropylene oxide.

Adding 0.04mol of 1, 2-diol-terminated three-arm polypropylene oxide and 0.03mol of tetraboric acid compound into a dry and clean reaction bottle, adding a proper amount of triethylamine, stirring and mixing uniformly, heating to 80 ℃, and reacting for 4 hours to obtain a first network polymer; adding 0.02mol of hydroxyl terminated polytetrahydrofuran containing side nitrile groups into another reaction bottle, adding 0.03mol of trimethyl-1, 6-hexamethylene diisocyanate, reacting for 2 hours in a nitrogen atmosphere, adding a proper amount of first network polymer, continuously stirring and reacting for 1 hour, and obtaining a dynamic polymer elastomer with good resilience after the reaction is finished, wherein the dynamic polymer elastomer can be used as an energy absorption buffer gasket for damping and silencing precise instruments or electronic products.

Example 24

Taking a compound (a), a compound (b) and styrene as raw materials, taking dithiobenzoic acid cumyl ester as a chain transfer agent, and carrying out RAFT copolymerization at 110 ℃ to obtain the polystyrene containing borane and phosphane side groups. Taking AIBN as an initiator, and carrying out free radical copolymerization on styrene and 3-acrylamide dopamine to prepare the polystyrene-based compound (c).

Adding a certain amount of toluene solvent into a dry and clean reaction bottle, adding 0.03mol of tricresyl borate into the reaction bottle, 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 6mmol of a styrene-based compound (c), heating to 60 ℃, dissolving by stirring, continuing to react for 4h at 60 ℃, then introducing nitrogen to remove water and oxygen for 1h, then adding 0.03mol of 1, 6-hexamethylene diisocyanate, reacting for 2h at room temperature, adding a proper amount of caprolactam to remove unreacted isocyanate, then adding 5mmol of polystyrene containing borane and phosphine side groups and 0.02mol of diethyl azodicarboxylate, continuing to react for 1h at room temperature, then adding 5 wt% of graphene powder and 0.2 wt% of sodium dodecyl benzene sulfonate, and (4) after shaking and mixing uniformly, continuing to react for 2 hours to obtain the double-network dynamic polymer organogel. In this embodiment, a polymer sample can be made into a graphene conductive gel material for use, and external acting force and the environment can be sensed and monitored by measuring the conductivity of the material under the stress action in different environments.

Example 25

Taking a compound (a), 4-vinylpyridine and styrene as raw materials, taking BPO as an initiator, and carrying out RAFT copolymerization at 110 ℃ to obtain the polystyrene (b) containing borane and pyridine side groups.

Reacting 2-aminomethyl phenylboronic acid with a styrene-maleic anhydride copolymer by taking p-toluenesulfonic acid as a catalyst to obtain the phenylboronic acid graft modified styrene-maleic anhydride copolymer.

50g of phenylboronic acid graft modified styrene-maleic anhydride copolymer, 20g of polystyrene (b), 5.36g of trimethylolpropane, 2.12g of 4,4' -diaminobibenzyl, 0.18g of p-toluenesulfonic acid, 1.8g of di-n-butyltin dilaurate, 6.0g of dioctyl phthalate, 10g of foaming agent F141b, 0.24g of stearic acid, 0.06g of antioxidant 168 and 0.12g of antioxidant 1010 are uniformly mixed, added into a small internal mixer for internal mixing and blending, and the mixing temperature is controlled to be below 40 ℃. And 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 hard polystyrene-based polymer foam material, wherein the pore diameter of foam in the sample is uniform, and the obtained polystyrene foam material can be used as a foam heat-preservation packaging box for preserving heat and protecting internal articles.

Example 26

Reacting allyl hydroxyethyl ether with equivalent molar weight and (6-phenyl-2, 2' -bipyridine) -4-carboxylic acid under the catalysis of DCC and DMAP to obtain an olefin compound containing a ligand, adding 10 molar equivalent weight of the olefin compound containing the ligand into toluene, cooling a reaction container to 5 ℃, dropwise adding 13 molar equivalent weight of cyclopentadiene at low temperature while stirring, heating to reflux temperature after dropwise adding, and continuing stirring to react to obtain the norbornene monomer compound (a). The polynorbornene compound (b) is prepared by addition polymerization reaction of norbornene monomer compound (a) and norbornene with metallocene catalyst/methylaluminoxane as a catalyst system.

Preparing dihydroxy modified norbornene by taking 3- (allyloxy) -1, 2-propylene glycol and cyclopentadiene as raw materials through a Diels-Alder reaction; the preparation method comprises the following steps of taking dihydroxy modified norbornene and norbornene as a catalytic system, and carrying out addition polymerization reaction to prepare the polynorbornene compound (c).

Taking ethyl 5-hexene-1-yl carbamate and cyclopentadiene as raw materials, and preparing carbamate modified norgliptin through Diels-Alder reaction; using metallocene catalyst/methyl aluminoxane as catalyst system to prepare polynorbornene compound (d) by addition polymerization reaction of norbornene modified by carbamate and norbornene.

Adding 200ml of o-dichlorobenzene solvent into a dry and clean reaction bottle, adding 0.02mol of boron trioxide, dropwise adding an appropriate amount of acetic acid aqueous solution for hydrolysis for 30min, adding an appropriate amount of triethylamine, adjusting the pH value of the solution to 7.5-8, stirring and mixing for 10min, adding 5mmol of polynorbornene compound (c), heating to 80 ℃, stirring and reacting for 3h, adding 0.03mol of 1,2,7, 8-diepoxyoctane, continuing to react for 3h, adding 5mmol of polynorbornene compound (b), 5mmol of polynorbornene compound (d) and 0.02mol of PtCl₂(DMSO)₂Reacting for 2h, and carrying out vacuum filtration to obtain a dynamic polymer solid. The polymer sample is placed into a mould to be heated and pressed for forming, and the polymer sheet with shape memory property and energy absorption and buffering property can be obtained.

Example 27

Reacting triphenyl methane triisocyanate with 4-hydroxymethyl-tetrathiafulvalene in an equimolar amount to prepare the isocyanate compound containing tetrathiafulvalene. The polyamino compound (a) is prepared by condensation reaction of 1 molar equivalent of 4-aminophenylboronic acid and 2 molar equivalents of dimethylmethoxy-3- (2-aminoethylthio) propylsilane.

Weighing 30g of polyethylene glycol 400 in a dry and clean flask, heating to 110 ℃ to remove water for 1h, adding 24g of undecane-1, 6, 11-triyl triisocyanate and 15g of tetrathiafulvalene-containing isocyanate compound, reacting for 3h under the protection of nitrogen at 80 ℃, then cooling to 60 ℃, adding 2.02g of chain extender dimethylolpropionic acid, 1.50g of triethylamine, 8.8g of acetone and 0.12g of stannous octoate, carrying out reflux reaction for 2h, then adding 2.8g of polyamino compound (a) as a cross-linking agent, continuing to react for 1h, after the reaction is finished, removing the acetone in vacuum, cooling to room temperature, and finally obtaining the polyurethane-based polymer material with high elasticity, wherein the polyurethane-based polymer material can be applied to automobiles as a damping material to reduce noise and damp.

Example 28

Taking potassium persulfate as an initiator, and carrying out free radical polymerization on acrylamide, N- (3-pyridyl) acrylamide and acrylamide-p-phenylphosphate to obtain the acrylamide copolymer (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 potassium persulfate is taken as an initiator, and the 2- (hydroxymethyl) -4-vinylphenol, acrylamide and 2-aminoethyl acrylate are subjected to free radical polymerization to obtain the acrylamide copolymer (b).

Taking a certain amount of phosphate buffer solution (pH 7.0), adding 4mmol of acrylamide copolymer (b), stirring and dissolving completely, sequentially adding a proper amount of pyridine and 0.05mol of 1, 4-phenyl diboronic acid, placing in a water bath kettle at 60 ℃, heating for reacting for 2 hours, then adding 4mmol of acrylamide copolymer (a), then adding 0.01mol of ethylene glycol diglycidyl ether and 5 wt% of surface modified Fe₃O₄Performing ultrasonic treatment for 1min to uniformly disperse the metal particles in the particles, 5 wt% of metal magnetic powder and 1 wt% of bentonite, placing the mixture in a constant-temperature water bath at 60 ℃ for reaction for 2h, and obtaining the ionic liquid gel dispersed with the magnetic particles after the reaction is finished. In this example, the polymerization obtainedThe gel can show the shape memory capacity by utilizing the electromagnetic wave heating control because the magnetic particles are wrapped in the gel, and simultaneously can regulate and control the energy absorption and buffering capacity of the gel.

Example 29

The amino calix [4] arene reacts with excessive 1, 6-hexamethylene diisocyanate to prepare the calixarene blocked isocyanate.

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 (a).

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, and after pentaerythritol 3-bromopropionate is obtained through esterification reaction, the pentaerythritol 3-bromopropionate reacts with sodium azide with equal molar amount to obtain pentaerythritol tetraazide.

Using dicyclohexylcarbodiimide and 4-dimethylaminopyridine as catalysts, and sequentially carrying out amidation and esterification on polyamide with the molecular weight of about 2,000 and 5-alkynyl caproic acid and propargyl alcohol with equimolar weight to prepare alkynyl terminated polyamide. 2 molar equivalents of 1-azido-6-phenylhexane were reacted with 1 molar equivalent of the alkynyl-terminated polyamide (a), N-diisopropylethylamine, Cu (PPh) was added₃)₃Br was used as a catalyst, and reacted for 12 hours at 60 ℃ with stirring to obtain phenylhexane-terminated polyamide.

Adding a certain amount of tetrahydrofuran solvent into a dry and clean reaction bottle, sealing, carrying out bubbling deoxygenation for 1h by using argon gas, then adding 0.01mol of polyvinyl alcohol, 4mmol of 4,4' -biphenyl diboronic acid and a proper amount of triethylamine into the reaction bottle, heating to 60 ℃ under a stirring state, reacting for 4h, then adding 2mmol of calixarene terminated isocyanate, 1mmol of toluene diisocyanate, continuing to react for 2h, and then adding 2mmol of phenylhexane terminated polyamide. After the reaction is finished, the solvent is removed by decompression suction filtration, and then the polymer colloid is obtained by purification. In this embodiment, the material can be used for shock absorption and cushioning of electronic appliances, and can provide sufficient flexibility during shock absorption.

Example 30

4-mercaptomethylbenzeneboronic acid and gamma-mercaptopropyldimethylmethoxysilane are used as raw materials, the molar ratio of the raw materials to the raw materials is controlled to be 1:2, and a trimercapto compound (a) is obtained through condensation reaction at the temperature of 60 ℃.

Under the protection of nitrogen, 2 molar equivalents of methyl p-hydroxybenzoate are dissolved in tetrahydrofuran, and a catalyst triethylamine is added and mixed uniformly. A tetrahydrofuran solution containing 1 molar equivalent of terephthaloyl chloride was added dropwise at 0 to 5 ℃ and the mixture was kept and reacted for 10 hours to obtain a liquid crystal compound (b).

Under the condition of anhydrous vacuumizing at 90 ℃, dissolving limonene oxide and a catalyst (c) in toluene, keeping the molar ratio of the limonene oxide to the catalyst at 50:1, introducing 10bar of carbon dioxide into a reaction container, and after the reaction is completed, precipitating a crude product with methanol to obtain a poly-limonene carbonate chain segment. The resulting poly (limonene carbonate) segments and 1, 3-propanediol were dissolved in toluene, and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, catalyst, was added to react at 80 ℃ for 3 hours to obtain poly (limonene carbonate) (d) having an average molecular weight of about 2,000 and both ends terminated with hydroxyl groups. Under the protection of nitrogen, 1 molar equivalent of hydroxyl-terminated poly (limonene carbonate) (d) and 1.1 molar equivalent of liquid crystal compound (b) are blended to carry out transesterification reaction, methanol is distilled out, and after the reaction is completed, the liquid crystal-poly (limonene carbonate) multi-stage polymer is obtained.

4-mercaptobutyric acid and 4-hydroxymethyl-tetrathiafulvalene with equal molar equivalent are blended and react under the catalysis of DCC and DMAP to obtain the mercapto-functionalized tetrathiafulvalene. The liquid crystal-poly-limonene carbonate multi-stage polymer containing 10 molar equivalents of side alkenyl is fully mixed with 3 molar equivalents of mercapto-functionalized tetrathiafulvalene, 1 molar equivalent of trimercapto compound (a) and 1 molar equivalent of 1, 6-hexanedithiol, and the mixture is dissolved in tetrahydrofuran and reacts with an ultraviolet lamp in the presence of a photoinitiator BDK to prepare the dynamic polymer. The main raw materials of the product are renewable raw materials, and the product can be widely used as a disposable packaging material for damping and protecting external impact stress.

Example 31

Adding 50ml of methyl hydroxyl-terminated silicone oil and 0.03mol of boric acid into a dry and clean three-neck flask, dropwise adding a proper amount of triethylamine, heating to 80 ℃, and reacting for 4 hours to obtain a first network; 50ml of methyl hydrogen silicone oil (molecular weight about 30,000) was added, and after 1 hour of nitrogen gas introduction, 2.46g of diallyl isophthalate, 1.52g of 4-methyl-4-pentenoic acid, and 0.5g of ZnCl were added₂2g of silica, 2ml of 1% Pt (dvs) -xylene solution as a catalyst, heating to 80 ℃, and continuing to react for 24 hours under the protection of nitrogen, finally obtaining a rubber-like polymer sample which has certain strength and surface elasticity and can be hardened when being impacted by external force so as to disperse, absorb and dissipate energy. In the embodiment, the damping characteristic of the polymer material can be used as a vibration isolation rubber support to isolate the vibration of bridges and buildings.

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

1. A energy absorption method based on hybrid cross-linked dynamic polymer is characterized in that the hybrid cross-linked dynamic polymer is provided and used as an energy absorption material for energy absorption; wherein the hybrid cross-linked dynamic polymer comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction and common covalent cross-links formed by common covalent bonds, wherein the common covalent cross-links reach above the gel point of the common covalent cross-links in at least one cross-linked network.

2. The energy absorbing method based on hybrid cross-linked dynamic polymer according to claim 1, wherein the boron-containing dynamic covalent bond is selected from the group consisting of organic boron anhydride bond, inorganic boron anhydride bond, organic-inorganic boron anhydride bond, saturated five-membered ring organic borate bond, unsaturated five-membered ring organic borate bond, saturated six-membered ring organic borate bond, unsaturated six-membered ring organic borate 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, organic borate monoester bond, inorganic borate monoester bond, organic borate silicone bond, inorganic borate silicone bond.

3. The energy absorbing method based on hybrid cross-linked dynamic polymer according to claim 2, wherein the organoboron anhydride linkages are selected from at least one of the following structures:

the inorganic boron anhydride linkage is selected from the following structures:

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、Y₄Each of which isIndependently 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:

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, 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:

the unsaturated five-membered ring organic boric acid ester bond is selected from the following structures:

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:

the unsaturated six-membered ring organic boric acid ester bond is selected from the following structures:

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:

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:

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:

the unsaturated six-membered ring inorganic borate ester bond is selected from at least one of the following structures:

an aromatic ring of any number of elements, the aromatic ring containing two adjacent carbon atoms, which is 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:

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;

an aromatic ring having an arbitrary number of elements; wherein, the organic boric acid monoester bonds formed after the 6 and 7 structures are cyclized are not the saturated five-membered ring organic boric acid ester bonds and are notSaturated five-membered ring organic boric acid ester bonds, saturated six-membered ring organic boric acid ester bonds and unsaturated six-membered ring organic boric acid ester bonds;

the inorganic boric acid monoester bond is selected from at least one of the following structures:

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, 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;

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 bonds, the unsaturated five-membered ring inorganic boric acid ester bonds, the saturated six-membered ring inorganic boric acid ester bonds and the unsaturated five-membered ring inorganic boric acid ester bondsSaturated six-membered ring inorganic borate ester bonds;

the organic borate silicone bond is selected from at least one of the following structures:

the inorganic borate silicon ester bond is selected from at least one of the following structures:

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, 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.

4. The hybrid cross-linked dynamic polymer-based energy absorption method according to claim 1, wherein the non-hydrogen bond type supramolecular interactions are selected from the group consisting of metal-ligand interactions, ionic interactions, ion-dipole interactions, host-guest interactions, metallophilic interactions, dipole-dipole interactions, halogen bond interactions, lewis acid-base pair interactions, cation-pi interactions, anion-pi interactions, benzene-fluorobenzene interactions, pi-pi stacking interactions, ionic hydrogen bonding interactions, radical cation dimerization, phase separation interactions, crystallization interactions.

5. The method for energy absorption based on hybrid cross-linked dynamic polymer according to claim 1, wherein the dynamic polymer further comprises hydrogen bonding.

6. The hybrid cross-linked dynamic polymer-based energy absorption method according to any one of claims 1 and 5, wherein the hybrid cross-linked dynamic polymer has one of the following structures:

the first method comprises the following steps: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule effect and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches more than a gel point;

and the second method comprises the following steps: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point;

and the third is that: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond and an unsaturated six-membered ring organic borate bond;

and fourthly: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring inorganic borate bond, an unsaturated five-membered ring inorganic borate bond, a saturated six-membered ring inorganic borate bond and an unsaturated six-membered ring inorganic borate bond;

and a fifth mode: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point; wherein, the boron-containing dynamic covalent bond is selected from organic boric acid monoester bond, organic boric acid silicon ester bond, inorganic boric acid monoester bond and inorganic boric acid silicon ester bond;

and a sixth mode: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one metal-ligand action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point;

seventh, the method comprises: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one ionic action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point;

an eighth method: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one ion-dipole effect and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links reaches above a gel point;

ninth, the method comprises the following steps: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one host-guest action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point;

the tenth way: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one Lewis acid-base pair effect and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point;

an eleventh aspect: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one pi-pi stacking effect and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point;

the twelfth way: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond, an unsaturated six-membered ring organic borate bond, an organic borate single ester bond and an organic borate silicon ester bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, pi-pi stacking interaction;

a thirteenth species: the hybrid cross-linked dynamic polymer only contains a cross-linked network, and the cross-linked network simultaneously contains at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-linking formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-linking reaches above a gel point; wherein the boron-containing dynamic covalent bond is selected from 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 monoester bond and inorganic borate silicon bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, pi-pi stacking interaction;

a fourteenth mode: the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network only comprises common covalent cross-links formed by common covalent bonds, and the cross-linking degree of the common covalent cross-links is more than the gel point of the hybrid cross-linked dynamic polymer, the other cross-linked network comprises dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond, and supramolecular cross-links formed by at least one non-hydrogen bond type supramolecular action and optionally at least one hydrogen bond action, and the sum of the cross-linking degrees of the dynamic covalent cross-links and the supramolecular cross-links is more than the gel point of the hybrid cross-;

the fifteenth mode: the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is above the gel point of the cross-linked network, and the other cross-linked network comprises supramolecular cross-linking formed by at least one non-hydrogen bond type supramolecular action and optionally at least one hydrogen bond action, and the cross-linking degree of the supramolecular cross-linking is above the gel point of the supramolecular cross-linking;

sixteenth, the method comprises: the hybrid cross-linked dynamic polymer comprises two cross-linked networks, wherein one cross-linked network simultaneously contains at least one non-hydrogen bond type supramolecular function and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is above the gel point of the cross-linked network, the other cross-linked network contains dynamic covalent cross-linking formed by at least one boron-containing dynamic covalent bond, and the cross-linking degree of the dynamic covalent cross-linking is above the gel point of the cross-linked network, and at least one hydrogen bond function is optionally contained in at least one cross-linked network;

seventeenth means for: the hybrid crosslinked dynamic polymer comprises two crosslinked networks, wherein one crosslinked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent crosslinks formed by common covalent bonds, and the crosslinking degree of the common covalent crosslinks is above the gel point of the crosslinked network;

eighteenth: the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network only comprises common covalent cross-links formed by common covalent bonds, and the cross-linking degree of the common covalent cross-links is more than the gel point of the cross-linked network, the other cross-linked network comprises dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond, and the cross-linking degree of the dynamic covalent cross-links is more than the gel point of the cross-linked network, the last cross-linked network comprises supramolecular cross-links formed by at least one non-hydrogen bond type supramolecular interaction, and the cross-linking degree of the supramolecular cross-links is more than the gel point of the cross-linked network, and at least one hydrogen bond;

the nineteenth: the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network only contains common covalent cross-links formed by common covalent bonds, and the cross-linking degree of the common covalent cross-links is more than the gel point of the hybrid cross-linked dynamic polymer, the other cross-linked network contains dynamic covalent cross-links formed by at least one boron-containing dynamic covalent bond and the sum of the cross-linking degrees of the dynamic covalent cross-links and the supramolecular cross-links formed by at least one non-hydrogen bond type supramolecular action is more than the gel point of the hybrid cross-linked dynamic polymer, and the last cross-linked network contains supramolecular cross-links formed by at least one hydrogen bond action, and the cross-linking degree of the supramolecular;

the twentieth: the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network simultaneously comprises at least one boron-containing dynamic covalent bond and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is higher than the gel point of the cross-linked network, the other cross-linked network comprises supramolecular cross-linking formed by at least one non-hydrogen bond type supramolecular action, and the cross-linking degree of the supramolecular cross-linking is higher than the gel point of the cross-linked network, and the last cross-linked network comprises supramolecular cross-linking formed by at least one hydrogen bond action, and the cross-linking degree of the supramolecular cross-;

a twenty-first: the hybrid cross-linked dynamic polymer comprises three cross-linked networks, wherein one cross-linked network simultaneously contains at least one non-hydrogen bond type supramolecular function and common covalent cross-linking formed by common covalent bonds, and the cross-linking degree of the common covalent cross-linking is higher than the gel point of the cross-linked network, the other cross-linked network contains dynamic covalent cross-linking formed by at least one boron-containing dynamic covalent bond, and the cross-linking degree of the dynamic covalent cross-linking is higher than the gel point of the cross-linked network, and the last cross-linked network contains supramolecular cross-linking formed by at least one hydrogen bond function, and the cross-linking degree of the supramolecular cross-linking is higher;

the twenty-second method: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond and an unsaturated six-membered ring organic borate bond;

a twenty-third: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring inorganic borate bond, an unsaturated five-membered ring inorganic borate bond, a saturated six-membered ring inorganic borate bond and an unsaturated six-membered ring inorganic borate bond;

the twenty-fourth: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein, the boron-containing dynamic covalent bond is selected from organic boric acid monoester bond, organic boric acid silicon ester bond, inorganic boric acid monoester bond and inorganic boric acid silicon ester bond;

twenty-fifth: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and at least one boron-containing dynamic covalent bond, at least one metal-ligand action and common covalent cross-links formed by common covalent bonds are contained in the cross-linked networks, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above a gel point;

twenty-sixth: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one ionic action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above a gel point;

twenty-seventh: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and at least one boron-containing dynamic covalent bond, at least one ion-dipole effect and common covalent cross-links formed by common covalent bonds are contained in the cross-linked networks, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above a gel point;

the twenty-eighth type: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one host-guest action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above a gel point;

twenty-ninth: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one Lewis acid-base pair effect and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above a gel point;

thirtieth: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one pi-pi stacking function and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above a gel point;

a thirty-first type: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from a saturated five-membered ring organic borate bond, an unsaturated five-membered ring organic borate bond, a saturated six-membered ring organic borate bond, an unsaturated six-membered ring organic borate bond, an organic borate single ester bond and an organic borate silicon ester bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, pi-pi stacking interaction;

thirty-second: the hybrid cross-linked dynamic polymer comprises two or more cross-linked networks, and the cross-linked networks comprise at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supermolecule action, at least one optional hydrogen bond action and common covalent cross-links formed by common covalent bonds, wherein the cross-linking degree of the common covalent cross-links in at least one network reaches above the gel point; wherein the boron-containing dynamic covalent bond is selected from 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 monoester bond and inorganic borate silicon bond; said supramolecular interaction selected from the group consisting of metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, lewis acid-base pair interaction, and pi-pi stacking interaction.

7. The hybrid crosslinked dynamic polymer-based energy absorption method according to claim 6, wherein non-crosslinked polymers with crosslinking degree below the gel point and/or polymer particles with crosslinking degree above the gel point are dispersed in the hybrid crosslinked dynamic polymer crosslinked network.

8. The energy absorption method based on hybrid cross-linked dynamic polymer according to claim 1, wherein the formulation components constituting the hybrid cross-linked dynamic polymer composition comprise any one or more of the following additives/additives: other polymers, auxiliaries/additives, fillers;

wherein, the other polymer is selected from any one or more of the following polymers: natural high molecular compounds, synthetic resins, synthetic rubbers, synthetic fibers;

wherein, the auxiliary agent/additive is selected from any one or more of the following components: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, crosslinking agents and auxiliary crosslinking agents, curing agents, chain extenders, toughening agents, coupling agents, lubricants, mold release agents, plasticizers, foaming agents, dynamic regulators, antistatic agents, emulsifiers, dispersing agents, colorants, fluorescent whitening agents, flatting agents, flame retardants, nucleating agents, rheological agents, thickening agents 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.

9. The hybrid cross-linked dynamic polymer-based energy absorption method according to any one of claims 1 and 8, wherein the morphology of the hybrid cross-linked dynamic polymer has any one of the following: common solids, elastomers, gels, foams.

10. The method for energy absorption based on hybrid cross-linked dynamic polymers according to any one of claims 1 and 8, characterized in that it is applied for damping, cushioning, protection against impact, sound damping, sound insulation, shock absorption.

11. An energy-absorbing hybrid crosslinked dynamic polymer, characterized in that it comprises only one crosslinked network, and the crosslinked network comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction, optionally at least one hydrogen bond interaction, and common covalent crosslinks formed by common covalent bonds, wherein the degree of crosslinking of the common covalent crosslinks is above the gel point.

12. An energy-absorbing hybrid crosslinked dynamic polymer, characterized in that it comprises two crosslinked networks, and in the crosslinked networks comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction, optionally at least one hydrogen bond interaction, and common covalent crosslinks formed by common covalent bonds, wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein, the boron-containing dynamic covalent bond is selected from organic borate ester bonds.

13. An energy absorbing hybrid cross-linked dynamic polymer comprising two cross-linked networks and containing in the cross-linked networks at least one boron containing dynamic covalent bond, at least one metal-ligand interaction and common covalent crosslinks formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein, the boron-containing dynamic covalent bond is selected from inorganic borate ester bonds.

14. An energy absorbing hybrid cross-linked dynamic polymer comprising two cross-linked networks and containing in the cross-linked networks at least one boron containing dynamic covalent bond, at least one metal-ligand interaction, a hydrogen bonding interaction and common covalent crosslinks formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein the boron-containing dynamic covalent bond is selected from inorganic borate bonds.

15. An energy absorbing hybrid cross-linked dynamic polymer comprising two cross-linked networks and in the cross-linked networks at least one boron containing dynamic covalent bond, at least one metal-ligand interaction, at least one supramolecular interaction selected from the group consisting of ionic interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bond interaction, lewis acid-base pair interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, pi-pi stacking interaction, ionic hydrogen bonding interaction, radical cationic dimerization, phase separation interaction, crystallization interaction, and common covalent crosslinks formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein the boron-containing dynamic covalent bond is selected from inorganic borate bonds.

16. An energy absorbing hybrid cross-linked dynamic polymer comprising two cross-linked networks and in the cross-linked networks at least one boron containing dynamic covalent bond, at least one non-hydrogen bonding supramolecular interaction, optionally at least one hydrogen bonding interaction and common covalent cross-links formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein at least one network contains both common covalent crosslinks and boron-containing dynamic covalent bonds; wherein, the boron-containing dynamic covalent bond is selected from inorganic borate ester bonds.

17. An energy absorbing hybrid cross-linked dynamic polymer comprising two cross-linked networks and in the cross-linked networks at least one boron containing dynamic covalent bond, at least one non-hydrogen bonding supramolecular interaction, optionally at least one hydrogen bonding interaction and common covalent cross-links formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein only boron-containing dynamic covalent bond crosslinks in at least one network; wherein, the boron-containing dynamic covalent bond is selected from inorganic borate ester bonds.

18. An energy-absorbing hybrid crosslinked dynamic polymer, characterized in that it comprises two crosslinked networks, and in the crosslinked networks comprises at least one boron-containing dynamic covalent bond, at least one non-hydrogen bond type supramolecular interaction, optionally at least one hydrogen bond interaction, and common covalent crosslinks formed by common covalent bonds, wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein the non-hydrogen bonded supramolecular interaction is selected from ionic interaction, metallophilic interaction, dipole-dipole interaction, halogen bond interaction, lewis acid-base pair interaction, cation-pi interaction, anion-pi interaction, benzene-fluorobenzene interaction, ionic hydrogen bonding interaction, radical cation dimerization interaction, phase separation interaction, crystallization interaction.

19. An energy absorbing hybrid cross-linked dynamic polymer comprising two cross-linked networks and in the cross-linked networks at least one boron containing dynamic covalent bond, at least one non-hydrogen bonding supramolecular interaction, optionally at least one hydrogen bonding interaction and common covalent cross-links formed by common covalent bonds; wherein the degree of crosslinking of the common covalent crosslinks in at least one network is above the gel point; wherein, the boron-containing dynamic covalent bond is selected from inorganic borate bond; the form of the hybrid cross-linked dynamic polymer is selected from organic gel, oligomer swelling gel, plasticizer swelling gel, ionic liquid swelling gel, common solid, foam and elastomer.

20. An energy absorbing hybrid cross-linked dynamic polymer comprising at least three cross-linked networks and, within the cross-linked networks, at least one boron containing dynamic covalent bond, at least one non-hydrogen bonding supramolecular interaction, optionally at least one hydrogen bonding interaction, and common covalent cross-links formed by common covalent bonds, wherein the degree of cross-linking of the common covalent cross-links in at least one of the networks is above the gel point.

21. The energy-absorbing hybrid cross-linked dynamic polymer according to any one of claims 11 to 20, wherein it is applied to shock absorbing materials, cushioning materials, impact resistant protective materials, damping materials, sound insulating materials, sports protective articles, military police protective articles, self-healing coatings, self-healing panels, self-healing adhesives, bulletproof glass interlayer rubbers, ductile materials, shape memory materials, seals, toys.