CN111378183A

CN111378183A - Hybrid dynamic polymer containing reversible free radical type dynamic covalent bond and application thereof

Info

Publication number: CN111378183A
Application number: CN201911250608.9A
Authority: CN
Inventors: 不公告发明人
Original assignee: Weng Qiumei
Current assignee: Xiamen Xiaoyang Sports Technology Co ltd
Priority date: 2019-01-01
Filing date: 2019-12-09
Publication date: 2020-07-07

Abstract

The invention discloses a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which contains at least one reversible free radical type dynamic covalent bond and at least one hydrogen bond; based on the dynamic reversible characteristics of reversible free radical type dynamic covalent bonds and hydrogen bond actions, the hybrid dynamic polymer material is endowed with good self-repairing performance, reworkable performance, recoverability and the like, so that the hybrid dynamic polymer material is widely applied to self-repairing materials, tough materials, shape memory materials, heat-insulating materials, toy materials, energy storage device materials, organic thermosensitive materials, temperature sensing materials and the like.

Description

Hybrid dynamic polymer containing reversible free radical type dynamic covalent bond and application thereof

Technical Field

The invention relates to the field of intelligent polymers, in particular to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds and application thereof.

Background

After the traditional polymer material has cracks or fractures and other damages in the using process, the damage can not be repaired, so that the problems of short service life, high recycling and reprocessing cost and the like of the material are easily caused; the traditional cross-linked polymer material can not be plasticized, processed, recycled and regenerated after being prepared and molded, which can cause serious resource waste and environmental pollution. Many researchers have therefore introduced dynamic covalent structures and supramolecular interactions into polymer systems to solve the above problems.

For example, hydrogen bonding groups are introduced into the polymer, and based on the supermolecular dynamics of the hydrogen bonding action formed by the hydrogen bonding groups, exchange and recombination can occur spontaneously or under the external stimulation action such as heating after the polymer material is damaged, so that the self-repairing performance is obtained. However, since hydrogen bonds are weak interactions, it is difficult to achieve both self-repairability and high mechanical properties using only hydrogen bonds, greatly limiting the range of applications. For another example, a dynamic covalent bond with dynamic reversibility is introduced into a polymer to obtain a polymer material with self-repairing performance, reworkable performance and good mechanical strength, but the dynamic covalent structure therein often has the problems of harsh dynamic transition conditions, poor dynamic reversibility, single dynamic performance and the like, which brings great difficulty to practical application.

The introduction of these dynamic structures can alleviate the problems of the polymer material, such as the inability to self-repair and the difficulty in recycling, to a certain extent, but they cannot completely get rid of the above problems due to their own structural and performance deficiencies. Therefore, it is desired to develop a novel intelligent polymer to solve the problems of the prior art.

Disclosure of Invention

The present invention addresses the above-mentioned background by providing a hybrid dynamic polymer comprising at least one reversible free radical type dynamic covalent bond and at least one hydrogen bonding interaction. The hybrid dynamic polymer has excellent structural stability and mechanical property, and the reversible free radical type dynamic covalent bond in the hybrid dynamic polymer can have abundant and stable dynamic reversibility under general mild conditions, and shows good self-repairability, reworkability, recyclability and other properties. The polymer is introduced with at least one hydrogen bond function, so that the self-repairing performance and the supplementary enhancement can be improved, and the toughness and the tear resistance of the material can be greatly improved. Through reasonable structural design, a good shape memory function can be obtained. The hybrid dynamic polymer can be widely applied to the fields of self-repairing materials, toughness materials, shape memory materials, heat insulation materials, toy materials, energy storage device materials, organic heat-sensitive materials, temperature sensing materials and the like.

The invention is realized by the following technical scheme:

the invention relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which is characterized by containing at least two crosslinking networks and at least one reversible free radical type dynamic covalent bond and at least one hydrogen bonding interaction.

In a preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one cross-linked network only contains dynamic covalent cross-links, the cross-linking degree of the cross-linked network is above the gel point, and the cross-linked network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is above a gel point, the crosslinking degree of the hydrogen bond crosslinking is below the gel point, and the crosslinking network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is below a gel point, the crosslinking degree of the hydrogen bond crosslinking is above the gel point, and the crosslinking network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one crosslinking network contains dynamic covalent crosslinking and hydrogen bonding crosslinking, the crosslinking degree of the dynamic covalent crosslinking is below a gel point, the crosslinking degree of the hydrogen bonding crosslinking is below the gel point, but the sum of the crosslinking degrees of the two crosslinking degrees is above the gel point, and the crosslinking network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is above a gel point, the crosslinking degree of the hydrogen bond crosslinking is above the gel point, and the crosslinking network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises both dynamic covalent crosslinking and hydrogen bonding crosslinking, the degree of crosslinking of the dynamic covalent crosslinking is above the gel point, the degree of crosslinking of the hydrogen bonding crosslinking is below the gel point, and the crosslinked network comprises at least one dynamic covalent bond; the other crosslinked network contains only dynamic covalent crosslinks, the degree of crosslinking being above the gel point, the crosslinked network containing at least one dynamic covalent bond; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises dynamic covalent crosslinking and hydrogen bonding crosslinking, the crosslinking degree of the dynamic covalent crosslinking is below the gel point, the crosslinking degree of the hydrogen bonding crosslinking is above the gel point, and the crosslinked network comprises at least one dynamic covalent bond; the other crosslinked network contains only dynamic covalent crosslinks, the degree of crosslinking being above the gel point, the crosslinked network containing at least one dynamic covalent bond; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises both dynamic covalent crosslinking and hydrogen bonding crosslinking, the degree of crosslinking of the dynamic covalent crosslinking is below the gel point, the degree of crosslinking of the hydrogen bonding crosslinking is below the gel point, but the sum of the degrees of crosslinking of the two is above the gel point, and the crosslinked network comprises at least one dynamic covalent bond; the other crosslinked network contains only dynamic covalent crosslinks, the degree of crosslinking being above the gel point, the crosslinked network containing at least one dynamic covalent bond; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises both dynamic covalent crosslinking and hydrogen bonding crosslinking, the degree of crosslinking of the dynamic covalent crosslinking is above the gel point, the degree of crosslinking of the hydrogen bonding crosslinking is above the gel point, and the crosslinked network comprises at least one dynamic covalent bond; the other crosslinked network contains only dynamic covalent crosslinks, the degree of crosslinking being above the gel point, the crosslinked network containing at least one dynamic covalent bond; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein each of the two crosslinked networks comprises dynamic covalent crosslinking and hydrogen bonding crosslinking, the degree of crosslinking of the dynamic covalent crosslinking is above the gel point, the degree of crosslinking of the hydrogen bonding crosslinking is below or above the gel point, and each of the two crosslinked networks comprises at least one dynamic covalent bond; the two cross-linked networks are different; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least three crosslinked networks; at least one cross-linked network only contains dynamic covalent cross-links, the cross-linking degree is above the gel point, and the cross-linked network contains at least one dynamic covalent bond; at least one of the crosslinked networks contains only hydrogen-bonded crosslinks, and the degree of crosslinking is above the gel point.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least three crosslinked networks; at least one cross-linked network simultaneously contains dynamic covalent cross-linking and hydrogen bond cross-linking, the cross-linking degree of the dynamic covalent cross-linking is above the gel point, the cross-linking degree of the hydrogen bond cross-linking is below or above the gel point, and the cross-linked network contains at least one dynamic covalent bond.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; both the two crosslinking networks only contain dynamic covalent crosslinking, the crosslinking degree is above the gel point, and the crosslinking networks contain at least one dynamic covalent bond; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; both the two crosslinking networks only contain dynamic covalent crosslinking, the crosslinking degree is above the gel point, and the crosslinking networks contain at least one dynamic covalent bond; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least two crosslinked networks; at least one cross-linked network only contains dynamic covalent cross-links, the cross-linking degree is above the gel point, and the cross-linked network contains at least one dynamic covalent bond; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least two crosslinked networks; at least one cross-linked network only contains dynamic covalent cross-links, the cross-linking degree is above the gel point, and the cross-linked network contains at least one dynamic covalent bond; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least two crosslinked networks; at least one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is above the gel point, the crosslinking degree of the hydrogen bond crosslinking is below or above the gel point, and the crosslinking network contains at least one dynamic covalent bond; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least two crosslinked networks; at least one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is above the gel point, the crosslinking degree of the hydrogen bond crosslinking is below or above the gel point, and the crosslinking network contains at least one dynamic covalent bond; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles.

The reversible radical type dynamic covalent bond described in the present invention contains one of the following structural components:

wherein each W is independently selected from an oxygen atom, a sulfur atom;

wherein, W₁Is a divalent linking group; the divalent linking groups are independently selected from but not limited to: direct key

W at different positions₁Are the same or different; w₁Preferably from a direct bond

Wherein, W₂Is a divalent linking group; the divalent linking groups are independently selected from but not limited to:

w at different positions₂Are the same or different; w₂Is preferably selected from

Wherein, W₃Is a divalent linking group; the divalent linking groups are independently selected from but not limited to:

w at different positions₃Are the same or different; w₃Is preferably selected from

Wherein, W₄Is a divalent linking group; the divalent linking groups are independently selected from but not limited to: direct key

W at different positions₄Are the same or different; w₄Is preferably selected from

Wherein V, V ' are independently selected from carbon atom and nitrogen atom, different positions have the same or different structure of V, V ', when V, V ' is selected from nitrogen atom, the compound is connected with V, V

Is absent;

wherein Z is selected from tellurium atom, antimony atom and bismuth atom; wherein k is linked to Z

The number of (2); when Z is a tellurium atom, k is 1, meaning that there is only one

Is connected with Z; when Z is an antimony atom or a bismuth atom, k is 2,is shown as having two

To Z are two

Are the same or different in structure;

wherein each D is independently selected from carbon atoms, silicon atoms, germanium atoms and tin atoms, preferably from germanium atoms and tin atoms;

wherein R is₁Each independently selected from hydrogen atom, halogen atom, hetero atom group, substituent, R at different positions₁Are the same or different in structure;

wherein the substituent contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes but is not limited to a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, R₁Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing; r₁Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heteroaromatic hydrocarbon group and C substituted by acyl, acyloxy, acylamino, oxyacyl, sulfuryl, aminoacyl, phenylene_1-20Hydrocarbyl/heterohydrocarbyl; r₁Further preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group;

wherein R is₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; each R is₂Is connected withThe structures are the same or different; when R is₂When selected from substituents, it is selected from, but not limited to: hydroxy, phenyl, phenoxy, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group;

wherein R is₃Selected from cyano, C_1-10Alkoxyacyl group, C_1-10Alkyl acyl radical, C_1-10Alkylaminoacyl, phenyl, substituted phenyl, arylalkyl, substituted arylalkyl; wherein, the substituent atom or the substituent group is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent group and heteroatom-containing substituent group;

wherein R is¹、R²、R³、R⁴Each independently selected from hydrogen atom, halogen atom, heteroatom group, substituent; the substituent contains a heteroatom or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes a linear structure, a branched structure or a cyclic structure, the cyclic structure is selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and a combination thereof, and the aliphatic ring and the aromatic ring are preferred; in general terms, R¹、R²、R³、R⁴Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl radical, C_1-20Heterohydrocarbyl, substituted C_1-20Hydrocarbyl or substituted C_1-20Heterohydrocarbyl and combinations of two or more of the foregoing; r¹、R²、R³、R⁴Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Heteroalkyl, cyclic structure C_1-20Alkyl, C of cyclic structure_1-20Heteroalkyl group, C_1-20Aryl radical, C_1-20A heteroaryl group;

wherein R is⁵、R⁶、R⁷、R⁸Each independently selected from any suitable atom (including hydrogen atom), substituent, or groupA polymer chain; when R is⁵、R⁶、R⁷、R⁸When each is independently selected from the substituent group, the substituent group is preferably a substituent group with steric hindrance effect so as to increase steric hindrance and promote homolytic cleavage of dynamic covalent bonds; the substituents with steric hindrance are selected from, but not limited to: cyano radicals, C_1-20Alkyl radical, C_1-20Cycloalkyl, aralkyl, heteroaralkyl and the groups formed by the above groups substituted by any substituent atom or substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; by way of example, typical sterically hindered substituents include, but are not limited to: cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, pyridyl, C_1-5Alkyl-substituted phenyl, C_1-5Alkoxy-substituted phenyl, C_1-5Alkylthio-substituted phenyl, C_1-5Alkylamino substituted phenyl, cyano substituted phenyl;

wherein, L is a divalent linking group, and the structures of L at different positions are the same or different; wherein the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, each L is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, a divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. Wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; l is each independently preferably selected from the group consisting of acyl, acyloxy, acylthio, acylamino, oxyacyl, thioacyl, phenyleneRadical, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl; wherein said substituted divalent C_1-20The structure of the substituent group in the hydrocarbon group/heterohydrocarbon group is preferably an acyl group, an acyloxy group, an acylthio group, an acylamino group, an oxyacyl group, a thioacyl group, an aminoacyl group, a phenylene group, and more preferably the substituted divalent C_1-20The hydrocarbyl/heterohydrocarbyl group being linked to R via said substituent group₁To the carbon atom(s) of (a);

wherein the content of the first and second substances,

represents that the ring has a conjugated structure; wherein the content of the first and second substances,

is a five-membered nitrogen heterocyclic structure with a conjugated structure; wherein the content of the first and second substances,

the two five-membered nitrogen heterocycles form a carbon-carbon single bond, a carbon-nitrogen single bond or a nitrogen-nitrogen single bond between the two ring-forming atoms; according to different

The linking mode, the formula (20) includes but is not limited to one or more of the following isomers:

it should be noted that under appropriate conditions, interconversion between the various isomers can occur, and therefore, the six isomer motifs described above are regarded as the same structural motif in the present invention;

wherein the content of the first and second substances,

is a nitrogen-containing aliphatic heterocyclic ring, the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 3 to 10, more preferably from 5 to 8; among the ring-forming atoms of the alicyclic ring, except that at least one ring-forming atom is a nitrogen atomThe remaining ring-forming atoms are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms are substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0,1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula; said

Preferably at least one of the following structures, but the invention is not limited thereto:

said

More preferably at least one of the following structures, but the present invention is not limited thereto:

wherein the content of the first and second substances,

is an aromatic ring; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-constituting atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms,An oxygen atom, a sulfur atom, a boron atom, a phosphorus atom, a silicon atom, a hydrogen atom attached to a ring-forming atom being substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; in general terms, the aromatic rings include, but are not limited to: furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, benzene, pyridine, pyrazine, pyridazine, pyrimidine, 1,3, 5-triazine, indene, benzofuran, isobenzofuran, benzopyrrole, isobenzopyrrole, benzo [ b]Thiophene, benzo [ c]Thiophene, benzimidazole, purine, benzopyrazole, benzoxazole, benzisoxazole, benzothiazole, naphthalene, naphthyridine, quinoxaline, quinazoline, quinoline, isoquinoline, pteridine, indane, tetrahydronaphthalene, anthracene, phenanthrene, acridine, dihydroanthracene, xanthene, thiaanthracene, fluorene, carbazole, biphenyl, binaphthyl, bianthracene, 10, 11-dihydro-5H-dibenzo [ a, d ] o]Cycloheptane, dibenzocycloheptene, 4-B-dibenzocycloheptenone, iminodibenzyl, naphthylene, dibenzocyclooctyne, azabicyclooctyne, and substituted versions of any two or more of the foregoing;

wherein the content of the first and second substances,

indicates that n is connected with

Of an aromatic ring of (a) in different positions

Are the same or different; wherein, the symbols are the sites connecting with other structures in the formula;

wherein the content of the first and second substances,

refers to a linkage to a polymer chain or any other suitable group/atom (including a hydrogen atom).

In the present invention, the reversible radical type dynamic covalent bond, the radicals generated during the dynamic reversible transformation thereof include, but are not limited to: an aryl semipinacol radical, an aryl thienone/aronothienone radical, an aryl pyrrol-olone/indolone radical, an aryl cyclopentenedione/indene dione radical, an aryl chromene radical, an aryl dicyano carbon radical, a diaryl carbon radical, a cyanodiarylcarbon radical, an organotellurium radical, an organoselenium radical, an organobismuth radical, an organogermanium radical, an organotin radical, a nitroxide radical, a thionitrogen radical, a cyclohexadienone radical, an adamantyl-substituted carbon radical, an aryl furanone radical, an aryl biimidazole radical, a phenalene radical, a dioxelene radical, a cyanoacyl carbon radical, a fluorenyl carbon radical.

In the invention, the reversible free radical type dynamic covalent bond can be activated under a certain condition, and dissociation, bonding and exchange reaction of the bond are generated, so that the dynamic covalent reversible property (dynamic covalency) is embodied, and the exchange of a polymer chain and the change of a topological structure are realized. The term "certain conditions" refers to heating, illumination, radiation or any combination of two or three of the above three conditions, that is, the dynamic polymer can directly realize the breaking, exchange and recombination of dynamic covalent bonds through heating, illumination or radiation, thereby obtaining dynamic covalent properties. In the present invention, it is not excluded to use a combination of heating and two or three of the forms of light, radiation, etc. simultaneously to obtain a faster dynamic responsiveness and a more efficient dynamic covalent reversible transformation process.

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 hydrogen bond groups existing on the polymer cross-linked network skeleton chain and the non-cross-linked polymer main chain end group, side chain/branched chain end group, and are called chain end group hydrogen bond groups; or can be simultaneously present on at least two of the polymer chain skeleton, the side group and the end group; other ingredients, such as optional fillers, small molecules, crosslinked particles, inorganic particles, also may be present in the dynamic polymer, referred to as other hydrogen bonding groups. When hydrogen bonding groups are present simultaneously on at least two of the backbone, pendant group, terminal group or other components of the polymer chain, hydrogen bonding may occur between hydrogen bonding groups in different positions, e.g., backbone hydrogen bonding groups may form hydrogen bonding with pendant hydrogen bonding groups, in particular instances.

Wherein, the hydrogen bonding group preferably comprises the following structural components:

more preferably at least one of the following structural components:

further preferably at least one of the following structural components:

wherein the content of the first and second substances,

In the present invention, the hydrogen bonding refers to a hydrogen bonding formed by a hydrogen bonding group other than a dynamic covalent bonding structure.

In an embodiment of the present invention, the pendant hydrogen bonding group is independent of the dynamic covalent bond, which means that the dynamic covalent bond and the pendant hydrogen bonding group do not exist in the same dynamic polymer pendant group at the same time, that is, the dynamic covalent bond and the pendant hydrogen bonding group do not exist in the same pendant group at the same time.

In an embodiment of the present invention, the dynamic structure contained in the hybrid dynamic polymer, i.e. the reversible free radical type dynamic covalent bond and hydrogen bond interaction, can be introduced into the dynamic polymer by any suitable means. Wherein the dynamic structure can be introduced into the polymer at least during the process of obtaining said dynamic structure, or a compound containing said dynamic structure is previously formed by a suitable reaction, and then the dynamic structure is introduced into the polymer by a reaction/polymerization process between any suitable reactable groups contained therein, but the present invention is not limited thereto.

The invention also relates to a hybrid dynamic polymer containing dynamic covalent bonds of the reversible free radical type, characterized in that it contains only one crosslinked network and in that it contains at least two dynamic covalent bonds of the reversible free radical type and at least one hydrogen bonding interaction.

In a preferred embodiment of the invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is below the gel point, and the crosslinked network comprises at least two dynamic covalent bonds.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is below the gel point and the degree of crosslinking for hydrogen bonding crosslinking is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is below the gel point, the degree of crosslinking for hydrogen bonding crosslinking is below the gel point, but the sum of the degrees of crosslinking is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is below or above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is below or above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which is characterized in that the hybrid dynamic polymer is in a non-crosslinking structure and contains at least two reversible free radical type dynamic covalent bonds and at least one hydrogen bonding function.

In a preferred embodiment of the invention, the hybrid dynamic polymer is a linear structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a cyclic structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a branched structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer has a star-shaped structure and contains at least two dynamic covalent bonds and at least one hydrogen bond.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a hyperbranched structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding function.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a dendritic structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a comb structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer has a cluster structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding function.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which is characterized in that the hybrid dynamic polymer only contains a crosslinking network, and the hybrid dynamic polymer contains a reversible free radical type dynamic covalent bond and at least one side group hydrogen bond;

wherein the reversible radical type dynamic covalent bond is selected from one of the reversible radical type dynamic covalent bonds described in the structural general formula (1), (2), (3), (4), (5), (8), (9), (10), (11), (14), (15), (16), (17), (18), (21), (22), (23), (24), (25), (26), (27) and (28) and the preferable structure of the structural general formula.

In a preferred embodiment of the invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is above the gel point and the degree of crosslinking of the hydrogen bond crosslinks is below the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by pendant hydrogen bond groups.

In another preferred embodiment of the invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is below the gel point and the degree of crosslinking of the hydrogen bond crosslinks is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by pendant hydrogen bond groups.

In another preferred embodiment of the invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is below the gel point and the degree of crosslinking of the hydrogen bonding crosslinks is below the gel point, but the sum of the degrees of crosslinking of the two is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bonding crosslinks are formed by pendant hydrogen bonding groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is above the gel point and the degree of crosslinking of the hydrogen bond crosslinks is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by pendant hydrogen bond groups.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bond crosslinks is below or above the gel point, said crosslinked network comprising one of said dynamic covalent bonds, said hydrogen bond crosslinks being formed by pendant hydrogen bond groups; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bond crosslinks is below or above the gel point, said crosslinked network comprising one of said dynamic covalent bonds, said hydrogen bond crosslinks being formed by pendant hydrogen bond groups; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which is characterized by containing only one crosslinking network, and containing one reversible free radical type dynamic covalent bond and at least containing side group hydrogen bond action and skeleton hydrogen bond action at the same time.

In a preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one cross-linked network, wherein the degree of cross-linking of dynamic covalent cross-linking is above the gel point and the degree of cross-linking of hydrogen bond cross-linking is below the gel point, the cross-linked network comprises one of the dynamic covalent bonds, and the hydrogen bond cross-linking is formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is below the gel point and the degree of crosslinking of hydrogen bond crosslinks is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one cross-linked network, wherein the degree of cross-linking of dynamic covalent cross-linking is below the gel point, the degree of cross-linking of hydrogen bond cross-linking is below the gel point, but the sum of the degrees of cross-linking is above the gel point, and the cross-linked network comprises one of the dynamic covalent bonds, and the hydrogen bond cross-linking is formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bond crosslinks is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by participation of pendant hydrogen bond groups and backbone hydrogen bond groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one cross-linked network, wherein the degree of cross-linking of dynamic covalent cross-linking is above the gel point, and the degree of cross-linking of hydrogen bond cross-linking is below or above the gel point, the cross-linked network comprises one of the dynamic covalent bonds, and the hydrogen bond cross-linking is formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one cross-linked network, wherein the degree of cross-linking of dynamic covalent cross-linking is above the gel point, and the degree of cross-linking of hydrogen bond cross-linking is below or above the gel point, the cross-linked network comprises one of the dynamic covalent bonds, and the hydrogen bond cross-linking is formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which is characterized in that the hybrid dynamic polymer only contains a crosslinking network, and the hybrid dynamic polymer contains a reversible free radical type dynamic covalent bond and at least one side group hydrogen bond; said pendant hydrogen bonding interactions are formed by pendant hydrogen bonding groups that are independent of said dynamic covalent bonds;

wherein the reversible radical type dynamic covalent bond is selected from one reversible radical type dynamic covalent bond described in structural general formulas (6), (7), (12), (13), (19) and (20) and the preferable structure of the structural general formula;

wherein, the side group hydrogen bond group comprises the following structural components:

further preferably at least one of the following structural components:

wherein, each Y is independently selected from hydrogen atom, heteroatom group and micromolecular hydrocarbyl; wherein, the structure of Y is not particularly limited, including but not limited to a linear structure, a branched structure, or a cyclic structure; wherein the cyclic structure is not particularly limited and may be selected from the group consisting of aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof; the chemical composition of Y is not particularly limited, with or without heteroatoms;

wherein Y is substituted with

Any one group is connected with each other to form a bridge or not connected with each other to form a bridge;

wherein the content of the first and second substances,

indicating attachment to a polymer chain.

In a preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is below the gel point, said crosslinked network comprising one said dynamic covalent bond and at least one said pendant hydrogen bonding.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is below the gel point and the degree of crosslinking for hydrogen bonding crosslinking is above the gel point, said crosslinked network comprising one said dynamic covalent bond and at least one said pendant hydrogen bonding interaction.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is below the gel point and the degree of crosslinking of hydrogen bonding crosslinks is below the gel point, but the sum of the degrees of crosslinking of both crosslinks is above the gel point, and said crosslinked network comprises one said dynamic covalent bond and at least one said pendant hydrogen bonding.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bonding crosslinks is above the gel point, and said crosslinked network comprises one of said dynamic covalent bonds and at least one of said pendant hydrogen bonding interactions.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bonding crosslinks is below or above the gel point, said crosslinked network comprising one said dynamic covalent bond and at least one said pendant hydrogen bonding interaction; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bonding crosslinks is below or above the gel point, said crosslinked network comprising one said dynamic covalent bond and at least one said pendant hydrogen bonding interaction; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles.

The invention also relates to a hybrid dynamic polymer containing the reversible free radical type dynamic covalent bond, which is characterized in that the hybrid dynamic polymer is in a non-crosslinking structure and contains the reversible free radical type dynamic covalent bond and at least one hydrogen bond function; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

In a preferred embodiment of the present invention, the hybrid dynamic polymer is linear in structure and contains a reversible free radical type dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a branched structure and contains a reversible free radical type dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

In another preferred embodiment of the invention, the hybrid dynamic polymer has a star-shaped structure and contains a reversible free radical dynamic covalent bond and at least one hydrogen bonding function; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a hyperbranched structure and contains a reversible free radical type dynamic covalent bond and at least one hydrogen bonding interaction; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a dendritic structure and contains a reversible free radical type dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a comb structure and contains a reversible free radical dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

The invention also relates to a hybrid dynamic polymer containing the reversible free radical type dynamic covalent bond, which is characterized in that the hybrid dynamic polymer is in a non-crosslinking structure and contains the reversible free radical type dynamic covalent bond and at least one hydrogen bond function;

In a preferred embodiment of the invention, the hybrid dynamic polymer is a linear structure and contains one of the dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a cyclic structure and contains one of the dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a branched structure and contains one of the dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a star-shaped structure and contains one of the dynamic covalent bonds and at least one hydrogen bond.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a hyperbranched structure and comprises one of the dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, said hybrid dynamic polymer is a dendritic structure and contains one of said dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a comb structure and contains one of the dynamic covalent bonds and at least one hydrogen bonding.

In another preferred embodiment of the present invention, said hybrid dynamic polymer is a cluster structure and contains one of said dynamic covalent bonds and at least one hydrogen bonding.

In the present invention, when the hybrid dynamic polymer has a crosslinked structure, there is no covalently crosslinked network crosslinked with ordinary covalent bonds in the hybrid dynamic polymer, that is, there is no ordinary covalently crosslinked three-dimensional infinite network in which the degree of covalent crosslinking of ordinary covalent bonds is above the gel point. However, the hybrid dynamic polymer may contain components that are commonly covalently crosslinked dispersed in the hybrid dynamic polymer in particulate form (including but not limited to spherical, fibrous, flake, rod, random). When the dynamic covalent bond in the hybrid dynamic polymer with the crosslinking structure is broken below the gel point, the covalent crosslinking network in which the dynamic covalent bond is located is degraded, that is, the dynamic covalent crosslinking is a necessary condition for forming and maintaining the covalent crosslinking.

In embodiments of the present invention, the formulation components for preparing the hybrid dynamic polymer may further comprise any one or more of the following additives or additives: auxiliary agent, filler and swelling agent. The auxiliary agent is selected from any one or more of the following components: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants, toughening agents, coupling agents, solvents, lubricants, mold release agents, plasticizers, thickeners, thixotropic agents, leveling agents, colorants, optical brighteners, delustering agents, antistatic agents, dehydrating agents, sterilization and mold inhibitors, foaming agents, co-foaming agents, nucleating agents, and rheological agents; the filler is selected from any one or more of the following materials: inorganic non-metallic fillers, organic fillers, organometallic compound fillers; the swelling agent is selected from any one or more of the following components: water, organic solvent, ionic liquid, oligomer and plasticizer.

In the embodiment of the invention, the hybrid dynamic polymer can be in the form of solution, emulsion, paste, gum, common solid, gel (including hydrogel, organogel, oligomer swelling gel, plasticizer swelling gel, ionic liquid swelling gel), elastomer, foam, and the like.

In embodiments of the invention, the hybrid dynamic polymer may be applied to the following materials or articles: the self-repairing material comprises a self-repairing coating material, a self-repairing plate, a self-repairing sealing material, a self-repairing binder, a tough material, a shape memory material, a heat insulation material, a toy material, an energy storage device material and the like.

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

(1) the hybrid dynamic polymer contains at least one reversible free radical type dynamic covalent bond, and can show abundant dynamic covalent reversible characteristics/dynamic covalency under certain conditions. The dynamic reversible transformation of the reversible free radical type dynamic covalent bond has various activation forms, namely multiple dynamic stimulus response forms, including but not limited to heating, illumination, radiation and other forms, and the dynamic transformation condition has the characteristics of wide activation temperature range, relatively mild activation temperature, various activated illumination and radiation forms, wide illumination wavelength range, rapid dynamic response and the like.

(2) The free radical generated in the process of dynamic transformation of the reversible free radical type dynamic covalent bond has high stability, shows good dynamic covalent reversible characteristics, and can obtain stable and multiple self-repairing performances. In addition, the free radical has high catalytic and initiating activity, so that the effects of functionalization, application expansion, service life prolonging and the like can be conveniently achieved. For example, the free radicals generated by the dynamic covalent bonds in the dynamic transformation process have the capability of initiating free radical polymerization, reacting with sulfydryl and the like, and chain extension, crosslinking, grafting and the like are conveniently carried out, so that the performance of the hybrid dynamic polymer is changed or improved, and meanwhile, better self-repairing performance and self-reinforcing performance can be obtained when the material is damaged, which are very beneficial to enriching the service performance of the material, prolonging the service life of the material and improving the use safety, but the free radicals are performance characteristics which cannot be provided by the traditional dynamic covalent structures.

(3) The reversible free radical type dynamic covalent bond of the invention generates a dynamic reversible transformation process under the conditions of heating, illumination or radiation and the like, can not only obtain the self-repairing performance and the self-enhancing performance, but also cause the changes of color, fluorescence, oxidation resistance and electrical conductivity, and can further enrich the service performance of the material. For example, the self-repairing state of the material can be visually fed back through the color and fluorescence change in the dynamic conversion process of the hybrid dynamic polymer, and the organic thermosensitive material can also be prepared; the free radicals generated in the dynamic transformation process can also absorb harmful free radicals in the polymer matrix, so that the oxidation resistance of the material is improved; the free radicals generated in the dynamic transformation process of the dynamic covalent bond are also beneficial to improving the conductivity of the material, and the requirements of special application scenes are met. These special properties may well enhance the utility and applicability of the material, which is not available with other types of dynamic covalent structures.

(4) The hybrid dynamic polymer contains hydrogen bond action/crosslinking, so that the self-repairing performance of the material can be effectively improved, a supplementary reinforcing effect can be achieved, and the toughness and tear resistance can be improved; meanwhile, the magic viscosity-elasticity conversion behavior, the thickening effect and the like can be realized by utilizing the strong dynamic hydrogen bond effect. Through reasonable design and use of structures such as hydrogen bond group position, structure, tooth number and the chain structure of polymer chain, hydrogen bond action strength and supermolecule dynamic property can be well regulated and controlled, and hydrogen bond action with large-scale adjustability such as bonding strength, dynamic property, responsiveness, crosslinking density and the like is obtained, meanwhile, the toughness of the material and the properties such as regulating and controlling glass transition temperature can be further improved, the polymer material with rich structure, various performances and more hierarchical dynamic reversible effect is obtained, and the requirements of different use scenes on the material performance are met.

(5) The partially-hybridized dynamic polymer contains at least two reversible free radical type dynamic covalent bonds, and based on the structural characteristics of the reversible free radical type dynamic covalent bonds and the difference of dynamic reversible characteristics caused by the structural characteristics, the prepared hybridized dynamic polymer can show richer color change and fluorescence change compared with a hybridized dynamic polymer only containing one reversible free radical type dynamic covalent bond, and is more favorable for feeding back the self-repairing state of a material and expanding the application of the hybridized dynamic polymer on a thermosensitive material, a temperature measuring material and a temperature sensing material.

(6) The partial hybrid dynamic polymer in the invention contains at least one side group hydrogen bond effect in addition to the reversible free radical type dynamic covalent bond to obtain dynamic reversibility, thereby obtaining the supermolecule dynamic property. The side group hydrogen bond effect has the characteristics of higher degree of freedom, quicker response, stronger dynamic property, easier regulation and control of hydrogen bond density and the like, a quick self-repairing process is easily obtained, and the tear resistance can be better improved; and the number of teeth of the side group hydrogen bond, the density of the side group hydrogen bond and the linkage of the side group hydrogen bond group and the polymer chain are adjusted, so that the supermolecule action strength and the supermolecule dynamic property can be greatly regulated, and good structural stability and the supermolecule dynamic property can be obtained by reasonably designing and selecting the proper side group hydrogen bond group. The combination of the dynamic structure can provide good dynamic reversible performance for the polymer, and therefore self-repairing performance, reworkability, recyclable performance and the like can be obtained. Particularly, when the hydrogen bond group of the side group of the hybrid dynamic polymer is independent of the dynamic covalent bond, the dynamic covalent property of the reversible free radical type dynamic covalent bond and the supermolecule dynamic property of the hydrogen bond of the side group can be fully exerted, so that the orthogonal dynamic reversible characteristic is obtained, and the self-repairing performance of the material is improved.

(7) The invention organically combines a reversible free radical type dynamic covalent bond and hydrogen bond action/crosslinking together to jointly construct a hybrid dynamic polymer, and based on the dynamic reversible transformation process of the dynamic structure, the hybrid dynamic polymer endows the polymer with good self-repairability, reworkability, recyclability and other dynamic performances, effectively solves the problems that the service life of a material of the polymer is short because the material cannot be repaired after cracks are generated in the using process, effectively solves the resource waste caused by the fact that the crosslinked polymer material cannot be plastically processed after being cured and molded, effectively solves the problem that the resource utilization rate is low because the material cannot be recycled after the service cycle is finished, and the like, and is undoubtedly very beneficial under the large background that the current resource and environmental problems are severe, which can not be realized by the traditional crosslinked polymer system.

(8) The polymer chain structure of the hybrid dynamic polymer has diversity, and the abundant structural characteristics endow the hybrid dynamic polymer with abundant mechanical strength and other comprehensive properties, and can meet the requirements of different use scenes in a wider range. Wherein, the hybrid dynamic polymer can be a cross-linked structure and a non-cross-linked structure. Wherein the non-crosslinked structure includes but is not limited to linear, cyclic, branched and gel point below two-dimensional, three-dimensional cluster and the like structure and the 'combination form' structure of the above structures; wherein, the crosslinking structure can only contain one crosslinking network or two or more crosslinking networks; the crosslinking form and the crosslinking degree of each crosslinking network can be reasonably regulated and controlled according to actual needs so as to obtain better service performance. In addition, in the hybrid dynamic polymer with a crosslinking structure, non-crosslinked hydrogen bond polymers or polymer particles crosslinked by hydrogen bonds can be dispersed, so that polymers with richer supramolecular dynamics and other comprehensive properties can be obtained, and the requirements of different application scenes are met.

(9) In the invention, for the hybrid dynamic polymer with a crosslinking structure, especially containing at least two crosslinking networks, the networks can provide excellent mechanical strength and modulus for the polymer when being combined together in an interpenetrating or semi-interpenetrating mode, and the hybrid dynamic polymer has unique advantages in preparing high-strength and high-toughness polymer gel materials; the cross-linking forms of each cross-linking network of the hybrid dynamic polymer are rich, and the cross-linking forms can be a combination partially containing only dynamic covalent cross-linking and partially containing only hydrogen bond cross-linking, or a combination partially containing only dynamic covalent cross-linking and partially containing both dynamic covalent cross-linking and hydrogen bond cross-linking, or a combination partially containing only hydrogen bond cross-linking and partially containing both dynamic covalent cross-linking and hydrogen bond cross-linking, or a combination containing both dynamic covalent cross-linking and hydrogen bond cross-linking in each cross-linking network, and the cross-linking degrees of various cross-linking actions can be reasonably designed and regulated according to actual use requirements so as to better balance the structural stability and other properties of the material, for example, when the cross-linking degree of dynamic covalent cross-linking is above a gel point, better covalent stability is easily obtained; when the crosslinking degree of hydrogen bond crosslinking is above the gel point, a high-strength supermolecule effect is easily obtained, and the toughness and tear resistance of the material are also improved; through the cross-linking form and the cross-linking degree of the cross-linking network and the structural characteristics of dynamic covalent bonds and hydrogen bond structures (such as hydrogen bond structures with different numbers of teeth and different types) with different structures contained in the cross-linking network, the hybrid dynamic polymer has richer performance characteristics and meets the requirements of different application scenes on the material performance.

(10) The non-crosslinked hybrid dynamic polymer in the present invention has higher plasticity, and is more beneficial to the recovery and reprocessing of materials than the crosslinked hybrid dynamic polymer. The non-crosslinking structure can be a linear, cyclic, branched and two-dimensional or three-dimensional cluster structure below a gel point and the like and a 'combination form' structure of the structures, and has respective topological structure characteristics, so that the hybrid dynamic polymer is endowed with rich performance. For example, the linear structure has the characteristics of simple structure, convenient preparation, easy regulation and control of the number and proportion of dynamic structures and the like; compared with a linear structure, the cyclic structure has smaller hydrodynamic volume, is less prone to entanglement and has special mechanical property under the condition of the same molecular weight, and can be converted into a linear or branched structure in the dynamic reversible conversion process, so that the toughness of the material is improved; the branched structure has rich branched chain structures, is easy to graft and modify, is convenient to introduce functional polymer chains or functional groups, and each branched chain is easy to intertwine with each other, thereby being beneficial to improving the elasticity of the material; and the structures such as two-dimensional and three-dimensional clusters below the gel point can play the functions of filling and local enhancement.

(11) In the invention, the hybrid dynamic polymers with different structural components and topological structures can be obtained by regulating and controlling the component parameters of the dynamic covalent bond structure, the hydrogen bond group structure, the molecular composition of the raw material compound, the number of the raw material functional groups, the molecular weight, the raw material proportion and the like, and the hybrid dynamic polymers with different external shapes, rich internal structures, adjustable material properties and wide application fields are prepared.

(12) The method and the way for preparing the hybrid dynamic polymer provided by the invention are various, and the auxiliary agent, the filler and the swelling agent can be added to modify the hybrid dynamic polymer material according to the actual requirements in the preparation process, so that the service performance of the material is further enriched, and the application range of the material is greatly widened.

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

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.

In the present invention, even if the dynamic covalent bond and the hydrogen bonding group have the same basic structure, the difference in the properties may be caused by the difference in the linking group, the substituent, the isomer, and the like. In the present invention, unless otherwise specified, dynamic covalent bonds and hydrogen bonding groups having the same basic structure but different structures due to a linker, a substituent, an isomer, and the like are generally regarded as different structures. The invention can reasonably design, select and regulate the dynamic covalent bond and hydrogen bond group structure according to the requirement to obtain the best performance, which is also the advantage of the invention.

The term "polymerization" reaction/action as used in the present invention, unless otherwise specified, refers to a process in which a reactant of lower molecular weight forms a product of higher molecular weight by polycondensation, polyaddition, ring-opening polymerization, or the like, i.e., a chain extension process/action other than crosslinking. 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. It is to be noted that "polymerization" referred to in the present invention includes a linear growth process, a branching process, a ring formation process, and the like of a reactant molecular chain other than the crosslinking process of the reactant molecular chain. In embodiments of the present invention, "polymerization" includes chain growth processes caused by the bonding of covalent bonds as well as hydrogen bonding.

The term "crosslinking" reaction/action as used in the present invention refers to the process of intermolecular and/or intramolecular formation of a product having a three-dimensional infinite network type by covalent and/or hydrogen bonding. In the crosslinking process, polymer chains generally grow continuously in two/three dimensions, gradually form clusters (which can be two-dimensional or three-dimensional), and then develop into three-dimensional infinite network crosslinking, which can be regarded as a special form of polymerization. Just as a three-dimensional infinite network is reached during the crosslinking process. Therefore, the degree of crosslinking, referred to as the gel point, is also referred to as the percolation threshold. A crosslinked product above the gel point (inclusive, the same applies hereinafter) having a three-dimensional infinite network structure, the crosslinked network constituting a whole and spanning the entire polymer structure; the crosslinked product below the gel point, which is only a loose inter-chain linking structure, does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can constitute a whole across the entire polymer structure. Unless otherwise specified, the crosslinked structure in the present invention is a three-dimensional infinite network structure above the gel point, and the non-crosslinked (structure) specifically means linear, cyclic, branched, and two-dimensional, three-dimensional clusters and the like structures below the gel point and "combination" structures of the above structures.

Wherein, the linear structure means that the polymer molecular chain is in a regular or irregular long-chain linear shape and is generally formed by connecting a plurality of repeating units on a continuous length, and the side group in the polymer molecular chain generally does not exist in a branched chain; for "linear structures," they are generally formed by polymerization of monomers that do not contain long chain pendant groups by polycondensation, polyaddition, ring opening, or the like.

Wherein, the "cyclic" structure refers to that the polymer molecular chain exists in the form of cyclic chain, which includes cyclic structures in the form of single ring, multiple rings, bridge ring, nested ring, wheel ring, grommet, theta-shaped cyclic structure, 8-shaped cyclic structure, etc.; as the "cyclic structure", it can be formed by intramolecular and/or intermolecular cyclization of a linear or branched polymer, and can also be produced by ring-expanding polymerization or the like.

The branched structure refers to a structure containing side chains, branched chains and the like on a polymer molecular chain, including but not limited to star-shaped, H-shaped, comb-shaped, dendritic, hyperbranched structures and combinations thereof, and further combinations thereof with linear, cyclic and cluster structures, such as a linear chain end connected with a cyclic structure, a cyclic structure combined with a comb-shaped structure, a dendritic chain end connected with a cyclic chain, and the like; for "side chain, branched chain and branched chain structures of polymer", it may have a multi-stage structure, for example, one or more stages of branches may be continued on the branches of the polymer molecular chain. As the "branched structure", there are a number of methods for its preparation, which are generally known to those skilled in the art, and which can be formed, for example, by polycondensation of monomers containing long-chain pendant groups, or by chain transfer of radicals during polyaddition, or by radiation and chemical reactions to extend branched structures out of linear molecular chains. The branched structure is further subjected to intramolecular and/or intermolecular reaction (crosslinking) to produce a cluster and a crosslinked structure.

The "cluster" structure refers to a two-dimensional/three-dimensional structure below the gel point, which is generated by intramolecular and/or intermolecular reaction of polymer chains.

The "combination type" structure refers to two or more of two-dimensional and three-dimensional clusters below linear, cyclic, branched and gel points contained in one polymer structure, such as dumbbell type linear-cyclic combination structure, tadpole type linear-cyclic combination structure, star type-cyclic combination structure, cyclic comb type chain, and also includes different rings, different branches, different clusters and combination structures thereof with other topological structures, and the like. Wherein, the dumbbell type linear-annular combined structure is formed by combining two single-ring structure polymer chains through a linear structure polymer chain; the tadpole type line-ring combined structure is formed by combining a single-ring structure polymer chain and one or more linear structure polymer chains; the star-ring combined structure is formed by taking a polymer chain of a star structure as a core and covalently connecting a single-ring structure at the tail end of a branched chain of the polymer chain; the ring-shaped comb-shaped chain is formed by taking the ring-shaped chain as a side chain of the comb-shaped chain and forming the ring-shaped chain with the side chain.

In the present invention, "backbone" refers to a structure in the chain length direction of a polymer chain. For crosslinked polymers, the term "backbone" refers to any segment present in the backbone of the crosslinked network, i.e., the backbone chain in the crosslinked network that connects adjacent crosslinks. For polymers of non-crosslinked structure, the "backbone", unless otherwise specified, refers to the chain with the most mer. Wherein, the side chain refers to a chain structure which is connected with the main chain of the polymer and is distributed beside the main chain; the "branched chain"/"branched chain" may have a side chain or other chain structure branched from any chain. Wherein, the "side group" refers to a chemical group which is connected with any chain of the polymer and is arranged beside the chain. Wherein, the "terminal group" refers to a chemical group attached to any chain of the polymer and located at the end of the chain. Unless otherwise specified, a pendant group refers specifically to groups and subgroups thereof having a molecular weight of not more than 1000Da attached to the side of the backbone of the polymer chain. When the molecular weight of the side chain, branched chain, does not exceed 1000Da, itself and the groups thereon are considered side groups. For simplicity, when the molecular weight of the side chain, branched chain, exceeds 1000Da, they are collectively referred to as side chains unless otherwise specified. The "side chain" and "side group" may have a multi-stage structure, that is, the side chain/side group may be continued to have a side chain/side group, and the side chain/side group of the side chain/side group may be continued to have a side chain/side group. In the present invention, for hyperbranched and dendritic chains and their related chain structures, the outermost polymer chain segment can be considered as a side chain, and the rest as a main chain; for polymers of the star configuration, each arm is considered a side chain.

The term "common covalent bond" as used herein refers to a covalent bond in the conventional sense except for dynamic covalent bond, which is an interaction formed by sharing electron pairs between atoms, and is difficult to break at normal temperature (generally not higher than 100 ℃) and normal time (generally less than 1 day), and includes, but is not limited to, normal carbon-boron bond, carbon-carbon bond, carbon-oxygen bond, carbon-hydrogen bond, carbon-nitrogen bond, carbon-sulfur bond, nitrogen-hydrogen bond, nitrogen-oxygen bond, hydrogen-oxygen bond, nitrogen-nitrogen bond, etc.

In the present invention, the hybrid dynamic polymer may be a non-crosslinked structure or a crosslinked structure. When the hybrid dynamic polymer is a non-crosslinked structure, it is selected from, but not limited to, linear, cyclic, branched, and two-dimensional, three-dimensional clusters below the gel point, and "combinations" of the above structures. When the hybrid dynamic polymer has a crosslinked structure, it may contain only one crosslinked network or two or more crosslinked networks. In the crosslinked network, a polymer having a crosslinking degree of crosslinking by hydrogen bonding which is caused by hydrogen bonding and is not more than the gel point, or polymer particles having a crosslinking degree of crosslinking by hydrogen bonding which is caused by hydrogen bonding and is not less than the gel point may be dispersed.

In the invention, when the hybrid dynamic polymer has a cross-linked structure, a covalent cross-linked network which is cross-linked by common covalent bonds does not exist in the hybrid dynamic polymer, namely, a common covalent cross-linked three-dimensional infinite network with the covalent cross-linking degree of the common covalent bonds above a gel point does not exist, so that good self-repairing performance, reworkable performance and recoverable performance are obtained. It should be noted that the hybrid dynamic polymer may contain components that are commonly covalently crosslinked and dispersed in the hybrid dynamic polymer in the form of particles (including but not limited to spheres, fibers, flakes, rods, and irregular shapes). When the dynamic covalent bond in the hybrid dynamic polymer with the crosslinking structure is broken below the gel point, the covalent crosslinking network in which the dynamic covalent bond is located is degraded, that is, the dynamic covalent crosslinking is a necessary condition for forming and maintaining the covalent crosslinking.

The hybrid dynamic polymer of the present invention comprises at least two crosslinked networks, which 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; in particular, when the networks are combined together in an interpenetrating or semi-interpenetrating manner, the excellent mechanical strength and modulus can be provided for the polymer, and the polymer gel material has unique advantages in the preparation of high-strength and high-toughness polymer gel materials. The crosslinked network may be a combination of a portion containing only dynamic covalent crosslinking and a portion containing only hydrogen bonding crosslinking, or a combination of a portion containing only dynamic covalent crosslinking and a portion containing both dynamic covalent crosslinking and hydrogen bonding crosslinking, or a combination of a portion containing only hydrogen bonding crosslinking and a portion containing both dynamic covalent crosslinking and hydrogen bonding crosslinking, or a combination of both dynamic covalent crosslinking and hydrogen bonding crosslinking in each crosslinked network, but the invention is not limited thereto.

The crosslinking degree of dynamic covalent crosslinking and hydrogen bond crosslinking in the hybrid dynamic polymer crosslinking network can be reasonably designed and regulated according to actual use requirements. When the crosslinking degree of dynamic covalent crosslinking is above the gel point, better covalent stability is easily obtained; when the crosslinking degree of hydrogen bond crosslinking is above the gel point, a high-strength supermolecule effect is easily obtained, and the toughness and tear resistance of the material are improved. Preferably, the degree of crosslinking of the dynamic covalent crosslinks in at least one of said crosslinked networks is above the gel point to better balance the mechanical strength and dynamic reversibility.

The polymer with the cross-linking degree of the hydrogen bond cross-linking formed by the action of the hydrogen bond below the gel point can be dispersed in the hybrid dynamic polymer cross-linking network, the hydrogen bond-containing polymer can provide supermolecule dynamic property, and richer supermolecule dynamic property can be obtained through the interaction of the hydrogen bond group in the polymer and the hydrogen bond group in the cross-linking network, so that the hybrid dynamic polymer cross-linking network also has a positive effect on improving the toughness property and the tear resistance of the material.

The hybrid dynamic polymer cross-linked network can be dispersed with polymer particles with the cross-linking degree of hydrogen bond cross-linking formed by the action of hydrogen bonds above the gel point, and the hydrogen bond cross-linked supermolecule polymer particles are compounded in the cross-linked network in a dispersed form to provide the functions of filling enhancement and dynamic supplementation.

The degree of crosslinking of dynamic covalent crosslinks referred to in the present invention refers to the sum of the degrees of crosslinking of all dynamic covalent crosslinks contained in the crosslinked network.

In the present invention, the degree of crosslinking of a kind of crosslinking is not less than (inclusive of) the gel point, which means that a three-dimensional infinite network structure can be formed only by the crosslinking.

In a preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one cross-linked network only contains dynamic covalent cross-links, the cross-linking degree of the cross-linked network is above the gel point, and the cross-linked network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point. In the embodiment, the dynamic covalent crosslinking and the hydrogen bond crosslinking are respectively positioned in the two crosslinking networks, so that the mutual influence is small during preparation, and the two dynamic structures play a role in the two crosslinking networks in a synergistic manner, so that good dynamic covalent property and supermolecule dynamic property can be obtained, and excellent self-repairing performance is provided.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is above a gel point, the crosslinking degree of the hydrogen bond crosslinking is below the gel point, and the crosslinking network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point. In the embodiment, the two cross-linked networks have hydrogen bond functions, so that abundant supramolecular dynamics can be obtained, the rapid self-repairing performance is facilitated, and the toughness and the tear resistance of the material are conveniently improved.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is below a gel point, the crosslinking degree of the hydrogen bond crosslinking is above the gel point, and the crosslinking network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point. In the embodiment, the two crosslinking networks both contain hydrogen bond crosslinking above gel points, and rich supermolecule dynamics can be obtained by regulating and controlling the tooth number, position and the like of the hydrogen bond, so that the super-toughness performance and the excellent tear resistance can be conveniently obtained.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one crosslinking network contains dynamic covalent crosslinking and hydrogen bonding crosslinking, the crosslinking degree of the dynamic covalent crosslinking is below a gel point, the crosslinking degree of the hydrogen bonding crosslinking is below the gel point, but the sum of the crosslinking degrees of the two crosslinking degrees is above the gel point, and the crosslinking network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structural and dynamic reversibility. The network structure is also beneficial to obtaining a hierarchical dynamic reversible effect.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is above a gel point, the crosslinking degree of the hydrogen bond crosslinking is above the gel point, and the crosslinking network contains at least one dynamic covalent bond; the other network contains only hydrogen-bonded crosslinks, the degree of crosslinking being above the gel point. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structural and dynamic reversibility. The crosslinking degree of the hydrogen bond crosslinking of the two crosslinking networks is above the gel point, so that higher supermolecule action strength can be obtained, and a good shape memory function can be conveniently obtained.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises both dynamic covalent crosslinking and hydrogen bonding crosslinking, the degree of crosslinking of the dynamic covalent crosslinking is above the gel point, the degree of crosslinking of the hydrogen bonding crosslinking is below the gel point, and the crosslinked network comprises at least one dynamic covalent bond; the other crosslinked network contains only dynamic covalent crosslinks, the degree of crosslinking being above the gel point, the crosslinked network containing at least one dynamic covalent bond; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same. In this embodiment, the degree of crosslinking of the dynamic covalent crosslinks of both crosslinked networks is above the gel point, which provides good structural stability and mechanical strength to the polymer, and which allows for abundant, synergistic, and/or orthogonal dynamic covalences. The hydrogen bond crosslinking plays roles of supplementing and reinforcing and providing supermolecule dynamic property, and has positive effect on improving the toughness and tear resistance of the material.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises dynamic covalent crosslinking and hydrogen bonding crosslinking, the crosslinking degree of the dynamic covalent crosslinking is below the gel point, the crosslinking degree of the hydrogen bonding crosslinking is above the gel point, and the crosslinked network comprises at least one dynamic covalent bond; the other crosslinked network contains only dynamic covalent crosslinks, the degree of crosslinking being above the gel point, the crosslinked network containing at least one dynamic covalent bond; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same. In this embodiment, dynamic covalent crosslinking and hydrogen bonding crosslinking act synergistically in different crosslinking networks to provide both dynamic reversible performance and self-healing performance for the polymer. The network structure easily provides abundant supramolecular dynamics, and facilitates obtaining super-toughness performance and excellent tear resistance.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises both dynamic covalent crosslinking and hydrogen bonding crosslinking, the degree of crosslinking of the dynamic covalent crosslinking is below the gel point, the degree of crosslinking of the hydrogen bonding crosslinking is below the gel point, but the sum of the degrees of crosslinking of the two is above the gel point, and the crosslinked network comprises at least one dynamic covalent bond; the other crosslinked network contains only dynamic covalent crosslinks, the degree of crosslinking being above the gel point, the crosslinked network containing at least one dynamic covalent bond; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same. The network structure is easy to obtain abundant and hierarchical dynamic covalent properties.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein one crosslinked network comprises both dynamic covalent crosslinking and hydrogen bonding crosslinking, the degree of crosslinking of the dynamic covalent crosslinking is above the gel point, the degree of crosslinking of the hydrogen bonding crosslinking is above the gel point, and the crosslinked network comprises at least one dynamic covalent bond; the other crosslinked network contains only dynamic covalent crosslinks, the degree of crosslinking being above the gel point, the crosslinked network containing at least one dynamic covalent bond; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same. In the embodiment, the crosslinking degree of the dynamic covalent crosslinking of the two crosslinking networks is above the gel point, orthogonal and/or synergistic dynamic covalency can be obtained, and the hydrogen bond crosslinking in the crosslinking networks provides the effects of supplementing and enhancing the toughness of the material.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks, wherein each of the two crosslinked networks comprises dynamic covalent crosslinking and hydrogen bonding crosslinking, the degree of crosslinking of the dynamic covalent crosslinking is above the gel point, the degree of crosslinking of the hydrogen bonding crosslinking is below or above the gel point, and each of the two crosslinked networks comprises at least one dynamic covalent bond; the two cross-linked networks are different; the dynamic covalent bonds in the two crosslinked networks may or may not be the same, preferably not the same. In the embodiment, by designing the structures of the two dynamic cross-linked networks, the performances of different dynamic covalent bonds and hydrogen bonds can be fully exerted, and the dynamic cross-linked structures are introduced into different polymer matrixes, so that the outstanding, orthogonal or synergistic dynamic reversible effect is obtained, and the aim of accurately controlling the performances of dynamic polymers can be fulfilled.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least three crosslinked networks; at least one cross-linked network only contains dynamic covalent cross-links, the cross-linking degree is above the gel point, and the cross-linked network contains at least one dynamic covalent bond; at least one of the crosslinked networks contains only hydrogen-bonded crosslinks, and the degree of crosslinking is above the gel point. In the embodiment, three or more crosslinking networks can be combined together in an interpenetrating or semi-interpenetrating mode, so that the excellent structural stability, mechanical strength and modulus are obtained, and the method has unique advantages particularly in the preparation of high-strength dynamic polymer gel materials. The dynamic covalent crosslinking and the hydrogen bond crosslinking are respectively in different crosslinking networks, so that the mutual interference in preparation can be reduced, the orthogonal dynamic reversibility is convenient to obtain, and a good shape memory function can be obtained through reasonable structural design.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least three crosslinked networks; at least one cross-linked network simultaneously contains dynamic covalent cross-linking and hydrogen bond cross-linking, the cross-linking degree of the dynamic covalent cross-linking is above the gel point, the cross-linking degree of the hydrogen bond cross-linking is below or above the gel point, and the cross-linked network contains at least one dynamic covalent bond. The network structure is easy to obtain excellent structural stability, mechanical strength and modulus, and is particularly convenient for preparing high-strength dynamic polymer gel materials. The dynamic covalent crosslinking and the hydrogen bond crosslinking in the crosslinking network jointly provide the polymer with dynamic reversible performance and self-repairing performance.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; both the two crosslinking networks only contain dynamic covalent crosslinking, the crosslinking degree is above the gel point, and the crosslinking networks contain at least one dynamic covalent bond; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network. In the embodiment, the two dynamic covalent cross-linked networks provide structural balance and dynamic covalence, and the hydrogen-bond-containing polymer dispersed in the cross-linked networks can provide supermolecule dynamics and has a positive effect on improving the tear resistance of the material.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises two crosslinked networks; both the two crosslinking networks only contain dynamic covalent crosslinking, the crosslinking degree is above the gel point, and the crosslinking networks contain at least one dynamic covalent bond; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles. In this embodiment, the two dynamic covalent cross-linked networks provide structural balance and dynamic covalency, dispersing the supramolecular polymer particles complexed in the cross-linked networks, providing packing enhancement and the role of complementing the dynamics.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least two crosslinked networks; at least one cross-linked network only contains dynamic covalent cross-links, the cross-linking degree is above the gel point, and the cross-linked network contains at least one dynamic covalent bond; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network. In this embodiment, two or more crosslinked networks together provide superior mechanical strength and structural stability, wherein the dynamic covalent crosslinks provide dynamic covalent and self-healing properties to the polymer. The hydrogen bond-containing polymer dispersed in the cross-linked network can provide supramolecular dynamics and has a positive effect on improving the tear resistance of the material.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least two crosslinked networks; at least one cross-linked network only contains dynamic covalent cross-links, the cross-linking degree is above the gel point, and the cross-linked network contains at least one dynamic covalent bond; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles. In this embodiment, two or more crosslinked networks together provide superior mechanical strength and structural stability, wherein the dynamic covalent crosslinks provide dynamic covalent and self-healing properties to the polymer. The supramolecular polymer particles are dispersed and compounded in the cross-linked network, and the filling enhancement and the dynamic supplement effects are provided.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least two crosslinked networks; at least one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is above the gel point, the crosslinking degree of the hydrogen bond crosslinking is below or above the gel point, and the crosslinking network contains at least one dynamic covalent bond; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network. In the embodiment, two or more crosslinking networks together provide excellent mechanical strength and structural stability, and dynamic covalent crosslinking and hydrogen bond crosslinking together provide dynamic reversible performance and self-repairing performance for the polymer. The hydrogen bond groups in the hydrogen bond-containing polymer dispersed in the cross-linked network can interact with the hydrogen bond groups in the cross-linked network, so that more abundant supramolecular dynamics is obtained, and the toughness and tear resistance of the material can be greatly improved.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises at least two crosslinked networks; at least one crosslinking network simultaneously contains dynamic covalent crosslinking and hydrogen bond crosslinking, the crosslinking degree of the dynamic covalent crosslinking is above the gel point, the crosslinking degree of the hydrogen bond crosslinking is below or above the gel point, and the crosslinking network contains at least one dynamic covalent bond; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles. In the embodiment, two or more crosslinking networks together provide excellent mechanical strength and structural stability, and dynamic covalent crosslinking and hydrogen bond crosslinking together provide dynamic reversible performance and self-repairing performance for the polymer. The supramolecular polymer particles are dispersed and compounded in the cross-linked network, and the filling enhancement and the dynamic supplement effects are provided.

In the present invention, the reversible radical-type dynamic covalent bond is selected from at least one of the following structures:

wherein each W is independently selected from an oxygen atom, a sulfur atom;

Is absent;

Is connected with Z; when Z is an antimony atom or a bismuth atom, k is 2, which means that there are two

To Z are two

Are the same or different in structure;

wherein R is₁Each independently selected from hydrogen atom, halogen atom, hetero atom group, substituent, R at different positions₁Are the same or different in structure; wherein the substituent contains a hetero atom or does not contain a hetero atom, and the number of carbon atoms is not particularly limited, but preferably the number of carbon atoms is1 to 20, more preferably 1 to 10, and the structure thereof is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, R₁Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. In order to promote the reversible breakage of dynamic covalent bonds, the oxidation resistance of the formed carbon free radicals is increased so as to stabilize the formed carbon free radicals, facilitate the coupling or reversible exchange of further free radicals and obtain better dynamic reversible performance, R₁Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Aryl radical, C_1-20Heteroaromatic hydrocarbon group and C substituted by acyl, acyloxy, acylamino, oxyacyl, sulfuryl, aminoacyl, phenylene_1-20Hydrocarbyl/heterohydrocarbyl; r₁Further preferably selected from the group consisting of a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, phenyl group, hydroxyl group, cyano group, carboxyl group, methyloxyacyl group, ethyloxyacyl group, propyloxyacyl group, butyloxyacyl group, methylaminoacyl group, ethylaminoacyl group, propylaminoylgroup, butylaminoacyl group;

wherein R is₂Each independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; each R is₂Are the same or different; when R is₂When selected from substituents, it is selected from, but not limited to: hydroxy, phenyl, phenoxy, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group;

wherein R is₃Selected from cyano, C_1-10Alkoxyacyl group, C_1-10Alkyl acyl radical, C_1-10Alkylaminoacyl, phenyl, substituted phenyl, arylalkyl, substituted arylalkyl; wherein the substituent atom or substituent is not particularly limited and is selected from, but not limited to, halogenAny one or more of an atom, a hydrocarbyl substituent, and a heteroatom-containing substituent;

wherein R is¹、R²、R³、R⁴Each independently selected from hydrogen atom, halogen atom, heteroatom group, substituent; the substituent contains a heteroatom or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably the number of carbon atoms is 1 to 20, more preferably 1 to 10, the structure of the substituent is not particularly limited, and the substituent includes a linear structure, a branched structure or a cyclic structure, the cyclic structure is selected from an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and a combination thereof, and the aliphatic ring and the aromatic ring are preferred; in general terms, R¹、R²、R³、R⁴Each independently preferably selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl radical, C_1-20Heterohydrocarbyl, substituted C_1-20Hydrocarbyl or substituted C_1-20Heterohydrocarbyl, and combinations of two or more of the foregoing. In order to increase the steric hindrance of the nitrogen atom in the dynamic covalent structure, promote the reversible cleavage of the dynamic covalent bond, facilitate the stabilization of the formed nitroxide/thioazide radicals, and further the coupling or reversible exchange of the radicals, resulting in better dynamic reversible performance, R¹、R²、R³、R⁴Each independently preferably selected from hydrogen atom, hydroxyl group, cyano group, carboxyl group, C_1-20Alkyl radical, C_1-20Heteroalkyl, cyclic structure C_1-20Alkyl, C of cyclic structure_1-20Heteroalkyl group, C_1-20Aryl radical, C_1-20A heteroaryl group; in general terms, in the formulae (12), (14)

The structure of (a) is preferably at least one of the following structures, but the present invention is not limited thereto:

said

wherein R is⁵、R⁶、R⁷、R⁸Each independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; when R is⁵、R⁶、R⁷、R⁸When each is independently selected from the substituent group, the substituent group is preferably a substituent group with steric hindrance effect so as to increase steric hindrance and promote homolytic cleavage of dynamic covalent bonds; the substituents with steric hindrance are selected from, but not limited to: cyano radicals, C_1-20Alkyl radical, C_1-20Cycloalkyl, aralkyl, heteroaralkyl and the groups formed by the above groups substituted by any substituent atom or substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; by way of example, typical sterically hindered substituents include, but are not limited to: cyano, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, pyridyl, C_1-5Alkyl-substituted phenyl, C_1-5Alkoxy-substituted phenyl, C_1-5Alkylthio-substituted phenyl, C_1-5Alkylamino substituted phenyl, cyano substituted phenyl;

wherein, L is a divalent linking group, and the structures of L at different positions are the same or different; wherein the divalent linking group contains or does not contain a heteroatom, the number of carbon atoms is not particularly limited, preferably 1 to 20, more preferably 1 to 10, the structure of the divalent linking group is not particularly limited, and includes, but is not limited to, a linear structure, a branched structure containing a pendant group, or a cyclic structure selected from the group consisting of an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof, preferably an aliphatic ring and an aromatic ring; in general terms, each L is independently selected from a heteroatomRadical linking group, heteroatom radical linking group, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing. Wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. In order to promote reversible cleavage of dynamic covalent bonds, increase oxidation resistance of the formed carbon radical, stabilize the formed carbon radical, facilitate further coupling or reversible exchange of radicals, and obtain better dynamic reversible performance, L is preferably selected from acyl, acyloxy, acylthio, acylamino, oxyacyl, sulfuryl, phenylene, divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl; wherein said substituted divalent C_1-20The structure of the substituent group in the hydrocarbon group/heterohydrocarbon group is preferably an acyl group, an acyloxy group, an acylthio group, an acylamino group, an oxyacyl group, a thioacyl group, an aminoacyl group, a phenylene group, and more preferably the substituted divalent C_1-20The hydrocarbyl/heterohydrocarbyl group being linked to R via said substituent group₁To the carbon atom(s) of (a); in general terms, in the formulae (8), (9), (10), (11), (12), (13), (14), (15)

wherein R is selected from any suitable atom, substituent, substituted polymer chain; wherein R represents the number of R connected with a benzene ring, and the value of R is an integer selected from 0 to 5; wherein m is the number of the repeating units, and can be a fixed value or an average value;

said

Further preferred is at least one of the following structures, but the present invention isThe invention is not limited thereto:

wherein, the definitions, selection ranges and preferred ranges of R, R and m are as described above;

wherein the content of the first and second substances,

wherein the content of the first and second substances,

is a nitrogen-containing aliphatic heterocyclic ring, the number of ring-forming atoms of the ring is not particularly limited, and is preferably from 3 to 10, more preferably from 5 to 8; except that at least one of the ring-forming atoms is a nitrogen atom, the rest of the ring-forming atoms are selected from but not limited to carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms and silicon atomsThe hydrogen atom to which the atom is attached is substituted or unsubstituted with any suitable substituent atom, substituent group; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0,1 or an integer greater than 1; wherein, the symbol is the site connecting with other structures in the formula, if not specifically noted, the following symbol is the same meaning, and the description is not repeated; in order to increase the steric hindrance of the nitrogen atom in the dynamic covalent structure, promote the reversible cleavage of the dynamic covalent bond, facilitate the stabilization of the formed nitrogen-oxygen/nitrogen-sulfur free radical, and further the coupling or reversible exchange of the free radical to obtain better dynamic reversible performance

said

wherein the content of the first and second substances,

is an aromatic ring; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms are optionally substituted by any suitable substituent atom, substituent group or not; wherein, the substituent atom or substituent is not particularly limited and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent; in general terms, the aromatic rings include, but are not limited to: furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, benzene, pyridine, pyrazine, pyridazine, pyrimidine, 1,3, 5-triazine, indene, benzofuran, isobenzofuran, benzopyrrole, isobenzopyrrole, benzo [ b]Thiophene, benzo [ c]Thiophene, benzimidazole, purine, benzopyrazole, benzoxazole, benzisoxazole, benzothiazole, naphthalene, naphthyridine, quinoxaline, quinazoline, quinoline, isoquinoline, pteridine, indane, tetrahydronaphthalene, anthracene, phenanthrene, acridine, dihydroanthracene, xanthene, thiaanthracene, fluorene, carbazole, biphenyl, binaphthyl, bianthracene, 10, 11-dihydro-5H-dibenzo [ a, d ] o]Cycloheptane, dibenzocycloheptene, 4-B-dibenzocycloheptenone, iminodibenzyl, naphthylene, dibenzocyclooctyne, azabicyclooctyne, and substituted versions of any two or more of the foregoing;

wherein the content of the first and second substances,

indicates that n is connected with

Of an aromatic ring of (a) in different positions

Are the same or different; unless otherwise indicated, appear hereinafter

Are the same as defined above; in order to promote the reversible breakage of dynamic covalent bonds, increase the oxidation resistance of the formed carbon free radicals, stabilize the formed carbon free radicals, facilitate the coupling or reversible exchange of further free radicals and obtain better dynamic reverse performance,

wherein L is₁Is a divalent linking group; the divalent linking groups are independently selected from but not limited to:

l in different positions₁Are the same or different; wherein L is₂Is a divalent linking group; the divalent linking groups are independently selected from but not limited to: direct key

L in different positions₂Are the same or different;

wherein the content of the first and second substances,

represents a linkage to a polymer chain or any other suitable group/atom (including a hydrogen atom); each one of

Are the same or different; each one ofAn

A connecting ring or a non-connecting ring; unless otherwise indicated, appear hereinafter

The same meaning is used.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (1) is shown below, but the present invention is not limited thereto:

wherein, W₁、

The definition, selection range and preferable range of (2) are as described above.

The reversible radical type dynamic covalent bond having the general structural formula of formula (2) is preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein each G is independently selected from

The structures of G at different positions are the same or different; unless otherwise noted, G appearing hereinafter has the same meaning and will not be described repeatedly;

wherein the content of the first and second substances,

to be connected with n

An aromatic ring of (2); wherein the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure, and a fused ring structure; the number of ring-forming atoms of the ring is not particularly limited; the ring-forming atoms of the aromatic ring are selected from, but not limited to, carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, silicon atoms, and the hydrogen atoms attached to the ring-forming atoms are optionally substituted by any suitable substituent atom, substituent group or not; wherein, the substituent atom or substituent is not particularly limited, and is selected from any one or more of halogen atom, alkyl substituent and heteroatom-containing substituent. At different positions

Are the same or different; unless otherwise indicated, appear hereinafter

The same meanings are given, and description thereof will not be repeated; by way of example, the

May be selected from at least one of the following structures, but the present invention is not limited thereto:

wherein, W, W₂、L₁、L₂、

As defined above.

The reversible radical-type dynamic covalent bond having the general structural formula of formula (2) is further preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein, W, W₂、L₁、

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (2) is shown below, but the present invention is not limited thereto:

wherein, W, W₂、L₁、

The reversible radical type dynamic covalent bond having the general structural formula of formula (3) is preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein G, W,

The definition, selection range and preferred range of (1) are as described above;

the reversible radical-type dynamic covalent bond having the general structural formula of formula (3) is further preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein, W, L₁、

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (3) is shown below, but the present invention is not limited thereto:

wherein, W, L₁、

The reversible radical type dynamic covalent bond having the general structural formula of formula (4) is preferably selected from one of the following structures, but the present invention is not limited thereto:

more preferably one of the following structures, but the invention is not limited thereto:

wherein, G, W₃、V、V’、

The definition, selection range and preferred range of (1) are as described above; wherein G at different positions,

Are identical or different.

The reversible radical-type dynamic covalent bond having the general structural formula of formula (4) is further preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein, W₃、L₁、

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (4) is shown below, but the present invention is not limited thereto:

wherein, W₃、L₁、

The definition, selection of ranges, preferred ranges are as described above.

The reversible radical type dynamic covalent bond having the general structural formula of formula (5) is preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (5) is shown below, but the present invention is not limited thereto:

wherein L is₁、

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (6) is shown below, but the present invention is not limited thereto:

wherein R is₂、L₁、

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (7) is shown below, but the present invention is not limited thereto:

wherein L is₁、

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (8) is shown below, but the present invention is not limited thereto:

wherein R is₂、m、

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (9) is shown below, but the present invention is not limited thereto:

wherein m is,

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (10) is shown below, but the present invention is not limited thereto:

wherein, W₁、m、

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (11) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (12) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (13) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as defined above.

By way of example, a typical structure of a reversible radical-type dynamic covalent bond having the general structural formula of formula (14) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (15) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (16) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (17) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (18) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

as defined above.

The reversible radical-type dynamic covalent bond having the general structural formula of formula (19) is preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein, G, W, W₄、

the reversible radical-type dynamic covalent bond having the general structural formula of formula (19) is further preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein, W, W₄、L₁、

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (19) is shown below, but the present invention is not limited thereto:

wherein, W, W₄、L₁、

As defined above.

The reversible radical-type dynamic covalent bond having the general structural formula of formula (20) is preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein G is,

The reversible radical-type dynamic covalent bond having the general structural formula of formula (20) is further preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein L is₁、

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (20) is shown below, but the present invention is not limited thereto:

wherein L is₁、

As defined above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (21) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the structure of (2) is as described above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (22) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the structure of (2) is as described above.

The reversible radical type dynamic covalent bond having the general structural formula of formula (23) is preferably selected from one of the following structures, but the present invention is not limited thereto:

wherein, W, W₄、

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (23) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the structure of (2) is as described above.

By way of example, a typical structure of a reversible radical-type dynamic covalent bond having the general structural formula of formula (24) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the definition is as described above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (25) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the definition is as described above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (26) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the definition is as described above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (27) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the definition is as described above.

As an example, the structure of a typical reversible radical-type dynamic covalent bond having the general structural formula of formula (28) is shown below, but the present invention is not limited thereto:

wherein the content of the first and second substances,

the definition is as described above.

The dynamic covalent bond in the present invention refers to a reversible free radical type dynamic covalent bond (referred to as "dynamic covalent bond", hereinafter the same is used), which can be activated under certain conditions, and undergoes bond dissociation, bonding and exchange reactions, exhibiting dynamic covalent reversible characteristics (dynamic covalent property), and realizing exchange of polymer chains and change of topological structure, wherein "certain conditions" refers to heating, light irradiation, radiation or a combination of any two or three of the above three conditions, i.e. the hybrid dynamic polymer can directly realize breaking, exchange and recombination of dynamic covalent bonds through heating, or light irradiation, or radiation, etc., thereby obtaining dynamic covalent property.

In the invention, during the dynamic transformation process of the dynamic covalent bond, namely the dissociation, bonding, exchange reaction and the like of the bond, the generated free radical has higher stability, shows good reversible property of the dynamic covalent bond and obtains stable and multiple self-repairing performance. In addition, the free radical has higher catalytic and initiating activity, and is convenient for chain extension, crosslinking, grafting and the like, so that the performance of the dynamic polymer is changed or improved, and better self-repairing performance and self-reinforcing performance can be obtained when the material is damaged. For example, when the polymer structure contains sulfydryl, the free radical generated in the dynamic conversion process can capture the hydrogen atom on the sulfydryl to generate a sulfydryl free radical which generates a sulfydryl-alkene click reaction with electron-deficient alkene/alkyne in the polymer structure, so that better self-repairing and self-enhancing performances are obtained; for another example, under suitable conditions, the radicals generated during the dynamic transformation process can also directly initiate the radical polymerization of vinyl monomers or initiate the radical polymerization of vinyl groups contained in the polymer, thereby obtaining self-repairing and self-reinforcing properties. Wherein the vinyl monomer includes but is not limited to: (meth) styrenes, (meth) acrylic acids and esters thereof, (meth) acrylamides, fumarates, cyanoacrylates, cyanoacrylamides, vinyl acetates, vinyl pyrrolidones, vinyl halides, vinyl pyridines.

In the invention, in the process of dynamic transformation of the dynamic covalent bond under the dynamic transformation conditions of heating, illumination, radiation and the like, the self-repairing performance and the self-enhancement performance are obtained, and the change of color, fluorescence, oxidation resistance and conductivity can be caused, so that the service performance of the material is further enriched. For example, the self-repairing state of the material can be visually fed back through the color and fluorescence change of the dynamic transformation process of the dynamic polymer; the free radicals generated in the dynamic transformation process can also absorb harmful free radicals in the polymer matrix, so that the oxidation resistance of the material is improved; the free radicals generated in the dynamic transformation process of the dynamic covalent bond are also beneficial to improving the conductivity of the material, and the requirements of special application scenes are met.

In the present invention, in order to avoid the radical oxidation, resulting in the decrease of the radical concentration, and affecting the dynamic reversible performance of the hybrid dynamic polymer, the structure of the hybrid dynamic polymer and the preparation and dynamic process of the hybrid dynamic polymer can be controlled at least from the following aspects (but the present invention is not limited thereto): the dynamic covalent structure is introduced with atoms/groups with larger steric hindrance and/or conjugation, the steric hindrance is formed by the large steric hindrance groups to reduce the reaction of free radicals and oxygen, and the atoms/groups with conjugation are connected, so that a delocalized electron structure is formed by conjugated pi electrons and active free radicals, and the structural stability of active free radicals is improved; the preparation of the hybrid dynamic polymer and the dynamic reversible process thereof isolate the oxidizing atmosphere or reduce the oxygen content. For the preparation process and the dynamic reversible transformation process of the hybrid dynamic polymer in a solid state, the oxidation side reaction of the hybrid dynamic polymer can be reduced or eliminated by introducing an oxidation resistant group or adding a proper amount of antioxidant/reducing agent in the structure of the hybrid dynamic polymer in advance.

In the present invention, the reversible radical type dynamic covalent bond is present at any suitable position in the polymer, including but not limited to: crosslinked network polymer chains, side chains, branched chains, pendant groups, end groups, and non-crosslinked polymer backbones, side chains, branched chains, pendant groups, end groups. Preferably, the dynamic covalent bonds are present on a polymer chain backbone, more preferably on a crosslinked network chain backbone and a non-crosslinked backbone.

In an embodiment of the present invention, the hydrogen bonding, which is any suitable supramolecular interaction established by hydrogen bonding, is generally a hydrogen bond linkage between Z and Y mediated by hydrogen between the hydrogen atom covalently linked to atom Z with large electronegativity and atom Y with large electronegativity and small radius, to generate a Z-H … Y form, wherein Z, Y is any suitable atom with large electronegativity and small radius, which may be the same kind of element or different kind of element, and may be selected from atoms of F, N, O, C, S, Cl, P, Br, I, etc., more preferably F, N, O atom, and more preferably O, N atom. The hydrogen bond function can exist as supramolecular polymerization and/or crosslinking and/or intrachain cyclization, namely the hydrogen bond can only play a role of connecting two or more chain segment units to increase the size of a polymer chain but not play a role of supramolecular crosslinking, or the hydrogen bond only plays a role of interchain supramolecular crosslinking, or only plays a role of intrachain cyclization, or the combination of any two or more of the three.

In the embodiment of the present invention, the number of teeth refers to the number of hydrogen bonds formed by a donor (H, i.e., hydrogen atom) and an acceptor (Y, i.e., electronegative atom to accept hydrogen atom) of hydrogen bonding groups, each H … Y being combined into one tooth. In the following formula, the hydrogen bonding of monodentate, bidentate and tridentate hydrogen bonding groups is schematically illustrated, respectively.

The bonding of the monodentate, bidentate and tridentate hydrogen bonds can be specifically exemplified as follows:

in embodiments of the present invention, the greater the number of teeth of the hydrogen bond, the greater the synergistic effect, and the greater the strength of the hydrogen bond. If the number of teeth of the hydrogen bond is large, the strength is high, the dynamic property of the hydrogen bond crosslinking is weak, and the effects of promoting the hybrid dynamic polymer to keep a balanced structure and improving the mechanical properties (modulus, strength and hardness) can be achieved. If the number of teeth of the hydrogen bond is small, the strength is low, and the dynamics of hydrogen bond crosslinking is strong. In embodiments of the present invention, it is preferred that no more than four-tooth hydrogen bonding crosslinks be present to achieve a relatively balanced supramolecular interaction strength and supramolecular dynamics.

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 hydrogen bond groups existing on the polymer cross-linked network skeleton chain and the non-cross-linked polymer main chain end group, side chain/branched chain end group, and are called chain end group hydrogen bond groups; or can be simultaneously present on at least two of the polymer chain skeleton, the side group and the end group; other ingredients, such as optional fillers, small molecules, crosslinked particles, inorganic particles, also present in the hybrid dynamic polymer, are referred to as other hydrogen bonding groups. When hydrogen bonding groups are present simultaneously on at least two of the backbone, pendant group, terminal group or other components of the polymer chain, hydrogen bonding may occur between hydrogen bonding groups in different positions, e.g., backbone hydrogen bonding groups may form hydrogen bonding with pendant hydrogen bonding groups, in particular instances.

The hydrogen bonding described in the present invention is provided by hydrogen bonding groups. The degree of crosslinking of the hydrogen bond crosslinks formed by hydrogen bonding may be above the gel point or below the gel point. When the crosslinking degree of hydrogen bond crosslinking is above the gel point, high-strength supermolecule action strength is easily obtained, and the mechanical strength and modulus of the material are conveniently improved; when the crosslinking degree of hydrogen bond crosslinking is below the gel point, the supermolecule dynamic property of the material is stronger, the material is easy to obtain faster self-repairing performance, and the tear resistance and the tensile toughness of the material are also favorably improved. In the invention, the crosslinking degree of the hydrogen bond crosslinking can be reasonably designed and regulated according to the actual application requirement.

In the embodiment of the present invention, since some hydrogen bonds have no directionality and selectivity, in a specific case, hydrogen bonding interactions can be formed between hydrogen bonding groups at different positions, hydrogen bonding interactions can be formed between hydrogen bonding groups at the same or different positions in the same or different polymer molecules, and hydrogen bonding interactions can also be formed between hydrogen bonding groups contained in other components in the polymer, such as optional fillers, small molecules, crosslinked particles, inorganic particles, and the like. In the present invention, intrachain rings may be formed in addition to interchain crosslinks. It is to be noted that the present invention does not exclude that some of the hydrogen bonding actions formed do not form interchain crosslinking actions, nor intrachain rings, but only non-crosslinking polymerization, grafting, etc.

The hybrid dynamic polymer contains at least one hydrogen bonding; wherein the hydrogen bonding group for forming the hydrogen bonding action exists in at least one of the skeleton hydrogen bonding group, the side group hydrogen bonding group, the chain end group hydrogen bonding group and other 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. Wherein, the hydrogen bonding group preferably comprises the following structural components:

more preferably at least one of the following structural components:

further preferably at least one of the following structural components:

wherein the content of the first and second substances,

By way of example, the following backbone hydrogen bonding groups may be mentioned, but the invention is not limited thereto:

by way of example, the following side groups and/or hydrogen bonding groups in the chain end groups may be mentioned, without the invention being restricted thereto:

wherein x, m and n are the number of repeating units, and may be fixed values or average values, preferably less than 20, and more preferably less than 5.

The other hydrogen bonding groups, which may be any suitable hydrogen bonding structures, are described.

The hydrogen bonding/crosslinking has various action types, including but not limited to hydrogen bonding/crosslinking formed by one or more hydrogen bonding groups in skeleton hydrogen bonding groups, side group hydrogen bonding groups, chain end group hydrogen bonding groups or other hydrogen bonding groups, and hydrogen bonding/crosslinking with adjustable supramolecular action strength, supramolecular dynamic property and supramolecular crosslinking density in a large range is obtained. Different hydrogen bonding actions have respective structural differences and performance characteristics, for example, the hydrogen bonding action formed by the participation of a side group hydrogen bonding group and a chain end group hydrogen bonding group has the characteristics of higher degree of freedom, quicker response, stronger dynamic property, easier regulation and control of hydrogen bonding density and the like, a quick self-repairing process is easily obtained, and the tear resistance can be better improved; the skeleton hydrogen bond group is positioned on a skeleton chain, so that the mechanical strength and the structural stability are easier to improve, a high-strength hybrid dynamic polymer material is convenient to obtain, and other hydrogen bond groups can further enrich the hydrogen bond action form; at least one side group hydrogen bond group and at least one skeleton hydrogen bond group are simultaneously introduced into the polymer, so that the supramolecular action strength and the supramolecular dynamic property are balanced, and the excellent self-repairing performance and the material toughness performance are obtained.

The hydrogen bond crosslinking can be generated in the process of dynamic covalent crosslinking of the hybrid dynamic polymer; or hydrogen bond crosslinking is generated in advance and then dynamic covalent crosslinking is carried out; it is also possible, but not limiting to the invention, to generate hydrogen bonding crosslinks during subsequent formation of the hybrid dynamic polymer after formation of the dynamic covalent crosslinks.

The hybrid dynamic polymer containing at least two crosslinking networks can be prepared by a step method and a synchronous method. When the hybrid dynamic polymer is prepared by a step method, a first network can be prepared by using a monomer or a prepolymer, a catalyst and an initiator, and then a prepared second network is added to carry out solution blending or melt blending to obtain a cross-linked network which is blended with each other, wherein the second network can be swelled by means of a solvent and then blended with the first network; or preparing a first network, placing the crosslinked first network into a second network monomer or prepolymer melt or solution containing a catalyst, an initiator and the like to swell the first network, and then polymerizing and crosslinking the second network monomer or prepolymer in situ to form a second network, and simultaneously obtaining the hybrid dynamic polymer which is mutually interpenetrated or partially mutually interpenetrated, wherein the crosslinking degree of the first network is preferably slightly crosslinked above the gel point so as to facilitate the interpenetration effect of the second network. For the hybrid 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. When the hybrid dynamic polymer containing two cross-linked network structures is prepared by adopting a synchronous method, a first network and a second network can be prepared by utilizing a monomer or a prepolymer, a catalyst and an initiator respectively, and then the prepared two networks are placed in the same reactor to be mixed to obtain a cross-linked network which is mutually blended, wherein the formed networks can be swelled by a solvent during blending, and then the mixed networks are blended to obtain the hybrid dynamic polymer; or mixing two or more monomers or prepolymers and then reacting in the same reactor according to respective polymerization and crosslinking processes to obtain the hybrid dynamic polymer which is mutually interpenetrated or partially mutually interpenetrated.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which only contains a crosslinking network, and at least two reversible free radical type dynamic covalent bonds and at least one hydrogen bonding interaction are contained in the hybrid dynamic polymer.

The hybrid dynamic polymer only contains one cross-linked network, has a relatively simple structure, is easy to prepare, and can obtain good mechanical strength and modulus. The crosslinked network may contain only dynamic covalent crosslinks; or contain only hydrogen bond crosslinks; or both dynamic covalent and hydrogen bonding crosslinking. Preferably, the degree of crosslinking of the dynamic covalent crosslinks in the crosslinked network is above the gel point to better balance mechanical strength and dynamic reversibility. In addition, the crosslinked network of the hybrid dynamic polymer may be dispersed with a polymer having a degree of crosslinking by hydrogen bonding which is not more than the gel point, or may be dispersed with polymer particles having a degree of crosslinking by hydrogen bonding which is not more than the gel point.

In a preferred embodiment of the invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is below the gel point, and the crosslinked network comprises at least two dynamic covalent bonds. In the embodiment, as long as the crosslinking degree of one dynamic covalent bond is more than the gel point, better structural stability can be ensured, and the hydrogen bond crosslinking plays a role in providing supramolecular dynamics and supplementing reinforcement and has a positive effect on improving the toughness of the material. The cross-linked network contains at least two dynamic covalent bonds, and abundant dynamic covalency can be obtained.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is below the gel point and the degree of crosslinking for hydrogen bonding crosslinking is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds. In the embodiment, hydrogen bond crosslinking provides a good balanced structure for the polymer, and is convenient for obtaining rapid self-repairing performance and super-toughness performance. The crosslinking degree of dynamic covalent crosslinking is low, so that the crosslinking degree can be conveniently regulated and controlled according to use requirements, and the requirements of specific application scenes are met.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is below the gel point, the degree of crosslinking for hydrogen bonding crosslinking is below the gel point, but the sum of the degrees of crosslinking is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds. In the embodiment, the crosslinking degree of hydrogen bond crosslinking and dynamic covalent crosslinking is below the gel point, so that the structure can be conveniently regulated and controlled in the preparation process, and the influence on the acquisition of another crosslinking form due to overhigh crosslinking degree of one crosslinking structure is reduced. The two crosslinking forms provide dynamic reversible performance and structural balance together, and provide self-repairing performance cooperatively.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds. In the embodiment, the crosslinking degrees of dynamic covalent crosslinking and hydrogen bond crosslinking are both above the gel point, so that better mechanical property and dynamic reversible property can be obtained. Through reasonable structural design, a good shape memory function can be obtained. The cross-linked network contains at least two dynamic covalent bonds, and abundant dynamic covalency can be obtained.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network. In this embodiment, dynamic covalent crosslinking provides balanced structure, dynamic covalent and self-healing properties. The hydrogen bond-containing polymer dispersed in the cross-linked network can provide supramolecular dynamics and has a positive effect on improving the tear resistance of the material.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles. In this embodiment, dynamic covalent crosslinking provides balanced structure, dynamic covalent and self-healing properties. The supramolecular polymer particles are dispersed and compounded in the cross-linked network, and the filling enhancement and the dynamic supplement effects are provided.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is below or above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structure, dynamic reversible properties. The hydrogen bond groups in the hydrogen bond-containing polymer dispersed in the cross-linked network can interact with the hydrogen bond groups in the cross-linked network, so that more abundant supramolecular dynamics is obtained, and the toughness and tear resistance of the material can be greatly improved.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is below or above the gel point, and the crosslinked network comprises at least two dynamic covalent bonds; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structure, dynamic reversible properties. The supramolecular polymer particles are dispersed and compounded in the cross-linked network, and the filling enhancement and the dynamic supplement effects are provided.

The hybrid dynamic polymer contains at least two reversible free radical type dynamic covalent bonds, wherein the definition and the preferred range of the reversible free radical type dynamic covalent bonds are as described above and are not described in detail herein.

The hybrid dynamic polymer contains at least two dynamic covalent bonds, so that richer dynamic covalent properties can be obtained, and better self-repairing performance and reworkable performance can be conveniently provided. The dynamic covalent bond generates free radicals in the dynamic reversible transformation process under thermal activation or light activation, and can cause the change of color, fluorescence, oxidation resistance and conductivity, and the combination use of at least two dynamic covalent bonds can not only obtain the dynamic reversible performance, but also expand the application of the dynamic reversible covalent bond based on the special performance change. For example, based on the color change of two or more dynamic covalent bonds, organic thermosensitive materials with multiple thermochromatic changes, such as thermochromatic toy materials, imaging materials, anti-counterfeiting coating materials, biosensing materials, color-changing paper, color-changing ink, color-changing clothes, color-changing plastics and the like, can be prepared; for another example, based on the thermal activation temperature difference of different dynamic covalent bonds and the color and fluorescence difference of different radicals generated by thermal activation, the temperature measuring material/temperature sensing material with the temperature sensing function can be prepared, and the application range of the temperature measuring material/temperature sensing material is further widened. These clearly represent the novelty of the present invention.

The hybrid dynamic polymer contains at least one hydrogen bonding; wherein the hydrogen bonding group for forming the hydrogen bonding action exists in at least one of the skeleton hydrogen bonding group, the side group hydrogen bonding group, the chain end group hydrogen bonding group and other hydrogen bonding groups. The definitions and preferred ranges of the skeleton hydrogen bond group, the pendant hydrogen bond group, the chain-end hydrogen bond group and other hydrogen bond groups are as described above, and are not repeated herein.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which is a non-crosslinked structure and contains at least two reversible free radical type dynamic covalent bonds and at least one hydrogen bonding function.

The hybrid dynamic polymer is a non-crosslinked structure, and the non-crosslinked structure is selected from structures such as linear, cyclic, branched and two-dimensional and three-dimensional clusters below gel points, and a combination structure of the structures. The linear structure has the characteristics of simple structure, convenience in preparation, easiness in regulating and controlling the number and proportion of dynamic structures and the like; compared with a linear structure, the cyclic structure has smaller hydrodynamic volume, is less prone to entanglement and has special mechanical property under the condition of the same molecular weight, and can be converted into a linear or branched structure in the dynamic reversible conversion process, so that the toughness of the material is improved; the branched structure has rich branched chain structures, is easy to graft and modify, is convenient to introduce functional polymer chains or functional groups, and each branched chain is easy to intertwine with each other, thereby being beneficial to improving the elasticity of the material; and the structures such as two-dimensional and three-dimensional clusters below the gel point can play the functions of filling and local enhancement. The hybrid dynamic polymer with the non-crosslinking structure is preferably a linear structure and a branched structure.

In a preferred embodiment of the invention, the hybrid dynamic polymer is a linear structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding. The linear structure is simple, the preparation is more convenient, and the proportion and the number of dynamic covalent bonds and hydrogen bond groups in the polymer can be conveniently regulated and controlled.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a cyclic structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding. The ring structure is various in types and rich in structure. Compared with a linear structure, the cyclic structure has smaller hydrodynamic volume, is less prone to entanglement and has special mechanical properties under the condition of the same molecular weight, and can be converted into a linear or branched structure in the dynamic reversible conversion process.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a branched structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding. The branched structure is relatively regular, and in the process of dynamic reversible transformation, the branched structure can be transformed into a cross-linked structure through exchange and recombination of dynamic covalent bonds, so that better self-repairing performance is obtained, and even enhancement is realized.

In another preferred embodiment of the present invention, the hybrid dynamic polymer has a star-shaped structure and contains at least two dynamic covalent bonds and at least one hydrogen bond. By adjusting the composition and chain segment length of each branched chain in the star-shaped structure, the polymer structure is conveniently designed, and the service performance of the material is expanded.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a hyperbranched structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding function. The hyperbranched structure has high branching degree, is beneficial to reducing the viscosity of fluid and is convenient for preparation and molding processing. The hyperbranched structure is easy to obtain more active terminals, can be conveniently subjected to structural modification, improves the solubility of the hyperbranched structure or introduces specific functionality. The cross-linked structure is easy to obtain in the dynamic reversible transformation process of the dynamic covalent bond in the hyperbranched structure, so that better self-repairing performance is obtained, and even enhancement is realized.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a dendritic structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding. The dendritic structure is highly branched and regular in structure, has smaller hydrodynamic radius and more active tail ends, and is convenient to obtain special physicochemical properties and functionalize the surface of the polymer.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a comb structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding. The comb structure has abundant side chain structures, so that functional polymer chain segments are conveniently introduced, and good mechanical strength can be obtained by mutually intertwining the side chains.

In another preferred embodiment of the present invention, the hybrid dynamic polymer has a cluster structure and contains at least two dynamic covalent bonds and at least one hydrogen bonding function. The cluster structure is special in structure and can play the functions of filling and local enhancement.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which only contains a crosslinking network and contains a reversible free radical type dynamic covalent bond and at least one side group hydrogen bonding interaction;

The hybrid dynamic polymer contains at least one side group hydrogen bonding function; wherein the pendant hydrogen bonding interactions are formed by pendant hydrogen bonding groups. Wherein, the definition and the preferable range of the pendant hydrogen bonding group are as described in the foregoing, and are not repeated herein.

In a preferred embodiment of the invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is above the gel point and the degree of crosslinking of the hydrogen bond crosslinks is below the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by pendant hydrogen bond groups. In the embodiment, the dynamic covalent crosslinking provides structural stability and dynamic covalence, and the hydrogen bond crosslinking provides supermolecule dynamic property and supplementary reinforcement effect, and has positive effect on improving the toughness of the material.

In another preferred embodiment of the invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is below the gel point and the degree of crosslinking of the hydrogen bond crosslinks is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by pendant hydrogen bond groups. In the embodiment, hydrogen bond crosslinking provides a good balanced structure for the polymer, and is convenient for obtaining rapid self-repairing performance and super-toughness performance. The crosslinking degree of dynamic covalent crosslinking is low, so that the crosslinking degree can be conveniently regulated and controlled according to use requirements, and the requirements of specific application scenes are met.

In another preferred embodiment of the invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is below the gel point and the degree of crosslinking of the hydrogen bonding crosslinks is below the gel point, but the sum of the degrees of crosslinking of the two is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bonding crosslinks are formed by pendant hydrogen bonding groups. In the embodiment, the crosslinking degree of hydrogen bond crosslinking and dynamic covalent crosslinking is below the gel point, so that the structure can be conveniently regulated and controlled in the preparation process, and the influence on the acquisition of another crosslinking form due to overhigh crosslinking degree of one crosslinking structure is reduced. The two crosslinking forms provide dynamic reversible performance and structural balance together, and provide self-repairing performance cooperatively.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of the dynamic covalent crosslinks is above the gel point and the degree of crosslinking of the hydrogen bond crosslinks is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by pendant hydrogen bond groups. In the embodiment, the crosslinking degrees of dynamic covalent crosslinking and hydrogen bond crosslinking are both above the gel point, so that better mechanical property and dynamic reversible property can be obtained. Through reasonable structural design, a good shape memory function can be obtained.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bond crosslinks is below or above the gel point, said crosslinked network comprising one of said dynamic covalent bonds, said hydrogen bond crosslinks being formed by pendant hydrogen bond groups; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structure, dynamic reversible properties. The hydrogen bond groups in the hydrogen bond-containing polymer dispersed in the cross-linked network can interact with the hydrogen bond groups in the cross-linked network, so that more abundant supramolecular dynamics is obtained, and the toughness and tear resistance of the material can be greatly improved.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bond crosslinks is below or above the gel point, said crosslinked network comprising one of said dynamic covalent bonds, said hydrogen bond crosslinks being formed by pendant hydrogen bond groups; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structure, dynamic reversible properties. The supramolecular polymer particles are dispersed and compounded in the cross-linked network, and the filling enhancement and the dynamic supplement effects are provided.

The dynamic covalent bond contained in the hybrid dynamic polymer provides dynamic covalence for the polymer, and the dynamic covalent cross-linking formed by the dynamic covalent bond can provide good balanced structure and mechanical strength for the polymer. The hybrid dynamic polymer contains at least one pendant hydrogen bonding interaction. The hydrogen bond effect has the characteristics of higher degree of freedom, quicker response, stronger dynamic property, easier regulation and control of hydrogen bond density and the like, a quick self-repairing process is easily obtained, and the tear resistance can be better improved; and the number of teeth of the side group hydrogen bond, the density of the side group hydrogen bond and the linkage of the side group hydrogen bond group and the polymer chain are adjusted, so that the supermolecule action strength and the supermolecule dynamic property can be greatly regulated, and good structural stability and the supermolecule dynamic property can be obtained by reasonably designing and selecting the proper side group hydrogen bond group. The combination of the dynamic structure can provide good dynamic reversible performance for the polymer, and therefore self-repairing performance, reworkability, recyclable performance and the like can be obtained.

It should be noted that the hydrogen bonding group of the pendant group of the hybrid dynamic polymer is independent of the dynamic covalent bond, which means that the hydrogen bonding group of the pendant group and the dynamic covalent bond do not exist in the same dynamic polymer pendant group at the same time, that is, the hydrogen bonding group of the pendant group and the dynamic covalent bond do not exist in the same pendant group at the same time. Otherwise, the orthogonal reversible property of dynamic covalency and supramolecular dynamics cannot be exerted.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which only contains a crosslinking network, and contains a reversible free radical type dynamic covalent bond and at least contains side group hydrogen bonding and skeleton hydrogen bonding at the same time.

The hybrid dynamic polymer contains a reversible free radical type dynamic covalent bond, wherein the definition and the preferred range of the reversible free radical type dynamic covalent bond are as described in the foregoing, and are not described in detail herein.

The hybrid dynamic polymer at least contains a side group hydrogen bond group and a skeleton hydrogen bond group. The definitions and preferred ranges of the pendant hydrogen bonding groups and the skeleton hydrogen bonding groups are as described above, and are not repeated herein.

In a preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one cross-linked network, wherein the degree of cross-linking of dynamic covalent cross-linking is above the gel point and the degree of cross-linking of hydrogen bond cross-linking is below the gel point, the cross-linked network comprises one of the dynamic covalent bonds, and the hydrogen bond cross-linking is formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups. In the embodiment, the dynamic covalent crosslinking provides structural stability and dynamic covalence, and the hydrogen bond crosslinking provides supermolecule dynamic property and supplementary reinforcement effect, and has positive effect on improving the toughness of the material.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is below the gel point and the degree of crosslinking of hydrogen bond crosslinks is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups. In the embodiment, hydrogen bond crosslinking provides a good balanced structure for the polymer, and is convenient for obtaining rapid self-repairing performance and super-toughness performance. The crosslinking degree of dynamic covalent crosslinking is low, so that the crosslinking degree can be conveniently regulated and controlled according to use requirements, and the requirements of specific application scenes are met.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one cross-linked network, wherein the degree of cross-linking of dynamic covalent cross-linking is below the gel point, the degree of cross-linking of hydrogen bond cross-linking is below the gel point, but the sum of the degrees of cross-linking is above the gel point, and the cross-linked network comprises one of the dynamic covalent bonds, and the hydrogen bond cross-linking is formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups. In the embodiment, the crosslinking degree of hydrogen bond crosslinking and dynamic covalent crosslinking is below the gel point, so that the structure can be conveniently regulated and controlled in the preparation process, and the influence on the acquisition of another crosslinking form due to overhigh crosslinking degree of one crosslinking structure is reduced. The two crosslinking forms provide dynamic reversible performance and structural balance together, and provide self-repairing performance cooperatively.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bond crosslinks is above the gel point, and the crosslinked network comprises one of the dynamic covalent bonds, and the hydrogen bond crosslinks are formed by participation of pendant hydrogen bond groups and backbone hydrogen bond groups. In the embodiment, the crosslinking degrees of dynamic covalent crosslinking and hydrogen bond crosslinking are both above the gel point, so that better mechanical property and dynamic reversible property can be obtained. Through reasonable structural design, a good shape memory function can be obtained.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one cross-linked network, wherein the degree of cross-linking of dynamic covalent cross-linking is above the gel point, and the degree of cross-linking of hydrogen bond cross-linking is below or above the gel point, the cross-linked network comprises one of the dynamic covalent bonds, and the hydrogen bond cross-linking is formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structure, dynamic reversible properties. The hydrogen bond groups in the hydrogen bond-containing polymer dispersed in the cross-linked network can interact with the hydrogen bond groups in the cross-linked network, so that more abundant supramolecular dynamics is obtained, and the toughness and tear resistance of the material can be greatly improved.

In another preferred embodiment of the present invention, the hybrid dynamic polymer comprises only one cross-linked network, wherein the degree of cross-linking of dynamic covalent cross-linking is above the gel point, and the degree of cross-linking of hydrogen bond cross-linking is below or above the gel point, the cross-linked network comprises one of the dynamic covalent bonds, and the hydrogen bond cross-linking is formed by the participation of pendant hydrogen bond groups and backbone hydrogen bond groups; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structure, dynamic reversible properties. The supramolecular polymer particles are dispersed and compounded in the cross-linked network, and the filling enhancement and the dynamic supplement effects are provided.

The dynamic covalent bond contained in the hybrid dynamic polymer provides dynamic covalence for the polymer, and the dynamic covalent cross-linking formed by the dynamic covalent bond can provide good balanced structure and mechanical strength for the polymer. The hybrid dynamic polymer at least contains side group hydrogen bond function and skeleton hydrogen bond function. The side group hydrogen bond effect has the characteristics of higher degree of freedom, quicker response, stronger dynamic property, easier regulation and control of hydrogen bond density and the like, a quick self-repairing process is easily obtained, and the tear resistance can be better improved; the mechanical strength and the structural stability are easily improved due to the skeleton hydrogen bond action, and the high-strength hybrid dynamic polymer material is conveniently obtained; at least one side group hydrogen bond group and at least one skeleton hydrogen bond group are simultaneously introduced into the polymer, so that the supramolecular action strength and the supramolecular dynamic property are balanced, and the excellent self-repairing performance and the material toughness performance are obtained. The combination of the dynamic structure can provide good dynamic reversible performance for the polymer, and therefore good self-repairing performance, reworkability, recyclable performance and the like are obtained.

The hybrid dynamic polymer also optionally contains hydrogen bonding action formed by chain end group hydrogen bonding groups and other hydrogen bonding groups. The chain end hydrogen bonding group is in contact with other hydrogen bonding groups, which may be any suitable hydrogen bonding structure.

further preferably at least one of the following structural components:

wherein Y is substituted with

wherein the content of the first and second substances,

indicating attachment to a polymer chain.

By way of example, the following pendant hydrogen bonding groups may be mentioned, but the invention is not limited thereto:

In a preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is above the gel point and the degree of crosslinking for hydrogen bonding crosslinking is below the gel point, said crosslinked network comprising one said dynamic covalent bond and at least one said pendant hydrogen bonding. In the embodiment, the dynamic covalent crosslinking provides structural stability and dynamic covalence, and the hydrogen bond crosslinking provides supermolecule dynamic property and supplementary reinforcement effect, and has positive effect on improving the toughness of the material.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking for dynamic covalent crosslinking is below the gel point and the degree of crosslinking for hydrogen bonding crosslinking is above the gel point, said crosslinked network comprising one said dynamic covalent bond and at least one said pendant hydrogen bonding interaction. In the embodiment, hydrogen bond crosslinking provides a good balanced structure for the polymer, and is convenient for obtaining rapid self-repairing performance and super-toughness performance. The crosslinking degree of dynamic covalent crosslinking is low, so that the crosslinking degree can be conveniently regulated and controlled according to use requirements, and the requirements of specific application scenes are met.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is below the gel point and the degree of crosslinking of hydrogen bonding crosslinks is below the gel point, but the sum of the degrees of crosslinking of both crosslinks is above the gel point, and said crosslinked network comprises one said dynamic covalent bond and at least one said pendant hydrogen bonding. In the embodiment, the crosslinking degree of hydrogen bond crosslinking and dynamic covalent crosslinking is below the gel point, so that the structure can be conveniently regulated and controlled in the preparation process, and the influence on the acquisition of another crosslinking form due to overhigh crosslinking degree of one crosslinking structure is reduced. The two crosslinking forms provide dynamic reversible performance and structural balance together, and provide self-repairing performance cooperatively.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bonding crosslinks is above the gel point, and said crosslinked network comprises one of said dynamic covalent bonds and at least one of said pendant hydrogen bonding interactions. In the embodiment, the crosslinking degrees of dynamic covalent crosslinking and hydrogen bond crosslinking are both above the gel point, so that better mechanical property and dynamic reversible property can be obtained. Through reasonable structural design, a good shape memory function can be obtained.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bonding crosslinks is below or above the gel point, said crosslinked network comprising one said dynamic covalent bond and at least one said pendant hydrogen bonding interaction; the polymers having a degree of crosslinking below the gel point, crosslinked by hydrogen bonds, are dispersed in the crosslinked network. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structure, dynamic reversible properties. The hydrogen bond groups in the hydrogen bond-containing polymer dispersed in the cross-linked network can interact with the hydrogen bond groups in the cross-linked network, so that more abundant supramolecular dynamics is obtained, and the toughness and tear resistance of the material can be greatly improved.

In another preferred embodiment of the present invention, said hybrid dynamic polymer comprises only one crosslinked network, wherein the degree of crosslinking of dynamic covalent crosslinks is above the gel point and the degree of crosslinking of hydrogen bonding crosslinks is below or above the gel point, said crosslinked network comprising one said dynamic covalent bond and at least one said pendant hydrogen bonding interaction; polymers having a degree of crosslinking above the gel point by hydrogen bonding are dispersed in the crosslinked network in the form of particles. In this embodiment, dynamic covalent and hydrogen bonding crosslinking together provide balanced structure, dynamic reversible properties. The supramolecular polymer particles are dispersed and compounded in the cross-linked network, and the filling enhancement and the dynamic supplement effects are provided.

It should be noted that the pendant hydrogen bond group contained in the hybrid dynamic polymer is independent of the dynamic covalent bond, which means that the dynamic covalent bond and the pendant hydrogen bond group do not exist in the same dynamic polymer pendant group at the same time, that is, the dynamic covalent bond and the pendant hydrogen bond do not exist in the same pendant group at the same time. Otherwise, the orthogonal reversible property of dynamic covalency and supramolecular dynamics cannot be exerted.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which is a non-crosslinked structure and contains one reversible free radical type dynamic covalent bond and at least one hydrogen bonding function; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

The definition and the preferred range of the reversible free radical type dynamic covalent bond contained in the hybrid dynamic polymer are as described above, and are not described in detail herein.

The definition and the preferred range of the chain-end hydrogen bonding groups contained in the hybrid dynamic polymer are as described above and will not be described in detail herein.

The hydrogen bonding effect in the hybrid dynamic polymer is formed by chain end base hydrogen bonding groups, the hybrid dynamic polymer has the characteristics of higher degree of freedom, quicker response, stronger dynamic property, easier regulation and control of hydrogen bonding density and the like, and the supermolecule polymerization is conveniently carried out based on the position characteristics of the hydrogen bonding groups, and the dynamic covalent bonds and the hydrogen bonding effect are introduced into the polymer, so that the orthogonal and synergistic dynamic reversibility can be fully exerted, and good self-repairing performance and super-stretching toughness are provided for the polymer together.

The hybrid dynamic polymer is a non-crosslinked structure, and the non-crosslinked structure is selected from structures such as linear, cyclic, branched and two-dimensional and three-dimensional clusters below gel points, and a combination structure of the structures. The linear structure has the characteristics of simple structure, convenience in preparation, easiness in regulating and controlling the number and proportion of dynamic structures and the like; compared with a linear structure, the cyclic structure has smaller hydrodynamic volume, is less prone to entanglement and has special mechanical property under the condition of the same molecular weight, and can be converted into a linear or branched structure in the dynamic reversible conversion process, so that the toughness of the material is improved; the branched structure has rich branched chain structures, is easy to graft and modify, is convenient to introduce functional polymer chains or functional groups, and each branched chain is easy to intertwine with each other, thereby being beneficial to improving the elasticity of the material; and the structures such as two-dimensional and three-dimensional clusters below the gel point can play the functions of filling and local enhancement. The hybrid dynamic polymer having a non-crosslinked structure is preferably a linear structure or a branched structure, and more preferably a linear structure.

In a preferred embodiment of the present invention, the hybrid dynamic polymer is linear in structure and contains a reversible free radical type dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups. The linear structure is simple, the preparation is more convenient, and the proportion and the number of dynamic covalent bonds in the polymer can be conveniently regulated and controlled.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a branched structure and contains a reversible free radical type dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups. The branched structure is relatively regular, and in the process of dynamic reversible transformation, the branched structure can be transformed into a cross-linked structure through exchange and recombination of dynamic covalent bonds, so that better self-repairing performance is obtained, and even enhancement is realized.

In another preferred embodiment of the invention, the hybrid dynamic polymer has a star-shaped structure and contains a reversible free radical dynamic covalent bond and at least one hydrogen bonding function; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups. By adjusting the composition and chain segment length of each branched chain in the star-shaped structure, the polymer structure is conveniently designed, and the service performance of the material is expanded.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a hyperbranched structure and contains a reversible free radical type dynamic covalent bond and at least one hydrogen bonding interaction; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups. The hyperbranched structure has high branching degree, is beneficial to reducing the viscosity of fluid and is convenient for preparation and molding processing. The hyperbranched structure is easy to obtain more active terminals, can be conveniently subjected to structural modification, improves the solubility of the hyperbranched structure or introduces specific functionality. The cross-linked structure is easy to obtain in the dynamic reversible transformation process of the dynamic covalent bond in the hyperbranched structure, so that better self-repairing performance is obtained, and even enhancement is realized.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a dendritic structure and contains a reversible free radical type dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups. The dendritic structure is highly branched and regular in structure, has smaller hydrodynamic radius and more active tail ends, and is convenient to obtain special physicochemical properties and functionalize the surface of the polymer.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a comb structure and contains a reversible free radical dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups. The comb structure has abundant side chain structures, so that functional polymer chain segments are conveniently introduced, and good mechanical strength can be obtained by mutually intertwining the side chains.

The invention also relates to a hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, which is a non-crosslinked structure and contains one reversible free radical type dynamic covalent bond and at least one hydrogen bonding function;

wherein the reversible free radical type dynamic covalent bond is selected from one of the reversible free radical type dynamic covalent bonds described in the structural general formula (1), (2), (3), (4), (5), (8), (9), (10), (11), (14), (15), (16), (17), (18), (21), (22), (23), (24), (25), (26), (27) and (28) and the preferable structure of the structural general formula;

The hybrid dynamic polymer is a non-crosslinked structure, wherein the non-crosslinked structure is selected from structures such as linear, cyclic, branched and two-dimensional and three-dimensional clusters below gel points, and a combination structure of the structures. The linear structure has the characteristics of simple structure, convenience in preparation, easiness in regulating and controlling the number and proportion of dynamic structures and the like; compared with a linear structure, the cyclic structure has smaller hydrodynamic volume, is less prone to entanglement and has special mechanical property under the condition of the same molecular weight, and can be converted into a linear or branched structure in the dynamic reversible conversion process, so that the toughness of the material is improved; the branched structure has rich branched chain structures, is easy to graft and modify, is convenient to introduce functional polymer chains or functional groups, and each branched chain is easy to intertwine with each other, thereby being beneficial to improving the elasticity of the material; and the structures such as two-dimensional and three-dimensional clusters below the gel point can play the functions of filling and local enhancement. The hybrid dynamic polymer having a non-crosslinked structure is preferably a linear structure or a branched structure, and more preferably a linear structure.

In a preferred embodiment of the invention, the hybrid dynamic polymer is a linear structure and contains one of the dynamic covalent bonds and at least one hydrogen bonding. The linear structure is simple, the preparation is more convenient, and the proportion and the number of dynamic covalent bonds and hydrogen bond groups in the polymer can be conveniently regulated and controlled.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a cyclic structure and contains one of the dynamic covalent bonds and at least one hydrogen bonding. The ring structure is various in types and rich in structure. Compared with a linear structure, the cyclic structure has smaller hydrodynamic volume, is less prone to entanglement and has special mechanical properties under the condition of the same molecular weight, and can be converted into a linear or branched structure in the dynamic reversible conversion process.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a branched structure and contains one of the dynamic covalent bonds and at least one hydrogen bonding. The branched structure is relatively regular, and in the process of dynamic reversible transformation, the branched structure can be transformed into a cross-linked structure through exchange and recombination of dynamic covalent bonds, so that better self-repairing performance is obtained, and even enhancement is realized.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a star-shaped structure and contains one of the dynamic covalent bonds and at least one hydrogen bond. By adjusting the composition and chain segment length of each branched chain in the star-shaped structure, the polymer structure is conveniently designed, and the service performance of the material is expanded.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a hyperbranched structure and comprises one of the dynamic covalent bonds and at least one hydrogen bonding. The hyperbranched structure has high branching degree, is beneficial to reducing the viscosity of fluid and is convenient for preparation and molding processing. The hyperbranched structure is easy to obtain more active terminals, can be conveniently subjected to structural modification, improves the solubility of the hyperbranched structure or introduces specific functionality. The cross-linked structure is easy to obtain in the dynamic reversible transformation process of the dynamic covalent bond in the hyperbranched structure, so that better self-repairing performance is obtained, and even enhancement is realized.

In another preferred embodiment of the present invention, said hybrid dynamic polymer is a dendritic structure and contains one of said dynamic covalent bonds and at least one hydrogen bonding. The dendritic structure is highly branched and regular in structure, has smaller hydrodynamic radius and more active tail ends, and is convenient to obtain special physicochemical properties and functionalize the surface of the polymer.

In another preferred embodiment of the present invention, the hybrid dynamic polymer is a comb structure and contains one of the dynamic covalent bonds and at least one hydrogen bonding. The comb structure has abundant side chain structures, so that functional polymer chain segments are conveniently introduced, and good mechanical strength can be obtained by mutually intertwining the side chains.

In another preferred embodiment of the present invention, said hybrid dynamic polymer is a cluster structure and contains one of said dynamic covalent bonds and at least one hydrogen bonding. The cluster structure is special in structure and can play the functions of filling and local enhancement.

In the present invention, besides the dynamic structure, i.e. the structure of the dynamic covalent bond and the hydrogen bond group, the connecting component between the dynamic structures, i.e. the connecting component between the dynamic covalent bond and/or the hydrogen bond group, also has an influence on the dynamic performance and other comprehensive properties of the hybrid dynamic polymer.

In embodiments of the invention, the component for linking the dynamic covalent bonds and/or hydrogen bonding groups may be a small molecule linker and/or a polymer segment. Wherein said small molecule linking group refers to a small molecule hydrocarbon group having a molecular weight of not more than 1000Da, generally containing 1 to 71 carbon atoms, which may or may not contain a heteroatom group. In general terms, the small molecule hydrocarbyl group may be selected from any of the following groups, any unsaturated form, any substituted form, any hybridized form, and combinations thereof: c_1-71Alkyl, ring C_3-71Alkyl, phenyl, benzyl, aryl; wherein, the small molecule alkyl can also be selected from liquid crystal chain segment. The polymer chain segment includes, but is not limited to, a polymer chain segment whose main chain is a carbon chain structure, a carbon-hetero chain structure, a carbon element chain structure, an element-hetero chain structure, or a carbon-hetero element chain structure. The carbon chain structure is a structure of which the main chain skeleton only contains carbon atoms; the carbon heterochain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms and any one or more heteroatoms, wherein the heteroatoms comprise but are not limited to sulfur, oxygen and nitrogen; the carbon element chain structure is a structure that a main chain skeleton simultaneously contains carbon atoms and any one or more element atoms, wherein the element atoms comprise but are not limited to silicon, boron and aluminum; the element chain structure is a structure that a main chain skeleton only contains element atoms; the elementThe structure of the vegetable chain is a structure of a main chain skeleton which only contains at least one heteroatom and at least one element atom; the carbon-heteroatom chain structure is a structure of which a main chain skeleton simultaneously contains carbon atoms, heteroatoms and element atoms.

In one embodiment of the present invention, the polymer segment is preferably a polymer segment whose main chain has a carbon chain structure or a carbon hetero chain structure, because of its abundant structure and excellent performance. By way of example, preferred carbon-and hetero-carbon-chain polymer segments include, but are not limited to, homopolymers, copolymers, modifications, derivatives, and the like of, for example, acrylic polymers, saturated olefinic polymers, unsaturated olefinic polymers, polystyrenic polymers, halogen-containing olefinic polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, poly (2-oxazoline) polymers, polyether polymers, polyester polymers, biopolyester polymers, polycarbonate polymers, polyurethane polymers, polyurea polymers, polyamide polymers, polyamine polymers, liquid crystal polymers, epoxy polymers, polythioether polymers, and the like.

In another embodiment of the present invention, the polymer segment is preferably an elemental heterochain structure, such as various types of polyorganosiloxane polymers, which generally have good corrosion resistance, oil and water resistance, high and low temperature resistance, and good tensile toughness.

In another embodiment of the present invention, it is preferable that the glass transition temperature of the polymer chain segment is not higher than 25 ℃, which is expressed as flexibility at room temperature, so that the processing and preparation of subsequent products are facilitated at room temperature, flexible and viscous products are facilitated to be obtained, and the hardness of the material matrix is also facilitated to be adjusted by increasing the crosslinking density or using other additives, so that the material matrix is used as a matrix, which is beneficial to expressing the non-dynamic covalent property, and obtaining a good energy absorption effect. In another embodiment of the present invention, it is preferable that the glass transition temperature of the polymer segment is higher than 25 ℃ but lower than 40 ℃ to facilitate the introduction of temperature sensitivity, moderate elasticity, and the like. In another embodiment of the present invention, the glass transition temperature of the polymer segment is preferably not lower than 40 ℃, which is advantageous for introducing the characteristics of shape memory, high-temperature dimensional stability, low-temperature and normal-temperature hardness, and the like. In another embodiment of the present invention, it is preferable that the glass transition temperature of the polymer segment is not lower than 100 ℃.

In embodiments of the present invention, the small molecule and/or polymer segment used to link the dynamic covalent bonds and/or hydrogen bonding groups may have any suitable topology, including but not limited to linear structures, branched structures (including but not limited to star, H, dendritic, comb, hyperbranched), cyclic structures (including but not limited to single ring, multiple ring, bridge, grommet, wheel ring), two-dimensional/three-dimensional cluster structures, and combinations of two or any of them; among them, a linear structure which facilitates synthesis and control of the structure, a branched structure which is abundant in the structure, and a two-dimensional/three-dimensional cluster structure which can be locally reinforced are preferable, and a linear structure and a branched structure are more preferable. In the present invention, it is not even excluded to use the crosslinked polymer particles for further polymerization/crosslinking etc. reactions and linkages.

The various polymers and chain segments thereof selected in the invention can be directly selected from commercial raw materials and can also be polymerized by a proper polymerization method.

The term "molecular weight" as used herein refers to the relative molecular mass of a substance, and for small molecule compounds, small molecule groups, and certain macromolecular compounds and macromolecular groups having a fixed structure, the molecular weight is generally monodispersed, i.e., has a fixed molecular weight; and for oligomers, polymers, oligomer residues, polymer residues, and the like having a polydisperse molecular weight, the molecular weight generally refers to the average molecular weight. Wherein, the small molecular compound and the small molecular group in the invention refer to a compound or a group with the molecular weight not more than 1000 Da; the macromolecular compound and the macromolecular group refer to compounds or groups with molecular weight more than 1000 Da.

In the present invention, when the polymer is prepared, according to the actual requirements of the preparation process, the forming process, the use performance requirements and the like, the additives, the fillers and the swelling agents can be selectively added or used as the formulation components of the polymer, which can improve the material processing performance, improve the product quality and yield, reduce the product cost or endow the product with certain specific application performance, but the additives or the used substances are not necessary.

Wherein, the auxiliary agent can include but is not limited to one or a combination of several of the following, such as synthesis auxiliary agents, including catalysts and initiators; stabilizing aids including antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants; the auxiliary agent for improving the mechanical property comprises a toughening agent and a coupling agent; the auxiliary agents for improving the processing performance comprise a solvent, a lubricant, a release agent, a plasticizer, a thickening agent, a thixotropic agent and a flatting agent; the color light changing auxiliary agent comprises a coloring agent, a fluorescent whitening agent and a delustering agent; other auxiliary agents include antistatic agents, sterilization and mildew proofing agents, foaming agents, foam stabilizers, nucleating agents, rheological agents and the like.

In the present invention, the filler includes, but is not limited to, inorganic non-metallic fillers, organic fillers, and 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, silica, graphite, carbon black, graphene oxide, fullerene, carbon nano tube, black phosphorus nano sheet, molybdenum disulfide, diatomite, red mud, wollastonite, silicon-aluminum carbon black, aluminum hydroxide, magnesium hydroxide, nano Fe₃O₄Particulate, nano gamma-Fe₂O₃Particulate, nano MgFe₂O₄Particulate, nano-MnFe₂O₄Granular, nano CoFe₂O₄Particles, quantum dots (including but not limited to silicon quantum dots, germanium quantum dots, cadmium sulfide quantum dots, cadmium selenide quantum dots, cadmium telluride quantum dots, zinc selenide quantum dots, lead sulfide quantum dots, lead selenide quantum dots, indium phosphide quantum dots, and indium arsenide quantum dots), upconversion crystal particles (including but not limited to NaYF)₄:Er、CaF₂:Er、Gd₂(MoO₄)₃:Er、Y₂O₃:Er、Gd₂O₂S:Er、BaY₂F₈:Er、LiNbO₃:Er,Yb,Ln、Gd₂O₂:Er,Yb、Y₃Al₅O₁₂:Er,Yb、TiO₂:Er,Yb、YF₃:Er,Yb、Lu₂O₃:Yb,Tm、NaYF₄:Er,Yb、LaCl₃:Pr、NaGdF₄:Yb,Tm@NaGdF₄Core-shell nanostructure of Ln, NaYF₄:Yb,Tm、Y2BaZnO₅:Yb,Ho、NaYF₄:Yb,Er@NaYF₄Core-shell nanostructures of Yb, Tm, NaYF₄:Yb,Tm@NaGdF₄Core-shell nanostructure of Yb), oil shale powder, expanded perlite powder, aluminum nitride powder, boron nitride powder, vermiculite, iron mud, white mud, alkali mud, boron mud, glass beads, resin beads, glass powder, glass fibers, carbon fibers, quartz fibers, carbon-core boron fibers, titanium diboride fibers, calcium titanate fibers, silicon carbide fibers, ceramic fibers, whiskers and the like. In one embodiment of the present invention, inorganic non-metallic fillers having electrical conductivity, including but not limited to graphite, carbon black, graphene, carbon nanotubes, carbon fibers, are preferred, which facilitate obtaining a composite material having electrical conductivity and/or electrothermal function. In another embodiment of the present invention, the non-metallic filler having the function of generating heat under the action of infrared and/or near-infrared light is preferable, and includes but is not limited to graphene, graphene oxide, carbon nanotube, black phosphorus nanosheet, nano-Fe₃O₄The composite material which can be heated by infrared and/or near infrared light is conveniently obtained. In another embodiment of the present invention, inorganic non-metallic fillers with thermal conductivity, including but not limited to graphite, graphene, carbon nanotubes, aluminum nitride, boron nitride, silicon carbide, are preferred, which facilitate obtaining composite materials with thermal conductivity.

The metal filler includes metal compounds, including but not limited to any one or any several of the following: metal powders, fibers including but not limited to powders, fibers of copper, silver, nickel, iron, gold, and the like, and alloys thereof; nano metal particles including but not limited to nano gold particles, nano silver particlesNano palladium particle, nano iron particle, nano cobalt particle, nano nickel particle, 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 be heated electromagnetically and/or near-infrared, including but not limited to nanogold, nanosilver, and nanopalladium, are preferred for remote heating. In another embodiment of the present invention, liquid metal fillers are preferred, which can enhance the thermal and electrical conductivity of the flexible substrate while maintaining the flexibility and ductility of the substrate.

The organic filler comprises any one or more of ① natural organic filler, ② synthetic resin filler, ③ synthetic rubber filler, ④ synthetic fiber filler, ⑤ foamable polymer particles, ⑥ conjugated polymer and ⑦ organic functional dye/pigment, and the organic filler with the properties of ultraviolet absorption, fluorescence, luminescence, photo-thermal property and the like has important significance to the invention and can fully utilize the properties to obtain multifunctionality.

The organic metal compound filler contains a metal organic complex component, wherein a metal atom is directly connected with a carbon atom to form a bond (including a coordination bond, a sigma bond and the like), and the metal organic complex component can be a small molecule or a large molecule and can be in an amorphous or crystal structure. Metal organic compounds tend to have excellent properties including uv absorption, fluorescence, luminescence, magnetism, catalysis, photo-thermal, electromagnetic heat, and the like.

Wherein, the type of the 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 microspheresBeads, organometallic compounds, organic materials with photothermal 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.

Wherein, the swelling agent can include but is not limited to water, organic solvent, ionic liquid, oligomer and plasticizer. The oligomers can also be regarded as plasticizers.

Wherein the ionic liquid in the swelling agent is generally composed of an organic cation and an inorganic anion, and the cation is selected from, by way of example, but not limited to, alkyl quaternary ammonium ions, alkyl quaternary phosphine ions, 1, 3-dialkyl-substituted imidazolium ions, N-alkyl-substituted pyridinium ions, and the like; the anion is selected from the group including but not limited to halogen, tetrafluoroborate, hexafluorophosphate, and also CF₃SO₃ ^-、(CF3SO₂)₂N^-、C₃F₇COO^-、C₄F₉SO₃ ^-、CF₃COO^-、(CF₃SO₂)₃C^-、(C₂F₅SO₂)₃C^-、(C₂F₅SO₂)₂N^-、SbF₆ ^-、AsF₆ ^-And the like. In the ionic liquid used in the present invention, the cation is preferably an imidazolium cation, and the anion is preferably a hexafluorophosphate ion or a tetrafluoroborate ion.

In embodiments of the invention, the hybrid dynamic polymer may or may not have one or more glass transition temperatures. The hybrid dynamic polymer has at least one glass transition temperature lower than 0 ℃, or between 0 and 25 ℃, or between 25 and 100 ℃, or higher than 100 ℃; wherein, the hybrid dynamic polymer with the glass transition temperature lower than 0 ℃ has better low-temperature service performance and is convenient to be used as a binder, an elastomer, gel and the like; the hybrid dynamic polymer with the glass transition temperature of 0-25 ℃ can be used at normal temperature and can be conveniently used as an elastomer, gel, foam and a common solid; hybrid dynamic polymers with glass transition temperatures between 25-100 ℃ facilitate the achievement of common solids, foams and gels above room temperature; the hybrid 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 bearing material. The hybrid dynamic polymer with the glass transition temperature lower than 25 ℃ can show excellent dynamic property, self-repairability and recyclability; for the hybrid dynamic polymer with the glass transition temperature higher than 25 ℃, the hybrid dynamic polymer can show good shape memory capacity and bearing capacity; in addition, the existence of hydrogen bond action can further regulate and control the glass transition temperature of the hybrid dynamic polymer and supplement the dynamic property, the crosslinking degree and the mechanical strength of the hybrid dynamic polymer. For the hybrid dynamic polymers of the present invention, it is preferred that at least one glass transition temperature is not greater than 50 deg.C, more preferably at least one glass transition temperature is not greater than 25 deg.C, and most preferably no glass transition temperature is greater than 25 deg.C. Systems that do not have a glass transition temperature above 25 c are particularly suitable for use as self-healing materials due to their good flexibility and flowability/creep at the temperatures of daily use. The glass transition temperature of the hybrid dynamic polymer can be measured at least by a glass transition temperature measurement method commonly used in the art, such as DSC and DMA.

In the embodiment of the invention, the hybrid dynamic polymer can be in the form of solution, emulsion, paste, gum, common solid, gel (including hydrogel, organogel, oligomer swelling gel, plasticizer swelling gel, ionic liquid swelling gel), elastomer, foam, and the like. The various polymers or their compositions have features and advantages. The solution and the emulsion have good fluidity, can be prepared into hybrid dynamic polymer solutions with different concentrations by utilizing reasonable solvents, and can be easily prepared into a functional coating material with self-repairing performance. Wherein, the paste is generally thick paste, can be coated and is convenient for preparing a thick film functional coating material. Among them, gums are generally concentrated liquids, viscous liquids, or low glass transition temperature polymers that can exhibit good moldability and fillability. Wherein the content of soluble low molecular weight components contained in common solid and foam materials is generally not higher than 10 wt%, and the content of low molecular weight components contained in gel is generally not lower than 50 wt%. 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. The gel is generally higher in softness and lower in solid content, and the swelling agent has the functions of conduction, conveying and the like and has outstanding advantages. 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 organogel, and has good elasticity and soft and comfortable characteristics. Materials of different morphologies may have suitable uses in different fields.

In an embodiment of the present invention, the 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, three methods, namely a mechanical foaming method, a physical foaming method and a chemical foaming method, are mainly adopted for foaming.

The mechanical foaming method is that during the preparation of dynamic polymer, large amount of air or other gas is introduced into emulsion, suspension or solution of polymer via strong stirring to form homogeneous foam, which is then physically or chemically changed to form foam. Air can be introduced and an emulsifier or surfactant can be added to shorten the molding cycle.

Wherein, the physical foaming method is to realize the foaming of the polymer by using the physical principle in the preparation process of the dynamic polymer, and the method comprises the following steps: (1) inert gas foaming, i.e. by pressing inert gas into molten polymer or pasty material under pressure, then raising the temperature under reduced pressure to expand the dissolved gas and foam; (2) evaporating, gasifying and foaming low-boiling-point liquid, namely pressing the low-boiling-point liquid into the polymer or dissolving the liquid into the polymer (particles) under certain pressure and temperature conditions, heating and softening the polymer, and evaporating and gasifying the liquid to foam; (3) dissolving out method, i.e. soaking liquid medium into polymer to dissolve out solid matter added in advance to make polymer have lots of pores and be foamed, for example, mixing soluble matter salt with polymer, etc. first, after forming into product, placing the product in water to make repeated treatment, dissolving out soluble matter to obtain open-cell foamed product; (4) the hollow microsphere method is that hollow microspheres are added into the material and then compounded to form closed cell foamed polymer; (5) a filling expandable particle method of mixing filling expandable particles and expanding the expandable particles during molding or mixing to actively foam the polymer 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 physical foaming method has the advantages of low toxicity in operation, low cost of foaming raw materials, no residue of foaming agent and the like. In addition, the preparation method can also adopt a freeze drying method.

The chemical foaming method is a method for foaming a dynamic polymer by generating gas along with a chemical reaction in a foaming process of the dynamic polymer, and includes, but is not limited to, the following two 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 the preparation process of the dynamic polymer, a person skilled in the art can select a proper foaming method and a proper foam material forming method according to the actual preparation situation and the target polymer performance to prepare the foam material.

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. In the open pore structure, the cells are communicated with each other or completely communicated with each other, gas or liquid can pass through the single dimension or the three dimensions, and the cell diameter is different from 0.01 to 3 mm. The closed cell structure has an independent cell structure, the inner cells are separated from each other by a wall membrane, most of the inner cells are not communicated with each other, and the cell diameters are different from 0.01 mm to 3 mm. The contained cells have a structure which is not communicated with each other, and the structure is a semi-open cell structure. For the foam structure formed with closed cells, it can be made into an open cell structure by mechanical pressing or chemical method, and the skilled person can select the foam structure according to actual needs.

In embodiments of the present invention, dynamic polymer foams are classified by their hardness into three categories, soft, rigid and semi-rigid: (1) a flexible foam having a modulus of elasticity of less than 70MPa at 23 ℃ and 50% relative humidity; (2) a rigid foam having an elastic modulus greater than 700MPa at 23 ℃ and 50% relative humidity; (3) semi-rigid (or semi-flexible) foams, foams between the two above categories, having a modulus of elasticity between 70MPa and 700 MPa.

In embodiments of the present invention, dynamic polymer foams can be further classified by their density into low-foaming, medium-foaming, and high-foaming. Low-foaming foams having a density of more than 0.4g/cm³The foaming multiplying power is less than 1.5; the medium-foamed foam material has a density of 0.1-0.4 g/cm³The foaming ratio is 1.5-9; and a high-foaming foam material having a density of less than 0.1g/cm³The expansion ratio is greater than 9.

Those skilled in the art can select suitable foaming method and forming method to prepare dynamic polymer foam product according to actual conditions and requirements.

In the invention, based on the dynamic reversibility of reversible free radical type dynamic covalent bond and hydrogen bond action, the hybrid dynamic polymer material with self-repairability, reworkability and recoverability can be prepared, so that the hybrid dynamic polymer material has wide application prospect, and particularly has remarkable application effect in the fields of functional coatings, buildings, medical treatment, chemical industry, household appliance manufacturing, automobile industry, bionics, energy sources, intelligent materials and the like.

For example, based on the dynamic covalence and the supermolecule dynamic property of the hybrid dynamic polymer, a polymer functional coating with a self-repairing function can be prepared, the service life of the coating can be prolonged by utilizing the self-repairing property of the polymer functional coating, and long-term protection of a substrate material is realized; the binder with self-repairing performance can be prepared to increase the reliability and the service life of microelectronic products, for example, the binder is used for bonding electrodes in batteries and capacitors and is applied to the preparation of energy storage device materials, when the electrodes are damaged, the damaged electrodes are repaired through the reversible transformation process of the dynamic structure of the binder, and the purpose of increasing the service life of the electrode materials is achieved; through reasonable selection of material components, especially reasonable selection of a hydrogen bond structure, the polymer material with the shape memory function can be prepared and used as a shape memory medical instrument with good convenience, comfortableness and recycling; the polymer plugging glue and the sealant material which have good plasticity and can be recycled can also be prepared, and the material with magic viscosity-elasticity conversion behavior can be obtained by utilizing the dynamic property of hydrogen bond groups and can be used as a toy material; the self-repairing function is introduced into the polymer material, so that the material can be automatically repaired after being damaged, for example, the self-repairing function is used as a self-repairing polymer sealing material, such as a dustproof plug/waterproof plug, a sealing ring and the like, and the self-repairing polymer sealing material is widely applied to the fields of electronic appliances, foods, medicines and the like, for example, the self-repairing polymer sealing material is used as a dustproof plug/waterproof plug at a charger interface, a data line interface and the like of a mobile phone, a tablet personal computer, a notebook, a camera and the like, and can play the common functions of dustproof and waterproof of a common dustproof plug/waterproof plug and the like, and can repair open pores and cracks generated in the long-term plugging and bending processes. As a self-repairing gel material, the material with a bionic repairing effect can be obtained, and the material has a wide application prospect in the field of biological medical treatment; by controlling the internal form of the hybrid dynamic polymer foam material and selecting a proper process, the foam plastic product with low density, high specific strength and uniform foam pore size distribution can be prepared, and can be applied to the fields of household appliances, automobile industry, buildings and the like, for example, the foam plastic product can be used as a light heat-insulating material, and when the foam material reaches the use period, the foam material can be recycled by virtue of the dynamic reversible property of the foam material, so that the environmental pollution and the regeneration and use of the formed material are reduced; according to reasonable control of a cross-linking structure including the cross-linking degree, a polymer film, a sheet, a bar, a plate, a profiled bar and the like with good mechanical properties and other comprehensive properties and also with good self-repairing performance can be prepared, when external or internal cracks generated in the use process of a polymer material are damaged, the polymer can simulate the organism damage healing process, and the purpose of repairing and inhibiting the material damage is achieved, so that the service life of the material is prolonged, and in addition, through the dynamic characteristics of the polymer material, a product can be obtained by carrying out secondary processing and forming in a proper processing mode, and the resource recycling is realized; based on colored free radicals generated in the dynamic reversible transformation process of the dynamic covalent bond under thermal activation, the thermochromic organic thermosensitive material can be prepared, such as thermochromic toy materials, imaging materials, anti-counterfeiting coating materials, biosensing materials, color-changing paper, color-changing ink, color-changing clothes, color-changing plastics and the like; based on the thermal activation temperature difference of different dynamic covalent bonds and the color and fluorescence difference of different free radicals generated by thermal activation, the temperature measuring material/temperature sensing material with the temperature sensing function can also be prepared. By adding the heat-conducting filler, the heat-conducting glue with heat-conducting and heat-radiating functions and the heat-conducting/heat-radiating patch can be prepared and applied to electronic products, such as heat conduction/heat radiation of electronic chip packaging, mobile phones, tablet computers, notebook computers, computer servers and the like.

The hybrid dynamic polymer materials of the present invention are further described below with reference to some 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

Taking azobisisobutyronitrile as an initiator and N- (2-amino-2-oxoethyl) acrylamide as a monomer, stirring and reacting for 24 hours at 70 ℃ under nitrogen atmosphere to obtain an acrylamide homo-copolymer (a), and drying and grinding the acrylamide homo-copolymer to obtain hydrogen bond crosslinked polymer particles. Taking 5 molar equivalent hydroxyl double-terminated polybutadiene (b), 2.5 molar equivalent compound (c) and 5 molar equivalent compound (d), placing the mixture in a reaction container, dissolving the mixture with a proper amount of tetrahydrofuran, adding 30 molar equivalent dicyclohexylcarbodiimide and 5 molar single-amount 4-dimethylaminopyridine, stirring the mixture at room temperature for reaction for 24 hours, adding 30 wt% of hydrogen bond cross-linking polymer particles, 0.8 wt% of nano-palladium, 0.5 wt% of carbon nano-tubes, 0.3 wt% of composite antibacterial agent KHFS-ZN and 0.3 wt% of dispersing agent N, uniformly mixing, pouring the product into a mold, naturally drying the product for 24 hours, and then drying the product in a vacuum oven at 60 ℃ for 6 hours to obtain the dynamic polymer elastomer. The tensile strength of the elastomer sample was 8.6MPa and the elongation at break was 345%. When the elastic body sample has cracks, the cracks can be repaired through direct heating, or local remote sensing repair of the cracks is performed through near infrared light irradiation based on the near infrared thermal effect of the elastic body. The dynamic polymer in the embodiment has lower glass transition temperature, shows good low temperature resistance and rebound resilience, and can be used as a self-repairable sealing material.

Example 2

Taking 3.5 molar equivalent hydroxyl-terminated four-arm polyethylene glycol (molecular weight is 5000) and 7 molar equivalent compound (a), placing the mixture in a reaction container, dissolving the mixture with a proper amount of tetrahydrofuran, then adding a proper amount of stannous octoate catalyst, and reacting the mixture at 80 ℃ for 6 hours to prepare the hydrogen bond crosslinked polyethylene glycol. Taking 10 molar equivalent polyoxypropylene diamine (b) (molecular weight is 2000), 5 molar equivalent compound (c), 20 molar equivalent 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 4 molar equivalent 4-dimethylaminopyridine, placing the mixture into a reaction vessel, dissolving the mixture with a proper amount of tetrahydrofuran, stirring the mixture at room temperature for 8 hours, adding 50 wt% of hydrogen bond crosslinked polyethylene glycol, 180 wt% of polyethylene glycol oligomer, 5 wt% of nano silver antibacterial solution and 5 wt% of liquid gallium, stirring and mixing the mixture uniformly, pouring the reaction solution into a cylindrical polytetrafluoroethylene mold, and drying the mixture in a vacuum oven at 80 ℃ for 2 hours to obtain the oligomer swelling gel. The tensile strength of the gel sample is 6.6MPa, the elongation at break is 1180%, after the gel is cut off, the gel can be repaired by heating, and the mechanical strength can be restored to more than 90%. The oligomer swelling gel in the embodiment also has good biocompatibility, skin-friendly property, bending resistance, thermal conductivity and shape memory function, and can be used as human tissues and organs with self-repairing performance, such as ligaments and skins, or as orthopedic rehabilitation bracket materials and orthopedic device materials with shape memory function.

Example 3

Placing a compound (a) with 5.5 molar equivalents and triethylamine with 20 molar equivalents into a reaction container, dissolving the compound (a) with a proper amount of dichloromethane, slowly dropwise adding dichloromethane solution dissolved with 2,2' -oxydiacetylchloride with 5 molar equivalents into the reaction container under the cooling of an ice bath, and stirring the mixture at room temperature for reaction for 12 hours after dropwise adding to prepare hydroxyl-terminated oligomer; dissolving 0.5 mol of single amount of the oligomer and 1 mol of single amount of the compound (b) in proper amount of toluene, then adding proper amount of stannous octoate catalyst, stirring and reacting for 24 hours at room temperature to obtain a dynamic polymer solution. The solution is coated on a polymer plate to form a coating film with a certain thickness, then scratches with a certain depth are scratched on the surface of the coating film, and scratch repair can be realized by irradiating the coating film for a period of time under ultraviolet light. The polymer solution in the embodiment can be used for preparing the self-repairable functional coating.

Example 4

Dissolving 60 molar equivalents of N-isopropylacrylamide, 40 molar equivalents of 2-bromoethylacrylate and 0.05 molar equivalents of azobisisobutyronitrile in DMF, and reacting at 70 ℃ for 24 hours under nitrogen atmosphere with stirring to obtain an acrylamide-acrylate copolymer (a); and then taking potassium carbonate as a catalyst, carrying out reflux reaction on the copolymer (a) with 0.1 molar equivalent and the compound (b) with 0.5 molar equivalent in acetonitrile for 48h, and purifying to obtain the dynamic covalent cross-linked copolymer. Taking dibutyltin dilaurate as a catalyst, and stirring and reacting polyoxypropylene triol (with the molecular weight of 3000) and excessive isophorone diisocyanate at 70 ℃ for 1h to prepare an isocyanate-terminated prepolymer; taking 10 molar equivalents of the prepolymer, recording the mass of the prepolymer as 100 parts and 30 parts of dynamic covalent crosslinked copolymer (b), adding a proper amount of tetrahydrofuran, stirring and swelling for 1h, adding 15 molar equivalents of compound (c), stirring and reacting for 3h at 65 ℃, then pouring the reactant into a mold, standing and reacting for 3h at 85 ℃, and removing the solvent to obtain the dynamic polymer elastomer. The tensile strength of this elastomer sample was 70.6MPa and the elongation was 184%. When the elastomer is subjected to heat preservation at 60 ℃ for 12 hours after cracks appear, the mechanical strength can be recovered to 68%, and when the temperature is increased to 120 ℃ and the heat preservation is carried out for 1 hour, the mechanical strength can be recovered to 92%. The elastomer material can be made into mechanical parts or sealing ring materials of vacuum devices for use.

Example 5

Sequentially adding a certain amount of compound (a), diethylene glycol and potassium hydroxide into a high-pressure reaction kettle, and carrying out vacuum dehydration for 3h at 110 ℃; then a certain amount of propylene oxide is continuously added, the polymerization temperature is controlled at 120 ℃, the reaction pressure is 0.1MPa, and the polyether polyol is prepared after the reaction is carried out for 12 hours. Using stannous octoate as a catalyst, reacting a compound (b) with a molar ratio of 3:1 with 1,3, 5-tri (6-hydroxyhexyl) -1,3, 5-triazine-2, 4, 6-trione at 100 ℃ for 6h, removing the solvent after the reaction is finished, and crushing to obtain the hydrogen bond crosslinked polymer particles. Taking 100 parts of the prepared polyether polyol, 3 parts of a compound (c), 1.2 parts of deionized water, 15 parts of monofluoroethane HCFC-141b, 1.5 parts of N, N-dimethylcyclohexylamine, 5 parts of carbon fiber, 5 parts of nano ferroferric oxide, 15 parts of tricresyl phosphate, 2 parts of boron nitride, 3 parts of ammonium polyphosphate and 5 parts of a foam homogenizing agent AK8803, putting the mixture into a container, stirring and mixing the mixture uniformly at a high speed, adding 20 parts of hydrogen bond crosslinked polymer particles and 14 parts of polyphenyl polymethylene polyisocyanate, wherein the isocyanate index is 1.05, stirring the mixture rapidly for 5 to 10 seconds, immediately pouring the mixture into a mold for foaming, solidifying the mixture for 10 minutes at normal temperature, taking out the foam, and curing the foam at room temperature for 7 days to obtain the polyurethane hard foam. The foam has uniform and dense and polygonal cell structure, and has a foam density of 214kg/m³The compressive strength was 940 kPa. The foam material has the characteristics of high specific strength, wear resistance, environmental protection, flame retardance and the like, and is suitable for being used as instrument panels and interior trim materials of automobiles, trains, airplanes and the like. When the foam material has cracks, the cracks can be repaired in the forms of direct heating or ultraviolet illumination, or the internal cracks of the foam can be repaired by remote sensing through controlling an external alternating magnetic field based on the magnetic-thermal effect of the foam material.

Example 6

Taking 1 molar equivalent of hydroxyl-terminated polybutadiene-acrylonitrile and 0.5 molar equivalent of compound (a), placing the mixture in a reaction container, performing reduced pressure dehydration and drying at 120 ℃ for 2 hours, cooling to below 60 ℃, adding 3.3 moles of single amount of toluene diisocyanate, and stirring at 80 ℃ for reaction for 2 hours to obtain an isocyanate-terminated prepolymer; taking 1.2 molar equivalent of the compound (b), 0.3 wt% of antioxidant 1010, 0.2 wt% of stannous octoate, 1 wt% of glass fiber and a proper amount of acetone, uniformly mixing, adding the mixture into the prepolymer, reacting for 12 hours at 70 ℃ under a nitrogen atmosphere, and removing the acetone under reduced pressure after the reaction is finished to obtain the polyurethane elastomer. The elastomer has good tensile toughness, and after cracks appear, the cracks can be quickly healed through heating and ultraviolet irradiation for a period of time, and the elastomer can be used as a self-repairing tough material.

Example 7

The preparation method comprises the steps of extracting limonene oxide from orange peels, carrying out polymerization reaction on the limonene oxide and carbon dioxide under the catalysis of β -diimine zinc to obtain polycarbonate PLimC, reacting the PLimC with a proper amount of 2-aminoethanethiol under nitrogen atmosphere and 365nm ultraviolet illumination for 30min by using benzoin dimethyl ether as a photoinitiator to obtain amino graft modified polycarbonate, reacting the amino graft modified polycarbonate with excessive ethyl isocyanate at 80 ℃ for 6h by using stannous octoate as a catalyst, removing excessive ethyl isocyanate and the catalyst after the reaction is finished to obtain carbamido modified polycarbonate, reacting the carbamido modified polycarbonate with 4-dimethylaminopyridine as a catalyst and 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide as a dehydrating agent, reacting the amino graft modified polycarbonate with 0.1 molar equivalent of amino graft modified polycarbonate and 3 molar equivalent of a compound (a) at 30 ℃ for 18h by adding 5 molar equivalent of n-butyric acid, stirring and reacting for 6h at 30 ℃, removing excessive n-butyric acid, the catalyst, inorganic salt and the like after the reaction is finished, obtaining covalent crosslinking modified polycarbonate I, carrying out a covalent crosslinking reaction on the polyurethane, adding a proper amount of the polyamine modified polycarbonate with 0.5-10 h, adding a proper amount of a covalent crosslinking modifier, a polyurethane, a covalent polyurethane, a crosslinking modifier with a crosslinking modifier, a flame-10-0.5-0-10-0-10-0-mole crosslinking mechanical equivalent of a polyamine-0-equivalent of a polymer, heating crosslinking polymer, a flame-10-0-10-0-equivalent polyurethane-0-10-0-4-0-10-0-.

Example 8

1,3, 5-tri (2-methoxy-2-propyl) benzene is used as an initiator, isobutene is used as a monomer, allyl trimethylsilane is used as a quenching agent, and the allyl-terminated three-arm polyisobutylene (a) is prepared through active cationic polymerization. The benzoin dimethyl ether is used as a photoinitiator, the three-arm polyisobutylene (a) and excessive 4-sulfydryl-N-methyl benzamide react for 30min under the irradiation of 365nm ultraviolet light, and the polyisobutylene is modified by amide hydrogen bond groups. Taking 10 molar equivalents of three-arm polyisobutylene, 12 molar equivalents of the compound (b), 6 molar equivalents of 1- (2-mercaptoethyl) -3-pentylthiourea and 30 wt% of amide hydrogen bond group modified polyisobutylene, placing the mixture into a glass reaction vessel, adding a dichloromethane solvent, stirring and dissolving, adding 2 wt% of benzoin dimethyl ether, 0.5 wt% of graphene nanosheet, 0.5 wt% of nano-palladium and 0.3 wt% of antioxidant BHT, and then reacting for 30min under 365nm ultraviolet irradiation to obtain the polyisobutylene elastomer. The tensile strength of the elastomer is 4.9MPa, the elongation at break is 685%, the elastomer can be rapidly repaired by directly heating or irradiating the elastomer by near infrared light after being cut off, and the mechanical strength can be restored to 88%. The elastomer material also has the characteristics of excellent chemical resistance, water resistance, aging resistance, high barrier property and the like, and can be prepared into a bonding material or a sealing material with self-repairing performance and reusability for use.

Example 9

Taking 10 molar equivalent polyethylene glycol (molecular weight is 800), 5 molar equivalent compound (a), 5 molar equivalent 4-dimethylamino pyridine and 20 molar equivalent dicyclohexyl carbodiimide, placing the mixture in a reaction vessel, dissolving the mixture with a proper amount of dichloromethane, stirring the mixture at room temperature for 24 hours, and removing impurities and solvent after the reaction is finished to obtain the dynamically crosslinked polyethylene glycol. Taking 4 molar equivalents of 3,6, 9-trioxaundecanedioic acid, 5 molar equivalents of compound (b) and 60 wt% of dynamic covalent crosslinked polyethylene glycol, placing the mixture in a reaction container, fully swelling the mixture with a proper amount of tetrahydrofuran, adding 2.5 molar equivalents of 4-dimethylaminopyridine and 20 molar equivalents of dicyclohexylcarbodiimide, stirring the mixture at room temperature for reaction for 24 hours, adding 0.5 molar equivalent of compound (a), continuing the reaction for 18 hours, then adding 15 wt% of black phosphorus nanosheet, 10 wt% of carbon black and 200 wt% of 1-ethyl-3-methylimidazolium tetrafluoroborate, uniformly stirring the mixture, pouring the product into a mold, and drying the product in a vacuum oven for 12 hours to obtain the ionic liquid swelling gel. The gel sample had a tensile strength of 10.6MPa, an elongation at break of 480% and an electrical conductivity of 1.8 x 10 at 25 ℃^-4S/cm, and the conductivity of the sample can be greatly improved by carrying out ultraviolet illumination or heating for a period of time. When the gel is damaged, the damage repair is realized by direct heating or ultraviolet irradiation, and the remote sensing repair of the material can be realized by irradiating the gel with near infrared light based on the near infrared light thermal effect of the gel sample. The gel material in the embodiment can be used as an electrode material or a conductive sealing material of a self-repairable supercapacitor.

Example 10

Taking 5.5 molar equivalents of 1, 6-adipic acid, 2.5 molar equivalents of the compound (a) and 2.5 molar equivalents of the compound (b), putting the mixture into a reaction vessel, adding a proper amount of dichloromethane solvent, stirring and dissolving, adding 10 molar equivalents of N, N-diisopropylcarbodiimide and 2.5 molar equivalents of 4-dimethylaminopyridine, stirring and reacting for 24 hours at room temperature, adding 1.2 molar equivalents of the compound (c), and continuing to react for 24 hours to obtain a dynamic polymer solution. The polymer solution can show different colors at different heating temperatures, and can be used as a temperature sensing material.

Example 11

Taking azo dimethoxy isoheptonitrile as an initiator, toluene as a solvent, methyl methacrylate as a monomer and a compound (a) as a cross-linking agent, wherein the molar ratio of the two is 80:1, and stirring and reacting for 72 hours at a constant temperature of 40 ℃ under an argon atmosphere to prepare the dynamic covalent cross-linked polymer. Taking 30 molar equivalent of methyl methacrylate, 10 molar equivalent of 4-acrylamido-N-ethylbutanamide, 1 molar equivalent of compound (a), 5 wt% of graphene and 30 wt% of dynamic covalent cross-linked polymer, putting the materials in a reaction vessel, dissolving the materials with a proper amount of toluene, stirring and swelling for 30min under a nitrogen atmosphere, adding 3 wt% of azodimethoxy isoheptonitrile, stirring uniformly, and standing and reacting for 72h at 40 ℃ under an argon atmosphere to obtain the dynamic polymer organogel. The gel sample had a tensile strength of 11.8MPa and an elongation at break of 224%. The organogel has good conductivity, and when the temperature of the organogel is raised, the conductivity of the organogel can be greatly improved, the organogel can be used as an electrode material of a rechargeable battery, not only has a supporting effect, but also can realize damage repair through a dynamic reversible process of the action of a contained dynamic covalent bond and a hydrogen bond when an electrode is damaged or cracked, and the safety of the battery is improved.

Example 12

Taking dibutyltin dilaurate as a catalyst, and reacting N-methyl-N-hydroxyethyl amino azobenzene with excessive hexamethylene diisocyanate to obtain the compound (a). Compound (c) is prepared by reacting compound (b) with excess hexamethylene diisocyanate using dibutyltin dilaurate as a catalyst. Taking 1 molar equivalent of polyether polyol HK-330N (hydroxyl value is 34 +/-2 mgKOH/g, average functionality is 3), 3 molar equivalent of flame retardant grade polyether polyol YB-3028 (hydroxyl value is 26 +/-2 mgKOH/g, average functionality is 2), 1.6 wt% of triethylene diamine, 0.02 wt% of bis-dimethylaminoethyl ether, 1.5 wt% of an organosilicon foam stabilizer, 2.5 wt% of deionized water, 0.3 wt% of chopped glass fiber, and 0.2 wt% of glass beads, placing the mixture in a container, stirring and mixing uniformly, adding 1 molar equivalent of isocyanate (a) and 4 molar equivalents of compound (c), quickly stirring, pouring the mixture into a mold for free foaming, and naturally curing for 7 days to obtain the polyurethane soft foam. The pore diameter distribution of the pores of the soft foam sample is uniform, and the pore walls of the pores are thinner; the density of which is 51kg/m³The rebound resilience was 62%, the tensile strength was 145kPa, the elongation at break was 105%, and the permanent set under compression was 6.4%. The soft foam material has the characteristics of high flame retardance, self-extinguishing property, anti-dripping, low heat conductivity coefficient and the like, and is very suitable for being used as a building and industrial heat-insulating material. In addition, after the foam material reaches the service cycle, polyurethane sections, plates and the like can be prepared again through a heating process, and the foam material has good economical efficiency and environmental protection.

Example 13

Benzoin dimethyl ether is used as a photoinitiator, 4-vinylaniline and (1, 3-dimercaptopropane-2-yl) tert-butyl carbamate with the molar ratio of 2:1 react for 30min under 365nm ultraviolet light to prepare the arylamine curing agent (a). Triethylamine is used as a catalyst, tetrahydrofuran is used as a solvent, and a compound (b) and chlorodimethylsilane in a molar ratio of 1:3 are added into the mixtureStirring and reacting for 6 hours at room temperature under argon atmosphere to obtain a hydrosilicon end-capped intermediate product; and then taking toluene as a solvent, and carrying out stirring reaction on the intermediate product and allyl glycidyl ether at a molar ratio of 1:2.5 for 3 hours at 60 ℃ under the action of Karstedt catalyst to obtain a compound (c). Taking 30 molar equivalents of the compound (c), recording the mass as 100 parts, placing the compound (c) in a container, and heating to 80 ℃ to obtain a component A; weighing 5 parts of foaming agent Celogen-OT, 5 parts of surfactant Pluronic L-68, 15 parts of glass beads (10-100 mu m), 5 parts of black phosphorus nanosheets, 5 parts of calcium carbonate, 1.5 parts of melamine and 5 parts of toluene, placing the materials in another container, and stirring and mixing the materials uniformly to obtain a component B; and adding the component B into the component A, stirring at a high speed, uniformly mixing, adding 20 molar equivalents of the arylamine curing agent (a), pouring the reaction liquid into a mold coated with a release agent, heating to 120 ℃ for foaming, and curing in the mold at 70 ℃ for 2 hours to obtain a foam product. The foam had a density of 295kg/m³The tensile strength was 85 kPa. When cracks appear on the surface of the foam, the cracks can be repaired by direct heating, and the cracks can be repaired by locally heating the cracks through infrared or near-infrared illumination based on the photothermal effect of the foam. The foam material also has excellent flame retardance and self-extinguishing property, and can be made into heat-insulating materials, light-weight high-strength composite sandwich plates and the like for use.

Example 14

Pentaerythritol and epsilon-caprolactone with the molar ratio of 1:80 react for 72 hours at 180 ℃ in argon atmosphere to prepare hydroxyl-terminated star-shaped polycaprolactone; reacting hydroxyl-terminated star-shaped polycaprolactone with excessive succinic anhydride at room temperature for 4 hours under nitrogen atmosphere by using triethylamine as a catalyst and dichloromethane as a solvent, and then carrying out reflux reaction for 1 hour to prepare carboxyl-terminated star-shaped polycaprolactone; and reacting the carboxyl-terminated star-shaped polycaprolactone with excessive thionyl chloride at 80 ℃ for 12 hours to prepare the acyl chloride-terminated star-shaped polycaprolactone. Reacting the star-shaped polycaprolactone terminated by acyl chloride and the ureido pyrimidone derivative (a) at the molar ratio of 1:4 at room temperature for 24 hours by using triethylamine as a catalyst and dichloromethane as a solvent to obtain the hydrogen bond crosslinking modified polycaprolactone. And (b) reacting the star-shaped polycaprolactone terminated by acyl chloride with the compound (b) at room temperature for 24h by taking triethylamine as a catalyst and dichloromethane as a solvent in an equal molar ratio to obtain the dynamic covalent crosslinking modified polycaprolactone. And (2) taking 50 parts of each of the two crosslinked polycaprolactones, 1.5 parts of paraffin, 0.8 part of carbon fiber, 8 parts of stearic acid and 5 parts of barium sulfate, placing the two crosslinked polycaprolactones in a torque rheometer for melting and blending for 10min at 120 ℃, and placing the blended material in a press mold of a vulcanizing press, wherein the press mold temperature is 140 ℃, the press mold pressure is 10MPa, and the press mold time is 10min, so as to obtain the dynamic polymer solid. And cutting a cut mark with a certain depth on the surface of the sample strip by using a knife, repairing and healing the cut mark by heating, and recovering the mechanical strength of the repaired sample strip by 90%. The solid sample also has good shape memory. The dynamic polymer solid in the embodiment can be used as a shape memory material with a self-repairing function, such as a fastening pin, an orthopedic rehabilitation bracket material, an orthopedic material and the like.

Example 15

Taking 1 molar equivalent of polyether triol PPG-3000, placing in a reaction container, dehydrating and drying at 110 ℃ under reduced pressure for 2h, cooling to below 60 ℃, adding 3.3 moles of single amount of toluene diisocyanate, and reacting at 80 ℃ for 2h to obtain an isocyanate group terminated prepolymer; taking 1.2 molar equivalent of dihydric alcohol (a), 1 molar equivalent of 1-ethyl-3- (5-hydroxypentyl) thiourea, 0.15 wt% of antioxidant BHT, 0.2 wt% of stannous octoate, 0.1 wt% of nano zinc oxide, 0.8 wt% of silicon dioxide, 0.3 wt% of nylon fiber, 0.8 wt% of fatty alcohol-polyoxyethylene ether and a proper amount of acetone, uniformly mixing, adding into the prepolymer, then reacting at 70 ℃ under a nitrogen atmosphere for 12 hours, and after the reaction is finished, removing the acetone under reduced pressure to obtain the polyurethane elastomer. This elastomer sample all has better infiltration nature and cohesiveness to substrates such as metal, plastics, pottery, glass, cloth, and need not to carry out special surface treatment to the bonding substrate, and especially adapted is used as building glass or car windshield's joint strip, and it not only can provide good bonding fixed action, in addition after glass is broken, can will remain the joint strip molecule through the heating effect and dissociate, convenient clearance change.

Example 16

Taking azobisisobutyronitrile as an initiator, taking N- (2- (methylamino) -2-oxoethyl) acrylamide as a polymerization monomer, taking tetrahydrofuran as a solvent, stirring and reacting for 24 hours at 65 ℃ under a nitrogen atmosphere, and after the reaction is finished, purifying to obtain the polyacrylamide particles (a). Reacting N, N-diallyl carbamoyl chloride with N-butylamine in an equal molar ratio to prepare 1, 1-diallyl-3-butyl urea; and reacting benzoin dimethyl ether serving as a photoinitiator with excessive 2-aminoethanethiol to prepare a compound (b). Taking 10 molar equivalent carboxyl double-terminated polyethylene glycol (molecular weight is 1200), 5 molar equivalent hexamethylene diamine and 1 molar equivalent compound (b), placing the mixture into a reaction vessel, dissolving the mixture with a proper amount of dichloromethane, then adding 40 molar equivalent dicyclohexyl carbodiimide and 10 molar equivalent 4-dimethylamino pyridine, stirring the mixture at room temperature for reaction for 24 hours under nitrogen atmosphere, then adding 2.5 molar equivalent compound (c), 5 wt% of graphene and 30 wt% of polyacrylamide particles (a), continuing the reaction for 24 hours, placing the obtained product into a mold, drying the product at room temperature for 24 hours, then drying the product in a vacuum oven at 60 ℃ for 12 hours, and finally obtaining the ordinary solid of the dynamic polymer. The solid sample has good conductivity, and the conductivity of the solid sample can increase along with the increase of the temperature in a certain temperature range. After the sample is cut off, the section is wetted by a proper amount of solvent, and the temperature is kept at 120 ℃ for a period of time, so that the cut mark can be quickly healed, and the conductivity can be gradually recovered. The solid sample in the embodiment can be used as an electrode material of a rechargeable battery, is applied to the field of energy sources, not only provides good conductivity, but also can realize crack healing through the self-repairing process when electrode crack damage occurs in the using process, prolongs the service life of the electrode and improves the use stability.

Example 17

Taking azobisisobutyronitrile as an initiator, taking 2-isocyanate ethyl acrylate and n-butyl acrylate with the molar ratio of 1:8 as comonomers, and stirring and reacting at 70 ℃ for 24 hours under nitrogen atmosphere to obtain an acrylate copolymer (a); taking 0.1 molar equivalent copolymer (a) and 1 molar equivalent compound (b), placing the copolymer (a) and the compound (b) in a reaction container, dissolving the copolymer (b) with a proper amount of diethyl ether, adding a small amount of stannous octoate catalyst, reacting for 12h at 70 ℃, adding 20 molar equivalents n-butylamine, continuing to react for 12h, and then removing the excessive n-butylamine and the catalyst to obtain the dynamically crosslinked acrylate copolymer. Taking dibutyltin dilaurate as a catalyst, and carrying out stirring reaction on polyoxypropylene triol (with the molecular weight of 3000) and excessive isophorone diisocyanate at 70 ℃ for 1h to obtain the isocyanate group-terminated polyoxypropylene PPG-NCO. Taking 10 molar equivalents of PPG-NCO, recording the mass of the PPG-NCO as 100 parts, placing the PPG-NCO in a reaction vessel, dissolving the PPG-NCO in a proper amount of tetrahydrofuran, adding 200 parts of dynamically crosslinked acrylate copolymer, stirring and swelling for 30min, adding 15 molar equivalents of a compound (c), stirring and reacting at 60 ℃ for 2h, pouring the product into a mold, standing and reacting at 80 ℃ for 4h, and removing impurities and a solvent after the reaction is finished to obtain the dynamic polymer elastomer. The tensile strength of this elastomer sample was 78.8MPa and the elongation at break was 267%. The elastomers also have good tear resistance. After a sample is cut, slightly attaching to a cut surface, and then keeping the temperature in a vacuum oven at 70 ℃ for 12 hours, wherein the mechanical strength of the elastomer can only recover 76%; and the mechanical strength can be recovered to 92 percent after the heat preservation is carried out for 1 hour at the temperature of 120 ℃. The elastomer in this embodiment can be used as a sealing material for mechanical parts or vacuum devices.

Example 18

31.5 molar equivalent hydrogen double-end-capped polydimethylsiloxane (a) (the molecular weight is 700) and 30 molar equivalent compound (b) are taken and placed in a reaction vessel, dissolved by proper amount of toluene, 2 drops of xylene solution of platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (the platinum content is 0.003 wt%) are added, the mixture is stirred and reacted for 48 hours at 60 ℃ under argon atmosphere, 5 molar equivalent vinyltrimethylsilane is added, the reaction is continued for 6 hours, and after the reaction is finished, the excessive vinyltrimethylsilane, catalyst and solvent are removed, so that the hydrogen bond cross-linked polydimethylsiloxane is obtained. Taking 40 molar equivalent hydrogen double-end-capped polydimethylsiloxane (a) (with the molecular weight of 700) and 20 molar equivalent compound (c), placing the mixture in another reaction vessel, dissolving the mixture with a proper amount of toluene, adding 40 wt% of hydrogen bond cross-linked polydimethylsiloxane, stirring and swelling the mixture for 30min, adding 2 drops of a xylene solution of a platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (wherein the platinum content is 0.003 wt%), stirring the mixture for reaction for 48h at 60 ℃ in an argon atmosphere, and removing a catalyst and a solvent after the reaction is finished to obtain the dynamic polymer elastomer. The glass transition temperature of the elastomer is low, the rebound resilience and the toughness can be kept in a wide temperature range, and the tensile strength is 10.6MPa, and the elongation at break is 832 percent. And cutting a cut mark with a certain depth on the surface of the sample by using a knife, pressing the cut mark, and placing the cut mark in a vacuum oven at 80 ℃ for heat preservation for 2 hours to realize the healing of the cut mark. The elastomer also has good water resistance, oil resistance, aging resistance and weather resistance, and can be prepared into sealing materials for use, such as sealing materials for doors, windows, panels, body cavities and the like of automobiles, ships, airplanes or spacecrafts.

Example 19

Using stannous octoate as a catalyst, and reacting polyethylene glycol monomethyl ether (molecular weight is 1200) with excessive hexamethylene diisocyanate to prepare polyethylene glycol monomethyl ether with one end being isocyanate group; then reacting with polyethylene glycol acrylate (molecular weight is 475) to obtain the compound (a). Taking 70 molar equivalent of the compound (a), 2 molar equivalent of the compound (b), 180 wt% of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ionic liquid and 3 wt% of gallium indium liquidStirring and mixing the alloy state for 30min, adding 3 wt% of azodimethoxy isoheptonitrile, pouring the obtained mixture into a cylindrical container, and reacting at constant temperature of 40 ℃ for 72h under argon atmosphere to obtain the ionic liquid swelling gel. The gel sample had a tensile strength of 2.5MPa, an elongation at break of 390%, and an electrical conductivity of 8.3 x 10 at 25 ℃^-4S/cm, 80 ℃ conductivity 1.6 x 10^-3S/cm. After the gel is cut open, the gel can be repaired by heating or ultraviolet illumination. The gel material has good thermal stability and a wider electrochemical window, can be used as an electrolyte material of a lithium battery or a magnesium battery or a super capacitor, not only can provide stable electrochemical properties, but also can heal cracks through the self-repairing process when the cracks appear, maintain stable performance, improve use safety and prolong service life.

Example 20

Taking azobisisobutyronitrile as an initiator, taking N-octyl methacrylate, N-isopropylacrylamide and hydroxyethyl acrylamide with a molar ratio of 7:1:2 as comonomers, and stirring at 70 ℃ for reaction for 24 hours to obtain the acrylate copolymer (a). Adding 2 molar equivalents of the acrylate copolymer (a) and 6 molar equivalents of the dibasic acid (b) into a reaction vessel, dissolving with a proper amount of tetrahydrofuran, adding 3 molar equivalents of 4-dimethylaminopyridine and 18 molar equivalents of dicyclohexylcarbodiimide, stirring at room temperature for reaction for 16 hours, then placing the product into a flat mold, and drying in a vacuum oven at 60 ℃ for 6 hours to obtain the dynamic polymer solid film. The tensile strength of the film sample was 2.3MPa and the elongation at break was 420%. After being cut into pieces, the film is placed in a 130 ℃ oven for heat preservation for 2 hours, the film can be formed again, and the mechanical strength can be restored to more than 95%. The film material in the present embodiment can be used as a recyclable medical film, gloves, and the like.

Example 21

The compound (a) is prepared by the reaction of lauryl alcohol and 5-norbornene-2-carbonyl chloride with triethylamine as a catalyst. Using stannous octoate as a catalyst, and reacting 5-norbornene-2-methanol with ethyl isocyanate to prepare the compound (b). The compound (c) is prepared by reacting 2, 3-bis (4- (2-hydroxyethyl) phenyl) -2, 3-bis (4- (trifluoromethyl) phenyl) succinonitrile with excess 5-norbornene-2-carbonyl chloride using triethylamine as a catalyst. 120 molar equivalent of the compound (a), 5 molar equivalent of the compound (b) and 0.02 molar equivalent of Grubbs three-generation catalyst are taken and stirred for reaction for 3 hours under nitrogen atmosphere by using chloroform as a solvent to prepare the polynorbornene copolymer. Taking 100 mol equivalent of the compound (a), 5mol equivalent of the compound (b), 5mol equivalent of the compound (c), 40 wt% of the prepared polynorbornene copolymer and 0.02 mol equivalent of Grubbs three-generation catalyst, putting the materials into a reaction vessel, adding a proper amount of chloroform solvent, stirring and dissolving, then stirring and reacting for 6 hours under a nitrogen atmosphere, then adding 1.5 wt% of boron nitride, 1 wt% of silicon dioxide, 0.5 wt% of melamine cyanurate and 0.5 wt% of dispersing agent N, continuing stirring and reacting for 2 hours, and removing the catalyst and the solvent after the reaction is finished to obtain the dynamic polymer elastomer. After the elastomer is cut off, the elastomer can be repaired by heating. The elastomer also has the characteristics of heat dissipation, flame retardance, wear resistance, tear resistance and the like, and can be used as building sealing strips, door and window adhesive tapes or dust plugs of electronic equipment and the like.

Example 22

The maleic anhydride grafted polypropylene is prepared by taking dicumyl peroxide as an initiator, polypropylene as a matrix resin and maleic anhydride as a grafting modifier, wherein the mass ratio of the polypropylene to the maleic anhydride to the dicumyl peroxide is 100:5:0.4, and performing melt grafting reaction. Dissolving 0.8g of n-butylamine in DMF, adding a proper amount of p-toluenesulfonic acid, adding 50g of maleic anhydride grafted polypropylene in batches at 65 ℃, stirring for reacting for 6 hours, and removing excessive n-butylamine, catalyst and solvent after the reaction is finished to obtain the hydrogen bond crosslinked polypropylene. Dissolving 1.25g of the compound (a) in DMF, adding a proper amount of p-toluenesulfonic acid, adding 50g of maleic anhydride grafted polypropylene in batches at 65 ℃, stirring for reacting for 6 hours, removing a catalyst and a solvent after the reaction is finished, and dynamically and covalently crosslinking the polypropylene. Taking 50 parts of dynamic covalent cross-linked polypropylene, 25 parts of hydrogen bond cross-linked polypropylene, 3 parts of dibutyl phthalate, 5 parts of tricresyl phosphate, 0.3 part of barium stearate, 0.3 part of glass fiber, 0.1 part of antistatic agent SN, 0.1 part of zinc oxide and antioxidant BHT, banburying the materials in a banbury mixer at the banburying temperature of 130 ℃ for 10min, after the banburying is finished, putting the materials in a double-roller mill for flaking, putting the materials in a proper mold for compression molding, wherein the mold pressing temperature is 160 ℃, the mold pressing time is 30min, the mold pressing pressure is 8MPa, and after the mold opening, putting the materials in a vacuum oven at 70 ℃ for heat preservation for 5h to obtain the ordinary solid of the dynamic polymer. The tensile strength of the solid sample was 29.7MPa, and the flexural strength was 51.2 MPa. After the solid is crushed, hot pressing forming can be carried out again. The dynamic polymer in this embodiment can be used as a reworkable and recyclable pipe, sheet, profile, automobile interior part, instrument housing, and the like.

Example 23

The compound (a) is prepared by reacting 2, 3-bis (4-hydroxyphenyl) -2, 3-bis (4-methoxyphenyl) succinonitrile with excess epibromohydrin under nitrogen atmosphere at 60 ℃ for 12h by using potassium carbonate as a catalyst and DMF as a solvent. Using stannous octoate as a catalyst, and reacting a compound (b) with a molar ratio of 3:1 and polyoxypropylene triol (with a molecular weight of 600) at 100 ℃ for 6 hours to prepare hydrogen bond crosslinked polyoxypropylene. Taking 20 molar equivalents of polythiol Capcure3-800, wherein the molecular formula is shown in formula (c), 1 wt% of 4-dimethylaminopyridine and 40 wt% of hydrogen-bond crosslinked polypropylene oxide, taking tetrahydrofuran as a solvent, stirring and swelling for 30min, then adding 30 molar equivalents of compound (a) and 5 molar equivalents of tert-butyl (ethylene oxide-2-methyl) carbamate, stirring and mixing at 1500rpm for 2min at a high speed, pouring the obtained reactant into a mold, placing the mold in a vacuum oven, reacting for 3h at 25 ℃ and reacting for 2h at 65 ℃ in sequence, and removing the catalyst and the solvent after the reaction is finished to finally obtain the dynamic polymer elastomer. The elastomer had a bond strength of 1.4MPa and an elongation at break of 5.7%. After a sample is cut by a small knife, the cut surface can be pressed and tightly attached, the temperature is kept at 70 ℃ for 15min, the section can be bonded again, the bonding strength can be restored to 60%, the heat preservation time is increased to 45min, the bonding strength can be restored to 85%, the heat preservation time is increased to 1.5h, the bonding strength can be restored to 95%, and the self-repairing process can be repeated for multiple times. The elastomer has good wettability to base materials such as metal, ceramic, glass, plastic and the like, can be used as a bonding material or a sealant material with a self-repairing function, and is applied to bonding and sealing of high-vacuum and high-air-tightness parts in the fields of aerospace, electronics, machinery and the like.

Example 24

Polyether amine (b) was prepared by reacting polyether amine D2000 and butyryl chloride in a molar ratio of 1:2 using pyridine as a catalyst. Taking 3mol of single-amount compound (a), 5mol of single-amount polyether amine D2000, 4mol of single-amount compound (c) and 5mol of equivalent polyether amine (b), putting the materials into a reaction container, dissolving the materials with a proper amount of ethyl acetate, adding 16 mol of single-amount N-hydroxysuccinimide and 16 mol of single-amount dicyclohexylcarbodiimide, stirring the mixture for reaction for 24 hours at room temperature under a nitrogen atmosphere, pouring the product into a mold after the reaction is finished, and drying the product in a vacuum oven at 60 ℃ for 6 hours to obtain the dynamic polymer solid film. The film sample has good tensile toughness, good oil resistance and strong gas barrier property. The stretch-broken film can be wetted by a proper amount of solvent and bonded together, then the temperature is kept at 120 ℃ for 30min, the film can be bonded again, and the stretch-broken film can be used as a recyclable preservative film or a medical film material.

Example 25

Putting 14 molar equivalents of polytetrahydrofuran diol, 5 molar equivalents of the compound (a) and 4 molar equivalents of the compound (b) into a reaction vessel, adding a proper amount of tetrahydrofuran solvent, stirring for dissolving, adding a proper amount of 4-dimethylaminopyridine and dicyclohexylcarbodiimide, and stirring for reacting for 24 hours at room temperature to obtain the dynamically crosslinked polytetrahydrofuran diol. Taking 7 molar equivalents of acrylamide, 3 molar equivalents of hydroxyethyl acrylate and 0.3 wt% of azobisisobutyronitrile, placing the materials in a reaction vessel, dissolving the materials with a proper amount of tetrahydrofuran, stirring and reacting the materials at 70 ℃ for 20 hours under a nitrogen atmosphere, adding 80 wt% of dynamically crosslinked polytetrahydrofuran diol, 0.5 wt% of nano-palladium, 0.3 wt% of silicon carbide, 0.15 wt% of composite antibacterial agent KHFS-ZN and 0.5 wt% of sodium dodecyl alkyl sulfonate after the reaction is finished, pouring the obtained product into a mold after uniform mixing, and drying the product in a vacuum drying oven at 80 ℃ for 6 hours to obtain the dynamic polymer elastomer. The elastomer sample has excellent mechanical strength, tensile toughness and rebound resilience, and the tensile strength is 14.7MPa and the elongation at break is 215 percent. When cracks appear on the surface of the elastomer, the cracks can be repaired through direct heating, and the cracks can also be repaired through remote sensing heating through near-infrared illumination based on the high-efficiency near-infrared thermal effect of the nano palladium. The elastomer material in this embodiment can be used as a toy material or a sealing material having self-repairing properties.

Example 26

Taking boron trifluoride diethyl etherate as a catalyst, taking propylene glycol, propylene oxide and 2-methyl-2-propyl (3- (2-epoxyethane) propyl) carbamate with the molar ratio of 1:15:1 as raw materials, and carrying out cationic ring-opening polymerization to prepare modified polypropylene oxide glycol; and then pyridine is used as a catalyst to react with excessive butyl-3-enoyl chloride to prepare the vinyl double-end-capped polypropylene oxide (a). Taking 6 molar equivalents of vinyl double-terminated polypropylene oxide, 2 molar equivalents of a compound (b), 10 molar equivalents of hydrogen double-terminated polydimethylsiloxane (molecular weight is 500), taking toluene as a solvent, adding a proper amount of a dimethylbenzene solution of a platinum (0) -1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane complex (wherein the platinum content is 0.003 wt%) and 0.1 wt% of cellulose nanocrystal, stirring and reacting for 24 hours at 70 ℃ in an argon atmosphere, and removing a catalyst and the solvent after the reaction is finished to obtain the dynamic polymer solid. The solid has good tensile toughness, and after a sample is broken, the sample can be repaired through the actions of heating or ultraviolet illumination and the like. The polymer also has good water resistance, corrosion resistance, aging resistance and heat conduction performance, can be used as a self-repairing and recyclable heat conduction bonding material, and is applied to heat conduction bonding of electronic products or heat conduction packaging of electronic chips.

Example 27

Taking 2 molar equivalents of the compound (a), 5 molar equivalents of the compound (b) and 8 molar equivalents of 3-aminopropyl double-ended polydimethylsiloxane, placing the mixture into a reaction vessel, dissolving the mixture with a proper amount of dichloromethane, uniformly stirring, adding 4 molar equivalents of 4-dimethylaminopyridine and 50 molar equivalents of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide, stirring at room temperature for reaction for 24 hours, and removing the catalyst and the solvent after the reaction is finished to obtain the dynamic polymer elastomer. The tensile strength of the elastomer was 3.5MPa, and the elongation at break was 710%. The samples were cut to pieces and then hot pressed at 110 ℃. The elastomer also has the characteristics of good low-temperature toughness, weather resistance, flame retardance and the like, and can be used as a waterproof and dustproof plug of an electronic product.

Example 28

Taking 1.5 mol of a single amount of the compound (a) and 2 mol of a single amount of polyoxypropylene triamine (b) (the molecular weight is 3000), placing the mixture into a reaction vessel, dissolving the mixture by using a proper amount of ethyl acetate, adding 7.2 mol of single amount of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 0.5 mol equivalent of 4-dimethylaminopyridine, stirring the mixture for reaction for 16 hours at room temperature under a nitrogen atmosphere, pouring the reaction product into a flat plate mold, and drying the reaction product in a vacuum oven at 50 ℃ to finally obtain the dynamic polymer solid film. The film sample has good tensile toughness, oil resistance and gas barrier property. After the surface of the film is scratched to a certain depth, the scratch repair can be realized by directly heating or irradiating for a period of time by ultraviolet light or visible light. After the film is cut to pieces, it can be reshaped by hot pressing. The dynamic polymer film material in the embodiment can be used as recyclable preservative films, medical films and other materials.

Example 29

And (3) carrying out ring-opening polymerization for 6h at 160 ℃ by using the stannous octoate as a catalyst and the compound (a) as an initiator to prepare the hydroxyl-terminated star-shaped polylactide. Taking 10 molar equivalents of the polylactide, 12.5 molar equivalents of 1, 6-adipic acid, 7.5 molar equivalents of 4-dimethylaminopyridine and 45 molar equivalents of dicyclohexylcarbodiimide, placing the materials in a reaction vessel, dissolving the materials with a proper amount of dichloromethane, stirring the materials at room temperature for reaction for 12 hours, adding 5 molar equivalents of 2-imidazolidinone-4-carboxylic acid (b), and continuing the reaction for 6 hours to obtain the dynamically crosslinked polylactide. Weighing 50 parts of the polylactide, 0.5 part of antioxidant BHT, 0.5 part of chopped glass fiber, 0.8 part of silicon dioxide, 0.15 part of silicon nitride, 0.5 part of nano silver and 75 parts of tributyl citrate, melting and blending for 10min at 180 ℃, then placing the mixed material in a flat mold, and carrying out compression molding to obtain the tough plasticizer swelling gel. The gel sample had a tensile strength of 4.4MPa and an elongation at break of 475%. After the gel is cut by a knife, the cut marks can be pressed and tightly adhered, and the gel is re-adhered after heat preservation for 1h at 120 ℃ or 30min through 365nm ultraviolet illumination, and the mechanical strength can be restored to 84%. The plasticizer swelling gel in the embodiment also has the characteristics of heat conduction, antibiosis, wear resistance and the like, and can be used as a sealing material with self-repairing performance and applied to buildings and industries.

Example 30

Using toluene as a solvent, and reacting hydroxyl-terminated four-arm polyethylene glycol PEG-4000 with excessive thionyl chloride to prepare star-shaped polyethylene glycol substituted by chlorine at the end; then DMF is taken as a solvent, and reacts with sodium azide to prepare the azido-terminated star-shaped polyethylene glycol. Taking 1 molar equivalent of azido-terminated star polyethylene glycol, 4 molar equivalents of propargyl thymine (a), 0.38 molar equivalents of sodium ascorbate and 0.48 molar equivalents of copper sulfate, taking an ethanol-deionized water mixed solution with the same volume ratio as a solvent, and stirring for reaction at room temperature for 3 hours to obtain star polyethylene glycol (b). Taking 1 molar equivalent of terminal azido star polyethylene glycol, 4 molar equivalents of 6- (4-ethynylbenzyl) -1,3, 5-triazine-2, 4-diamine (c), 0.38 molar equivalent of sodium ascorbate and 0.48 molar equivalent of copper sulfate, taking ethanol-deionized water mixed liquor with the same volume ratio as a solvent, stirring at room temperature for reaction for 3h, and obtaining star polyethylene glycol (d). Taking 2.5 molar equivalent of end azido-based four-arm polyethylene glycol, 5 molar equivalent of diynyl compound (e), 0.96 molar equivalent of sodium ascorbate, 1 molar equivalent of polyethylene glycol (b), 1 molar equivalent of polyethylene glycol (c) and 1.2 molar equivalent of copper sulfate, taking an ethanol-deionized water mixed solution as a solvent, placing the mixed material in a mold for reaction for 3 hours, placing a product in an EDTA-aqueous solution after the reaction is finished, removing the copper sulfate and the ethanol, placing the product in a large amount of deionized water, and obtaining the dynamic polymer hydrogel after reaching water absorption swelling balance. The swelling rate of the gel sample is 850%, the tensile strength is 4.6MPa, the elongation at break is 1125%, after the sample is cut, the gel can be repaired and healed through the action of heating or ultraviolet irradiation and the like, and the mechanical property can be recovered to more than 90%. The gel material also has the characteristics of low biological toxicity, good skin-friendly property, shape memory function and the like. The gel material can be used as human tissue and organ with self-repairing property, such as ligament, skin, etc.

Example 31

Tetrahydrofuran is used as a solvent, dicyclohexylcarbodiimide and 4-dimethylaminopyridine are used as a catalytic system, and 3, 5-bis ((6-propionamidopyridine-2-yl) carbamoyl) benzoic acid and tetraethylene glycol in a molar ratio of 2:1 are subjected to esterification reaction to prepare the compound (a). Chloroform is used as a solvent, benzoin dimethyl ether is used as a photoinitiator, and 5-ethyl-5- (hexenyl) pyrimidine-2, 4, 6-trione and 1,3, 5-benzene trithiophenol in a molar ratio of 3:1 are subjected to mercapto-olefin free radical addition reaction to prepare the compound (b). Taking 1.5 molar equivalents of the compound (a), 1 molar single amount of the compound (b), 0.15 molar equivalent of hydroxyl-terminated styrene-butadiene liquid rubber, 0.1 molar equivalent of the compound (c), 0.075 molar equivalent of 4-dimethylaminopyridine and 0.6 molar equivalent of dicyclohexylcarbodiimide, putting the materials into a reaction vessel, adding a proper amount of dichloromethane solvent, stirring and reacting for 24 hours at room temperature, pouring the obtained product into a mold, naturally drying for 24 hours, and then drying for 6 hours in a vacuum oven at 60 ℃ to obtain the dynamic polymer elastomer. The elastomer samples have excellent mechanical strength and tensile toughness. The cut mark with a certain depth is cut on the elastic body by a blade, and the sample can be healed by heating to 80 ℃ and preserving the temperature for a period of time. The elastomer also has a shape memory function and good texture and touch, and can be used as a medical instrument material with the shape memory function.

Example 32

Taking 4.5 molar equivalents of the compound (a) and 7.5 molar equivalents of amino double-terminated polyethylene glycol, dissolving with tetrahydrofuran, adding a proper amount of N-hydroxysuccinimide and dicyclohexylcarbodiimide, stirring at room temperature for 24 hours for reaction, adding 5 molar equivalents of N-octanoic acid, continuing to react for 6 hours, and removing excessive N-octanoic acid, catalyst and other non-crosslinking components after the reaction is finished to obtain the dynamically crosslinked polyethylene glycol. Under the catalysis of potassium carbonate, 6-chloro-1-hexene reacts with excessive cyanuric acid to prepare an intermediate product; then, reacting the intermediate product with 5-mercaptopentane-1, 3-diol by using benzoin dimethyl ether as a photoinitiator to prepare a compound (b); taking 10 molar equivalents of the compound (a), 5 molar equivalents of the compound (b), 10 molar equivalents of 2, 2' -oxydiethanol and 70 wt% of dynamically crosslinked polyethylene glycol, putting the mixture into a reaction container, adding a proper amount of dichloromethane solvent, fully swelling, then adding a proper amount of 4-dimethylaminopyridine and dicyclohexylcarbodiimide, stirring at room temperature for reaction for 24 hours, pouring the obtained product into a mold, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain the dynamic polymer elastomer. The tensile strength of this elastomer sample was 18.9MPa and the elongation at break was 352%. The samples were crushed and could be re-compression molded at 125 ℃. The dynamic polymer contains a plurality of hydrogen bond actions, is easy to realize dynamic viscosity-elasticity conversion, and can be used as a toy material with magic effect.

Example 33

Taking 1 molar equivalent of the compound (a), 1 molar equivalent of hydroxyethyl methacrylate, 1 molar equivalent of polyethylene glycol monomethyl ether (molecular weight is 1500), 4 molar equivalent of dicyclohexylcarbodiimide and 0.5 molar equivalent of 4-dimethylaminopyridine, putting the mixture into a reaction vessel, adding a proper amount of tetrahydrofuran solvent, reacting at room temperature for 24 hours, and purifying to obtain the compound (b) after the reaction is finished. Taking 150 molar equivalent dibutyl maleate, 25 molar equivalent compound (b), 25 molar equivalent methacrylamide and 1 molar equivalent azodiisobutyronitrile, placing the dibutyl maleate, the compound (b), the methacrylamide and the azodiisobutyronitrile into a reaction vessel, adding a proper amount of anisole, stirring and reacting for 24 hours at 65 ℃ in an argon atmosphere, then adding 5 wt% of bentonite, 25 wt% of calcium carbonate, 2.5 wt% of fatty alcohol polyoxyethylene ether sulfate, 5 wt% of nano titanium dioxide, 0.1 wt% of composite antibacterial agent KHFS-ZN, 0.1 wt% of aluminum nitride, 0.5 wt% of carbon nano tube and 0.8 wt% of organosilicon antifoaming agent, placing the obtained materials into a stirrer, and stirring at a high speed for 30 minutes to obtain the dynamic polymer paste. The polymer paste has the characteristics of water resistance, pollution resistance, bacteriostasis, self repair and the like, can be used as a heat-conducting paste and applied to heat conduction and heat dissipation of electronic products, and can generate color change when the temperature of a heat dissipation assembly is increased.

Example 34

The compound (a) is prepared by reacting triphenylmethane triisocyanate with a proper amount of butyl mercaptan by using stannous octoate as a catalyst. Reacting glycerol triol with excessive 2-bromine isobutyryl bromide at room temperature for 24 hours by using triethylamine as a catalyst and dichloromethane as a solvent to prepare tribromide; and then cuprous bromide and pentamethyldiethylenetriamine are used as a catalytic system, o-dichlorobenzene is used as a solvent, and the tribromide and excessive 4-hydroxy-2, 2,6, 6-tetraethyl piperidine oxygen free radical react for 4 hours at 90 ℃ under the protection of argon to prepare the compound (b). And (3) putting 4 molar equivalents of the compound (b) and 6 molar equivalents of the compound (c) into a reaction vessel, dissolving with a proper amount of dichloromethane, adding a proper amount of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stirring at room temperature for reacting for 24 hours, and purifying to obtain the dynamic covalent cross-linked polymer after the reaction is finished. Taking 10 molar equivalent poly (butylene adipate) (molecular weight 2000), recording the mass as 100 parts, placing the poly (butylene adipate) (molecular weight 2000) in a reaction container, carrying out vacuum dehydration and drying for 1h at 120 ℃, cooling to 60 ℃, adding 6.5 molar equivalent diphenylmethane diisocyanate, 5 molar equivalent compound (a), 40 parts of dynamic covalent cross-linked polymer, 5 parts of nano silica, 10 parts of tricresyl phosphate, 3 parts of talcum powder, 1 part of mildew preventive BCM and 5 parts of recycled rubber particles, stirring for reaction for 30min, adding a tetrahydrofuran solution dissolved with 1 molar equivalent compound (b), continuously stirring for reaction for 3h, pouring the product into a mold, standing for reaction for 16h at 60 ℃, and reducing the pressure to remove the solvent to obtain the dynamic polymer elastomer. The tensile strength of this elastomer sample was 45.8MPa, the elongation 588% and the tear strength 280 kN/m. And scribing a cutting mark with a certain depth on the surface of the elastomer by using a blade, slightly pressing and tightly adhering the cutting mark, and then keeping the temperature in a vacuum oven at 120 ℃ for a period of time to realize the healing of the cutting mark, wherein the mechanical strength is recovered by 84%. The elastomer also has the characteristics of wear resistance, antibiosis, water resistance, skid resistance, bending resistance and the like. Based on the above properties, the elastomer can be used to make self-repairable slip-resistant liners, polyurethane screens, and the like.

Example 35

Taking 50 molar equivalents of the compound (a), 50 molar equivalents of the compound (b) and 0.05 molar equivalent of azobisisobutyronitrile, putting the mixture into a reaction vessel, and stirring and reacting for 24 hours at 70 ℃ under nitrogen atmosphere to prepare the hydrogen bond crosslinked acrylate copolymer. Putting 80 molar equivalent of polyethylene glycol monomethyl ether methacrylate, 5 molar equivalent of a compound (c), 50 wt% of dynamically crosslinked acrylate copolymer and 0.05 molar equivalent of azodiisobutyronitrile into a container, adding 140 wt% of dimethyl sulfoxide and 4 wt% of carbon nano tubes, fully swelling, pouring the mixture into a cylindrical container, and stirring and reacting at 70 ℃ for 24 hours under nitrogen atmosphere to prepare the tough organogel. The tensile strength was measured to be 11.2MPa and the elongation at break was 357%. After cutting off the gel, the gel can be repaired by heating at 120 ℃ or ultraviolet irradiation. The organic gel has the characteristics of heat conduction, heat dissipation, flame retardance and the like, and can be used as a heat conduction/heat dissipation patch of an electronic product with self-repairing performance, such as a mobile phone, a tablet personal computer, a notebook computer, a computer server and the like.

Example 36

150g of polyvinyl chloride with the molecular weight of 60000, 2.4mol of 4-mercaptobenzyl alcohol, 3.6mol of potassium carbonate and 0.6mol of tetrabutylammonium bromide are taken and placed in a reaction vessel, dissolved by a proper amount of cyclohexane and stirred for reaction for 4 hours at 60 ℃, so that the modified polyvinyl chloride (a) with the grafting rate of 25 mol% is prepared. Dissolving 20g of modified polyvinyl chloride (a) and 0.1mol of compound (b) in tetrahydrofuran, adding a proper amount of stannous octoate catalyst, stirring and reacting for 8 hours at 60 ℃ in a nitrogen atmosphere, and removing excessive compound (b), catalyst and solvent after the reaction is finished to obtain the hydrogen bond crosslinked polyvinyl chloride. Taking 20g of modified polyvinyl chloride (a), 0.03mol of compound (c) and 10g of polyvinyl chloride crosslinked by hydrogen bonds, adding a proper amount of tetrahydrofuran, stirring and swelling for 30min, adding a proper amount of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stirring and reacting for 36h at room temperature under a nitrogen atmosphere, adding 40g of epoxidized soybean oil, 40g of chlorinated paraffin, 1.2g of cellulose nanocrystal, 0.15g of nano-silver and 0.6g of antimony trioxide, uniformly mixing, placing the mixed material in a mold, and drying for 6h in a vacuum oven at 70 ℃ to obtain the plasticizer swelling gel. The gel sample had a tensile strength of 7.5MPa and an elongation at break of 230%. The broken gel samples are adhered together, and then the samples can be healed under the action of heating or ultraviolet irradiation, and the mechanical strength can be recovered by 80%. The gel also has the characteristics of good heat conduction and radiation performance, antibacterial property and the like, and can be used as a heat radiation patch of electronic products and electronic equipment.

Example 37

Taking azobisisobutyronitrile as an initiator and acrylamide as a polymerization monomer, stirring and reacting for 24 hours at 65 ℃ under nitrogen atmosphere, purifying and drying to obtain the polyacrylamide particles. Reacting chloropropylmethylsiloxane-dimethylsiloxane copolymer (wherein the content of chloropropylmethylsiloxane is 15 mol%) with excessive sodium azide at 70 ℃ for 24h by taking tetrahydrofuran as a solvent to prepare the azido-modified polysiloxane (a). Taking 2.5 molar equivalents of azido modified polysiloxane (a), 15 molar equivalents of compound (b), 7.5 molar equivalents of compound (c), 16.5 molar equivalents of cuprous iodide and 21.5 molar equivalents of triethylamine, placing the mixture in a reaction vessel, dissolving the mixture with a proper amount of tetrahydrofuran, stirring the mixture for reaction for 24 hours at room temperature under a nitrogen atmosphere, then adding 10 wt% of polyacrylamide particles, 5 wt% of graphene oxide, 1 wt% of boron nitride and 0.5 wt% of sodium dodecyl sulfate, stirring and mixing the mixture for 30 minutes, and removing the solvent under reduced pressure to obtain the dynamic polymer elastomer. And (3) fitting the cross section of the stretch-broken sample, and preserving the heat in a vacuum oven at 120 ℃ for 30min, wherein the sample can be bonded again. The dynamic polymer in this example is suitable for use as a tough material having self-healing properties and being reusable.

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 hybrid dynamic polymer comprising reversible free radical type dynamic covalent bonds, characterized in that it comprises at least two crosslinked networks and comprises at least one reversible free radical type dynamic covalent bond and at least one hydrogen bonding interaction.

2. A hybrid dynamic polymer comprising reversible free radical type dynamic covalent bonds, characterized in that it comprises only one crosslinked network and comprises at least two reversible free radical type dynamic covalent bonds and at least one hydrogen bonding interaction.

3. A hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, characterized in that it is a non-crosslinked structure and contains therein at least two reversible free radical type dynamic covalent bonds and at least one hydrogen bonding interaction.

4. A hybrid dynamic polymer comprising reversible free radical type dynamic covalent bonds, characterized in that it comprises only one crosslinked network and comprises a reversible free radical type dynamic covalent bond and at least one pendant hydrogen bonding interaction;

wherein, the reversible free radical type dynamic covalent bond is selected from one of the following structures:

wherein each W is independently selected from an oxygen atom, a sulfur atom;

wherein, W₁Is a divalent linking group; the divalent linking groups are each independently selected from: a direct bond-),

W at different positions₁Are the same or different;

wherein, W₂Is a divalent linking group; the divalent linking groups are each independently selected from:

w at different positions₂Are the same or different;

wherein, W₃Is a divalent linking group; the divalent linking groups are each independently selected from:

w at different positions₃Are the same or different;

wherein, W₄Is a divalent linking group; the divalent linking groups are each independently selected from: a direct bond-),

W at different positions₄Are the same or different;

Is absent;

To Z are two

Are the same or different in structure;

wherein each D is independently selected from carbon atoms, silicon atoms, germanium atoms and tin atoms;

wherein R is₁Each independently selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl/heterohydrocarbyl, substituted C_1-20Hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing;

wherein R is₂Each independently selected from hydroxy, phenyl, phenoxy, C_1-10Alkyl radical, C_1-10Alkoxy radical, C_1-10Alkoxyacyl group, C_1-10An alkanoyloxy group, a trimethylsilyloxy group, a triethylsiloxy group;

wherein R is₃Selected from cyano, C_1-10Alkoxyacyl group, C_1-10Alkyl acyl radical, C_1-10Alkylaminoacyl, phenyl, substituted phenyl, arylalkyl, substituted arylalkyl;

wherein R is¹、R²、R³、R⁴Each independently selected from a hydrogen atom, a halogen atom, a hetero atom group, C_1-20Hydrocarbyl radical, C_1-20Heterohydrocarbyl, substituted C_1-20Hydrocarbyl or substituted C_1-20Heterohydrocarbyl and combinations of two or more of the foregoing;

wherein R is⁵、R⁶、R⁷、R⁸Each independently selected from hydrogen atom, cyano, C_1-20Alkyl radical, C_1-20Cycloalkyl, aralkyl, heteroaralkyl and the groups formed by the above groups substituted by any substituent atom or substituent group;

wherein L is a divalent linking group, each of which is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, and a divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20Hydrocarbyl/heterohydrocarbyl and two or more of the aboveA divalent linking group formed by a combination of a plurality of species;

wherein the content of the first and second substances,

the two five-membered nitrogen heterocycles form a carbon-carbon single bond, a carbon-nitrogen single bond or a nitrogen-nitrogen single bond between the two ring-forming atoms;

wherein the content of the first and second substances,

is a nitrogen-containing aliphatic heterocycle; the ring-forming atoms of the aliphatic ring are selected from carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms and silicon atoms;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula;

wherein the content of the first and second substances,

is an aromatic ring; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro structure and a fused ring structure; the ring-forming atoms of the aromatic ring are selected from carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, boron atoms, phosphorus atoms, and silicon atoms;

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; at different positions

wherein the content of the first and second substances,

5. A hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, characterized in that it contains only one crosslinked network and contains one reversible free radical type dynamic covalent bond and at least contains pendant group hydrogen bonding and backbone hydrogen bonding simultaneously.

6. A hybrid dynamic polymer comprising reversible free radical type dynamic covalent bonds, characterized in that it comprises only one crosslinked network and comprises a reversible free radical type dynamic covalent bond and at least one pendant hydrogen bonding interaction; said pendant hydrogen bonding interactions are formed by pendant hydrogen bonding groups that are independent of said dynamic covalent bonds;

wherein each W is independently selected from an oxygen atom, a sulfur atom;

W at different positions₄Are the same or different;

wherein L is a divalent linking group, each of which is independently selected from the group consisting of a heteroatom linking group, a heteroatom group linking group, and a divalent C_1-20Hydrocarbyl/heterohydrocarbyl, substituted divalent C_1-20A divalent linking group formed from hydrocarbyl/heterohydrocarbyl and combinations of two or more of the foregoing;

wherein the content of the first and second substances,

wherein the content of the first and second substances,

wherein the content of the first and second substances,

indicates that n is connected with

wherein the content of the first and second substances,

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; at different positions

wherein the content of the first and second substances,

represents a linkage to a polymer chain or any other suitable group/atom (including a hydrogen atom);

wherein, each Y is independently selected from hydrogen atom, heteroatom group and micromolecular hydrocarbyl;

wherein Y is substituted with

wherein the content of the first and second substances,

indicating attachment to a polymer chain.

7. A hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, characterized in that it is a non-crosslinked structure and contains therein a reversible free radical type dynamic covalent bond and at least one hydrogen bonding; wherein said hydrogen bonding is formed by terminal hydrogen bonding groups.

8. A hybrid dynamic polymer containing reversible free radical type dynamic covalent bonds, characterized in that it is a non-crosslinked structure and contains therein a reversible free radical type dynamic covalent bond and at least one hydrogen bonding;

wherein each W is independently selected from an oxygen atom, a sulfur atom;

W at different positions₁Are the same or different;

w at different positions₂Are the same or different;

w at different positions₃Are the same or different;

W at different positions₄Are the same or different;

Is absent;

To Z are two

Are the same or different in structure;

wherein R is⁵、R⁶、R⁷、R⁸Are independently selectedFrom hydrogen atoms, cyano groups, C_1-20Alkyl radical, C_1-20Cycloalkyl, aralkyl, heteroaralkyl and the groups formed by the above groups substituted by any substituent atom or substituent group;

wherein the content of the first and second substances,

wherein the content of the first and second substances,

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; wherein, the symbols are the sites connecting with other structures in the formula；

Wherein the content of the first and second substances,

wherein the content of the first and second substances,

indicates that n is connected with

Wherein n is 0, 1 or an integer greater than 1; at different positions

wherein the content of the first and second substances,

9. A hybrid dynamic polymer containing a reversible free radical type dynamic covalent bond according to any one of claims 1 to 8, wherein said hybrid dynamic polymer formulation further comprises any one or more of the following additives or utilizable materials: auxiliary agent, filler and swelling agent.

10. A hybrid dynamic polymer containing dynamic covalent bonds of the reversible free radical type according to any of claims 1, 2,4, 5, 6, characterized by the fact that the morphology of said hybrid dynamic polymer has any of the following: common solids, gels, elastomers, foams.

11. A hybrid dynamic polymer containing reversible radical-type dynamic covalent bonds, according to any of claims 3, 7, 8, characterized by the fact that it has the morphology of any of the following: solutions, emulsions, pastes, glues, common solids, foams.

12. Hybrid dynamic polymer containing dynamic covalent bonds of the reversible free radical type according to any of claims 1 to 11, characterized in that it is applied to the following materials or products: self-repairing materials, toughness materials, shape memory materials, heat insulation materials, toy materials, energy storage device materials, organic heat-sensitive materials and temperature sensing materials.