A dilatant electronic product protective case

Abstract

The present invention relates to a dilatant electronic product protective cover / case, which is characterized in that it contains at least a dilatant component. The dilatant electronic product protective cover / case contains a dilatant component, enabling it to carry out anti-impact energy absorption protection when accidents such as dropping, impact, bumping, and scratching occur to the electronic product, overcoming the problems of the existing electronic product protective cover / case with a single energy absorption mechanism and poor anti-impact effect, and being able to effectively reduce problems such as breakage, cracks, and failure caused by accidents during the use of the electronic product.

Description

Technical Field

[0001] The present invention relates to a protective cover / case for electronic products, and particularly to a dilatant protective cover / case for electronic products. Background Art

[0002] With the development of technology and the improvement of people's living standards, electronic products are favored by more and more consumers, especially mobile phones, tablet computers, laptop computers, etc., making them an essential tool and carrier in life, entertainment, communication, and office. Along with the development trend of electronic products towards being thinner, more personalized, functional, and having larger screens, their usage experience has been gradually improved. However, during the use of electronic products, it is inevitable to encounter accidental situations such as the dropping, impact, compression, and scratching of electronic products, resulting in a decline in the appearance quality of electronic products, and even directly unable to continue using due to the damage of electronic product components, causing great property losses to consumers. Therefore, after purchasing electronic products, people usually choose to buy protective covers / cases for electronic products to avoid the above-mentioned accidents during the use of electronic products. In terms of its material, the protective cover / case for electronic products generally includes categories such as leather, silicone, cloth, hard plastic, soft plastic, velvet, and silk. Although the existing protective covers / cases for electronic products can play a certain role in decoration and beauty and avoid physical scratching, they cannot effectively absorb impact energy during the dropping, impact, etc. of electronic products to protect the electronic products from damage. Currently, the development of protective covers / cases for electronic products mostly stays at the appearance design of the protective covers for electronic products, while ignoring the development of protective covers / cases for electronic products with excellent impact resistance and special functions / usage performances. However, these functions / performances are very important during the use of electronic products, and even directly determine the usage stability and service life of electronic products.

[0003] Moreover, during the use of the protective cover / case for electronic products, it is also inevitable to have problems such as knocking, scratching, and even damage and cracks under dropping or severe collision. The structure of the existing protective covers / cases for electronic products is not reversible and cannot effectively repair and heal the structural damage, which is also not conducive to improving the service life of electronic products. In addition, the single function of traditional protective covers / cases for electronic products is also reflected in the lack of shape memory function, inability to be molded multiple times, difficulty in recycling and reuse, etc., and it cannot specifically respond to mechanical forces and achieve functional applications. The lack of usage performance and functional deficiencies of the protective covers / cases for electronic products in the prior art seriously restrict the application promotion of the protective covers / cases for electronic products and the improvement of the consumption experience.

[0004] Therefore, there is an urgent need to develop a new type of energy-absorbing protective case / shell for electronic products, especially one that combines good mechanical strength, toughness, tear resistance, and impact resistance, and preferably also has characteristics such as self-repairability, reprocessability, recyclability, shape memory, and mechanical force response, to solve the problems existing in the prior art. Summary of the Invention

[0005] In view of the above background, the present invention provides a dilatant protective case / shell for electronic products, which is characterized in that it contains at least a dilatant component. The dilatant protective case / shell for electronic products contains a dilatant component, enabling it to provide anti-impact and energy-absorbing protection when accidents such as dropping, hitting, bumping, and scratching occur to the electronic product, overcoming the problems of single energy-absorbing mechanism and poor anti-impact effect of existing protective cases / shells for electronic products, and effectively reducing problems such as breakage, cracks, and failure caused by accidents during the use of electronic products.

[0006] The present invention is realized through the following technical solutions:

[0007] The present invention provides a dilatant protective case / shell for electronic products, which is characterized in that it contains at least one dilatant component with a simple solid structure; the dilatant component is made of an intrinsic dilatant polymer.

[0008] The present invention also provides a dilatant protective case / shell for electronic products, which is characterized in that it contains at least one dilatant component with a simple hollow structure; the polymer matrix of the dilatant component is made of an intrinsic dilatant polymer.

[0009] The present invention also provides a dilatant protective case / shell for electronic products, which is characterized in that it contains at least one dilatant component with a solid cell structure; wherein, the cell of the solid cell structure is filled with a dilatant material, and the polymer matrix constituting the dilatant component does not have dilatancy.

[0010] The present invention also provides a dilatant protective case / shell for electronic products, which is characterized in that it contains at least one dilatant component with a solid cell structure; wherein, the cell of the solid cell structure is filled with a non-dilatant component, and the polymer matrix constituting the dilatant component has dilatancy.

[0011] The present invention also provides a dilatant protective case / shell for electronic products, which is characterized in that it contains at least one dilatant component with a solid cell structure; wherein, the cell of the solid cell structure is filled with a dilatant material, and the polymer matrix constituting the dilatant component has dilatancy.

[0012] The present invention also provides a dilatant electronic product protective cover / case, which is characterized in that it contains at least one dilatant component with a hollow cell structure; wherein, there is no filler other than gas in the cell of the hollow cell structure, and the polymer matrix constituting the dilatant component has dilatancy.

[0013] The present invention also provides a dilatant electronic product protective cover / case, which is characterized in that it contains at least one dilatant component with a hollow cell structure; wherein, the cell of the hollow cell structure is filled with a non-dilatant material, and the polymer matrix constituting the dilatant component has dilatancy.

[0014] The present invention also provides a dilatant electronic product protective cover / case, which is characterized in that it contains at least one dilatant component with a hollow cell structure; wherein, the cell of the hollow cell structure is filled with a dilatant material, and the polymer matrix constituting the dilatant component has dilatancy.

[0015] The present invention also provides a dilatant electronic product protective cover / case, which is characterized in that it contains at least one dilatant component, and the dilatant component contains at least two of a vitrified dilatant polymer component, a dynamic dilatant polymer component, a tangling dilatant polymer component, a dispersive dispersion composition, and a pneumatic dilatant structure to obtain at least two kinds of dilatancy.

[0016] The present invention also provides a dilatant electronic product protective cover / case, which is characterized in that it contains at least a dilatant component and has force responsiveness.

[0017] The present invention also provides a dilatant electronic product protective cover / case, which is characterized in that it contains at least one dilatant component with a hollow cell structure and at least one non-dilatant component with a simple solid structure, the cell wall of the hollow cell structure does not have dilatancy, and the cell is filled with a dilatant material containing an organic borate bond.

[0018] The present invention also provides a dilatant electronic product protective cover / case, which is characterized in that it contains at least one dilatant component with a hollow cell structure and at least one non-dilatant component with a simple solid structure, the polymer matrix of the dilatant component does not have dilatancy, the cell wall of the hollow cell structure does not have dilatancy, the cell is filled with a dilatant polymer material based on an inorganic borate bond, and the polymer main chain contains a carbon chain structure or a carbon hetero-chain structure.

[0019] The present invention also provides a dilatant electronic product protective cover / case, which is characterized in that it contains at least one dilatant component with a hollow cell structure and a non-dilatant component with a simple solid structure, the cell wall of the hollow cell structure does not have dilatancy, and the cell is filled with a dilatant material containing at least two different dynamic covalent bonds and / or non-covalent interactions.

[0020] The present invention also provides a dilatant electronic product protective cover / case, characterized in that it contains at least one dilatant component with a hollow cell structure and at least one non-dilatant component with a simple solid structure, the cell wall of the hollow cell structure has dilatancy, and there is no filler other than gas in the cell sac.

[0021] The present invention also provides a dilatant electronic product protective cover / case, characterized in that it contains at least one dilatant component with a hollow cell structure and at least one non-dilatant component with a simple solid structure, the cell wall of the hollow cell structure has dilatancy, and the cell sac is filled with a non-dilatant material.

[0022] The present invention also provides a dilatant electronic product protective cover / case, characterized in that it contains at least one dilatant component with a hollow cell structure and at least one non-dilatant component with a simple solid structure, the cell wall of the hollow cell structure has dilatancy, and the cell sac is filled with a dilatant material.

[0023] In the present invention, the dilatant component has a simple solid structure, a simple hollow structure, or a cell structure.

[0024] In an embodiment of the present invention, the dilatancy of the dilatant component includes but is not limited to dynamic dilatancy, vitrifying dilatancy, entangling dilatancy, dispersive dilatancy, pneumatic dilatancy, and their physical mixture forms, chemical hybrid forms, and combinations of the two forms.

[0025] In an embodiment of the present invention, when the dilatant component contains two or more types of dilatancy, it includes but is not limited to the following forms: physical mixture of vitrifying dilatancy and dynamic dilatancy, physical mixture of vitrifying dilatancy and entangling dilatancy, physical mixture of vitrifying dilatancy and dispersive dilatancy, physical combination of vitrifying dilatancy and pneumatic dilatancy, physical mixture of vitrifying dilatancy, dynamic dilatancy, and dispersive dilatancy, physical mixture of vitrifying dilatancy, dynamic dilatancy, and entangling dilatancy, combination of physical mixture of vitrifying dilatancy and dynamic dilatancy with pneumatic dilatancy, combination of physical mixture of vitrifying dilatancy and dispersive dilatancy with pneumatic dilatancy, combination of physical mixture of vitrifying dilatancy, dynamic dilatancy, and dispersive dilatancy with pneumatic dilatancy, chemical hybrid form with both vitrifying dilatancy and dynamic dilatancy on the polymer chain, chemical hybrid form with both vitrifying dilatancy and entangling dilatancy on the polymer chain, chemical hybrid form with vitrifying dilatancy, dynamic dilatancy, and entangling dilatancy on the polymer chain, and mixture / combination of chemical hybrid form with both vitrifying dilatancy and dynamic dilatancy on the polymer chain with other forms.

[0026] In the present invention, the temperature range (temperature span) of any of the glass transition temperatures in the vitreous dilatant polymer is not particularly limited, but depends on its service temperature range.

[0027] In the present invention, vitreous dilatancy can be obtained by introducing a vitreous dilatant polymer component into the polymer. The vitreous dilatant polymer component refers to a polymer segment (including oligomer segments, the same below) having at least one glass transition temperature, preferably a polymer segment having at least one glass transition temperature in the range of -40°C to 60°C. The polymer segment can be a soft segment of the dilatant polymer or a segment between crosslinking points. In the present invention, the vitreous dilatant polymer component can be chemically linked to the polymer chain of the dilatant polymer crosslinked network to become a connecting segment of the crosslinked network, or can be dispersed in the crosslinked network in the form of physical blending. Preferably, it is introduced into the polymer chain of the crosslinked network in a chemical linking form to obtain a more reliable and stable dilatancy process.

[0028] In a preferred embodiment of the present invention, the soft segment and / or the segment between crosslinking points of the vitreous dilatant polymer has only one glass transition temperature, and the glass transition temperature is in the range of -40°C to 60°C; preferably in the range of -10°C to 40°C.

[0029] In another preferred embodiment of the present invention, the soft segment and / or the segment between crosslinking points of the vitreous dilatant polymer has at least two glass transition temperatures. One glass transition temperature is in the range of -60°C to 0°C, preferably in the range of -40°C to 0°C; another glass transition temperature is in the range of 0°C to 80°C, preferably in the range of 0°C to 40°C; preferably, the two glass transition temperatures overlap.

[0030] In another preferred embodiment of the present invention, the soft segment and / or the segment between crosslinking points of the vitreous dilatant polymer has at least two glass transition temperatures. One glass transition temperature is in the range of -40°C to 60°C, preferably in the range of -10°C to 40°C; another glass transition temperature is in the range of -100°C to -40°C; preferably in the range of -80°C to -50°C.

[0031] In the present invention, the dynamic dilatant polymer refers to a polymer (including oligomers) containing at least one strong dynamic non-covalent interaction and / or strong dynamic covalent bond. It is achieved through the appropriate dynamic covalent bonds / non-covalent interactions contained in the polymer of the present invention.

[0032] In the embodiments of the present invention, typical strong dynamic non-covalent interactions include but are not limited to: monodentate hydrogen bonding, bidentate hydrogen bonding, monodentate metal-ligand interaction, bidentate metal-ligand interaction, ionic interaction, ion cluster interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bond interaction, Lewis acid-base pair interaction, cation-π interaction, anion-π interaction, benzene-fluorobenzene interaction, π-π stacking interaction, ionic hydrogen bond interaction, radical cation dimerization; typical strong dynamic covalent bonds include but are not limited to: boron-containing dynamic covalent bonds, metal acid ester-based dynamic covalent bonds, reversible radical-based dynamic covalent bonds. Among them, monodentate hydrogen bonding, bidentate hydrogen bonding, monodentate metal-ligand interaction, ionic interaction, ion cluster interaction, ion-dipole interaction, host-guest interaction, Lewis acid-base pair interaction, ionic hydrogen bond interaction, inorganic boric acid monoester bond, saturated five-membered ring inorganic borate ester bond, unsaturated five-membered ring inorganic borate ester bond, saturated six-membered ring inorganic borate ester bond, unsaturated six-membered ring inorganic borate ester bond, organic boric acid monoester bond, saturated five-membered ring organic borate ester bond, unsaturated five-membered ring organic borate ester bond, saturated six-membered ring organic borate ester bond, unsaturated six-membered ring organic borate ester bond (especially saturated five-membered ring organic borate ester bond / unsaturated five-membered ring organic borate ester bond / saturated six-membered ring organic borate ester bond / unsaturated six-membered ring organic borate ester bond connected with aminomethylbenzene group), inorganic boric acid silicate ester bond, organic boric acid silicate ester bond, dynamic titanic acid silicate ester bond are preferred, and monodentate hydrogen bonding, bidentate hydrogen bonding, monodentate metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, ionic hydrogen bond interaction, inorganic boric acid monoester bond, organic boric acid monoester bond, saturated five-membered ring organic borate ester bond / unsaturated five-membered ring organic borate ester bond / saturated six-membered ring organic borate ester bond / unsaturated six-membered ring organic borate ester bond connected with aminomethylbenzene group, inorganic boric acid silicate ester bond, organic boric acid silicate ester bond, dynamic titanic acid silicate ester bond are more preferred because of their high dynamics and good controllability.

[0033] In the present invention, the dynamic covalent bond includes a boron-containing dynamic covalent bond and a boron-free dynamic covalent bond.

[0034] Among them, the boron-containing dynamic covalent bonds include, but are not limited to, organic boric anhydride bonds, inorganic boric anhydride bonds, organic-inorganic boric anhydride bonds, saturated five-membered ring organic borate ester bonds, unsaturated five-membered ring organic borate ester bonds, saturated six-membered ring organic borate ester bonds, unsaturated six-membered ring organic borate ester bonds, saturated five-membered ring inorganic borate ester bonds, unsaturated five-membered ring inorganic borate ester bonds, saturated six-membered ring inorganic borate ester bonds, unsaturated six-membered ring inorganic borate ester bonds, organic boric acid monoester bonds, inorganic boric acid monoester bonds, organic boric acid silyl ester bonds, and inorganic boric acid silyl ester bonds. Among them, the boron-free dynamic covalent bonds include, but are not limited to, dynamic disulfide bonds, dynamic diselenide bonds, dynamic selenosulfide bonds, dynamic selenonitrogen bonds, acetal-based dynamic covalent bonds, dynamic covalent bonds based on carbon-nitrogen double bonds, dynamic covalent bonds based on reversible free radicals, binding exchangeable acyl bonds, dynamic covalent bonds induced by steric effects, reversible addition-fragmentation chain transfer dynamic covalent bonds, dynamic siloxane bonds, dynamic silyl ether bonds, exchangeable dynamic covalent bonds based on alkyl azolium, unsaturated carbon-carbon double bonds that can undergo olefin cross-metathesis, unsaturated carbon-carbon triple bonds that can undergo alkyne cross-metathesis, [2+2] cycloaddition dynamic covalent bonds, [4+2] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, thiol-Michael addition dynamic covalent bonds, amine-ene-Michael addition dynamic covalent bonds, dynamic covalent bonds based on triazolinedione-indole, dynamic covalent bonds based on diazabicyclic carbenes, dynamic covalent bonds based on benzoyl, hexahydrotriazine-based dynamic covalent bonds, dynamic exchangeable trialkylsulfonium bonds, dynamic acid ester bonds, and diketeneamine dynamic covalent bonds.

[0035] In the present invention, non-covalent interactions include supramolecular interactions, phase separation, and crystallization. Among them, the supramolecular interactions include, but are not limited to, at least one of the following: hydrogen bond interaction, metal-ligand interaction, ionic interaction, ion cluster interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bond interaction, Lewis acid-base pair interaction, cation-π interaction, anion-π interaction, benzene-fluorobenzene interaction, π-π stacking interaction, ion-hydrogen bond interaction, and radical cation dimerization.

[0036] In the present invention, the force responsiveness of the dilatant component and the non-dilatant component is achieved by introducing force-sensitive groups and / or force-responsive components into the component. Among them, the force-sensitive groups are connected to the polymer chain of the component in a covalent and / or non-covalent manner, endowing the component with force responsiveness; the force-responsive components are only dispersed in the component in a physical blending manner, endowing the component with force responsiveness.

[0037] In the present invention, the force-sensitive group refers to an entity containing a mechanically sensitive moiety (i.e., force-sensitive moiety), wherein the force-sensitive moiety includes but is not limited to covalent chemical groups, supramolecular complexes, supramolecular assemblies, compositions, aggregates, which undergo specific chemical and / or physical changes in structure under the action of mechanical force, including but not limited to chemical bond cleavage, bond formation, isomerization, decomposition, and physical dissociation, disassembly, separation, thereby directly and / or indirectly causing changes in chemical and / or physical signals, generating new groups / new substances, including but not limited to color, luminescence, fluorescence, spectral absorption, magnetism, electricity, conductivity, heat, nuclear magnetic resonance, infrared, Raman, pH, free radicals, catalysis, redox, addition, condensation, substitution, exchange, elimination, decomposition, polymerization, crosslinking, coordination, hydrogen bond binding, host-guest binding, ionic bond binding, pi-pi stacking signal / property changes, and ionic bond binding, degradation, viscosity signal / property changes, and release of new molecules, generation of new reactive groups, achieving specific response to mechanical force and obtaining force-induced response performance / effect. The dilatancy described in the present invention does not belong to the force responsiveness.

[0038] In the present invention, introducing a force-sensitive component / group having force-induced color change, force-induced fluorescence / phosphorescence change, force-induced luminescence, force-induced catalytic luminescence and other force-responsive effects into the component can not only directly perform stress induction and damage warning on the electronic product protective cover / case, but also enhance the use experience and visual enjoyment of the electronic product protective cover / case based on its visual force-responsive effect. For example, by applying mechanical forces such as pressing, scratching / friction on the protective cover / case, functions such as color change, luminescence and patterning of the protective cover / case can be realized. Introducing a force-sensitive component / group having force-induced radical-initiated polymerization, force-induced grafting, force-induced self-healing, force-induced crosslinking, force-induced catalytic crosslinking, force-induced strengthening and other force-responsive effects into the component can make the electronic product protective cover / case maintain flexibility, texture and touch under low mechanical force, while when the electronic product drops / slides or is subjected to mechanical forces such as impact, extrusion, collision, etc., the force-sensitive groups contained therein are activated, quickly enhancing its strength and rigidity, achieving repair of mechanical damage and enhancement of energy absorption and impact resistance performance, and providing more effective energy absorption protection for the electronic product. In particular, when introducing force-sensitive groups into the component, energy can also be absorbed through processes such as bond cleavage, bond formation, dissociation under force, which can provide an additional energy absorption effect, enhance the impact resistance ability, and also facilitate the extension of the service life of the protective cover / case. The combined use of force responsiveness and dilatancy can achieve orthogonal and / or synergistic effects, which can act independently or synergistically to achieve the effect of energy absorption and impact resistance and intelligence.

[0039] In the present invention, the force-responsive component, which is generally not a polymer by itself, can generate a force response when mechanical force is directly applied to it, and after being blended with a dilatant polymer, it can cause a force-induced response under mechanical force, so that the dilatant polymer has a force-induced response. It includes but is not limited to force-responsive crystals, force-responsive assemblies, force-responsive aggregates, and force-responsive compositions. The force-responsive component is physically blended and dispersed in the dilatant polymer or its components, and optionally cooperates and / or orthogonally with force-sensitive groups contained on the dilatant polymer chain to generate force-induced response properties / effects.

[0040] In the present invention, a component having force responsiveness (including a force-responsive dilatant component and a force-responsive non-dilatant component) may contain one or more force-sensitive groups. When only one force-sensitive group is contained, the force response process has better controllability, and its structure is relatively simple, which is convenient for preparation; when at least two force-sensitive groups are contained, two or more force-sensitive groups can be reasonably designed and combined according to needs to obtain diverse and / or synergistic and / or orthogonal and / or sequential force responsiveness / effects, etc.; preferably, different force-sensitive groups with different primitive structures are used to better control the performance, so as to meet the requirements of various force response performances and uses to the greatest extent.

[0041] In the present invention, the dilatant electronic product protective case / shell, in addition to containing at least one dilatant component, may also contain one or more non-dilatant components.

[0042] In the present invention, the non-dilatant components contained in the dilatant electronic product protective case / shell do not have dilatancy, and include but are not limited to metals, ceramics, glasses, hard plastics, elastomers, furs, artificial leathers, fabrics, flannelette, woods, bamboos, etc. The non-dilatant components can make the electronic product protective case / shell beautiful, increase the texture / touch, and play a supporting role, and thereby enhance / promote the dilatancy or force responsiveness.

[0043] In the present invention, the polymer matrix of the dilatant component is preferably a crosslinked structure to provide better mechanical strength and structural stability.

[0044] In an embodiment of the present invention, the polymer matrix of the dilatant component can be crosslinked by ordinary covalent bonds to form an ordinary covalent crosslinked network, or crosslinked by dynamic covalent bonds to form a dynamic covalent crosslinked network, or crosslinked by non-covalent interactions to form a non-covalent crosslinked network, or crosslinked by ordinary covalent bonds and dynamic covalent bonds and / or non-covalent interactions simultaneously to form a hybrid crosslinked network, or crosslinked by dynamic covalent bonds and non-covalent interactions simultaneously to form a hybrid dynamic crosslinked network, as well as hybrid networks and multi-networks of the above crosslinked networks. In addition, when the dilatant component and the non-dilatant component contain force-sensitive groups, in addition to the aforementioned crosslinking effects, the components can also be crosslinked by the contained force-sensitive groups, and when the components are crosslinked only by force-sensitive groups, this network is called a force-sensitive group crosslinked network.

[0045] In an embodiment of the present invention, the crosslinked network of the polymer matrix of the component may also contain non-crosslinked components. In particular, when a non-crosslinked structure is dispersed or blended in the crosslinked network of the polymer matrix of the dilatant component, it is preferably a non-crosslinked dilatant polymer, and more preferably the non-crosslinked dilatant polymer contains at least one strong dynamic dynamic covalent bond and / or strong dynamic non-covalent interaction, which is convenient for obtaining additional dynamic dilatancy and also facilitates further improving the energy absorption performance through the viscous flow of its segments.

[0046] In the present invention, when preparing the dilatant component and the non-dilatant component with a polymer as the matrix, it may also contain any one or any combination of the following additives or substances that can be used: auxiliaries, fillers, swelling agents. The auxiliaries are selected from any one or any combination of the following: catalysts, initiators, antioxidants, light stabilizers, heat stabilizers, dispersants, emulsifiers, flame retardants, toughening agents, coupling agents, compatibilizers, solvents, lubricants, mold release agents, plasticizers, thickeners, thixotropic agents, leveling agents, colorants, fluorescent brighteners, matting agents, phase change additives, antistatic agents, dehydrating agents, bactericidal and mildew-proof agents, foaming agents, co-foaming agents, nucleating agents, rheological agents; the fillers are selected from any one or any combination of the following: inorganic non-metallic fillers, metal fillers, organic fillers, organometallic compound fillers; the swelling agents are selected from any one or any combination of the following: water, organic solvents, ionic liquids, oligomers, plasticizers.

[0047] In the present invention, the dilatant component has one or a combination of the following morphologies: elastomer, gel (including hydrogel, organogel, oligomer swollen gel, plasticizer swollen gel, ionic liquid swollen gel), foam material.

[0048] In the present invention, the non-dilatant component has one or a combination of the following morphologies: ordinary solid, elastomer, gel (including hydrogel, organogel, oligomer swollen gel, plasticizer swollen gel, ionic liquid swollen gel), foam material.

[0049] In the present invention, the dilatant component refers to a composition composed of a polymer matrix containing dilatant components / compositions / structures and dispersoids dispersed therein, as well as optional auxiliaries, fillers, etc., and is prepared by means of molding, injection molding, casting, foaming, lamination, 3D printing, etc.

[0050] In the present invention, the non-dilatant component can be made from a non-dilatant polymer matrix and optional auxiliaries, fillers, etc., through molding, injection molding, casting, foaming, lamination, 3D printing, etc., to obtain a non-dilatant component product with a certain shape and size.

[0051] In the present invention, the dilatant component contained in the dilatant electronic product protective cover / case can be directly made into the protective cover / case, and can exist only in a part of the protective cover / case, such as at the border, corners, bottom plate, buttons, screen, etc. of the protective cover / case. Together with the non-dilatant component of the protective cover / case, it provides anti-impact and energy absorption functions and other service performances for the electronic product.

[0052] According to a preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, and the dilatant electronic product protective cover / case only contains dilatant components, as shown in the attached Figures 1 to 9 .

[0053] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, and the dilatant electronic product protective cover / case only contains dilatant components; the electronic product protective cover / case is an integrated structure, which includes a bottom plate and two groups of side frames, as shown in the attached Figure 1 .

[0054] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, and the dilatant electronic product protective cover / case only contains dilatant components; the electronic product protective cover / case is an integrated structure, which includes a bottom plate and two groups of side frames, and several button grooves are provided on the side frames, as shown in the attached Figure 2 .

[0055] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, and the dilatant electronic product protective cover / case only contains dilatant components; the electronic product protective cover / case is an integrated structure, which includes a bottom plate and a group of side frames, as shown in the attached Figure 3 .

[0056] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case only contains dilatant components. The electronic product protective cover / case is an integrated structure, which includes a bottom plate and a set of side frames. The bottom plate is provided with a camera opening and a hollow structure, as shown in the attached Figure 4 .

[0057] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case only contains dilatant components. The electronic product protective cover / case is an integrated structure, which includes a bottom plate and three side frames, as shown in the attached Figure 5 .

[0058] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case only contains dilatant components. The electronic product protective cover / case is an integrated structure, which includes a bottom plate and four corner sleeves, as shown in the attached Figure 6 .

[0059] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case only contains dilatant components. The electronic product protective cover / case is an integrated structure, which includes two sets of side frames, as shown in the attached Figure 7 .

[0060] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case only contains dilatant components. The electronic product protective cover / case is an integrated structure, which includes a bottom plate and two sets of side frames, and has a convex structure at the corners, as shown in the attached Figure 8 .

[0061] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains two dilatant components. The two dilatant components are respectively made into a shell and a lining, and then the lining is nested / fitted into the shell to obtain the electronic product protective cover / case, as shown in the attached Figure 9 .

[0062] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains dilatant components and non-dilatant components, as shown in the attached Figures 10 to 32 .

[0063] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, wherein the dilatant electronic product protective cover / case contains a dilatant component and a hard plastic component; the electronic product protective cover / case uses hard plastic as the housing, and the dilatant component is attached to the bottom plate on the side close to the cavity of the hard plastic housing in the form of a lining, as shown in the attached Figure 10 .

[0064] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, wherein the dilatant electronic product protective cover / case contains a dilatant component and a hard plastic component; the electronic product protective cover / case uses hard plastic as the housing, and the dilatant component is attached to the frame on the side close to the cavity of the hard plastic housing in the form of a lining, as shown in the attached Figure 11 、 12 .

[0065] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, wherein the dilatant electronic product protective cover / case contains a dilatant component and a hard plastic component; the electronic product protective cover / case uses hard plastic as the housing, and the dilatant component is attached to the corner on the side close to the cavity of the hard plastic housing in the form of a lining, as shown in the attached Figure 13 、 14 .

[0066] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, wherein the dilatant electronic product protective cover / case contains a dilatant component and a hard plastic component; the electronic product protective cover / case uses hard plastic as the outer housing and the dilatant component as the inner housing, and the inner and outer housings are combined together to obtain the electronic product protective cover / case, as shown in the attached Figure 15 .

[0067] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, wherein the dilatant electronic product protective cover / case contains a dilatant component and a hard plastic component; the electronic product protective cover / case uses hard plastic as the outer housing and the dilatant component as the inner housing, and the inner and outer housings are combined together to obtain the electronic product protective cover / case; the hard plastic used has high transparency, as shown in the attached Figure 16 .

[0068] According to another preferred embodiment of the present invention, there is provided a dilatant electronic product protective cover / case, wherein the dilatant electronic product protective cover / case contains a dilatant component and an elastomer component; the electronic product protective cover / case uses an elastomer as the outer housing and the dilatant component as the inner housing, and the inner and outer housings are combined together to obtain the electronic product protective cover / case, as shown in the attached Figure 17 .

[0069] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a flannelette component; the electronic product protective cover / case uses the dilatant component as the shell, and the flannelette component is attached to the bottom plate on the side close to the cavity of the dilatant shell in the form of a lining; wherein the flannelette component is preferably ultra-fine fiber cloth, as shown in the attached Figure 18 .

[0070] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a fur component; the electronic product protective cover / case uses the dilatant component as the shell, and the fur component is attached to the bottom plate on the side far from the cavity of the dilatant shell, as shown in the attached Figure 19 .

[0071] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a bamboo-wood component; the electronic product protective cover / case uses the bamboo-wood component as the shell, and the dilatant component is combined inside the bamboo-wood shell in the form of a lining, as shown in the attached Figure 20 , 21 .

[0072] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a non-dilatant component; the electronic product protective cover / case uses the dilatant component as the shell, and the non-dilatant component is a wrapping layer, which is wrapped on the surface of the dilatant shell to obtain the electronic product protective cover / case; wherein the non-dilatant component is selected from at least one of elastomer, fur, artificial leather, fabric, and flannelette, as shown in the attached Figure 22 .

[0073] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a metal component; the electronic product protective cover / case uses the dilatant component as the shell, and the metal component is a metal ring buckle; the metal ring buckle is combined on the bottom plate of the dilatant shell on the side far from the cavity, as shown in the attached Figure 23 .

[0074] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a ceramic component; the electronic product protective cover / case uses ceramic as the housing, and the dilatant component is attached to the side of the ceramic housing close to the cavity in the form of a lining, as shown in the attached Figure 24 , 25 .

[0075] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a leather component; the electronic product protective cover / case includes a fixed sleeve, an upper cover plate, and a connecting member connecting the fixed sleeve and the upper cover plate; wherein the fixed sleeve is made of the dilatant component, the upper cover plate is made of the leather component, and the connecting member is made of leather, an elastomer, and hard plastic, as shown in the attached Figure 26 .

[0076] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a non-dilatant component; the electronic product protective cover / case includes a fixed sleeve, an upper cover plate, a lower cover plate, and a connecting member connecting the upper cover plate and the upper cover plate; wherein the fixed sleeve is made of the dilatant component, the upper cover plate and the lower cover plate are made of at least one of an elastomer, fur, artificial leather, fabric, and flannelette, or are made by compounding at least one of an elastomer, fur, artificial leather, fabric, and flannelette with materials such as metal, ceramic, glass, and hard plastic, and the connecting member is made of leather, an elastomer, and hard plastic, as shown in the attached Figure 27 , 28 , 29.

[0077] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a non-dilatant component; the non-dilatant component is selected from at least one of an elastomer, fur, and artificial leather. The electronic product protective cover / case uses the non-dilatant component as a wrapping layer, and the dilatant component is wrapped inside. The wrapping layer is provided with at least one foldable groove, and four elastic bands are provided on one side of the wrapping layer for fixing the electronic product, as shown in the attached Figure 30 , 31 .

[0078] According to another preferred embodiment of the present invention, a dilatant electronic product protective cover / case is provided. The dilatant electronic product protective cover / case contains a dilatant component and a non-dilatant component; the electronic product protective cover / case includes a fixed sleeve case, an upper cover plate, a lower cover plate, and a connecting member connecting the upper cover plate and the upper cover plate; wherein the fixed sleeve case is made of a dilatant component, and the upper cover plate and the lower cover plate are made of at least one of elastomer, fur, artificial leather, fabric, flannelette, or are made by compounding at least one of elastomer, fur, artificial leather, fabric, flannelette with materials such as metal, ceramic, glass, hard plastic, etc., and the connecting member is made of leather, elastomer, hard plastic, as shown in the attached specification Figure 32 .

[0079] When the dilatant electronic product protective cover / case is applied to the anti-impact and energy absorption protection of electronic products, it can effectively weaken and prevent the structural damage and product failure of electronic products in accidents such as dropping, falling, collision, extrusion, etc.

[0080] Compared with the prior art, the present invention has the following beneficial effects:

[0081] (1) The present invention provides a dilatant electronic product protective cover / case, which contains at least one dilatant component with a simple solid structure and is made of an intrinsic dilatant polymer (composition). The dilatant component with a simple solid structure can provide effective anti-impact and energy absorption effects for electronic products based on its dilatancy and the sacrificial nature of the dynamic covalent bonds and / or non-covalent interactions contained therein, avoiding damage to electronic products when accidents such as dropping, impact, bumping, scratching, etc. occur. Reasonably regulating the chemical composition and topological structure of the dilatant component with a simple solid structure is more conducive to achieving a wide range of adjustable mechanical strength, toughness, energy absorption, and other service performance, and can improve the service life of the protective cover / case, especially the durability of directly making the electronic product protective cover / case only with the dilatant component. The dilatant component with a simple solid structure uses an intrinsic dilatant polymer (composition) as the polymer matrix to prepare the dilatant component, which helps to achieve sensitive, adjustable, and long-term stable dilatancy.

[0082] (2) The present invention also provides a dilatant electronic product protective cover / case, which contains at least one dilatant component with a simple hollow structure; the polymer matrix of the dilatant component is made of an intrinsic dilatant polymer. Using an intrinsic dilatant polymer as the polymer matrix to prepare the dilatant component helps to achieve sensitive, adjustable, and long-term stable dilatancy, providing a long-term stable anti-impact and energy absorption effect on the electronic product. Compared with the dilatant component with a solid structure, it also has the characteristics of light weight, high specific strength, and good compressibility. In addition to buffering and anti-impact through the dilatancy of the component and the sacrificial nature of the contained dynamic covalent bonds and / or non-covalent interactions, it can provide additional buffering and shock absorption through its compressibility, making it easier to prepare an electronic product protective cover / case with excellent anti-impact performance and light weight. The simple hollow structure also helps with the heat dissipation of the electronic product.

[0083] (3) The present invention also provides a dilatant electronic product protective cover / case, which contains at least one dilatant component with a solid cell structure; wherein, the cell cavity of the solid cell structure is filled with a dilatant material, and the polymer matrix constituting the dilatant component does not have dilatancy. The solid cell structure in the dilatant component uses a non-dilatant polymer as the matrix, which can improve the resilience of the component and help achieve a rapid shape recovery after the component deforms. The cell core of the solid cell structure contains a dilatant material, providing an anti-impact and energy absorption effect for the electronic product.

[0084] (4) The present invention also provides a dilatant electronic product protective cover / case, which contains at least one dilatant component with a solid cell structure; wherein, the cell cavity of the solid cell structure is filled with a non-dilatant component, and the polymer matrix constituting the dilatant component has dilatancy. The dilatant component with a solid cell structure uses a dilatant polymer as the matrix, which can achieve a sensitive and rapid dilatancy process when the electronic product is subjected to force, especially a severe impact, for timely anti-impact buffering. Filling a non-dilatant component at the cell core of the cell structure can further enrich and expand other use properties of the electronic product protective cover / case. Through the selection and combination of the polymer matrix and the material in the cell cavity, dilatant components and electronic product protective covers / cases with various properties can be designed and obtained.

[0085] (5) The present invention also provides a dilatant electronic product protective cover / case, which contains at least one dilatant component with a solid cell structure; wherein, the cell cavity of the solid cell structure is filled with a dilatant material, and the polymer matrix constituting the dilatant component has dilatancy. Using a dilatant polymer as the matrix and filling the cell core with a dilatant material for the solid cell structure can better combine various dilatant components to obtain a synergistic dilatancy, and thus provide better anti-impact and energy absorption performance.

[0086] (6) The present invention also provides a dilatant electronic product protective cover / case, which contains at least one dilatant component with a hollow cell structure; wherein, there is no filler other than gas in the cell sac of the hollow cell structure, and the polymer matrix constituting the dilatant component has dilatancy. The dilatant component with a hollow cell structure uses a dilatant polymer as the matrix, and can achieve a sensitive and rapid dilatant process when the electronic product is subjected to force, especially severe impact, so as to perform timely anti-impact buffering. There is no filler at the cell core of the cell structure, so that the protective cover / case containing the dilatant component has good compression resilience. The synergistic effect of the hysteresis caused and the dilatancy of the polymer matrix of the component can significantly enhance the anti-impact energy absorption effect, and obtain a more excellent anti-impact energy absorption effect than the solid structure. The said hollow cell structure helps to reduce the density of the dilatant component, and is convenient for obtaining a lightweight electronic product protective cover / case.

[0087] (7) The present invention also provides a dilatant electronic product protective cover / case, which contains at least one dilatant component with a hollow cell structure; wherein, the cell sac of the hollow cell structure is filled with a non-dilatant material, and the polymer matrix constituting the dilatant component has dilatancy. The cell core of the hollow cell structure in the dilatant component does not have dilatancy, but the polymer matrix of the dilatant component has dilatancy, so that the electronic product protective cover / case containing this dilatant component can always maintain consistent slow resilience and anti-impact properties, can improve the holding feeling of the protective cover / case, and the hollow cell structure can improve the compression resilience of the dilatant component. The synergistic effect of the hysteresis caused and the dilatancy results in a doubling of the energy absorption effect, and obtains a more excellent energy absorption effect than the solid structure. The cell core of the dilatant component is filled with a non-dilatant material, which can further enrich and expand other use properties of the electronic product protective cover / case. Through the selection and combination of the polymer matrix and the material in the cell sac, dilatant components and electronic product protective covers / cases with various properties can be designed and obtained.

[0088] (8) The present invention also provides a dilatant electronic product protective cover / case, which contains at least one dilatant component with a hollow cell structure; wherein, the cell sac of the hollow cell structure is filled with a dilatant material, and the polymer matrix constituting the dilatant component has dilatancy. Both the cell core of the hollow cell structure in the dilatant component and the polymer matrix of the component have dilatancy, which is convenient for regulating the dilatancy of the component in a larger range, realizing cooperative dilatancy and thereby enhancing the anti-impact energy absorption. The hollow cell structure can improve the compression resilience of the dilatant component. The synergistic effect of the hysteresis caused and the dilatancy results in a doubling of the energy absorption effect, and obtains a more excellent energy absorption effect than the solid structure.

[0089] (9) The present invention also provides a dilatant electronic product protective cover / case, which contains at least one dilatant component. The dilatant component contains at least two of a vitrifying dilatant polymer component, a dynamic dilatant polymer component, a tangling dilatant polymer component, a dispersive dispersion composition, and a pneumatic dilatant structure, so as to obtain at least two types of dilatancy. By physically mixing various dilatant components, compositions, and structures, or chemically hybridizing various dilatant mechanisms, or simultaneously using physical mixing and chemical hybridization, dilatancy formation factors with different mechanisms and dilatant mixtures with different compositions are introduced into the dilatant component, which can endow it with richer and synergistic dilatant properties, and can also regulate the slow resilience of the dilatant component, thereby endowing the electronic product protective cover / case containing the dilatant component with more excellent impact resistance and energy absorption performance and other comprehensive usage performances, and can greatly broaden the usage scope and application environment of the prepared electronic product protective cover / case.

[0090] (10) The present invention also provides a dilatant electronic product protective cover / case, which contains at least a dilatant component and has force responsiveness. By introducing force-sensitive components / groups with force-responsive effects such as force-induced color change, force-induced fluorescence / phosphorescence change, force-induced luminescence, and force-induced catalytic luminescence into the components of the electronic product protective cover / case, in addition to directly sensing stress and warning of damage to the electronic product protective cover / case, it can also enhance the usage experience and visual enjoyment of the electronic product protective cover / case based on its visual force-responsive effects. For example, by applying mechanical forces such as pressing, scratching / friction to the protective cover / case, functions such as color change, luminescence, and patterning of the protective cover / case can be achieved. By introducing force-sensitive components / groups with force-responsive effects such as force-induced free radical-initiated polymerization, force-induced grafting, force-induced self-repair, force-induced crosslinking, force-induced catalytic crosslinking, and force-induced strengthening into the components, the electronic product protective cover / case can maintain flexibility, texture, and touch under low mechanical forces, while when the electronic product drops / slips or is subjected to mechanical forces such as impact, extrusion, and collision, the force-sensitive groups contained therein are activated, rapidly enhancing its strength and rigidity, achieving repair of mechanical damage and enhancing energy absorption and impact resistance performance, and providing more effective energy absorption protection for the electronic product. In particular, when introducing force-sensitive groups into the components, energy can also be absorbed through processes such as bond breaking, bond formation, and dissociation under force, which can provide an additional energy absorption effect, enhance the impact resistance ability, and also facilitate the extension of the service life of the protective cover / case. The combined use of force responsiveness and dilatancy can achieve orthogonal and / or synergistic effects, which can act independently or synergistically, achieving the effect of energy absorption, impact resistance, and intelligence.

[0091] (11) The present invention also provides a dilatant electronic product protective case, which contains at least one dilatant component with a hollow cell structure and at least one non-dilatant component with a simple solid structure. The cell wall of the hollow cell structure does not have dilatancy, and the cell sac is filled with a dilatant material containing an organic borate bond. The organic borate bond has strong dynamics and mild dynamic conditions, and can achieve the dissociation and recombination of dynamic covalent bonds without the need for a catalyst, high temperature, light, or specific pH, reducing the limitations of the use environment, obtaining stable dynamic dilatancy, and having low temperature sensitivity in its dynamic response process, which can greatly improve the low-temperature resistance of the dilatant component, enabling the electronic product protective case to provide effective anti-impact and energy-absorbing protection at lower temperatures. The non-dilatant component can provide better support for the polymer. Combining it with the dilatant component can not only expand the use performance of the material but also synergistically enhance the anti-impact performance of the electronic product protective case.

[0092] (12) The present invention also provides a dilatant electronic product protective case, which contains at least one dilatant component with a hollow cell structure and at least one non-dilatant component with a simple solid structure. The polymer matrix of the dilatant component does not have dilatancy, the cell wall of the hollow cell structure does not have dilatancy, and the cell sac is filled with a dilatant polymer material based on an inorganic borate bond. The polymer main chain contains a carbon chain structure or a carbon hetero-chain structure. The dilatant polymer material is filled in the capsule, and its main chain structure is easy to regulate and introduce and has strong dynamics, facilitating the regulation of the dilatancy of the dilatant component, enabling it to exhibit rich and adjustable dilatant characteristics. The non-dilatant component can provide better support for the polymer. Combining it with the dilatant component can not only expand the use performance of the material but also enhance the anti-impact energy absorption of the electronic product protective case.

[0093] (13) The present invention also provides a dilatant electronic product protective case, which contains at least one dilatant component with a hollow cell structure and a non-dilatant component with a simple solid structure. The cell wall of the hollow cell structure does not have dilatancy, and the cell sac is filled with a dilatant material containing at least two different dynamic covalent bonds and / or non-covalent interactions. The cell sac of the dilatant component with the hollow cell structure is filled with an intrinsic dilatant polymer material, which can make full use of the difference in the dynamics of the contained dynamic covalent bonds and non-covalent interactions, enabling the dilatant component to exhibit an orthogonal and synergistic dynamic dilatant effect.

[0094] (14) In the present invention, the dilatancy of the dilatancy component includes but is not limited to dynamic dilatancy, vitreous dilatancy, entanglement dilatancy, dispersive dilatancy, pneumatic dilatancy, and their physical mixing forms, chemical hybridization forms, and combinations of the two forms. The dilatancy mechanisms have their respective performance characteristics and can meet the needs of different application scenarios. For example, vitreous dilatancy is highly sensitive to temperature, showing good temperature responsiveness and reliability, but is also greatly affected by temperature. Dynamic dilatancy is less sensitive to temperature than vitreous dilatancy, and has the characteristics of fast dynamic transition speed, which can broaden the dilatancy temperature range of the polymer, avoid the problem of sharp decline in dilatancy at low temperature and the problem of the material becoming hard and brittle and lacking flexibility at low temperature; it is far more effective than using vitreous dilatancy alone and is also difficult to achieve by adjusting the glass transition temperature of vitreous dilatancy, and the achieved effect is even unexpected. Pneumatic dilatancy can control the strength of dilatancy by means of the pore structure of dilatant foam / slow rebound foam. Through the design of a special open-cell pore structure, the dilatant foam / slow rebound foam can obtain certain dilatancy characteristics under energy impact, improving the energy absorption and protection performance of the foam. Pneumatic dilatancy is not sensitive to temperature, facilitating the maintenance of relatively stable dilatancy performance within a wide temperature range, and this partially open-cell pore structure can reduce the shrinkage rate of the foam after cooling, improving the shape stability of the dilatant foam. The structure and properties of the solid microparticles and dispersion liquid required for dispersive dilatancy are rich. By appropriately combining and using the dispersion liquid of solid microparticles, more diverse dilatancy performances can be obtained. In addition, because the dispersion liquid of inorganic particles also has the characteristic of good puncture resistance, it is convenient to obtain more excellent comprehensive performance while obtaining dilatancy. When used as an electronic product protective cover / case, in addition to providing better energy absorption and protection performance, it can also prevent the electronic product from being broken and damaged by collisions and sharp objects (such as knives, gunshots, etc.).

[0095] (15) Introduce dynamic covalent bonds and / or non-covalent interactions / supramolecular interactions into the dilatant component described in the present invention. Based on its dynamics, in addition to regulating the dynamic dilatant properties, it can also provide good stimulus responsiveness and dynamic reversibility for the dilatant component, thereby obtaining plasticity, self-repairability, reprocessability and recyclability, facilitating the repair of structural damages such as cracks and scratches in the electronic product protective cover / case, as well as reprocessing and recycling the electronic product protective cover / case, thereby extending the service life, improving the resource utilization rate, and reducing environmental pollution, etc. These special properties all reflect the creativity and novelty of the present invention. In particular, introducing weak dynamic covalent bonds and / or non-covalent interactions / supramolecular interactions into the dilatant component, reasonably designing and regulating the crosslinked structure, can also endow the protective cover / case with shape memory function, facilitating the fitting and disassembly of the electronic product, and under the impact of external energy, the weak dynamic covalent bonds and non-covalent interactions / supramolecular interactions therein can also act as sacrificial bonds to absorb the impact energy and provide more effective energy absorption and impact resistance for the electronic product; introducing strong dynamic covalent bonds and / or non-covalent interactions / supramolecular interactions into the dilatant component to obtain dynamic dilatancy, providing more effective energy absorption and protection for the electronic product, as well as improving the toughness and tear resistance of the electronic product protective cover / case, effectively reducing the internal defects of the material caused by internal stress, and obtaining an electronic product protective cover / case with better performance; introducing at least one weak dynamic covalent unit and at least one strong dynamic covalent unit into the dilatant component can obtain richer dynamics and dynamic dilatancy, providing better energy absorption and protection performance and other service performances. When the dilatant component undergoes dynamic crosslinking or hybrid dynamic crosslinking with various dynamic covalent bonds and / or non-covalent interactions / supramolecular interactions, based on the stimulus responsiveness and dynamic reversibility of the dynamic crosslinked structure, it can dissociate and reorganize the local crosslinked structure of the electronic product protective cover / case under the action of specific stimuli, causing its local mechanical strength and modulus to decrease, obtaining a gradient of mechanical property differences, realizing the local softening of the electronic product protective cover / case, facilitating the fitting and disassembly of the protective cover / case, improving the user experience, and also facilitating better design and control of the three-dimensional dimensions of the protective cover / case while maintaining a tight fit, achieving the expected energy absorption and impact resistance performance.

[0096] (16) The dilatant component in the present invention itself has a rich structure, as well as good designability and controllability. The present invention can reasonably design, select and combine the polymer matrix type / polymer matrix structure, dilatant components, components and structures in the dilatant component, and reasonably design and control the macroscopic structure of the dilatant component, so as to prepare dilatant components with different structures, shapes and adjustable properties. For example, by controlling the internal structure of the dilatant component, it can be designed into a simple solid structure to endow the component with good strength and modulus, or it can contain a hollow structure inside, so as to prepare a dilatant component with light weight, good compressibility and good shock absorption and buffering performance. It can also contain a cellular structure inside, and by reasonably selecting the type and content of the cell core, the dilatant component has good slow rebound performance and shock absorption and buffering performance, and absorbs a large amount of impact energy during use; in addition, by selecting different polymer matrices and different polymer structures, dilatant components with different chemical compositions, topological structures, glass transition temperatures and mechanical properties can be obtained, so that the electronic product protective cover / case made of the dilatant component and the electronic product protective cover / case containing the dilatant component can have stronger designability and controllability in performance, and obtain an electronic product protective cover / case with excellent impact resistance and other service performances, which is far from being achieved by the existing electronic product protective covers / cases. This also reflects that the dilatant electronic product protective cover / case in the present invention improves and solves the current situation that the design and development of the existing electronic product protective covers / cases only stay on the appearance design from multiple dimensions such as the internal structure of its materials, macroscopic structure and the appearance structure of the protective cover / case.

[0097] (17) The dilatant electronic product protective cover / case in the present invention can be prepared only from one or more dilatant components, or the dilatant components can be compounded in non-dilatant components in the form of lining, sandwich, etc. by means of adhesion, sewing, nesting, clamping, filling, etc. In addition to making the appearance of the electronic product protective cover / case more diverse, more importantly, it can give full play to the structural and performance characteristics of various component materials themselves, enrich and expand the service performance of the protective cover / case, and can also produce a synergistic effect with the dilatant components, enhancing the comprehensive impact resistance and energy absorption effect of the protective cover / case on the electronic product. All these undoubtedly reflect the novelty and practicality of the present invention.

[0098] These and other features and advantages of the present invention will become apparent with reference to the following description of the embodiments, examples and the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0099] To more clearly illustrate the technical solution of the present invention, the accompanying drawings required for the present invention will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can be obtained based on these drawings without creative efforts.

[0100] Figure 1 It is a schematic structural diagram of a typical mobile phone case / shell of the present invention.

[0101] Figure 2 It is a schematic structural diagram of a typical tablet computer case / shell of the present invention.

[0102] Figure 3 It is a schematic structural diagram of another typical mobile phone case / shell of the present invention.

[0103] Figure 4 It is a schematic structural diagram of another typical mobile phone case / shell of the present invention.

[0104] Figure 5 It is a schematic structural diagram of another typical tablet computer case / shell of the present invention.

[0105] Figure 6 It is a schematic structural diagram of another typical mobile phone case / shell of the present invention.

[0106] Figure 7 It is a schematic structural diagram of another typical mobile phone case / shell of the present invention.

[0107] Figure 8 It is a schematic structural diagram of another typical mobile phone case / shell of the present invention.

[0108] Figure 9 It is a schematic cross-sectional structural diagram of another typical electronic product case / shell of the present invention; wherein, a is a dilatant outer shell and b is a dilatant inner lining.

[0109] Figure 10 It is a schematic structural diagram of another typical mobile phone case / shell of the present invention; wherein, a is a hard plastic shell and b is a dilatant inner lining.

[0110] Figure 11 It is a schematic structural diagram of another typical mobile phone case / shell of the present invention, Figure 12 It is its schematic cross-sectional structural diagram; wherein, a is a hard plastic shell and b is a dilatant inner lining.

[0111] Figure 13 It is a schematic structural diagram of another typical mobile phone case / shell of the present invention, Figure 14It is a schematic diagram of its decomposition structure; wherein, a is a hard plastic shell, and b is a dilatant lining.

[0112] Figure 15 It is a schematic cross-sectional structure diagram of another typical electronic product protective cover / case of the present invention; wherein, a is a hard plastic outer shell, and b is a dilatant inner shell.

[0113] Figure 16 It is a schematic cross-sectional structure diagram of another typical electronic product protective cover / case of the present invention; wherein, a is a hard plastic outer shell, and b is a dilatant inner shell.

[0114] Figure 17 It is a schematic cross-sectional structure diagram of another typical electronic product protective cover / case of the present invention; wherein, a is an elastomer outer shell, and b is a dilatant inner shell.

[0115] Figure 18 It is a schematic structure diagram of another typical mobile phone protective cover / case of the present invention; wherein, a is a dilatant shell, and b is a flannelette lining.

[0116] Figure 19 It is a schematic cross-sectional structure diagram of another typical electronic product protective cover / case of the present invention; wherein, a is a dilatant shell, and b is a fur component.

[0117] Figure 20 It is a schematic structure diagram of another typical mobile phone protective cover / case of the present invention, Figure 21 It is a schematic cross-sectional structure diagram thereof; wherein, a is a bamboo and wood shell, and b is a dilatant lining.

[0118] Figure 22 It is a schematic cross-sectional structure diagram of another typical electronic product protective cover / case of the present invention; wherein, a is a dilatant shell, and b is a non-dilatant wrapping layer.

[0119] Figure 23 It is a schematic structure diagram of another typical mobile phone protective cover / case of the present invention; wherein, a is a dilatant shell, and b is a metal buckle component.

[0120] Figure 24 It is a schematic structure diagram of another typical mobile phone protective cover / case of the present invention, Figure 25 It is a schematic diagram of its decomposition structure; wherein, a is a ceramic shell, and b is a dilatant lining.

[0121] Figure 26 It is a schematic structure diagram of another typical mobile phone protective cover / case of the present invention; wherein, a is a dilatant fixed sleeve shell, b is an upper cover plate, and c is a connecting piece.

[0122] Figure 27 It is a schematic structure diagram of another typical tablet computer protective cover / case of the present invention,Figure 28 is a side view thereof, Figure 29 is a schematic structural view in an inclined standing state; wherein, a is a dilatant fixing sleeve, b is an upper cover plate, c is a lower cover plate, and d is a connecting member.

[0123] Figure 30 is a schematic structural view of another typical electronic product protective case / shell of the present invention, Figure 31 is a side view thereof; wherein, a is a non-dilatant wrapping layer, b is a dilatant inner layer, and c is an elastic band.

[0124] Figure 32 is a schematic structural view of another typical mobile phone protective case / shell of the present invention; wherein, a is a dilatant fixing sleeve, b is an upper cover plate, c is a lower cover plate, and d is a connecting member. Specific Embodiments

[0125] Some terms and nouns involved in the present invention are described and defined below.

[0126] In the present invention, the term "polymerization" reaction / action, unless otherwise specified, refers to the process in which reactants with lower molecular weights form products with higher molecular weights through polycondensation, addition polymerization, ring-opening polymerization and other reaction forms, that is, the chain growth process / action other than crosslinking. Among them, the reactants can be monomers, oligomers, prepolymers and other compounds with polymerization ability (that is, capable of spontaneously polymerizing or polymerizing under the action of an initiator or external energy). The product obtained by polymerizing one reactant is called a homopolymer. It should be noted that the "polymerization" described in the present invention includes the linear growth process, branching process, ring-forming process, etc. of the reactant molecular chains other than the crosslinking process of the reactant molecular chains. In the embodiments of the present invention, "polymerization" includes the chain growth process caused by the bonding of force-sensitive groups, dynamic covalent bonds and ordinary covalent bonds and non-covalent interactions / supramolecular interactions.

[0127] As used herein, the term "crosslinking" reaction / action refers to the process of forming a three-dimensional infinite network-type product through intermolecular and / or intramolecular covalent bonds and / or non-covalent interactions. During the crosslinking process, polymer chains generally first grow continuously in two-dimensional / three-dimensional directions, gradually forming clusters (which can be two-dimensional or three-dimensional), and then developing into a three-dimensional infinite network. Crosslinking can be regarded as a special form of polymerization. During the crosslinking process, when a three-dimensional infinite network is just reached. Therefore, the degree of crosslinking, called the gel point, is also called the percolation threshold. The crosslinked product above the gel point (including, the same below) has a three-dimensional infinite network structure, and the crosslinked network forms a whole and spans the entire polymer structure; the crosslinked product below the gel point is only a loose inter-chain linking structure and does not form a three-dimensional infinite network structure, and does not belong to a crosslinked network that can form a whole and span 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 refers to linear, cyclic, branched, and two-dimensional and three-dimensional clusters below the gel point and the "combined form" structure of the above structures.

[0128] In the present invention, the "linear" structure refers to that the polymer molecular chain presents a regular or irregular long-chain linear shape, generally formed by connecting many repeating units in a continuous length, and the side groups in the polymer molecular chain generally do not exist as branched chains; for the "linear structure", it is generally polymerized from monomers without long-chain side groups through polycondensation reaction, addition polymerization reaction or ring-opening reaction, etc.

[0129] In the present invention, the "cyclic" structure refers to that the polymer molecular chain exists in the form of a cyclic chain, which includes cyclic structures in the forms of monocyclic, polycyclic, bridged cyclic, nested cyclic, catenane, rotaxane, etc.; for the "cyclic structure", it can be formed by intramolecular and / or intermolecular cyclization of linear or branched polymers, or can be prepared by methods such as ring-expansion polymerization reaction.

[0130] In the present invention, the "branched" structure refers to a structure containing side chains, branched chains, and bifurcated chains on the polymer molecular chain, including but not limited to star-shaped, H-shaped, comb-shaped, dendritic, hyperbranched, and their combined structures, as well as further combinations with linear and cyclic structures, such as a linear chain end connected to a cyclic structure, a cyclic structure combined with a comb-shaped structure, a dendritic chain end connected to a cyclic chain, and so on; for the "structures such as side chains, branched chains, and bifurcated chains of the polymer", they can have a multi-level structure. For example, on the branched chain of the polymer molecular chain, there can be one or more levels of branched chains. For the "branched structure", there are many preparation methods, which are generally well-known to those skilled in the art. For example, it can be formed by polycondensation reaction of monomers containing long-chain side groups, or formed by chain transfer reaction of free radicals during addition polymerization, or formed by extending branched structures on the linear molecular chain through radiation and chemical reactions. Further intramolecular and / or intermolecular reactions (crosslinking) of the branched structure can generate cluster and crosslinked structures.

[0131] In the present invention, the "cluster" structure refers to a two-dimensional / three-dimensional structure below the gel point generated by intramolecular and / or intermolecular reactions of polymer chains.

[0132] In the present invention, the "crosslinked" structure specifically refers to a three-dimensional infinite network structure possessed by the polymer.

[0133] In the present invention, the "combined form" structure specifically refers to a polymer structure containing two or more of the structures such as linear, cyclic, branched, and two-dimensional and three-dimensional clusters below the gel point. For example, using a cyclic chain as the side chain of a comb-shaped chain, the cyclic chain with side chains forms a cyclic comb-shaped chain, the cyclic chain and the straight chain form a tadpole-shaped chain and a dumbbell-shaped chain, and it also includes combined structures of different cyclic, different branched, different clusters, and their combinations with other topological structures, and so on.

[0134] In the present invention, the "skeleton" refers to the structure in the chain length direction of the polymer chain. Unless otherwise specified, it refers to the chain with the most repeating units. Among them, the "side chain" refers to the chain structure connected to the polymer main chain and distributed beside the main chain; among them, the "branched chain" / "forked chain" can be a side chain or other chain structures branched from any chain. Among them, the "side group" refers to the chemical group connected to any polymer chain and distributed beside the chain. Among them, the "end group" refers to the chemical group connected to any polymer chain and located at the end of the chain. Unless otherwise specified, the side group specifically refers to the group with a molecular weight not exceeding 1000 Da and its subgroups connected beside the polymer chain skeleton. When the molecular weight of the side chain or forked chain does not exceed 1000 Da, it and the groups thereon are regarded as side groups. For simplicity, when the molecular weight of the side chain or forked chain exceeds 1000 Da, unless otherwise specified, they are uniformly referred to as side chains. The above "side chain" and "side group" can have a multi-level structure, that is, the side chain / side group can continue to carry a side chain / side group, and the side chain / side group of the side chain / side group can continue 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 segments can be regarded as side chains, and the rest can be regarded as the main chain.

[0135] For the sake of simplicity in description, in the specification of the present invention, the conjunction "and / or" is used to indicate that the said term can include three cases: selected from the options before the conjunction "and / or", or selected from the options after the conjunction "and / or", or selected from both the options before and after the conjunction "and / or".

[0136] It should be further noted that in the present invention, for the quantifiers "group", "series", "sub-series", "class", "sub-class", "species" used to describe different structures, the range of "group" is greater than that of "series", the range of "series" is greater than that of "sub-series", the range of "sub-series" is greater than that of "class", the range of "class" is greater than that of "sub-class", and the range of "sub-class" is greater than that of "species". That is, a group can contain many series, a series can contain many sub-series, a sub-series can contain many classes, a class can contain many sub-classes, and a sub-class can contain many species. Even if the force-sensitive groups, dynamic covalent bonds, non-covalent motifs / supramolecular motifs have the same motif structure, differences in their properties may still occur due to differences in linking groups, substituents, isomers, composite structures, etc. In the present invention, unless otherwise specified, structures of force-sensitive groups, dynamic covalent bonds, non-covalent motifs / supramolecular motifs that have the same motif structure but are different due to linking groups, substituents, isomers, composite structures, etc. are generally regarded as different species structures. The present invention can reasonably design, select, and regulate force-sensitive groups, dynamic covalent bonds, non-covalent motifs / supramolecular motifs as needed to obtain optimal performance, which is also an advantage of the present invention. In the present invention, when multiple force-sensitive groups, dynamic covalent bonds, or non-covalent motifs / supramolecular motif structures are required, it is preferred to use different classes of structures, and more preferably different series of structures, in order to better perform orthogonal / synergistic regulation, etc.

[0137] In the present invention, the term "molecular weight" represents the relative molecular mass of a substance. For small molecule compounds, small molecule groups, and some macromolecular compounds and macromolecular groups with a fixed structure, their molecular weights generally have monodispersity, that is, they have a fixed molecular weight; while for oligomers, polymers, oligomer residues, polymer residues and other substances with polydisperse molecular weights, their molecular weights generally refer to the average molecular weight. Among them, small molecule compounds and small molecule groups in the present invention specifically refer to compounds or groups with a molecular weight not exceeding 1000 Da; macromolecular compounds and macromolecular groups specifically refer to compounds or groups with a molecular weight greater than 1000 Da.

[0138] The term "heteroatom" used in the present invention refers to common non-carbon atoms such as nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, silicon atoms, boron atoms, etc.

[0139] In the present invention, the "heteroatom linking group" can be any suitable linking group containing a heteroatom, and it can be selected from any one or any combination of the following: ether group, sulfide group, thioether group, divalent tertiary amine group, trivalent tertiary amine group, divalent silicon group, trivalent silicon group, tetravalent silicon group, divalent phosphorus group, trivalent phosphorus group, divalent boron group, trivalent boron group.

[0140] As used herein, the term "hydrocarbyl" includes aliphatic hydrocarbyl (abbreviated as "aliphatic hydrocarbon group") and aromatic hydrocarbyl (abbreviated as "aryl group"); the hydrocarbyl group may be a saturated hydrocarbyl group or an unsaturated hydrocarbyl group; the topological structure of the hydrocarbyl group may be a straight-chain structure, a branched-chain structure or a cyclic structure; the term "alkyl group" refers to a saturated aliphatic hydrocarbyl group; the term "heterohydrocarbyl group" refers to a hydrocarbyl group formed by replacing some carbon atoms in the hydrocarbyl group with heteroatoms; the term "substituted hydrocarbyl group" refers to a hydrocarbyl group formed by replacing some or all of the hydrogen atoms in the hydrocarbyl group with halogen atoms, heteroatoms or any other suitable substituent. In the present invention, the "hydrocarbyl" mentioned includes any isomeric form of the hydrocarbyl group that exists. For example, the propyl group includes, but is not limited to, n-propyl and isopropyl. In the present invention, the range of the number of carbon atoms in the group is marked in subscript form at the subscript position of C, indicating the range of the number of carbon atoms in the group. For example, C 10 represents "having 10 carbon atoms", and C 1-10 represents "having 1 to 10 carbon atoms". When a group can be selected from C 1-10 hydrocarbyl, it can be selected from any hydrocarbyl group with the number of carbon atoms within the range indicated by the subscript, that is, it can be selected from any one of C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 hydrocarbyl group.

[0141] As used herein, the electronic products refer to electronic products used in daily life, handheld / portable test / detection / analysis instruments or equipment used in scientific research or industrial production, etc. By way of example, the electronic products referred to in the present invention include, but are not limited to: mobile phones, tablet computers, laptop computers, wearable electronic products (such as electronic watches, VR virtual reality hardware), palmtop computers, electronic dictionaries, digital cameras, video cameras, handheld game consoles, projectors, printers, monitors, e-readers, telephones, audio equipment, radios, recording pens, mobile storage disks, barcode scanners, RFID readers / wireless radio frequency identifiers, POS machines, portable pH meters, portable gas detectors, portable air quality detectors, portable multimeters, etc. The electronic products referred to in the present invention are preferably mobile phones, tablet computers, laptop computers, e-readers, and handheld game consoles.

[0142] In the present invention, the dilatant protective cover / case is preferably based on a polymer material, more preferably based on an elastomer material; however, as can be described later in the specification, the present invention is not limited thereto.

[0143] In the present invention, the so-called "ordinary covalent bond" refers to the covalent bond other than the dynamic covalent bond in the traditional sense. It is an interaction formed by sharing electron pairs between atoms and is difficult to break at normal temperatures (generally not higher than 100 °C) and within normal time periods (generally less than 1 day). It includes but is not limited to common carbon-boron bonds, carbon-carbon bonds, carbon-oxygen bonds, carbon-hydrogen bonds, carbon-nitrogen bonds, carbon-sulfur bonds, nitrogen-hydrogen bonds, nitrogen-oxygen bonds, hydrogen-oxygen bonds, nitrogen-nitrogen bonds, etc.

[0144] As used herein, the term "energy absorption" in the present invention refers to the absorption, dissipation, and dispersion of energy generated by physical impacts caused by forms such as impact, vibration, shock, explosion, etc., but does not include the absorption of only heat energy and / or electrical energy, so as to achieve effects such as anti-impact (protection), shock absorption, and buffering.

[0145] In the present invention, the so-called "component", unless otherwise specified, includes both chemical / supramolecular chemical structural components and physically mixed components. The so-called "containing", unless otherwise specified, can either be a chemical structural connection / binding or a physical mixture in a specific manner.

[0146] In the present invention, the so-called "dilatancy", also known as shear thickening, refers to a property in which, under the action of shear force or other mechanical external forces, the viscosity and / or strength and / or hardness of a material increase as the rate of force application increases.

[0147] In the present invention, the dilatancy component has a simple solid structure, a simple hollow structure, or a cellular structure.

[0148] In the present invention, the component with a simple solid structure refers to a component that does not contain a pore structure or a phase separation structure inside. Even if it contains only one (polymer) material, there is no phase separation; when different materials are contained, there is also no phase separation between different materials.

[0149] In the present invention, the component with a simple hollow structure refers to a component that contains a pore structure inside. The pores include but are not limited to closed pore structures, partially closed pore structures, and open pore structures, and their shapes include but are not limited to spherical, ellipsoidal, cubic, cuboid, polyhedral, cylindrical, conical, and concave-angle shapes. Preferred are spherical, ellipsoidal, cubic, cylindrical, and concave-angle shapes, and more preferred are spherical, ellipsoidal, and concave-angle shapes; the pore walls are of a simple solid structure, and there are no other substances except gas inside the pores.

[0150] In the present invention, the components of the cellular structure refer to those containing a pore structure and / or a phase separation structure (including sea-island structure, layered structure, bicontinuous structure, dispersed column structure, woven structure and their combined structures, etc.) inside the components, and containing a filler material inside the pore structure (including between layers, etc.) and / or polymer segments in the phase separation between layers; wherein, the pore walls and / or the phase separation layer walls of the cellular structure are called cell walls, and the cell walls can have a multi-layer structure, and the cell walls can be composed of a polymer material, an inorganic material, or an organic-inorganic hybrid material formed by a polymer material and an inorganic material. Preferably, the cell walls of the cellular structure are composed of a polymer material; the material constituting the cell walls can have dilatancy or no dilatancy; the pore hollow structure and / or the phase separation layer hollow structure of the cellular structure are called cell capsules, and the filler material and / or polymer segments inside the cell capsules of the cellular structure are called cell cores; when the filler material and / or polymer segments (cell cores) in the cell capsules are in a full state, the obtained cellular structure is a solid cellular structure; when the filler material and / or polymer segments (cell cores) in the cell capsules are in an unfilled state, the obtained cellular structure is a hollow cellular structure; when the filler material and / or polymer segments in some cell capsules are in a full state and some are in an unfilled state, the obtained cellular structure is a void hybrid cellular structure. The cellular structure can be generated by the phase separation of different polymer segments in the same polymer chain, or by the phase separation between different polymers and / or other components, or by a processing method. The shapes of the cell capsules include but are not limited to spherical, ellipsoidal, cubic, cuboid, polyhedral, columnar, conical, concave-angle, layered, preferably spherical, ellipsoidal, cubic, columnar, concave-angle, and more preferably spherical, ellipsoidal, concave-angle.

[0151] In the embodiments of the present invention, the dilatancy of the dilatant component includes but is not limited to dynamic dilatancy, vitreous dilatancy, entanglement dilatancy, dispersion dilatancy, pneumatic dilatancy and their physical mixing forms, chemical hybrid forms, and combinations of the two forms.

[0152] In the present invention, the methods for the dilatant component to achieve dilatancy include, but are not limited to, the following: achieving dilatancy through the glass transition of the segments in the structure of the polymer itself, which is called "vitrification dilatancy"; caused by introducing strongly dynamic non-covalent interactions and / or dynamic covalent bonds into the structure of the polymer itself, and the polymer achieves dilatancy through the strong dynamics of the strongly dynamic non-covalent interactions and / or dynamic covalent bonds, which is called "dynamic dilatancy". It should be noted that the so-called dynamic dilatancy also includes the dilatancy formed based on the dynamic covalent bonds / non-covalent interactions between inorganic / organic particles and between them and polymers / small molecules, etc.; composed of a dispersion / dispersion of solid microparticles dispersed in a dispersion medium (which can be selected from liquids, solids, gels, emulsions, creams), and achieving dilatancy through the fluidity of the dispersion / dispersion, which is called "dispersion dilatancy"; achieved by regulating the cell structure (foam) of the cell (pore) structure, the cell (pore) structure of the cell structure (foam) is mainly a closed-cell structure, but its cell structure also contains small-sized open cells. Therefore, when the cell structure (foam) is compressed or backflushed, gas slowly escapes or enters, and thus exhibits dilatant characteristics, which is called "pneumatic dilatancy"; achieving dilatancy by utilizing the entanglement of molecular chains, resulting in the inability of polymer chains to move in time under shear action, which is called "entanglement dilatancy".

[0153] In the present invention, the physical mixing form of dilatancy refers to different intrinsic dilatant polymers and / or different non-dilatant polymers and / or different dispersion dilatant compositions being physically blended together to jointly achieve the dilatancy of the component matrix, and the components in the system are independent of each other. In the present invention, the chemical hybridization form of dilatancy refers to different dilatant structures (mainly vitrification dilatant structures and dynamic dilatant structures) existing simultaneously in the same polymer chain or the same polymer network and being connected to each other in a chemical manner (including covalent bonds, ionic bonds, metal bonds, supramolecular interactions, etc.).

[0154] In the embodiments of the present invention, vitrification dilatancy, dynamic dilatancy, and entanglement dilatancy are intrinsic properties caused by the chemical / supramolecular chemical structure of the polymer. A polymer having at least one of these dilatancies is an intrinsic dilatant polymer, which has dilatancy by itself without the need for filling, dispersion, or mixing, etc., and can be directly used as a polymer matrix to prepare a dilatant component, but it does not exclude being used jointly with dilatant or non-dilatant materials with other mechanisms through chemical hybridization and / or physical mixing.

[0155] In the present invention, an intrinsic dilatant polymer means that the polymer itself has dilatancy and can have dilatancy without the need for methods such as compounding, filling, and dispersion; a non-intrinsic dilatant polymer needs to obtain dilatancy by preparing composite materials, compositions, etc. through methods such as compounding, filling, and dispersion. The intrinsic dilatant polymer (composition) can exhibit creep or slow recovery characteristics under specific conditions, that is, when the polymer is subjected to an external force, deformation will occur; after the external force is removed, the material will not rebound; or will not immediately rebound / recover the deformation, but will slowly rebound / recover the deformation, and there is no residual deformation or only a small amount of residual deformation. In the present invention, through compounding methods such as blending and / or network interpenetration with non-dilatant polymer and / or filler components, the composite (composition) containing the intrinsic dilatant polymer can still have dilatancy, but may not exhibit creep or slow recovery characteristics, or may have lower creep or slow recovery characteristics, or only have high resilience. The polymer composite (composition) containing a dispersion can also have dilatancy, but may not exhibit creep or slow recovery characteristics, or may have lower creep or slow recovery characteristics, or only have high resilience. The polymer (composition) containing pneumatic dilatancy usually has slow resilience.

[0156] In an embodiment of the present invention, when the dilatant component contains two or more types of dilatancy, it includes but is not limited to the following forms: physical mixture of vitreous dilatancy and dynamic dilatancy, physical mixture of vitreous dilatancy and entanglement dilatancy, physical mixture of vitreous dilatancy and dispersive dilatancy, physical combination of vitreous dilatancy and pneumatic dilatancy, physical mixture of vitreous dilatancy, dynamic dilatancy and dispersive dilatancy, physical mixture of vitreous dilatancy, dynamic dilatancy and entanglement dilatancy, physical mixture of vitreous dilatancy and dynamic dilatancy and then combination with pneumatic dilatancy, physical mixture of vitreous dilatancy and dispersive dilatancy and then combination with pneumatic dilatancy, physical mixture of vitreous dilatancy, dynamic dilatancy and dispersive dilatancy and then combination with pneumatic dilatancy, chemical hybridization form with both vitreous dilatancy and dynamic dilatancy on the polymer chain, chemical hybridization form with both vitreous dilatancy and entanglement dilatancy on the polymer chain, chemical hybridization form with vitreous dilatancy, dynamic dilatancy and entanglement dilatancy on the polymer chain, chemical hybridization form with both vitreous dilatancy and dynamic dilatancy on the polymer chain and other forms of mixing / combination.

[0157] In the present invention, the vitreous dilatancy has a high sensitivity to temperature, showing good temperature responsiveness and reliability, but is also greatly affected by temperature. The dynamic dilatancy has a lower sensitivity to temperature than the vitreous dilatancy, and characteristics such as a fast dynamic transition speed can widen the dilatancy temperature range of the polymer, avoiding the problems of a sharp drop in dilatancy at low temperatures and the lack of flexibility due to the hardening and brittleness of the material at low temperatures; it is far more effective than using only the vitreous dilatancy alone, and is also difficult to achieve by adjusting the glass transition temperature of the vitreous dilatancy, and the achieved effect is even unexpected. The pneumatic dilatancy can control the strength of the dilatancy by means of the pore structure of the dilatant foam / slow rebound foam. Through the design of a special open-cell pore structure, the dilatant foam / slow rebound foam can obtain certain dilatancy characteristics under energy impact, improving the energy absorption and protection performance of the foam. The pneumatic dilatancy has the characteristic of being insensitive to temperature, facilitating the maintenance of relatively stable dilatancy performance within a wide temperature range, and this locally open-cell pore structure can reduce the shrinkage rate after the foam cools, improving the shape stability of the dilatant foam. The dispersive dilatancy requires a rich structure and performance of solid microparticles and dispersions. By appropriately combining the dispersions of solid microparticles, more diverse dilatancy performances can be obtained. In addition, because the dispersion of inorganic particles also has the characteristic of good puncture resistance, it is convenient to obtain more excellent comprehensive performance while obtaining dilatancy. When used as an electronic product protective cover / case, in addition to providing better energy absorption and protection performance, it can also prevent the electronic product from being cracked and damaged by collisions and sharp objects (such as knives, gunshots, etc.).

[0158] In the present invention, by reasonably combining and using multiple dilatant forming factors, richer dilatant properties and other comprehensive properties can be obtained. For example, a dilatant material with multiple dilatant properties, good low-temperature dilatant properties / low-temperature resistance, and good mechanical properties and structural support properties at high temperatures can be obtained. The combination of two or more dilatant properties has richer performance characteristics compared to only containing a single dilatant property. For example, the mixture of vitreous dilatancy and dynamic dilatancy can broaden the dilatant temperature range of the dilatant material. Among them, the temperature sensitivity of dynamic dilatancy is relatively low, which can avoid the problem of a sharp drop in dilatancy at low temperatures; the physical mixture of vitreous dilatancy and dispersive dilatancy can make the dilatant material more sensitive to temperature, showing better temperature responsiveness and reliability. Introducing the composition of dispersive dilatancy can also endow the material with functions of preventing spiking and cutting, enhancing the practicality of the material; the physical combination of vitreous dilatancy and pneumatic dilatancy is convenient for maintaining relatively stable dilatant properties within a relatively wide temperature range, and also helps the forming stability of dilatant polymer foams, avoiding the shrinkage of the foam from affecting the dimensional stability of the material; the physical mixture of vitreous dilatancy, dynamic dilatancy and dispersive dilatancy can broaden the dilatant temperature range of the dilatant material. Among them, the temperature sensitivity of dynamic dilatancy is relatively low, which can avoid the problem of a sharp drop in dilatancy at low temperatures. Introducing the composition of dispersive dilatancy can also endow the material with functions of preventing spiking and cutting, enhancing the practicality of the material; the combination of the physical mixture of vitreous dilatancy and dynamic dilatancy and pneumatic dilatancy enables the dilatant material to effectively absorb energy within a relatively wide temperature range. Especially at low temperatures, it can still maintain good energy absorption performance, and the existence of the pneumatic dilatancy structure can improve the forming stability of the foam; the combination of the physical mixture of vitreous dilatancy and dispersive dilatancy and pneumatic dilatancy can prevent the dilatancy of the dilatant material from dropping sharply at low temperatures. The existence of the pneumatic dilatancy structure can also improve the forming stability of the foam. Introducing the composition of dispersive dilatancy can also endow the material with functions of preventing spiking and cutting; the combination of the physical mixture of vitreous dilatancy, dynamic dilatancy and dispersive dilatancy and pneumatic dilatancy can give full play to the performance characteristics of various dilatancies, obtaining better dilatant properties, especially the dilatancy at low temperatures. At the same time, the existence of the pneumatic dilatancy structure can also improve the forming stability of the foam. Introducing the composition of dispersive dilatancy can also endow the material with functions of preventing spiking and cutting. These are undoubtedly not possessed by traditional polymers, which all reflect the novelty and creativity of the method for realizing polymer dilatancy in the present invention.

[0159] In the present invention, for the dilatant component, when its form is an elastomer, gel or fluid, preferably its ball rebound rate is less than 80%, more preferably the rebound rate is less than 50%, further preferably less than 25%, and even more preferably less than 10%, where the test method is ASTM D-2632 "Rubber Property-Resiliency by Vertical Rebound" (ASTM D-2632, "Rubber property - vertical rebound"); when its form is foam, preferably its ball rebound rate is less than 25%, more preferably the rebound rate is less than 10%, even more preferably less than 5%, and even more preferably less than 1%, where the test method is ASTM D-3574H "Flexible Cellular Materials-Slab, Bonded and Molded Urethane Foams, Test H, Resilience (Ball Rebound) Test" (ASTM D-3574H, "Flexible porous materials - slab, bonded and molded polyurethane foams, test H, rebound (ball rebound) test").

[0160] In the present invention, the ball rebound rate refers to the ratio of the rebound height of a steel ball with a specified mass and shape when it falls onto the surface of the specimen to the falling height. That is, a steel ball with a specified mass and shape falls from a fixed height onto the surface of the specimen, the rebound height of the steel ball is measured, and the percentage of the ratio of the rebound height (denoted as h) to the falling height (denoted as H) is the rebound rate of the specimen (denoted as R), which can be calculated by the following formula:

[0161] Rebound rate R = h / H * 100%;

[0162] where h is the rebound height, with the unit of millimeter (mm);

[0163] where H is the falling height, with the unit of millimeter (mm).

[0164] In the present invention, for the dilatant component with slow resilience, its resilience time under normal temperature and pressure is not particularly limited. For the intrinsic polymer with slow resilience, the resilience time is preferably from 0.5 second to 120 seconds, more preferably from 1 second to 60 seconds, and still more preferably from 1 second to 10 seconds. For the composite type with slow resilience, the resilience time is preferably from 0.1 second to 120 seconds, more preferably from 0.2 second to 60 seconds, and still more preferably from 0.5 second to 10 seconds. Herein, the resilience time refers to the time required for the sample to basically recover after applying pressure to the sample to cause a specified deformation, maintaining for a specified time. When the polymer morphology is an elastomer or a gel, the time required for the sample to recover to the position with 3% deformation of the initial thickness after maintaining 60 seconds when pressing into the sample by 40% of the initial thickness under pressure is recorded as its slow resilience time; when the polymer morphology is a foam, the time required for the sample to recover to the position with 5% deformation of the initial thickness after maintaining 60 seconds when pressing into the sample by 75% of the initial thickness under pressure is recorded as its slow resilience time.

[0165] In the present invention, the vitreous dilatant polymer has at least one or more glass transition temperatures, and preferably at least one glass transition temperature of its soft segment or the segment between crosslinking points is in the range of -40°C to 60°C. In the present invention, having the glass transition temperature is one of the necessary conditions for the polymer in the present invention to have vitreous dilatancy, that is, the vitreous dilatancy at least utilizes the glass transition of the polymer, especially the glass transition of the structure of its soft segment or the segment between crosslinking points. The glass transition temperature refers to the transition temperature at which the polymer changes from a brittle glassy state to an elastic rubbery state, that is, the temperature at which the glass transition occurs, which can be a temperature point or a temperature range (also called the glass transition region). When the polymer temperature drops and is lower than its glass transition temperature, the molecular chains and segments of the polymer are frozen, showing brittleness; as the polymer temperature rises and exceeds its Tg, the molecular chains and segments of the polymer can move, showing viscous flow or the high elasticity of the rubbery state; near the glass transition temperature, the polymer segments in the polymer are in a freeze-thaw state, the segments can move but the molecular chain movement is restricted, showing good viscoelasticity, and thus obtaining dilatant properties. When the glass transition temperature of the polymer is near room temperature, the polymer can show room temperature vitreous dilatant properties; when its glass transition temperature is near other temperatures, vitreous dilatancy can be achieved within other temperature ranges.

[0166] In the present invention, the glass transition temperature (Tg) of the polymer can be measured by those skilled in the art through well-known testing methods. By way of example, it can be measured at least by differential scanning calorimetry (DSC), dynamic mechanical analysis / dynamic mechanical analysis (DMA), dynamic mechanical thermal analysis / dynamic mechanical thermal analysis (DMTA), and other commonly used methods for measuring the glass transition temperature in the art.

[0167] In the present invention, there is no particular limitation on the temperature range (temperature span) of any of the glass transition temperatures in the vitreous dilatant polymer, but it depends on its service temperature range. When there is only one glass transition temperature and the range is wide, or there are multiple glass transition temperatures and the combined temperature range is wide, the polymer can achieve the dilatant process within a wide temperature range, and thus obtain a wide dilatant service temperature range, and can also to a certain extent avoid the problem of the polymer hardening caused by temperature reduction (i.e., the low-temperature hardening problem); when the glass transition temperature range is narrow, the dilatant temperature range of the polymer is narrow, and the temperature controllability of the dilatant process is better and the temperature dependence is higher.

[0168] In the present invention, vitreous dilatancy can be obtained by introducing a vitreous dilatant polymer component into the polymer, wherein the vitreous dilatant polymer component refers to a polymer segment (including oligomer segments, the same below) having at least one glass transition temperature, preferably a polymer segment having at least one glass transition temperature in the range of -40°C to 60°C, and the polymer segment can be the soft segment or the segment between crosslinking points of the dilatant polymer. In the present invention, the vitreous dilatant polymer component can be chemically linked to the polymer chain of the dilatant polymer crosslinked network to become the connecting segment of the crosslinked network, or can be dispersed in the crosslinked network in the form of physical blending, and preferably introduced into the polymer chain of the crosslinked network in a chemical linking form to obtain a more reliable and stable dilatant process.

[0169] In a preferred embodiment of the present invention, the soft segment and / or the segment between crosslinking points of the vitreous dilatant polymer has only one glass transition temperature, and the glass transition temperature is in the range of -40°C to 60°C; preferably in the range of -10°C to 40°C. In this embodiment, the soft segment and / or the segment between crosslinking points of the polymer has only one glass transition temperature. When it has a narrow glass transition temperature span, the vitreous dilatancy / slow rebound process has a more significant temperature dependence and responsiveness, that is, it can exhibit viscoelasticity within a narrow temperature range; when it has a wide glass transition temperature span, the temperature dependence of its dilatancy / slow rebound process is lower, and it can adapt to a wider application temperature.

[0170] In another preferred embodiment of the present invention, the soft segments and / or the segments between crosslinking points of the vitreous dilatant polymer have at least two glass transition temperatures, one of which is in the range of -60°C to 0°C, preferably in the range of -40°C to 0°C; the other glass transition temperature is in the range of 0°C to 80°C, preferably in the range of 0°C to 40°C; preferably, the two glass transition temperatures overlap. In this embodiment, through the combination of different soft segment glass transition temperatures, the polymer has a relatively wide vitreous dilatancy / slow rebound temperature range, enabling the polymer material to have a very wide vitreous dilatancy / slow rebound service temperature. In the embodiments of the present invention, the vitreous dilatant polymer can be prepared at least by mixing soft segments and / or segments between crosslinking points of different compositions and / or mixing soft segments and / or segments between crosslinking points of different molecular weights and / or the action of different soft segments and / or segments between crosslinking points to obtain a wide and continuous plurality of glass transition processes, so as to broaden its service temperature range, such as from the extremely low temperature in polar regions in winter to the high temperature in deserts in summer.

[0171] In another preferred embodiment of the present invention, the soft segments and / or the segments between crosslinking points of the vitreous dilatant polymer have at least two glass transition temperatures, one of which is in the range of -40°C to 60°C, preferably in the range of -10°C to 40°C; the other glass transition temperature is in the range of -100°C to -40°C; preferably in the range of -80°C to -50°C. In this embodiment, through the combination of different soft segment glass transition temperatures, especially those with relatively low glass transition temperatures, the dilatant polymer can have excellent low-temperature dilatancy, effectively avoiding problems such as the hardening of the material and the loss of dilatancy at low temperatures, enabling the dilatant material to still be able to effectively absorb energy at low temperatures or even extremely low temperatures, and better adapting to the application scenarios at low temperatures or even extremely low service temperatures.

[0172] In the present invention, by regulating the chemical composition and topological structure of the polymer soft segments or the segments between crosslinking points, the glass transition temperature of the polymer can be regulated to be close to the service temperature of the dilatant material, so as to obtain the maximum vitreous dilatancy / slow resilience.

[0173] In an embodiment of the present invention, the chemical composition of the soft segment or the segment between crosslinking points of the vitreous dilatant polymer is not particularly limited, but depending on its use temperature range, it is selected from, but not limited to, polymer segments having a main chain of carbon chain structure, carbon hetero-chain structure, element organic chain structure, silicon element organic chain structure, polysiloxane chain structure, preferably carbon chain structure, carbon hetero-chain structure, element hetero-chain structure, silicon element organic chain structure, polysiloxane chain structure, because of the easy availability of raw materials and the mature preparation technology. By way of example, the polymer soft segment or the segment between crosslinking points may be a segment based on the following polymers, but the present invention is not limited thereto: homopolymers, copolymers, modified products, derivatives, etc. of acrylate polymers, saturated olefin polymers, unsaturated olefin polymers, halogen-containing olefin polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, polyether polymers, polyester polymers, biodegradable polyester polymers, epoxy polymers, polysulfide polymers, silicone polymers, etc.; preferably homopolymers, copolymers, modified products, derivatives, etc. of acrylate polymers, unsaturated olefin polymers, polyether polymers, epoxy polymers, polysulfide polymers, polyorganosilicon polymers, etc.By way of example, the polymer soft segments or segments between crosslinking points may be segments based on the following polymers, but the present invention is not limited thereto: polyvinyl methyl ether (Tg = -13 °C), polyvinyl ethyl ether (Tg = -42 °C), polyvinyl propyl ether (Tg = -48 °C), polyvinyl isopropyl ether (Tg = -14 °C), polyvinyl butyl ether (Tg = -53 °C), polyvinyl isobutyl ether (Tg = -13 °C), poly(methyl acrylate) (Tg = 10 °C), poly(ethyl acrylate) (Tg = -23 °C), poly(n-butyl acrylate) (Tg = -54 °C), poly(isobutyl acrylate) (Tg = -4 °C), poly(tert-butyl acrylate) (Tg = 43 °C), poly(2-ethylhexyl acrylate) (Tg = -70 °C), poly(n-octyl acrylate) (Tg = -15 °C), poly(2-hydroxyethyl acrylate) (Tg = -15 °C), poly(2-hydroxypropyl acrylate) (Tg = -7 °C), poly(isopropyl methacrylate) (Tg = 48 °C), poly(butyl methacrylate) (Tg = 20 °C), poly(isobutyl methacrylate) (Tg = 53 °C), poly(hexyl methacrylate) (Tg = -5 °C), poly(2-hydroxyethyl methacrylate) (Tg = 55 °C), poly(2-methoxyethyl acrylate) (Tg = -34 °C), poly(2-methoxyethyl) methacrylate (Tg = 20 °C), poly(2-propoxyethoxy)ethyl acrylate (Tg = -57 °C), poly(2-tetrahydrofuranyl)methyl acrylate (Tg = -13 °C), poly(benzyl acrylate) (Tg = 4 °C), poly(2-phenoxyethyl acrylate) (Tg = 6 °C), poly(2-(phenylthio)ethyl acrylate) (Tg = 12 °C), poly(2-(2-phenoxyethoxy)ethyl acrylate) (Tg = 12 °C), poly(methyl methacrylate) (Tg = 105 °C), poly(ethyl methacrylate) (Tg = 65 °C), poly(2-hydroxypropyl methacrylate) (Tg = 73 °C), poly(cyclohexyl methacrylate) (Tg = 83 °C), poly(isobornyl methacrylate) (Tg = 110 °C), poly(phenyl acrylate) (Tg = 63 °C), poly(vinyl acetate) (Tg = 32 °C), poly(vinyl chloride) (Tg = 78 °C), poly(acrylic acid) (Tg = 105 °C), poly(methacrylic acid) (Tg = 185 °C), polyacrylonitrile (Tg = 96 °C), polyacrylamide (Tg = 165 °C), polystyrene (Tg = 100 °C), polymethylstyrene (Tg = 173 °C), poly(cis-1,4-butadiene) (Tg = 131 °C), polyethylene, ethylene-propylene copolymer, polyisobutylene, polychlorinated polybutadiene, poly(cis-1,4-isoprene), poly(trans-1,4-isoprene), styrene-butadiene copolymer, polynorbornene, polyformaldehyde, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, ethylene oxide-propylene oxide copolymer (such as polyethylene oxide-polypropylene oxide copolymer), polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, hydrogen-containing polysiloxane, etc., including homopolymers, copolymers, modified products, derivatives, etc.Segments with different glass transition temperatures can achieve vitreous dilatancy at different temperatures, so that the corresponding materials can use their vitreous dilatancy in different temperature ranges. Among them, homopolymers, copolymers, modified products, and derivatives of the above-mentioned unsaturated olefin polymers, polyether polymers, silicone polymers, etc. have relatively low glass transition temperatures. Among them, silicone polymers such as homopolymers, copolymers, modified products, and derivatives of polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, and hydrogen-containing polysiloxane have relatively low glass transition temperatures, usually ranging from -130°C to -60°C; unsaturated olefin polymers such as polyisobutene, polybutadiene, polychlorinated polybutadiene, poly-cis-1,4-isoprene, poly-trans-1,4-isoprene, styrene-butadiene copolymer, and butadiene-acrylonitrile copolymer have relatively low glass transition temperatures, usually ranging from -110°C to -10°C.

[0174] In an embodiment of the present invention, the molecular weight of the soft segment or the segment between crosslinking points of the vitreous dilatant polymer is not particularly limited, and it can be a macromolecular chain segment with a molecular weight greater than 1000 Da, or an oligomer or small molecule linking segment with a molecular weight lower than 1000 Da.

[0175] In an embodiment of the present invention, the topological structure of the soft segment or the segment between crosslinking points of the vitreous dilatant polymer is not particularly limited, and it includes but is not limited to linear structures, branched structures (including but not limited to star-shaped, H-shaped, dendritic, comb-shaped, hyperbranched), cyclic structures (including but not limited to monocyclic, polycyclic, bridged cyclic, catenane, rotaxane), two-dimensional / three-dimensional cluster structures, and combinations of two or any several of them; among them, linear structures and branched structures are preferred. Among them, the linear structure has a simple structure, is easy to regulate synthesis and control the structure, and is easy to obtain a single glass transition temperature or a glass transition region with a narrow temperature range, improving the dependence and responsiveness of the vitreous dilatancy / slow rebound performance on the ambient temperature. The branched structure has side chains, branched chains, and bifurcated chains and other structures that are easy to reduce and regulate the glass transition temperature of the polymer, improving the low-temperature dilatancy / slow rebound performance.

[0176] In the present invention, the polymer component with vitreous dilatancy can be chemically linked to the polymer chain of the dilatant polymer crosslinked network, or dispersed in the crosslinked network in a physical blending form. Preferably, it is introduced into the polymer chain of the crosslinked network in a chemical linking form to obtain a more reliable and stable dilatancy process. The polymer component with vitreous dilatancy described in the present invention can be at least the soft segment and / or the segment between crosslinking points of the dilatant polymer.

[0177] In the present invention, the vitreous dilatancy caused by the glass transition of the polymer has a working temperature range that can be adjusted according to the design and selection of appropriate polymer segments or their compositions, making it easy to obtain a dilatant material with a specific working temperature range.

[0178] In an embodiment of the present invention, by reasonably regulating the glass transition temperature of the vitreous dilatant polymer, the dilatant polymer material has stable vitreous dilatancy at a single temperature (narrow temperature range), multiple temperatures, or a wide temperature range, enabling the dilatant polymer material in the present invention to better meet the requirements of the dilatancy performance of the application scenario at different temperatures. For example, a dilatant polymer material with a single glass transition temperature and a small span of the glass transition temperature has a high sensitivity of dilatancy to temperature, showing good temperature responsiveness and reliability; another example is a dilatant polymer material with multiple glass transition temperatures, which can have dilatancy at multiple temperature points / temperature intervals and can better adapt to application scenarios that require use at multiple different temperatures; another example is a dilatant polymer material with a wide span of the glass transition temperature, which can play an effective energy absorption role from the extremely low temperature in polar regions in winter to the high temperature in deserts in summer. In particular, a dilatant polymer material with dilatancy near room temperature can provide dilatancy and slow resilience at room temperature to protect electronic products from impact; a dilatant polymer material with dilatancy at room temperature and low temperature can effectively avoid the problem of the material becoming hard and losing dilatancy at low temperature, enabling the dilatant polymer material to still effectively absorb energy at low temperature and better adapt to application scenarios at low temperature or even extremely low use temperatures; a dilatant polymer material with glass transition temperatures near room temperature and medium to high temperatures respectively can not only maintain stable dilatancy at room temperature but also avoid the problems of reduced material supportability and sharp decline or even complete loss of dilatancy when the temperature rises, improving the practicality and reliability of the dilatant polymer material; a dilatant polymer material with glass transition temperatures at low temperature, room temperature, and medium to high temperatures respectively can achieve dilatancy in a wider temperature range and can better adapt to more stringent application scenarios of dilatant polymer materials.

[0179] In the present invention, the dynamic dilatant polymer refers to a polymer (including oligomer) containing at least one strong dynamic non-covalent interaction and / or strong dynamic dynamic covalent bond, which is achieved through the appropriate dynamic covalent bond / non-covalent interaction contained in the polymer of the present invention.

[0180] In the present invention, the dynamic dilatant polymer may contain only strong dynamic non-covalent interactions, only strong dynamic dynamic covalent bonds, or both strong dynamic non-covalent interactions and strong dynamic dynamic covalent bonds.

[0181] In an embodiment of the present invention, it is preferred that the groups constituting the strong dynamic dynamic units in the dynamic dilatant polymer are located at the end groups, side groups or side chains of the polymer crosslinking network to obtain better dynamicity and dilatancy.

[0182] In an embodiment of the present invention, the dynamic exchange rate of the strong dynamic supramolecular interaction / dynamic covalent bond is preferably in the range of 100000 - 0.0001 s -1 , and according to different performance requirements and usage occasions, if necessary, it can be preferably in the range of 1000 - 0.001 s -1 , it can be preferably in the range of 100 - 0.01 s -1 , it can also be preferably in the range of 10 - 0.1 s -1 . Different exchange rates combined with different polymer structures, such as crosslinking degree, polymer chain topology, crosslinking network topology, glass transition temperature, composite structure, etc., can provide different force response rates and dilatancy, resulting in different viscous-elastic transitions or elastic enhancements, thereby producing different energy absorption effects and rebound responses. The technical solution of the present invention can skillfully and effectively design and regulate the dynamic dilatancy by designing and selecting appropriate dynamic units (i.e., the dynamic covalent bonds and non-covalent interactions described in the present invention) and polymer structures to meet the requirements of different performances in different occasions to the greatest extent.

[0183] In an embodiment of the present invention, typical strong dynamic non-covalent interactions include but are not limited to: monodentate hydrogen bonding, bidentate hydrogen bonding, monodentate metal-ligand interaction, bidentate metal-ligand interaction, ionic interaction, ionic cluster interaction, ion-dipole interaction, host-guest interaction, metallophilic interaction, dipole-dipole interaction, halogen bond interaction, Lewis acid-base pair interaction, cation-π interaction, anion-π interaction, benzene-fluorobenzene interaction, π-π stacking interaction, ionic hydrogen bond interaction, radical cation dimerization; typical strong dynamic dynamic covalent bonds include but are not limited to: boron-containing dynamic covalent bonds, metal acid ester-based dynamic covalent bonds, reversible radical-based dynamic covalent bonds. Among them, monodentate hydrogen bonding, bidentate hydrogen bonding, monodentate metal-ligand interaction, ionic interaction, ionic cluster interaction, ion-dipole interaction, host-guest interaction, Lewis acid-base pair interaction, ionic hydrogen bond interaction, inorganic boric acid monoester bond, saturated five-membered ring inorganic boric acid ester bond, unsaturated five-membered ring inorganic boric acid ester bond, saturated six-membered ring inorganic boric acid ester bond, unsaturated six-membered ring inorganic boric acid ester bond, organic boric acid monoester bond, saturated five-membered ring organic boric acid ester bond, unsaturated five-membered ring organic boric acid ester bond, saturated six-membered ring organic boric acid ester bond, unsaturated six-membered ring organic boric acid ester bond (especially saturated five-membered ring organic boric acid ester bond / unsaturated five-membered ring organic boric acid ester bond / saturated six-membered ring organic boric acid ester bond / unsaturated six-membered ring organic boric acid ester bond connected with aminomethylbenzene group), inorganic boric acid silicate ester bond, organic boric acid silicate ester bond, dynamic titanic acid silicate ester bond are preferred, and monodentate hydrogen bonding, bidentate hydrogen bonding, monodentate metal-ligand interaction, ionic interaction, ion-dipole interaction, host-guest interaction, ionic hydrogen bond interaction, inorganic boric acid monoester bond, organic boric acid monoester bond, saturated five-membered ring organic boric acid ester bond / unsaturated five-membered ring organic boric acid ester bond / saturated six-membered ring organic boric acid ester bond / unsaturated six-membered ring organic boric acid ester bond connected with aminomethylbenzene group, inorganic boric acid silicate ester bond, organic boric acid silicate ester bond, dynamic titanic acid silicate ester bond are more preferred because of their high dynamicity and good controllability.

[0184] In the present invention, the dynamic dilatancy caused by strong dynamic non-covalent interactions and / or dynamic covalent bonds has the characteristics of rich regulation means and fast dynamic transformation speed. In an embodiment of the present invention, by designing and selecting suitable dynamic dilatant polymers, various combined dilatancies containing dynamic dilatancy can also be effectively designed and regulated to obtain excellent comprehensive dilatancy.

[0185] In the present invention, it is most preferred to adopt dynamic dilatancy.

[0186] In the present invention, in the dynamic dilatant polymer, the chemical composition of the soft segment of the polymer or the segment between crosslinking points is not particularly limited, but depending on its service temperature range, it is selected from, but not limited to, polymer segments with a main chain of carbon chain structure, carbon hetero-chain structure, element organic chain structure, silicon element organic chain structure, polysiloxane chain structure, preferably carbon chain structure, carbon hetero-chain structure, element hetero-chain structure, silicon element organic chain structure, polysiloxane chain structure, because the raw materials are easily available and the preparation technology is mature. By way of example, the soft segment of the polymer or the segment between crosslinking points may be a segment based on the following polymers, but the present invention is not limited thereto: homopolymers, copolymers, modified products, derivatives, etc. of acrylate polymers, saturated olefin polymers, unsaturated olefin polymers, halogen-containing olefin polymers, polyacrylonitrile polymers, polyvinyl alcohol polymers, polyether polymers, polyester polymers, biodegradable polyester polymers, epoxy polymers, polysulfide polymers, organosilicon polymers, etc.; preferably homopolymers, copolymers, modified products, derivatives, etc. of acrylate polymers, unsaturated olefin polymers, polyether polymers, epoxy polymers, polysulfide polymers, polyorganosilicon polymers, etc. In an embodiment of the present invention, the soft segment of the dynamic dilatant polymer or the segment between crosslinking points preferably has a low glass transition temperature, preferably not higher than 25 °C, more preferably not higher than 0 °C, more preferably not higher than -40 °C, more preferably not higher than -100 °C, so as to have a wide service temperature range, that is, it can be used at low temperatures (such as in northern regions, the Arctic and Antarctic regions) and high temperatures (such as in southern regions).

[0187] In an embodiment of the present invention, a dynamic dilatant polymer component can be dispersed in a polymer crosslinked network with vitreous dilatancy in a non-crosslinked form to provide dynamic dilatancy for the dilatant polymer; the dynamic dilatant polymer component can also be crosslinked by strong dynamic dynamic covalent bonds and / or strong dynamic non-covalent interactions contained therein to form a polymer crosslinked network with dynamic dilatancy, providing dynamic dilatancy. Preferably, the vitreous dilatant polymer component is crosslinked by strong dynamic dynamic covalent bonds and / or strong dynamic non-covalent interactions to provide dynamic dilatancy; the dynamic dilatant polymer component can also be crosslinked by strong dynamic dynamic covalent bonds and / or strong dynamic non-covalent interactions contained therein to form a polymer crosslinked network with dynamic dilatancy, and then combined with a polymer crosslinked network with vitreous dilatancy in the form of physical dispersion, or interpenetration, or partial interpenetration, etc., to provide dynamic dilatancy. In an embodiment of the present invention, strong dynamic dynamic covalent bonds and / or strong dynamic non-covalent interactions can also be introduced into a polymer crosslinked network with vitreous dilatancy to obtain a dynamic dilatant polymer component, providing dynamic dilatancy. However, the present invention is not limited thereto, that is, as long as the dynamic dilatancy is achieved by containing the dynamic covalent bond / non-covalent interaction, such as chemical hybridization and / or physical mixing of the aforementioned vitreous dilatancy mechanism; the specific implementation method depends on specific performance requirements and material structures, and different implementation methods have their own advantages, which is also the flexibility and expandability of the present invention.

[0188] In the present invention, a entangled dilatant polymer refers to a polymer that can cause the polymer chains to be unable to move in time under shear action due to polymer chain entanglement, and thereby achieve dilatancy. In an embodiment of the present invention, preferably, the glass transition temperature of the molecular chains of the entangled dilatant polymer is not higher than -20 °C, more preferably not higher than -40 °C, more preferably not higher than -60 °C, and more preferably not higher than -100 °C. In an embodiment of the present invention, the molecular weight of the entangled dilatant polymer needs to reach a sufficiently high level to obtain an entanglement effect under shear, preferably not less than 100 kDa, and more preferably not less than 1000 kDa.

[0189] In an embodiment of the present invention, an entangled dilatant polymer component can be dispersed in a polymer crosslinked network with vitreous dilatancy in a non-crosslinked form to provide entangled dilatancy for the dilatant polymer; the entangled dilatant polymer component can also be connected to the crosslinked network in the form of side chains or end chains by covalent bonds or non-covalent interactions to provide entangled dilatancy.

[0190] In the present invention, the thixotropic composition contains at least solid microparticles and a dispersion medium. Among them, the volume fraction of the solid microparticles is preferably not less than 20%, more preferably not less than 30%, and even more preferably not less than 40%.

[0191] Among them, the solid microparticles include two categories: nanoparticles and microparticles. By way of example, the former includes but is not limited to nano-silica, nano-alumina, nano-montmorillonite, nano-calcium carbonate, graphene, microcrystalline cellulose, nano-poly(methyl methacrylate) particles, nano-polystyrene particles, nano-iron oxide particles, nano-mica, nano-silicon nitride, etc.; the latter includes but is not limited to sub-micron or micron-sized silica particles, alumina particles, poly(methyl methacrylate) particles, polystyrene particles, starch particles, mica, silicon nitride, etc. The shape of the solid microparticles can be spherical, ellipsoidal, disc-shaped, other regular and irregular polyhedrons, etc., and their surfaces can be smooth or rough, preferably spherical and ellipsoidal; their surfaces can also be optionally modified organically and / or inorganically.

[0192] Among them, when the dispersion medium is selected from liquids, it includes but is not limited to organic substances, mineral oils, polymer matrices, etc. Specifically, by way of example, the dispersion medium includes but is not limited to water, polyethylene glycol, polypropylene glycol, liquid paraffin, vegetable oil, mineral oil, silicone oil, ionic liquid, plasticizer, liquid metal, thixotropic fluid (such as boron-containing dynamic polymer) and their mixtures, etc.; when the dispersion medium is selected from solids, it includes but is not limited to cross-linked polymers with low Tg, gels, thixotropic cross-linked polymers (such as boron-containing cross-linked dynamic polymers and hybrid cross-linked dynamic polymers).

[0193] In an embodiment of the present invention, when the solid microparticles in the dispersion are inorganic substances and the dispersion medium is an organic substance, the dispersion can also optionally contain a coupling agent and / or a surfactant to make the solid microparticles more uniformly dispersed in the dispersion medium, such as silane coupling agents KH550, KH560, A1120, etc., and coupling agents such as titanate esters, aluminate esters, organic chromium complexes, phosphate esters, zirconate esters, stannate esters, etc.

[0194] In the present invention, the dilatant dispersion / dispersion product is preferably swollen or dispersed in a polymer network (including vitreous dilatant polymers); or is dispersed in a self-supporting polymer material with pores and cavities (including vitreous dilatant polymers) by means such as coating and impregnation to provide dilatancy. Such polymer materials include, but are not limited to, polymer foams, fibrous fabrics, etc. By way of example, the polymer foams include, but are not limited to, polyurethane foams, polyamide foams, polyvinyl chloride foams, polyethylene foams, polypropylene foams, ethylene-vinyl acetate copolymer foams, silicone foams, etc. By way of example, the polymers on which the fibrous fabrics are based include, but are not limited to, ultra-high molecular weight polyethylene, polypropylene, polyurethane, polyamide, polyaramide, polyester, polyarylate, polyurea, polyoxymethylene, polyimide, polyamide-hydrazide, polybenzimidazole, polyacrylonitrile, polyvinyl acetal, polyvinyl chloride, polyvinylidene chloride, silk, wool, cotton, hemp, cellulose esters, cellulose, and other polymer alloys containing two or more polymers; the fibers of the fibrous fabrics can be homogeneous or can have a single-layer or multi-layer sheath-core structure; the fibrous fabrics can be two-dimensional or three-dimensional, and since the three-dimensional fibrous fabrics have a higher porosity, they can accommodate more dispersion / dispersion product and provide better dilatant properties. In the present invention, it is more preferred that during processing and molding, the dilatant dispersion / dispersion product is directly dispersed in the polymer matrix to form a phase-separated dispersed phase.

[0195] In the present invention, the commercial sources of the solid microparticles and the dispersion / dispersion product required to achieve the dilatant properties are abundant, and the dispersion process does not require complex chemical reactions, and has the characteristics of high performance controllability. The dispersion of inorganic particles also has the characteristic of puncture resistance.

[0196] In the present invention, when the morphology of the dilatant polymer is a foam, by regulating the open-cell structure of the foam, generally when the proportion of the open-cell surface area decreases, the rebound time increases and the dilatancy increases. In order to obtain appropriate dilatancy, it is preferably that the ratio of the open-cell area to the cell surface area is 3% to 20%, more preferably 5% to 15%, and even more preferably 5% to 10%.

[0197] In the present invention, the cell structure with local open cells is regarded as a pneumatic dilatant structure.

[0198] In the present invention, the pore structure of the polymer foam with pneumatic dilatant fluidity can be obtained at least by adding an appropriate amount of pore-opening agent / pore-forming agent. The pore-opening agent / pore-forming agent can play a role in breaking the pore walls when the polymer reacts to form a foam, thereby promoting the formation of an open-cell structure. The types and addition contents of the pore-opening agent / pore-forming agent are not particularly limited and can be reasonably adjusted according to actual needs to obtain polymer foams with different open-cell area ratios and adjustable dilatant fluidity. By way of example, for polyurethane foams, the pore-opening agent / pore-forming agent can be selected from but not limited to: ethylene oxide homopolymer polyols with a molecular weight higher than 5000 Da and a hydroxyl functionality of not less than 5 or random copolymer polyols of ethylene oxide and a small amount of propylene oxide, and propylene oxide homopolymer monools with a molecular weight of 1000 - 8500 Da and a hydroxyl functionality of 1. In the present invention, a three-dimensional structure with open or semi-open cells can also be obtained by fiber forming; a rich pore structure can also be obtained by 3D printing.

[0199] In the present invention, the pneumatic dilatant fluidity is insensitive to temperature, which is convenient for maintaining relatively stable dilatant fluidity performance within a wide temperature range. Moreover, this locally open-cell structure can reduce the shrinkage rate of the foam after cooling and improve the forming stability of the dilatant fluidity foam.

[0200] In the present invention, the entangled dilatant fluidity is achieved through the entanglement of polymer molecular chains. Preferably, the glass transition temperature (Tg) of the molecular chains of the polymer is not higher than -20 °C, more preferably not higher than -40 °C, more preferably not higher than -60 °C, and more preferably not higher than -100 °C; its molecular weight needs to be high enough to obtain an entanglement effect under shear. Preferably, the molecular weight is not less than 100 kDa, and more preferably not less than 1000 kDa.

[0201] In the present invention, the components constituting the dilatant fluidity assembly, especially the polymer components, in addition to containing ordinary covalent bonds, can also contain at least one dynamic unit. The dynamic unit includes dynamic covalent bonds and non-covalent interactions.

[0202] In the dilatant component described in the present invention, dynamic covalent bonds and / or non-covalent interactions / supramolecular interactions are introduced. Based on their dynamics, in addition to regulating the dynamic dilatant properties, it can also provide good stimulus responsiveness and dynamic reversibility for the dilatant component, and thereby obtain plasticity, self-repairability, reprocessability and recyclability, which is convenient for repairing structural damages such as cracks and scratches on the electronic product protective cover / case, reprocessing and recycling the electronic product protective cover / case, and thereby improving the service life of the material, enhancing the utilization rate of resources, and reducing environmental pollution. These special properties all reflect the creativity and novelty of the present invention. In particular, introducing weak dynamic covalent bonds and / or non-covalent interactions / supramolecular interactions into the dilatant component, rationally designing and regulating the cross-linked structure, can also endow the protective cover / case with shape memory function, which is convenient for putting on and removing the electronic product, and under the impact of external energy, the weak dynamic covalent bonds and non-covalent interactions / supramolecular interactions therein can also act as sacrificial bonds to absorb the impact energy and provide more effective energy absorption and impact resistance for the electronic product; introducing strong dynamic covalent bonds and / or non-covalent interactions / supramolecular interactions into the dilatant component to obtain dynamic dilatancy, providing more effective energy absorption protection for the electronic product, as well as enhancing the toughness and tear resistance of the electronic product protective cover, effectively reducing the internal defects of the material caused by internal stress, and obtaining an electronic product protective cover / case with better performance; introducing at least one weak dynamic covalent unit and at least one strong dynamic covalent unit into the dilatant component can obtain richer dynamics and dynamic dilatancy, providing better energy absorption protection performance and other service performances.

[0203] In an embodiment of the present invention, when the dilatant component undergoes dynamic cross-linking or hybrid dynamic cross-linking with various dynamic covalent bonds and / or non-covalent interactions / supramolecular interactions, based on the stimulus responsiveness and dynamic reversibility of the dynamic cross-linked structure, it can dissociate and recombine the local cross-linked structure of the electronic product protective cover under the action of specific stimuli, reduce its local mechanical strength and modulus, obtain gradient mechanical property differences, realize local softening of the electronic product protective cover / case, facilitate the putting on and removing of the protective cover / case, contribute to improving the user experience, and is also convenient for better designing and controlling the three-dimensional dimensions of the protective cover / case while maintaining tight fitting, so as to achieve the expected energy absorption and impact resistance performance.

[0204] In the present invention, the dynamic covalent bonds include boron-containing dynamic covalent bonds and boron-free dynamic covalent bonds.

[0205] In the present invention, the boron-containing dynamic covalent bond contains boron atoms in its dynamic structural composition, including but not limited to fifteen types of bonds: organic boric anhydride bond, inorganic boric anhydride bond, organic-inorganic boric anhydride bond, saturated five-membered ring organic borate ester bond, unsaturated five-membered ring organic borate ester bond, saturated six-membered ring organic borate ester bond, unsaturated six-membered ring organic borate ester bond, saturated five-membered ring inorganic borate ester bond, unsaturated five-membered ring inorganic borate ester bond, saturated six-membered ring inorganic borate ester bond, unsaturated six-membered ring inorganic borate ester bond, organic boric acid monoester bond, inorganic boric acid monoester bond, organic boric acid silicate ester bond, and inorganic boric acid silicate ester bond; among them, each type of boron-containing dynamic covalent bond may contain various boron-containing dynamic covalent bond structures. The boron-containing dynamic covalent bond described in the present invention, when selected from two or more types, may be selected from different structures within the same type of boron-containing dynamic covalent bond, or may be selected from different structures of different types of boron-containing dynamic covalent bonds. Among them, in order to achieve orthogonal and / or cooperative dynamic properties, it is preferably selected from different structures of different types of boron-containing dynamic covalent bonds.

[0206] In the present invention, the organic boric anhydride bond is selected from but not limited to at least one of the following structures:

[0207]

[0208] Among them, each boron atom in the organic boric anhydride bond is connected to at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; represents the connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same boron atom can form a ring, and on different boron atoms can also form a ring. The rings include but not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and their combinations.

[0209] In an embodiment of the present invention, the organic boric anhydride bond can be formed by the reaction of organic boric acid moieties contained in the compound raw materials, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing the organic boric anhydride bond.

[0210] In the present invention, the inorganic boric anhydride bond is selected from but not limited to the following structures:

[0211]

[0212] Among them, Y1, Y2, Y3, and Y4 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom, preferably an oxygen atom, and at least one of Y1 and Y2 is selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom; at least one of Y3 and Y4 is selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom, where a, b, c, and d respectively represent the number of connections to Y1, Y2, Y3, and Y4; when Y1, Y2, Y3, and Y4 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a, b, c, and d = 0; when Y1, Y2, Y3, and Y4 are each independently selected from an oxygen atom and a sulfur atom, a, b, c, and d = 1; when Y1, Y2, Y3, and Y4 are each independently selected from a nitrogen atom and a boron atom, a, b, c, and d = 2; when Y1, Y2, Y3, and Y4 are each independently selected from a silicon atom, a, b, c, and d = 3; different on the same atom can be connected to form a ring, and those on different atoms can also be connected to form a ring, and the rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

[0213] In an embodiment of the present invention, the inorganic boric anhydride bond can be formed by the reaction of inorganic boric acid units contained in the compound raw materials, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing inorganic boric anhydride bonds.

[0214] In the present invention, the organic-inorganic boric anhydride bond is selected from but not limited to the following structures:

[0215]

[0216] Among them, Y1 and Y2 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom, preferably an oxygen atom, and at least one of Y1 and Y2 is selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom; among them, the boron atom in the structure is connected to at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; Represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom, where a and b respectively represent the number of connections to Y1 and Y2; when Y1 and Y2 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a = b = 0; when Y1 and Y2 are each independently selected from an oxygen atom, a sulfur atom, a = b = 1; when Y1 and Y2 are each independently selected from a nitrogen atom, a boron atom, a = b = 2; when Y1 and Y2 are each independently selected from a silicon atom, a = b = 3; different can be connected to form a ring, and those on different atoms can also be connected to form a ring, and the rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

[0217] In an embodiment of the present invention, the organic-inorganic boric anhydride bond can be formed by the reaction of an organic boric acid moiety and an inorganic boric acid moiety contained in the compound raw material, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the organic-inorganic boric anhydride bond.

[0218] In the present invention, the saturated five-membered ring organic borate ester bond is selected from but not limited to the following structures:

[0219]

[0220] Among them, the boron atom needs to be connected to a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; Represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same carbon atom can be connected to form a ring, and those on different carbon atoms

[0221] In an embodiment of the present invention, the saturated five-membered ring organic borate ester bond can be formed by the reaction of a 1,2-diol moiety and an organic boric acid moiety contained in the compound raw material, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the saturated five-membered ring organic borate ester bond.

[0222] In the present invention, the unsaturated five-membered ring organic borate ester bond is selected from but not limited to the following structures:

[0223]

[0224] Among them, the boron atom needs to be connected to a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; Represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; Represents an aromatic ring of any arity, preferably a six-membered ring, and the aromatic ring contains two adjacent carbon atoms, which are located in an unsaturated five-membered ring organoborate bond; the hydrogen atoms on the ring-forming atoms of the aromatic ring can be substituted by any substituent or not substituted.

[0225] In an embodiment of the present invention, the unsaturated five-membered ring organoborate bond can be formed by the reaction of the o-diphenol moiety contained in the compound raw material with the organoboric acid moiety, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the unsaturated five-membered ring organoborate bond.

[0226] In the present invention, the saturated six-membered ring organoborate bond is selected from but not limited to the following structures:

[0227]

[0228] Among them, the boron atom needs to be connected to a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; Represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same carbon atom can form a ring, and on different carbon atoms can also form a ring, and the rings include but are not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof.

[0229] In an embodiment of the present invention, the saturated six-membered ring organoborate bond can be formed by the reaction of the 1,3-diol moiety contained in the compound raw material with the organoboric acid moiety, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the saturated six-membered ring organoborate bond.

[0230] In the present invention, the unsaturated six-membered ring organoborate bond is selected from but not limited to the following structures:

[0231]

[0232] Among them, the boron atom needs to be connected to a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; Represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; represents an aromatic ring of any arity, preferably a six-membered ring, and the aromatic ring contains two adjacent carbon atoms, which are located in the unsaturated six-membered ring organoborate bond; the hydrogen atoms on the ring-forming atoms of the aromatic ring can be substituted by any substituent or not substituted; different can be connected to form a ring, and those on different carbon atoms can also be connected to form a ring.

[0233] In an embodiment of the present invention, the unsaturated six-membered ring organoborate bond can be formed by the reaction of the 2-hydroxymethylphenol moiety contained in the compound raw material with the organoboric acid moiety, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the unsaturated six-membered ring organoborate bond.

[0234] In the present invention, for the saturated five-membered ring organoborate bond, unsaturated five-membered ring organoborate bond, saturated six-membered ring organoborate bond, and unsaturated six-membered ring organoborate bond, the boron atom in their structures is preferably connected to the aminomethylphenyl group ( * represents the position connected to the boron atom); the organoboric acid moiety forming the saturated five-membered ring organoborate bond, unsaturated five-membered ring organoborate bond, saturated six-membered ring organoborate bond, and unsaturated six-membered ring organoborate bond is preferably the aminomethylphenylboronic acid (ester) moiety.

[0235] Since the aminomethylphenylboronic acid (ester) moiety has high reactivity when reacting with 1,2-diol moiety and / or o-diphenol moiety and / or 1,3-diol moiety and / or 2-hydroxymethylphenol moiety, the formed boron-containing dynamic covalent bond has strong dynamic reversibility, can undergo dynamic reversible reactions under relatively mild neutral conditions, can exhibit sensitive dynamic characteristics and significant energy absorption effects, and will show greater advantages as an energy absorption material.

[0236] In the present invention, the saturated five-membered ring inorganic borate bond is selected from but not limited to at least one of the following structures:

[0237]

[0238] wherein, Y1 is selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom; represents the connection to the polymer chain, crosslinked network chain or any other suitable group / atom, where a represents the number of connections connected to Y1; when Y1 is selected from an oxygen atom, a sulfur atom, a = 1; when Y1 is selected from a nitrogen atom, a boron atom, a = 2; when Y1 is selected from a silicon atom, a = 3; different can be connected to form a ring, and those on different carbon atoms It can also be connected into a ring, and the ring includes but is not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof.

[0239] In an embodiment of the present invention, the saturated five-membered ring inorganic borate bond can be formed by the reaction of 1,2-diol units contained in the compound raw materials with inorganic boric acid units, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing saturated five-membered ring inorganic borate bonds.

[0240] In the present invention, the unsaturated five-membered ring inorganic borate bond is selected from but not limited to at least one of the following structures:

[0241]

[0242] Among them, Y1 is selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom; represents the connection with a polymer chain, a crosslinked network chain, or any other suitable group / atom, where a represents the number of connections to Y1; when Y1 is selected from an oxygen atom or a sulfur atom, a = 1; when Y1 is selected from a nitrogen atom or a boron atom, a = 2; when Y1 is selected from a silicon atom, a = 3; represents an aromatic ring of any arity, preferably a six-membered ring, and the aromatic ring contains two adjacent carbon atoms, which are located in the unsaturated five-membered ring inorganic borate bond; the hydrogen atoms on the ring-forming atoms of the aromatic ring can be substituted by any substituent or can be unsubstituted.

[0243] In an embodiment of the present invention, the unsaturated five-membered ring inorganic borate bond can be formed by the reaction of o-diphenol units contained in the compound raw materials with inorganic boric acid units, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing unsaturated five-membered ring inorganic borate bonds.

[0244] In the present invention, the saturated six-membered ring inorganic borate bond is selected from but not limited to at least one of the following structures:

[0245]

[0246] Among them, Y1 is selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom, preferably an oxygen atom; represents the connection with a polymer chain, a crosslinked network chain, or any other suitable group / atom, where a represents the number of connections to Y1; when Y1 is selected from an oxygen atom or a sulfur atom, a = 1; when Y1 is selected from a nitrogen atom or a boron atom, a = 2; when Y1 is selected from a silicon atom, a = 3; different on the same carbon atom can be connected into a ring, and It can also be connected into a ring, and the ring includes but is not limited to an aliphatic ring, an ether ring, a condensed ring, and combinations thereof.

[0247] In an embodiment of the present invention, the saturated six-membered ring inorganic borate bond can be formed by the reaction of the 1,3-diol moiety contained in the compound raw material with the inorganic boric acid moiety, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the saturated six-membered ring inorganic borate bond.

[0248] In the present invention, the unsaturated six-membered ring inorganic borate bond is selected from but not limited to at least one of the following structures:

[0249]

[0250] Wherein, Y1 is selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom, where a represents the number of connections to Y1; when Y1 is selected from an oxygen atom or a sulfur atom, a = 1; when Y1 is selected from a nitrogen atom or a boron atom, a = 2; when Y1 is selected from a silicon atom, a = 3; represents an aromatic ring of any arity, preferably a six-membered ring, and the aromatic ring contains two adjacent carbon atoms, which are located in the unsaturated six-membered ring inorganic borate bond; the hydrogen atoms on the ring-forming atoms of the aromatic ring can be substituted by any substituent or not substituted; the different on the same carbon atom can be connected into a ring, and the on different carbon atoms can also be connected into a ring.

[0251] In an embodiment of the present invention, the unsaturated six-membered ring inorganic borate bond can be formed by the reaction of the 2-hydroxymethylphenol moiety contained in the compound raw material with the inorganic boric acid moiety, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the unsaturated six-membered ring inorganic borate bond.

[0252] In the present invention, the organic borate monoester bond is selected from but not limited to at least one of the following structures:

[0253]

[0254] Wherein, the boron atom is connected to at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; I1 is selected from a divalent linking group; I2 is selected from a double bond directly connecting two carbon atoms, a trivalent carbene group directly connecting two carbon atoms a divalent non-carbon atom, a linking group containing at least two backbone atoms; represents an aromatic ring of any arity, preferably a six-membered ring; the hydrogen atoms on the ring-forming atoms of the aromatic ring can be substituted by any substituent or can remain unsubstituted; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same carbon atom or boron atom can form a ring, and those on different carbon atoms or boron atoms can also form a ring, or can form a ring together with the substituted atoms (substituents) in I1 and I2. The rings include but are not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Among them, the organic borate monoester bond formed after the 6,7 structure forms a ring is not the saturated five-membered ring organic borate ester bond, the unsaturated five-membered ring organic borate ester bond, the saturated six-membered ring organic borate ester bond, and the unsaturated six-membered ring organic borate ester bond described above.

[0255] In an embodiment of the present invention, the organic borate monoester bond can be formed by the reaction of a monoalcohol group contained in a compound raw material with an organic borate group, or can be introduced into a polymer by a polymerization / crosslinking reaction between the reactive groups contained in a compound raw material containing an organic borate monoester bond.

[0256] In the present invention, the inorganic borate monoester bond is selected from but not limited to at least one of the following structures:

[0257]

[0258] wherein, Y1 to Y 13 each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably an oxygen atom, and Y1, Y2; Y3, Y4; Y5, Y6, Y7, Y8; Y9, Y 10 、Y 11 、Y 12 at least one selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom; Y 14 selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom; I1 is selected from divalent linking groups; I2 is selected from a double bond directly connecting two carbon atoms, a trivalent carbene group directly connecting two carbon atoms divalent non-carbon atoms, linking groups containing at least two backbone atoms; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom, where a to n respectively represent the number of connections to Y1 to Y 14 connected; when Y1 to Y 13 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a to m = 0; when Y1 to Y 14When each is independently selected from an oxygen atom and a sulfur atom, a to n = 1; when Y1 to Y 14 When each is independently selected from a nitrogen atom and a boron atom, a to n = 2; when Y1 to Y 14 When each is independently selected from a silicon atom, a to n = 3; represents an aromatic ring of any valence, preferably a six-membered ring; the hydrogen atoms on the ring-forming atoms of the aromatic ring may or may not be substituted by any substituent; different on the same carbon atom may be connected to form a ring, and those on different carbon atoms may also be connected to form a ring, or may form a ring together with the substituted atoms (substituents) in I1 and I2. The rings include but are not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof. Among them, the inorganic borate monoester bond formed after the 5, 6, 7, and 8 structures form a ring is not the saturated five-membered ring inorganic borate ester bond, unsaturated five-membered ring inorganic borate ester bond, saturated six-membered ring inorganic borate ester bond, and unsaturated six-membered ring inorganic borate ester bond described above.

[0259] In an embodiment of the present invention, the inorganic borate monoester bond can be formed by the reaction of the monoalcohol group element contained in the compound raw material with the inorganic borate group element, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the inorganic borate monoester bond.

[0260] In the present invention, the organoborosilicate bond is selected from at least one of the following structures but not limited thereto:

[0261]

[0262] Among them, at least one boron atom is connected to at least one carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; represents the connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same atom may be connected to form a ring, and those on different atoms may also be connected to form a ring. The rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

[0263] In an embodiment of the present invention, the organoborosilicate bond can be formed by the reaction of the silanol group element contained in the compound raw material with the organoborate group element, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the organoborosilicate bond.

[0264] In the present invention, the inorganic borosilicate bond is selected from at least one of the following structures but not limited thereto:

[0265]

[0266] Among them, Y1, Y2, and Y3 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom, preferably an oxygen atom, and at least one of Y1 and Y2 is selected from an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, and a silicon atom; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom, where a, b, and c respectively represent the number of connections to Y1, Y2, and Y3; when Y1, Y2, and Y3 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a, b, and c = 0; when Y1, Y2, and Y3 are each independently selected from an oxygen atom and a sulfur atom, a, b, and c = 1; when Y1, Y2, and Y3 are each independently selected from a nitrogen atom and a boron atom, a, b, and c = 2; when Y1, Y2, and Y3 are each independently selected from a silicon atom, a, b, and c = 3; different on the same atom can be connected to form a ring, and those on different atoms can also be connected to form a ring, and the rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

[0267] In an embodiment of the present invention, the inorganic borosilicate bond can be formed by the reaction of a silanol group element contained in a compound raw material with an inorganic boric acid group element, or can be introduced into a polymer by the polymerization / crosslinking reaction between reactive groups contained in a compound raw material containing an inorganic borosilicate bond.

[0268] The organic boric acid group element described in the embodiment of the present invention is selected from but not limited to any of the following structures:

[0269]

[0270] Among them, K1, K2, and K3 are monovalent organic groups or monovalent organosilicon groups directly connected to an oxygen atom, which are directly connected to the oxygen atom through a carbon atom or a silicon atom, and are selected from any of the following structures: small molecule hydrocarbon groups, small molecule silyl groups, polymer chain residues; K4 is a divalent organic group or divalent organosilicon group directly connected to two oxygen atoms, which are directly connected to the oxygen atom through a carbon atom or a silicon atom, and is selected from any of the following structures: divalent small molecule hydrocarbon groups, divalent small molecule silyl groups, divalent polymer chain residues; M1 + 、M2 + 、M3 + are monovalent cations, preferably selected from Na + 、K + 、NH4 + ; M4 2+ is a divalent cation, preferably selected from Mg 2+, Ca 2+ , Zn 2+ , Ba 2+ ; X1, X2, and X3 are halogen atoms, preferably selected from chlorine atoms and bromine atoms; D1 and D2 are groups connected to the boron atom, D1 and D2 are different and each independently selected from a hydroxyl group (-OH), an ester group (-OK1), a salt group (-OM1 * ), a halogen atom (-X1), wherein K1, M1 + , and the definition of X1 is consistent with that described above and will not be elaborated here; wherein, the boron atom in the structure needs to be connected to a carbon atom through a boron-carbon bond, and at least one organic group is connected to the boron atom through the boron-carbon bond; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same boron atom can be connected to form a ring, and the rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

[0271] The inorganic boric acid moiety described in the embodiments of the present invention is selected from but not limited to the following structures:

[0272]

[0273] wherein, W1, W2, and W3 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an oxygen atom, a sulfur atom, a nitrogen atom, a boron atom, a silicon atom, preferably an oxygen atom, and at least one of W1, W2, and W3 is selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom, wherein x, y, and z respectively represent the number of connections to W1, W2, and W3; when W1, W2, and W3 are each independently selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, x, y, and z = 0; when W1, W2, and W3 are each independently selected from an oxygen atom, a sulfur atom, x, y, and z = 1; when W1, W2, and W3 are each independently selected from a nitrogen atom, a boron atom, x, y, and z = 2; when W1, W2, and W3 are each independently selected from a silicon atom, x, y, and z = 3; different on the same atom can be connected to form a ring, and on different atoms can also be connected to form a ring, and the rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

[0274] The inorganic boric acid moiety described in the embodiments of the present invention is preferably introduced by using inorganic borane, inorganic boric acid, inorganic boric anhydride, inorganic borate, inorganic borate ester, inorganic boron halide as raw materials.

[0275] In the embodiments of the present invention, the 1,2 - diol moiety is ethylene glycol and the residue formed after at least one non - hydroxyl hydrogen atom is lost from its substituted form;

[0276] In the embodiments of the present invention, the 1,3 - diol moiety is 1,3 - propanediol and the residue formed after at least one non - hydroxyl hydrogen atom is lost from its substituted form;

[0277] For the 1,2 - diol moiety and the 1,3 - diol moiety, they can have a linear structure or a cyclic group structure.

[0278] For the linear 1,2 - diol moiety structure, it can be selected from any one or more of the structures in Class B and their isomeric forms:

[0279] Class B:

[0280]

[0281] For the linear 1,3 - diol moiety structure, it can be selected from any one or more of the structures in Class C and their isomeric forms:

[0282] Class C:

[0283]

[0284] Among them, R1 - R3 are monovalent groups connected to the 1,2 - diol moiety; R4 - R8 are monovalent groups connected to the 1,3 - diol moiety; represents the connection to a polymer chain, a cross - linked network chain or any other suitable group / atom; among them, R1 - R8 are each independently selected from any one of the following structures: hydrogen atom, heteroatom group, small - molecule hydrocarbon group, polymer chain residue.

[0285] Among them, the isomeric forms of B1 - B4 and C1 - C6 are each independently selected from any one of position isomerism, conformational isomerism, and chiral isomerism.

[0286] For the cyclic 1,2 - diol moiety structure, it can be formed by connecting two carbon atoms in an ethylene glycol molecule through the same group; among them, the cyclic group structure is a 3 - to 200 - membered ring, preferably a 3 - to 10 - membered ring, more preferably a 3 - to 6 - membered ring, the number of cyclic group structures is 1, 2 or more, and the cyclic group structure is selected from but not limited to any one of the following: aliphatic ring, ether ring, condensed ring and their combinations; examples of suitable cyclic group structures are:

[0287]

[0288] For the cyclic 1,3-diol moiety, it can be formed by connecting two carbon atoms in a 1,3-propanediol molecule through the same group; wherein, the cyclic group structure is a 3- to 200-membered ring, preferably a 3- to 10-membered ring, more preferably a 3- to 6-membered ring, the number of cyclic group structures is 1, 2 or more, and the cyclic group structure is selected from but not limited to any of the following: aliphatic ring, ether ring, condensed ring and their combinations; examples of suitable cyclic group structures are:

[0289]

[0290] The o-diphenol moiety described in the present invention is o-diphenol and the residue formed after losing at least one non-hydroxyl hydrogen atom of its substituted form, hybridized form and their combinations, examples of suitable o-diphenol moiety structures are:

[0291]

[0292] The 2-hydroxymethylphenol moiety described in the present invention is 2-hydroxymethylphenol and the residue formed after losing at least one non-hydroxyl hydrogen atom of its substituted form, hybridized form and their combinations, examples of suitable 2-hydroxymethylphenol moiety structures are:

[0293]

[0294] The monoalcohol moiety described in the embodiments of the present invention refers to a structural moiety composed of a hydroxyl group and a carbon atom directly connected to the hydroxyl group ( wherein, the carbon atom can be a non-aromatic hydrocarbon carbon atom or an aromatic hydrocarbon carbon atom), and in the case of forming an unsaturated / saturated five-membered ring organic borate bond, unsaturated / saturated six-membered ring organic borate bond, unsaturated / saturated five-membered ring inorganic borate bond, unsaturated / saturated six-membered ring inorganic borate bond by 1,2-diol moiety, o-diphenol moiety, 1,3-diol moiety, 2-hydroxymethylphenol moiety, the monoalcohol moiety is not the hydroxyl group in 1,2-diol moiety, o-diphenol moiety, 1,3-diol moiety, 2-hydroxymethylphenol moiety, except for this case, the monoalcohol moiety can also be selected from any one hydroxyl group in a suitable binary (polyhydric) alcohol compound and / or group. Examples of suitable structures containing monoalcohol moiety are:

[0295]

[0296] The silanol moiety described in the embodiments of the present invention refers to a structural moiety composed of a silicon atom and a hydroxyl group or a group that can be hydrolyzed to obtain a hydroxyl group connected to the silicon atom ( Among them, Z can be selected from halogen, cyano, cyanato, thiocyanato, alkoxy, amino, sulfate group, borate group, acyl group, acyloxy group, acylamino group, ketoxime group, alkoxide group, etc., preferably halogen, alkoxy).

[0297] In the present invention, the dynamic covalent bonds containing boron selected have strong dynamics and mild dynamic reaction conditions. Polymer synthesis and dynamic reversible effects can be achieved without the need for catalysts, high temperatures, light, or specific pH conditions, which can further improve the preparation efficiency, reduce the limitations of the use environment, and expand the application scope of polymers.

[0298] In the present invention, the boron-free dynamic covalent bonds do not contain boron atoms in their dynamic structural composition, and include but are not limited to dynamic disulfide bonds, dynamic polysulfide bonds, dynamic selenosulfide bonds, dynamic selenonitrogen bonds, acetal-based dynamic covalent bonds, carbon-nitrogen double bond-based dynamic covalent bonds, reversible radical-based dynamic covalent bonds, binding-exchangeable acyl bonds, steric effect-induced dynamic covalent bonds, reversible addition-fragmentation chain transfer dynamic covalent bonds, dynamic siloxane bonds, dynamic silyl ether bonds, alkyl azolium-based exchangeable dynamic covalent bonds, unsaturated carbon-carbon double bonds that can undergo olefin cross-metathesis, unsaturated carbon-carbon triple bonds that can undergo alkyne cross-metathesis, [2+2] cycloaddition dynamic covalent bonds, [4+2] cycloaddition dynamic covalent bonds, [4+4] cycloaddition dynamic covalent bonds, thiol-Michael addition dynamic covalent bonds, amine-ene-Michael addition dynamic covalent bonds, triazolinedione-indole-based dynamic covalent bonds, diazabenzylidene-based dynamic covalent bonds, benzoyl-based dynamic covalent bonds, hexahydrotriazine-based dynamic covalent bonds, dynamic exchangeable trialkylsulfonium bonds, dynamic acid ester bonds, diketeneamine dynamic covalent bonds, these twenty-seven groups of bonds; among them, in each group of boron-free dynamic covalent bonds, there can be multiple types of boron-free dynamic covalent bond structures. The boron-free dynamic covalent bonds described in the present invention, when selected from two or more, can be selected from different structures of the same type of dynamic covalent bonds in the same group of boron-free dynamic covalent bonds, or can be selected from different structures of different types of dynamic covalent bonds in the same group of boron-free dynamic covalent bonds, or can be selected from different structures of different groups of boron-free dynamic covalent bonds. Among them, in order to achieve orthogonal and / or cooperative dynamic properties, it is preferably selected from different structures of different groups of boron-free dynamic covalent bonds.

[0299] In the present invention, the dynamic disulfide bond includes dynamic disulfide bonds and dynamic polysulfide bonds, which can be activated under certain conditions and undergo bond dissociation, bonding, and exchange reactions, showing dynamic reversible characteristics; the dynamic disulfide bonds described in the present invention are selected from the following structures:

[0300]

[0301] Among them, x is the number of S atoms, x≥2, Denotes a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom.

[0302] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of the dynamic disulfide bond include, but are not limited to, temperature regulation, addition of redox agents, addition of catalysts, addition of initiators, light irradiation, radiation, microwave, plasma action, pH adjustment and other action modes. For example, by heating, the dynamic disulfide bond can be broken to form sulfur radicals, thereby occurring the dissociation and exchange reaction of the dynamic disulfide bond. After cooling, the dynamic disulfide bond is re-formed and stabilized, so that the polymer can obtain self-healing property and reprocessability. Light irradiation can also break the dynamic disulfide bond to form sulfur radicals, thereby occurring the dissociation and exchange reaction of the disulfide bond. After removing the light irradiation, the dynamic disulfide bond is re-formed, so that the polymer can obtain self-healing property and reprocessability. Radiation, microwave and plasma can generate free radicals in the system to act on the dynamic disulfide bond to obtain self-healing property and reprocessability. The presence of a catalyst can promote the formation and exchange of the dynamic disulfide bond, thereby accelerating the self-healing process and obtaining reprocessability. Among them, the catalysts include, but are not limited to, rhodium(Ⅰ) hydridotetrakis(triphenylphosphine), 1,8-diazabicyclo[5.4.0]undec-7-ene, cuprous chloride, methacrylate-copper composite catalyst, alkylphosphines (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine). In the embodiments of the present invention, the dynamic reaction of the disulfide bond can also be realized by adding a redox agent to the system. Among them, the reducing agent can promote the dissociation of the dynamic disulfide bond to form mercapto groups, thereby obtaining recyclability and reprocessability; the oxidizing agent can promote the formation of the dynamic disulfide bond, thereby obtaining secondary moldability. Among them, the reducing agents include, but are not limited to, sodium metabisulfite, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, alkyl mercaptans (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, etc.), alkylphosphines (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, etc.); the oxidizing agents include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (such as benzoyl peroxide, hydrogen peroxide, ozone, p-benzoquinone dioxime, disulfide). The dynamic polymer can also generate free radicals by adding an initiator to the system and then under the action of heating, light irradiation, radiation, microwave and plasma, promoting the dissociation or exchange of the dynamic disulfide bond to obtain self-healing property or recyclability for recycling.Among them, the initiator includes, but is not limited to, any one or several of the following initiators: photoinitiators, such as 2,2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, and α-ketoglutaric acid; organic peroxides, such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy pivalate, di-tert-butyl peroxide, dicumyl peroxide; azo compounds, such as azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides, such as ammonium persulfate, potassium persulfate, etc.; among them, the initiator is preferably 2,2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

[0303] In an embodiment of the present invention, the dynamic disulfide bond can be formed by the oxidative coupling reaction of thiol groups contained in the compound raw materials and the bonding reaction of sulfur radicals, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing a disulfide bond. Among them, there is no particular limitation on the compound raw material containing a disulfide bond, and polyols, isocyanates, epoxides, alkenes, alkynes, carboxylic acids, esters, amides containing disulfide bonds and sulfur, thiol compounds are preferably used, and polyols, isocyanates, epoxides, alkenes, alkynes containing disulfide bonds are more preferably used.

[0304] In the present invention, the dynamic diselenide bond includes dynamic biselenide bonds and dynamic polyselenide bonds, which can be activated under certain conditions, and bond dissociation, bonding, and exchange reactions occur, showing dynamic reversible characteristics; the dynamic diselenide bond in the present invention is selected from the following structures:

[0305]

[0306] where x is the number of Se atoms, x≥2, represents the connection to the polymer chain, crosslinked network chain, or any other suitable group / atom.

[0307] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of the dynamic selenium bonds include, but are not limited to, temperature adjustment, addition of redox agents, addition of catalysts, addition of initiators, light irradiation, radiation, microwave, plasma action, etc., so that the polymer exhibits good self-healing properties, recyclability, stimulus responsiveness, etc. For example, heating can cause the breakage of the dynamic selenium bonds to form selenium free radicals, thereby causing the dissociation and exchange reactions of the dynamic bonds. After cooling, the dynamic selenium bonds are re-formed and stabilized, showing self-healing and reprocessability; good self-healing performance can be obtained for the polymer containing dynamic bonds by laser irradiation; self-healing and reprocessability can be obtained by using radiation, microwave and plasma to generate free radicals in the system to act on the dynamic selenium bonds. Recyclability can also be obtained for the dynamic polymer by adding a redox agent to the system; the reducing agent can promote the dissociation of the dynamic selenium bonds into selenols, causing the dissociation of the dynamic polymer; the oxidizing agent can oxidize selenols to form dynamic selenium bonds, thereby obtaining reprocessability. Among them, the types of the reducing agent include, but are not limited to, sodium metabisulfite, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, tris(2-carboxyethyl)phosphine hydrochloride, alkyl thiols (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, etc.), alkyl phosphines (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, etc.); the types of the oxidizing agent include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (such as benzoyl peroxide, hydrogen peroxide, ozone, p-benzoquinone dioxime, disulfide). The dynamic polymer can also generate free radicals by adding an initiator to the system and then under the action of heating, light irradiation, radiation, microwave and plasma, promoting the dissociation or exchange of the dynamic selenium bonds to obtain self-healing or recyclability.Among them, the initiator includes, but is not limited to, any one or more of the following initiators: photoinitiators such as 2,2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, and α-ketoglutaric acid; organic peroxides such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy pivalate, di-tert-butyl peroxide, cumene hydroperoxide; azo compounds such as azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides such as ammonium persulfate, potassium persulfate, etc.; among them, the initiator is preferably 2,2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

[0308] In an embodiment of the present invention, the dynamic diselenide bond can be formed by the oxidative coupling reaction of selenol contained in the compound raw material and the bonding reaction of selenium radicals, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the dynamic diselenide bond. Among them, there is no particular limitation on the compound raw material containing the dynamic diselenide bond, and polyols, isocyanates, epoxides, alkenes, alkynes, carboxylic acids, diselenides (such as sodium diselenide, dichlorodiselenide) containing the dynamic diselenide bond are preferred, and polyols, isocyanates, epoxides, alkenes, alkynes containing the dynamic diselenide bond are more preferred.

[0309] In the present invention, the dynamic selenosulfide bond can be activated under certain conditions, and bond dissociation, bonding, and exchange reactions occur, showing dynamic reversible characteristics; the dynamic selenosulfide bond in the present invention is selected from at least one of the following structures:

[0310] |-Se-s-|,

[0311] wherein, represents the connection to the polymer chain, crosslinked network chain, or any other suitable group / atom.

[0312] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of the dynamic selenium-sulfur bond include, but are not limited to, temperature regulation, addition of redox agents, addition of catalysts, addition of initiators, light irradiation, radiation, microwave, plasma action, etc., so that the polymer exhibits good self-healing properties, recyclability, stimulus responsiveness, etc. For example, heating can cause the cleavage of the dynamic selenium-sulfur bond to form sulfur radicals and selenium radicals, thereby occurring the dissociation and exchange reactions of the dynamic bond. After cooling, the dynamic selenium-sulfur bond is re-formed and stabilized, showing self-healing and reprocessing properties; good self-healing properties can be obtained for the polymer containing sulfur-selenium bonds by laser irradiation; self-healing and reprocessing properties can be obtained by generating radicals in the system through radiation, microwave and plasma to act on the dynamic selenium-sulfur bond. Recyclability can also be obtained for the dynamic polymer by adding redox agents to the system. Among them, the types of the reducing agents include, but are not limited to, sodium metabisulfite, sodium borohydride, dithiothreitol, 2-mercaptoethanol, glutathione, tris(2-carboxyethyl)phosphine hydrochloride, alkyl mercaptans (such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, etc.), alkyl phosphines (such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, etc.); the types of the oxidizing agents include, but are not limited to, air, lead dioxide, manganese dioxide, organic peroxides (such as benzoyl peroxide, hydrogen peroxide, ozone, p-benzoquinone dioxime, disulfide), etc. The dynamic polymer can also generate radicals by adding initiators to the system and then under the action of heating, light irradiation, radiation, microwave and plasma, promoting the dissociation or exchange of the dynamic selenium-sulfur bond to obtain self-healing properties or recyclability. Among them, the initiators include, but are not limited to, any one or any several of the following initiators: photoinitiators, such as 2,2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone and α-ketoglutaric acid; organic peroxides, such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy pivalate, di-tert-butyl peroxide, cumene hydroperoxide; azo compounds, such as azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides, such as ammonium persulfate, potassium persulfate, etc.; among them, the initiators are preferably 2,2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

[0313] In an embodiment of the present invention, the dynamic selenium-sulfur bond can be formed through the oxidative coupling reaction of thiol and selenol contained in the compound raw material, the bonding reaction of sulfur radical and selenol radical, or introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing selenium-sulfur bond. Among them, there is no particular limitation on the compound raw material containing selenium-sulfur bond, and polyols, isocyanates, epoxides, alkenes, alkynes, and carboxylic acids containing selenium-sulfur bond are preferred, and polyols, isocyanates, epoxides, alkenes, alkynes containing selenium-sulfur bond are more preferred.

[0314] In the present invention, the dynamic selenium-nitrogen bond can be activated under certain conditions and undergo bond dissociation, bonding, and exchange reactions, showing dynamic reversible characteristics; the dynamic selenium-nitrogen bond in the present invention is selected from the following structures:

[0315]

[0316] Among them, X is selected from halogen ions, preferably chloride ions and bromide ions. represents the connection to the polymer chain, crosslinked network chain, or any other suitable group / atom.

[0317] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of the dynamic selenium-nitrogen bond include, but are not limited to, temperature adjustment, addition of acid-base catalysts and other action modes, so that the polymer exhibits good self-healing property, recyclability for recycling, stimulus responsiveness, etc. Among them, the acid-base catalysts can be selected from: (1) inorganic acids, organic acids and their acid salts. Examples of inorganic acids include sulfuric acid, hydrochloric acid, phosphoric acid, etc.; examples of organic acids include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.; examples of salts include sulfates, bisulfates, hydrogen phosphates, etc. (2) Group IA alkali metals and their compounds, such as lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, potassium carbonate, cesium carbonate, etc. (3) Group IIA alkali metals and their compounds, such as calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide, etc. (4) Aluminum metal and its compounds, such as aluminum powder, aluminum oxide, sodium aluminate, a complex of hydrated aluminum oxide and sodium hydroxide, alkoxyaluminum compounds, etc. (5) Organic compounds, such as ammonium chloride, triethylamine, triethylamine hydrochloride, pyridine, hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine, o-benzylhydroxylamine hydrochloride, butyraldehyde oxime, benzaldehyde oxime, hydrazine monohydrate, N,N'-diphenylthiourea, scandium trifluoromethanesulfonate (Sc(OTf)3), etc. (6) Divalent copper compounds, such as copper acetate, etc. (7) Trivalent iron compounds, such as aqueous ferric chloride solution, ferric sulfate hydrate, ferric nitrate hydrate, etc. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferred.

[0318] In the embodiments of the present invention, the dynamic selenium-nitrogen bond can be formed by the reaction of a selenium halide and a pyridine derivative contained in the compound raw materials.

[0319] In the present invention, the acetal-based dynamic covalent bonds include dynamic ketal bonds, dynamic acetal bonds, dynamic thioketal bonds, and dynamic thioacetal bonds, which can be activated under certain conditions and undergo bond dissociation, ketalization reactions, and exchange reactions, demonstrating dynamic reversible characteristics; among them, the "certain conditions" for activating the dynamic reversibility of the acetal-based dynamic covalent bonds refer to heating, suitable acidic aqueous conditions, etc. The acetal-based dynamic covalent bonds in the present invention are selected from at least one of the following structures:

[0320]

[0321] Among them, X1, X2, X3, and X4 are each independently selected from an oxygen atom, a sulfur atom, and a nitrogen atom, preferably an oxygen atom and a sulfur atom; R1 and R2 are each independently selected from a hydrogen atom, a heteroatom group, a small molecule hydrocarbon group, and a polymer chain residue; R3 and R4 are each independently selected from a single bond, a heteroatom linking group, a divalent or polyvalent small molecule hydrocarbon group, and a divalent or polyvalent polymer chain residue; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom, wherein different can be connected to form a ring, and the rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

[0322] In an embodiment of the present invention, the acetal-based dynamic covalent bond can dissociate in an acidic aqueous solution and form under anhydrous acidic conditions, having good pH stimulus responsiveness. Therefore, dynamic reversibility can be obtained by adjusting the acidic environment.

[0323] In an embodiment of the present invention, the acids that can be used for the dynamic ketal reaction include but are not limited to p-toluenesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid, oxalic acid, carbonic acid, propionic acid, nonanoic acid, silicic acid, acetic acid, nitric acid, chromic acid, phosphoric acid, 4-chloro-benzenesulfinic acid, p-methoxybenzoic acid, 1,4-benzenedicarboxylic acid, 4,5-difluoro-2-nitrobenzeneacetic acid, 2-bromo-5-fluorobenzenepropionic acid, bromoacetic acid, chloroacetic acid, phenylacetic acid, adipic acid, etc. The state of the acid used in the present invention is not limited, and it can be a pure acid, an organic solution of the acid, an aqueous solution of the acid, or even in the form of acid vapor. The present invention can also use different states of the acid in a combined form, such as first using an organic solution of p-toluenesulfonic acid to promote the formation of dynamic covalent bonds, and then using an aqueous solution of hydrochloric acid to dissociate the dynamic covalent bonds to obtain recyclability for recycling.

[0324] In an embodiment of the present invention, the acetal-based dynamic covalent bond can be formed by a condensation reaction of a ketone group and an aldehyde group contained in a compound raw material with a hydroxyl group and a mercapto group, or can be formed by an exchange reaction of the acetal-based dynamic covalent bond with an alcohol, a thiol, an aldehyde, and a ketone, or can be introduced into a polymer by a polymerization / crosslinking reaction between reactive groups contained in a compound raw material containing an acetal-based dynamic covalent bond. Among them, there is no particular limitation on the compound raw material containing an acetal-based dynamic covalent bond, and polyols, polythiols, polyamines, isocyanates, epoxides, alkenes, alkynes, and carboxylic acids containing an acetal-based dynamic covalent bond are preferred, and polyols, polyamines, isocyanates, epoxides, alkenes, and alkynes containing an acetal-based dynamic covalent bond are more preferred.

[0325] In the present invention, the dynamic covalent bonds based on carbon-nitrogen double bonds include dynamic imine bonds, dynamic oxime bonds, dynamic hydrazone bonds, and dynamic acylhydrazone bonds, which can be activated under certain conditions and undergo dissociation, condensation, and exchange reactions of dynamic covalent bonds, demonstrating dynamic reversibility. Among them, the "certain conditions" for activating the dynamic reversibility of the dynamic covalent bonds based on carbon-nitrogen double bonds refer to suitable pH aqueous conditions, the presence of suitable catalysts, heating conditions, pressure conditions, etc. The dynamic covalent bonds based on carbon-nitrogen double bonds in the present invention are selected from at least one of the following structures:

[0326]

[0327] Among them, R1 is a divalent or polyvalent small hydrocarbon group; represents the connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom.

[0328] In an embodiment of the present invention, the suitable pH aqueous conditions for promoting the dissociation and condensation reactions of the dynamic covalent bonds based on carbon-nitrogen double bonds refer to swelling the dynamic polymer in an aqueous solution with a certain pH value or wetting its surface with an aqueous solution with a certain pH value, so that the dynamic covalent bonds based on carbon-nitrogen double bonds in the dynamic polymer have dynamic reversibility. Among them, the above-mentioned aqueous solution can be entirely aqueous solution, or an organic solution containing water, oligomer, plasticizer, ionic liquid. The pH value of the selected aqueous solution changes according to the type of the dynamic covalent bonds based on carbon-nitrogen double bonds. For example, for dynamic benzoyl imine bonds, an acidic solution with pH ≤ 6.5 can be selected to cause hydrolysis, and for dynamic acylhydrazone bonds, an acidic solution with pH ≤ 4 can be selected to cause hydrolysis.

[0329] Among them, the acid-base catalysts for the dissociation, condensation, and exchange reactions of dynamic covalent bonds based on carbon-nitrogen double bonds can be selected from: (1) inorganic acids, organic acids, and their acid salts. Examples of inorganic acids include sulfuric acid, hydrochloric acid, phosphoric acid, etc.; examples of organic acids include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.; examples of salts include sulfates, bisulfates, hydrogen phosphates, etc. (2) Group IA alkali metals and their compounds, such as lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, potassium carbonate, cesium carbonate, etc. (3) Group IIA alkali metals and their compounds, such as calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide, etc. (4) Aluminum metal and its compounds, such as aluminum powder, aluminum oxide, sodium aluminate, a complex of hydrated aluminum oxide and sodium hydroxide, alkoxyaluminum compounds, etc. (5) Organic compounds, such as ammonium chloride, triethylamine, triethylamine hydrochloride, pyridine, hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine, o-benzylhydroxylamine hydrochloride, butyraldoxime, benzaldoxime, hydrazine monohydrate, N,N'-diphenylthiourea, scandium trifluoromethanesulfonate (Sc(OTf)3), etc. (6) Divalent copper compounds, such as copper acetate, etc. (7) Trivalent iron compounds, such as aqueous ferric chloride, ferric sulfate hydrate, ferric nitrate hydrate, etc. Among them, sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, calcium hydroxide, triethylamine, pyridine, and copper acetate are preferred.

[0330] In an embodiment of the present invention, the dynamic covalent bond based on carbon-nitrogen double bonds can be formed by the condensation reaction of keto groups, aldehyde groups, and acyl groups contained in the compound raw materials with amino groups, hydrazino groups, and acylhydrazino groups, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing dynamic covalent bonds based on carbon-nitrogen double bonds. Among them, there is no particular limitation on the compound raw materials containing dynamic covalent bonds based on carbon-nitrogen double bonds. Polyols, polythiols, polyamines, isocyanates, epoxides, alkenes, alkynes, and carboxylic acids containing dynamic covalent bonds based on carbon-nitrogen double bonds are preferred, and polyols, polyamines, isocyanates, epoxides, alkenes, and alkynes containing dynamic covalent bonds based on carbon-nitrogen double bonds are more preferred.

[0331] In the present invention, the dynamic covalent bond based on reversible radicals can be activated under certain conditions to generate radicals and undergo bond formation or exchange reactions, showing dynamic reversible characteristics; among them, the "exchange reaction of dynamic covalent bonds based on reversible radicals" refers to the formation of new dynamic covalent bonds elsewhere by the intermediate radicals formed after the dissociation of old dynamic covalent bonds in the polymer, thereby resulting in chain exchange and changes in the polymer topological structure. The dynamic covalent bond based on reversible radicals in the present invention is selected from at least one of the following structures:

[0332]

[0333] Among them, each W is independently selected from an oxygen atom and a sulfur atom;

[0334] Among them, each W1 is independently selected from a single bond, an ether group, a thioether group, a secondary amino group and its substituents, a divalent methyl group and its substituents, preferably a direct bond, an ether group, a thioether group; the structures of W1 at different positions are the same or different;

[0335] Among them, each W2 is independently selected from an ether group, a thioether group, a secondary amino group and its substituents, a divalent methyl group and its substituents, preferably a thioether group, a secondary amino group; the structures of W2 at different positions are the same or different;

[0336] Among them, each W3 is independently selected from an ether group, a thioether group, preferably an ether group; the structures of W3 at different positions are the same or different;

[0337] Among them, each W4 is independently selected from an ether group, a thioether group, a secondary amino group and its substituents, preferably an ether group; the structures of W4 at different positions are the same or different;

[0338] Among them, V and V' are each independently selected from a carbon atom and a nitrogen atom, and the structures of V and V' at different positions are the same or different. When V and V' are selected from nitrogen atoms, the does not exist;

[0339] Among them, Z is selected from a selenium atom, a tellurium atom, an antimony atom, a bismuth atom; among them, k is the number of connected to Z; when Z is a selenium atom or a tellurium atom, k is 1, indicating that there is only one connected to Z; when Z is an antimony atom or a bismuth atom, k is 2, indicating that there are two connected to Z, and the structures of the two are the same or different;

[0340] Among them, each R1 is independently selected from a hydrogen atom, a halogen atom, a heteroatom group, C 1-20 hydrocarbon group / heterohydrocarbon group, substituted C 1-20 hydrocarbon group / heterohydrocarbon group, and substituents formed by a combination of two or more of the above groups; each R1 is independently preferably selected from a hydrogen atom, a hydroxyl group, a cyano group, a carboxyl group, C 1-20 alkyl group, C 1-20 aryl group, C 1-20 heteroaryl group, and acyl group, acyloxy group, amide group, oxyacyl group, thioacyl group, aminoacyl group, C-substituted by a phenyl group 1-20Hydrocarbyl / Heterohydrocarbyl; R1 is further preferably selected from a hydrogen atom, methyl, ethyl, propyl, butyl, phenyl, hydroxyl, cyano, carboxyl, methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, butyloxycarbonyl, methylaminoacyl, ethylaminoacyl, propylaminoacyl, butylaminoacyl;

[0341] Wherein, each R2 is independently selected from any suitable atom (including a hydrogen atom), substituent, substituted polymer chain; the structures of each R2 are the same or different; when R2 is selected from substituents, it is selected from but not limited to: hydroxyl, phenyl, phenoxy, C 1-10 alkyl, C 1-10 alkoxy, C 1-10 alkoxycarbonyl, C 1-10 alkylcarbonyloxy, trimethylsilyloxy, triethylsilyloxy; wherein, the substituted atom or substituent is not particularly limited, and it is selected from but not limited to any one or more of halogen atoms, hydrocarbyl substituents, and heteroatom-containing substituents;

[0342] Wherein, each R3 is independently selected from cyano, C 1-10 alkoxycarbonyl, C 1-10 alkylcarbonyl, C 1-10 alkylaminoacyl, phenyl, substituted phenyl, aryl, substituted aryl; wherein, the substituted atom or substituent is not particularly limited, and it is selected from but not limited to any one or more of halogen atoms, hydrocarbyl substituents, and heteroatom-containing substituents;

[0343] Wherein, R 1 、R 2 、R 3 、R 4 are each independently selected from a hydrogen atom, a halogen atom, a heteroatom group, a substituent; R 1 、R 2 、R 3 、R 4 are each independently preferably selected from a hydrogen atom, a halogen atom, a heteroatom group, C 1-20 hydrocarbyl, C 1-20 heterohydrocarbyl, substituted C 1-20 hydrocarbyl or substituted C 1-20 heterohydrocarbyl and substituents formed by a combination of two or more of the above groups; more preferably from a hydrogen atom, hydroxyl, cyano, carboxyl, C 1-20 alkyl, C 1-20 heteroalkyl, cyclic C 1-20 alkyl, cyclic C 1-20 heteroalkyl, C 1-20 aryl, C 1-20 heteroaryl;

[0344] Wherein, R 5 、R 6, R 7 , R 8 are each independently selected from any suitable atom (including a hydrogen atom), substituent, or substituted polymer chain; when R 5 , R 6 , R 7 , R 8 are each independently selected from substituents, preferably the substituents are sterically hindered substituents; the sterically hindered substituents are selected from, but not limited to: cyano, C 1-20 alkyl, C 1-20 cycloalkyl, aryl, heteroaryl, and groups formed by any of the above groups being substituted by any substituted atom or substituent; wherein, the substituted atom or substituent is not particularly limited and is selected from, but not limited to, any one or more of halogen atoms, hydrocarbon substituents, and heteroatom-containing substituents; 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 1-5 alkyl-substituted phenyl, C 1-5 alkoxy-substituted phenyl, C 1-5 alkylthio-substituted phenyl, C 1-5 alkylamino-substituted phenyl, cyano-substituted phenyl;

[0345] wherein, Ls are each independently selected from heteroatom linking groups, heteroatom group linking groups, divalent C 1-20 hydrocarbon / heterohydrocarbon, substituted divalent C 1-20 hydrocarbon / heterohydrocarbon, and divalent linking groups formed by a combination of two or more of the above groups; wherein, the substituted atom or substituent is not particularly limited and is selected from, but not limited to, any one or more of halogen atoms, hydrocarbon substituents, and heteroatom-containing substituents; the Ls are each independently preferably selected from acyl, acyloxy, acylthio, amido, oxyacyl, thioacyl, phenylene, divalent C 1-20 hydrocarbon / heterohydrocarbon, substituted divalent C 1-20 hydrocarbon / heterohydrocarbon; wherein the substituent group in the substituted divalent C 1-20 hydrocarbon / heterohydrocarbon preferably has a structure of acyl, acyloxy, acylthio, amido, oxyacyl, thioacyl, aminoacyl, phenylene, and more preferably the substituted divalent C 1-20 hydrocarbon / heterohydrocarbon is connected to the carbon atom connecting R1 through the substituent group;

[0346] wherein, represents that the ring has a conjugated structure; wherein, is a five-membered nitrogen heterocyclic structure with a conjugated structure; wherein, a polycyclic structure formed by a carbon-carbon single bond, a carbon-nitrogen single bond, or a nitrogen-nitrogen single bond between one ring-forming atom of each of the two five-membered nitrogen heterocycles; according to different connection modes, including but not limited to one or more of the following isomers: It should be noted that under appropriate conditions, various isomers can be interconverted. Therefore, in the present invention, the above six isomeric units are regarded as the same structural unit;

[0347] wherein, is a nitrogen-containing aliphatic heterocycle, and the number of ring-forming atoms of the ring is not particularly limited, preferably from 3 to 10, more preferably from 5 to 8; among the ring-forming atoms of the aliphatic heterocycle, except for at least one ring-forming atom being a nitrogen atom, the 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 connected to the ring-forming atoms are replaced or not replaced by any suitable substituting atoms or substituents; wherein, the substituting atoms or substituents are not particularly limited, and are selected from but not limited to any one or more of halogen atoms, hydrocarbon group substituents, and heteroatom-containing substituents;

[0348] wherein, represents a nitrogen-containing aliphatic heterocycle connected with n , wherein the value of n is 0, 1 or an integer greater than 1; wherein, the site marked with * is the site connected to other structures in the formula; the is preferably at least one of the following structures, but the present invention is not limited thereto:

[0349]

[0350] the is more preferably at least one of the following structures, but the present invention is not limited thereto:

[0351]

[0352]

[0353] wherein, is an aromatic ring; the ring structure of the aromatic ring is selected from a monocyclic structure, a polycyclic structure, a spiro ring 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 connected to the ring-forming atoms are replaced or not replaced by any suitable substituting atoms or substituents; wherein, the substituting atoms or substituents are not particularly limited, and are selected from but not limited to any one or more of halogen atoms, hydrocarbon group substituents, and heteroatom-containing substituents;

[0354] Among them, represents an aromatic ring connected to n , and the structures at different positions are the same or different; among them, the site marked with * is the site connected to other structures in the formula;

[0355] Among them, represents the connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; each structure is the same or different; different can be connected to form a ring, and the said ring includes but is not limited to an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, and combinations thereof.

[0356] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of the reversible radical-based dynamic covalent bond include but are not limited to action modes such as temperature regulation, addition of initiators, light irradiation, radiation, microwave, plasma action, etc. For example, by heating, the said dynamic covalent bond can be broken to form free radicals, thereby occurring the dissociation and exchange reaction of the dynamic covalent bond. After cooling, the dynamic covalent bond is re-formed and stabilized, so that the polymer can obtain self-healing and reprocessing properties. Light irradiation can also break the said dynamic covalent bond to form free radicals, thereby occurring the dissociation and exchange reaction of the dynamic covalent bond. After removing the light irradiation, the dynamic covalent bond is re-formed, so that the polymer can obtain self-healing and reprocessing properties. Radiation, microwave, and plasma can generate free radicals in the system to act on the dynamic covalent bond to obtain self-healing and reprocessing properties. The initiator can generate free radicals, promote the dissociation or exchange of the dynamic covalent bond, and obtain self-healing or recyclability. Among them, the said initiator includes but is not limited to any one or any several of the following initiators: photoinitiators, such as 2,2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, and α-ketoglutaric acid; organic peroxides, such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, di-tert-butyl peroxide, cumene hydroperoxide; azo compounds, such as azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides, such as ammonium persulfate, potassium persulfate, etc.; among them, the initiator is preferably 2,2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

[0357] In an embodiment of the present invention, the polymer contains dynamic covalent bonds based on reversible free radicals, which can be formed by the bonding reaction of free radicals contained in the compound raw materials or other suitable coupling reactions; they can be generated in situ in the polymer, or introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing dynamic covalent bonds based on reversible free radicals. Among them, there is no particular limitation on the compound raw materials containing dynamic covalent bonds based on reversible free radicals. Polyols, polythiols, polyamines, isocyanates, epoxides, alkenes, alkynes, and carboxylic acids containing dynamic covalent bonds based on reversible free radicals are preferred, and polyols, polyamines, isocyanates, epoxides, alkenes, and alkynes containing dynamic covalent bonds based on reversible free radicals are more preferred.

[0358] In the present invention, the binding exchangeable acyl bond can be activated under certain conditions and undergo a binding acyl exchange reaction with a nucleophilic group (such as a binding transesterification reaction, a binding amide exchange reaction, a binding carbamate exchange reaction, a binding vinylamide or vinyl carbamate insertion exchange reaction, etc.), demonstrating dynamic reversibility; among them, the "binding acyl exchange reaction" refers to that the binding exchangeable acyl bond first binds to a nucleophilic group to form an intermediate structure, and then undergoes an acyl exchange reaction to form a new dynamic covalent bond, thereby resulting in chain exchange and changes in the polymer topology. During this process, the crosslinking degree of the polymer can remain unchanged; among them, the "certain conditions" for activating the dynamic reversibility of the binding exchangeable acyl bond refer to the presence of a suitable catalyst, heating conditions, pressure conditions, etc.; among them, the "nucleophilic group" refers to active groups such as hydroxyl, mercapto, and amino groups present in the polymer system for carrying out the binding acyl exchange reaction. The nucleophilic group can be on the same polymer network / chain as the binding exchangeable acyl bond, or on different polymer networks / chain, or can be introduced by small molecules or polymers containing nucleophilic groups. The binding exchangeable acyl bond described in the present invention is selected from at least one of the following structures:

[0359]

[0360] Among them, X1 and X2 are selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; Y is selected from an oxygen atom, a sulfur atom, and a secondary amino group; Z1 and Z2 are selected from an oxygen atom and a sulfur atom; R5 is selected from a hydrogen atom, a heteroatom group, a small hydrocarbon group, and a polymer chain residue; among them, when X1 and X2 are oxygen atoms or sulfur atoms, R1, R2, R3, and R4 do not exist; when X1 and X2 are nitrogen atoms, R1 and R3 exist, R2 and R4 do not exist, and R1 and R3 are each independently selected from a hydrogen atom, a heteroatom group, a small hydrocarbon group, and a polymer chain residue; when X1 and X2 are carbon atoms or silicon atoms, R1, R2, R3, and R4 exist, and are each independently selected from a hydrogen atom, a heteroatom group, a small hydrocarbon group, and a polymer chain residue; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom. Among them, the binding exchangeable acyl bond is preferably selected from a binding exchangeable ester bond, a binding exchangeable thioester bond, a binding exchangeable amide bond, a binding exchangeable carbamate bond, a binding exchangeable thiocarbamate bond, a binding exchangeable urea bond, a binding exchangeable vinylamide bond, and a binding exchangeable vinylcarbamate bond.

[0361] In the present invention, some of the binding acyl exchange reactions need to be carried out under catalyst conditions, and the catalyst includes catalysts for transesterification reactions (including esters, thioesters, carbamates, thiocarbamates, etc.) and amine exchange reactions (including amides, carbamates, thiocarbamates, ureas, vinylamides, vinylcarbamates, etc.). By adding the catalyst, the occurrence of the binding acyl exchange reaction can be promoted, so that the dynamic polymer exhibits good dynamic properties.

[0362] Among them, the catalysts for transesterification reaction can be selected from: (1) inorganic acids, organic acids and their acid salt catalysts. Examples of inorganic acids include sulfuric acid, hydrochloric acid, phosphoric acid, etc.; examples of organic acids include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.; examples of salts include sulfates, bisulfates, hydrogen phosphates, etc. (2) Group IA alkali metals and their compounds, such as lithium, lithium oxide, lithium acetylacetonate, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium carbonate, cesium carbonate, etc. (3) Group IIA alkali metals and their compounds, such as calcium, calcium oxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, magnesium ethoxide. (4) Aluminum metals and their compounds, such as aluminum powder, aluminum oxide, sodium aluminate, a complex of hydrated aluminum oxide and sodium hydroxide, alkoxyaluminum compounds. (5) Tin compounds, including inorganic tin and organic tin. Examples of inorganic tin include tin oxide, tin sulfate, stannous oxide, stannous chloride, etc. Examples of organic tin include dibutyltin oxide, dibutyltin dilaurate, dibutyltin dichloride, tributyltin acetate, tributyltin chloride, trimethyltin chloride, etc. (6) Compounds of Group IVB elements, such as titanium dioxide, tetramethyl titanate, isopropyl titanate, isobutyl titanate, tetrabutyl titanate, zirconium dioxide, zirconium sulfate, zirconium tungstate, tetramethyl zirconate. (7) Anionic pillared compounds, whose main component is generally composed of hydroxides of two metals, called double metal hydroxide LDH, and its calcined product is LDO, such as hydrotalcite {Mg6(CO3)[Al(OH)6]2(OH)4·4H2O}. (8) Supported solid catalysts, such as complexes of KF / CaO, K2CO3 / CaO, KF / γ-Al2O3, K2CO3 / γ-Al2O3, KF / Mg-La, K2O / activated carbon, K2CO3 / coal ash powder, KOH / NaX, KF / MMT (montmorillonite), etc. (9) Organic zinc compounds, such as zinc acetate, zinc acetylacetonate, etc. (10) Organic compounds, such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 2-methylimidazole (2-MI), triphenylphosphine, etc. Among them, organotin compounds, titanate compounds, organic zinc compounds, supported solid catalysts, TBD, and 2-MI are preferred; more preferably, TBD and zinc acetate are used in combination for synergistic catalysis, and 2-MI and zinc acetylacetonate are used in combination for synergistic catalysis.

[0363] Among them, the catalysts for amine exchange reaction can be selected from: nitric acid, hydrochloric acid, aluminum chloride, ammonium chloride, triethylamine hydrochloride, hydroxylamine, hydroxylamine hydrochloride, hydroxylamine sulfate, N-methylhydroxylamine hydrochloride, benzylamine hydrochloride, o-benzylhydroxylamine, o-benzylhydroxylamine hydrochloride, butyraldoxime, benzaldehyde oxime, hydrazine monohydrate, N,N'-diphenylthiourea, scandium trifluoromethanesulfonate (Sc(OTf)3), montmorillonite KSF, hafnium tetrachloride (HfCl4), Hf4Cl5O24 H 24 , HfCl4 / KSF-polyDMAP, transglutaminase (TGase); divalent copper compounds, such as, for example, copper acetate; trivalent iron compounds, such as, for example, aqueous ferric chloride, iron sulfate hydrate, iron nitrate hydrate, etc. Among them, copper acetate is preferred; Sc(OTf)3 and HfCl4 are used in combination and synergistically catalyzed; HfCl4 / KSF-polyDMAP; glycerol, boric acid, iron nitrate hydrate are used in combination and synergistically catalyzed.

[0364] In the embodiments of the present invention, some bonding acyl exchange reactions can also be carried out by microwave radiation or heating. For example, ordinary carbamate bonds, thiocarbamate bonds, and urea bonds can undergo acyl exchange reactions when heated to 160 - 180 °C with an auxiliary pressure of 4 MPa; vinylacetamide bonds and vinylcarbamate bonds can undergo acyl exchange reactions by Michael addition when heated above 100 °C; The carbamate bond with a structure can undergo an acyl exchange reaction with a molecular chain containing a phenolic hydroxyl group or a benzyl hydroxyl group when heated above 90 °C. The present invention preferably carries out a reversible reaction under normal temperature and normal pressure conditions by adding a catalyst that can be used for the bonding acyl exchange reaction.

[0365] In the embodiments of the present invention, the bonding exchangeable acyl bond can be formed by the condensation reaction of acyl, thioacyl, aldehyde, carboxyl, acyl halide, acid anhydride, active ester, isocyanate groups contained in the compound raw materials with hydroxyl, amino, and mercapto groups, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing the bonding exchangeable acyl bond. Among them, there is no particular limitation on the compound raw materials containing the bonding exchangeable acyl bond. Polyols, polythiols, polyamines, isocyanates, epoxides, alkenes, alkynes, and carboxylic acids containing the bonding exchangeable acyl bond are preferred, and polyols, polyamines, isocyanates, epoxides, alkenes, and alkynes containing the bonding exchangeable acyl bond are more preferred.

[0366] In the present invention, the dynamic covalent bond induced by the steric effect contains a "large group with steric effect" and can be activated at room temperature or certain conditions, and undergoes bond dissociation, bonding, and exchange reactions, showing dynamic reversible characteristics. The dynamic covalent bond induced by the steric effect in the present invention is selected from at least one of the following structures:

[0367]

[0368] Among them, X1 and X2 are selected from carbon atoms, silicon atoms and nitrogen atoms, preferably carbon atoms and nitrogen atoms; Z1 and Z2 are selected from oxygen atoms and sulfur atoms, preferably oxygen atoms; when X1 and X2 are nitrogen atoms, R1 and R3 exist, R2 and R4 do not exist, and R1 and R3 are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; when X1 and X2 are carbon atoms or silicon atoms, R1, R2, R3 and R4 exist, and are each independently selected from hydrogen atoms, heteroatom groups, small molecule hydrocarbon groups, polymer chain residues; among them, Rh is a large group with steric hindrance directly connected to the nitrogen atom, and it can be selected from C 3-20 alkyl, cyclo-C 3-20 alkyl, phenyl, benzyl, aryl group and unsaturated forms, substituted forms, hybridized forms and combinations of the above groups, more preferably isopropyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, benzyl, methylbenzyl, most preferably tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, phenyl, benzyl, methylbenzyl; represents a nitrogen-containing ring with any number of elements, which can be an aliphatic ring or an aromatic ring, and it can be an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and their combinations. The ring-forming atoms are each independently selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms or other heteroatoms. The hydrogen atoms on the ring-forming atoms can be substituted by any substituent or not substituted. The formed ring is preferably a pyrrole ring, an imidazole ring, a pyrazole ring, a piperidine ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring; n represents the number of connections connected to the ring-forming atoms of the cyclic group structure.

[0369] In the "large group with steric hindrance" described in the present invention, which is directly connected to the nitrogen atom or forms a cyclic structure with the nitrogen atom, it can weaken the chemical bond strength between the carbon atom and the adjacent nitrogen atom in the carbonyl group or thiocarbonyl group, so that the carbon-nitrogen bond exhibits the properties of a dynamic covalent bond, and a dynamic reversible reaction can occur at room temperature or certain conditions. It should be noted that the steric hindrance in the "large group with steric hindrance" is not the larger the better, but of moderate size, and makes the carbon-nitrogen bond have appropriate dynamic reversibility. The "certain conditions" for activating the dynamic reversibility of the dynamic covalent bond induced by steric hindrance include but are not limited to action modes such as heating, pressurization, light irradiation, radiation, microwave, plasma action, etc., so that the polymer exhibits good self-healing properties, recyclability by recycling, stimulus responsiveness, etc. For example, the dynamic covalent bond of the structure can undergo a dynamic exchange reaction at 60 °C, showing dynamic characteristics.

[0370] In the present invention, the dynamic covalent bond induced by steric effect is preferably selected from an amide bond induced by steric effect, a carbamate bond induced by steric effect, a thiocarbamate bond induced by steric effect, and a urea bond induced by steric effect.

[0371] In an embodiment of the present invention, the dynamic covalent bond induced by steric effect can be formed by a condensation reaction between an acyl group, a thioacyl group, an aldehyde group, a carboxyl group, an acyl halide, an acid anhydride, an active ester, an isocyanate group contained in a compound raw material and an amino group connected with a large group having steric effect, or can be introduced into a polymer by a polymerization / crosslinking reaction between reactive groups contained in a compound raw material containing a dynamic covalent bond induced by steric effect. Among them, there is no particular limitation on the compound raw material containing a dynamic covalent bond induced by steric effect, and polyols, polythiols, polyamines, isocyanates, epoxides, alkenes, alkynes, and carboxylic acids containing a dynamic covalent bond induced by steric effect are preferred, and polyols, polyamines, isocyanates, epoxides, alkenes, and alkynes containing a dynamic covalent bond induced by steric effect are more preferred.

[0372] In the present invention, the reversible addition-fragmentation chain transfer dynamic covalent bond can be activated in the presence of an initiator and undergo a reversible addition-fragmentation chain transfer reaction, showing dynamic reversible characteristics. The reversible addition-fragmentation chain transfer dynamic covalent bond in the present invention is selected from at least one of the following structures:

[0373]

[0374] Among them, R1 to R 10 each independently selected from a hydrogen atom, a heteroatom group, a small hydrocarbon group, a polymer chain residue; X1, X2, X3 each independently selected from a single bond, a divalent or polyvalent small hydrocarbon group, preferably a divalent C 1-20Alkyl groups and their substituted forms, hybridized forms, and combinations thereof, more preferably divalent isopropyl, divalent cumyl, divalent isopropyl ester, divalent isopropyl carboxyl, divalent isopropyl nitrile, divalent nitrile cumyl, divalent acrylate n-mer, divalent acrylate ester n-mer, divalent styrene n-mer and their substituted forms, hybridized forms, and combinations thereof, where n is greater than or equal to 2; Z1, Z2, and Z3 are each independently selected from a single bond, a heteroatom linking group, a divalent or polyvalent small hydrocarbon group, preferably a heteroatom linking group having an electron-withdrawing effect or linked to a group having an electron-withdrawing effect, a divalent or polyvalent small hydrocarbon group having an electron-withdrawing effect or linked to a group having an electron-withdrawing effect; where, as the preference for Z2 and Z3, they can be selected from an ether group, a sulfur group, a selenium group, a divalent silicon group, a divalent amine group, a divalent phosphate group, a divalent phenyl group, a methylene group, an ethylene group, a divalent styrene group, a divalent isopropyl group, a divalent cumyl group, a divalent isopropyl ester group, a divalent isopropyl carboxyl group, a divalent isopropyl nitrile group, a divalent nitrile cumyl group; where, groups having an electron-withdrawing effect include but are not limited to a carbonyl group, an aldehyde group, a nitro group, an ester group, a sulfonic acid group, an acylamino group, a sulfone group, a trifluoromethyl group, an aryl group, a cyano group, a halogen atom, an alkene, an alkyne, and combinations thereof; Represents the connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom.

[0375] The reversible addition-fragmentation chain transfer dynamic covalent bonds described in the present invention are preferably polyacrylic acid groups and their ester groups, polymethacrylic acid groups and their ester groups, polystyrene groups, polymethylstyrene groups, allyl thioether groups, dithioester groups, diselenoester groups, trithiocarbonate groups, triselenocarbonate groups, diselenothiocarbonate groups, dithiose lenocarbonate groups, bisdithioester groups, bisdiselenoester groups, bis(trithiocarbonate) groups, bis(triselenocarbonate) groups, dithiocarbamate groups, diselenocarbamate groups, dithiocarbonate groups, diselenocarbonate groups, and their corresponding derivative groups.

[0376] The "reversible addition-fragmentation chain transfer reaction" described in the present invention refers to a process in which a reactive free radical reacts with the reversible addition-fragmentation chain transfer dynamic covalent bond described in the present invention to form an intermediate. The intermediate can break to form a new reactive free radical and a new reversible addition-fragmentation chain transfer dynamic covalent bond, and this process is reversible. This process is similar to the reversible addition-fragmentation chain transfer process in reversible addition-fragmentation chain transfer polymerization, but is not exactly the same as the reversible addition-fragmentation chain transfer process in reversible addition-fragmentation chain transfer polymerization. First, reversible addition-fragmentation chain transfer polymerization is a solution polymerization process, while the "reversible addition-fragmentation chain transfer reaction" described in the present invention can be carried out in solution or in the solid state; in addition, in the reversible addition-fragmentation chain transfer reaction, an appropriate amount of a substance that can generate reactive free radicals can be added to generate reactive free radicals under certain conditions, so that the reversible addition-fragmentation chain transfer dynamic covalent bond has good dynamic reversibility and promotes the progress of the reversible addition-fragmentation chain transfer reaction. For example, when the reversible addition-fragmentation chain transfer dynamic covalent bond in the present invention is an allyl sulfide group, a substance that can generate an appropriate amount of sulfur free radicals can be added to the system to promote the reaction.

[0377] Among them, the initiators that can be selected in the reversible addition-fragmentation chain transfer exchange reaction include, but are not limited to, any one or any combination of the following initiators: photoinitiators, such as 2,2-dimethoxy-2-phenylacetophenone (DMPA), 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), benzophenone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, and α-ketoglutaric acid; organic peroxides, such as lauroyl peroxide, benzoyl peroxide (BPO), diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxy pivalate, di-tert-butyl peroxide, cumene hydroperoxide; azo compounds, such as azobisisobutyronitrile (AIBN), azobisisoheptonitrile; inorganic peroxides, such as ammonium persulfate, potassium persulfate, etc.; among them, the initiators are preferably 2,2-dimethoxy-2-phenylacetophenone, azobisisobutyronitrile, lauroyl peroxide, benzoyl peroxide, potassium persulfate.

[0378] In an embodiment of the present invention, for the reversible addition-fragmentation chain transfer dynamic covalent bond, it can be introduced into the polymer by a polymerization / crosslinking reaction between the reactive groups contained in a compound raw material containing the reversible addition-fragmentation chain transfer dynamic covalent bond.

[0379] In the present invention, the dynamic siloxane bond can be activated under the condition of a catalyst or heating and undergoes a siloxane exchange reaction, showing dynamic reversible characteristics; wherein, the "siloxane exchange reaction" refers to the formation of new siloxane bonds elsewhere accompanied by the dissociation of old siloxane bonds, thereby resulting in chain exchange and changes in the polymer topological structure. The dynamic siloxane bond in the present invention is selected from the following structures:

[0380]

[0381] wherein, represents the connection with a polymer chain, a crosslinked network chain or any other suitable group / atom; can form a ring or not form a ring.

[0382] In the present invention, the siloxane reaction needs to be carried out under a catalyst or heating conditions, wherein the dynamic siloxane bond preferably undergoes a siloxane bond exchange reaction under the presence of a catalyst. The catalyst can promote the occurrence of the siloxane equilibrium reaction, so that the dynamic polymer exhibits good dynamic characteristics. Among them, the catalyst used for the siloxane equilibrium reaction can be selected from: (1) alkali metal hydroxides, such as lithium hydroxide, potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, etc. (2) alkali metal alkoxides, alkali metal polyalkoxides, such as potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium propoxide, potassium n-butoxide, potassium isobutoxide, sodium tert-butoxide, potassium tert-butoxide, lithium pentanolate, potassium ethylene glycolate, sodium glycerol, 1,4-butanediol potassium, 1,3-propanediol sodium, pentaerythritol lithium, sodium cyclohexanol, etc. (3) Siliconates, for example, potassium triphenylsiliconate, sodium dimethylphenylsiliconate, lithium tri-tert-butoxysiliconate, potassium trimethylsiliconate, sodium trimethylsiliconate, sodium triethylsiliconate, lithium (4-methoxyphenyl)dimethylsiliconate, tri-tert-pentaneoxysilanol, potassium diphenylsilanediol, potassium benzyltrimethylammoniumbis(catechol)phenylsiliconate, and the like. (4) Quaternary ammonium bases, for example, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), trimethylbenzylammonium hydroxide, tetrabutylammonium hydroxide, (1-hexadecyl)trimethylammonium hydroxide, methyltriethylammonium hydroxide, phenyltrimethylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetrapropylammonium hydroxide, tetraoctylammonium hydroxide, triethylbenzylammonium hydroxide, choline, [3-(methacrylamido)propyl]dimethyl(3-thiopropyl)ammonium hydroxide inner salt, phenyltriethylammonium hydroxide, N,N,N-trimethyl-3-(trifluoromethyl)aniline hydroxide, N-ethyl-N,N-dimethyl -ethylammonium, tetradecylammonium hydroxide, tetrapentylammonium hydroxide, N,N,N-trimethyl-1-adamantylammonium hydroxide, tetraoctadecylammonium hydroxide, N,N-dimethyl-N-[3-(thioxo)propyl]-1-nonaneammonium hydroxide inner salt, (methoxycarbonylsulfamoyl)triethylammonium hydroxide, 3-sulfopropyldodecyldimethylbetaine, 3-(N,N-dimethylpalmitylamino)propanesulfonate, methacryloylethylsulfobetaine, N,N-dimethyl-N-(3-sulfopropyl)-1-octadecylammonium inner salt, tributylmethylammonium hydroxide, tri(2-hydroxyethyl)methylammonium hydroxide, tetradecylsulfobetaine, etc. In the present invention, the catalyst used for the siloxane equilibration reaction is preferably a quaternary ammonium base, a silicon alkoxide, and an alkali metal hydroxide catalyst, and more preferably a catalyst such as lithium hydroxide, potassium hydroxide, trimethylsiliconate potassium, tetramethylammonium hydroxide (TMAH), and tetraethylammonium hydroxide (TEAH).

[0383] In an embodiment of the present invention, the dynamic siloxane bond can be formed by the condensation reaction between silanol groups and silanol precursors contained in the compound raw materials, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing dynamic siloxane bonds. Among them, there is no particular limitation on the compound raw materials containing dynamic siloxane bonds. Polyols, polysilanols, polyamines, isocyanates, siloxane compounds, silanes, epoxides, alkenes, and alkynes containing dynamic siloxane bonds are preferred, and polyols, polysilanols, isocyanates, siloxane compounds, silanes, and alkenes containing dynamic siloxane bonds are more preferred. Among them, the silanol precursor refers to a structural unit (Si-X1) composed of a silicon atom and a group that can be hydrolyzed to obtain a hydroxyl group connected to the silicon atom. Among them, X1 is a group that can be hydrolyzed to obtain a hydroxyl group, and it can be selected from halogen, cyano, cyanate, thiocyanate, alkoxy, amino, sulfate group, borate group, acyl group, acyloxy group, acylamino group, ketoxime group, alkoxide group. Suitable examples of silanol precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO4CH3, Si-OB(OCH3)2, Si-NH2, Si-N(CH3)2, Si-OCH3, Si-COCH3, Si-OCOCH3, Si-CONH2, Si-O-N=C(CH3)2, Si-ONa.

[0384] In the present invention, the dynamic silyl ether bond can be activated under heating conditions and undergo a silyl ether bond exchange reaction, demonstrating dynamic reversible characteristics; among them, the "silyl ether bond exchange reaction" refers to the formation of new silyl ether bonds elsewhere accompanied by the dissociation of old silyl ether bonds, thereby resulting in chain exchange and changes in the polymer topology. The dynamic silyl ether bond in the present invention is selected from the following structures:

[0385]

[0386] Among them, represents the connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; can form a ring or not. Among them, the dynamic silyl ether bond is more preferably selected from the following structures:

[0387]

[0388] In an embodiment of the present invention, the dynamic silyl ether bond can be formed by the condensation reaction of silanol groups, silanol precursors contained in the compound raw materials with hydroxyl groups in the system, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw materials containing dynamic silyl ether bonds. Among them, there is no particular limitation on the compound raw materials containing dynamic silyl ether bonds. Polyols, polysilanols, polyamines, isocyanates, siloxane compounds, silicon hydrides, epoxides, alkenes, and alkynes containing dynamic silyl ether bonds are preferred, and polyols, polysilanols, isocyanates, siloxane compounds, silicon hydrides, and alkenes containing dynamic silyl ether bonds are more preferred. Among them, the silanol precursor refers to a structural unit (Si-X1) composed of a silicon atom and a group that can be hydrolyzed to obtain a hydroxyl group connected to the silicon atom. Among them, X1 is a group that can be hydrolyzed to obtain a hydroxyl group, and it can be selected from halogen, cyano, cyanate, thiocyanate, alkoxy, amino, sulfate, borate, acyl, acyloxy, acylamino, ketoxime, and alcoholate groups. Suitable examples of silanol precursors are: Si-Cl, Si-CN, Si-CNS, Si-CNO, Si-SO4CH3, Si-OB(OCH3)2, Si-NH2, Si-N(CH3)2, Si-OCH3, Si-COCH3, Si-OCOCH3, Si-CONH2, Si-O-N=C(CH3)2, Si-ONa.

[0389] In the present invention, the exchangeable dynamic covalent bond based on alkyl azolium can be activated under certain conditions and undergoes a dynamic exchange reaction with haloalkyl, showing dynamic reversible characteristics. The exchangeable dynamic covalent bond based on alkyl azolium in the present invention is selected from at least one of the following structures:

[0390]

[0391] Among them, X is a negative ion, which is selected from bromide ion and iodide ion, and bromide ion is preferred; represents the connection with the polymer chain, crosslinked network chain or any other suitable group / atom.

[0392] In an embodiment of the present invention, the haloalkyl can be an aliphatic haloalkyl or an aromatic haloalkyl. It can be present in any suitable end group, side group and / or side chain of the dynamic polymer, or exist in other components such as small molecules and oligomers in any suitable form. It can be on the same polymer network / chain as the exchangeable dynamic covalent bond based on alkyl azolium, or on different polymer networks / chains, or can be introduced by small molecules or polymers containing haloalkyl.

[0393] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of the exchangeable dynamic covalent bond based on alkyl azolium refer to the presence of haloalkyl and solvent, as well as appropriate temperature, humidity, pressure conditions, etc.

[0394] In the embodiments of the present invention, the exchangeable dynamic covalent bond based on alkyl azolium can be generated by the reaction of a triazolyl / pyridyl compound with a halogenated hydrocarbon, or can be introduced into a polymer by the polymerization / crosslinking reaction between the reactive groups contained in a compound raw material containing an exchangeable dynamic covalent bond based on alkyl azolium. Among them, the triazolyl compound can be generated by the reaction of an azide group contained in the compound raw material with an alkyne; among them, the halogenated hydrocarbon includes but is not limited to saturated halogenated hydrocarbons (such as chloromethane, bromocyclohexane, 1,2-dibromoethane, triiodomethane, etc.), unsaturated halogenated hydrocarbons (such as vinyl bromide, 3-chlorocyclohexene, 4-bromo-1-buten-3-yne, 1-bromo-2-iodocyclobutene, etc.), halogenated aromatic hydrocarbons (such as chlorobenzene, β-bromonaphthalene, benzyl chloride, o-dichlorobenzene, etc.); among them, there is no particular limitation on the compound raw material containing an exchangeable dynamic covalent bond based on alkyl azolium, and polyols, isocyanates, epoxides, alkenes, alkynes, carboxylic acids, esters, amides containing an exchangeable dynamic covalent bond based on alkyl azolium are preferred, and polyols, isocyanates, epoxides, alkenes, alkynes containing an exchangeable dynamic covalent bond based on alkyl azolium are more preferred.

[0395] In the present invention, the unsaturated carbon-carbon double bond capable of undergoing olefin cross-metathesis reaction can be activated in the presence of a catalyst and undergo olefin cross-metathesis reaction, showing dynamic reversible characteristics; among them, the "olefin cross-metathesis reaction" refers to the carbon framework rearrangement reaction between unsaturated carbon-carbon double bonds catalyzed by a metal catalyst; among them, the "rearrangement reaction" refers to the generation of a new carbon-carbon double bond elsewhere and the dissociation of the old carbon-carbon double bond, resulting in chain exchange and changes in the polymer topology. In the present invention, the structure of the unsaturated carbon-carbon double bond capable of undergoing olefin cross-metathesis reaction is not particularly limited, and preferably has a structure with small steric hindrance and high reaction activity as shown below:

[0396]

[0397] In an embodiment of the present invention, the catalyst for catalyzing olefin cross-metathesis reaction includes, but is not limited to, metal catalysts based on ruthenium, molybdenum, tungsten, titanium, palladium, nickel, etc.; among them, the catalyst is preferably a catalyst based on ruthenium, molybdenum, and tungsten, and more preferably a ruthenium catalyst with higher catalytic efficiency and insensitivity to air and water, especially commercially available catalysts such as Grubbs first-generation, second-generation, and third-generation catalysts, Hoveyda-Grubbs first-generation and second-generation catalysts, etc.

[0398] In the present invention, the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross-metathesis reaction can be activated in the presence of a catalyst and undergo alkyne cross-metathesis reaction, showing dynamic reversible characteristics; among them, the "alkyne cross-metathesis reaction" refers to the carbon framework rearrangement reaction between unsaturated carbon-carbon triple bonds catalyzed by a metal catalyst; among them, the "rearrangement reaction" refers to the generation of a new carbon-carbon triple bond elsewhere and the dissociation of the old carbon-carbon triple bond, resulting in chain exchange and changes in the polymer topological structure. In the present invention, the structure of the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross-metathesis reaction is not particularly limited, and is preferably a structure with small steric hindrance and high reaction activity shown below:

[0399]

[0400] In an embodiment of the present invention, the catalyst for catalyzing alkyne cross-metathesis reaction includes, but is not limited to, metal catalysts based on molybdenum, tungsten, etc.; among them, the catalyst is preferably a catalyst having compatibility with functional groups.

[0401] In an embodiment of the present invention, the unsaturated carbon-carbon double bond capable of undergoing olefin cross-metathesis reaction and the unsaturated carbon-carbon triple bond capable of undergoing alkyne cross-metathesis reaction can be from a selected polymer precursor already containing an unsaturated carbon-carbon double bond / unsaturated carbon-carbon triple bond, or can be generated or introduced on the basis of a polymer precursor without an unsaturated carbon-carbon double bond / unsaturated carbon-carbon triple bond. However, since the reaction conditions for generating carbon-carbon double bonds / carbon-carbon triple bonds are usually relatively harsh, it is therefore preferred to use a polymer precursor already containing carbon-carbon double bonds / carbon-carbon triple bonds for the reaction to achieve the purpose of introducing carbon-carbon double bonds / carbon-carbon triple bonds.

[0402] Among them, polymer precursors containing unsaturated carbon-carbon double bonds / unsaturated carbon-carbon triple bonds, by way of example, include but are not limited to cis-butadiene rubber, 1,2-butadiene rubber, isoprene rubber, polynorbornene, chloroprene rubber, styrene-butadiene rubber, nitrile rubber, polychloroprene, brominated polybutadiene, ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), unsaturated polyester, unsaturated polyether and their copolymers, 1,4-butenediol, 1,5-bis(p-hydroxyphenyl)-1,4-pentadien-3-one, monoricinolein, maleic acid, fumaric acid, trans-methylbutenedioic acid (mesaconic acid), cis-methylbutenedioic acid (citraconic acid), chloromaleic acid, 2-methylenebutanedioic acid (itaconic acid), 4,4'-stilbenedicarboxylic acid, 1,5-bis(p-hydroxyphenyl)-1,4-pentadien-3-one, fumaroyl chloride, 1,4-phenylenediacryloyl chloride, citraconic anhydride, maleic anhydride, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, dimethyl citraconate, 1,4-dichloro-2-butene, 1,4-dibromo-2-butene, etc. Oligomers with carbon-carbon double bonds / carbon-carbon triple bonds on the end-group functionalized chain backbone can also be selected.

[0403] In the present invention, the [2+2] cycloaddition dynamic covalent bond is formed based on the [2+2] cycloaddition reaction, can be activated under certain conditions, and undergoes bond dissociation, bonding and exchange reactions, showing dynamic reversible characteristics; among them, the [2+2] cycloaddition reaction refers to the reaction in which two π electrons are provided by one unsaturated double bond and another unsaturated double bond or unsaturated triple bond respectively to react and add to form a four-membered ring structure. The [2+2] cycloaddition dynamic covalent bond in the present invention is selected from at least one of the following structures:

[0404]

[0405] Among them, D1 to D6 are each independently selected from a carbon atom, an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom, and a silicon atom, preferably a carbon atom, and at least one of D1 and D2 is selected from a carbon atom, an oxygen atom, a nitrogen atom, or a silicon atom; a1 to a6 respectively represent the number of connections to D1 to D6; when D1 to D6 are each independently selected from an oxygen atom, a sulfur atom, or a selenium atom, a1 to a6 = 0; when D1 to D6 are each independently selected from a nitrogen atom, a1 to a6 = 1; when D1 to D6 are each independently selected from a carbon atom or a silicon atom, a1 to a6 = 2; Q1 to Q6 are each independently selected from a carbon atom and an oxygen atom; b1 to b6 respectively represent the number of connections to Q1 to Q6; when Q1 to Q6 are each independently selected from an oxygen atom, b1 to b6 = 0; when Q1 to Q6 are each independently selected from a carbon atom, b1 to b6 = 2; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same atom can be connected to form a ring, and those on different atoms can also be connected to form a ring, and the rings include but are not limited to aliphatic rings, aromatic rings, ether rings, fused rings, and combinations thereof.

[0406] In an embodiment of the present invention, the unsaturated double bond for carrying out the [2+2] cycloaddition reaction can be selected from a carbon-carbon double bond, a carbon-oxygen double bond, a carbon-sulfur double bond, a carbon-nitrogen double bond, and a nitrogen-nitrogen double bond; the unsaturated triple bond for forming the [2+2] cycloaddition dynamic covalent bond can be selected from a carbon-carbon triple bond; among them, the unsaturated double bond and the unsaturated triple bond are preferably directly connected to an electron-withdrawing group or an electron-donating group, and the electron-withdrawing group includes but is not limited to a carbonyl group, an aldehyde group, a nitro group, an ester group, a sulfonic acid group, an amide group, a sulfone group, a trifluoromethyl group, an aryl group, a cyano group, a halogen atom, an alkene, an alkyne, and combinations thereof; the electron-donating group includes but is not limited to a hydroxyl group, a p-methoxyphenyl group, a thioether group, an amino group, a secondary amino group, a tertiary amino group, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and combinations thereof.

[0407] In an embodiment of the present invention, the [2+2] cycloaddition dynamic covalent bond can be formed by the [2+2] cycloaddition reaction between the unsaturated carbon-carbon double bonds, azo groups, carbonyl groups, aldehyde groups, thiocarbonyl groups, imino groups, cumulated dienes, and ketene groups contained in the compound raw materials themselves, or between them and the unsaturated carbon-carbon triple bond. It can also be introduced into the polymer by the polymerization / cross-linking reaction between the reactive groups contained in the compound raw materials containing the [2+2] cycloaddition dynamic covalent bond. Among them, the compound raw materials containing unsaturated carbon-carbon double bonds are preferably ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, maleic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α,β-unsaturated nitro compounds, cyclooctene, norbornene, maleic anhydride, p-benzoquinone, butynedioic acid, azodicarboxylate, dithioester, maleimide, fullerene, and derivatives of the above compounds, etc. Among them, there is no particular limitation on the compound raw materials containing the [2+2] cycloaddition dynamic covalent bond. Polyols, isocyanates, epoxides, alkenes, alkynes, carboxylic acids, esters, amides, sulfur, and mercapto compounds containing the [2+2] cycloaddition dynamic covalent bond are preferred, and polyols, isocyanates, epoxides, alkenes, and alkynes containing the [2+2] cycloaddition dynamic covalent bond are more preferred.

[0408] In the present invention, the [4+2] cycloaddition dynamic covalent bond is formed based on the [4+2] cycloaddition reaction, and can be activated under certain conditions, and the bond dissociation, bonding, and exchange reactions occur, showing dynamic reversible characteristics. Among them, the [4+2] cycloaddition reaction refers to the reaction in which the dienophile group provides 4 π electrons and the dienophile group provides 2 π electrons to form a cyclic group structure by addition. The [4+2] cycloaddition dynamic covalent bond in the present invention is selected from at least one of the following structures:

[0409]

[0410] Among them, K1, K2, K5~K 10 are each independently selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, and a selenium atom, and at least one of the atoms in K1, K2 or K5, K6 or K7, K8 or K9, K 10 is selected from a carbon atom, a nitrogen atom, or a silicon atom; c1~c 10 respectively represent the number of connections connected to K1~K 10 ; when K1, K2, K5~K 10 are each independently selected from an oxygen atom, a sulfur atom, and a selenium atom, c1, c2, c5~c 10 =0; when K1, K2, K5~K 10 are each independently selected from a nitrogen atom, c1, c2, c5~c10 = 1; when K1, K2, K5 to K 10 are each independently selected from a carbon atom and a silicon atom, c1, c2, c5 to c 10 = 2; K3 and K4 are each independently selected from an oxygen atom, a sulfur atom, and a nitrogen atom; c3 and c4 respectively represent the number of connections to K3 and K4; when K3 and K4 are each independently selected from an oxygen atom and a sulfur atom, c3, c4 = 0; when K3 and K4 are each independently selected from a nitrogen atom, c3, c4 = 1; I1 and I2 are each independently selected from an oxygen atom, a sulfur atom, a secondary amino group and its substituted forms, an amide group, an ester group, and a divalent small hydrocarbon group, more preferably from an oxygen atom, a methylene group, 1,2-diethylene, 1,2-vinylene, 1,1'-vinylene, a substituted form of a secondary amino group, an amide group, and an ester group; The represented cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of its cyclic group structure are each independently selected from a carbon atom, a nitrogen atom, or other heteroatoms. The cyclic group structure is preferably a 6- to 50-membered ring, more preferably a 6- to 12-membered ring; the hydrogen atoms on each ring-forming atom may or may not be substituted. Among them, when the ring-forming atom is selected from a nitrogen atom, the nitrogen atom may carry a positive charge; the represented cyclic group structure is preferably a benzene ring, a naphthalene ring, an anthracene ring, and substituted forms of the above groups; n represents the number of connections to the ring-forming atoms of the cyclic group structure; represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same atom can be connected to form a ring, and on different atoms can also be connected to form a ring. The rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings, and combinations thereof.

[0411] Among them, the [4+2] cycloaddition dynamic covalent bond can be connected to a photocontrol locking element to form a photocontrol DA structure. The photocontrol locking element can react with the dynamic covalent bond and / or the photocontrol locking element under specific light irradiation conditions to change the dynamic covalent bond structure, thereby achieving the purpose of locking / unlocking the DA reaction; among them, when the dynamic covalent bond is locked, it cannot or is more difficult to carry out the DA equilibrium reaction, and when the dynamic covalent bond is unlocked, it can carry out the DA equilibrium reaction to achieve dynamic characteristics.

[0412] In the present invention, the photocontrol locking element contains the following structural units:

[0413]

[0414] Among them, represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different can be connected to form a ring, and those on different atoms can also be connected to form a ring, and the said rings include but are not limited to aliphatic rings, aromatic rings, ether rings, fused rings and their combinations;

[0415] The photo-controlled [4+2] cycloaddition dynamic covalent bond connected to the photo-controlled locking motif is preferably selected from at least one of the following general formula structures:

[0416]

[0417] wherein, K1, K2, K3, K4, K5, K6 are each independently selected from a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, and at least one of K1, K2, or K3, K4, or K5, K6 is selected from a carbon atom; a1, a2, a3, a4, a5, a6 respectively represent the number of connections connected to K1, K2, K3, K4, K5, K6; when K1, K2, K3, K4, K5, K6 are each independently selected from an oxygen atom, a sulfur atom, a1, a2, a3, a4, a5, a6 = 0; when K1, K2, K3, K4, K5, K6 are each independently selected from a nitrogen atom, a1, a2, a3, a4, a5, a6 = 1; when K1, K2, K3, K4, K5, K6 are each independently selected from a carbon atom, a1, a2, a3, a4, a5, a6 = 2; I1, I2, I3 each independently do not exist, or each independently is selected from an oxygen atom, 1,1'-carbonyl, methylene and its substituted forms, 1,2-ethylene and its substituted forms, 1,1'-vinyl and its substituted forms; when I1, I2, I3 each independently do not exist, b = 2; when I1, I2, I3 each independently is selected from an oxygen atom, 1,1'-carbonyl, methylene and its substituted forms, 1,2-ethylene and its substituted forms, 1,1'-vinyl and its substituted forms, b = 1; M is selected from an oxygen atom, a nitrogen atom, a divalent alkoxy chain preferably an oxygen atom, a nitrogen atom; c represents the number of connections connected to M; when M is selected from an oxygen atom, a divalent alkoxy chain, c = 0; when M is selected from a nitrogen atom, c = 1; C1, C2, C3, C4, C5, C6 represent carbon atoms at different positions; different ones on the same atom can be connected to form a ring, and those on different atoms It can also form a ring. Preferably, a ring is formed between K1 and K2, between K3 and K4, between K5 and K6, between C1 and C2, between C3 and C4, and between C5 and C6. The formed ring can be a ring with any number of elements, preferably a five-membered ring and a six-membered ring. It can be an aliphatic ring, an aromatic ring, an ether ring, a condensed ring, or a combination thereof. The ring-forming atoms are each independently selected from carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, selenium atoms, or other heteroatoms. The hydrogen atoms on the ring-forming atoms can be substituted by any substituent or not substituted. Among them, the rings formed between K1 and K2, between K3 and K4, and between K5 and K6 preferably have the following structures:

[0418]

[0419] The rings formed between C1 and C2 and between C3 and C4 preferably have the following structures:

[0420]

[0421] The rings formed between C5 and C6 preferably have the following structures:

[0422]

[0423] In an embodiment of the present invention, the dienophile group used for the [4+2] cycloaddition reaction can be any suitable group containing conjugated dienes and their derivatives. Examples of suitable conjugated dienes and their derivatives include butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene, and their derivatives, etc. The dienophile group used for forming the [4+2] cycloaddition dynamic covalent bond contains any suitable unsaturated double bond or unsaturated triple bond, such as carbon-carbon double bond, carbon-carbon triple bond, carbon-oxygen double bond, carbon-sulfur double bond, carbon-nitrogen double bond, nitrogen-nitrogen double bond, etc. Among them, the unsaturated double bond or unsaturated triple bond in the dienophile group and the dienophile group preferably is directly connected to an electron-withdrawing group or an electron-donating group. The electron-withdrawing group includes but is not limited to carbonyl group, aldehyde group, nitro group, ester group, sulfonic acid group, acylamino group, sulfone group, trifluoromethyl group, aryl group, cyano group, halogen atom, alkene, alkyne, and their combination. The electron-donating group includes but is not limited to hydroxyl group, p-methoxyphenyl group, thioether group, amino group, secondary amino group, tertiary amino group, methyl group, ethyl group, isopropyl group, isobutyl group, and their combination.

[0424] In an embodiment of the present invention, the [4+2] cycloaddition dynamic covalent bond can be formed by a [4+2] cycloaddition reaction between a compound raw material containing a dienophile group and a compound raw material containing a dienophile group, or can be introduced into a polymer by a polymerization / crosslinking reaction between reactive groups contained in a compound raw material containing a [4+2] cycloaddition dynamic covalent bond. Among them, the compound raw material containing a dienophile group can be selected from butadiene, pentadiene, hexadiene, cyclopentadiene, cyclohexadiene, tetrazine, benzene, anthracene, furan, fulvene, graphene and derivatives of the above compounds, etc.; among them, the compound raw material containing a dienophile group can be selected from ethylene, propylene, acrolein, acrylonitrile, acrylate, methacrylate, maleic acid, cinnamyl alcohol, cinnamaldehyde, cinnamic acid, cinnamide, coumarin, pyrimidine, chalcone, polygonum cuspidatum, α,β-unsaturated nitro compound, cyclooctene, norbornene, maleic anhydride, p-benzoquinone, butynedioic acid, azodicarboxylate, dithioester, maleimide, fullerene and derivatives of the above compounds, etc.; among them, there is no particular limitation on the compound raw material containing a [4+2] cycloaddition dynamic covalent bond, and polyols, isocyanates, epoxides, alkenes, alkynes, carboxylic acids, esters, amides and sulfur, mercapto compounds containing a [4+2] cycloaddition dynamic covalent bond are preferred, and polyols, isocyanates, epoxides, alkenes, alkynes containing a [4+2] cycloaddition dynamic covalent bond are more preferred.

[0425] In the present invention, the [4+4] cycloaddition dynamic covalent bond is formed based on a [4+4] cycloaddition reaction, and can be activated under certain conditions, and bond dissociation, bonding and exchange reactions occur, showing dynamic reversible characteristics; among them, the [4+4] cycloaddition reaction refers to a reaction in which two conjugated diene groups each provide 4 π electrons to form a cyclic group structure by addition. The [4+4] cycloaddition dynamic covalent bond in the present invention is selected from the following structures:

[0426]

[0427] Among them, The represented cyclic group structure is an aromatic ring or a hybrid aromatic ring, and the ring-forming atoms of the cyclic group structure are each independently selected from carbon atoms, nitrogen atoms or other heteroatoms. The cyclic group structure is preferably a 6- to 50-membered ring, more preferably a 6- to 12-membered ring; the hydrogen atoms on each ring-forming atom can be substituted or unsubstituted. Among them, when the ring-forming atom is a nitrogen atom, the nitrogen atom can carry a positive charge; the cyclic group structure is preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyridine, a quinoline, an acridine and a substituted form of the above groups; I6 to I 14Each independently selected from an oxygen atom, a sulfur atom, an amide group, an ester group, an imine group, a divalent small hydrocarbon group, more preferably from an oxygen atom, a methylene group, 1,2-diethylene, 1,2-vinylene, an amide group, an ester group, an imine group; Represents a connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom; different on the same atom can be connected to form a ring, and those on different atoms can also be connected to form a ring, and the rings include but are not limited to aliphatic rings, ether rings, condensed rings, and combinations thereof.

[0428] In an embodiment of the present invention, the conjugated diene group used for the [4+4] cycloaddition reaction can be any suitable group containing conjugated dienes and their derivatives, such as benzene, anthracene, naphthalene, furan, cyclopentadiene, cyclohexadiene, pyrone, pyridone, and their derivatives.

[0429] In an embodiment of the present invention, the [4+4] cycloaddition dynamic covalent bond can be formed by a [4+4] cycloaddition reaction between compound raw materials containing conjugated diene groups, or can be introduced into a polymer by a polymerization / crosslinking reaction between reactive groups contained in compound raw materials containing [4+4] cycloaddition dynamic covalent bonds.

[0430] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of [2+2] cycloaddition dynamic covalent bonds, [4+2] cycloaddition dynamic covalent bonds, and [4+4] cycloaddition dynamic covalent bonds include, but are not limited to, temperature regulation, addition of catalysts, light irradiation, radiation, microwave and other action modes. For example, by heating the [2+2] cycloaddition dynamic covalent bond at a higher temperature, it can be dissociated, and then heating it under lower temperature conditions can cause it to reform the [2+2] cycloaddition dynamic covalent bond; furan and maleimide can undergo a [4+2] cycloaddition reaction to form dynamic covalent bonds at room temperature or under heating conditions, and the formed dynamic covalent bond can be dissociated at a temperature higher than 110 °C, and then cooling can cause it to reform the dynamic covalent bond. For another example, the [2+2] cycloaddition dynamic covalent bond can undergo a [2+2] cycloaddition reaction to form a dynamic covalent bond under long-wavelength light irradiation conditions, and then undergo dissociation of the dynamic covalent bond under short-wavelength light irradiation conditions to re-obtain unsaturated carbon-carbon double bonds; for example, cinnamoyl unsaturated carbon-carbon double bonds can undergo a [2+2] cycloaddition reaction to form dynamic covalent bonds under ultraviolet light irradiation conditions with λ greater than 280 nm, and undergo bond dissociation under ultraviolet light irradiation conditions with λ less than 280 nm to re-obtain cinnamoyl unsaturated carbon-carbon double bonds; coumarin unsaturated carbon-carbon double bonds can undergo a [2+2] cycloaddition reaction to form dynamic covalent bonds under ultraviolet light irradiation conditions with λ greater than 319 nm, and undergo bond dissociation under ultraviolet light irradiation conditions with λ less than 319 nm to re-obtain coumarin unsaturated carbon-carbon double bonds. For another example, anthracene and maleic anhydride can undergo a [4+2] cycloaddition reaction to form dynamic covalent bonds under ultraviolet light irradiation conditions with λ = 250 nm. For another example, anthracene can undergo a [4+4] cycloaddition reaction to form dynamic covalent bonds under ultraviolet light irradiation conditions with λ = 365 nm, and then undergo bond dissociation under ultraviolet light irradiation conditions with λ less than 300 nm. In addition, [2+2], [4+2], and [4+4] cycloaddition reactions can also be carried out to form dynamic covalent bonds under the catalytic conditions of catalysts. Among them, the catalysts include, but are not limited to, Lewis acids, Lewis bases, and metal catalysts; the Lewis acids include, but are not limited to, metal chlorides, metal iodides, trifluoromethanesulfonates, alkylmetal compounds, boranes, boron trifluoride and its derivatives, diarylboron difluoride, scandium triflate, etc., preferably titanium tetrachloride, aluminum trichloride, aluminum tribromide, ethylaluminum dichloride, iron tribromide, iron trichloride, tin tetrachloride, borane, boron trifluoride, boron trifluoride ether complex, scandium trifluoromethanesulfonate; the Lewis bases include, but are not limited to, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), N-heterocyclic carbene (NHC), quinidine, quinine, etc.; the metal catalysts include, but are not limited to, catalysts based on iron, cobalt, palladium, ruthenium, nickel, copper, silver, gold, molybdenum.

[0431] In the present invention, the thiol-Michael addition dynamic covalent bond can be activated under certain conditions, and undergoes bond dissociation, bonding and exchange reactions, showing dynamic reversibility; the thiol-Michael addition dynamic covalent bond in the present invention is selected from at least one of the following structures:

[0432]

[0433] wherein, X is selected from a keto group, an ester group, an amide group, a thiocarbonyl group, a sulfone group; Y is an electron-withdrawing group, including but not limited to an aldehyde group, a carboxyl group, a nitro group, a phosphate group, a sulfonic acid group, an acylamino group, a sulfone group, a trifluoromethyl group, a cyano group, a halogen atom and combinations thereof; represents a connection to a polymer chain, a crosslinked network chain or any other suitable group / atom, wherein different on the same carbon atom can be connected to form a ring, and on different carbon atoms can also be connected to form a ring, and the carbon atom and on X can also be connected to form a ring, and the rings include but are not limited to aliphatic rings, aromatic rings, ether rings, condensed rings and combinations thereof.

[0434] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of thiol-Michael addition dynamic covalent bonds include, but are not limited to, temperature regulation, addition of catalysts, pH adjustment and other action modes. For example, the dissociated thiol-Michael addition dynamic covalent bonds can be regenerated or undergo dynamic covalent bond exchange by heating, enabling the polymer to obtain self-healing and reprocessing properties. For another example, for thiol-Michael addition dynamic covalent bonds, a neutral or weakly alkaline solution can be selected to cause dissociation, thus being in a dynamic reversible equilibrium. For yet another example, the presence of a catalyst can promote the formation and exchange of dynamic covalent bonds. The catalysts for thiol-Michael addition reactions include, but are not limited to, Lewis acids, organophosphides, organic base catalysts, nucleophilic catalysts, ionic liquid catalysts, etc.; the Lewis acids include, but are not limited to, metal chlorides, metal iodides, trifluoromethanesulfonates, alkylmetal compounds, boranes, boron trifluoride and its derivatives, arylboron difluorides, scandium triflate, etc.; the organophosphides include, but are not limited to, potassium phosphate, tri-n-propylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, triphenylphosphine; the organic base catalysts include, but are not limited to, ethylenediamine, triethanolamine, triethylamine, pyridine, diisopropylethylamine, etc.; the nucleophilic catalysts include, but are not limited to, 4-dimethylaminopyridine, tetrabutylammonium bromide, tetramethylguanidine, 1,5-diazabicyclo[4,3,0]non-5-ene, 1,8-diazabicyclo[5,4,0]-undec-7-ene, 1,5,7-triazabicyclo[4,4,0]dec-5-ene, 1,4-diazabicyclo[2,2,2]octane, imidazole, 1-methylimidazole; the ionic liquid catalysts include, but are not limited to, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-(4-sulfonic acid)butylpyridine, 1-butyl-3-methylimidazolinium tetrahydroborate, 1-allyl-3-methylimidazolium chloride, etc.

[0435] In an embodiment of the present invention, the thiol-Michael addition dynamic covalent bond can be formed by the thiol-Michael addition reaction of thiol contained in the compound raw material with conjugated olefins or conjugated alkynes, or can be introduced into the polymer by the polymerization / crosslinking reaction between the reactive groups contained in the compound raw material containing the thiol-Michael addition dynamic covalent bond. Among them, the compound raw material containing conjugated olefins or conjugated alkynes can be selected from acrolein, acrylic acid, acrylate, propargylate, methacrylate, acrylamide, methacrylamide, acrylonitrile, crotonate, maleate, fumarate, acetylenedicarboxylate, itaconic acid, cinnamate, vinyl sulfone, maleic anhydride, maleimide and derivatives of the above compounds, etc.; among them, there is no particular limitation on the compound raw material containing the thiol-Michael addition dynamic covalent bond, and polyols, isocyanates, epoxides, alkenes, alkynes, carboxylic acids, esters, amides containing the thiol-Michael addition dynamic covalent bond are preferred, and polyols, isocyanates, epoxides, alkenes, alkynes containing the thiol-Michael addition dynamic covalent bond are more preferred.

[0436] In the present invention, the amine-ene Michael addition dynamic covalent bond can be activated under certain conditions, and bond dissociation, bonding and exchange reactions occur, showing dynamic reversible characteristics; the amine-ene Michael addition dynamic covalent bond in the present invention is selected from the following structures:

[0437]

[0438] Among them, represents the connection with the polymer chain, crosslinked network chain or any other suitable group / atom.

[0439] In an embodiment of the present invention, the "certain conditions" for activating the dynamic reversibility of the amine-ene Michael addition dynamic covalent bond include but are not limited to temperature adjustment, pH adjustment and other action modes. For example, for the amine-ene Michael addition dynamic covalent bond, a weakly acidic (pH≤5.3) solution can be selected to cause dissociation, so as to be in a dynamic reversible equilibrium. For another example, the dissociated amine-ene Michael addition dynamic covalent bond can be regenerated or the dynamic covalent bond can be exchanged by heating at 50-100 °C, so that the polymer can obtain self-healing and reprocessing properties.

[0440] In an embodiment of the present invention, the amine-ene Michael addition dynamic covalent bond can be prepared by using terephthalaldehyde, malonic acid, diethyl malonate as raw materials to prepare an intermediate product, and then reacting it with an amino compound through an amine-ene Michael addition reaction.

[0441] In the present invention, the triazoline dione-indole-based dynamic covalent bond can be activated under certain conditions, and bond dissociation, bonding, and exchange reactions occur, demonstrating dynamic reversibility. The triazoline dione-indole-based dynamic covalent bond in the present invention is selected from the following structures:

[0442]

[0443] Among them, represents the connection to a polymer chain, a crosslinked network chain, or any other suitable group / atom.

[0444] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of the triazoline dione-indole-based dynamic covalent bond include, but are not limited to, temperature regulation, pressurization, addition of a catalyst, and other action modes. For example, indole and diazoline dione can form a triazoline dione-indole-based dynamic covalent bond under the condition of 0 °C, and then bond dissociation can be achieved by heating, and the dynamic covalent bond can be regenerated or the dynamic covalent bond can be exchanged by cooling, so that the polymer can obtain self-healing and reprocessing properties. For another example, for the triazoline dione-indole-based dynamic covalent bond, a neutral or weakly alkaline solution can be selected to cause dissociation, so as to be in a dynamic reversible equilibrium. For another example, the presence of a catalyst can promote the formation and exchange of dynamic covalent bonds. The addition reaction catalyst can be selected from Lewis acids. The Lewis acids include, but are not limited to, metal chlorides, metal iodides, trifluoromethanesulfonates, alkylmetal compounds, boranes, boron trifluoride and its derivatives, arylboron difluoride, scandium trifluoroalkylsulfonate, etc.

[0445] In the embodiments of the present invention, the triazoline dione-indole-based dynamic covalent bond can be formed by the aldol-olefin addition reaction of the diazoline dione group and its derivatives contained in the compound raw materials with indole and its derivatives. Among them, the raw materials of indole and its derivatives can be selected from indole-3-propionic acid, indole-3-butyric acid, indole-4-carboxylic acid, indole-5-carboxylic acid, indole-6-carboxylic acid, 4-(aminomethyl)indole, 5-(aminomethyl)indole, 3-(2-hydroxyethyl)indole, indole-4-methanol, indole-5-methanol, 3-mercaptoindole, 3-ethynylindole, 5-amino-2-phenylindole, 2-phenyl-1H-indole-6-amine, 2-phenyl-1H-indole-3-acetaldehyde, (2-phenyl-1H-indole-3-alkyl)carboxylic acid, ethyl 6-amino-2-phenyl-1H-indole-3-carboxylate, 2-(2-aminophenyl)indole, 2-phenylindole-3-acetonitrile, 4,6-diamidino-2-phenylindole dihydrochloride, etc.

[0446] In the present invention, the dynamic covalent bond based on diazabicycloalkene can be activated under certain conditions, and bond dissociation, bonding and exchange reactions occur, demonstrating dynamic reversibility. The dynamic covalent bond based on diazabicycloalkene in the present invention is selected from at least one of the following structures:

[0447]

[0448] Wherein, represents the connection to a polymer chain, a crosslinked network chain or any other suitable group / atom. Among them, the on different carbon atoms can be connected to form a ring, and the ring includes but is not limited to an aliphatic ring, an aromatic ring, an ether ring, a condensed ring and combinations thereof.

[0449] In the embodiments of the present invention, the "certain conditions" for activating the dynamic reversibility of the dynamic covalent bond based on diazabicycloalkene include but are not limited to action modes such as temperature adjustment and addition of a solvent. For example, the dynamic covalent bond based on diazabicycloalkene can be heated under a temperature condition higher than 90 °C to dissociate it into a diazabicycloalkene structure, and then the dynamic covalent bond can be regenerated by cooling or dynamic covalent bond exchange can be carried out, so that the polymer can obtain self-healing and reprocessability.

[0450] In the embodiments of the present invention, the dynamic covalent bond based on diazabicycloalkene can be formed by the diazabicycloalkene group contained in the compound raw material itself or its reaction with a thiocyanato group.

[0451] In the present invention, the dynamic covalent bond based on benzoyl can be activated under certain conditions, break to form free radicals, and the free radicals can re-form the d...

Claims

1. A dilatant electronic product protective case / shell, characterized in that, It uses a dilatant component as a fixed casing, polyvinyl chloride artificial leather as the upper cover body, and thermoplastic vulcanizate as the connecting piece. The dilatant component is a simple solid structure and has force responsiveness. The preparation method is as follows: Take 150 molar equivalents of hexyl methacrylate, 30 molar equivalents of 4-acrylaminobutyric acid, 8 molar equivalents of compound (a), and 1.2 molar equivalents of azobisisobutyronitrile, place them in a reaction vessel, dissolve with tetrahydrofuran, and under a nitrogen atmosphere, stir and react at 70 °C for 24 h to obtain a single-network polyacrylate; take 90 molar equivalents of hexyl methacrylate, 60 molar equivalents of carboxybetaine methyl methacrylate, 30 molar equivalents of 2-hydroxyethyl acrylate, and 1.2 molar equivalents of azobisisobutyronitrile, place them in a reaction vessel, dissolve with tetrahydrofuran, and then under a nitrogen atmosphere, stir and react at 70 °C for 24 h to prepare an acrylate copolymer; take 50 g of the single-network polyacrylate, 30 g of the acrylate copolymer, and 2 g of 2-isocyanatoethyl acrylate and add them to 140 mL of 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid, stir and swell for 30 min, then add stannous octoate, first react at room temperature for 8 h, and then place the product in a 60 °C mold for molding to obtain a gel-form dilatant fixed casing.

2. The dilatant electronic product protective cover / case according to claim 1, wherein, The dilatant electronic product protective cover / casing contains a dilatant component and a leather component; the electronic product protective cover / casing includes a fixed casing, an upper cover plate, and a connecting piece connecting the fixed casing and the upper cover plate; Among them, the fixed casing is made of a dilatant component, the upper cover plate is made of a leather component, and the connecting piece is made of leather, an elastomer, and hard plastic.

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