阅读说明：本技术 一种基于配位键的自适应智能材料及其制备方法和应用 (Self-adaptive intelligent material based on coordination bond and preparation method and application thereof ) 是由 李承辉 王洪芹 陶涵清 高文通 于 2021-09-18 设计创作，主要内容包括：本发明公开了一种基于配位键的自适应智能材料,其具有由多齿柔性配体和金属中心配位形成的自适应网络结构,所述多齿柔性配体通过氨基、羧基、吡啶基或咪唑基与所述金属中心形成配位键。该自适应智能材料具有三维结构并含有大量配位键,能够保证材料刚性和优异的力学强度,另外配位键的可交换性赋予材料良好可加工回收性。该类基于配位键的自适应智能材料可应用于密封剂、胶粘剂、快速自修复涂层、温敏变刚度自修复工程材料、增材制造等领域。(The invention discloses a coordination bond-based self-adaptive intelligent material which has a self-adaptive network structure formed by coordination of multidentate flexible ligands and a metal center, wherein the multidentate flexible ligands form coordination bonds with the metal center through amino groups, carboxyl groups, pyridyl groups or imidazolyl groups. The self-adaptive intelligent material has a three-dimensional structure and contains a large number of coordination bonds, the rigidity and excellent mechanical strength of the material can be ensured, and in addition, the interchangeability of the coordination bonds endows the material with good processability and recoverability. The self-adaptive intelligent material based on the coordination bond can be applied to the fields of sealants, adhesives, quick self-repairing coatings, temperature-sensitive variable-stiffness self-repairing engineering materials, additive manufacturing and the like.)

1. A coordination bond-based adaptive smart material is characterized by having an adaptive network structure formed by coordination of multidentate flexible ligands and a metal center, wherein the multidentate flexible ligands form coordination bonds with the metal center through amino groups, carboxyl groups, pyridyl groups or imidazolyl groups.

2. The adaptive smart material of claim 1, wherein the multidentate flexible ligand is selected from one or more of a compound of formula I, a compound of formula II, or a compound of formula III;

the compound of the formula I isWherein R is₁～R₃Is independently selected from-CH₂CH₂SCH₂CH₂NH₂、CH₂CH₂SCH₂CH₂COOH、

The compound of the formula II isWherein R is₄～R₇Is independently selected from-CH₂CH₂SCH₂CH₂NH₂、-CH₂CH₂SCH₂CH₂CONH₂、-CH₂CH₂SCH₂CH₂COOH、

The compound of the formula III isWherein R is₈～R₁₁Is independently selected from-CH₂SCH₂CH₂NH₂or-CH₂SCH₂CH₂COOH。

3. The adaptive smart material of claim 1, wherein the metal center is Zn²⁺、Cu²⁺、Fe^{3 +}、Co²⁺、Ni²⁺One kind of (1).

4. The adaptive smart material of claim 1, wherein the multidentate flexible ligand is obtained by a thiol-click reaction between a flexible molecule and a ligand under the action of a photoinitiator and ultraviolet light.

5. The adaptive smart material of claim 4, wherein the flexible molecule is one of pentaerythritol tetra-3-mercapto acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or tetramethyltetravinylcyclotetrasiloxane.

6. The adaptive smart material of claim 4, wherein the ligand is one of N-allylimidazole, acrylamide, acrylic acid, 4-vinylpyridine, 3-mercaptopropionic acid, cysteamine, 4-pyridineethanethiol, or 1H-imidazole-1-ethanethiol.

7. The adaptive smart material of claim 4, wherein the photoinitiator is one of benzoin dimethyl ether, benzoin ethyl ether, diphenylethanone, or benzophenone.

8. The method for preparing the adaptive intelligent material according to any one of claims 1 to 7, which is characterized by comprising the following steps:

(1) and (3) dripping the metal salt solution into the solution of the multidentate flexible ligand under the stirring condition, and continuing stirring for reaction for 3-6 hours after dripping is finished to obtain the metal salt.

9. An indicator method according to claim 8, wherein the multidentate flexible ligand is prepared by:

(0-1) adding a ligand and a photoinitiator into the solution of the flexible molecules, uniformly mixing, irradiating by using ultraviolet light, and stirring and reacting for 60-180 min under a sealed condition to obtain the polymer.

10. The application of the self-adaptive intelligent material of any one of claims 1 to 7 in the fields of sealants, adhesives, self-repair coatings, temperature-sensitive variable-stiffness self-repair engineering materials or additive manufacturing materials.

Technical Field

The invention belongs to the field of novel materials, and particularly relates to a coordination bond-based self-adaptive intelligent material and a preparation method and application thereof.

Background

Polymeric materials traditionally include two categories, namely thermosets and thermoplastics. The thermosetting polymer is characterized by an irreversible cross-linked polymer network structure, so that the thermosetting polymer has excellent mechanical strength and solvent resistance, but cannot be reprocessed or recycled after being cured and molded due to the irreversibility of cross-linking; in contrast, thermoplastic polymers are formed from high molecular weight polymer segments through non-covalent interactions, are easily reshaped, reprocessed, and recycled by heating, but are weak in durability, creep resistance, and the like. Therefore, the polymer material which is designed and synthesized to have both thermosetting rigidity and thermoplastic processability and recyclability has great application value.

In recent years, there have been related researches to prepare a polymer material having both thermosetting rigidity and thermoplastically processable and recyclable property by introducing exchangeable covalent chemical bonds into a polymer network, such as transesterification, Diels-Alder reaction, disulfide bond, borate bond and imine bond, wherein the exchangeable covalent chemical bonds can form an adaptive network structure in the polymer, and the structure has a three-dimensional network structure on one hand, which can retain the characteristic of thermosetting material rigidity, and on the other hand, due to the dynamic property of the exchangeable chemical bonds, the polymer can be processed and recycled like a thermoplastic material. However, the materials adopt exchangeable covalent chemical bonds, and the bond energy is higher than that of non-covalent exchangeable chemical bonds, which still causes problems for the application of the materials, for example, polymer materials prepared by the exchangeable covalent chemical bonds often need higher temperature to realize reprocessing and recycling, and the higher processing temperature can have adverse effect on the aging resistance of the polymer materials.

Disclosure of Invention

Aiming at the problems of the existing exchangeable covalent chemical bonds in the aspect of preparing self-adaptive intelligent materials, the invention provides a self-adaptive intelligent material based on coordination bonds, and a preparation method and application thereof. The material has simple synthesis mode and is insensitive to water vapor.

In order to achieve the purpose, the invention adopts the following technical scheme:

a coordination bond-based adaptive smart material has an adaptive network structure formed by coordination of multidentate flexible ligands and a metal center, wherein the multidentate flexible ligands form coordination bonds with the metal center through amino groups, carboxyl groups, pyridyl groups or imidazolyl groups.

Preferably, the multidentate flexible ligand is selected from one or more of a compound of formula I, a compound of formula II, or a compound of formula III; the compound of the formula I isWherein R is₁～R₃Is independently selected from-CH₂CH₂SCH₂CH₂NH₂、CH₂CH₂SCH₂CH₂COOH、

The compound of the formula II isWherein R is₄～R₇Is independently selected from-CH₂CH₂SCH₂CH₂NH₂、-CH₂CH₂SCH₂CH₂CONH₂、-CH₂CH₂SCH₂CH₂COOH、

The compound of the formula III isWherein R is₈～R₁₁Is independently selected from-CH₂SCH₂CH₂NH₂or-CH₂SCH₂CH₂COOH。

Preferably, the multidentate flexible ligand is obtained by a thiol click reaction between a flexible molecule and a ligand under the action of a photoinitiator and ultraviolet light.

Preferably, the metal center is Zn²⁺、Cu²⁺、Fe³⁺、Co²⁺、Ni²⁺One kind of (1).

Preferably, the flexible molecule is one of pentaerythritol tetra-3-mercaptoacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate or tetramethyltetravinylcyclotetrasiloxane.

Preferably, the ligand is one of N-allyl imidazole, acrylamide, acrylic acid, 4-vinylpyridine, 3-mercaptopropionic acid, cysteamine, 4-pyridine ethanethiol or 1H-imidazole-1-ethanethiol.

Preferably, when the flexible molecule is pentaerythritol tetra-3-mercaptoacrylate, the ligand is preferably one of N-allyl imidazole, acrylamide, acrylic acid or 4-vinyl pyridine; when the flexible molecule is one of pentaerythritol triacrylate or pentaerythritol tetraacrylate, the ligand is preferably one of 3-mercaptopropionic acid, cysteamine, 4-pyridylethylthiol or 1H-imidazole-1-ethanethiol, and when the flexible molecule is tetramethyltetravinylcyclotetrasiloxane, the ligand is preferably one of 3-mercaptopropionic acid or cysteamine.

Preferably, the photoinitiator is one of benzoin dimethyl ether, benzoin ethyl ether, diphenyl ethyl ketone or benzophenone.

The invention also provides a preparation method of the self-adaptive intelligent material, which comprises the following steps:

(1) and (3) dripping the metal salt solution into the solution of the multidentate flexible ligand under the stirring condition, and continuing stirring for reaction for 3-6 hours after dripping is finished to obtain the metal salt.

Preferably, the stirring speed in the step (1) is 100-200 r/min.

Preferably, the temperature of the reaction in step (1) is room temperature.

Preferably, the step (1) further comprises the steps of removing the solvent after the reaction, performing suction filtration and forming. Preferably, the molding is injection molding or hot press molding. Preferably, the molding temperature is 80-120 ℃. Preferably, the solvent removal is solvent removal by distillation under reduced pressure.

Preferably, the multidentate flexible ligand is prepared by the following method:

(0-1) adding a ligand and a photoinitiator into the solution of the flexible molecules, uniformly mixing, irradiating by using ultraviolet light, and stirring and reacting for 60-180 min under a sealed condition to obtain the polymer.

Preferably, the temperature of the reaction in step (0-1) is room temperature.

Preferably, the stirring speed in the step (0-1) is 100-200 r/min.

Preferably, the wavelength of the ultraviolet light in the step (0-1) is 365 nm.

Preferably, the metal salt solution in step (1) is prepared by the following method:

(0-2) putting the metal salt in a solvent, and uniformly mixing by ultrasonic waves.

Preferably, the power of the ultrasound is 30-120W, the time of the ultrasound is 30-120 min, and the temperature of the ultrasound is room temperature.

The solvent of each solution in the above technical solution is not particularly limited in the present invention, and an organic solvent well known to those skilled in the art may be used, and the solvent is preferably one or more of benzene, toluene, xylene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, dichloromethane, chloroform, methanol, ethanol, isopropanol, diethyl ether, ethyl acetate, propyl acetate, acetonitrile, pyridine, phenol, diethanolamine, tetrahydrofuran, and acetonitrile, and most preferably one or more of methanol, dichloromethane, and tetrahydrofuran.

The application range of the self-adaptive intelligent material is not particularly limited, and the self-adaptive intelligent material can relate to the fields of chemical industry, machinery, construction, transportation, aerospace, ships, electronic devices and the like, and comprises the following applications:

the first type: as a sealant, adhesive or fast self-healing coating.

The second type: the material is used as a temperature-sensitive variable-stiffness self-repairing engineering material.

In the third category: as an additive manufacturing material.

The invention has the beneficial effects that:

(1) the invention adopts the coordination bonds capable of being dynamically exchanged to construct the three-dimensional network structure of the self-adaptive network and further forms the polymer of the self-adaptive network containing the coordination bonds. Coordination bonds are typical non-covalent exchangeable chemical bonds and are first applied to building adaptive networks. The whole preparation process of the self-adaptive intelligent material can be completed at room temperature, and the self-adaptive intelligent material has the characteristics of mild reaction conditions, simple steps, higher yield and capability of being prepared in a large scale.

(2) The coordination bonds in the self-adaptive intelligent material form a three-dimensional cross-linked structure, the energy of the coordination bonds can be flexibly regulated and controlled by regulating the combination of the ligand and the metal ions, so that the rigidity and the mechanical strength of the material can be controlled, and in addition, the dynamic property of the coordination bonds can also be flexibly regulated and controlled, so that the reprocessing and recycling difficulty of the material can be regulated and controlled. The invention designs coordination combination with medium strength for considering good mechanical strength and reprocessing recovery performance, and obtains the polymer material with high mechanical rigidity and excellent recoverability.

(3) The incorporation of traditional inorganic metal-ligand coordination bonds often results in crystallization, which results in poor processability and is not practical. The coordination structures adopted by the invention are all polydentate ligands, and all contain flexible chains consisting of polyatomic groups, and the flexible chains do not contain aromatic groups. The unique design of the present invention ensures that the synergistic combination of the polydentate ligands and the flexible chains results in the formation of a reproducible polymeric material without the formation of crystalline structures upon combination with metal ions.

(4) The self-adaptive intelligent material of the invention contains a large number of coordination self-adaptive networks inside, the dynamic activity of the coordination bond has high temperature sensitivity and can be defined as follows: the rigidity change is (storage modulus at 30 ℃ to 120 ℃) storage modulus at 30 ℃ to 100%, the material shows the continuous change of the storage modulus in a wide temperature range, and can be used for preparing the temperature-sensitive variable-rigidity self-repairing engineering material.

(5) The self-adaptive intelligent material provided by the invention can be applied to the field of additive manufacturing, the high temperature sensitivity of the coordination bond endows the material with good plastic processability, meanwhile, the self-repairing performance can effectively prevent potential damage of an additive manufactured product due to generated microcracks, and the overall performance of the product cannot be influenced in the repairing process.

(6) The self-adaptive intelligent material provided by the invention is different from the traditional cross-linked polymer, is a material obtained by cross-linking a micromolecular ligand and a metal center, and has excellent variable rigidity property.

Drawings

Fig. 1 is a graph of the change of storage modulus with temperature under the rheological test of the adaptive smart material in embodiment 1 of the present invention.

Fig. 2 is a diagram for recycling the adaptive smart material in the embodiment 1 of the present invention.

Fig. 3 is a tensile stress-strain diagram of the self-adaptive intelligent material after reprocessing and recycling in embodiment 1 of the present invention.

Fig. 4 is a schematic diagram of self-repair of the adaptive smart material in embodiment 1 of the present invention.

Fig. 5 is a schematic diagram of a 3D printing additive manufacturing process of the adaptive smart material in embodiment 1 of the present invention.

Detailed Description

In order to further illustrate the present invention, the following examples are provided to describe the adaptive smart material and the method for preparing the same in detail, but they should not be construed as limiting the scope of the present invention.

Example 1

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol tetra-3-mercaptopropionate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at the speed of 100r/min, and stirring for 30min until the pentaerythritol tetra-3-mercaptopropionate is completely dissolved; adding 44.20g N-allyl imidazole and 1.05g benzoin dimethyl ether into the solution as a photoinitiator, adopting 365nm ultraviolet radiation, controlling the reaction temperature and room temperature under the sealed condition, stirring at 200r/min, and reacting for 60min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 17.45g of copper chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 30min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into the solution containing the multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 4 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product, wherein the hot-press temperature is preferably 80 ℃, so as to obtain the self-adaptive intelligent material based on the coordination bond.

Example 2

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol tetra-3-mercaptopropionate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at the speed of 100r/min, and stirring for 30min until the pentaerythritol tetra-3-mercaptopropionate is completely dissolved; adding 29.05g of acrylamide and 1.05g of benzoin dimethyl ether (DMPA) into the solution as a photoinitiator, adopting 365nm ultraviolet radiation, controlling the reaction temperature under a sealed condition and room temperature, stirring at the speed of 200r/min, and reacting for 180min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 13.26g of nickel chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 2h, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature; removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product, wherein the hot-press temperature is preferably 80 ℃, so as to obtain the self-adaptive intelligent material.

Example 3

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol tetra-3-mercaptopropionate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at the speed of 200r/min, and stirring for 10min until the pentaerythritol tetra-3-mercaptopropionate is completely dissolved; adding 29.47g of acrylic acid and 0.98g of benzoin ethyl ether into the solution to serve as a photoinitiator, adopting 365nm ultraviolet radiation, controlling the reaction temperature and room temperature under the sealed condition, stirring at 100r/min, and reacting for 180min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: 27.89g of zinc chloride is taken, 50mL of methanol is added as a solvent, and the mixture is uniformly mixed by ultrasonic, wherein the ultrasonic power is 30W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 3 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and injection molding on the obtained crude product, wherein the injection molding temperature is 120 ℃, so as to obtain the self-adaptive intelligent material.

Example 4

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol tetra-3-mercaptopropionate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at the speed of 100r/min, and stirring for 30min until the pentaerythritol tetra-3-mercaptopropionate is completely dissolved; adding 42.97g of 4-vinylpyridine and 0.98g of benzoin ethyl ether into the solution to serve as a photoinitiator, adopting 365nm ultraviolet radiation, controlling the reaction temperature under a sealed condition and room temperature, stirring at a speed of 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 13.29g of cobalt chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 90min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 150r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product at the hot-press temperature of 100 ℃ to obtain the self-adaptive intelligent material.

Example 5

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol tetraacrylate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at the speed of 200r/min, and stirring for 10min until the pentaerythritol tetraacrylate is completely dissolved; adding 43.75g of cysteamine and 1.19g of diphenylethanone into the solution as photoinitiators, adopting 365nm ultraviolet radiation, controlling the reaction temperature and room temperature under sealed conditions, stirring at 100r/min, and reacting for 180min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 19.09g of copper chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 30W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 3 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product, wherein the hot-press temperature is 80 ℃, so as to obtain the self-adaptive intelligent material.

Example 6

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol tetraacrylate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at a speed of 100r/min, and stirring for 30min until the pentaerythritol tetraacrylate is completely dissolved; adding 43.75g of 3-mercaptopropionic acid and 1.19g of diphenylethanone into the solution as photoinitiators, adopting 365nm ultraviolet radiation, controlling the reaction temperature under a sealed condition and room temperature, stirring at the speed of 200r/min, and reacting for 60min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 38.71g of zinc chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 30min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 100r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product, wherein the hot-press temperature is 80 ℃, so as to obtain the self-adaptive intelligent material.

Example 7

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol tetraacrylate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at the speed of 150r/min, and stirring for 20min until the pentaerythritol tetraacrylate is completely dissolved; adding 78.98g of 4-pyridine ethanethiol and 1.45g of benzoin dimethyl ether into the solution as photoinitiators, adopting 365nm ultraviolet radiation, controlling the reaction temperature and room temperature under sealed conditions, stirring at a speed of 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 19.09g of copper chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic treatment, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product at the hot-press temperature of 120 ℃ to obtain the self-adaptive intelligent material.

Example 8

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol tetraacrylate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at a speed of 100r/min, and stirring for 30min until the pentaerythritol tetraacrylate is completely dissolved; adding 61.36g of 1H-imidazole-1-ethanethiol and 1.03g of benzophenone serving as photoinitiators into the solution, adopting 365nm ultraviolet radiation, controlling the reaction temperature under a sealed condition to be room temperature, stirring at a speed of 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 19.09g of copper chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic treatment, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product, wherein the hot-press temperature is 80 ℃, so as to obtain the self-adaptive intelligent material.

Example 9

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol triacrylate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at a speed of 100r/min, and stirring for 30min until the pentaerythritol triacrylate is completely dissolved; adding 38.76g of cysteamine and 1.32g of diphenylethanone into the solution as photoinitiators, adopting 365nm ultraviolet radiation, controlling the reaction temperature and room temperature under sealed conditions, stirring at a speed of 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 13.61g of ferric chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and injection molding on the obtained crude product at the injection molding temperature of 100 ℃ to obtain the self-adaptive intelligent material.

Example 10

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol triacrylate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at a speed of 100r/min, and stirring for 30min until the pentaerythritol triacrylate is completely dissolved; adding 53.35g of 3-mercaptopropionic acid and 1.32g of diphenylethanone into the solution as photoinitiators, adopting 365nm ultraviolet radiation, controlling the reaction temperature under a sealed condition and room temperature, stirring at the speed of 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 34.30g of zinc chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product at the hot-press temperature of 100 ℃ to obtain the self-adaptive intelligent material.

Example 11

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol triacrylate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at a speed of 100r/min, and stirring for 30min until the pentaerythritol triacrylate is completely dissolved; adding 69.97g of 4-pyridine ethanethiol and 1.29g of benzoin dimethyl ether into the solution as photoinitiators, adopting 365nm ultraviolet radiation, controlling the reaction temperature under a sealed condition and room temperature, stirring at the speed of 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 10.87g of nickel chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product at the hot-press temperature of 120 ℃ to obtain the self-adaptive intelligent material.

Example 12

Preparation of multidentate flexible ligands: adding 50.00g of pentaerythritol triacrylate into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at a speed of 100r/min, and stirring for 30min until the pentaerythritol triacrylate is completely dissolved; adding 64.44g of 1H-imidazole-1-ethanethiol and 0.92g of benzophenone serving as photoinitiators into the solution, adopting 365nm ultraviolet radiation, controlling the reaction temperature under a sealed condition to be room temperature, stirring at a speed of 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 11.28g of copper chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product at the hot-press temperature of 120 ℃ to obtain the self-adaptive intelligent material.

Example 13

Preparation of multidentate flexible ligands: adding 50.00g of tetramethyltetravinylcyclotetrasiloxane into a flask, adding 100mL of tetrahydrofuran as a solvent, controlling the reaction temperature at room temperature, stirring at a speed of 100r/min for 30min until the tetrahydrofuran is completely dissolved, adding 73.9g of 3-mercaptopropionic acid and 0.38g of benzoin dimethyl ether as photoinitiators into the solution, adopting 365 nm-wavelength ultraviolet irradiation, controlling the reaction temperature at room temperature under a sealed condition, stirring at a speed of 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 10.97g of zinc chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product, wherein the hot-press temperature is 80 ℃, so as to obtain the self-adaptive intelligent material.

Example 14

Preparation of multidentate flexible ligands: adding 50.00g of tetramethyltetravinylcyclotetrasiloxane into a flask, adding 100mL of dimethylformamide as a solvent, controlling the reaction temperature at room temperature, stirring at 100r/min for 30min until the mixture is completely dissolved, adding 49.3g of cysteamine and 0.38g of benzoin dimethyl ether into the solution as photoinitiators, adopting 365nm ultraviolet radiation, controlling the reaction temperature at room temperature under a sealed condition, stirring at 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 20.52g of copper chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product, wherein the hot-press temperature is 80 ℃, so as to obtain the self-adaptive intelligent material.

Example 15

Preparation of multidentate flexible ligands: adding 50.00g of tetramethyltetravinylcyclotetrasiloxane into a flask, adding 100mL of dimethylformamide as a solvent, controlling the reaction temperature at room temperature, stirring at 100r/min for 30min until the mixture is completely dissolved, adding 49.3g of cysteamine and 0.38g of benzoin dimethyl ether into the solution as photoinitiators, adopting 365nm ultraviolet radiation, controlling the reaction temperature at room temperature under a sealed condition, stirring at 200r/min, and reacting for 120min to obtain a solution containing a multidentate flexible ligand;

preparation of metal salt solution: taking 30.00g of cobalt chloride, adding 50mL of methanol as a solvent, and uniformly mixing by ultrasonic, wherein the ultrasonic power is 120W, the ultrasonic time is 120min, and the ultrasonic temperature is room temperature;

adding a metal salt solution into a solution containing a multidentate flexible ligand in a dropwise manner, keeping mechanical stirring for carrying out coordination reaction in the dropwise adding process, and continuing stirring for reaction for 6 hours after the dropwise adding is finished, wherein the stirring speed is 200r/min, and the reaction temperature is room temperature;

removing the solvent by a reduced pressure distillation mode to separate out the polymer in the mixed system to obtain a crude product;

and carrying out suction filtration, drying and hot-press molding on the obtained crude product at the hot-press temperature of 100 ℃ to obtain the self-adaptive intelligent material.

Example 16

The adaptive smart materials of embodiments 1-15, wherein the stiffness change (storage modulus at 30 ℃ to storage modulus at 120 ℃) and storage modulus at 30 ℃ is 100%, and the summary of the main stiffness change performance and the self-healing performance is shown in table 1:

TABLE 1 Performance test Table

The above examples only illustrate some of the raw material ratios in this patent, and they are not illustrated herein. Modifications and substitutions to methods, steps or conditions of the present application are intended to be within the scope of the present application without departing from the spirit and substance of the present application.