A method for preparing a polymer gel material by oxygen initiation

Abstract

The present invention relates to the technical field of gel preparation, and in particular to a method for preparing a polymer gel material by oxygen initiation. First, the monomer and the cross-linking agent are dissolved in a solvent and mixed evenly to obtain a prepolymer solution; then the prepolymer solution is added to an alkyl boron reagent, and the reaction is initiated by oxygen to obtain a polymer gel material, and the reaction time can be as fast as 1 minute; this method does not require deoxygenation operation, the prepolymer solution is convenient for storage and transportation, and the use of oxygen initiation enables large-scale preparation of functional gel materials; the oxygen-initiated preparation process does not require the use of additional heating or lighting equipment, and can mass-produce gel materials in different molds such as metal, plastic, and silica gel.

Description

Technical Field

[0001] The present invention relates to the technical field of gel preparation, and in particular to a method for preparing a polymer gel material by oxygen initiation. Background Art

[0002] Gel materials have both excellent mechanical properties and biocompatibility, and are widely used in drug release, bionic devices, wound dressings, ion skin, etc. Using a free radical process to prepare polymer gel materials is the most widely used method in academia and industry. However, this process will undergo inhibition in the presence of oxygen. Therefore, the preparation process usually requires complicated pre-deoxygenation operations, and then a thermal initiator or a photoinitiator is added, and a heating or lighting device is used to complete the preparation process. For example, Gong et al. used a method of multiple ultraviolet light initiations to prepare a double network structure gel with excellent mechanical properties; He et al. utilized the ultraviolet light initiation preparation process under low temperature conditions to obtain a gel material with ultra-high conductivity.

[0003] Regarding the method for preparing polymer gel materials by a free radical process, there is a lack of a gel preparation method that is easy to operate, does not require pre-deoxygenation, and can be prepared rapidly on a large scale. Summary of the Invention

[0004] To solve the above problems, the purpose of the present invention is to provide a method for preparing a polymer gel material by oxygen initiation; first, the monomer and the cross-linking agent are dissolved in a solvent and mixed evenly to obtain a prepolymer solution; then the prepolymer solution is added to an alkyl boron reagent, and the reaction is initiated by oxygen to obtain a polymer gel material, and the reaction time can be as fast as 1 minute; this method does not require deoxygenation operation, the prepolymer solution is convenient for storage and transportation, and using oxygen initiation can carry out large-scale preparation of functional gel materials; the oxygen-initiated preparation process does not require the use of additional heating or lighting equipment, and can mass-produce gel materials in different molds such as metal, plastic, and silica gel.

[0005] The present invention realizes the rapid large-scale preparation of hydrogel materials by the mechanism of rapid reaction of alkyl boron with oxygen to release free radicals, which initiates the rapid reaction of monomers and cross-linking agents in the reaction system. Without the need for pre-deoxygenation, the present invention adopts a method of co-initiating free radicals with a free radical alkyl boron reagent and oxygen, providing a reliable method for the rapid preparation of polymer gel materials with simple operation, in-situ preparation, and large-scale synthesis.

[0006] The purpose of the present invention is to solve the problem that the process of preparing polymer gel materials by a free radical method is limited by the need for deoxygenation operation and synthesis equipment, resulting in the inability to prepare rapidly and on a large scale, and provides a method for rapidly and large-scale synthesizing gel materials by co-initiating alkyl boron and oxygen.

[0007] The object of the present invention can be achieved by the following technical solutions:

[0008] The first object of the present invention is to provide a method for preparing a polymer gel material by oxygen initiation, comprising the following steps:

[0009] (1) Dissolve the monomer and the crosslinking agent in a solvent, and mix evenly to obtain a prepolymer solution;

[0010] (2) Add the prepolymer solution prepared in step (1) to an alkyl boron reagent, and initiate the reaction with oxygen to obtain a polymer gel material.

[0011] In one embodiment of the present invention, in step (1), the monomer is selected from one or more of the substances shown by the structural formulas of formula (I), formula (II), formula (III), formula (IV) or formula (V);

[0012]

[0013] Among them, R1 is selected from one of hydrogen or an alkane chain; R2 is selected from one of hydrogen or an alkane chain; R3 is selected from one of a sulfonic acid group or an alkane chain; R4 is selected from one of hydrogen or an alkane chain; R5 is selected from an alkane chain; R6 is selected from one of hydrogen or an alkane chain; R7 is selected from one of a catechol group or an alkane chain; R8 is selected from one of hydrogen or methyl; n is a positive integer greater than or equal to 1.

[0014] In one embodiment of the present invention, in step (1), the crosslinking agent is selected from one or more of acrylamide-based crosslinking agents or polyethylene glycol-based crosslinking agents;

[0015] The chemical structural formula of the acrylamide-based crosslinking agent is shown by formula (VI), and the chemical structural formula of the polyethylene glycol-based crosslinking agent is shown by formula (VII);

[0016]

[0017] Among them, R9 is selected from one of hydrogen or methyl; R 10 is selected from one of hydrogen or methyl; n is a positive integer greater than or equal to 1.

[0018] In one embodiment of the present invention, in step (1), the solvent is selected from one or more of water, dimethyl sulfoxide, N, N-dimethylformamide, benzene, toluene, ethyl acetate, petroleum ether, dichloromethane, chloroform, anisole, acetonitrile or tetrahydrofuran.

[0019] In one embodiment of the present invention, in step (1), the dosage ratio of the monomer, the crosslinking agent and the solvent is 1319 mol / L: 1 mol / L: 5 - 200 mL.

[0020] In one embodiment of the present invention, the dosage ratio of the monomer, crosslinking agent, and solvent is 1319 mol / L: 1 mol / L: 22.4 mL.

[0021] In one embodiment of the present invention, in step (2), the alkylboron reagent is selected from one or more of alkylboron or catecholborane;

[0022] The chemical structural formula of the alkylboron is as shown in formula (VIII), and the chemical structural formula of the catecholborane is as shown in formula (IX);

[0023]

[0024] wherein, R 11 is selected from one of alkyl hydrocarbons; R 12 is selected from one of alkyl hydrocarbons.

[0025] In one embodiment of the present invention, in step (2), the dosage ratio of the monomer to the alkylboron reagent in the prepolymer solution is 10 - 3000 mol / L: 1 mol / L.

[0026] In one embodiment of the present invention, the dosage ratio of the monomer to the alkylboron reagent in the prepolymer solution is 341 mol / L: 1 mol / L.

[0027] In one embodiment of the present invention, in step (2), during the reaction process, the reaction temperature is 0 - 30 °C; the reaction time is 1 min - 10 min.

[0028] In one embodiment of the present invention, the reaction product is placed in a mold to obtain a polymer gel material having the same shape as the mold.

[0029] In one embodiment of the present invention, the material of the mold is selected from one of silica gel, iron, polytetrafluoroethylene, or polyimide.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The alkylboron reagent and prepolymer solution used in the present invention have stable properties and can be stored for a long time. This method does not require deoxygenation operations such as liquid nitrogen freezing and evacuation or nitrogen bubbling, and can directly carry out large-scale rapid gel preparation processes; alkylboron reacts with oxygen to release alkyl free radicals. The more oxygen there is, the more violent the reaction of alkylboron, and the faster the reaction rate; the reaction time can be as fast as 1 minute.

[0032] (2) The method for preparing a polymer gel material by oxygen initiation in the present invention does not require deoxygenation operation. The prepolymer solution is convenient for storage and transportation, and large-scale preparation of functional gel materials can be carried out by using oxygen initiation; the oxygen-initiated preparation process does not require the use of additional heating or lighting equipment, and gel materials can be mass-produced in different molds such as metal, plastic, and silica gel. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a schematic diagram of the preparation of a polymer gel material by oxygen initiation in the present invention;

[0034] Figure 2 It is a schematic diagram of the polymer gel material prepared in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0035] The first object of the present invention is to provide a method for preparing a polymer gel material by oxygen initiation, comprising the following steps:

[0036] (1) Dissolve the monomer and the crosslinking agent in a solvent and mix well to obtain a prepolymer solution;

[0037] (2) Add the prepolymer solution prepared in step (1) to an alkyl borate reagent, and initiate the reaction with oxygen to obtain a polymer gel material.

[0038] In an embodiment of the present invention, in step (1), the monomer is selected from one or more of the substances represented by the structural formulas of formula (I), formula (II), formula (III), formula (IV), or formula (V);

[0039]

[0040] Among them, R1 is selected from one of hydrogen or an alkane chain; R2 is selected from one of hydrogen or an alkane chain; R3 is selected from one of a sulfonic acid group or an alkane chain; R4 is selected from one of hydrogen or an alkane chain; R5 is selected from an alkane chain; R6 is selected from one of hydrogen or an alkane chain; R7 is selected from one of a catechol group or an alkane chain; R8 is selected from one of hydrogen or methyl; n is a positive integer greater than or equal to 1.

[0041] In an embodiment of the present invention, in step (1), the crosslinking agent is selected from one or more of acrylamide-based crosslinking agents or polyethylene glycol-based crosslinking agents;

[0042] The chemical structural formula of the acrylamide-based crosslinking agent is as shown in formula (VI), and the chemical structural formula of the polyethylene glycol-based crosslinking agent is as shown in formula (VII);

[0043]

[0044] Among them, R9 is selected from one of hydrogen or methyl; R10 selected from one of hydrogen or methyl; n is a positive integer greater than or equal to 1.

[0045] In one embodiment of the present invention, in step (1), the solvent is selected from one or more of water, dimethyl sulfoxide, N,N-dimethylformamide, benzene, toluene, ethyl acetate, petroleum ether, dichloromethane, chloroform, anisole, acetonitrile or tetrahydrofuran.

[0046] In one embodiment of the present invention, in step (1), the dosage ratio of the monomer, the crosslinking agent and the solvent is 1319 mol / L: 1 mol / L: 5 - 200 mL.

[0047] In one embodiment of the present invention, the dosage ratio of the monomer, the crosslinking agent and the solvent is 1319 mol / L: 1 mol / L: 22.4 mL.

[0048] In one embodiment of the present invention, in step (2), the alkyl borane reagent is selected from one or more of alkyl borane or catechol borane;

[0049] The chemical structural formula of the alkyl borane is as shown in formula (VIII), and the chemical structural formula of the catechol borane is as shown in formula (IX);

[0050]

[0051] wherein, R 11 is selected from one of alkyl hydrocarbons; R 12 is selected from one of alkyl hydrocarbons.

[0052] In one embodiment of the present invention, in step (2), the dosage ratio of the monomer to the alkyl borane reagent in the prepolymer solution is 10 - 3000 mol / L: 1 mol / L.

[0053] In one embodiment of the present invention, the dosage ratio of the monomer to the alkyl borane reagent in the prepolymer solution is 341 mol / L: 1 mol / L.

[0054] In one embodiment of the present invention, in step (2), during the reaction, the reaction temperature is 0 - 30 °C; the reaction time is 1 min - 10 min.

[0055] In one embodiment of the present invention, the reaction product is placed in a mold to obtain a polymer gel material having the same shape as the mold.

[0056] In one embodiment of the present invention, the material of the mold is selected from one of silica gel, iron, polytetrafluoroethylene or polyimide.

[0057] The present invention will be described in detail below with reference to specific drawings and examples.

[0058] In the following examples, the reagents used are commercially available unless otherwise specified, and the detection methods are conventional detection methods in the art unless otherwise specified. In the following examples, the reaction process is initiated by oxygen, and only the reaction temperature and reaction time are given in the actual writing.

[0059] Example 1: Dissolve the monomers acrylamide (i.e., AAm, the same below) and 2-acrylamido-2-methylpropanesulfonic acid (i.e., AMPS, the same below) in an aqueous solution, and then add the crosslinking agent N,N'-methylenebisacrylamide (i.e., MBAA, the same below) to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). Pour the solution into a mold, add the triethylboron reagent ([Et3B]=0.0089 mol / L), and the volume of the aqueous solution is 22.4 mL (the experimental process is as Figure 1 shown). The reaction temperature is 25 °C and the reaction time is 1 minute to obtain a polymer hydrogel material with the same shape as the mold (as Figure 2 described). The value of the storage modulus in the rheological characterization is more than 2 times the value of the loss modulus, proving that it is a gel material with typical solid-like properties.

[0060] Example 2: Dissolve the monomers N-isopropylacrylamide (i.e., NIPAM, the same below) and 2-acrylamido-2-methylpropanesulfonic acid in an aqueous solution, and then add the crosslinking agent N,N'-methylenebisacrylamide to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). Pour the solution into a mold, and the volume of the aqueous solution is 22.4 mL. Under room temperature conditions, add the triethylboron reagent ([Et3B]=0.0089 mol / L), the reaction temperature is 25 °C, and the reaction time is 1 minute to obtain a polymer hydrogel material with the same shape as the mold. The value of the storage modulus in the rheological characterization is more than 2 times the value of the loss modulus, proving that it is a gel material with typical solid-like properties.

[0061] Example 3: The monomer N,N-dimethylacrylamide (i.e., DMAA, the same hereinafter) and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an aqueous solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution. The solution ([DMAA]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L) was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute to obtain a polymer hydrogel material with exactly the same shape as the mold. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0062] Example 4: The monomer acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in a chloroform solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the chloroform solution was 5 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute to obtain a polymer hydrogel material with exactly the same shape as the mold. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0063] Example 5: The monomer N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in a chloroform solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and the volume of the chloroform solution was 200 mL. A triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The reaction temperature was 25 °C, and the reaction time was 1 minute to obtain a polymer hydrogel material with exactly the same shape as the mold. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0064] Example 6: The monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in chloroform solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The chloroform solution had a volume of 22.4 mL. The reaction temperature was 25 °C and the reaction time was 1 minute to obtain a polymer hydrogel material with the same shape as the mold. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0065] Example 7: The monomers acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The N,N-dimethylformamide solution had a volume of 22.4 mL. The reaction temperature was 25 °C and the reaction time was 1 minute to obtain a polymer hydrogel material with the same shape as the mold. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0066] Example 8: The monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and the N,N-dimethylformamide solution had a volume of 22.4 mL. Triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The reaction temperature was 25 °C and the reaction time was 1 minute to obtain a polymer hydrogel material with the same shape as the mold. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0067] Example 9: The monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The volume of N,N-dimethylformamide solution was 22.4 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0068] Example 10: The monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in tetrahydrofuran solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added. The volume of tetrahydrofuran was 22.4 mL. The reaction temperature was 0 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0069] Example 11: The monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in tetrahydrofuran solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and the volume of tetrahydrofuran was 22.4 mL; triethylboron reagent ([Et3B]=0.0089 mol / L) was added. The reaction temperature was 10 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0070] Example 12: Monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in a tetrahydrofuran solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and benzylcatecholborane (concentration: 0.3034 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 22.4 mL. The reaction temperature was 30 °C, the reaction time was 10 minutes, the reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical gel material with solid-like properties.

[0071] Example 13: Monomers acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an ethanol solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and benzylcatecholborane (concentration: 0.0089 mol / L) was added at room temperature. The volume of the ethanol solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 7 minutes. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical gel material with solid-like properties.

[0072] Example 14: Monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an ethanol solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and the volume of the ethanol solution was 22.4 mL. Triethylboron reagent ([Et3B]=0.0089 mol / L) was added. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical gel material with solid-like properties.

[0073] Example 15: The monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an ethanol solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0010 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the ethanol solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in the rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0074] Example 16: The monomers methyl acrylate (MA, the same below) and acrylamide were dissolved in an ethanol solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [MA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the ethanol solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in the rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0075] Example 17: The monomers ethyl acrylate (i.e., EA, the same below) and acrylamide were dissolved in an ethanol solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [EA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the ethanol solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in the rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0076] Example 18: n-Butyl acrylate (i.e., BA, the same hereinafter) and acrylamide were dissolved in an ethanol solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [BA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the ethanol solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0077] Example 19: Methyl acrylate and acrylamide monomers were dissolved in a tetrahydrofuran solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [MA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0078] Example 20: Ethyl acrylate and acrylamide monomers were dissolved in a tetrahydrofuran solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [EA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0079] Example 21: n-Butyl acrylate and acrylamide were dissolved in a tetrahydrofuran solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [BA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The prepolymer solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0080] Example 22: Methyl acrylate and acrylamide were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [MA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The prepolymer solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the N,N-dimethylformamide solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0081] Example 23: Ethyl acrylate and acrylamide were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [EA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The prepolymer solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the N,N-dimethylformamide solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0082] Example 24: n-Butyl acrylate and acrylamide were dissolved in N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [BA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of N,N-dimethylformamide solution was 22.4 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0083] Example 25: The monomers methyl methacrylate (i.e., MMA, the same below) and acrylamide were dissolved in acetonitrile solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [MMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of acetonitrile solution was 22.4 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0084] Example 26: Ethyl methacrylate and acrylamide were dissolved in acetonitrile solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [EMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of acetonitrile solution was 22.4 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0085] Example 27: The monomer n-butyl methacrylate (i.e., BMA, the same hereinafter) and acrylamide were dissolved in an acetonitrile solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [BMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The prepolymer solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the acetonitrile solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0086] Example 28: The monomers methyl methacrylate and acrylamide were dissolved in a tetrahydrofuran solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [MMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The prepolymer solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0087] Example 29: The monomers ethyl methacrylate and acrylamide were dissolved in a tetrahydrofuran solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [EMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The prepolymer solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0088] Example 30: n-Butyl methacrylate and acrylamide were dissolved in a tetrahydrofuran solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [BMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0089] Example 31: Methyl methacrylate and acrylamide monomers were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [MMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the N,N-dimethylformamide solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0090] Example 32: Ethyl methacrylate and acrylamide monomers were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [EMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the N,N-dimethylformamide solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0091] Example 33: n-Butyl methacrylate and acrylamide were dissolved in N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [BMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of N,N-dimethylformamide solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0092] Example 34: Monomer acrylic acid (i.e., AA, the same below) and acrylamide were dissolved in acetonitrile solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of acetonitrile solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0093] Example 35: Monomer acrylic acid and acrylamide were dissolved in acetonitrile solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of acetonitrile solution was 50 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0094] Example 36: Monomer acrylic acid and acrylamide were dissolved in an acetonitrile solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the acetonitrile solution was 80 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0095] Example 37: Monomer acrylic acid and acrylamide were dissolved in a tetrahydrofuran solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 50 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0096] Example 38: Monomer acrylic acid and acrylamide were dissolved in a tetrahydrofuran solution, and then the cross-linking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0097] Example 39: Monomer acrylic acid and acrylamide were dissolved in a tetrahydrofuran solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold. At room temperature, triethylboron reagent ([Et3B]=0.0089 mol / L) was added, and the solution was poured into the mold. The volume of the tetrahydrofuran solution was 100 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0098] Example 40: Monomer acrylic acid and acrylamide were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold. At room temperature, triethylboron reagent ([Et3B]=0.0089 mol / L) was added, and the solution was poured into the mold. The volume of the N,N-dimethylformamide solution was 50 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0099] Example 41: Monomer acrylic acid and acrylamide were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold. At room temperature, triethylboron reagent ([Et3B]=0.0089 mol / L) was added, and the solution was poured into the mold. The volume of the N,N-dimethylformamide solution was 22.4 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0100] Example 42: Acrylic acid and acrylamide were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the N,N-dimethylformamide solution was 120 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical gel material with solid-like properties.

[0101] Example 43: The monomers acrylic acid and acrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical gel material with solid-like properties.

[0102] Example 44: The monomers acrylic acid and N-isopropylacrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=1 mol / L, [AA]=1 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical gel material with solid-like properties.

[0103] Example 45: Monomer acrylic acid and N,N-dimethylacrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=1 mol / L, [AA]=1 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold. At room temperature, triethylboron reagent ([Et3B]=0.0089 mol / L) was added, and the solution was poured into the mold. The volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0104] Example 46: Monomer methacrylic acid and acrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [MAA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold. At room temperature, triethylboron reagent ([Et3B]=0.0089 mol / L) was added, and the solution was poured into the mold. The volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0105] Example 47: Monomer methacrylic acid and N-isopropylacrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [MAA]=0.0034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold. At room temperature, triethylboron reagent ([Et3B]=0.0089 mol / L) was added, and the solution was poured into the mold. The volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus characterized by rheology was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0106] Example 48: The monomers methacrylic acid and N,N-dimethylacrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=3 mol / L, [MAA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0107] Example 49: The monomers poly(ethylene glycol) monomethyl ether acrylate (OEGA, the same below) and acrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [OEGA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0108] Example 50: The monomers poly(ethylene glycol) monomethyl ether acrylate and N-isopropylacrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [OEGA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0109] Example 51: Polyethylene glycol monomethyl ether acrylate monomer and N,N-dimethylacrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=3 mol / L, [OEGA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0110] Example 52: Polyethylene glycol monomethyl ether methacrylate (OEOMA) monomer and acrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [OEOMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0111] Example 53: Polyethylene glycol monomethyl ether methacrylate monomer and N-isopropylacrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [OEOMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0112] Example 54: The monomer methoxypolyethylene glycol methacrylate and N,N-dimethylacrylamide were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [OEOMA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 22.4 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in the rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0113] Example 55: The monomers acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 200 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in the rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0114] Example 56: The monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 50 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in the rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0115] Example 57: The monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an aqueous solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the aqueous solution was 120 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0116] Example 58: The monomers acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in a chloroform solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the chloroform solution was 50 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0117] Example 59: The monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in a chloroform solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the chloroform solution was 60 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a typical solid-like gel material.

[0118] Example 60: The monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in a chloroform solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The chloroform solution had a volume of 55 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0119] Example 61: The monomers acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The N,N-dimethylformamide solution had a volume of 55 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0120] Example 62: The monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The N,N-dimethylformamide solution had a volume of 55 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The rheological characterization showed that the storage modulus value was more than twice the loss modulus value, proving that it was a gel material with typical solid-like properties.

[0121] Example 63: The monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in N,N-dimethylformamide solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=2 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The N,N-dimethylformamide solution had a volume of 40 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0122] Example 64: The monomers acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in tetrahydrofuran solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The tetrahydrofuran solution had a volume of 40 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0123] Example 65: The monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in tetrahydrofuran solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The tetrahydrofuran solution had a volume of 55 mL. The reaction temperature was 25 °C and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0124] Example 66: The monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in a tetrahydrofuran solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=2 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the tetrahydrofuran solution was 45 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0125] Example 67: The monomers acrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an acetonitrile solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=2 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the acetonitrile solution was 60 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0126] Example 68: The monomers N-isopropylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an acetonitrile solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=2 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the acetonitrile solution was 60 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0127] Example 69: The monomers N,N-dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid were dissolved in an acetonitrile solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([DMAA]=3 mol / L, [AMPS]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the acetonitrile solution was 55 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties..

[0128] Example 70: The monomers methyl acrylate and acrylamide were dissolved in an ethanol solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([AAm]=3 mol / L, [MA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the ethanol solution was 20 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties..

[0129] Example 71: The monomers ethyl acrylate and acrylamide were dissolved in an ethanol solution, and then the crosslinking agent N,N-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=2 mol / L, [EA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the ethanol solution was 25 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice the value of the loss modulus, proving that it was a gel material with typical solid-like properties

[0130] Example 72: n-Butyl acrylate and acrylamide were dissolved in an ethanol solution, and then the crosslinking agent N,N'-methylenebisacrylamide was added to obtain a prepolymer solution ([NIPAM]=3 mol / L, [BA]=0.034 mol / L, [MBAA]=0.0023 mol / L). The solution was poured into a mold, and a triethylboron reagent ([Et3B]=0.0089 mol / L) was added at room temperature. The solution was poured into the mold, and the volume of the ethanol solution was 25 mL. The reaction temperature was 25 °C, and the reaction time was 1 minute. A polymer hydrogel material with the same shape as the mold was obtained. The value of the storage modulus in rheological characterization was more than twice that of the loss modulus, proving that it was a gel material with typical solid-like properties.

[0131] The above description of the embodiments is to enable those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative efforts. Therefore, the present invention is not limited to the above embodiments, and all improvements and modifications made by those skilled in the art without departing from the scope of the present invention according to the disclosure of the present invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a polymer gel material by oxygen initiation, characterized in that, It includes the following steps: (1) Dissolve the monomer and the crosslinking agent in a solvent and mix well to obtain a prepolymer solution; (2) Add the prepolymer solution prepared in step (1) to an alkyl borane reagent and initiate the reaction with oxygen to obtain a polymer gel material; In step (1), the monomer is selected from one or more of the substances shown by the structural formulas such as formula (I), formula (II), formula (III), formula (IV) or formula (V); Among them, R1 is selected from one of hydrogen or an alkane chain; R2 is selected from one of hydrogen or an alkane chain; R3 is selected from one of a sulfonic acid group or an alkane chain; R4 is selected from one of hydrogen or an alkane chain; R5 is selected from an alkane chain; R6 is selected from one of hydrogen or an alkane chain; R7 is selected from one of a catechol group or an alkane chain; R8 is selected from one of hydrogen or methyl; n is a positive integer greater than or equal to 1; In step (1), the crosslinking agent is selected from one or more of acrylamide-based crosslinking agents or polyethylene glycol-based crosslinking agents; The chemical structural formula of the acrylamide-based crosslinking agent is shown by formula (VI), and the chemical structural formula of the polyethylene glycol-based crosslinking agent is shown by formula (VII); Among them, R9 is selected from one of hydrogen or methyl; R 10 is selected from one of hydrogen or methyl; n is a positive integer greater than or equal to 1; In step (1), the dosage ratio of the monomer, the crosslinking agent and the solvent is 1319 mol / L: 1 mol / L: 5 - 200 mL; In step (2), the dosage ratio of the monomer in the prepolymer solution to the alkyl borane reagent is 10 - 3000 mol / L: 1 mol / L; during the reaction process, the reaction temperature is 0 - 30 °C; the reaction time is 1 min - 10 min.

2. The method for preparing a polymer gel material by oxygen initiation according to claim 1, wherein, In step (1), the solvent is selected from one or more of water, dimethyl sulfoxide, N, N-dimethylformamide, benzene, toluene, ethyl acetate, petroleum ether, dichloromethane, chloroform, anisole, acetonitrile or tetrahydrofuran.

3. The method for preparing a polymer gel material by oxygen initiation according to claim 1, characterized in that, The dosage ratio of the monomer, the crosslinking agent and the solvent is 1319 mol / L: 1 mol / L: 22.4 mL.

4. A method for preparing a polymer gel material by oxygen initiation according to claim 1, characterized in that, In step (2), the alkyl borane reagent is selected from one or more of alkyl boranes or catechol borane; The chemical structural formula of the alkyl borane is shown by formula (VIII), and the chemical structural formula of the catechol borane is shown by formula (IX); Among them, R 11 is selected from one of alkyl hydrocarbons; R 12 is selected from one of alkyl hydrocarbons.

5. A method for preparing a polymer gel material by oxygen initiation according to claim 1, characterized in that, The dosage ratio of the monomer in the prepolymer solution to the alkyl borane reagent is 341 mol / L: 1 mol / L.

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