CN111635542B - Cross-linked polyglutamic acid hydrogel and preparation method thereof - Google Patents
Cross-linked polyglutamic acid hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a crosslinked polyglutamic acid hydrogel and a preparation method thereof. The method comprises the following steps: adding gamma-polyglutamic acid into the acidic solution to obtain a first solution; mixing the first solution with a cross-linking agent to obtain a second solution; and (3) placing the second solution in a microwave reactor for crosslinking reaction, and then dialyzing to obtain the crosslinked polyglutamic acid hydrogel. The method has the advantages of lower energy consumption, simple and safe reaction, high water absorption of the obtained hydrogel, high swelling speed, higher reaction efficiency, obviously reduced reaction time, fewer reaction steps and short preparation period compared with the traditional preparation method. In addition, the method is carried out in aqueous solution, and is more environment-friendly.
Description
Technical Field
The invention relates to the technical field of polymer chemistry, in particular to a crosslinked polyglutamic acid hydrogel and a preparation method thereof.
Background
Polyglutamic acid (PGA) is a polyamino acid material obtained by fermentation of microorganisms, consisting of glutamic acid units forming peptide bonds through α -amino and γ -carboxyl groups. The polyglutamic acid has high water absorption and water solubility, so that the polyglutamic acid can be dissolved when contacting water, and can rapidly absorb moisture in air to dissolve even if being placed in the air, and the application range of the untreated polyglutamic acid is greatly limited. The polyglutamic acid can form hydrogel with high water absorbability, biocompatibility and biodegradability after being crosslinked. In recent years, polyglutamic acid hydrogel has been widely used in the fields of medicine, cosmetics, food, textile, sewage treatment, etc. due to its excellent properties.
There are two main methods for preparing polyglutamic acid hydrogel: physical crosslinking and chemical crosslinking. Japanese patent laid-open No. 6-322358 reports the preparation of a super absorbent hydrogel by crosslinking an aqueous solution of polyglutamic acid by a gamma-ray crosslinking technique. The method of physical radiation crosslinking is adopted, the reaction condition is mild, the production process is simple, no crosslinking agent is required to be added, the product is not required to be additionally sterilized, and no secondary pollution is caused. However, the equipment required for radiation crosslinking is huge, nitrogen or vacuum protection is required in the whole radiation process, the cost is high, and various side reactions can be generated. In addition, the installation and management of the radiation devices are troublesome. Most of the reported preparation methods for preparing the polyglutamic acid hydrogel by the chemical crosslinking method need complicated reaction conditions and preparation operation processes, the obtained hydrogel has low water absorption rate and long reaction time, and the preparation of the polyglutamic acid hydrogel is difficult.
The patent with the publication number CN 102321256 discloses a preparation method of biocompatible gamma-polyglutamic acid hydrogel. The chitosan oligosaccharide aqueous solution is prepared by using polyglutamic acid as a main raw material and chitosan oligosaccharide as a cross-linking agent in an aqueous solution. However, this reaction requires activation of the polyglutamic acid carboxyl group with the activators carbodiimide and N-hydroxysuccinimide. Two chemical reagents other than the cross-linking agent are used in the reaction process, so that the difficulty of later purification is increased, and the risk is increased for the safety of the product.
The dihalogen alkane is used as a cross-linking agent to ensure that the polyglutamic acid can be used for producing hydrogel in dimethyl sulfoxide and sodium bicarbonate (preliminary research on synthesis and modification of the polyglutamic acid super absorbent resin, nanjing university of industry, 2005.5.). However, the method must have a laboratory to prepare free polyglutamic acid, then dissolve it in dimethyl sulfoxide (DMSO) according to a certain mass ratio, and pass through NaHCO 3 The catalytically crosslinked polyglutamic acid of (1). The method has harsh reaction conditions, low water absorption of the product and easy occurrence of side reactions.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for producing a crosslinked polyglutamic acid hydrogel, and the resulting crosslinked polyglutamic acid hydrogel.
The method uses a microwave reactor to replace the traditional crosslinking process, and overcomes many defects of the traditional preparation of the crosslinked polyglutamic acid hydrogel.
The microwave has double effects of heating and non-heating on the crosslinking reaction. The microwave reactor generates an alternating electric field, the electric field acts on an object in the microwave field, and small molecules with unbalanced charge distribution quickly absorb electromagnetic waves to enable polar molecules to rotate and collide for more than 25 hundred million times/s, so that the polar molecules swing along with the change of an external electric field and generate a heat effect; meanwhile, the thermal motion of molecules and the interaction between adjacent molecules prevent the swing rule of the molecules along with the change of an electric field, so that friction action is generated among the molecules, part of energy is converted into molecular heat energy to cause the aggravation of molecular motion, and the molecules are in a metastable state due to the high-speed rotation and vibration of the molecules, thereby being beneficial to further ionization of the molecules or being in a preparation state of reaction.
The specific technical scheme of the invention is as follows:
1. a preparation method of a crosslinked polyglutamic acid hydrogel comprises the following steps:
adding gamma-polyglutamic acid into an acidic solution to obtain a first solution;
mixing the first solution with a cross-linking agent to obtain a second solution;
and (3) placing the second solution in a microwave reactor for crosslinking reaction, and then dialyzing to obtain the crosslinked polyglutamic acid hydrogel.
2. The production method according to item 1, wherein the pH of the first solution is 2 to 6.5, preferably 2 to 4.
3. The production method according to any one of items 1 to 2, wherein the crosslinking agent is one or more selected from diglycidyl ether, divinyl sulfone, 1,2,7,8-diepoxyoctane, 1,3-diepoxybutane, and sodium trimetaphosphate.
4. The production method according to any one of items 1 to 3, wherein the gamma-polyglutamic acid has a molecular weight of 500k to 1500kDa, preferably 500k to 1200kDa, and more preferably 800k to 1100kDa.
5. The production method according to any one of items 1 to 4, wherein the mass ratio of the crosslinking agent to the γ -polyglutamic acid is from 3 to 18.
6. The production method according to any one of claims 1 to 5, wherein the reaction temperature of the microwave reaction is 25 to 80 ℃, preferably 40 to 70 ℃; preferably, the reaction time of the microwave reaction is 0.5 to 4 hours, preferably 0.5 to 3 hours, and more preferably 1 to 3 hours.
7. A crosslinked polyglutamic acid hydrogel prepared by the preparation method of any one of items 1 to 6.
8. A crosslinked polyglutamic acid hydrogel, wherein the crosslinked polyglutamic acid hydrogel is prepared by a method comprising the steps of:
adding gamma-polyglutamic acid into the acidic solution to obtain a first solution;
mixing the first solution with a cross-linking agent to obtain a second solution;
and (3) placing the second solution in a microwave reactor for crosslinking reaction, and then dialyzing to obtain the crosslinked polyglutamic acid hydrogel.
9. The crosslinked polyglutamic acid hydrogel of item 8, wherein the pH of the first solution is 2 to 6.5, preferably 2 to 4.
10. The crosslinked polyglutamic acid hydrogel of any one of claims 8-9, wherein the crosslinking agent is selected from one or more of diglycidyl ether, divinyl sulfone, 1,2,7,8-diepoxyoctane, 1,3-diepoxybutane, and sodium trimetaphosphate.
11. The crosslinked polyglutamic acid hydrogel according to any one of claims 8 to 10, wherein the gamma-polyglutamic acid has a molecular weight of 500k-1500kDa, preferably 500k-1200kDa, and more preferably 800k-1100kDa.
12. The crosslinked polyglutamic acid hydrogel according to any one of claims 8 to 11, wherein the mass ratio of the crosslinking agent to the γ -polyglutamic acid is from 3 to 18.
13. The crosslinked polyglutamic acid hydrogel according to any one of claims 8 to 12, wherein the reaction temperature of the microwave reaction is from 25 to 80 ℃, preferably from 40 to 70 ℃; preferably, the microwave reaction time is 0.5 to 4 hours, preferably 0.5 to 3 hours, and more preferably 1 to 3 hours.
ADVANTAGEOUS EFFECTS OF INVENTION
The method has the advantages of lower energy consumption, simple and safe reaction, high water absorption of the obtained hydrogel and high swelling speed. Compared with the traditional preparation method, the method has the advantages of higher reaction efficiency, obviously reduced reaction time, fewer reaction steps and short preparation period. In addition, the method is carried out in aqueous solution, and is more environment-friendly.
Detailed Description
The present invention will be described in detail below. While specific embodiments of the invention have been shown, it should be understood that the invention may be embodied in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
It should be noted that certain terms are used throughout the description and claims to refer to particular components. As one skilled in the art will appreciate, various names may be used to refer to a component. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description which follows is a preferred embodiment of the invention, however, the description is given for the purpose of illustrating the general principles of the invention and not for the purpose of limiting the scope of the invention. The scope of the present invention is defined by the appended claims.
The term "kDa" refers to 1000Da.
The term "Da" refers to a unit of weight average molecular weight of polyglutamic acid.
The invention provides a preparation method of a cross-linked polyglutamic acid hydrogel, which comprises the following steps:
adding gamma-polyglutamic acid into the acidic solution to obtain a first solution;
mixing the first solution with a cross-linking agent to obtain a second solution;
and (3) placing the second solution in a microwave reactor for crosslinking reaction, and then dialyzing to obtain the crosslinked polyglutamic acid hydrogel.
The acidic solution is known to those skilled in the art and may be, for example, a hydrochloric acid solution, an acetic acid solution, a lactic acid solution, or the like.
The "crosslinking agent" is also called a bridging agent, which forms bridges between polymer molecular chains to become an insoluble substance of a three-dimensional structure.
In a preferred embodiment of the present invention, wherein the concentration of the gamma-polyglutamic acid in the first solution is 130-350mg/g, preferably 150-200mg/g, for example, the concentration of the gamma-polyglutamic acid in the first solution may be 130mg/g, 140mg/g, 150mg/g, 160mg/g, 170mg/g, 180mg/g, 190mg/g, 200mg/g, 210mg/g, 220mg/g, 230mg/g, 240mg/g, 250mg/g, 260mg/g, 270mg/g, 280mg/g, 290mg/g, 300mg/g, 310mg/g, 320mg/g, 330mg/g, 340mg/g, 350mg/g or any range therebetween.
The concentration of the gamma-polyglutamic acid in the first solution is the ratio of the dosage of the gamma-polyglutamic acid to the sum of the dosage of the solution and the dosage of the gamma-polyglutamic acid.
In a preferred embodiment of the present invention, wherein the pH of the first solution is 2-6.5, preferably 2-4, for example, the pH of the first solution may be 2, 3, 4, 5, 6, 6.5 or any range therebetween.
In a preferred embodiment of the present invention, wherein the crosslinking agent is selected from one or more of diglycidyl ether, divinyl sulfone, 1,2,7,8-diepoxyoctane, 1,3-diepoxybutane and sodium trimetaphosphate.
The diglycidyl ether can be 1,4-butanediol diglycidyl ether or polyethylene glycol diglycidyl ether.
In a preferred embodiment of the present invention, wherein the molecular weight of the gamma-polyglutamic acid is 500k-1500kDa, preferably 500k-1200kDa, and more preferably 800k-1100kDa, for example, the molecular weight of the gamma-polyglutamic acid may be 500kDa, 600kDa, 700kDa, 800kDa, 900kDa, 1000kDa, 1100kDa, 1200kDa, 1300kDa, 1400kDa, 1500kDa or any range therebetween.
In a preferred embodiment of the present invention, wherein the mass ratio of the crosslinking agent to the γ -polyglutamic acid is 3 to 18, preferably 5 to 18, and more preferably 5 to 9, for example, the mass ratio of the crosslinking agent to the γ -polyglutamic acid may be 3.
In a preferred embodiment of the present invention, wherein the reaction temperature of the microwave reaction is 25-80 ℃, preferably 40-70 ℃; preferably, the reaction time of the microwave reaction is 0.5-4h, preferably 0.5-3h, and more preferably 1-3h, for example, the reaction temperature can be 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any range therebetween; the reaction time may be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, or any range therebetween.
The temperature of the microwave reaction means a temperature of the reaction system at the time of the crosslinking reaction, that is, a temperature required for the reaction system at the time of the crosslinking reaction.
Compared with the traditional preparation method, the preparation method reduces the dosage of the cross-linking agent, has higher reaction efficiency, obviously reduced reaction time, fewer reaction steps and short preparation period, and the obtained hydrogel has high water absorption and high swelling speed.
The invention provides a crosslinked polyglutamic acid hydrogel which is prepared by the preparation method.
The cross-linked polyglutamic acid hydrogel prepared by the method has high water absorption rate and high swelling speed.
The invention provides a crosslinked polyglutamic acid hydrogel which is prepared by a method comprising the following steps:
adding gamma-polyglutamic acid into the acidic solution to obtain a first solution;
mixing the first solution with a cross-linking agent to obtain a second solution;
and (3) placing the second solution in a microwave reactor for crosslinking reaction, and then dialyzing to obtain the crosslinked polyglutamic acid hydrogel.
Compared with the traditional preparation method, the method reduces the dosage of the cross-linking agent, has higher reaction efficiency, obviously reduced reaction time, fewer reaction steps and short preparation period, and the obtained hydrogel has high water absorption and high swelling speed.
The invention is described generally and/or specifically for the materials used in the tests and the test methods, in the following examples,% means wt%, i.e. percent by weight, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional reagent products commercially available, wherein Table 1 is a source of raw materials used in the examples.
Sources of raw materials used in the examples of Table 1
| Raw materials | Purity of | Manufacturer of the product |
| Gamma-polyglutamic acid | ≥90％ | BLOOMAGE BIOTECH Co.,Ltd. |
| 1,4 butanediol diglycidyl ether | ≥95％ | Is commercially available |
| 1,2,7,8-diepoxyoctane | ≥95％ | Is commercially available |
| Polyethylene glycol diglycidyl ether | ≥98％ | Is commercially available |
| Sodium trimetaphosphate | ≥95％ | Is commercially available |
Example 1
(1) Weighing 2g (calculated by pure product) of polyglutamic acid with the molecular weight of 500kDa, dissolving in 10g of purified water, adjusting the pH to 6.0, uniformly mixing, adding 0.36g of 1, 4-butanediol diglycidyl ether, and uniformly mixing.
(2) The reaction system was placed in a microwave reactor (model FC MCR-3S-T, manufacturer: kerui instruments Co., ltd., guyi) at a set temperature of 60 ℃ for 0.5h to form a hydrogel.
(3) And fully swelling and dialyzing the prepared hydrogel, and freeze-drying.
Example 2
(1) Weighing 2g (calculated by pure product) of polyglutamic acid with molecular weight of 1500kDa, dissolving in 8g of purified water, adjusting pH to 2.0, mixing uniformly, adding 0.06g of 1,2,7, 8-diepoxyoctane, and mixing uniformly.
(2) And placing the reaction system in a microwave reactor, setting the temperature to be 30 ℃, and reacting for 4 hours to form the hydrogel.
(3) And (3) fully swelling and dialyzing the prepared hydrogel, and freeze-drying.
Example 3
(1) Weighing 2g (calculated by pure product) of polyglutamic acid with the molecular weight of 1100kDa, dissolving in 10g of purified water, adjusting the pH to 4.0, uniformly mixing, adding 0.10g of 1, 4-butanediol diglycidyl ether, and uniformly mixing.
(2) And placing the reaction system in a microwave reactor, setting the temperature at 70 ℃, and reacting for 3 hours to form hydrogel.
(3) And fully swelling and dialyzing the prepared hydrogel, and freeze-drying.
Example 4
(1) Weighing 2g (calculated by pure product) of polyglutamic acid with the molecular weight of 1100kDa, dissolving the polyglutamic acid in 10g of purified water, adjusting the pH to 3.5, uniformly mixing, adding 0.12g of 1, 4-butanediol diglycidyl ether, and uniformly mixing.
(2) And placing the reaction system in a microwave reactor, setting the temperature to be 40 ℃, and reacting for 2 hours to form the hydrogel.
(3) And fully swelling and dialyzing the prepared hydrogel, and drying in vacuum.
Example 5
(1) Weighing 2g (calculated by pure product) of polyglutamic acid with the molecular weight of 800kDa, dissolving in 10g of purified water, adjusting the pH to 3, uniformly mixing, adding 0.18g of polyethylene glycol diglycidyl ether, and uniformly mixing.
(2) And placing the reaction system in a microwave reactor, setting the temperature at 50 ℃, and reacting for 1h to form the hydrogel.
(3) And fully swelling and dialyzing the prepared hydrogel, and drying in vacuum.
Example 6
(1) Weighing 2g (calculated by pure product) of polyglutamic acid with the molecular weight of 1200kDa, dissolving in 10g of purified water, adjusting the pH to 5, uniformly mixing, adding 0.3g of 1, 4-butanediol diglycidyl ether, and uniformly mixing.
(2) The reaction system is placed in a microwave reactor, the temperature is set to 65 ℃, and the reaction time is 0.5h to form hydrogel.
(3) And fully swelling and dialyzing the prepared hydrogel, and drying in vacuum.
Example 7
(1) Weighing 2g (calculated by pure product) of polyglutamic acid with the molecular weight of 1300kDa, dissolving in 10g of purified water, adjusting the pH value to 6.5, adding 0.08g of sodium trimetaphosphate after uniformly mixing, and uniformly mixing.
(2) And placing the reaction system in a microwave reactor, setting the temperature to be 25 ℃, and reacting for 4 hours to form the hydrogel.
(3) And fully swelling and dialyzing the prepared hydrogel, and drying in vacuum.
Example 8
(1) Weighing 2g (calculated by pure product) of polyglutamic acid with molecular weight of 1500kDa, dissolving in 10g of purified water, adjusting pH to 6, mixing uniformly, adding 0.06g of 1, 4-butanediol diglycidyl ether, and mixing uniformly.
(2) The reaction system is placed in a microwave reactor, the temperature is set to be 80 ℃, and the reaction time is 0.5h to form hydrogel.
(3) And fully swelling and dialyzing the prepared hydrogel, and drying in vacuum.
Example 9
A crosslinked polyglutamic acid hydrogel was prepared according to the method of example 4, except that 0.4g of 1, 4-butanediol diglycidyl ether was added and the reaction was incubated for 6 hours.
Example 10
A crosslinked polyglutamic acid hydrogel was prepared according to the method of example 4, except that the molecular weight of polyglutamic acid was 200 ten thousand.
Comparative example 1
A crosslinked polyglutamic acid hydrogel was prepared according to the method of example 4, except that the uniformly mixed reaction system was placed in a water bath environment at 40 ℃.
TABLE 2 quality of raw materials used in examples 1-10 and comparative example 1
Experimental example 1 measurement of maximum Water absorption Capacity and Water absorption Rate of Cross-Linked polyglutamic acid
A certain mass of the crosslinked polyglutamic acid obtained in examples 1-10 and comparative example 1 was weighed using an electronic balance, sealed in a microporous filter bag having a pore size of 0.45 μm, which allows water molecules to pass therethrough but does not allow the crosslinked polyglutamic acid to pass therethrough, and the filter bag was placed in distilled water, and weighed after sufficient water absorption, and the water absorption capacity and water absorption rate of the crosslinked polyglutamic acid were calculated, and the measurement results are shown in Table 3.
TABLE 3 comparison of maximum water absorption times and water absorption rates for samples
As can be seen from Table 3, the water absorption of the crosslinked polyglutamic acid hydrogel obtained in the examples was better, while the water absorption of the crosslinked polyglutamic acid hydrogel obtained in the comparative example was relatively poor, thus illustrating that the water absorption of the crosslinked polyglutamic acid hydrogel obtained by the microwave reaction was better compared to the conventional water bath heating.
Experimental example 2 measurement of Water absorption Capacity of Cross-Linked polyglutamic acid in soil
The humidity of the simulated soil was 20% under the dry soil condition, the crosslinked polyglutamic acid hydrogels obtained in examples 1 to 10 and comparative example 1 were placed in a microporous filter membrane bag, buried 3cm deep, and weighed after absorbing water for a certain period of time, and the water absorption times of crosslinked polyglutamic acid to soil moisture were calculated, respectively, and the measurement results are shown in table 4.
TABLE 4 Water absorption characteristics of the samples at 20% soil humidity
| Sample (I) | Sample weighing (g) | Time of Water absorption (h) | Absorbent weight (g) | Multiple of water absorption | Water absorption Rate (g/g. H) |
| Example 1 | 0.5009 | 24 | 98.2 | 196 | 8.2 |
| Example 2 | 0.5017 | 24 | 73.7 | 147 | 6.1 |
| Example 3 | 0.5032 | 24 | 137.4 | 273 | 11.4 |
| Example 4 | 0.5068 | 24 | 142.6 | 281 | 11.7 |
| Example 5 | 0.5020 | 24 | 133.5 | 266 | 11.1 |
| Example 6 | 0.5012 | 24 | 88.1 | 176 | 7.3 |
| Example 7 | 0.5023 | 24 | 60.9 | 121 | 5.1 |
| Example 8 | 0.5044 | 24 | 56.7 | 112 | 4.7 |
| Example 9 | 0.5082 | 24 | 39.8 | 78 | 3.3 |
| Example 10 | 0.5035 | 24 | 50.4 | 100 | 4.2 |
| Comparative example 1 | 0.5037 | 24 | 21.7 | 43 | 1.8 |
As can be seen from Table 4, the water absorption properties of the crosslinked polyglutamic acid hydrogels obtained in the examples are better, while the water absorption properties of the crosslinked polyglutamic acid hydrogels obtained in the comparative examples are poorer, which indicates that the crosslinked polyglutamic acid hydrogels obtained by crosslinking through the microwave reaction according to the present invention have better water absorption properties.
Experimental example 3 evaluation of skin feel by smearing
60 testers are selected to perform smearing skin feel test on the prepared hydrogel with the same concentration, the testers perform skin feel evaluation on the stickiness, the relative viscosity and the like of the sample after use, the skin feel is 10-0 points from good to bad, and the evaluation result is shown in table 5.
TABLE 5 skin feel evaluation results of the samples
| Sample (I) | Skin feel evaluation |
| Example 1 | 7.1 |
| Example 2 | 5.5 |
| Example 3 | 8.3 |
| Example 4 | 9.0 |
| Example 5 | 9.2 |
| Example 6 | 6.9 |
| Example 7 | 5.0 |
| Example 8 | 4.8 |
| Example 9 | 2.4 |
| Example 10 | 2.8 |
| Comparative example 1 | 1.1 |
As can be seen from Table 5, the skin feel evaluation of the crosslinked polyglutamic acid hydrogel prepared in the examples by the test personnel was superior, while the skin feel evaluation of the crosslinked polyglutamic acid hydrogel obtained in the comparative examples was inferior, which indicates that the skin feel of the crosslinked polyglutamic acid hydrogel prepared by the microwave reaction method of the present invention was superior.
In conclusion, the method can be used for preparing the cross-linked polyglutamic acid hydrogel with high water absorption rate and high water absorption rate. The method has the advantages of lower reaction energy consumption, simple and safe reaction, higher reaction efficiency, obviously reduced reaction time, fewer reaction steps, short preparation period and environmental friendliness compared with the traditional preparation method.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (13)
1. A preparation method of a crosslinked polyglutamic acid hydrogel comprises the following steps:
adding gamma-polyglutamic acid into an acidic solution to obtain a first solution;
mixing the first solution with a cross-linking agent to obtain a second solution;
placing the second solution in a microwave reactor for crosslinking reaction, and then dialyzing to obtain crosslinked polyglutamic acid hydrogel;
the molecular weight of the gamma-polyglutamic acid is 500k-1500kDa;
the mass ratio of the cross-linking agent to the gamma-polyglutamic acid is 3-18;
the reaction time of the microwave reaction is 0.5-4h.
2. The method of claim 1, wherein the first solution has a pH of 2 to 6.5.
3. The production method according to claim 1, wherein the pH of the first solution is 2 to 4.
4. The production method according to claim 1, wherein the crosslinking agent is one or more selected from diglycidyl ether, divinyl sulfone, 1,2,7,8-diepoxyoctane, 1,3-diepoxybutane, and sodium trimetaphosphate.
5. The method according to claim 1, wherein the gamma-polyglutamic acid has a molecular weight of 500k-1200kDa.
6. The method according to claim 1, wherein the gamma-polyglutamic acid has a molecular weight of 800k-1100kDa.
7. The production method according to claim 1, wherein the mass ratio of the crosslinking agent to the γ -polyglutamic acid is 5 to 18.
8. The production method according to claim 1, wherein the mass ratio of the crosslinking agent to the γ -polyglutamic acid is 5 to 9.
9. The production method according to any one of claims 1 to 8, wherein the reaction temperature of the microwave reaction is 25 to 80 ℃.
10. The production method according to any one of claims 1 to 8, wherein the reaction temperature of the microwave reaction is 40 to 70 ℃.
11. The production method according to any one of claims 1 to 8, wherein the reaction time of the microwave reaction is 0.5 to 3 hours.
12. The production method according to any one of claims 1 to 8, wherein the reaction time of the microwave reaction is 1 to 3 hours.
13. A crosslinked polyglutamic acid hydrogel prepared by the method of any one of claims 1 to 12.
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