CN111068098A - Preparation method of high-strength polyvinyl alcohol hydrogel film - Google Patents
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Abstract
The invention provides a preparation method of a high-strength polyvinyl alcohol hydrogel film, which takes polyvinyl alcohol as a raw material, firstly performs polyvinyl alcohol carboxylation, adds gelatin and chitosan to achieve the purpose of synergy, constructs a physical and chemical crosslinking system of the polyvinyl alcohol, and prepares the high-strength multi-network crosslinking hydrogel film. Due to the addition of the gelatin and the chitosan, the polyvinyl alcohol hydrogel film has higher strength and elongation, and is endowed with unique antibacterial performance and biocompatibility. The polyvinyl alcohol hydrogel film obtained by the invention has higher tensile strength, excellent moisture retention performance and antibacterial performance in physiological environment, and can be used in medical dressing and other aspects.
Description
Technical Field
The invention relates to a preparation method of a polyvinyl alcohol hydrogel film, in particular to a preparation method of a high-strength polyvinyl alcohol hydrogel film, belonging to the field of biological materials, in particular to the field of high-molecular wound dressings.
Background
The polyvinyl alcohol (PVA) hydrogel is chemically inactive, non-toxic, good in biocompatibility, excellent in mechanical property, high in water absorption, easy to machine and form, and widely applied to various fields of agriculture and forestry, medicine, daily chemical industry, environmental protection, desert control and the like.
Tens of thousands of patients each year suffer from epidermal or skin damage resulting from various accidents, with certain limitations due to skin self-repair, accompanied by scar formation. Wound dressings play a vital role in the wound healing process, protecting the wound site from further damage by foreign microorganisms and pain, and promoting healing of the wound site. Thus, the use of wound dressings is an effective adjunct to promoting skin tissue repair or healing. Traditional type skin dressing mainly is cotton or cotton (like cotton bandage, gauze etc.), can absorb most wound exudate during the use, and the wound top layer becomes extremely dry, leads to the wound healing speed to descend, easily causes the secondary damage to the wound when removing. Therefore, the traditional skin dressing can not meet the requirements of people on the dressing. The high polymer material with the characteristics of good moisturizing performance, low toxicity, high efficiency, designability and the like meets the requirements of people on novel dressings. Currently, polymer materials used in the field of dressings can be classified into synthetic polymer materials and natural polymer materials. Wherein, the synthetic polymer materials mainly comprise polyvinyl alcohol, polyethylene glycol, polylactic acid, polyethylene oxide, polyurethane and the like; in addition, synthetic polymer materials generally have excellent mechanical properties. The natural polymer material includes collagen, chitosan, cellulose, sericin, gelatin, etc. Natural polymers have well-defined biomedical applications and properties, such as non-toxicity and biodegradability, but insufficient stability and mechanical properties.
In conclusion, the development of a hydrogel membrane with good bonding effect, high strength, good biocompatibility and inherent antibacterial property under physiological conditions has urgent needs in biomedical application fields such as tissue and wound healing, wound dressing, bone tissue repair and regeneration and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a polyvinyl alcohol hydrogel film with high strength and antibacterial performance under physiological conditions.
The purpose of the invention is realized as follows:
a preparation method of a high-strength polyvinyl alcohol hydrogel film comprises the following steps:
the method comprises the following steps: graft modification of polyvinyl alcohol; weighing polyvinyl alcohol, 4-dimethylaminopyridine and succinic anhydride, mixing and heating in water to carry out hydroxylation reaction, then precipitating and washing in cold acetone, and drying in a vacuum drying oven overnight to obtain white precipitated carboxylated polyvinyl alcohol PVA-COOH;
step two: preparing PVA-COOH/gelatin solution; weighing carboxylated polyvinyl alcohol, dissolving the carboxylated polyvinyl alcohol in water to form a PVA-COOH solution, adding gelatin, heating and stirring until the solution becomes a transparent PVA-COOH/gelatin solution;
step three: preparing a PVA-COOH/gelatin/chitosan hydrogel film; dissolving chitosan in an acetic acid aqueous solution to obtain a chitosan solution; stirring and mixing the PVA-COOH/gelatin solution and the chitosan solution, weighing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, adding into the mixed solution, stirring, pouring the mixture on a polytetrafluoroethylene plate, standing overnight in a refrigerator, and drying in a vacuum oven for 24 hours to form a film, thus obtaining the high-strength polyvinyl alcohol hydrogel film.
The invention also includes such features:
in the first step, the raw material molar ratio is as follows: 4-dimethylaminopyridine: succinic anhydride 10: 1:10, the mass ratio of the polyvinyl alcohol to the water is 1: 100;
in the second step, the mass ratio of the raw materials is as follows: water 1: 25, carboxylated polyvinyl alcohol: gelatin: chitosan ═ 1: 0.3-0.7: 0.3-0.7; carboxylated polyvinyl alcohol: (gelatin + chitosan) ═ 1: 1;
the molar ratio of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to the N-hydroxysuccinimide in the third step is 1: 1;
the mass fraction of acetic acid in the chitosan solution in the third step is 1 percent;
in the first step, the temperature for dissolving the polyvinyl alcohol in water is 90 ℃, and the temperature for the carboxylation reaction is 75 ℃;
the temperature of the refrigerator in the third step is 4 ℃, and the drying temperature in the drying oven is 30 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the polyvinyl alcohol hydrogel film is simple, and the technological parameters are easy to control.
(2) The polyvinyl alcohol hydrogel film of the invention has stronger bonding performance as a human body auxiliary material.
(3) The raw materials used by the polyvinyl alcohol hydrogel film and the preparation process thereof are nontoxic and harmless, have no stimulation to human bodies, have good applicability in human body environment and have excellent biocompatibility.
(4) The polyvinyl alcohol hydrogel film has higher strength, and can meet the strength requirement as a wound auxiliary material.
(5) The polyvinyl alcohol hydrogel film is weakly acidic, has no irritation to skin, and can effectively inhibit bacterial growth.
(6) The strength and the elongation of the polyvinyl alcohol hydrogel film can be adjusted according to the composition ratio of the gelatin and the chitosan so as to meet the actual application requirements.
Drawings
FIG. 1 is an infrared spectrum of a hydrogel film of single components and varying proportions;
figure 2 is a tensile curve for hydrogel films of different proportions.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A high-strength polyvinyl alcohol hydrogel film is prepared by the following steps: graft modification of polyvinyl alcohol; preparing PVA-COOH/gelatin solution; preparing a chitosan solution; preparing PVA-COOH/gelatin/chitosan hydrogel film. The modification method of the polyvinyl alcohol comprises the following steps: weighing polyvinyl alcohol, DMAP and succinic anhydride according to a certain proportion, mixing and dissolving in water, heating for reacting for a period of time, precipitating in cold acetone, washing, and drying in a vacuum drying oven overnight to obtain carboxylated polyvinyl alcohol. The preparation method comprises the following steps: the carboxylated polyvinyl alcohol and the gelatin are weighed according to the proportion and are sequentially dissolved in water. The preparation method comprises the following steps: weighing a certain amount of chitosan, dissolving in acetic acid, and stirring overnight to obtain a chitosan solution. The preparation method of the hydrogel film comprises the following steps: weighing EDC and NHS according to a certain proportion, adding into the gelatin and chitosan mixed solution, reacting for a period of time, pouring the mixture on a polytetrafluoroethylene plate, placing in a refrigerator for a period of time, and then drying in a vacuum drying oven to form a film. The temperature for dissolving the polyvinyl alcohol in water is 90 ℃, the temperature for the carboxylation reaction is 75 ℃, the temperature for placing in a refrigerator is 4 ℃, and the drying temperature in a drying box is 30 ℃. Gelatin and chitosan: the mass ratio of the added amount is respectively 3: 7-7: 3, the adding ratio can be adjusted to meet different requirements. DMAP and succinic anhydride are added in a molar ratio of 1: 10. the mass fraction of acetic acid was 1%. The mass ratio of the addition amount of the carboxylated polyvinyl alcohol to the addition amount of the (gelatin + chitosan) is 1: 1. the molar ratio of EDC and NHS addition was 1: 1.
(1) the preparation of the high-strength polyvinyl alcohol hydrogel film comprises the carboxylation of polyvinyl alcohol, the preparation of PVA-COOH/gelatin solution and the preparation of PVA-COOH/gelatin/chitosan hydrogel film.
(2) The raw materials for the carboxylation of the polyvinyl alcohol are polyvinyl alcohol, 4-dimethylamino pyridine (DMAP) and succinic anhydride; the raw material molar ratio is, polyvinyl alcohol: DMAP: succinic anhydride 10: 1: 10; in addition, the mass ratio of polyvinyl alcohol to water was 1: 100.
(3) The PVA-COOH/gelatin solution is prepared from carboxylated polyvinyl alcohol, gelatin and chitosan; the mass ratio of the raw materials is, carboxylated polyvinyl alcohol: water 1: 25, carboxylated polyvinyl alcohol: gelatin: chitosan ═ 1: 0.3-0.7: 0.3-0.7; in addition, it is ensured that the carboxylated polyvinyl alcohol: (gelatin + chitosan) ═ 1: 1.
(4) the raw materials for preparing the PVA-COOH/gelatin/chitosan hydrogel are 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS); the raw material molar ratio is EDC: NHS ═ 1: 1.
(5) the specific preparation steps of the high-strength polyvinyl alcohol hydrogel film are as follows:
A. carboxylation of polyvinyl alcohol: weighing a certain mass of polyvinyl alcohol, dissolving in 100 parts of water, and heating to 90 ℃ under continuous stirring. After the polyvinyl alcohol was dissolved, the temperature of the solution was cooled to 75C. In a molar ratio of 1:10 DMAP and succinic anhydride are weighed and added into the polyvinyl alcohol solution, and the mixture is stirred at the constant speed of 400rpm/min for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature and added dropwise to the frozen acetone solution with stirring, resulting in a white precipitate. The white precipitate (PVA-COOH) was collected, washed three times with acetone to remove unreacted starting materials, and the precipitate was dried overnight in a vacuum oven at room temperature and stored for further use.
B. Preparation of PVA-COOH/gelatin solution: a certain mass of PVA-COOH powder is weighed and dissolved in 25 parts of water, and the mixture is continuously stirred for 1 hour at 90 ℃ to form a PVA-COOH solution. Mixing the raw materials in a ratio of 1:1, weighing carboxylated polyvinyl alcohol, (gelatin + chitosan) and preparing PVA-COOH/gelatin solution.
C. EDC and NHS were added to the mixed solution at a molar ratio of 1:1, stirred for 15 minutes, and then the mixture was poured onto a Teflon plate and left overnight in a refrigerator at 4 ℃ and then dried in a vacuum oven at 30 ℃ for 24 hours to prepare a hydrogel film.
Example 1
A. Graft modification of polyvinyl alcohol
5g of PVA powder and 500mL of deionized water were added to a 500mL three-necked flask and heated to 90C with constant stirring. After the polyvinyl alcohol had dissolved, the temperature of the solution was cooled to 75C, 1.385g DMAP was added and stirred for 1 h. Under the condition of 75C, 11.36g succinic anhydride is added into the polyvinyl alcohol blending solution, and the mixture is stirred at the constant speed of 400rpm/min for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature and added dropwise to the frozen acetone solution with stirring, resulting in a white precipitate. The white precipitate (PVA-COOH) was collected, washed three times with acetone to remove unreacted starting materials, and the precipitate was dried overnight in a vacuum oven at room temperature and stored for further use.
B. Preparation of PVA-COOH/gelatin solution
2.00g of PVA-COOH powder was placed in a three-necked flask, and 50mL of deionized water was added as a solvent, and stirred continuously at 90 ℃ for 1 hour to form a PVA-COOH solution. Then the PVA-COOH solution is cooled to room temperature, 0.6g of gelatin is added respectively, and the mixture is heated and stirred at 40 ℃ until the solution becomes transparent liquid, which is named as solution A for standby.
C. Preparation of PVA-COOH/gelatin/chitosan hydrogel film
1.4g of chitosan powder was added to 1% (w/v) acetic acid aqueous solution, and stirred continuously overnight at room temperature until chitosan was completely dissolved, which was named solution B. The A and B solutions were added to a 200ml three-port flask and mixed well. 1.2g of EDC and 0.7g of NHS were added to the mixed solution. After stirring for 15 minutes, the mixture was poured onto a teflon plate and placed in a refrigerator at 4 ℃ overnight, then dried in a vacuum oven at 30 ℃ for 24h to produce a hydrogel film, sample designated G30C 70.
Example 2
A. Graft modification of polyvinyl alcohol
5g of PVA powder and 500mL of deionized water were added to a 500mL three-necked flask and heated to 90C with constant stirring. After the polyvinyl alcohol had dissolved, the temperature of the solution was cooled to 75C, 1.385g DMAP was added and stirred for 1 h. Under the condition of 75C, 11.36g succinic anhydride is added into the polyvinyl alcohol blending solution, and the mixture is stirred at the constant speed of 400rpm/min for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature and added dropwise to the frozen acetone solution with stirring, resulting in a white precipitate. The white precipitate (PVA-COOH) was collected, washed three times with acetone to remove unreacted starting materials, and the precipitate was dried overnight in a vacuum oven at room temperature and stored for further use.
B. Preparation of PVA-COOH/gelatin solution
2.00g of PVA-COOH powder was placed in a three-necked flask, and 50mL of deionized water was added as a solvent, and stirred continuously at 90 ℃ for 1 hour to form a PVA-COOH solution. Then the PVA-COOH solution is cooled to room temperature, 0.8g of gelatin is added respectively, and the mixture is heated and stirred at 40 ℃ until the solution becomes transparent liquid, which is named as solution A for standby.
C. Preparation of PVA-COOH/gelatin/chitosan hydrogel film
1.2g of chitosan powder was added to 1% (w/v) acetic acid aqueous solution, and stirred continuously overnight at room temperature until chitosan was completely dissolved, which was named solution B. The A and B solutions were added to a 200ml three-port flask and mixed well. 1.2g of EDC and 0.7g of NHS were added to the mixed solution. After stirring for 15 minutes, the mixture was poured onto a teflon plate and placed in a refrigerator at 4 ℃ overnight, then dried in a vacuum oven at 30 ℃ for 24h to produce a hydrogel film, sample designated G40C 60.
Example 3
A. Graft modification of polyvinyl alcohol
5g of PVA powder and 500mL of deionized water were added to a 500mL three-necked flask and heated to 90C with constant stirring. After the polyvinyl alcohol had dissolved, the temperature of the solution was cooled to 75C, 1.385g DMAP was added and stirred for 1 h. Under the condition of 75C, 11.36g succinic anhydride is added into the polyvinyl alcohol blending solution, and the mixture is stirred at the constant speed of 400rpm/min for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature and added dropwise to the frozen acetone solution with stirring, resulting in a white precipitate. The white precipitate (PVA-COOH) was collected, washed three times with acetone to remove unreacted starting materials, and the precipitate was dried overnight in a vacuum oven at room temperature and stored for further use.
B. Preparation of PVA-COOH/gelatin solution
2.00g of PVA-COOH powder was placed in a three-necked flask, and 50mL of deionized water was added as a solvent, and stirred continuously at 90 ℃ for 1 hour to form a PVA-COOH solution. Then the PVA-COOH solution is cooled to room temperature, 1.0g of gelatin is added respectively, and the mixture is heated and stirred at 40 ℃ until the solution becomes transparent liquid, which is named as solution A for standby.
C. Preparation of PVA-COOH/gelatin/chitosan hydrogel film
1.0g of chitosan powder was added to 1% (w/v) acetic acid aqueous solution, and stirred continuously overnight at room temperature until chitosan was completely dissolved, which was named solution B. The A and B solutions were added to a 200ml three-port flask and mixed well. 1.2g of EDC and 0.7g of NHS were added to the mixed solution. After stirring for 15 minutes, the mixture was poured onto a teflon plate and placed in a refrigerator at 4 ℃ overnight, then dried in a vacuum oven at 30 ℃ for 24h to produce a hydrogel film, sample designated G50C 50.
Example 4
A. Graft modification of polyvinyl alcohol
5g of PVA powder and 500mL of deionized water were added to a 500mL three-necked flask and heated to 90C with constant stirring. After the polyvinyl alcohol had dissolved, the temperature of the solution was cooled to 75 ℃, 1.385g of DMAP was added and stirred for 1 h. 11.36g of succinic anhydride was added to the above polyvinyl alcohol blend solution at 75 ℃ and stirred at 400rpm/min for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature and added dropwise to the frozen acetone solution with stirring, resulting in a white precipitate. The white precipitate (PVA-COOH) was collected, washed three times with acetone to remove unreacted starting materials, and the precipitate was dried overnight in a vacuum oven at room temperature and stored for further use.
B. Preparation of PVA-COOH/gelatin solution
2.00g of PVA-COOH powder was placed in a three-necked flask, and 50mL of deionized water was added as a solvent, and stirred continuously at 90 ℃ for 1 hour to form a PVA-COOH solution. Then the PVA-COOH solution is cooled to room temperature, 1.2g of gelatin is added respectively, and the mixture is heated and stirred at 40 ℃ until the solution becomes transparent liquid, which is named as solution A for standby.
C. Preparation of PVA-COOH/gelatin/chitosan hydrogel film
0.8g of chitosan powder was added to 1% (w/v) acetic acid aqueous solution, and stirred continuously overnight at room temperature until chitosan was completely dissolved, which was named solution B. The A and B solutions were added to a 200ml three-port flask and mixed well. 1.2g of EDC and 0.7g of NHS were added to the mixed solution. After stirring for 15 minutes, the mixture was poured onto a teflon plate and placed in a refrigerator at 4 ℃ overnight, then dried in a vacuum oven at 30 ℃ for 24h to produce a hydrogel film, sample designated G60C 40.
Example 5
A. Graft modification of polyvinyl alcohol
5g of PVA powder and 500mL of deionized water were added to a 500mL three-necked flask and heated to 90C with constant stirring. After the polyvinyl alcohol had dissolved, the temperature of the solution was cooled to 75C, 1.385g DMAP was added and stirred for 1 h. Under the condition of 75C, 11.36g succinic anhydride is added into the polyvinyl alcohol blending solution, and the mixture is stirred at the constant speed of 400rpm/min for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature and added dropwise to the frozen acetone solution with stirring, resulting in a white precipitate. The white precipitate (PVA-COOH) was collected, washed three times with acetone to remove unreacted starting materials, and the precipitate was dried overnight in a vacuum oven at room temperature and stored for further use.
B. Preparation of PVA-COOH/gelatin solution
2.00g of PVA-COOH powder was placed in a three-necked flask, and 50mL of deionized water was added as a solvent, and stirred continuously at 90 ℃ for 1 hour to form a PVA-COOH solution. Then the PVA-COOH solution is cooled to room temperature, 1.4g of gelatin is added respectively, and the mixture is heated and stirred at 40 ℃ until the solution becomes transparent liquid, which is named as solution A for standby.
C. Preparation of PVA-COOH/gelatin/chitosan hydrogel film
0.6g of chitosan powder was added to 1% (w/v) acetic acid aqueous solution, and stirred continuously overnight at room temperature until chitosan was completely dissolved, which was named solution B. The A and B solutions were added to a 200ml three-port flask and mixed well. 1.2g of EDC and 0.7g of NHS were added to the mixed solution. After stirring for 15 minutes, the mixture was poured onto a teflon plate and placed in a refrigerator at 4 ℃ overnight, then dried in a vacuum oven at 30 ℃ for 24h to produce a hydrogel film, sample designated G70C 30.
The polyvinyl alcohol hydrogel films obtained in examples 1 to 5 and the comparative products were subjected to performance tests, the specific test methods were as follows:
infrared spectrum test: PVA, PVA-COOH, gelatin, sericin, chitosan and hydrogel films of various proportions were subjected to structural analysis using a Spectrum100 Fourier transform infrared spectrometer from Perkin Elmer, USA. The tested wavelength range is 450-4000 cm-1The number of scanning times is 4, and the resolution is 4cm-1。
And (3) testing tensile property: the hydrogel film samples were tested for tensile strength and elongation at break using a model 3365 universal materials testing machine from Instron, USA. The samples were cut to a size of 20X 10mm and the tensile strength of the samples was tested with a tensile program of 10mm/min set up in a universal material testing machine. The tensile strength of the sample was calculated according to formula (1) and the elongation at break of the sample was calculated according to formula (2).
TS=F/A (1)
Where TS represents tensile strength, E represents elongation at break, F represents maximum stress at break, a represents cross-sectional area of the sample, L represents length of the sample after break, and LS represents initial length of the sample.
Material | C30G70 | C40G60 | C50G50 | C60G40 | C70G30 |
pH value | 6.15 | 6.25 | 6.2 | 6.27 | 6.25 |
TABLE 1 PH of hydrogel films
TABLE 2 mechanical Properties of hydrogel films
In summary, the following steps: the invention provides a preparation method and application of a polyvinyl alcohol physical and chemical crosslinking hydrogel film, belonging to the field of biomedical materials. The invention takes polyvinyl alcohol as raw material, firstly carries out polyvinyl alcohol carboxylation, adds gelatin and chitosan to achieve the purpose of synergy, constructs a physical and chemical crosslinking system of the polyvinyl alcohol and prepares the high-strength multi-network crosslinking hydrogel film. Due to the addition of the gelatin and the chitosan, the polyvinyl alcohol hydrogel film has higher strength and elongation, and is endowed with unique antibacterial performance and biocompatibility. The polyvinyl alcohol hydrogel film obtained by the invention has higher tensile strength, excellent moisture retention performance and antibacterial performance in physiological environment, and can be used in medical dressing and other aspects.
Claims (7)
1. A preparation method of a high-strength polyvinyl alcohol hydrogel film is characterized by comprising the following steps:
the method comprises the following steps: graft modification of polyvinyl alcohol; weighing polyvinyl alcohol, 4-dimethylaminopyridine and succinic anhydride, mixing and heating in water to carry out hydroxylation reaction, then precipitating and washing in cold acetone, and drying in a vacuum drying oven overnight to obtain white precipitated carboxylated polyvinyl alcohol PVA-COOH;
step two: preparing PVA-COOH/gelatin solution; weighing carboxylated polyvinyl alcohol, dissolving the carboxylated polyvinyl alcohol in water to form a PVA-COOH solution, adding gelatin, heating and stirring until the solution becomes a transparent PVA-COOH/gelatin solution;
step three: preparing a PVA-COOH/gelatin/chitosan hydrogel film; dissolving chitosan in an acetic acid aqueous solution to obtain a chitosan solution; stirring and mixing the PVA-COOH/gelatin solution and the chitosan solution, weighing 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, adding into the mixed solution, stirring, pouring the mixture on a polytetrafluoroethylene plate, standing overnight in a refrigerator, and drying in a vacuum oven for 24 hours to form a film, thus obtaining the high-strength polyvinyl alcohol hydrogel film.
2. The method for preparing a high strength polyvinyl alcohol hydrogel film according to claim 1, wherein in the first step, the molar ratio of the raw materials is, polyvinyl alcohol: 4-dimethylaminopyridine: succinic anhydride 10: 1:10, the mass ratio of the polyvinyl alcohol to the water is 1: 100.
3. The method for preparing a high-strength polyvinyl alcohol hydrogel film according to claim 1, wherein the mass ratio of the raw materials in the second step is, carboxylated polyvinyl alcohol: water 1: 25, carboxylated polyvinyl alcohol: gelatin: chitosan ═ 1: 0.3-0.7: 0.3-0.7; carboxylated polyvinyl alcohol: (gelatin + chitosan) ═ 1: 1.
4. the method for preparing a high strength polyvinyl alcohol hydrogel film according to claim 1, wherein the molar ratio of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride to N-hydroxysuccinimide in the third step is 1: 1.
5. the method for preparing a high-strength polyvinyl alcohol hydrogel film according to claim 1, wherein the mass fraction of acetic acid in the chitosan solution in step three is 1%.
6. The method for preparing a high-strength polyvinyl alcohol hydrogel film according to claim 1, wherein the temperature of the polyvinyl alcohol dissolved in water in the first step is 90 ℃ and the temperature of the carboxylation reaction is 75 ℃.
7. The method for preparing a high strength polyvinyl alcohol hydrogel film according to claim 1, wherein the temperature of the refrigerator in the third step is 4 ℃ and the drying temperature in the drying oven is 30 ℃.
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CN112358635A (en) * | 2020-11-10 | 2021-02-12 | 中国科学院长春应用化学研究所 | Polyvinyl alcohol-based hydrogel film and preparation method thereof |
CN113004730A (en) * | 2021-02-26 | 2021-06-22 | 天津大学 | Trehalose modified polyvinyl alcohol anti-fog and anti-frost coating and preparation method thereof |
CN113045793A (en) * | 2021-04-02 | 2021-06-29 | 宁波因天之序生物科技有限公司 | Medical hemostatic sponge material and preparation method thereof |
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CN112358635B (en) * | 2020-11-10 | 2021-12-14 | 中国科学院长春应用化学研究所 | Polyvinyl alcohol-based hydrogel film and preparation method thereof |
CN113004730A (en) * | 2021-02-26 | 2021-06-22 | 天津大学 | Trehalose modified polyvinyl alcohol anti-fog and anti-frost coating and preparation method thereof |
CN113004730B (en) * | 2021-02-26 | 2022-03-25 | 天津大学 | Trehalose modified polyvinyl alcohol anti-fog and anti-frost coating and preparation method thereof |
CN113045793A (en) * | 2021-04-02 | 2021-06-29 | 宁波因天之序生物科技有限公司 | Medical hemostatic sponge material and preparation method thereof |
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