CN111068098A - Preparation method of high-strength polyvinyl alcohol hydrogel film - Google Patents

Preparation method of high-strength polyvinyl alcohol hydrogel film Download PDF

Info

Publication number
CN111068098A
CN111068098A CN201911372157.6A CN201911372157A CN111068098A CN 111068098 A CN111068098 A CN 111068098A CN 201911372157 A CN201911372157 A CN 201911372157A CN 111068098 A CN111068098 A CN 111068098A
Authority
CN
China
Prior art keywords
polyvinyl alcohol
solution
hydrogel film
pva
gelatin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911372157.6A
Other languages
Chinese (zh)
Inventor
孙志洁
张志�
巩建乐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Engineering University
Original Assignee
Harbin Engineering University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Engineering University filed Critical Harbin Engineering University
Priority to CN201911372157.6A priority Critical patent/CN111068098A/en
Publication of CN111068098A publication Critical patent/CN111068098A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28Polysaccharides or their derivatives
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/32Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/46Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • C08F8/14Esterification
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2489/00Characterised by the use of proteins; Derivatives thereof

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Veterinary Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Hematology (AREA)
  • Epidemiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

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

Preparation method of high-strength polyvinyl alcohol hydrogel film
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)
Figure BDA0002339958070000071
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
Figure BDA0002339958070000072
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 ℃.
CN201911372157.6A 2019-12-27 2019-12-27 Preparation method of high-strength polyvinyl alcohol hydrogel film Pending CN111068098A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911372157.6A CN111068098A (en) 2019-12-27 2019-12-27 Preparation method of high-strength polyvinyl alcohol hydrogel film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911372157.6A CN111068098A (en) 2019-12-27 2019-12-27 Preparation method of high-strength polyvinyl alcohol hydrogel film

Publications (1)

Publication Number Publication Date
CN111068098A true CN111068098A (en) 2020-04-28

Family

ID=70318890

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911372157.6A Pending CN111068098A (en) 2019-12-27 2019-12-27 Preparation method of high-strength polyvinyl alcohol hydrogel film

Country Status (1)

Country Link
CN (1) CN111068098A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114149598A (en) * 2021-12-14 2022-03-08 重庆医科大学 Diabetes microenvironment responsive composite intelligent hydrogel and preparation method and application thereof
CN115895154A (en) * 2022-11-29 2023-04-04 无锡学院 Degradable high-barrier film and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102028966A (en) * 2010-12-29 2011-04-27 苏州方策科技发展有限公司 Manufacturing method of chitosan hemostatic membrane with high water-absorbing swelling performance
CN103480034A (en) * 2013-09-29 2014-01-01 金陵科技学院 Irradiation crosslinked chitosan/gelatin/polyvinyl alcohol hydrogel dressing as well as preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102028966A (en) * 2010-12-29 2011-04-27 苏州方策科技发展有限公司 Manufacturing method of chitosan hemostatic membrane with high water-absorbing swelling performance
CN103480034A (en) * 2013-09-29 2014-01-01 金陵科技学院 Irradiation crosslinked chitosan/gelatin/polyvinyl alcohol hydrogel dressing as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DI ZHANG ET AL: "carboxyl modified poly vinyl ahcohol crosslinked chitosan hydrogel films for potential wound dressing", 《CARBOHYDRATE POLYMERS》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN114149598A (en) * 2021-12-14 2022-03-08 重庆医科大学 Diabetes microenvironment responsive composite intelligent hydrogel and preparation method and application thereof
CN114149598B (en) * 2021-12-14 2024-05-07 重庆医科大学 Composite intelligent hydrogel with diabetes mellitus microenvironment responsiveness as well as preparation method and application thereof
CN115895154A (en) * 2022-11-29 2023-04-04 无锡学院 Degradable high-barrier film and preparation method thereof

Similar Documents

Publication Publication Date Title
CN111068098A (en) Preparation method of high-strength polyvinyl alcohol hydrogel film
Amirian et al. In-situ crosslinked hydrogel based on amidated pectin/oxidized chitosan as potential wound dressing for skin repairing
CN106492260B (en) Alginate-based hydrogel dressing and preparation method thereof
US6162864A (en) Polyvinyl alcohol
CN105194740A (en) Postoperation anti-adhesion hydrogel and preparing method thereof
AU2005221699A1 (en) Compositions of alpha and beta chitosan and methods of preparing them
KR101678402B1 (en) Alginate hydrogel for wound healing and manufacturing method of the same
Huang et al. A tannin-functionalized soy protein-based adhesive hydrogel as a wound dressing
CN103480034B (en) Irradiation crosslinked chitosan/gelatin/polyvinyl alcohol hydrogel dressing as well as preparation method and application thereof
CN112876694B (en) Preparation method and application of acrylic acid/epsilon-polylysine adhesive antibacterial hydrogel
CN111481735A (en) Medical antibacterial wound-protecting hydrogel dressing and preparation method thereof
Hu et al. Multifunctional hydrogel based on dopamine-modified hyaluronic acid, gelatin and silver nanoparticles for promoting abdominal wall defect repair
CN104548188A (en) Hyaluronic acid-nano silver-based dressing and preparation method thereof
CN116650710A (en) Mussel inspired multifunctional double-network crosslinked hydrogel wound dressing
CN113663120B (en) Hemostatic sponge cushion core and preparation method thereof
Zhang et al. Water-retaining and separable adhesive hydrogel dressing for wound healing without secondary damage
Latańska et al. The use of chitin and chitosan in manufacturing dressing materials
CN103301504A (en) Preparation method of gamma-polyglutamate/sericin hydrogel dressing
CN107177980B (en) Contact wound dressing and preparation method thereof
CN108452366B (en) Cod skin gelatin composite hemostatic dressing and preparation method thereof
JPH1072509A (en) New polyvinyl-alcohol-based polymer
CN114479124B (en) Self-healing hydrogel, preparation method and application thereof
CN110124096B (en) Lysozyme/hyaluronic acid composite gel and preparation method and application thereof
KR101576244B1 (en) aloin loaded wound dressing composition based on hydrogel and manufacturing method thereof
Cao et al. Mechanoactive wound dressing using poly (N-isopropyl acrylamide) based hydrogels

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200428