阅读说明：本技术 一种糖类复合聚丙烯酰胺水凝胶及制备方法和应用 (Carbohydrate composite polyacrylamide hydrogel and preparation method and application thereof ) 是由 张利东 谭慧燕 于 2019-09-06 设计创作，主要内容包括：本发明公开了一种糖类复合聚丙烯酰胺水凝胶及制备方法和应用,制备包括如下步骤：丙烯酰胺水溶液中加入一定量的多糖、引发剂及交联剂,搅拌溶解后,转移至玻璃模具中,利用紫外光引发聚合制备多糖复合聚丙烯酰胺水凝胶。该水凝胶具有高弹性：拉伸到原长的20倍后,释放拉力,仍能快速回复；具有强韧性：针刺至95%的形变不会产生破坏痕迹,撕裂测试中,凝胶边缘1 mm的切口在往复拉伸10000次后仍保持不变；具有耐冻性：零下20度条件下仍能保持高的柔韧性；具有粘附性：常温下凝胶与橡胶表面的粘附强度至少达1000 N/m,与人体皮肤的粘附强度至少达500 N/m。基于这些优越的性能,该凝胶在医药贴,耐冻面膜等方面具有广泛的应用前景。(The invention discloses a saccharide composite polyacrylamide hydrogel and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding a certain amount of polysaccharide, an initiator and a cross-linking agent into the acrylamide aqueous solution, stirring and dissolving, transferring into a glass mold, and preparing the polysaccharide composite polyacrylamide hydrogel by ultraviolet light initiated polymerization. The hydrogel has high elasticity: after the stretching force is 20 times of the original length, the stretching force is released, and the rapid recovery can still be realized; has strong toughness: the deformation caused by needling to 95% does not generate damage traces, and in a tearing test, a cut with the edge of 1 mm of the gel still remains unchanged after being stretched for 10000 times in a reciprocating manner; has the freezing resistance: high flexibility can be still maintained under the condition of 20 ℃ below zero; has the following characteristics: the adhesive strength between the gel and the rubber surface at normal temperature is at least 1000N/m, and the adhesive strength between the gel and the human skin is at least 500N/m. Based on the superior performances, the gel has wide application prospects in the aspects of medical patches, freeze-resistant masks and the like.)

1. The preparation method of the carbohydrate composite polyacrylamide hydrogel is characterized by comprising the following specific steps of:

step 1: weighing acrylamide particles, dissolving the acrylamide particles in deionized water under magnetic stirring to prepare a colorless and transparent acrylamide aqueous solution; wherein, the solution concentration is: the concentration is 0.05-2.00 g/mL;

step 2, adding polysaccharide into an acrylamide aqueous solution, and continuing to stir by magnetic force to obtain a colorless transparent solution, wherein the mass ratio of the acrylamide to the polysaccharide is 100 ~ 1:1 ~ 3;

step 3, weighing an initiator and a cross-linking agent, and adding the initiator and the cross-linking agent into the solution prepared in the step 2, wherein the mass ratio of acrylamide to the cross-linking agent is 2000 ~ 200:1, and the mass ratio of acrylamide to the initiator is 200 ~ 20: 1;

and 4, step 4: taking two cleaned glass slides, cutting a silica gel sheet with the thickness of 0.2-5.0 mm into the size of the glass slide, and covering one of the glass slides; cutting off the middle part of the silica gel sheet, leaving a blank area, covering another clean glass slide on the silica gel sheet to form a glass slide/silica gel sheet/glass slide sandwich structure device with aligned edges; extracting air in the sandwich structure device by using an injector, and injecting inert gas; wherein the inert gas is nitrogen or argon;

and 5: injecting the solution prepared in step 3 into the sandwich structure device prepared in step 4, and irradiating under ultraviolet lamp at 25 deg.C for 20-120 min with light intensity of 20-100 mW/cm²And the wavelength of the light is 300-440 nm, or the sandwich structure device is transferred to a heating table at 60-90 ℃, the sandwich structure device is opened after heating for 0.5-2 h, and the colorless and transparent hydrogel formed by crosslinking the solution in the blank area is the carbohydrate composite polyacrylamide hydrogel.

2. The method according to claim 1, wherein the polysaccharide in step 2 is trehalose, agarose, dextran, mannose, erythrose, threose, arabinose, xylose, lyxose, galactan.

3. The method according to claim 1, wherein the crosslinking agent in step 3 is N, N' -methylenebisacrylamide, polyethylene glycol diacrylate or diethyl [ 2-methacryloxy ] phosphate; the initiator is ammonium persulfate, potassium persulfate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone or alpha-ketoglutaric acid.

4. A saccharide-based polyacrylamide hydrogel produced by the method of claim 1.

5. The carbohydrate-containing polyacrylamide hydrogel according to claim 4, wherein the hydrogel is stretched to 20 times its original length, and then releases the tensile force, and the deformation recovery time is 0.001-0.5 min; the deformation caused by needling to 95% does not generate damage traces; in a tearing test, an incision with the edge of 1 mm of the hydrogel still keeps the original shape after being stretched for 10000 times in a reciprocating manner and cannot be extended; the flexibility can be kept under the condition of-20 ℃; the adhesive strength of the hydrogel and the rubber surface at normal temperature is at least 1000N/m, and the adhesive strength of the hydrogel and the human skin is at least 500N/m.

6. The use of the saccharide-compounded polyacrylamide hydrogel according to claim 4 in medical patches and freeze-resistant masks.

Technical Field

The invention belongs to the field of composite material preparation, and particularly relates to a saccharide composite polyacrylamide hydrogel, and a preparation method and application thereof.

Background

The hydrogel has a three-dimensional cross-linked network structure, can absorb water, is insoluble in water, and is widely applied to aspects such as biomedical dressings, tissue engineering, drug delivery and release, sensors, micro devices and the like. With the complication of application, the requirements on hydrogel properties are higher and higher, the hydrogel is required to be capable of adapting to a wide temperature range, the hydrogel material is required to have strong toughness and can resist damage caused by external force, and the hydrogel material is required to be repeatedly used for many times and still maintain excellent mechanical properties. As a medical material, hydrogel is required to have good water retention and excellent adhesion.

Disclosure of Invention

The invention aims to provide a method for combining physics and chemistry aiming at the defects of the prior art, which comprises the following steps: namely, in a polysaccharide system, acrylamide polymerization is initiated by ultraviolet light to prepare the polysaccharide compounded polyacrylamide dual-network hydrogel and the application of the hydrogel in medical patches and freeze-resistant masks.

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

a preparation method of a saccharide composite polyacrylamide hydrogel comprises the following specific steps:

step 1: weighing acrylamide particles, dissolving the acrylamide particles in deionized water under magnetic stirring to prepare a colorless and transparent acrylamide aqueous solution; wherein, the solution concentration is: the concentration is 0.05-2.00 g/mL;

step 2, adding polysaccharide into an acrylamide aqueous solution, and continuing to stir by magnetic force to obtain a colorless transparent solution, wherein the mass ratio of the acrylamide to the polysaccharide is 100 ~ 1:1 ~ 3;

step 3, weighing an initiator and a cross-linking agent, and adding the initiator and the cross-linking agent into the solution prepared in the step 2, wherein the mass ratio of acrylamide to the cross-linking agent is 2000 ~ 200:1, and the mass ratio of acrylamide to the initiator is 200 ~ 20: 1;

and 4, step 4: taking two cleaned glass slides, cutting a silica gel sheet with the thickness of 0.2-5.0 mm into the size of the glass slide, and covering one of the glass slides; cutting off the middle part of the silica gel sheet, leaving a blank area, covering another clean glass slide on the silica gel sheet to form a glass slide/silica gel sheet/glass slide sandwich structure device with aligned edges; extracting air in the sandwich structure device by using an injector, and injecting inert gas; wherein the inert gas is nitrogen or argon;

and 5: injecting the solution prepared in step 3 into the sandwich structure device prepared in step 4, and irradiating under ultraviolet lamp at 25 deg.C for 20-120 min with light intensity of 20-100 mW/cm²The optical wavelength is 300-440 nm, or the sandwich structure device is transferred to a heating table at 60-90 ℃, after heating for 0.5-2 h, the sandwich structure device is opened, and the colorless and transparent hydrogel formed by crosslinking the solution in the blank area is the carbohydrate composite polyacrylamide hydrogel;

the polysaccharide in the step 2 is trehalose, agarose, glucan, mannose, erythrose, threose, arabinose, xylose, lyxose and galactan.

The cross-linking agent in the step 3 is N, N' -methylene bisacrylamide, polyethylene glycol diacrylate or [ 2-methacryloxy ] diethyl phosphate; the initiator is ammonium persulfate, potassium persulfate, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone or alpha-ketoglutaric acid.

A carbohydrate composite polyacrylamide hydrogel prepared by the method.

After the hydrogel is stretched to 20 times of the original length, the tensile force is released, and the deformation recovery time is 0.001-0.5 min; the deformation caused by needling to 95% does not generate damage traces; in a tearing test, an incision with the edge of 1 mm of the hydrogel still keeps the original shape after being stretched for 10000 times in a reciprocating manner and cannot be extended; the flexibility can be kept under the condition of-20 ℃; the adhesive strength of the hydrogel and the rubber surface at normal temperature is at least 1000N/m, and the adhesive strength of the hydrogel and the human skin is at least 500N/m.

An application of the saccharide composite polyacrylamide hydrogel in a medical patch and a freeze-resistant mask.

The invention has the advantages of

In order to prepare hydrogel with excellent properties and meet application requirements, the invention introduces edible natural nontoxic cheap and easily available polysaccharide material into a polyacrylamide reaction system to prepare hydrogel with high elasticity, toughness, freezing resistance and adhesiveness.

The composite polyacrylamide hydrogel is non-toxic, so that the hydrogel can be applied to the biomedical field related to human bodies, and the transparency of the hydrogel makes it possible to monitor the growth condition of wound surfaces in real time when the hydrogel is used as a medical patch. The composite hydrogel has high elasticity, can be stretched to 20 times of the original length and completely restored to the original state in 0.5 min, and can be stretched to 45 times of the original length at most. The hydrogel was tough, able to resist deformation by 95% compression without breaking, and was able to return to its original shape within 0.5 min when the external force was removed. The same conclusions are also presented in the notch shear test and the needle/knife puncture test during stretching. The hydrogel has good biaxial stretchability and no major-minor axis difference, can be randomly stretched along the biaxial direction, combines the hydrogel with the surface of rubber or human skin, and has the binding force of 1000N/m (rubber) and 500N/m (skin) through experimental detection, so that the polysaccharide composite hydrogel can be applied to the fields of medical patches and facial masks. And the good transparency and stretchability are still maintained at the temperature of-20 ℃, which shows that the freezing point of a hydrogel system is lowered due to the addition of the polysaccharide, and meanwhile, DMA tests also show that the composite polysaccharide hydrogel has stable mechanical properties at the temperature of-20-80 ℃, so that the temperature use range of the polysaccharide composite hydrogel is wider than that of the common acrylamide hydrogel. All results show that the polysaccharide is introduced into the acrylamide hydrogel, so that the property of the hydrogel is enhanced, and the application range of the hydrogel is greatly enriched.

Drawings

FIG. 1 test chart of hydrogel tensile test;

FIG. 2 is a graph of a hydrogel tensile test at low temperature;

FIG. 3 is an experimental diagram of polysaccharide composite hydrogel pressed by fine needles;

FIG. 4 is a graph of an experiment on adhesion of a polysaccharide composite hydrogel to a rubber surface;

FIG. 5 is a schematic view of a polysaccharide complex hydrogel applied to the back surface of an injured hand as a medicine.

Detailed Description

The present invention will be described in further detail with reference to the following examples, which are intended to provide those skilled in the art with a more complete, concise and complete understanding of the principles and spirit of the invention.

The acrylamide, polysaccharide, initiator and cross-linking agent used in the invention are all commercially available.

The polysaccharide used in the invention is: any one of trehalose, agarose, dextran, mannose, erythrose, threose, arabinose, xylose, lyxose, galactan, and the like, preferably, the polysaccharide is soluble in deionized water at room temperature.

The cross-linking agent used in the invention is any one of N, N' -methylene bisacrylamide, polyethylene glycol diacrylate and [ 2-methacryloxy ] diethyl phosphate; the initiator is any one of ammonium persulfate, potassium persulfate, (2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone) and alpha-ketoglutaric acid.

The low-temperature stretching performance test is to immerse the strip-shaped hydrogel in a liquid nitrogen and acetone mixed solution at the temperature of minus 20 ℃ for 30 min, take out the hydrogel, clamp the strip-shaped hydrogel by using forceps, manually stretch the gel, and observe whether the flexibility is still kept.

The gel has high elasticity, namely, the strip-shaped gel is stretched to 20 times of the original length at room temperature, the tension is released, and the gel shape recovery time is recorded.

The obdurability is realized by penetrating a steel needle with the diameter of 500 mm into gel until the gel is deformed by 95 percent, and observing whether the gel is punctured or not.

The adhesion test of the invention is to press and paste the gel on the surface of the rubber or the skin and carry out the standard 90 by using a mechanical stretching instrument^oPeel test, adhesion strength at normal and low temperatures.

The mechanical properties of the hydrogel such as stretching, compression, tearing and the like are represented by an HY-0580 universal stretcher, and the adhesive force between the hydrogel and the surfaces of rubber, skin and other substances is represented.