CN112625620B - Polyvinyl alcohol gel solution, adhesive, preparation method and application thereof - Google Patents

Polyvinyl alcohol gel solution, adhesive, preparation method and application thereof Download PDF

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Publication number
CN112625620B
CN112625620B CN202011522209.6A CN202011522209A CN112625620B CN 112625620 B CN112625620 B CN 112625620B CN 202011522209 A CN202011522209 A CN 202011522209A CN 112625620 B CN112625620 B CN 112625620B
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polyvinyl alcohol
adhesive
alcohol gel
freezing
materials
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CN112625620A (en
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王莉莉
徐崇智
刘硕
田心语
张宪胜
夏延致
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Qingdao University
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Qingdao University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on 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; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08—Materials for coatings
    • A61L29/085—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
    • A61L29/145—Hydrogels or hydrocolloids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a polyvinyl alcohol gel solution, an adhesive, a preparation method and an application thereof, wherein the polyvinyl alcohol gel solution takes polyvinyl alcohol and inorganic salt as raw materials, water as a solvent, the concentration of the polyvinyl alcohol is 3-30wt%, the concentration of the inorganic salt is 30-50wt%, and the inorganic salt is selected from one or more of calcium chloride, zinc chloride, lithium chloride, sodium phosphate, potassium acetate and the like. The polyvinyl alcohol gel solution is frozen together with the object to be bonded to obtain the polyvinyl alcohol gel adhesive. The adhesive can be applied to adhesion of rigid materials such as glass, metal, plastic and the like, and the application of polyvinyl alcohol in the field of adhesives is expanded.

Description

Polyvinyl alcohol gel solution, adhesive, preparation method and application thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a polyvinyl alcohol gel solution, an adhesive, and preparation methods and applications thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Adhesives are substances that are adhesive and, by virtue of their adhesive properties, join two separate materials together and are used in a very wide variety of applications. The types of adhesives are various, but most adhesives have the problems of low toxicity, low adhesiveness and the like, which seriously limit the application of the adhesives in the biomedical field, for example, cyanoacrylate derivatives have high adhesive force but poor biocompatibility; fibrin glue has insufficient adhesion and carries the risk of viruses; glutaraldehyde derivatives are susceptible to cellular viral reactions.
Chinese patent application No. 201310548359.8 discloses a cyanoacrylate medical adhesive which has high adhesive strength and good toughness of an adhesive film, but formaldehyde harmful to biological tissues is generated during storage and use of the cyanoacrylate medical adhesive. Although the generation of formaldehyde is inhibited by adding the formaldehyde inhibitor, the residual formaldehyde still can cause stimulation to the human body, and the effect and popularization of the medical adhesive are seriously influenced.
The Chinese patent with application number 201911223519.5 discloses a preparation and use method of a benzoxazine adhesive for polyethylene, wherein the adhesive improves the bonding strength of the adhesive to the surface of a polyethylene material, but benzoxazine has toxicity and is not in accordance with the concept of environmental protection.
As is well known, polyvinyl alcohol is a water-soluble high molecular polymer, has the advantages of biodegradability, nontoxicity, good biocompatibility and the like, and is widely applied to adhesive materials. However, the glue used in the prior art is an aqueous solution of polyvinyl alcohol, which has low adhesion, only has adhesion to materials such as paper, and cannot be applied to adhesion of rigid materials such as glass, metal, plastic, and the like. Therefore, how to further improve the adhesion by using the polyvinyl alcohol green material has important significance on the development of adhesion materials in the biomedical field.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a polyvinyl alcohol gel solution, an adhesive, a preparation method and application thereof. The raw materials used in the invention, the preparation and use processes are completely green, the preparation method is adjustable, the prepared adhesive can be applied to adhesion of rigid materials such as glass, metal, plastic and the like, the application of polyvinyl alcohol in the field of adhesives is expanded, and the adhesive can be applied to the surface of medical materials or devices, so that the use experience of patients is improved, and the compliance is improved.
In a first aspect of the present invention, the present invention provides a polyvinyl alcohol gel solution, which uses polyvinyl alcohol and inorganic salt as raw materials, and uses water as a solvent, wherein the concentration of the polyvinyl alcohol is 3-30wt%, and the concentration of the inorganic salt is 30-400wt%, wherein the inorganic salt is selected from one or more of calcium chloride, zinc chloride, lithium chloride, sodium phosphate, potassium acetate, and the like.
The use of these inorganic salts can improve the properties of polyvinyl alcohol gels. In some embodiments of the invention, more preferred inorganic salts are calcium chloride and lithium chloride. When the two inorganic salts are selected, the prepared polyvinyl alcohol gel can be used as a raw material for preparing the adhesive, and the adhesive prepared from the polyvinyl alcohol gel has good adhesive property and can be used for adhering glass materials, high polymer materials, metal materials, wood, medical materials or devices and the like. Such as glass, tin foil, polyethylene film, and the like; moreover, the adhesive can also have better transparency in a visible light range after being regulated and controlled.
In some embodiments of the invention, the concentration of polyvinyl alcohol is 10 to 30 wt%; the concentration of the inorganic salt is 30-50 wt%.
In some embodiments of the invention, the inorganic salt is calcium chloride or lithium chloride. In the study of the present invention, the inventors found that when the inorganic salt is calcium chloride or lithium chloride and the concentration thereof is 30 to 40wt% (not containing 40 wt%), the binder obtained by freezing treatment using the polyvinyl alcohol gel solution obtained as a raw material generally has transparency, and once it is higher than 40wt% (containing 40 wt%), the transparency characteristic disappears.
In some embodiments of the present invention, the starting material, polyvinyl alcohol, has a number average molecular weight of 40000-180000 and a degree of alcoholysis of 70% to 99.9%.
In a second aspect of the present invention, the present invention provides a method for preparing the polyvinyl alcohol gel solution described in the first aspect above, comprising: preparing a polyvinyl alcohol/inorganic salt mixed solution, and then defoaming the mixed solution. The polyvinyl alcohol/inorganic salt mixed solution according to the present invention is a mixed aqueous solution of polyvinyl alcohol and an inorganic salt, unless otherwise specified.
In the embodiment of the present invention, the defoaming treatment may be performed by a method commonly used in the art, but in some embodiments of the present invention, ultrasonic, vacuum or static treatment is more preferable, and ultrasonic defoaming is particularly preferable.
In a third aspect of the invention, there is provided the use of a polyvinyl alcohol gel solution as described in the first aspect above in the preparation of an adhesive.
In some embodiments of the invention, the adhesive may adhere glass materials, polymeric materials, metallic materials, wood, and medical materials or devices, among others. Such as glass, tin foil, polyethylene film, etc.
In some embodiments of the present invention, when the inorganic salt is calcium chloride or lithium chloride and the concentration is 30-40wt% (not including 40 wt%), the adhesive obtained by freezing the prepared polyvinyl alcohol gel has good adhesion performance and good visible light transmittance, and thus, the adhesive of the present invention is particularly suitable for medical fields requiring transparency.
In some embodiments of the present invention, the present invention provides an application of the above adhesive in a medical device, such as a medical endoscope, the adhesive of the present invention can be adhered to the surface of the medical endoscope, which can reduce the hardness of the surface of the endoscope and reduce the pain of a patient, and at the same time, the adhesive of the present invention has good light transmittance, and ensures the imaging quality of a lens, and also solves the problems that the traditional medical adhesive is easy to whiten and has great irritation to a human body in the using process.
In an embodiment of the present invention, there is also provided a method of using the adhesive, including: freezing polyvinyl alcohol gel solution as a raw material to obtain an adhesive, and coating the adhesive on the surface of an object to be adhered or in the object to be adhered;
or coating the surface of the object to be bonded or the inside of the object to be bonded with the polyvinyl alcohol gel solution, and then freezing.
In a fourth aspect of the present invention, there is provided a polyvinyl alcohol gel adhesive which uses the polyvinyl alcohol gel solution described in the first aspect as a raw material.
In some embodiments of the invention, the adhesive is obtained by freezing a polyvinyl alcohol gel adhesive solution; the freezing temperature is minus 10 ℃ to minus 80 ℃, the freezing time is 1h to 48h, and the frozen product can be unfrozen optionally after being frozen, wherein the unfreezing temperature is not more than 50 ℃.
In some embodiments of the invention, the freezing temperature is-20 to-50 ℃, and the number of freezing and thawing cycles is 0 to 10, preferably 1 to 10.
In some embodiments of the invention, the selection and concentration of the inorganic salt has a significant impact on the properties of the final adhesive. When the inorganic salt is one or more of calcium chloride, zinc chloride, lithium chloride, sodium phosphate and potassium acetate, the crystallization of the polyvinyl alcohol in the freezing process can be weakened by the inorganic salt, so that the performance of the polyvinyl alcohol is improved. In particular, in some embodiments of the present invention, the polyvinyl alcohol is present in a concentration of 10 to 30wt%, the inorganic salt is present in a concentration of 30 to 50wt%, and particularly 30 to 40wt%, and the adhesive prepared has excellent adhesion at a freezing temperature of-20 ℃ to-40 ℃ and high permeability at an inorganic salt concentration of 30 to 40wt% (not containing 40 wt%).
In some embodiments of the present invention, the inventors used inorganic salts such as sodium chloride, sodium oleate, and potassium chloride, and as a result, the above inorganic salts tend to precipitate polyvinyl alcohol from an aqueous solution at more than 5wt%, and the resulting polyvinyl alcohol gel does not have adhesiveness and a gel adhesive cannot be obtained.
The invention can effectively regulate and control the adhesiveness and light transmittance of the gel in a wide range by changing the concentration of the inorganic salt and the freezing temperature so as to meet the requirements of different use occasions.
For example, in some embodiments of the present invention, when the concentration of the polyvinyl alcohol is 10 to 30wt%, and the concentration of the inorganic salt is 30 to 50wt%, the adhesive of the present invention has a better adhesive ability, and compared to the prior art, which has no adhesive force or can only better adhere articles such as paper, the adhesive of the present invention can be used for adhering glass materials, polymer materials, metal materials, etc., and has a good adhesive effect and is not easy to peel.
For example, in some embodiments of the present invention, the freezing temperature of-10 ℃ to-80 ℃ can make the polyvinyl alcohol gel adhesive of the present invention have a good adhesion effect, and can bond a wide range of materials, such as metal materials, polymer materials, glass, wood, etc.; in order to obtain better and more accurate adhesion, the invention adjusts the freezing temperature within the range of-10 to-80 ℃, can regulate and control the bonding capacity of the polyvinyl alcohol gel adhesive to different materials, and has generally better bonding effect when the temperature ranges from-20 to-50 ℃; for example, in one or more embodiments of the present invention, the freezing temperature is-20 ℃, and the resulting adhesive has better adhesion to glass; for example, in one or more embodiments of the present invention, the freezing temperature of-50 ℃ is used to provide better adhesion to polyethylene film; for example, in one or more embodiments of the invention, the freezing temperature is-30 ℃ which provides better adhesion to the tin foil.
In a fifth aspect of the present invention, there is provided a composite material using the polyvinyl alcohol gel solution described in the first aspect above or the polyvinyl alcohol gel adhesive described in the fourth aspect above as a raw material. For example, when the polyvinyl alcohol gel solution of the invention is used in combination with other materials such as starch, the obtained substance still has good adhesion effect after being frozen.
In the preparation process of the composite material, the polyvinyl alcohol gel adhesive is used as an adhesive between materials or in the materials, and can be added in a proper procedure when in use; or the polyvinyl alcohol gel solution is mixed with materials in a proper process, and the mixture is frozen to play a role in adhesion, so that the adhesion of multiple layers of materials or the adhesion in the materials is realized. The timing of the addition of the binder can be readily determined by one skilled in the art based on common knowledge or conventional operating means.
In a sixth aspect of the present invention, the present invention provides the use of the polyvinyl alcohol gel adhesive according to the fourth aspect in the fields of medicine and materials. Including but not limited to glass materials, polymeric materials, metallic materials, wood, and the like.
In some embodiments of the present invention, the application comprises using a polyvinyl alcohol gel adhesive to adhere the surface or the interior of a material of the same or different material, such as multiple layers of different materials or a single material in a composite material, and adhering the polyvinyl alcohol gel adhesive to the surface of a medical endoscope, which can improve the use experience of the endoscope and increase patient compliance when adhering to the endoscope surface. When the polyvinyl alcohol gel adhesive is used on the surface of a medical endoscope, the surface hardness of the endoscope can be reduced, the pain of a patient can be reduced, meanwhile, the adhesive has good light transmittance, the imaging quality of a lens is ensured, and the problem that the traditional medical adhesive is easy to whiten and has great stimulation to a human body in the use process is solved.
Compared with the prior art, the invention has the advantages that:
the raw materials used in the invention do not relate to any toxic material, and the preparation process is green and environment-friendly; the polyvinyl alcohol gel adhesive obtained by the invention has strong adhesive capacity, has adhesive effect on rigid materials such as glass, metal, plastic and the like, is not limited to low adhesion on paper any more, and can also be applied to the fields of biomedical devices, sensors and the like; in addition, the polyvinyl alcohol gel adhesive can realize transparency, can not shield the surface appearance of an adhered body in special use occasions, and has wider application range.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 shows the effect of adhesion of the polyvinyl alcohol gel adhesive obtained in example 1 to glass, and it can be seen from the figure that the gel adhesive appears opaque and exhibits stringiness and adhesion to glass when two sheets of glass are separated by force.
FIG. 2 shows the effect of adhesion of the polyvinyl alcohol gel adhesive obtained in example 2 to glass, and it can be seen from the figure that the gel adhesive is transparent in appearance, and when two pieces of glass are separated by force, the gel adhesive shows a stringing phenomenon and exhibits adhesion to glass.
Fig. 3 shows the effect of adhesion of the polyvinyl alcohol gel adhesive obtained in example 3 to a polyethylene film. As can be seen from the figure, the gel adhesive appeared opaque and when the two polyethylene films were separated by force, the gel adhesive showed stringiness and adhesion to the polyethylene films.
Fig. 4 shows the effect of adhesion of the polyvinyl alcohol gel adhesive obtained in example 4 to an aluminum foil. As can be seen from the figure, the gel adhesive appeared opaque, and when the two aluminum foils were separated by force, the gel adhesive showed stringiness and adhesion to the aluminum foils.
FIG. 5 shows the effect of adhesion of the polyvinyl alcohol gel obtained in example 8 to an aluminum foil, and it can be seen from the graph that the hydrogel does not take the form of a binder but takes the form of a transparent sheet, there is no stringing between the hydrogel and the aluminum foil, and there is no effect of adhesion to the aluminum foil.
FIG. 6 shows the effect of adhesion of the polyvinyl alcohol gel obtained in example 9 to an aluminum foil, and it can be seen from the graph that the hydrogel does not take the form of a binder but takes the form of a non-transparent sheet, and that there is no stringing between the hydrogel and the aluminum foil, and there is no effect of adhesion to the aluminum foil.
FIG. 7 shows the effect of adhesion of the polyvinyl alcohol solution obtained in example 10 to an aluminum foil, and it can be seen from the figure that the polyvinyl alcohol obtained is in a solution state, has good fluidity, and has substantially no adhesion effect to an aluminum foil.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The reagents or starting materials used in the present invention can be purchased from conventional sources, and unless otherwise specified, the reagents or starting materials used in the present invention can be used in a conventional manner in the art or in accordance with the product specifications. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only. Unless otherwise specified, the elevated temperatures described in the following examples of the invention are from 90 to 100 ℃.
Example 1
Preparing a mixed solution of 20 wt% polyvinyl alcohol (M = 70000)/40 wt% calcium chloride at high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of glass, covering the other surface of the glass, and freezing the sandwich glass in a refrigerator at the freezing temperature of-20 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 1. The resulting polyvinyl alcohol gel adhesive showed good adhesion to glass but no transparency, as shown in figure 1.
Example 2
Preparing a mixed solution of 20 wt% polyvinyl alcohol (M = 70000)/30 wt% calcium chloride at high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of glass, covering the other surface of the glass, and freezing the sandwich glass in a refrigerator at the freezing temperature of-20 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 1. The resulting polyvinyl alcohol gel adhesive showed good adhesion to glass and was transparent as shown in fig. 2.
Example 3
Preparing a mixed solution of polyvinyl alcohol (M = 100000) with the concentration of 10 wt% and calcium chloride with the concentration of 40wt% at high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of a polyethylene film, covering the other surface of the polyethylene film, putting the sandwich type polyethylene film into a refrigerator for freezing at the freezing temperature of-50 ℃ for 24 hours, and thawing at the temperature of 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 1. The resulting polyvinyl alcohol gel adhesive showed good adhesion to polyethylene film but no transparency, as shown in fig. 3.
Example 4
Preparing a mixed solution of 20 wt% polyvinyl alcohol (M = 70000)/40 wt% calcium chloride at high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of an aluminum foil, covering the other surface of the aluminum foil, and freezing the sandwich type aluminum foil in a refrigerator at the freezing temperature of-30 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 2. The obtained polyvinyl alcohol gel adhesive showed good adhesion to aluminum foil, but did not have transparency, as shown in fig. 4.
Example 5
Preparing a mixed solution of polyvinyl alcohol (M = 100000) with the concentration of 10 wt% and calcium chloride with the concentration of 40wt% at high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of glass, covering the other surface of the glass, and freezing the sandwich glass in a refrigerator at the freezing temperature of-20 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 2. The adhesion effect was slightly inferior to that of example 1.
Example 6
Preparing a mixed solution of 20 wt% polyvinyl alcohol (M = 70000)/40 wt% calcium chloride at high temperature, uniformly mixing, and defoaming by ultrasonic. Freezing the obtained mixed solution in a refrigerator at-20 deg.C for 24 hr, and thawing at 4 deg.C for 6 hr with cycle number of 1. The resulting adhesive was applied uniformly to one side of the glass, and the other side of the glass was then covered. The adhesion effect was comparable to example 1.
Example 7
Preparing a mixed solution of polyvinyl alcohol (M = 100000) with the concentration of 10 wt% and calcium chloride with the concentration of 40wt% at high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of polytetrafluoroethylene, covering the polytetrafluoroethylene on the other surface, putting the sandwich type polytetrafluoroethylene into a refrigerator for freezing at the temperature of minus 20 ℃ for 24 hours, and unfreezing at the temperature of 4 ℃ for 6 hours, wherein the number of freezing and unfreezing cycles is 1. The resulting adhesive exhibits good adhesion to polytetrafluoroethylene.
Example 8
Preparing a mixed solution of 20 wt% polyvinyl alcohol (M = 70000)/10 wt% calcium chloride at high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of an aluminum foil, covering the other surface of the aluminum foil, and putting the sandwich type aluminum foil into a refrigerator for freezing at the temperature of minus 30 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and unfreezing cycles is 1. The polyvinyl alcohol gel obtained by the method is not in an adhesive state, but is in a sheet shape with good transparency, and has no adhesion effect on an aluminum foil, as shown in figure 5.
Example 9
Preparing 20 wt% polyvinyl alcohol (M = 70000) solution at high temperature, mixing uniformly, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of an aluminum foil, covering the other surface of the aluminum foil, and freezing the sandwich type aluminum foil in a refrigerator at the freezing temperature of-30 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 1. The polyvinyl alcohol gel obtained by the method is almost opaque, and has no adhesion effect on the aluminum foil adhesion, as shown in fig. 6.
Example 10
Preparing 10 wt% polyvinyl alcohol (M = 70000)/10 wt% sodium chloride mixture at high temperature, mixing uniformly, and defoaming with ultrasound. And uniformly coating the mixed solution on one surface of glass, covering the other surface of the glass, and freezing the sandwich glass in a refrigerator at the freezing temperature of-30 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 1. The polyvinyl alcohol gel obtained by the method is in a solution state, has high fluidity and does not have adhesion to an aluminum foil, and is shown in figure 7.
Example 11
Preparing a mixed solution of 20 wt% polyvinyl alcohol (M = 70000)/40 wt% lithium chloride at a high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of glass, covering the other surface of the glass, and freezing the sandwich glass in a refrigerator at the freezing temperature of-20 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 1. The polyvinyl alcohol gel adhesive obtained showed good adhesion to glass but no transparency, and the effect was inferior to that of example 5.
Example 12
Preparing a mixed solution of 20 wt% polyvinyl alcohol (M = 70000)/30 wt% calcium chloride/5 wt% starch at a high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of an aluminum foil, covering the other surface of the aluminum foil, and freezing the sandwich type aluminum foil in a refrigerator at the freezing temperature of-30 ℃ for 24 hours at 4 ℃ for 6 hours, wherein the number of freezing and thawing cycles is 2. The polyvinyl alcohol gel provided by the invention can still show the adhesion performance to the aluminum foil when being compounded with starch for use.
Example 13
Preparing a mixed solution of 20 wt% polyvinyl alcohol (M = 70000)/40 wt% calcium chloride at high temperature, uniformly mixing, and defoaming by ultrasonic. And uniformly coating the mixed solution on one surface of glass, covering the other surface of the glass, and freezing the sandwich glass in a refrigerator at the freezing temperature of-20 ℃ for 24 hours. The obtained polyvinyl alcohol gel adhesive had no transparency and exhibited good adhesion to glass, but the effect was inferior to that of example 1.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The polyvinyl alcohol gel adhesive is characterized in that the adhesive is obtained by taking polyvinyl alcohol gel solution as a raw material and freezing the polyvinyl alcohol gel solution;
the polyvinyl alcohol gel solution takes polyvinyl alcohol and inorganic salt as raw materials, and takes water as a solvent;
wherein, the concentration of the polyvinyl alcohol is 3-30wt%, and the concentration of the inorganic salt is 30-50 wt%;
wherein the inorganic salt is selected from one or more of calcium chloride, zinc chloride, lithium chloride, sodium phosphate and potassium acetate.
2. The polyvinyl alcohol gel adhesive according to claim 1, wherein the freezing temperature is-10 ℃ to-80 ℃, and the freezing time is 1h to 48 h.
3. The polyvinyl alcohol gel adhesive according to claim 1, wherein the freezing is followed by thawing at a temperature not exceeding 50 ℃.
4. The polyvinyl alcohol gel adhesive of claim 3 wherein the number of freeze-thaw cycles is from 1 to 10.
5. The polyvinyl alcohol gel adhesive as claimed in claim 1, wherein the polyvinyl alcohol has a number average molecular weight of 40000-180000 and a degree of alcoholysis of 70% to 99.9%.
6. The polyvinyl alcohol gel adhesive of claim 1, wherein the polyvinyl alcohol gel solution is prepared by a method comprising: preparing a polyvinyl alcohol/inorganic salt mixed solution, and then performing defoaming treatment on the mixed solution, wherein the defoaming treatment comprises ultrasonic treatment, vacuum treatment or static treatment.
7. Use of a polyvinyl alcohol gel adhesive according to any one of claims 1 to 6 in the field of materials;
wherein, the application comprises that the polyvinyl alcohol gel adhesive is used for bonding the surfaces or the interiors of materials of the same or different materials;
wherein the material is selected from a glass material, a polymer material, a metal material, and a wood base material.
8. Use of the polyvinyl alcohol gel adhesive according to any one of claims 1 to 6 in the medical field;
wherein the application comprises the use of a polyvinyl alcohol gel adhesive for adhering medical materials or medical devices.
9. The use of claim 8 wherein the medical device is a medical endoscope and the use is adhering a polyvinyl alcohol gel adhesive to a surface of a medical endoscope.
10. The method of using the polyvinyl alcohol gel adhesive of any one of claims 1 to 6: freezing polyvinyl alcohol gel solution as a raw material to obtain an adhesive, and coating the adhesive on the surface of an object to be adhered or in the object to be adhered; or coating the surface of the object to be bonded or the inside of the object to be bonded with the polyvinyl alcohol gel solution, and then freezing.
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