CN112538131B - Hydrogel bonding method, hydrogel bonded body and debonding method thereof - Google Patents

Hydrogel bonding method, hydrogel bonded body and debonding method thereof Download PDF

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CN112538131B
CN112538131B CN202011409874.4A CN202011409874A CN112538131B CN 112538131 B CN112538131 B CN 112538131B CN 202011409874 A CN202011409874 A CN 202011409874A CN 112538131 B CN112538131 B CN 112538131B
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hydrogel
bonding
bonding method
stretched
tape
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CN112538131A (en
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杨灿辉
洪伟
李奇
张平
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Southwest University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • 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
    • C09J133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised 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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide

Abstract

The invention provides a hydrogel bonding method, a hydrogel bonding body and a debonding method thereof, wherein the bonding method comprises the following steps: (1) Uniaxially stretching and fixing the first hydrogel to obtain stretched first hydrogel; (2) And respectively attaching the stretched first hydrogel and the second hydrogel to two surfaces of the hydrogel adhesive tape, and releasing the stretched first hydrogel to restore the original shape to obtain the hydrogel adhesive body with the orientation fold structure. The bonding method can realize high-strength bonding of the hydrogel material within 5 seconds, the obtained hydrogel bonding body can realize debonding as required through asymmetric elimination of an oriented fold structure, the operation is simple, and the stripping of the hydrogel material can be completed within 15 seconds. The on-demand bonding and debonding method provided by the invention does not need to use a specific chemical system or a severe trigger mechanism, and has extremely strong operability and excellent universality.

Description

Hydrogel bonding method, hydrogel bonded body and debonding method thereof
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a hydrogel bonding method, a hydrogel bonding body and a debonding method thereof.
Background
The hydrogel is an ideal biological material, can quickly absorb water in water to swell and retain a large amount of water, and is widely applied to the fields of tissue engineering, wound dressing, implantation medical instruments and the like. At present, the tough bonding method between hydrogels has made a great breakthrough, including biological adhesive tapes based on nano particles, biological glue, biological double-sided adhesives, and the like.
CN107840970a discloses a bilayer hydrogel for promoting interface bonding by adopting non-covalent action and a preparation method thereof, the preparation method specifically comprises: attaching two hydrogels with identical or different materials, and soaking in Fe-containing solution 3+ By Fe in the aqueous solution of (2) 3+ And COO in hydrogel - And a coordination bond is formed, so that double-layer hydrogel with excellent interface binding force is formed, and complex and uncontrollable process steps in the traditional preparation method are improved.
CN105079863a discloses a preparation method of aloe/sodium alginate double-layer hydrogel dressing, which specifically comprises the following steps: adding glycerol serving as a plasticizer into the sodium alginate aqueous solution to prepare a sodium alginate gel basal layer; adding the aloe water solution into the sodium alginate water solution to obtain aloe/sodium alginate mixed gel; dripping aloe/sodium alginate mixed gel on the surface of sodium alginate gel basal layer, drying, and soaking in CaCl 2 And (5) adding into the solution for 5-20 min to obtain the aloe/sodium alginate double-layer hydrogel dressing.
CN109868097a discloses a binder for binding a hydrogel material and a solid material, and a binding method, wherein the binder is a dispersion liquid formed by dispersing nano particles in a solvent; the solvent is a solvent capable of swelling the hydrogel, and the nanoparticles are one or more of metal nanoparticles, semiconductor nanoparticles, ceramic nanoparticles, polymer nanoparticles, carbon-based nanoparticles and liposome nanoparticles. The adhesive adopts nano particles as an adhesive medium of a hydrogel material and a solid material, can improve the interfacial peeling toughness, can be applied to the assembly of high polymer materials in different scales, and can also be applied to special glue and adhesive tape systems facing various environments.
CN111423603a discloses a method for bonding hydrogel and elastomer, and products and applications thereof, the bonding method comprises the following steps: coating the hydrogel primer coating solution on the surface of the formed hydrogel material, coating the elastomer primer coating solution on the surface of the formed elastomer, and then bonding the two to finish the bonding of the hydrogel and the elastomer. The bonding method can form a large number of stable and firm covalent bonds between the hydrogel and the elastomer material, thereby effectively avoiding the debonding phenomenon of the whole device in the deformation process.
However, most of the existing gel bonding techniques focus on strong bonding between hydrogel materials or between hydrogel materials and other materials, and studies on removal of the bonded structure have not yet been completed. It is particularly important for some fragile or expensive hydrogel materials to be able to be removed on demand after the function is completed. Although there are some methods available to achieve debonding of hydrogels, these methods are all accomplished by designing specific chemical systems, with harsh trigger mechanisms, requiring long time costs.
Therefore, developing a method that can realize strong adhesion between hydrogels and can realize debonding as required is a technical problem to be solved in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hydrogel bonding method, a hydrogel bonding body and a debonding method thereof, wherein an oriented fold structure is introduced on a bonding interface through the combination of uniaxial stretching, bonding and releasing means, so that the strong bonding between hydrogels is realized, the obtained hydrogel bonding body can be debonded as required, and the advantages of convenience, rapidness, strong universality and the like are realized.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of bonding hydrogels, the method comprising the steps of:
(1) Uniaxially stretching and fixing the first hydrogel to obtain stretched first hydrogel;
(2) And (3) respectively attaching the stretched first hydrogel and the second hydrogel obtained in the step (1) to two surfaces of the hydrogel adhesive tape, and releasing the stretched first hydrogel to restore the original shape to obtain the hydrogel adhesive body with the orientation fold structure.
The bonding method mainly comprises the two steps of firstly carrying out uniaxial stretching and fixing on a first hydrogel to be bonded, then respectively attaching the first hydrogel to be bonded and a second hydrogel to be bonded to two surfaces of a hydrogel adhesive tape, swelling the hydrogel adhesive tape by absorbing water, releasing the stretched hydrogel to restore to original shape, and forming an oriented fold structure on the bonding interface of the two hydrogels at the moment, wherein the stable existence of the fold structure enables the bonding strength between the first hydrogel and the second hydrogel to be obviously improved, so that the tough bonding between hydrogel materials is realized. The bonding method provided by the invention can be widely applied to various hydrogel materials, does not need a specific chemical system or a severe trigger mechanism, has simple steps, is easy to realize, can finish bonding within 5 seconds, and has excellent universality.
In the present invention, each of the first hydrogel and the second hydrogel independently includes any one of a polyacrylamide hydrogel, a polyisopropyl acrylamide hydrogel, a polyacrylic hydrogel, a polypeptide hydrogel, a polysaccharide hydrogel, a polyvinyl alcohol hydrogel, or a polyethylene glycol hydrogel.
In the present invention, the second hydrogel is an unstretched hydrogel or a uniaxially stretched and fixed hydrogel.
Preferably, the second hydrogel is a uniaxially stretched and fixed hydrogel, and the step (2) further includes a step of releasing the second hydrogel to recover its original shape after the fitting.
Preferably, the second hydrogel is a uniaxially stretched and fixed hydrogel, and the stretching magnification of the uniaxial stretching is the same as or different from the stretching magnification of the uniaxial stretching in the step (1).
In the present invention, the hydrogel tape is a dry hydrogel tape.
Preferably, the hydrogel tape has a thickness of 1 to 100 μm, such as 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm, 40 μm, 42 μm, 45 μm, 48 μm, 50 μm, 52 μm, 55 μm, 58 μm, 60 μm, 62 μm, 65 μm, 68 μm, 70 μm, 72 μm, 75 μm, 78 μm, 80 μm, 82 μm, 85 μm, 88 μm, 90 μm, 92 μm, 95 μm or 98 μm, and specific spot values between the above spot values are limited in breadth and for brevity the present invention is not intended to be exhaustive of the specific spot values included in the range.
As a preferable technical scheme of the invention, the thickness of the hydrogel adhesive tape is 1-100 mu m; if the thickness of the hydrogel tape is too low, the preparation cost of the hydrogel tape is increased; if the thickness of the hydrogel tape is too large, it is difficult to form a stable wrinkled structure in the bonding.
Preferably, the hydrogel tape material comprises polyacrylic acid (PAAc) or acrylic acid-acrylamide copolymer (PAAc-co-PAAm).
Preferably, the hydrogel adhesive tape is made of an acrylic acid-acrylamide copolymer, and the first hydrogel and the second hydrogel are both polyacrylamide hydrogels.
As a preferred technical scheme of the invention, the hydrogel adhesive tape is a dry hydrogel adhesive tape, and can absorb water on the surfaces of the first hydrogel and the second hydrogel in the bonding process and form intermolecular hydrogen bonds; meanwhile, the orientation fold structure on the bonding interface enables the bonding strength to be further improved, so that stable bonding with high strength is achieved.
Preferably, the hydrogel tape is prepared by a method comprising: carrying out polymerization reaction on a monomer, an initiator and a cross-linking agent to obtain a polymerization solution; and coating the polymerization solution on a substrate, and obtaining the hydrogel adhesive tape after crosslinking and drying.
Preferably, the monomers comprise a combination of acrylic acid and acrylamide.
Preferably, the molar ratio of acrylic acid to acrylamide is (1-5): 1, e.g., 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, or 4.8:1, etc.).
Preferably, the initiator is a water-soluble initiator, more preferably a water-soluble photoinitiator.
Preferably, the initiator is used in an amount of 0.025 to 5%, for example 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5% or 4.8%, based on 100% of the monomer, and the specific point values between the above point values are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values comprised in the range.
Preferably, the crosslinking agent is a silane coupling agent.
Preferably, the crosslinker is used in an amount of 0.01 to 20%, for example 0.02%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 3%, 5%, 7%, 9%, 10%, 11%, 13%, 15%, 17%, 19% or 19.5%, and specific point values between the above point values, based on 100% of the monomer, are not limited to space and for reasons of brevity, the invention does not include specific point values in the range.
Preferably, the polymerization is carried out under ultraviolet light irradiation.
Preferably, the crosslinking is performed under acidic conditions.
Preferably, the pH of the acidic condition is between 2 and 5, such as 2.1, 2.3, 2.5, 2.7, 2.9, 3, 3.1, 3.3, 3.5, 3.7, 3.9, 4, 4.1, 4.3, 4.5, 4.7 or 4.9, and the specific point values between the above-mentioned point values, are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values comprised in the range.
Preferably, the drying temperature is 50-80 ℃, such as 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 78 ℃, and specific point values between the above point values, limited in space and for the sake of brevity, the present invention is not exhaustive of the specific point values comprised in the range.
Preferably, the bonding method specifically comprises the following steps:
(1) Uniaxially stretching and fixing the first hydrogel to obtain stretched first hydrogel;
(2) And (3) respectively attaching the stretched first hydrogel obtained in the step (1) and the second hydrogel which is not stretched or is stretched and fixed uniaxially to two surfaces of the dried hydrogel adhesive tape, so that the dried hydrogel adhesive tape absorbs water and swells, and the stretched hydrogel is released to restore the original shape, so that the hydrogel adhesive body with the oriented fold structure is obtained.
In another aspect, the present invention provides a hydrogel adhesive body including a hydrogel tape, and first and second hydrogels adhered to both surfaces of the hydrogel tape; the hydrogel adhesive body is prepared by the adhesive method.
The hydrogel adhesive body provided by the invention is prepared by the adhesive method, and has an oriented fold structure on an adhesive interface between two hydrogels.
In another aspect, the present invention provides a method for debonding a hydrogel bonded body as described above, the debonding method comprising: either the first hydrogel or the second hydrogel is stretched, and then the other hydrogel is peeled off, so that the first hydrogel and the second hydrogel are debonded.
Preferably, the stretching magnification of the stretching is not lower than that of uniaxial stretching at the time of bonding.
The invention also provides a debonding method of the hydrogel adhesive body, wherein one hydrogel is stretched, an orientation fold structure of an adhesive interface is asymmetrically eliminated, the elimination of the fold structure reduces the adhesive strength between the hydrogels, and the two hydrogels can be easily peeled off, so that debonding of the two hydrogels is realized. The debonding method can realize the on-demand debonding of the hydrogel adhesive body within 15 seconds without the help of a complex external chemical environment, and has the characteristics of convenience, rapidness and easiness in operation.
In another aspect, the invention provides the use of the bonding method as described above or the debonding method as described above in a biological material.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for bonding the hydrogels, provided by the invention, the orientated fold structure is introduced into the bonding interface of the hydrogel materials through the combination of means such as uniaxial stretching, bonding and releasing, so that the tough bonding between the hydrogels is realized, the obtained hydrogel bonding body can be debonded as required, and the method has the advantages of convenience, rapidness, strong universality and the like. The bonding method can realize high-strength bonding of the hydrogel material within 5 seconds, and the breaking work of the obtained polyacrylamide hydrogel bonding body reaches 72-130J/m 2 The bonding strength is 8.3 to 11.7kPa; meanwhile, the hydrogel adhesive body can realize debonding according to the need through asymmetric elimination of an orientation fold structure, is simple to operate, and can finish stripping of a hydrogel material within 15 seconds. The on-demand bonding and debonding method provided by the invention does not need to use a specific chemical system or a severe trigger mechanism, and has extremely strong operability and excellent universality.
Drawings
FIG. 1 is a schematic structural view of a hydrogel adhesive body having an oriented pleated structure obtained in example 1, wherein the hydrogel adhesive body has a 1-first hydrogel, 2-second hydrogel, and 3-oriented pleated structure;
FIG. 2 is a graph showing the debonding force-displacement results of the hydrogel bonded body obtained in example 1;
FIG. 3 is a graph showing comparison of the results of work of fracture of the hydrogel adhesives obtained in examples 1 to 5 and comparative example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
An acrylic acid-acrylamide copolymer (PAAc-co-PAAm) hydrogel adhesive tape is prepared by the following steps:
(1) Uniformly mixing 12.97g of acrylic acid, 4.26g of acrylamide, 0.065g of a water-soluble azo initiator V-50, 0.228g of a silane coupling agent 3- (trimethoxysilyl) propyl acrylate and 120mL of water to form a precursor solution; irradiating the precursor solution for 4min under an ultraviolet lamp to obtain a polymerization solution;
(2) Spin-coating the polymerization solution obtained in the step (1) on an organic glass plate, controlling the spin-coating rotating speed to be 1000rpm and the spin-coating time to be 50s, so as to obtain a pre-polymerized film;
(3) Placing the pre-polymerized film obtained in the step (2) in an HCl solution with a pH value of 3.5 for 5min to finish crosslinking; then the sample was dried in an oven at 65℃for 3 hours to give the PAAc-co-PAAm hydrogel tape having a thickness of 5. Mu.m.
The first hydrogel and the second hydrogel according to the following examples and comparative examples of the present invention are both polyacrylamide (PAAm) hydrogels, and the preparation method is as follows: 8.53g of acrylamide, 0.0074g of methylenebisacrylamide, 0.32g of alpha-ketoglutaric acid and 60mL of water were mixed uniformly to form a precursor solution, and the precursor solution was irradiated under an ultraviolet lamp for 1h to obtain polyacrylamide (PAAm) hydrogel.
Example 1
The hydrogel bonding method specifically comprises the following steps:
(1) Uniaxially stretching and fixing the first hydrogel and the second hydrogel respectively, wherein the stretching multiplying power of the uniaxial stretching is 3, and the stretched first hydrogel and the stretched second hydrogel are obtained;
(2) And (3) respectively attaching the stretched first hydrogel and the stretched second hydrogel obtained in the step (1) to two surfaces of a dried hydrogel adhesive tape (provided in preparation example 1), so that the dried hydrogel adhesive tape absorbs water and swells, and releasing the stretched first hydrogel and the stretched second hydrogel to restore to original shapes, thereby obtaining the hydrogel adhesive body with an orientation fold structure.
The schematic structure of the hydrogel adhesive body with the oriented fold structure obtained in this example is shown in fig. 1, in which the 1-first hydrogel, the 2-second hydrogel and the 3-oriented fold structure are shown.
The hydrogel adhesive body prepared in this example was subjected to debonding, and the debonding method was as follows:
either the first hydrogel or the second hydrogel in the hydrogel adhesive body is stretched at a stretching ratio of 5, and the other hydrogel is peeled off to debond the first hydrogel and the second hydrogel.
Force-displacement curve in the process of debonding is tested by a uniaxial stretching method, uniaxial stretching is carried out by using a universal material testing machine, and the constant stretching speed is 60mm & min -1 As shown in FIG. 2, the obtained debonding force-displacement results are shown, and it is understood from FIG. 2 that when debonding is performed on demand, one of the hydrogels is stretched 4 times (stretching ratio 5, lambda app =5), the stripping of the two hydrogels can be realized under a small acting force; if not stretched (lambda) app =1), the force and energy required for debonding increases significantly.
Example 2
The hydrogel bonding method is different from example 1 only in that the stretching ratio of the first hydrogel and the second hydrogel in the step (1) is 2; other process steps were the same as in example 1, to obtain a hydrogel adhesive body having an oriented fold structure.
Example 3
The hydrogel bonding method is different from example 1 only in that the stretching ratio of the first hydrogel and the second hydrogel in the step (1) is 4; other process steps were the same as in example 1, to obtain a hydrogel adhesive body having an oriented fold structure.
Example 4
The difference between the method for bonding hydrogels and the method for bonding hydrogels according to example 1 is that the stretching ratio of the first hydrogel and the second hydrogel in the step (1) is 5; other process steps were the same as in example 1, to obtain a hydrogel adhesive body having an oriented fold structure.
Example 5
The difference between the method for bonding hydrogels and the method for bonding hydrogels according to example 1 is that the stretching ratio of the first hydrogel and the second hydrogel in the step (1) is 6; other process steps were the same as in example 1, to obtain a hydrogel adhesive body having an oriented fold structure.
Example 6
The hydrogel bonding method specifically comprises the following steps:
(1) Uniaxially stretching and fixing the first hydrogel, wherein the stretching multiplying power of the uniaxial stretching is 3, so that stretched first hydrogel is obtained;
(2) And (3) respectively attaching the stretched first hydrogel and the second hydrogel (which are not stretched) obtained in the step (1) to two surfaces of a dried hydrogel adhesive tape (provided in the preparation example 1), so that the dried hydrogel adhesive tape absorbs water and swells, and the stretched first hydrogel is released to restore to the original shape, thereby obtaining the hydrogel adhesive body with an oriented fold structure.
Comparative example 1
The hydrogel bonding method specifically comprises the following steps:
the first and second hydrogels were bonded to both surfaces of a dried hydrogel tape (provided in preparation example 1), respectively, and the dried hydrogel tape was allowed to absorb water and swell, to obtain a hydrogel adhesive body.
Comparative example 2
The hydrogel bonding method specifically comprises the following steps:
(1) Soaking the dried hydrogel adhesive tape (provided in preparation example 1) in deionized water for 1h to obtain a swollen hydrogel adhesive tape;
(2) And (3) respectively attaching the first non-stretched hydrogel and the second non-stretched hydrogel to the surface of the swollen hydrogel adhesive tape obtained in the step (1) to obtain a hydrogel adhesive body.
Comparative example 3
The difference between the method for bonding hydrogels and the method for bonding hydrogels according to example 1 is that in the step (1), the first hydrogel and the second hydrogel are both subjected to multiaxial stretching and fixed, and the stretching ratio is 2; other process steps were the same as in example 1, to obtain a hydrogel adhesive body having an orientation-free fold structure.
Performance test:
the hydrogel adhesive bodies provided in examples 1 to 6 and comparative examples 1 to 3 were tested for work of fracture and adhesive strength by lap shear, and the specific method was: the hydrogel adhesive bodies are respectively fixed on a clamp of a universal material testing machine for shearingStretching, constant shear stretching speed is 60mm min -1 。
The results of the breaking work of the hydrogel adhesives obtained in examples 1 to 5 and comparative example 1 are shown in fig. 3, which are graphs plotting the stretching ratio of the uniaxial stretching in step (1) on the horizontal axis and the breaking work on the vertical axis. As can be seen from fig. 3, the first hydrogel and the second hydrogel in comparative example 1 were not stretched before bonding, the stretching ratio was 1, the breaking work of the obtained hydrogel adhesive was minimum, and the bonding strength was extremely low; as the stretching multiplying power increases, the breaking work increases; when the stretching multiplying power reaches 4, the breaking work is highest, namely the bonding strength and the bonding stability are highest at the moment; with further increase of the stretch ratio, the breaking work is not obviously improved any more.
The test results obtained by the above method are shown in table 1.
TABLE 1
Work of fracture (J/m) 2 ) Bonding strength (kPa)
Example 1 129 11.3
Example 2 72 8.3
Example 3 130 11.7
Example 4 126 10.8
Example 5 129 11.1
Example 6 103 10.5
Comparative example 1 45 6.7
Comparative example 2 50 7.1
Comparative example 3 62 7.9
As can be seen from the data in Table 1, in the bonding methods according to examples 1 to 6 of the present invention, by uniaxially stretching a single hydrogel or uniaxially stretching both the first and second hydrogels, the bonding interface between the two hydrogels forms an oriented fold structure at various stretching ratios (2, 3, 4, 5 and 6), the work of fracture and the bonding strength are high, and a strong bond is formed between the hydrogels, so that the work of fracture of the polyacrylamide hydrogel bond reaches 72 to 130J/m 2 The bonding strength is 8.3 to 11.7kPa. If the hydrogel to be bonded is not stretched, no oriented fold structure is formed on the bonding interface (comparative examples 1, 2), high strength bonding cannot be formed;if the first and second hydrogels were subjected to multiaxial stretching (comparative example 3), non-oriented pleated structures were formed at the bonding interface, and the work of fracture and bonding strength were low, failing to achieve strong bonding.
The applicant states that the present invention is described by way of the above examples as a method of bonding a hydrogel, a hydrogel bonded body and a method of debonding the same, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.

Claims (22)

1. A method for bonding hydrogels, comprising the steps of:
(1) Uniaxially stretching and fixing the first hydrogel to obtain stretched first hydrogel;
(2) Respectively attaching the stretched first hydrogel and the unstretched or uniaxially stretched and fixed second hydrogel obtained in the step (1) to two surfaces of a dried hydrogel adhesive tape, so that the dried hydrogel adhesive tape absorbs water and swells, and the stretched hydrogel is released to recover the original shape, thereby obtaining a hydrogel adhesive body with an oriented fold structure;
the first hydrogel and the second hydrogel respectively and independently comprise any one of polyacrylamide hydrogel, poly isopropyl acrylamide hydrogel, polyacrylic acid hydrogel, polypeptide hydrogel, polysaccharide hydrogel, polyvinyl alcohol hydrogel or polyethylene glycol hydrogel.
2. The bonding method according to claim 1, wherein the second hydrogel is a uniaxially stretched and fixed hydrogel, and the stretching magnification of the uniaxial stretching is the same as or different from the stretching magnification of the uniaxial stretching in step (1).
3. The bonding method according to claim 1, wherein the hydrogel tape is a dried hydrogel tape.
4. The bonding method according to claim 1, wherein the hydrogel tape has a thickness of 1 to 100 μm.
5. The bonding method according to claim 1, wherein the material of the hydrogel tape comprises polyacrylic acid or an acrylic acid-acrylamide copolymer.
6. The method of claim 5, wherein the hydrogel tape is made of acrylic acid-acrylamide copolymer, and the first hydrogel and the second hydrogel are both polyacrylamide hydrogels.
7. The bonding method according to claim 1, wherein the hydrogel tape is prepared by a method comprising: carrying out polymerization reaction on a monomer, an initiator and a cross-linking agent to obtain a polymerization solution; and coating the polymerization solution on a substrate, and obtaining the hydrogel adhesive tape after crosslinking and drying.
8. The bonding method according to claim 7, wherein the monomer comprises a combination of acrylic acid and acrylamide.
9. The bonding method according to claim 8, wherein the molar ratio of the acrylic acid to the acrylamide is (1-5): 1.
10. The bonding method according to claim 7, wherein the initiator is a water-soluble initiator.
11. The bonding method according to claim 7, wherein the initiator is a water-soluble photoinitiator.
12. The bonding method according to claim 7, wherein the initiator is used in an amount of 0.025 to 5% based on 100% of the monomer.
13. The bonding method according to claim 7, wherein the crosslinking agent is a silane coupling agent.
14. The bonding method according to claim 7, wherein the amount of the crosslinking agent is 0.01 to 20% based on 100% of the amount of the monomer.
15. The bonding method according to claim 7, wherein the polymerization reaction is performed under ultraviolet light irradiation.
16. The bonding method according to claim 7, wherein the crosslinking is performed under acidic conditions.
17. The bonding method according to claim 16, wherein the pH of the acidic condition is 2 to 5.
18. The bonding method according to claim 7, wherein the drying temperature is 50 to 80 ℃.
19. A hydrogel adhesive body, characterized in that the hydrogel adhesive body comprises a hydrogel adhesive tape, and a first hydrogel and a second hydrogel adhered to two surfaces of the hydrogel adhesive tape; the hydrogel adhesive body is prepared by the adhesive method according to any one of claims 1 to 18.
20. A method of debonding a hydrogel adhesive body in accordance with claim 19, wherein the debonding method comprises: either the first hydrogel or the second hydrogel is stretched, and then the other hydrogel is peeled off, so that the first hydrogel and the second hydrogel are debonded.
21. The debonding method of claim 20, wherein the stretch ratio of the stretching is not lower than the stretch ratio of uniaxial stretching at the time of bonding.
22. Use of a bonding method according to any one of claims 1 to 18 or a debonding method according to claim 20 or 21 in biological material.
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