CN112538131A - 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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CN112538131A
CN112538131A CN202011409874.4A CN202011409874A CN112538131A CN 112538131 A CN112538131 A CN 112538131A CN 202011409874 A CN202011409874 A CN 202011409874A CN 112538131 A CN112538131 A CN 112538131A
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hydrogel
stretched
bonding
tape
debonding
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CN112538131B (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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Adhesives Or Adhesive Processes (AREA)

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 a 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 oriented wrinkle structure. The bonding method can realize high-strength bonding of the hydrogel material within 5s, the obtained hydrogel bonding body realizes debonding as required through asymmetric elimination of the oriented fold structure, the operation is simple, and the hydrogel material can be peeled within 15 s. The method for bonding and debonding on demand provided by the invention does not need to use a specific chemical system or a strict triggering 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 biomaterial, can quickly absorb water in water to swell and keep a large amount of water, and is widely applied to the fields of tissue engineering, wound dressings, implant interventional medical devices and the like. At present, the strong bonding method between the hydrogels has made a great breakthrough, including biological adhesive tapes, biological glue, biological double-sided adhesive tapes and the like based on nano-particles.
CN107840970A discloses a double-layer hydrogel for promoting interface bonding by using non-covalent interaction and a preparation method thereof, the preparation method specifically comprises: bonding two pieces of hydrogel with the same or different materials, and soaking in Fe-containing solution3+In an aqueous solution of (2), by Fe3+With COO in hydrogels-Forming coordination bonds, forming double-layer hydrogel with excellent interface binding force, and improving complex and uncontrollable process steps in the traditional preparation method.
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 a sodium alginate aqueous solution to prepare a sodium alginate gel substrate layer; adding aloe water solution into sodium alginate water solution to obtain aloe/sodium alginate mixed gel; dripping Aloe/sodium alginate mixed gel on sodium alginate gel substrate surface, drying, and soaking in CaCl2And (5) putting the aloe/sodium alginate double-layer hydrogel dressing in the solution for 5-20 min.
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 nanoparticles in a solvent; the solvent is 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 the nano particles as an adhesive medium of a hydrogel material and a solid material, can improve the interface 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 bonding method of hydrogel and elastomer, and its product and application, the bonding method includes 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 attaching the hydrogel primer coating solution and the elastomer to complete 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 conventional gel adhesion techniques focus on strong adhesion between hydrogel materials or between hydrogel materials and other materials, and studies on removal of the adhesion structure have not been made yet. For some fragile or expensive hydrogel materials, it is important to be able to remove the hydrogel material as needed after the hydrogel material is completed. Although there are methods to achieve debonding of hydrogels, these methods are all achieved by designing specific chemical systems, with harsh triggering mechanisms, requiring long time costs.
Therefore, it is an urgent technical problem in the art to develop a method that can achieve both strong adhesion between hydrogels and debonding as needed.
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.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for bonding a hydrogel, comprising the steps of:
(1) uniaxially stretching and fixing the first hydrogel to obtain a stretched first hydrogel;
(2) and (2) respectively attaching the stretched first hydrogel and the second hydrogel obtained in the step (1) to two surfaces of a hydrogel adhesive tape, and releasing the stretched first hydrogel to restore the original shape to obtain a hydrogel adhesive body with an oriented wrinkle structure.
The bonding method provided by the invention mainly comprises two steps, wherein first hydrogel to be bonded is subjected to uniaxial stretching and fixing, then the first hydrogel and second hydrogel to be bonded are respectively bonded to two surfaces of a hydrogel adhesive tape, the hydrogel adhesive tape absorbs water to swell, the stretched hydrogel is released to restore the original shape, at the moment, a wrinkle structure with orientation is formed on a bonding interface of the two hydrogels, the stable existence of the wrinkle structure enables the bonding strength between the first hydrogel and the second hydrogel to be remarkably improved, and the strong and tough bonding between the hydrogel materials is realized. The bonding method provided by the invention can be widely applied to various hydrogel materials, does not need to use a specific chemical system or a strict triggering mechanism, has simple steps, is easy to realize, can complete bonding within 5s, and has excellent universality.
In the present invention, the first hydrogel and the second hydrogel each independently include any one of a polyacrylamide hydrogel, a polyisopropylacrylamide hydrogel, a polyacrylic acid 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) of attaching further comprises a step of releasing the second hydrogel to restore its original shape.
Preferably, the second hydrogel is a hydrogel that is uniaxially stretched and fixed, and the stretching ratio of the uniaxial stretching is the same as or different from the stretching ratio of the uniaxial stretching in step (1).
In the invention, the hydrogel adhesive tape is a dry hydrogel adhesive tape.
Preferably, the hydrogel adhesive 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 point values therebetween are limited to the form of a broad list and are not included herein for brevity.
As a preferred technical scheme, the thickness of the hydrogel adhesive tape is 1-100 mu m; if the thickness of the hydrogel adhesive tape is too low, the preparation cost of the hydrogel adhesive tape is increased; if the thickness of the hydrogel tape is too large, it is difficult to form a stable wrinkle structure in the adhesive.
Preferably, the material of the hydrogel tape comprises polyacrylic acid (PAAc) or acrylic acid-acrylamide copolymer (PAAc-co-PAAm).
Preferably, the material of the hydrogel tape is 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 hydrogen bonds between molecules; meanwhile, the oriented fold structure on the bonding interface further improves the bonding strength, thereby realizing high-strength stable bonding.
Preferably, the hydrogel adhesive 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 performing crosslinking and drying to obtain the hydrogel adhesive tape.
Preferably, the monomer comprises a combination of acrylic acid and acrylamide.
Preferably, the molar ratio of acrylic acid to acrylamide is (1-5: 1), such as 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.
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%, such as 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 specific values therebetween are not exhaustive, and for the sake of brevity, the invention does not list the specific values included in the range.
Preferably, the crosslinking agent is a silane coupling agent.
Preferably, the amount of the crosslinking agent is 0.01 to 20%, such as 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%, based on 100% of the monomer, and the specific values between the above values are not exhaustive and are not intended to limit the scope of the invention to the specific values included in the ranges for brevity.
Preferably, the polymerization is carried out under irradiation of ultraviolet light.
Preferably, the crosslinking is carried out under acidic conditions.
Preferably, the pH of the acidic conditions is 2 to 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 values therebetween are not exhaustive and for the sake of brevity, the invention is not intended to include the specific values included within the ranges.
Preferably, the drying temperature is 50-80 ℃, for example, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 78 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the bonding method specifically includes the steps of:
(1) uniaxially stretching and fixing the first hydrogel to obtain a stretched first hydrogel;
(2) and (2) respectively attaching the stretched first hydrogel obtained in the step (1) and a second hydrogel which is not stretched or is stretched and fixed in a uniaxial manner to two surfaces of a dried hydrogel adhesive tape, so that the dried hydrogel adhesive tape absorbs water to swell, and the stretched hydrogel is released to recover the original shape, thereby obtaining the hydrogel adhesive body with an oriented wrinkle structure.
In another aspect, the present disclosure provides a hydrogel adhesive body, which includes a hydrogel tape, and a first hydrogel and a second hydrogel adhered to two surfaces of the hydrogel tape; the hydrogel adhesive body is prepared by the adhesion method described above.
The hydrogel adhesive body provided by the present invention is prepared by the above-described adhesion method, and has an oriented wrinkle structure at the adhesion interface between two hydrogels.
In another aspect, the present invention provides a method for debonding a hydrogel adhesive body as described above, the method comprising: either the first hydrogel or the second hydrogel is stretched and then the other hydrogel is peeled off, debonding the first hydrogel from the second hydrogel.
Preferably, the stretching ratio is not lower than the stretching ratio of uniaxial stretching at the time of bonding.
The present invention also provides a method for debonding a hydrogel adhesive body as described above, in which one of the hydrogels is stretched to asymmetrically eliminate an oriented wrinkle structure at an adhesive interface, and the elimination of the wrinkle structure reduces the adhesive strength between the hydrogels, thereby enabling easy peeling and achieving debonding of two hydrogels. The debonding method can realize the debonding of the hydrogel adhesive body as required within 15s without the help of a complex external chemical environment, and has the characteristics of convenience, rapidness and easy operation.
In another aspect, the present invention provides the use of a method of adhesion as described above or a method of debonding as described above in a biomaterial.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for bonding the hydrogel, the oriented wrinkle structure is introduced to the bonding interface of the hydrogel material through the combination of the measures of uniaxial stretching, attaching, releasing and the like, so that the strong and tough bonding between the hydrogels is realized, and 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 5s, and the breaking work of the obtained polyacrylamide hydrogel bonding body reaches 72-130J/m2The bonding strength is 8.3-11.7 kPa; meanwhile, the hydrogel adhesive can realize debonding as required through asymmetric elimination of the oriented fold structure, the operation is simple, and the stripping of the hydrogel material can be completed within 15 s. The method for bonding and debonding on demand provided by the invention does not need to use a specific chemical system or a strict triggering mechanism, and has extremely strong operability and excellent universality.
Drawings
FIG. 1 is a schematic structural diagram of a hydrogel adhesive body with an oriented wrinkle structure obtained in example 1, wherein 1 is a first hydrogel, 2 is a second hydrogel, and 3 is an oriented wrinkle structure;
FIG. 2 is a graph showing the results of the debonding force-displacement of the hydrogel adhesive obtained in example 1;
FIG. 3 is a graph showing a comparison of the work of rupture of the hydrogel adhesive bodies obtained in examples 1 to 5 and comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
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 water-soluble azo initiator V-50, 0.228g of silane coupling agent 3- (trimethoxysilyl) propyl acrylate and 120mL of water to form a precursor solution; irradiating the precursor solution under an ultraviolet lamp for 4min to obtain a polymerization solution;
(2) spin-coating the polymeric solution obtained in the step (1) on an organic glass plate, and controlling the spin-coating rotation speed to be 1000rpm and the spin-coating time to be 50s to obtain a pre-polymerized film;
(3) placing the pre-polymerized film obtained in the step (2) in HCl solution with the pH value of 3.5 for 5min to complete crosslinking; then the sample is dried in an oven at 65 ℃ for 3h to obtain the PAAc-co-PAAm hydrogel adhesive tape with the thickness of 5 μm.
The first hydrogel and the second hydrogel according to the following examples and comparative examples of the present invention were each a polyacrylamide (PAAm) hydrogel, and were prepared as follows: uniformly mixing 8.53g of acrylamide, 0.0074g of methylene bisacrylamide, 0.32g of alpha-ketoglutaric acid and 60mL of water to form a precursor solution, and irradiating the precursor solution under an ultraviolet lamp for 1h to obtain the polyacrylamide (PAAm) hydrogel.
Example 1
A hydrogel bonding method specifically comprises the following steps:
(1) respectively carrying out uniaxial stretching and fixing on the first hydrogel and the second hydrogel, wherein the stretching ratios of the uniaxial stretching are both 3, so as to obtain a stretched first hydrogel and a stretched second hydrogel;
(2) and (2) respectively attaching the stretched first hydrogel and the stretched second hydrogel obtained in the step (1) to two surfaces of a dried hydrogel tape (provided in preparation example 1), so that the dried hydrogel tape absorbs water to swell, and releasing the stretched first hydrogel and the stretched second hydrogel to restore the original shape to obtain a hydrogel adhesive body with an oriented wrinkle structure.
Fig. 1 is a schematic structural view of the hydrogel adhesive body having an oriented wrinkle structure obtained in this example, in which 1-first hydrogel, 2-second hydrogel, and 3-oriented wrinkle structure are shown.
The hydrogel adhesive prepared in this example was subjected to debonding by the following method:
either the first hydrogel or the second hydrogel in the hydrogel adhesive is stretched at a stretch ratio of 5, and the other hydrogel is peeled off to debond the first hydrogel and the second hydrogel.
The force-displacement curve during the debonding process was measured by uniaxial stretching, which was performed using a universal material testing machine at a constant stretching speed of 60 mm.min-1The resulting debonding force-displacement results are shown in FIG. 2, and it is understood from FIG. 2 that, when debonding is performed as needed, one of the hydrogels is stretched 4 times (stretch ratio 5, λ)app5), namely, the two hydrogels can be peeled off under a small force; if no stretching is performed (lambda)app1), the force and energy required for debonding increases significantly.
Example 2
A method for bonding hydrogels, which is different from example 1 only in that the first hydrogel and the second hydrogel in step (1) each have a draw ratio of 2; the other steps were the same as in example 1, and a hydrogel adhesive body having an oriented wrinkle structure was obtained.
Example 3
A method for bonding hydrogels, which is different from example 1 only in that the first hydrogel and the second hydrogel in step (1) each have a stretch ratio of 4; the other steps were the same as in example 1, and a hydrogel adhesive body having an oriented wrinkle structure was obtained.
Example 4
A method for bonding hydrogels, which is different from example 1 only in that the first hydrogel and the second hydrogel in step (1) each have a draw ratio of 5; the other steps were the same as in example 1, and a hydrogel adhesive body having an oriented wrinkle structure was obtained.
Example 5
A method for bonding hydrogels, which is different from example 1 only in that the first hydrogel and the second hydrogel in step (1) each have a stretch ratio of 6; the other steps were the same as in example 1, and a hydrogel adhesive body having an oriented wrinkle structure was obtained.
Example 6
A hydrogel bonding method specifically comprises the following steps:
(1) uniaxially stretching and fixing the first hydrogel, wherein the stretching magnification of the uniaxial stretching is 3, so as to obtain a stretched first hydrogel;
(2) and (3) respectively attaching the stretched first hydrogel and the second hydrogel (not stretched) obtained in the step (1) to two surfaces of a dried hydrogel tape (provided in preparation example 1), so that the dried hydrogel tape absorbs water to swell, and the stretched first hydrogel is released to recover the original shape, thereby obtaining the hydrogel adhesive body with the oriented wrinkle structure.
Comparative example 1
A hydrogel bonding method specifically comprises the following steps:
the first and second non-stretched hydrogels were attached 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, thereby obtaining a hydrogel adhesive body.
Comparative example 2
A 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 unstretched first hydrogel and the unstretched second hydrogel to the surface of the swollen hydrogel adhesive tape obtained in the step (1) to obtain a hydrogel adhesive body.
Comparative example 3
A method for bonding a hydrogel, which is different from example 1 only in that in step (1), both the first hydrogel and the second hydrogel are subjected to multiaxial stretching and fixed at a stretching ratio of 2; the other steps were the same as in example 1, and a hydrogel adhesive body having a non-oriented wrinkle structure was obtained.
And (3) performance testing:
the fracture work and the bonding strength of the hydrogel bonding bodies provided in the examples 1-6 and the comparative examples 1-3 are tested by a lap joint shearing method, and the specific method comprises the following steps: the hydrogel adhesive bodies are respectively fixed on a clamp of a universal material testing machine for shear type stretching, and the constant shear stretching speed is 60mm & min-1。
The results of the work at break of the hydrogel adhesive bodies obtained in examples 1 to 5 and comparative example 1 were plotted by plotting the stretching ratio of the uniaxial stretching in step (1) as the abscissa and the work at break as the ordinate, as shown in fig. 3. 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, and the obtained hydrogel adhesive had the minimum work of rupture and extremely low adhesive strength; with the increase of the stretching ratio, the breaking work is increased; when the stretching ratio reaches 4, the breaking work is highest, namely the bonding strength and the bonding stability are highest; with further increase of the draw ratio, the work at break no longer increases significantly.
The test results obtained by the above method are shown in table 1.
TABLE 1
Work of rupture (J/m)2) Adhesive 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 is clear from the data in Table 1, in the bonding methods provided in 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 formed an oriented wrinkle structure at various stretching ratios (2, 3, 4, 5 and 6), the work of rupture and bonding strength were high, and strong and tough bonding was formed between the hydrogels, so that the work of rupture of the polyacrylamide hydrogel adhesive was 72 to 130J/m2The adhesive strength is 8.3 to 11.7 kPa. If the hydrogel to be bonded is not stretched and no orientation wrinkle structure is formed at the bonding interface (comparative examples 1 and 2), a high-strength bond cannot be formed; if the first and second hydrogels were both subjected to multiaxial stretching (comparative example 3), a non-oriented wrinkle structure was formed at the bonding interface, and the work of rupture and bonding strength were low, and strong bonding could not be achieved.
The applicant states that the present invention is described in the above examples as a method for adhering a hydrogel, a hydrogel adhesive body and a method for debonding the hydrogel according to the present invention, but the present invention is not limited to the above process steps, i.e., the present invention is not meant to be implemented by relying on the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.

Claims (10)

1. A method for bonding a hydrogel, comprising the steps of:
(1) uniaxially stretching and fixing the first hydrogel to obtain a stretched first hydrogel;
(2) and (2) respectively attaching the stretched first hydrogel and the second hydrogel obtained in the step (1) to two surfaces of a hydrogel adhesive tape, and releasing the stretched first hydrogel to restore the original shape to obtain a hydrogel adhesive body with an oriented wrinkle structure.
2. The bonding method according to claim 1, wherein the first hydrogel and the second hydrogel each independently comprise any one of a polyacrylamide hydrogel, a polyisopropylacrylamide hydrogel, a polyacrylic acid hydrogel, a polypeptide hydrogel, a polysaccharide hydrogel, a polyvinyl alcohol hydrogel, or a polyethylene glycol hydrogel.
3. The bonding method according to claim 1 or 2, wherein the second hydrogel is an unstretched hydrogel or a uniaxially stretched and fixed hydrogel;
preferably, the second hydrogel is a hydrogel which is uniaxially stretched and fixed, and the step (2) of attaching further comprises the step of releasing the second hydrogel to restore the original shape;
preferably, the second hydrogel is a hydrogel that is uniaxially stretched and fixed, and the stretching ratio of the uniaxial stretching is the same as or different from the stretching ratio of the uniaxial stretching in step (1).
4. The bonding method according to claim 1 or 2, wherein the hydrogel tape is a dried hydrogel tape;
preferably, the thickness of the hydrogel adhesive tape is 1-100 μm;
preferably, the material of the hydrogel tape comprises polyacrylic acid or an acrylic acid-acrylamide copolymer.
5. The bonding method according to claim 4, wherein the hydrogel tape is made of acrylic acid-acrylamide copolymer, and the first hydrogel and the second hydrogel are both polyacrylamide hydrogels;
preferably, the hydrogel adhesive 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; coating the polymerization solution on a substrate, and performing crosslinking and drying to obtain the hydrogel adhesive tape;
preferably, the monomer comprises a combination of acrylic acid and acrylamide;
preferably, the molar ratio of the acrylic acid to the acrylamide is (1-5): 1;
preferably, the initiator is a water-soluble initiator, and further preferably a water-soluble photoinitiator;
preferably, the amount of the initiator is 0.025-5% based on 100% of the amount of the monomer;
preferably, the crosslinking agent is a silane coupling agent;
preferably, the amount of the cross-linking agent is 0.01-20% based on 100% of the amount of the monomer;
preferably, the polymerization reaction is carried out under ultraviolet light irradiation;
preferably, the crosslinking is carried out under acidic conditions;
preferably, the pH value of the acidic condition is 2-5;
preferably, the drying temperature is 50-80 ℃.
6. The bonding method according to any one of claims 1 to 5, comprising the steps of:
(1) uniaxially stretching and fixing the first hydrogel to obtain a stretched first hydrogel;
(2) and (2) respectively attaching the stretched first hydrogel obtained in the step (1) and a second hydrogel which is not stretched or is stretched and fixed in a uniaxial manner to two surfaces of a dried hydrogel adhesive tape, so that the dried hydrogel adhesive tape absorbs water to swell, and the stretched hydrogel is released to recover the original shape, thereby obtaining the hydrogel adhesive body with an oriented wrinkle structure.
7. A hydrogel adhesive, comprising a hydrogel tape, and a first hydrogel and a second hydrogel adhered to both surfaces of the hydrogel tape; the hydrogel adhesive body is prepared by the adhesive method according to any one of claims 1 to 6.
8. A method of debonding a hydrogel adhesive according to claim 7, the method comprising: either the first hydrogel or the second hydrogel is stretched and then the other hydrogel is peeled off, debonding the first hydrogel from the second hydrogel.
9. The debonding method according to claim 8, characterized in that the stretch ratio of the stretch is not lower than the stretch ratio of the uniaxial stretch at the time of bonding.
10. Use of a bonding method according to any one of claims 1 to 6 or a debonding method according to claim 8 or 9 in biomaterials.
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