CN113292742A - Preparation method of tough and anti-freezing hydrogel with self-adhesion property - Google Patents
Preparation method of tough and anti-freezing hydrogel with self-adhesion property Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000007710 freezing Methods 0.000 title claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 54
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 53
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 35
- MVBJSQCJPSRKSW-UHFFFAOYSA-N n-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]prop-2-enamide Chemical compound OCC(CO)(CO)NC(=O)C=C MVBJSQCJPSRKSW-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000001678 irradiating effect Effects 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 150000003254 radicals Chemical class 0.000 claims abstract description 4
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims description 23
- 229920001223 polyethylene glycol Polymers 0.000 claims description 23
- 125000004386 diacrylate group Chemical group 0.000 claims description 22
- 230000000977 initiatory effect Effects 0.000 claims description 22
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 16
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 15
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 5
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 claims description 5
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 4
- KHDZXBKJADQNKK-UHFFFAOYSA-N P(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C Chemical compound P(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C KHDZXBKJADQNKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 36
- 238000006116 polymerization reaction Methods 0.000 description 13
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 9
- 238000012377 drug delivery Methods 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 229960003638 dopamine Drugs 0.000 description 5
- 241000237536 Mytilus edulis Species 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 235000020638 mussel Nutrition 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 2
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002385 Sodium hyaluronate Polymers 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229960005274 benzocaine Drugs 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical group C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical group CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000010399 physical interaction Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002635 polyurethane Chemical group 0.000 description 1
- 239000004814 polyurethane Chemical group 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000004537 potential cytotoxicity Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229940010747 sodium hyaluronate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003894 surgical glue Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Classifications
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- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
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- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0014—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
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- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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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
- C08F220/52—Amides or imides
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- C08F220/56—Acrylamide; Methacrylamide
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- 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 discloses a preparation method of tough and anti-freezing hydrogel with self-adhesion, which comprises the following steps: step one, preparing a mixed solvent composed of glycerol and water, wherein the mass fraction of the glycerol in the mixed solvent is 10% -90%; adding an acrylamide comonomer, an N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; and step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, irradiating for a period of time at the temperature of 15-35 ℃ by using a light source corresponding to a photoinitiation system to enable the photoinitiation system to generate free radicals, and carrying out free radical polymerization on the acrylamide comonomer and the N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer until hydrogel is obtained. The hydrogel prepared by the invention has excellent mechanical property and self-adhesion property, and simultaneously has frost resistance.
Description
Technical Field
The invention relates to a preparation method of gel, in particular to a preparation method of tough and anti-freezing hydrogel with self-adhesion.
Background
Self-adhesive hydrogels with high water content and similar structures to natural soft tissues have shown great application prospects as important biomaterials in the fields of surgical sealants, wound dressings, drug delivery, wearable devices, and the like. However, conventional hydrogels have insufficient mechanical properties, lack of viscosity, and many hydrogels have properties that drop dramatically at extreme temperatures, which limits the applications of hydrogels.
In recent years, various hydrogels with self-adhesive properties have been synthesized, including hydrogel of cyanoacrylate group, polyurethane group, polyethylene glycol group, polyvinyl alcohol group and the like, but these hydrogels have problems of low adhesion to moist tissue, poor mechanical properties, high swelling rate, potential cytotoxicity and the like, and the application of the hydrogels is limited. In response to these disadvantages, methods have been proposed to improve the adhesion properties of hydrogels by physical interaction. For example, the roulen group in [ Acs Nano,2017, DOI:10.1021/acsnano.6b05318 (nanoclay-limited dopamine-based polymerized mussel-based adhesives and tough hydrogels) ] discloses an adhesive hydrogel composed of polydopamine, clay, polyacrylamide, which has both good adhesion and excellent mechanical properties, but the mechanical properties decrease at extreme temperatures, and further requires oxidation of dopamine to polydopamine followed by preparation of the hydrogel, which is time-consuming and cumbersome. This group then disclosed the preparation of hydrogels using the process of copolymerizing methacrylamide dopamine (MADA) and 2- (dimethylamino) ethyl methacrylate and forming an interpenetrating network with quaternized chitosan in [ Advanced Functional Materials,2019, DOI:10.1002/adfm.201805964 (mussel inspired contact activity antimicrobial hydrogels with high cell affinity, toughness and recyclability) ], which have good mechanical properties and viscosity but still require multi-step synthesis and are complicated to prepare quaternized chitosan. In addition CaoYIPING et al disclose in [ Macromolecular Rapid Communications,2019, DOI:10.1002/marc.201900450 (mussel inspired flexible, wearable and self-adhesive conductive hydrogel for strain sensors) ] the preparation of strain sensing wearable hydrogel using dopamine functionalized sodium hyaluronate with acrylamide and borax, which has a certain viscosity due to the presence of dopamine catechol groups, but the oxidizing agent usually rapidly oxidizes or crosslinks the catechol groups, resulting in short-term adhesiveness, disposability and limited reusability, in addition mechanical properties are to be improved.
The traditional hydrogel polymerization method mainly focuses on three aspects of ultraviolet polymerization, repeated freeze thawing and thermal polymerization, compared with the traditional hydrogel polymerization method, visible light polymerization has the advantages of safe radiation, high polymerization depth, low equipment price and the like, is applied to the fields of biological medicines, adhesives, digital printing, 3D printing and the like at present, and effectively solves the problems that the traditional hydrogel preparation process is easy to inactivate bioactive composite substances (DNA, protein and the like), has shallow polymerization depth, is polluted by radiation and ozone and the like.
In summary, it remains a challenge to prepare hydrogels with sufficient adhesion and excellent mechanical properties while meeting the requirements of simple and efficient preparation methods.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the tough and anti-freezing hydrogel which has good self-adhesion performance, does not obviously reduce the adhesion performance after being adhered for many times, has excellent mechanical performance, does not obviously reduce the mechanical performance of the hydrogel at extreme temperature, and has self-adhesion, simple and efficient preparation method.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention discloses a preparation method of a tough and anti-freezing hydrogel with self-adhesion, which comprises the following steps:
step one, preparing a mixed solvent composed of glycerol and water, wherein the mass fraction of the glycerol in the mixed solvent is 10% -90%;
adding an acrylamide comonomer, an N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the mass ratio of the total mass of the acrylamide comonomer and the N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer to the mixed solvent is 20-50%, and the ratio of the mass of the N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer to the mass of the total mass of the acrylamide comonomer and the N- [ tri (hydroxymethyl) methyl ] acrylamide (THMA) comonomer is 0.1-0.8; the ratio of the amount of the crosslinking agent to the total amount of N- [ tris (hydroxymethyl) methyl ] acrylamide and acrylamide comonomer is 0.01-0.05;
and step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and irradiating for a period of time at the temperature of 15-35 ℃ by using a light source corresponding to a photoinitiation system to enable the photoinitiation system to generate free radicals, and carrying out free radical polymerization on An Acrylamide (AAM) comonomer and an N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer until hydrogel is obtained.
The invention has the following technical advantages:
1. the hydrogel prepared by the invention has excellent mechanical property and self-adhesion property, has anti-freezing property, and has wide application prospect in the fields of wound dressing, drug delivery, wearable equipment and the like.
2. Visible light (405nm violet light, 420nm violet light, 450nm blue light, 532nm green light, 780nm femtosecond laser, 800nm femtosecond laser) which is low in energy and friendly to human is used.
3. The method adopts a one-step method to prepare the hydrogel, and is simple and efficient.
4. According to the invention, acrylamide and N- [ tri (hydroxymethyl) methyl ] acrylamide are used as comonomers, and the prepared hydrogel has self-adhesion performance, toughness, freezing resistance and self-repairing capability.
Detailed Description
The following embodiments of the present invention are described in detail, which are only preferred examples, and the present invention is implemented on the premise of the technical solution of the present invention, and detailed implementation and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.
The invention discloses a preparation method of a tough and anti-freezing hydrogel with self-adhesion, which comprises the following steps:
preparing a mixed solvent consisting of Glycerol (Glycerol) and water (deinized water), wherein the mass fraction of the Glycerol in the mixed solvent is 10-90%;
adding An Acrylamide (AAM) comonomer, an N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the mass ratio of the total mass of the acrylamide (AAM) comonomer and the N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer to the mixed solvent is 20-50%, and the ratio of the mass of the N- [ tris (hydroxymethyl) methyl ] acrylamide comonomer to the mass of the total mass of the acrylamide (AAM) comonomer and the N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer is 0.1-0.8; the amount of the cross-linking agent is 0.01 to 0.05 in terms of the amount of the sum of the acrylamide (AAM) comonomer and the N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer. The photoinitiator system is one of green, blue, purple and femtosecond laser initiation systems.
And step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and using a light source corresponding to a photoinitiation system at the temperature of 15-35 ℃. Irradiating for a period of time to enable the photoinitiation system to generate free radicals, and carrying out free radical polymerization reaction on An Acrylamide (AAM) comonomer and an N- [ tri (hydroxymethyl) methyl ] acrylamide (THMA) comonomer until hydrogel is obtained.
The photoinitiation system is a green light initiation system consisting of Eosin (EY), diphenyliodonium hexafluorophosphate (DPI) and Triethanolamine (TEOA), wherein the mass ratio of the eosin to the mixed solvent is 0.0175-0.070%, the mass ratio of the diphenyliodonium hexafluorophosphate to the mixed solvent is 0.04-0.86%, the mass ratio of the triethanolamine to the mixed solvent is 0.25-1%, the light source adopted in the third step is an LED, the wavelength range is 532nm, and the power density is 2-100 mW/cm2The irradiation time is 12 s-80 min;the cross-linking agent is polyethylene glycol diacrylate (PEGDA) or N, N-methylene Bisacrylamide (BIS), and EY is water-soluble. Preferably, the molecular weight of PEGDA is PEGDA-400. The PEGDA-400 has good water solubility and biocompatibility, and can be subjected to polymerization reaction by using a simple photoinitiation system, thereby being beneficial to efficiently preparing hydrogel.
In a second embodiment of the present invention, the photo-initiation system is a blue light-initiation system comprising Camphorquinone (CQ) and diphenyliodonium hexafluorophosphate (DPI), wherein the mass ratio of camphorquinone to mixed solvent is 0.12% to 1.30%, and the mass ratio of diphenyliodonium hexafluorophosphate to mixed solvent is 0.10 to 0.86%. The light source adopted in the third step is an LED, the wavelength is 450nm, and the power density is 5-100mW/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate (PEGDA) or N, N-methylene Bisacrylamide (BIS). Preferably, the molecular weight of PEGDA is PEGDA-400. The PEGDA-400 has good water solubility and biocompatibility, and can be subjected to polymerization reaction by using a simple photoinitiation system, thereby being beneficial to efficiently preparing hydrogel.
As a third embodiment of the invention, the photoinitiation system is a blue light initiation system consisting of Camphorquinone (CQ) and Ethyl Dimethylaminobenzoate (EDAB), wherein the mass ratio of the camphorquinone to the mixed solvent is 0.12-1.30%, the mass ratio of the ethyl dimethylaminobenzoate to the mixed solvent is 0.1-0.80%, the light source adopted in the third step is an LED, the wavelength is 450nm, and the power density is 5-100mW/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate (PEGDA) or N, N-methylene Bisacrylamide (BIS). Preferably, the molecular weight of PEGDA is PEGDA-400. The PEGDA-400 has good water solubility and biocompatibility, and can be subjected to polymerization reaction by using a simple photoinitiation system, thereby being beneficial to efficiently preparing hydrogel.
As a fourth embodiment of the invention, the photoinitiation system is a violet photoinitiation system consisting of Isopropyl Thioxanthone (ITX) and ethyl p-dimethylaminobenzoate (EDAB), wherein the mass of the isopropyl thioxanthone and the mixed solvent isThe weight ratio of p-dimethyl ethyl aminobenzoate to mixed solvent is 0.02-0.35%, the light source adopted in the third step is an LED, the wavelength is 420nm, and the power density is 2-60mW/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate (PEGDA) or N, N-methylene Bisacrylamide (BIS). Preferably, the molecular weight of PEGDA is PEGDA-400. The PEGDA-400 has good water solubility and biocompatibility, and can be subjected to polymerization reaction by using a simple photoinitiation system, thereby being beneficial to efficiently preparing hydrogel.
As a fifth embodiment of the present invention, the photoinitiation system is a phenyl-2, 4, 6-trimethylbenzoyllithium phosphite (LAP) violet photoinitiation system, wherein the mass ratio of the phenyl-2, 4, 6-trimethylbenzoyllithium phosphite to the mixed solvent is 0.05% -2.00%, the light source adopted in the third step is an LED, the wavelength is 405nm, and the power density is 5-100W/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate (PEGDA) or N, N-methylene Bisacrylamide (BIS). Preferably, the molecular weight of PEGDA is PEGDA-400. The PEGDA-400 has good water solubility and biocompatibility, and can be subjected to polymerization reaction by using a simple photoinitiation system, thereby being beneficial to efficiently preparing hydrogel.
In a sixth embodiment of the present invention, the photo-initiation system is Isopropyl Thioxanthone (ITX) femtosecond laser initiation system, wherein the mass ratio of isopropyl thioxanthone to mixed solvent is 0.5% -6%, the light source used in the third step is femtosecond laser with a wavelength of 780nm and a power density of 5-100W/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate (PEGDA) or N, N-methylene Bisacrylamide (BIS). Preferably, the molecular weight of PEGDA is PEGDA-400. The PEGDA-400 has good water solubility and biocompatibility, and can be subjected to polymerization reaction by using a simple photoinitiation system, thereby being beneficial to efficiently preparing hydrogel.
As a seventh embodiment of the present invention, the photoinitiation system is 2, 4, 6-trimethylbenzoylphenylphosphonic acid ethyl ester
An initiating system, wherein the mass ratio of the 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate to the mixed solvent is 0.05-5%, the light source adopted in the third step is femtosecond laser, the wavelength is 800nm, and the power density is 5-100W/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate (PEGDA) or N, N-methylene Bisacrylamide (BIS). Preferably, the molecular weight of PEGDA is PEGDA-400. The PEGDA-400 has good water solubility and biocompatibility, and can be subjected to polymerization reaction by using a simple photoinitiation system, thereby being beneficial to efficiently preparing hydrogel. The chemical molecular formula of the preparation material of the hydrogel in the method is as follows:
THMA/AAM/TEOA/PEGDA/DPI/EosinY/
TPO-L/ITX/CQ/EDAB/LA P/BIS
example 1
Preparing a mixed solvent consisting of Glycerol (Glycerol) and water (deinized water);
adding An Acrylamide (AAM) comonomer, an N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the photoinitiation system is a green light initiation system consisting of eosin (water-soluble EY), diphenyliodonium hexafluorophosphate (DPI) and Triethanolamine (TEOA). The cross-linking agent is polyethylene glycol diacrylate (PEGDA-400) or N, N-methylene Bisacrylamide (BIS).
And step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and irradiating for a certain time by using LED light sources with different power densities and wavelength ranges of 532nm at different temperatures of 15-35 ℃.
The above methodThe proportions of the components in the steps of the process and the experimental parameters are shown in the following table, wherein m is mGlycerol+mDeionized water，n＝nAAM+nTHMA：
The obtained hydrogel is transparent, has excellent mechanical property and viscosity, keeps stable mechanical property at extreme temperature, and has wide application prospect in the fields of wound dressing, drug delivery, wearable equipment and the like.
Example 2
Step one, preparing a mixed solvent consisting of glycerol and water;
adding An Acrylamide (AAM) comonomer, an N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the light initiation system is a blue light initiation system consisting of Camphorquinone (CQ) and diphenyliodonium hexafluorophosphate (DPI). The cross-linking agent is polyethylene glycol diacrylate (PEGDA-400) or N, N-methylene Bisacrylamide (BIS).
And step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and irradiating for a period of time by using LED light sources with the wavelength of 450nm and different power densities at different temperatures of 15-35 ℃.
The proportions of the components and experimental parameters in the steps of the method are shown in the following table, wherein m is mGlycerol+mDeionized water，n＝nAAM+nTHMA：
The obtained hydrogel is transparent, has excellent mechanical property and viscosity, keeps stable mechanical property at extreme temperature, and has wide application prospect in the fields of wound dressing, drug delivery, wearable equipment and the like.
Example 3
Step one, preparing a mixed solvent consisting of glycerol and water;
adding An Acrylamide (AAM) comonomer, an N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the light initiation system is a blue light initiation system consisting of Camphorquinone (CQ) and Ethyl Dimethylaminobenzoate (EDAB). The cross-linking agent is polyethylene glycol diacrylate (PEGDA-400) or N, N-methylene Bisacrylamide (BIS).
And step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and irradiating for a period of time by using LED light sources with the wavelength of 450nm and different power densities at different temperatures of 15-35 ℃.
The proportions of the components and experimental parameters in the steps of the method are shown in the following table, wherein m is mGlycerol+mDeionized water，n＝nAAM+nTHMA：
The obtained hydrogel is transparent, has excellent mechanical property and viscosity, keeps stable mechanical property at extreme temperature, and has wide application prospect in the fields of wound dressing, drug delivery, wearable equipment and the like.
Example 4
Step one, preparing a mixed solvent consisting of glycerol and water;
adding An Acrylamide (AAM) comonomer, an N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the light initiation system is a violet light initiation system consisting of Isopropyl Thioxanthone (ITX) and ethyl p-dimethylaminobenzoate (EDAB). The cross-linking agent is polyethylene glycol diacrylate (PEGDA-400) or N, N-methylene Bisacrylamide (BIS).
And step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and irradiating for a period of time by using LED light sources with different power densities and wavelengths of 420nm at different temperatures of 15-35 ℃.
The proportions of the components and experimental parameters in the steps of the method are shown in the following table, wherein m is mGlycerol+mDeionized water，n＝nAAM+nTHMA：
The obtained hydrogel is transparent, has excellent mechanical property and viscosity, keeps stable mechanical property at extreme temperature, and has wide application prospect in the fields of wound dressing, drug delivery, wearable equipment and the like.
Example 5
Step one, preparing a mixed solvent consisting of glycerol and water;
adding An Acrylamide (AAM) comonomer, an N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the photoinitiation system is a violet photoinitiation system consisting of phenyl-2, 4, 6-trimethyl benzoyl lithium phosphite (LAP). The cross-linking agent is polyethylene glycol diacrylate (PEGDA-400) or N, N-methylene Bisacrylamide (BIS).
And step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and irradiating for a period of time by using LED light sources with the wavelength of 405nm and different power densities at different temperatures of 15-35 ℃.
The proportions of the components and experimental parameters in the steps of the method are shown in the following table, wherein m is mGlycerol+mDeionized water，n＝nAAM+nTHMA：
The obtained hydrogel is transparent, has excellent mechanical property and viscosity, keeps stable mechanical property at extreme temperature, and has wide application prospect in the fields of wound dressing, drug delivery, wearable equipment and the like.
Example 6
Step one, preparing a mixed solvent consisting of glycerol and water;
adding An Acrylamide (AAM) comonomer, an N- [ tris (hydroxymethyl) methyl ] acrylamide (THMA) comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the photoinitiation system is an Isopropyl Thioxanthone (ITX) femtosecond laser initiation system, wherein the mass ratio of the isopropyl thioxanthone to the mixed solvent is 0.5-6%. The cross-linking agent is polyethylene glycol diacrylate (PEGDA-400) or N, N-methylene Bisacrylamide (BIS).
And step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and irradiating for a period of time by using femtosecond laser with the wavelength of 780nm and light sources at different power densities at different temperatures of 15-35 ℃.
The proportions of the components and experimental parameters in the steps of the method are shown in the following table, wherein m is mGlycerol+mDeionized water，n＝nAAM+nTHMA：
The obtained hydrogel is transparent, has excellent mechanical property and viscosity, keeps stable mechanical property at extreme temperature, and has wide application prospect in the fields of wound dressing, drug delivery, wearable equipment and the like.
Example 7
Step one, preparing a mixed solvent consisting of glycerol and water;
step two, acrylamide (AAM) comonomer, N- [ tri (hydroxymethyl) methyl]Adding acrylamide (THMA) comonomer, cross-linking agent and photoinitiation system into the mixture in the first stepIn the solvent, stirring in dark to form precursor solution; the photoinitiation system is 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate
The initiating system comprises 0.05-5% of 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate and a mixed solvent by mass. The cross-linking agent is polyethylene glycol diacrylate (PEGDA-400) or N, N-methylene Bisacrylamide (BIS).
And step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, and irradiating for a period of time by using a femtosecond laser with the wavelength of 800nm and a light source under different power densities at different temperatures of 15-35 ℃.
The proportions of the components and experimental parameters in the steps of the method are shown in the following table, wherein m is mGlycerol+mDeionized water，n＝nAAM+nTHMA：
The obtained hydrogel is transparent, has excellent mechanical property and viscosity, keeps stable mechanical property at extreme temperature, and has wide application prospect in the fields of wound dressing, drug delivery, wearable equipment and the like.
Claims (10)
1. A preparation method of tough and anti-freezing hydrogel with self-adhesion is characterized by comprising the following steps:
step one, preparing a mixed solvent composed of glycerol and water, wherein the mass fraction of the glycerol in the mixed solvent is 10% -90%;
adding an acrylamide comonomer, an N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer, a cross-linking agent and a photoinitiation system into the mixed solvent in the step one, and stirring in a dark place to form a precursor solution; the mass ratio of the total mass of the acrylamide comonomer and the N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer to the mixed solvent is 20-50%, and the ratio of the amount of the N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer to the amount of the total mass of the acrylamide comonomer and the N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer is 0.1-0.8; the ratio of the amount of the crosslinking agent to the total amount of N- [ tris (hydroxymethyl) methyl ] acrylamide and acrylamide comonomer is 0.01-0.05;
and step three, placing the precursor solution in the step two in a polytetrafluoroethylene mold, irradiating for a period of time at the temperature of 15-35 ℃ by using a light source corresponding to a photoinitiation system to enable the photoinitiation system to generate free radicals, and carrying out free radical polymerization on the acrylamide comonomer and the N- [ tri (hydroxymethyl) methyl ] acrylamide comonomer until hydrogel is obtained.
2. The method of preparing a tough, freeze resistant hydrogel with self adhesion properties according to claim 1, characterized in that: the photoinitiator system is one of green, blue, purple and femtosecond laser initiation systems.
3. The method of preparing a tough, freeze resistant hydrogel with self adhesion properties according to claim 2, characterized in that: the photoinitiation system is a green light initiation system consisting of eosin, diphenyliodonium hexafluorophosphate and triethanolamine, wherein the mass ratio of the eosin to the mixed solvent is 0.0175-0.070%, the mass ratio of the diphenyliodonium hexafluorophosphate to the mixed solvent is 0.04-0.86%, the mass ratio of the triethanolamine to the mixed solvent is 0.25-1%, the light source adopted in the third step is an LED, the wavelength range is 530-540nm, and the power density is 2-100 mw/cm2The irradiation time is 12 s-80 min; the cross-linking agent is polyethylene glycol diacrylate or N, N-methylene bisacrylamide.
4. The method of preparing a tough, freeze resistant hydrogel with self adhesion properties according to claim 2, characterized in that: the light initiation system is a blue light initiation system consisting of camphorquinone and diphenyliodonium hexafluorophosphate, wherein the mass ratio of the camphorquinone to the mixed solvent is 012% -1.30%, the mass ratio of the diphenyl iodonium hexafluorophosphate to the mixed solvent is 0.10-0.86%, the light source adopted in the third step is an LED, the wavelength is 450nm, and the power density is 5-100mW/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate or N, N-methylene bisacrylamide.
5. The method of preparing a tough, freeze resistant hydrogel with self adhesion properties according to claim 2, characterized in that: the light initiation system is a blue light initiation system consisting of camphorquinone and ethyl dimethylaminobenzoate, wherein the mass ratio of the camphorquinone to the mixed solvent is 0.12-1.30%, the mass ratio of the ethyl dimethylaminobenzoate to the mixed solvent is 0.1-0.80%, the light source adopted in the third step is an LED, the wavelength is 450nm, and the power density is 5-100mW/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate or N, N-methylene bisacrylamide.
6. The method of preparing a tough, freeze resistant hydrogel with self adhesion properties according to claim 2, characterized in that: the photo-initiation system is a violet photo-initiation system consisting of isopropyl thioxanthone and ethyl p-dimethylaminobenzoate, wherein the mass ratio of the isopropyl thioxanthone to the mixed solvent is 0.05-0.50%, the mass ratio of the ethyl p-dimethylaminobenzoate to the mixed solvent is 0.02-0.35%, the light source adopted in the third step is an LED, the wavelength is 420nm, and the power density is 2-60mW/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate or N, N-methylene bisacrylamide.
7. The method of preparing a tough, freeze resistant hydrogel with self adhesion properties according to claim 2, characterized in that: the photoinitiation system is a phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite purple photoinitiation system, wherein the mass ratio of the phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite to the mixed solvent is 0.05-2.00 percent, and the photoinitiation system is characterized in thatThe light source adopted in the third step is an LED, the wavelength is 405nm, and the power density is 5-100W/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate or N, N-methylene bisacrylamide.
8. The method of preparing a tough, freeze resistant hydrogel with self adhesion properties according to claim 2, characterized in that: the photoinitiation system is an isopropyl thioxanthone femtosecond laser initiation system, wherein the mass ratio of isopropyl thioxanthone to mixed solvent is 0.5-6%, the light source adopted in the third step is femtosecond laser, the wavelength is 780nm, and the power density is 5-100W/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate or N, N-methylene bisacrylamide.
9. The method of preparing a tough, freeze resistant hydrogel with self adhesion properties according to claim 2, characterized in that: the photoinitiation system is 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate initiation system, wherein the mass ratio of the 2, 4, 6-trimethyl benzoyl phenyl ethyl phosphonate to the mixed solvent is 0.05-5%, the light source adopted in the third step is femtosecond laser, the wavelength is 800nm, and the power density is 5-100W/cm2The irradiation time is 2 min-80 min; the cross-linking agent is polyethylene glycol diacrylate or N, N-methylene bisacrylamide.
10. Process for the preparation of tough, freeze resistant hydrogels with self adhesion properties according to one of claims 1 to 9 characterized by: the molecular weight of the polyethylene glycol diacrylate is PEGDA-400.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114404643A (en) * | 2021-12-24 | 2022-04-29 | 北京积水潭医院 | Tannin in-situ modified zwitterionic polymer medical adhesive and preparation method thereof |
| CN114456313A (en) * | 2021-12-24 | 2022-05-10 | 陕西科技大学 | Zwitterionic polymer hydrogel medical adhesive and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280048A (en) * | 2008-05-23 | 2008-10-08 | 北京联合大学生物化学工程学院 | Transparent aquagel having antibacterial action and preparation thereof |
| CN103864964A (en) * | 2014-02-26 | 2014-06-18 | 天津大学 | Water-soluble two-photon polymerization initiator as well as assembling method and use thereof |
| CN109851817A (en) * | 2019-01-29 | 2019-06-07 | 福建师范大学 | The preparation method of freeze proof/heat-resisting adherency hydrogel of laccol co-crosslinking |
| CN110790863A (en) * | 2019-12-05 | 2020-02-14 | 中国科学院新疆理化技术研究所 | Hydrogel with high transparency and strong acid-base stability |
| CN112142911A (en) * | 2020-09-11 | 2020-12-29 | 西安交通大学 | High-toughness hydrogel based on amino acid acrylamide derivative and preparation method thereof |
-
2021
- 2021-04-20 CN CN202110424953.0A patent/CN113292742A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280048A (en) * | 2008-05-23 | 2008-10-08 | 北京联合大学生物化学工程学院 | Transparent aquagel having antibacterial action and preparation thereof |
| CN103864964A (en) * | 2014-02-26 | 2014-06-18 | 天津大学 | Water-soluble two-photon polymerization initiator as well as assembling method and use thereof |
| CN109851817A (en) * | 2019-01-29 | 2019-06-07 | 福建师范大学 | The preparation method of freeze proof/heat-resisting adherency hydrogel of laccol co-crosslinking |
| CN110790863A (en) * | 2019-12-05 | 2020-02-14 | 中国科学院新疆理化技术研究所 | Hydrogel with high transparency and strong acid-base stability |
| CN112142911A (en) * | 2020-09-11 | 2020-12-29 | 西安交通大学 | High-toughness hydrogel based on amino acid acrylamide derivative and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JING CHEN等: ""An Adhesive Hydrogel with "Load-Sharing" Effect as Tissue Bandages for Drug and Cell Delivery"", 《ADV. MATER.》 * |
| JUNJIE LI等: ""An initiating system with high efficiency for PEGDA photopolymerization at 532nm"", 《JOURNAL OF PHOTOCHEMISTRY & PHOTOBIOLOGY, A: CHEMISTRY》 * |
| 邓琳等: ""UV-LED 光固化体系光引发剂研究新进展"", 《精细化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114404643A (en) * | 2021-12-24 | 2022-04-29 | 北京积水潭医院 | Tannin in-situ modified zwitterionic polymer medical adhesive and preparation method thereof |
| CN114456313A (en) * | 2021-12-24 | 2022-05-10 | 陕西科技大学 | Zwitterionic polymer hydrogel medical adhesive and preparation method thereof |
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