CN115572394A - Hydrogel with high mechanical strength and preparation method thereof - Google Patents
Hydrogel with high mechanical strength and preparation method thereof Download PDFInfo
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- CN115572394A CN115572394A CN202211240070.5A CN202211240070A CN115572394A CN 115572394 A CN115572394 A CN 115572394A CN 202211240070 A CN202211240070 A CN 202211240070A CN 115572394 A CN115572394 A CN 115572394A
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- hydrogel
- laponite
- photoinitiator
- high molecular
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229940094522 laponite Drugs 0.000 claims abstract description 51
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims abstract description 50
- -1 acrylamide-polyethylene Chemical group 0.000 claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229960002317 succinimide Drugs 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 238000000016 photochemical curing Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 108010010803 Gelatin Proteins 0.000 claims description 11
- 239000008273 gelatin Substances 0.000 claims description 11
- 229920000159 gelatin Polymers 0.000 claims description 11
- 235000019322 gelatine Nutrition 0.000 claims description 11
- 235000011852 gelatine desserts Nutrition 0.000 claims description 11
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 229920006158 high molecular weight polymer Polymers 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 35
- 238000006116 polymerization reaction Methods 0.000 abstract description 14
- 239000000499 gel Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 5
- 230000002787 reinforcement Effects 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 241000446313 Lamella Species 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 7
- 229920002521 macromolecule Polymers 0.000 description 6
- 239000003519 biomedical and dental material Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- LNROBZXAGDVENH-UHFFFAOYSA-N CC(C=C1)=C(C)C(C)=C1C(P(O)(O)O)=O Chemical compound CC(C=C1)=C(C)C(C)=C1C(P(O)(O)O)=O LNROBZXAGDVENH-UHFFFAOYSA-N 0.000 description 1
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 1
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 1
- 241000761557 Lamina Species 0.000 description 1
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000002744 extracellular matrix Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- 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
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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
- A61L26/0004—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing inorganic materials
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- A—HUMAN NECESSITIES
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- 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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- 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
- A61L26/0019—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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- 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
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- 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
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- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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Abstract
The invention relates to the technical field of hydrogel materials, in particular to a hydrogel with high mechanical strength and a preparation method thereof. The raw materials of the hydrogel comprise high molecular polymer, acrylamide-polyethylene glycol-succinimide acetate, laponite, photoinitiator and water; the side chain of the high molecular polymer contains an amino group. The invention adopts the unique multifunctional monomer acrylamide-polyethylene glycol-succinimide acetate, the multifunctional monomer can smoothly enter interlamination in the laponite and is combined with the laponite through polymerization with the laponite, and simultaneously, the other end of the multifunctional monomer can be chemically combined with the amino of the other high molecular polymer side chain to form a chemical bond, so that the three are chemically bonded together. And the distance between the laponite layers is increased, so that the high molecular polymer can smoothly enter the interlamination of the laponite and is dispersed in the laponite lamellar structure, and the reinforcement of the laponite to the gel structure can be realized.
Description
Technical Field
The invention relates to the technical field of hydrogel materials, in particular to a hydrogel with high mechanical strength and a preparation method thereof.
Background
A hydrogel is a flexible material consisting of a three-dimensionally crosslinked polymer network and a large amount of water. The hydrogel has biocompatibility and flexibility, and can show mechanical properties and physiological properties similar to those of human skin and various organs. The hydrogel is similar to the extracellular matrix part in nature, and can reduce friction and mechanical action on surrounding tissues after absorbing water, thereby obviously improving the biological performance of the material. Thus, many natural hydrogels and synthetic hydrogels are applicable to tissue engineering and regenerative medicine. The mechanical strength of the hydrogel is one of the important performance indexes of the hydrogel as a biomedical material, however, the general hydrogel material has some defects, which limit the practical application thereof, and the performance of the hydrogel needs to be further improved, such as: 1) Most of the gel has insufficient mechanical properties (modulus, strength, fracture energy and the like), is easy to fracture when stretched, and cannot meet the requirements of load flexible devices; 2) It is difficult to recover the original shape after repeated stretching cycles; 3) The hydrogel with certain mechanical strength formed by monomer polymerization has the problems of monomer residue and the like, and has limited biocompatibility.
Researchers have proposed a number of methods to improve the mechanical strength (toughness) of hydrogels, such as adding nanomaterials to hydrogels, or by structural design, providing interpenetrating network structures or double network structures to improve their mechanical properties. These systems are chemically synthesized hydrogel materials formed by polymerization reactions, and these polymerization systems generally include monomers, cross-linking agents, initiators, reinforcing agents, conductive substances, and the like. In the polymerization of this system, the monomer is liable to react incompletely, so that the gel contains residual monomers, crosslinking agents and the like, and when the gel is used as a biomedical material, the gel needs to be in contact with the skin surface of a human body, and the user may be irritated or sensitized.
The monomer residual rate of the polymerized gel is reduced and the comprehensive performance is kept excellent, which needs advanced polymerization technology, and the residual of small molecules such as monomers cannot be avoided by 100%. The hydrogel material which can not contain micromolecular monomers and the like can be prepared by adopting polymerization among macromolecules, but the hydrogel is directly prepared by macromolecular substances, the difficulty in improving the mechanical property is higher than that of a micromolecular monomer polymerization system, and the system for preparing the high-performance hydrogel with high mechanical property and high transparency by macromolecular polymerization is still less.
Therefore, it is urgently needed to provide a hydrogel with high mechanical strength and no small molecules and a preparation method thereof, so that the hydrogel has good biocompatibility and mechanical properties, and an excellent hydrogel biomedical material is developed.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the patent provides a hydrogel with high mechanical strength and without containing small molecular monomers and a preparation method thereof.
The invention conception of the invention is as follows: the method adopts a unique multifunctional monomer acrylamide-polyethylene glycol-succinimide acetate, the multifunctional monomer can smoothly enter into the middle lamella layer of the Laponite and is combined with the Laponite through polymerization with the Laponite, and meanwhile, the other end of the multifunctional monomer can be chemically combined with the amino of the side chain of another macromonomer (high molecular polymer) to form a chemical bond, so that the multifunctional monomer acrylamide-polyethylene glycol-succinimide acetate chemically bonds the Laponite and the Laponite. And the distance between the Laponite lamella is increased, so that the high molecular polymer can smoothly enter the Laponite middle lamella layer and is dispersed in the Laponite lamella structure, and the reinforcement of the Laponite to the gel structure can be realized.
The first aspect of the invention provides a hydrogel with high mechanical strength, wherein the raw materials of the hydrogel comprise high molecular polymer, acrylamide-polyethylene glycol-succinimide acetate, laponite, photoinitiator and water; the high molecular polymer contains a side chain, and the side chain contains an amino group.
Preferably, the laponite is nano laponite.
Preferably, the relative molecular mass of the acrylamide-polyethylene glycol-succinimide acetate is 1000-40000; further preferably, the relative molecular mass of the acrylamide-polyethylene glycol-succinimide acetate is 1000-20000; acrylamide-polyethylene glycol-succinimidyl acetate having a double bond at one end and Succinimidyl Carboxymethyl (SCM) ester at one end; acrylamide-polyethylene glycol-succinimide acetate is a macromolecular monomer based on PEG modification, and has the unique functions of linking with nano-laponite and high polymer materials containing amino to realize the interaction between macromolecules and avoid the use of micromolecular monomers and micromolecular cross-linking agents.
Preferably, the high molecular polymer comprises at least one of gelatin, chitosan and polyvinylamine.
Preferably, the chitosan is chitosan.
Preferably, the relative molecular mass of the high molecular polymer is 10 4 -10 6 。
Preferably, the photoinitiator comprises at least one of photoinitiator 184 (1-hydroxy-cyclohexyl-benzophenone), photoinitiator LAP (phenyl-2,4,6-lithium trimethylbenzoylphosphite), and photoinitiator 2959 (2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone).
Preferably, the hydrogel comprises the following raw materials, by weight, 1-20 parts of a high molecular polymer, 1-20 parts of acrylamide-polyethylene glycol-succinimide acetate, 0.5-10 parts of laponite, 0.05-1 part of a photoinitiator and 49-97.45 parts of water; more preferably, the hydrogel comprises, by weight, 5-15 parts of a high molecular polymer, 5-15 parts of acrylamide-polyethylene glycol-succinimide acetate, 1-7 parts of laponite, 0.1-0.5 part of a photoinitiator, and 62.5-88.9 parts of water.
Preferably, the hydrogel has a light transmittance of greater than 95%; more preferably, the hydrogel has a light transmittance of 97% or more.
Preferably, the hydrogel has an elongation at break of 800 to 1600%; further preferably, the hydrogel has an elongation at break of 850 to 1550%.
Preferably, the hydrogel has an elastic modulus of 1.2 to 1.7; further preferably, the hydrogel has an elastic modulus of 1.4 to 1.6.
The hydrogel provided by the first aspect of the invention has the following beneficial effects: laponite is a type of hydrogel mechanical (tensile) performance enhancer with a lamellar structure. Macromolecular substances with larger molecular weight are difficult to enter between the laminas of the Laponite, so that the Laponite which can be used for reinforcing small molecular monomers such as acrylamide and the like is difficult to realize the reinforcement by using the macromolecular monomers. The invention adopts the unique multifunctional monomer acrylamide-polyethylene glycol-succinimide acetate, the multifunctional monomer can smoothly enter the interlamination of the Laponite, and is combined with the Laponite through polymerization with the Laponite, and simultaneously, the other end of the multifunctional monomer can be chemically combined with the amino of the other high molecular polymer side chain to form a chemical bond, so that the three are chemically bonded together. And the spacing between the Laponite lamella is increased, so that the high molecular polymer can smoothly enter the Laponite middle lamella and disperse in the Laponite lamella structure, and the reinforcement of the Laponite to the gel structure can be realized.
A second aspect of the present invention provides a method for producing the hydrogel, the method comprising the steps of:
(1) Dissolving the laponite in water to prepare a solution A;
(2) Respectively adding the photoinitiator and the acrylamide-polyethylene glycol-succinimide acetate into the solution A, and dissolving to obtain a solution B;
(3) Dissolving the high molecular polymer in the solution B to prepare a solution C;
(4) And carrying out photocuring on the solution C to prepare the hydrogel.
Preferably, the photo-curing is ultraviolet light curing.
Preferably, the instrument used for light curing is a UV-LED light curing machine.
Preferably, the light-cured light reaction wavelength is 25-50nm; further preferably, the light-cured photoreaction wavelength is 30-40nm; still more preferably, the photoreaction wavelength of the photocuring is 35nm.
Preferably, the dissolving temperature is 20-40 ℃; further preferably, the dissolving temperature is 20-30 ℃; even more preferably, the temperature of dissolution is 25 ℃.
Preferably, the reaction temperature of the photocuring is 20-40 ℃; further preferably, the reaction temperature of the photocuring is 20-30 ℃; still more preferably, the reaction temperature of the photocuring is 25 ℃.
Preferably, the photo-curing reaction kettle is a polytetrafluoroethylene mold or a glass vessel.
A third aspect of the invention provides a dressing comprising the hydrogel.
A fourth aspect of the invention provides a wound packing product comprising the hydrogel.
Preferably, the wound packing product is a wound patch, bandage, gauze or dressing patch.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the unique multifunctional monomer acrylamide-polyethylene glycol-succinimide acetate, the multifunctional monomer can smoothly enter the interlamination of the Laponite, and is combined with the Laponite through polymerization with the Laponite, and simultaneously, the other end of the multifunctional monomer can be chemically combined with the amino of the other high molecular polymer side chain to form a chemical bond, so that the three are chemically bonded together. And the spacing of the Laponite lamella is increased, so that the high molecular polymer can smoothly enter the Laponite middle lamella and disperse in the Laponite lamella structure, and the reinforcement of the Laponite to the gel structure can be realized; the prepared conductive hydrogel has the advantages of no small molecular monomer residue, good safety, high tensile strength, high mechanical strength, high transparency and the like;
(2) The high molecular polymer is used as a reaction monomer, the high molecular polymer can be used as a cross-linking agent, and the system does not need to use a small molecular cross-linking agent, so that the problem of small molecular monomer and cross-linking agent residue is avoided after the polymerization reaction is finished. The common small molecule monomer is acrylic acid, acrylamide and other substances, the small molecule cross-linking agent is N, N' -methylene bisacrylamide, PEGDA and the like, the small molecules have certain toxicity, and the small molecule monomer residue is inevitably caused if the small molecule substances are adopted and further purification treatment after polymerization is not carried out. The invention adopts high molecular polymer as reaction monomer, which can effectively avoid the problem, and the raw materials adopted by the system are all commercial raw materials.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples can be prepared from conventional commercial sources or can be prepared by known methods, unless otherwise specified.
Example 1
A hydrogel 1 with high mechanical strength is prepared by the following steps:
(1) Weighing 0.5 g of nano Laponite, dissolving in 97.45 g of deionized water, and stirring to form a transparent solution A;
(2) Sequentially adding 1g of acrylamide-polyethylene glycol-succinimide acetate and 0.05g of photoinitiator (photoinitiator 184) into the solution A, and stirring to form a transparent solution B;
(3) Weighing 0.5 g of chitosan, and dissolving the chitosan in the solution B to prepare a transparent solution C;
(4) And (3) putting the transparent solution C into a polytetrafluoroethylene mold, carrying out photocuring reaction in a UV-LED photocuring machine at the wavelength of 35nm and the temperature of 25 ℃, and taking out the mold after ten minutes to prepare the hydrogel 1.
Example 2
A hydrogel 2 with high mechanical strength is prepared by the following steps:
(1) Weighing 10 g of nano Laponite, dissolving in 49 g of deionized water, and stirring to form a transparent solution A;
(2) Sequentially adding 20g of acrylamide-polyethylene glycol-succinimide acetate and 1g of photoinitiator (photoinitiator LAP) into the solution A, and stirring to form a transparent solution B;
(3) Weighing 20g of vinylamine, and dissolving the vinylamine in the solution B to prepare a transparent solution C;
(4) And (3) putting the transparent solution C into a polytetrafluoroethylene mold, carrying out photocuring reaction in a UV-LED photocuring machine at the wavelength of 35nm and the temperature of 25 ℃, and taking out the mold after ten minutes to prepare the hydrogel 2.
Example 3
A hydrogel 3 with high mechanical strength is prepared by the following steps:
(1) Weighing 3 g of nano Laponite, dissolving in 66.9 g of deionized water, and stirring to form a transparent solution A;
(2) Sequentially adding 20g of acrylamide-polyethylene glycol-succinimide acetate and 0.1g of photoinitiator (photoinitiator 2959) into the solution A, and stirring to form a transparent solution B;
(3) Weighing 10 g of gelatin, and dissolving the gelatin in the solution B to prepare a transparent solution C;
(4) And (3) putting the transparent solution C into a polytetrafluoroethylene mold, carrying out photocuring reaction in a UV-LED photocuring machine at the wavelength of 35nm and the temperature of 25 ℃, and taking out the mold after ten minutes to prepare the hydrogel 3.
Comparative example 1
A hydrogel 4 (without acrylamide-polyethylene glycol-succinimide acetate) is prepared by the following steps:
(1) Weighing 3 g of nano Laponite, dissolving in 86.9 g of deionized water, and stirring to form a transparent solution A;
(2) Adding 0.1g of photoinitiator (photoinitiator 2959) into the solution A, and stirring to form a transparent solution B;
(3) Weighing 10 g of gelatin, and dissolving the gelatin in the solution B to prepare a transparent solution C;
(4) And (3) putting the transparent solution C into a polytetrafluoroethylene mold, carrying out photocuring reaction in a UV-LED photocuring machine at the wavelength of 35nm and the temperature of 25 ℃, and taking out the mold after ten minutes to prepare the hydrogel 4.
Comparative example 2
A hydrogel 5 (replacing acrylamide-polyethylene glycol-succinimide acetate with GelMa) is prepared by the following steps:
(1) Weighing 3 g of nano Laponite, dissolving in 66.9 g of deionized water, and stirring to form a transparent solution A;
(2) Adding 20g of GelMa and 0.1g of photoinitiator (2959) into the solution A in sequence, and stirring to form a transparent solution B;
(3) Weighing 10 g of gelatin, and dissolving the gelatin in the solution B to prepare a transparent solution C;
(4) And (3) putting the transparent solution C into a polytetrafluoroethylene mold, carrying out photocuring reaction in a UV-LED photocuring machine at the wavelength of 35nm and the temperature of 25 ℃, and taking out the mold after ten minutes to prepare the hydrogel 5.
Comparative example 3
A hydrogel 6 (replacing acrylamide-polyethylene glycol-succinimide acetate with diacrylate polyethylene glycol with molecular weight more than 1 k) is prepared by the following steps:
(1) Weighing 3 g of nano Laponite, dissolving in 66.9 g of deionized water, and stirring to form a transparent solution A;
(2) Sequentially adding 20g of diacrylate polyethylene glycol and 0.1g of photoinitiator (2959) into the solution A, and stirring to form a transparent solution B;
(3) Weighing 10 g of gelatin, and dissolving the gelatin in the solution B to prepare a transparent solution C;
(4) And (3) putting the transparent solution C into a polytetrafluoroethylene mold, carrying out photocuring reaction in a UV-LED photocuring machine at the wavelength of 35nm and the temperature of 25 ℃, and taking out the mold after ten minutes to prepare the hydrogel 6.
Comparative example 4
A hydrogel 7 (without gelatin) is prepared by the following steps:
(1) Weighing 3 g of nano Laponite, dissolving in 76.9 g of deionized water, and stirring to form a transparent solution A;
(2) Sequentially adding 20g of acrylamide-polyethylene glycol-succinimide acetate and 0.1g of photoinitiator (photoinitiator 2959) into the solution A, and stirring to form a transparent solution B;
(3) And (3) putting the transparent solution B into a polytetrafluoroethylene mold, carrying out photocuring reaction in a UV-LED photocuring machine at the wavelength of 35nm and the temperature of 25 ℃, and taking out the mold after ten minutes to prepare the hydrogel 7.
Effect example 1
The hydrogel samples prepared in examples 1 to 3 and comparative examples 1 to 4 were respectively subjected to a performance test by the following methods: the light transmittance is detected by an ultraviolet spectrophotometer, the elongation at break is tested by a tensile machine, and the conductivity is tested by a universal meter. The test results are detailed in table 1.
TABLE 1 test results
Comparative example 1 failed to form a hydrogel, and comparative examples 2 and 3 failed to form a hydrogel with high mechanical strength. The comparative example 2 adopts GelMa as a macromolecular substance, gelMa is a substance containing side chain amino groups, and the GelMa is used as a reaction monomer, so that monomer residues can be avoided, but the high-tensile hydrogel material is difficult to obtain. Comparative example 3 is a macromonomer with double bonds at two ends, and the macromolecule itself is a cross-linking agent, and forms more cross-linking points during reaction, easily forms a more compact cross-linking structure in a gel structure, is more easily brittle, and does not have high tensile property.
Claims (10)
1. The hydrogel is characterized in that raw materials of the hydrogel comprise high molecular polymer, acrylamide-polyethylene glycol-succinimide acetate, laponite, photoinitiator and water; the high molecular polymer contains a side chain, and the side chain contains an amino group.
2. The hydrogel of claim 1, wherein the acrylamide-polyethylene glycol-succinimide acetate has a relative molecular mass of 1000 to 40000.
3. The hydrogel of claim 1, wherein the high molecular weight polymer comprises at least one of gelatin, chitosan, polyvinylamine.
4. The hydrogel of claim 1, wherein the photoinitiator comprises at least one of photoinitiator 184, photoinitiator LAP, and photoinitiator 2959.
5. The hydrogel according to claim 1, wherein the raw materials of the hydrogel comprise, by weight, 1-20 parts of high molecular polymer, 1-20 parts of acrylamide-polyethylene glycol-succinimide acetate, 0.5-10 parts of laponite, 0.05-1 part of photoinitiator, and 35-96.5 parts of water.
6. A process for the preparation of a hydrogel according to any one of claims 1 to 5, characterized in that it comprises the following steps:
(1) Dissolving the laponite in water to prepare a solution A;
(2) Respectively adding the photoinitiator and the acrylamide-polyethylene glycol-succinimide acetate into the solution A, and dissolving to obtain a solution B;
(3) Dissolving the high molecular polymer in the solution B to prepare a solution C;
(4) And carrying out photocuring on the solution C to prepare the hydrogel.
7. The hydrogel of claim 1, wherein the photocured photoreaction wavelength is 25-50nm.
8. The hydrogel of claim 1, wherein the reaction temperature for photocuring is 20-40 ℃.
9. A dressing comprising the hydrogel of any one of claims 1 to 5.
10. A wound packing product comprising a hydrogel according to any one of claims 1 to 5.
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| CN102321255A (en) * | 2011-06-25 | 2012-01-18 | 四川大学 | Ion type nano-composite hydrogel and preparation method thereof |
| CN113004459A (en) * | 2021-03-16 | 2021-06-22 | 佛山职业技术学院 | Preparation method of high-transparency, high-tensile and high-conductivity ionic hydrogel |
| CN114213678A (en) * | 2021-11-25 | 2022-03-22 | 同济大学 | High-tensile, self-adhesive, anti-freezing and water-retaining nano composite conductive hydrogel as well as preparation method and application thereof |
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| CN102321255A (en) * | 2011-06-25 | 2012-01-18 | 四川大学 | Ion type nano-composite hydrogel and preparation method thereof |
| CN113004459A (en) * | 2021-03-16 | 2021-06-22 | 佛山职业技术学院 | Preparation method of high-transparency, high-tensile and high-conductivity ionic hydrogel |
| CN114213678A (en) * | 2021-11-25 | 2022-03-22 | 同济大学 | High-tensile, self-adhesive, anti-freezing and water-retaining nano composite conductive hydrogel as well as preparation method and application thereof |
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| 张敏东: ""纳米复合水凝胶的研究进展"", 《高分子通报》, no. 6, 30 June 2010 (2010-06-30), pages 41 - 46 * |
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