CN113174064B - Preparation method of high-strength composite hydrogel - Google Patents
Preparation method of high-strength composite hydrogel Download PDFInfo
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- CN113174064B CN113174064B CN202110488789.XA CN202110488789A CN113174064B CN 113174064 B CN113174064 B CN 113174064B CN 202110488789 A CN202110488789 A CN 202110488789A CN 113174064 B CN113174064 B CN 113174064B
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 230000003993 interaction Effects 0.000 claims abstract description 7
- KCXFHTAICRTXLI-UHFFFAOYSA-M propane-1-sulfonate Chemical compound CCCS([O-])(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims abstract description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000005859 coupling reaction Methods 0.000 claims abstract description 3
- 238000012698 light-induced step-growth polymerization Methods 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 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 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- GTQHJCOHNAFHRE-UHFFFAOYSA-N 1,10-dibromodecane Chemical compound BrCCCCCCCCCCBr GTQHJCOHNAFHRE-UHFFFAOYSA-N 0.000 claims description 3
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 claims description 3
- -1 2-hydroxyethoxy Chemical group 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 claims description 2
- LVWSZGCVEZRFBT-UHFFFAOYSA-N 1,7-dibromoheptane Chemical compound BrCCCCCCCBr LVWSZGCVEZRFBT-UHFFFAOYSA-N 0.000 claims description 2
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 claims description 2
- WGAXVZXBFBHLMC-UHFFFAOYSA-N 1,9-dibromononane Chemical compound BrCCCCCCCCCBr WGAXVZXBFBHLMC-UHFFFAOYSA-N 0.000 claims description 2
- IYHLUGVVUPPBEJ-UHFFFAOYSA-N 1-butyl-3-ethenyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCC[NH+]1CN(C=C)C=C1 IYHLUGVVUPPBEJ-UHFFFAOYSA-N 0.000 claims description 2
- JVRWQHCUISDRGA-UHFFFAOYSA-N 1-ethenyl-3-ethyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCN1C[NH+](C=C)C=C1 JVRWQHCUISDRGA-UHFFFAOYSA-N 0.000 claims description 2
- XPGQFVAPXLLSAK-UHFFFAOYSA-N CCCCCCCCN(C1)C=CN1C=C.Br Chemical compound CCCCCCCCN(C1)C=CN1C=C.Br XPGQFVAPXLLSAK-UHFFFAOYSA-N 0.000 claims description 2
- CWWRRDJXJBRVBD-UHFFFAOYSA-N CCCCCCN(C1)C=CN1C=C.Br Chemical compound CCCCCCN(C1)C=CN1C=C.Br CWWRRDJXJBRVBD-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims 1
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- HSBMPUYCFQSKRP-UHFFFAOYSA-N 1-bromoimidazole Chemical compound BrN1C=CN=C1 HSBMPUYCFQSKRP-UHFFFAOYSA-N 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000010382 chemical cross-linking Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- PREZSYXZLYLHNH-UHFFFAOYSA-M 1-ethenyl-3-ethylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C=C)=C1 PREZSYXZLYLHNH-UHFFFAOYSA-M 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XALVOFYVVOAYPO-UHFFFAOYSA-M 1-butyl-3-ethenylimidazol-1-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C=C)=C1 XALVOFYVVOAYPO-UHFFFAOYSA-M 0.000 description 1
- MRWHNZBWUFEERI-UHFFFAOYSA-M 1-ethenyl-3-hexylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCN1C=C[N+](C=C)=C1 MRWHNZBWUFEERI-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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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
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- 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
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C08J2339/00—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 at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/168—Zinc halides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The invention provides a preparation method of high-strength composite hydrogel. Firstly, 1-vinyl imidazole and monomer A (1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane and the like) are subjected to coupling reaction to obtain a cross-linking agent A, and then 3- [2- (methacryloyloxy) ethyl]Trimethyl ammonium group]Adding propane-1-sulfonate (MPS), monomer B (imidazole bromide containing vinyl), cross-linking agent A and water-soluble photoinitiator into water, and adding N2And (2) carrying out ultraviolet light induced polymerization reaction under protection to establish covalent bond crosslinking and ionic interaction polyion liquid hydrogel, soaking the polyion liquid hydrogel in a metal ion salt solution, and chelating metal ions with imidazole active sites in the soaking process to obtain the high-strength composite hydrogel. The hydrogel prepared by the invention has excellent self-repairing property and mechanical property, good antibacterial property and potential application value in the aspects of bioengineering, metal catalysis and the like.
Description
Technical Field
The invention relates to a high-strength composite hydrogel, in particular to a preparation method of a high-strength double-network self-repairing hydrogel.
Background
Hydrogels are materials with a three-dimensional network structure formed by chemically or physically crosslinking hydrophilic polymers. The hydrogel has the characteristics of hydrophilicity, high water content, stimulation responsiveness and the like, can be endowed with more functionality by introducing functional monomers, polymers or loaded small molecules, and has wide application in the fields of biomedicine, metal catalysis and the like. Most hydrogels have poor strength and toughness and poor resistance to external mechanical forces, which limits the application range of hydrogels to some extent. The preparation of hydrogels with better mechanical properties by relatively simple methods has been one of the main problems that researchers need to solve.
Interpenetrating network hydrogels have a relatively special preparation method, generally by polymerizing two or more independent polymers one after another, interpenetrating them with each other to form an interpenetrating network structure. Compared with the hydrogel prepared by copolymer or homopolymer, the interpenetrating network hydrogel has better mechanical property. The physical crosslinked hydrogel is a polymer network formed by non-covalent bonds such as hydrogen bonds, van der waals force, metal coordination and the like, and the physical crosslinking points are generally dynamically reversible and can self-repair under certain conditions after being damaged. Chemically crosslinked hydrogels are crosslinked by covalent bonds and cannot be reconstituted after destruction. The hybridized crosslinking hydrogel through chemical crosslinking and physical crosslinking combines the self-repairing performance of the physical crosslinking hydrogel and the mechanical performance of the chemical crosslinking hydrogel, and has better comprehensive performance. The Chinese invention patent CN106750478B firstly prepares gelatin hydrogel with imidazole active sites, and then adopts divalent metal ion salt solution to soak the gelatin hydrogel, so that divalent metal ions are coordinated with the imidazole active sites, and the high-strength double-network antibacterial hydrogel is prepared.
Disclosure of Invention
The invention aims to provide a preparation method of high-strength composite hydrogel, which is simple, the hydrogel can be self-repaired at room temperature, the mechanical property is excellent, the hydrogel has certain antibacterial property, and the hydrogel has potential application value in the aspects of bioengineering, metal catalysis and the like.
In order to achieve the purpose, the self-repairing antibacterial hydrogel provided by the invention is characterized in that a first network structure is formed by crosslinked polyion liquid containing anion and cation functional groups, a second network is constructed by metal ion coordination imidazole active sites, and a covalent bond crosslinking network, a metal coordination effect and an ion interaction are established to form the high-strength self-repairing composite hydrogel.
The preparation method of the high-strength composite hydrogel provided by the invention comprises the following steps:
(1) dissolving 1-vinyl imidazole and monomer A in a solvent according to a certain proportion, mixing uniformly in N2Carrying out coupling reaction at 60-80 ℃ under protection to obtain a cross-linking agent A;
(2) reacting 3- [2- (methacryloyloxy) ethyl]Trimethyl ammonium group]Adding propane-1-sulfonate (MPS), monomer B, cross-linking agent A and water-soluble photoinitiator into water, and mixing thoroughlyHomogeneous, N2Under the protection of ultraviolet light, carrying out induced polymerization reaction to obtain polyion liquid hydrogel based on covalent bond crosslinking and ionic interaction;
(3) the polyion liquid hydrogel is soaked in the metal ion salt solution, metal ions are chelated with imidazole active sites in the soaking process, and the polyion liquid hydrogel is washed by deionized water after soaking is finished, so that the high-strength composite hydrogel is obtained, and the method is simple in experimental method, good in biocompatibility and capable of being used for large-scale production;
the monomer A is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 7-dibromoheptane, 1, 8-dibromooctane, 1, 9-dibromononane, 1, 10-dibromodecane and the like;
the monomer B is any one of 1-vinyl-3-ethylimidazole bromide, 1-vinyl-3-butylimidazole bromide, 1-vinyl-3-hexylimidazole bromide or 1-vinyl-3-octylimidazole bromide;
optimally, in the step (1), the molar ratio of the 1-vinyl imidazole to the monomer A is 2: 1; the dosage of the solvent is 1-5 times of the total mole number of the monomers;
preferably, in the step (1), the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and methanol;
preferably, in the step (2), the water-soluble photoinitiator is 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (Irgacure-2959);
optimally, in the step (3), the metal ion is Fe3+、Cu2+Or Zn2+The concentration of the metal ions is 12-24 mmol/L, and the soaking time is 2-4 h.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the invention designs a novel high-strength composite hydrogel which contains chemical crosslinking, metal coordination and ion interaction, can be self-repaired at room temperature after being damaged under external force, has good antibacterial property due to the existence of imidazole cations, and has potential application value in the fields of bioengineering, metal catalysis and the like.
(2) The high-strength composite hydrogel designed by the invention has the advantages of good water absorption capacity, excellent mechanical property, high rigidity and toughness, mild reaction conditions, strong operability, controllable technical process and contribution to large-scale production.
Drawings
FIG. 1 is a photograph of the high-strength composite hydrogel obtained in examples 1 to 3.
FIG. 2 is a graph showing the swelling percentage of the high-strength composite hydrogel obtained in examples 1 to 3 as a function of time.
Detailed Description
The following embodiments specifically describe the present invention, but the present invention is not limited to these embodiments.
The raw materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation method comprises the following steps: (1) 0.02mol of 1-vinylimidazole and 0.01mol of 1, 6-dibromohexane are weighed into a flask containing 15mL of methanol, mixed uniformly by magnetic stirring, and stirred under N2And under protection, stirring and reacting for 15h in an oil bath at 60 ℃, and standing and cooling at room temperature. After cooling, slowly dropping the reaction product into sufficient ether, washing, filtering, and vacuum drying at 40 ℃ to obtain the cross-linking agent A.
(2) 1mmol of 3- [2- (methacryloyloxy) ethyl ] trimethylammonium ] propane-1-sulfonate (MPS), 4mmol of 1-vinyl-3-ethylimidazolium bromide (VIM), 2mg of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (Irgacure-2959) and 0.013g of crosslinker A were weighed into 1.5g of water. And (3) stirring for 10min by magnetic force, blowing nitrogen into the system after the components are uniformly dispersed, sealing, performing ultrasonic treatment until the components are uniformly mixed, transferring the mixture into an ultraviolet lamp box, and performing irradiation reaction for 2h under ultraviolet light with the wavelength of 290-800 nm to obtain the polyion liquid hydrogel.
(3) Preparation of Fe3+And (3) soaking the polyion liquid hydrogel in 12mmol/L ferric trichloride ethanol solution for 2h, and repeatedly washing with deionized water for more than 3 times to obtain the high-strength composite hydrogel. After the hydrogel absorbs waterThe volume of the polymer can swell to 1.5 to 3 times of the original volume, the tensile strength is 0.80MPa, the tensile elastic modulus is 0.50MPa, and the elongation at break is 120 percent. Can be self-repaired at room temperature and has better antibacterial property.
Example 2
The preparation method comprises the following steps: (1) 0.02mol of 1-vinylimidazole and 0.01mol of 1, 4-dibromobutane are weighed into a flask containing 15mL of N, N-dimethylformamide and are stirred and mixed uniformly by magnetic force in N2And stirring and reacting for 24 hours in an oil bath at the temperature of 60 ℃ under protection, and standing and cooling at room temperature. After cooling, slowly dripping the reaction product into sufficient petroleum ether, washing, filtering, and vacuum drying at 40 ℃ to obtain the cross-linking agent A.
(2) 2mmol of 3- [2- (methacryloyloxy) ethyl ] trimethylammonium ] propane-1-sulfonate (MPS), 4mmol of 1-vinyl-3-butylimidazolium bromide, 2mg of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (Irgacure-2959) and 0.02g of crosslinker A were weighed into 1.5g of water. And (3) stirring for 10min by magnetic force, blowing nitrogen into the system after the components are uniformly dispersed, sealing, performing ultrasonic treatment until the components are uniformly mixed, transferring the mixture into an ultraviolet lamp box, and performing irradiation reaction for 2h under ultraviolet light with the wavelength of 290-800 nm to obtain the polyion liquid hydrogel.
(3) Preparation of Cu2+And (3) soaking the polyion liquid hydrogel in 15mmol/L ethanol solution of copper chloride for 3 hours, and then repeatedly washing the polyion liquid hydrogel for more than 3 times by using deionized water to obtain the high-strength composite hydrogel. After water absorption, the hydrogel can swell to 2-3 times of the original volume, the tensile strength is 0.65MPa, the tensile elastic modulus is 0.32MPa, and the elongation at break is 130%. Can be self-repaired at room temperature and has better antibacterial property.
Example 3
The preparation method comprises the following steps: (1) 0.02mol of 1-vinylimidazole and 0.01mol of 1, 10-dibromodecane are weighed and added into a flask containing 15mL of N, N-dimethylformamide, and the mixture is stirred and mixed evenly by magnetic force in N2And stirring and reacting for 24 hours in an oil bath at the temperature of 60 ℃ under protection, and standing and cooling at room temperature. After cooling, slowly dripping the reaction product into sufficient petroleum ether, washing, filtering, and vacuum drying at 40 ℃ to obtain the cross-linking agent A.
(2) 2mmol of 3- [2- (methacryloyloxy) ethyl ] trimethylammonium ] propane-1-sulfonate (MPS), 3mmol of 1-vinyl-3-hexylimidazolium bromide, 2mg of photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (Irgacure-2959) and 0.01g of crosslinker A were weighed into 1.5g of water. And (3) stirring for 10min by magnetic force, blowing nitrogen into the system after the components are uniformly dispersed, sealing, performing ultrasonic treatment until the components are uniformly mixed, transferring the mixture into an ultraviolet lamp box, and performing irradiation reaction for 2h under ultraviolet light with the wavelength of 290-800 nm to obtain the polyion liquid hydrogel.
(3) Preparation of Zn2+And (3) soaking the polyion liquid hydrogel in 15mmol/L ethanol solution of zinc chloride for 2.5h, and repeatedly washing with deionized water for more than 3 times to obtain the high-strength composite hydrogel. After water absorption, the hydrogel can swell to 2-3 times of the original volume, the tensile strength is 0.73MPa, the tensile elastic modulus is 0.38MPa, and the elongation at break is 125%. Can be self-repaired at room temperature and has better antibacterial performance.
Claims (6)
1. A high-strength composite hydrogel is characterized in that a first network structure is formed by cross-linked polyion liquid with anion and cation functional groups, a second network is constructed by metal ion coordination imidazole active sites, a covalent bond cross-linking network, a metal coordination effect and an ion interaction effect are established, and the high-strength self-repairing composite hydrogel is formed, and the preparation method comprises the following steps:
(1) crosslinking agent A: dissolving 1-vinyl imidazole and monomer A in a solvent according to a certain proportion, mixing uniformly in N2Carrying out coupling reaction at 60-80 ℃ under protection to obtain a cross-linking agent A, wherein the monomer A is any one of 1, 2-dibromoethane, 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, 1, 7-dibromoheptane, 1, 8-dibromooctane, 1, 9-dibromononane or 1, 10-dibromodecane;
(2) polyionic liquid hydrogel: reacting 3- [2- (methacryloyloxy) ethyl group]Trimethyl ammonium group]Adding propane-1-sulfonate (MPS), monomer B, cross-linking agent A and water-soluble photoinitiator into water, and mixing completely, wherein N is2Ultraviolet light induced polymerization under protectionObtaining the polyion liquid hydrogel based on covalent bond crosslinking and ionic interaction, wherein the monomer B is any one of 1-vinyl-3-ethylimidazole bromide, 1-vinyl-3-butylimidazole bromide, 1-vinyl-3-hexylimidazole bromide or 1-vinyl-3-octylimidazole bromide;
(3) compounding hydrogel: and (2) soaking the polyion liquid hydrogel by using a metal ion salt solution, chelating metal ions with imidazole active sites in the soaking process, and washing with deionized water after soaking is finished to obtain the high-strength composite hydrogel.
2. The high-strength composite hydrogel according to claim 1, wherein the cross-linked polyionic liquid is a first network structure containing cationic and anionic functional groups formed by polymerization of 3- [2- (methacryloyloxy) ethyl ] trimethyl ammonium ] propane-1-sulfonate (MPS), monomer B and cross-linking agent A, and the metal ions coordinate with imidazole active sites to form a second network, thereby establishing multiple interactions in the hydrogel.
3. The high strength composite hydrogel of claim 1, wherein: the solvent in the step (1) is any one of N, N-dimethylformamide, N-dimethylacetamide and methanol.
4. The high strength composite hydrogel of claim 1, wherein: the water-soluble photoinitiator in the step (2) is 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (Irgacure-2959).
5. The high strength composite hydrogel of claim 1, wherein: in the step (1), the mol ratio of the 1-vinyl imidazole to the monomer A is 2: 1; the amount of the solvent is 1-5 times of the total mole number of the monomers.
6. The high strength composite hydrogel of claim 1, wherein: the metal ion being Fe3+、Cu2+Or Zn2+The concentration of the metal ions is 12-24 mmol/L, and the soaking time is 2-4 h.
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