CN113185718A - PH/temperature double-sensitive type interpenetrating network hydrogel and preparation method thereof - Google Patents
PH/temperature double-sensitive type interpenetrating network hydrogel and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
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- 238000012650 click reaction Methods 0.000 claims abstract description 18
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- -1 tissue engineering Substances 0.000 claims abstract 2
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- 230000035484 reaction time Effects 0.000 claims description 8
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 7
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- 239000003513 alkali Substances 0.000 claims description 5
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- 125000003277 amino group Chemical group 0.000 claims description 4
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- 238000004108 freeze drying Methods 0.000 claims description 3
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- 239000012966 redox initiator Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 2
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 claims 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims 1
- 238000001879 gelation Methods 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
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- 238000012360 testing method Methods 0.000 description 6
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920001477 hydrophilic polymer Polymers 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
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- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229960003350 isoniazid Drugs 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- SPIGUVVOJXSWNX-UHFFFAOYSA-N n-(oxomethylidene)thiohydroxylamine Chemical compound SN=C=O SPIGUVVOJXSWNX-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a method for preparing pH/temperature double-sensitive interpenetrating network hydrogel by anhydride-amino click reaction in aqueous phase and free radical polymerization in one pot, which comprises the following steps: firstly, dissolving an amino-containing polymer, an anhydride-containing copolymer, a temperature-sensitive monomer, a cross-linking agent and an initiator in water, obtaining a first polymer network (pH sensitive network) by using an anhydride-amino click reaction, and forming a second network (temperature sensitive network) by free polymerization, thereby obtaining the double-sensitive interpenetrating network hydrogel. The preparation process is simple, the conditions are mild, the reaction speed is high, and the obtained pH/temperature sensitive interpenetrating network hydrogel combines the excellent performances of the two networks and can be used in the fields of drug sustained release, tissue engineering, water treatment and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to a method for preparing pH/temperature double-sensitive interpenetrating network hydrogel by using an anhydride-amino click reaction in water and a free radical polymerization one-pot method.
Background
Hydrogels are hydrophilic polymer networks that swell in water but are not soluble. Due to the special performance of the hydrogel, the hydrogel has wide application prospects in the aspects of biomedicine, water treatment, agriculture, building and the like. The intelligent hydrogel can respond to environmental stimuli (temperature, pH, an electric field, a magnetic field, chemical substances and the like), wherein the temperature and the pH are environmental changes commonly existing in organisms and in nature, and the research on the pH/temperature double-sensitive intelligent hydrogel has important significance. However, the properties of conventional hydrogels are often not sufficient for the application, and for this reason, many methods for hydrogel modification have been proposed by the materials scientist. The preparation of interpenetrating network hydrogels is a common hydrogel modification method. Interpenetrating network hydrogels are interwoven polymers formed by interpenetration of two or more crosslinked hydrophilic polymers, and the interaction between the components in the network often produces a synergistic effect, so that the performance of the interpenetrating network hydrogels is superior to that of a single polymer network. Interpenetrating network hydrogels prepared by different methods showed different properties. It is important to select an appropriate method for preparing the interpenetrating network hydrogel. Scientists have made a lot of interesting quests in this regard. The preparation of the hydrogel by using the click reaction is a novel technology and has wide application prospect. The click reaction is a general name of a reaction with the characteristics of modularization, rapidness, high efficiency, mild conditions and the like, and comprises a carbon-carbon multiple-bond addition reaction, a nucleophilic ring-opening reaction and the like, and no obvious limit exists between the reactions. At present, the kind of click reaction is expanding, and the reactions between amino-aldehyde group, mercapto-isocyanate, amino-epoxy group are also classified as click reactions. The traditional azide-alkynyl Husigen cycloaddition click reaction has the advantages of mild conditions, strong selectivity, high yield and the like, but a copper catalyst can remain in a product to influence the biocompatibility of the hydrogel. Therefore, it is of great significance to develop a click reaction for preparing hydrogel without a catalyst or an initiator and without an organic solvent.
Disclosure of Invention
The invention aims to prepare pH/temperature double-sensitive type interpenetrating network hydrogel by combining anhydride-amino click reaction with free radical polymerization, so as to overcome the problems in the preparation and application of the traditional hydrogel. The method adopts a one-pot method to prepare the pH/temperature double-sensitive interpenetrating network hydrogel through anhydride-amino click reaction and free radical polymerization in a water phase, and has the advantages of simple operation, mild conditions, short reaction time, environmental protection and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
(1) the polymer containing anhydride and amino, temperature sensitive monomer, cross-linking agent and photoinitiator are dissolved in water to form homogeneous solution.
(2) Adding a small amount of alkali to adjust the pH value of the solution to be more than 7, and forming the interpenetrating network hydrogel by anhydride-amino click reaction and free radical polymerization at room temperature or under heating.
(3) And then putting the prepared interpenetrating network hydrogel into distilled water, removing impurities remained in the hydrophilic network hydrogel, and freeze-drying or vacuum-drying to obtain the interpenetrating network hydrogel.
In the step (1), a polymer containing amino and acid anhydride is synthesized by a general method. The polymer containing amino groups may be a hyperbranched polymer or a linear polymer, either amino or hydrochloride salt of amino. The polymer containing the acid anhydride can be prepared by polymerizing maleic anhydride or other polymerizable acid anhydrides with different monomers, and can be a binary copolymer or a multi-copolymer.
The monomer adopted in the step (1) can be one or more of N-isopropylacrylamide, (methyl) acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like, wherein at least one temperature-sensitive monomer is adopted; the crosslinking agent used may be a water-soluble compound having a plurality of double bonds, such as N, N-methylenebisacrylamide and polyethylene glycol di (meth) acrylate. The photoinitiator is preferably 2, 2-dimethoxy-2-phenylacetophenone. The redox initiation system adopts potassium persulfate-ascorbic acid, ammonium persulfate-sodium bisulfite and other systems.
The pH value of the solution in the step (2) can be adjusted by adopting NaOH solution, or weak base triethylamine, 4-dimethylaminopyridine, pyridine or sodium carbonate. In order to increase the reaction rate, the reaction may be suitably heated, and generally not more than 60 ℃.
The reaction time in the step (2) can be adjusted according to the reaction conditions, and if the reaction temperature is low, the reaction time can be prolonged; if photopolymerization is adopted, the reaction time can be shortened; the reaction time can also be shortened by increasing the pH of the solution.
The soaking time of the distilled water in the step (3) is generally not less than 48 hours, and the water is frequently changed in the middle to promote the removal of impurities such as residual monomers.
The technical advantages of the invention are mainly reflected in that:
the method comprises the steps of firstly synthesizing a hydrophilic polymer containing amino and anhydride, and then preparing hydrogel through the reaction between the amino and the anhydride, wherein the reaction accords with the characteristic of click reaction, does not need a catalyst and can be quickly carried out in water; the amino group reacts with the acid anhydride to generate a carboxyl group, which imparts pH sensitivity to the hydrogel. The polymer is prepared by a photopolymerization or redox initiation system, the reaction time is short, the property of the polymer can be adjusted by controlling the feed ratio of the monomers, and the hydrogel can be endowed with temperature sensitivity by selecting the temperature-sensitive monomers. The pH/temperature double-sensitive interpenetrating network hydrogel is prepared by a one-pot method, and has the advantages of simple operation, mild condition, short reaction time, environmental protection and wide application prospect.
The present invention will be described in detail with reference to examples. It is to be understood, however, that the following examples are illustrative of embodiments of the present invention and are not to be construed as limiting the scope of the invention.
Drawings
FIG. 1 swelling curve (left) and gel mass fraction (right) of interpenetrating network hydrogel.
Figure 2 temperature (left), pH (right) reversibility and reproducibility of the swelling behavior of interpenetrating network hydrogels.
Fig. 3 FTIR spectrum (left) and SEM image (right) of the interpenetrating network hydrogel.
FIG. 4 release profiles of IPN hydrogels for isoniazid at different temperatures (left) and different pH (right).
Detailed Description
Example 1
0.3717 g of binary copolymer, 0.02828 g of polylysine, 0.1132 g N-isopropyl acrylamide and 1.54X 10-3g N, N-methylene bisacrylamide, 30. mu.L triethylamine, 2.70X 10-3g potassium persulfate, 1.76X 10-3And (3) adding the g ascorbic acid into 2mL of water in a certain sequence, and reacting at room temperature for 1 hour to obtain the interpenetrating network hydrogel, wherein the gel mass fraction is 62.42%, and the swelling degree is 1715%.
Example 2
0.3471 g of binary copolymer, 0.05282 g of polylysine, 0.1132 g N-isopropyl acrylamide and 1.54X 10-3g N, N-methylene bisacrylamide, 40. mu.L triethylamine, 2.70X 10-3g potassium persulfate, 1.76X 10-3And (3) adding the ascorbic acid into 2mL of water in a certain sequence, and reacting at room temperature for 1 hour to obtain the interpenetrating network hydrogel, wherein the gel mass fraction is 65.35%, and the swelling degree is 2465%.
Example 3
0.3257 g of binary copolymer, 0.0743 g of polylysine, 0.1132 g N-isopropyl acrylamide and 1.54X 10-3g N, N-methylene bisacrylamide, 50. mu.L triethylamine, 2.70X 10-3g potassium persulfate, 1.76X 10-3Adding the g ascorbic acid into 2mL of water in a certain sequence, and reacting at room temperature for 1 hour to obtain the interpenetrating network hydrogel, wherein the gel mass fraction is 67.22%, and the swelling degree is 3616%.
Example 4
0.3257 g of binary copolymer, 0.0743 g of polylysine, 0.1132 g N-isopropyl acrylamide and 1.54X 10-3g N, N-methylene bisacrylamide, 50. mu.L triethylamine, 2.70X 10-3g potassium persulfate, 1.76X 10-3Adding ascorbic acid g into 2mL of water in a certain order, and reacting in a water bath kettle at 50 ℃ for 5 minutes to obtain the interpenetrating network hydrogelThe mass fraction of the gel is 68.47 percent, and the swelling degree is 4389 percent.
Example 5
0.3717 g of binary copolymer, 0.02828 g of polylysine, 0.1132 g N-isopropyl acrylamide and 1.03X 10-3g N, N-methylene bisacrylamide, 30. mu.L triethylamine, 2.70X 10-3g potassium persulfate, 1.76X 10-3Adding the g ascorbic acid into 2mL of water in a certain sequence, and reacting for 5 minutes in a water bath kettle at 50 ℃ to obtain the interpenetrating network hydrogel, wherein the gel mass fraction is 55.17%, and the swelling degree is 1888%.
Example 6
Adding 0.130 g of polyacrylamide hydrochloride, 0.113 g of 0.113 g N-isopropyl acrylamide, 0.207 g of 2-acrylamide-2-methylpropanesulfonic acid, 0.24 g of cross-linking agent polyethylene glycol dimethacrylate, 0.147 g of PMA, 0.08 mL of photoinitiator solution and 3 mL of water into a test tube in a certain order, adjusting the pH value of the solution in the middle, uniformly mixing, heating and irradiating the test tube to obtain the interpenetrating network hydrogel, wherein the gel mass fraction is 62%, and the equilibrium swelling degree is 376%.
Example 7
0.200 g of polyacrylamide hydrochloride, 0.113 g of 0.113 g N-isopropyl acrylamide, 0.207 g of 2-acrylamide-2-methylpropanesulfonic acid, 0.24 g of cross-linking agent polyethylene glycol dimethacrylate, 0.224 g of PMA, 0.08 mL of photoinitiator solution and 3 mL of water are added into a test tube in sequence, the pH value of the solution is adjusted in the middle, the test tube is heated and illuminated after uniform mixing, and the interpenetrating network hydrogel is obtained, wherein the gel mass fraction is 66%, and the equilibrium swelling degree is 250%.
Example 8
0.130 g of polyacrylamide hydrochloride, 0.113 g of 0.113 g N-isopropyl acrylamide, 0.207 g of 2-acrylamide-2-methylpropanesulfonic acid, 0.24 g of cross-linking agent polyethylene glycol dimethacrylate, 0.145 g of PMA, 0.08 mL of photoinitiator solution and 3 mL of water are added into a test tube in sequence, the pH value of the solution is adjusted in the middle, the test tube is heated and illuminated after uniform mixing, and the interpenetrating network hydrogel is obtained, wherein the gel mass fraction is 58%, and the equilibrium swelling degree is 363%.
Claims (8)
1. A preparation method for preparing pH/temperature double-sensitive interpenetrating network hydrogel by anhydride-amino click reaction and free radical polymerization in an aqueous phase in a one-pot manner is characterized by comprising the following steps:
1) dissolving a polymer containing anhydride and amino, a monomer, a cross-linking agent and an initiator in water;
2) adding a small amount of alkali to adjust the pH value of the solution to be more than 7, and carrying out gelation through anhydride-amino click reaction to form a first network; forming a second network by free radical polymerization;
3) and finally, putting the prepared interpenetrating network hydrogel into distilled water, removing impurities remained in the hydrophilic network hydrogel, and freeze-drying or vacuum-drying to obtain the pH/temperature double-sensitive interpenetrating network hydrogel.
2. The click reaction of claim 1, wherein the anhydride-containing polymer is a copolymer of maleic anhydride or other polymerizable anhydride with different monomers (N-vinylpyrrolidone, 2-acrylamido-2-methylpropanesulfonic acid, etc.), a copolymer or a multipolymer, the molar ratio of the monomers can be adjusted as desired, and the amino-containing polymer is an amino compound or its hydrochloride, such as vinylamine, polylysine, polyacrylamide hydrochloride, etc.
3. The click reaction of claim 1, wherein the reaction of the anhydride with the amino group is carried out in water, and the pH of the water is adjusted to 7 or more with a base; the alkali can be strong alkali sodium hydroxide, or weak alkali sodium carbonate, triethylamine, 4-dimethylamino pyridine, etc.
4. The click reaction of claim 1, wherein the mole ratio of anhydride to amino groups can be adjusted as desired to adjust the performance of the first network; the reaction temperature is controlled at 15-60 ℃ and the reaction time is 0.1-24 hours.
5. The polymerization reaction according to claim 1, wherein the monomer is one or more of N-isopropylacrylamide, N-vinylcaprolactam, N-vinylpyrrolidone and the like, and at least one temperature-sensitive monomer; the crosslinking agent used may be a water-soluble compound having a plurality of double bonds, such as N, N-methylenebisacrylamide and polyethylene glycol dimethacrylate.
6. The radical polymerization according to claim 1, which can be initiated by photopolymerization or by redox systems, the photoinitiator used being preferably 2, 2-dimethoxy-2-phenylacetophenone of good biocompatibility; the redox initiation system adopts potassium persulfate-ascorbic acid, ammonium persulfate-sodium bisulfite and other systems.
7. The free radical polymerization of claim 1, wherein the molar ratio of the monomers can be adjusted as desired to adjust the properties of the network.
8. The method for preparing the interpenetrating network hydrogel of claim 1, wherein the hydrogel obtained is subjected to freeze drying or vacuum drying after being soaked in water to swell and balance.
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| CN113956399A (en) * | 2021-12-10 | 2022-01-21 | 沈阳先进涂层材料产业技术研究院有限公司 | Intelligent composite microgel based on polyvinylpyrrolidone and poly N-vinyl caprolactam as well as preparation method and application thereof |
| CN114058011A (en) * | 2022-01-11 | 2022-02-18 | 山西医科大学 | Preparation method and application of epsilon-polylysine derivative biological ink |
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