CN111363169A - Preparation method of pH sensitive hydrogel - Google Patents
Preparation method of pH sensitive hydrogel Download PDFInfo
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- CN111363169A CN111363169A CN202010196335.0A CN202010196335A CN111363169A CN 111363169 A CN111363169 A CN 111363169A CN 202010196335 A CN202010196335 A CN 202010196335A CN 111363169 A CN111363169 A CN 111363169A
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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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- 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
- A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
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- 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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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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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
- 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
- C08J2351/02—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 polysaccharides
Abstract
The invention relates to a preparation method of pH sensitive hydrogel, wherein the hydrogel adopts pH response main polymerization monomer raw materials of carboxymethyl chitosan and itaconic acid which are both from natural product compounds, and has the advantages of water-based environmental protection and good biocompatibility; the carboxyl of the polyvinyl modified carboxymethyl chitosan and polyitaconic acid in the hydrogel is ionized at a high pH value, and the amino of the polyvinyl modified carboxymethyl chitosan and poly N-isopropylacrylamide absorbs hydrogen ions to be ionized at a low pH value, so that the hydrogel disclosed by the invention has pH sensitivity due to the existence of different polymer units. The hydrogel has higher swelling rate at relatively mild pH and low swelling rate at relatively severe pH, so the hydrogel can be used for releasing medicaments, realizes the effectiveness of the medicaments for being administrated through gastrointestinal tracts, and has wide application prospect.
Description
The invention relates to a divisional application of a Chinese patent 'pH sensitive hydrogel and a preparation method and application thereof', wherein the application date is 2017, 9 and 8, and the application number is 201710807679.9.
Technical Field
The invention relates to a pH sensitive hydrogel and a preparation method and application thereof, belonging to the technical field of hydrogels.
Technical Field
Smart hydrogels are a class of hydrogels that are responsive to external stimuli such as changes in temperature, pH, solvent, ion concentration, light, electric field, magnetic field, etc. The characteristics lead the intelligent hydrogel to have good application prospects in the aspects of tissue engineering, biological separation, control release of immobilized enzyme and medicine and the like, wherein the pH sensitive gel has more researches.
The pH sensitive gel is a polymer hydrogel whose volume changes according to the pH value of the environment. The gel structure has groups capable of dissociating into ions (such as carboxyl, sulfonic acid group or amino group and the like), the groups can abstract or release protons according to the change of the pH value of the environment, when the external pH value changes, the dissociable groups can repel or attract with the groups, so that polymer chains correspondingly stretch or aggregate, and the gel is represented by volume reversible expansion or contraction on a macroscopic scale.
The macromolecular backbone chain of pH-sensitive hydrogels typically contains ionizable groups such as carboxylic acid groups or amino groups, etc.; because the groups can generate ionization or protonation with different degrees along with the change of the pH value of the environment medium, the internal osmotic pressure and the ionic bond acting force of the hydrogel are changed, thereby causing the swelling change of the volume and showing the pH sensitivity. For the pH sensitive hydrogel with the weak acidic groups, if the pH value of an environmental medium is greater than the ionization equilibrium constant (pKa) of the weak acidic groups, the weak acidic groups on the side chains of the hydrogel molecular chains are ionized to form charged anions, so that greater osmotic pressure is generated inside the hydrogel, and the hydrogel is swelled because the repulsive force of interaction between ions is increased. For the same reason, hydrogels with weakly basic groups swell when the pH of the surrounding medium is less than its ionization equilibrium constant, pKa. Based on the responsiveness of the pH sensitive hydrogel to the pH value of the environment, the corrosion inhibitor can be embedded in the hydrogel, and the release performance of the corrosion inhibitor embedded in the hydrogel can be further controlled by controlling the swelling and deswelling degrees of the hydrogel.
Chinese patent CN1834125A relates to a template copolymerization method for synthesizing a semi-interpenetrating network reversible pH sensitive hydrogel. Synthesizing pH sensitive gel by a template copolymerization method, selecting an ionic monomer sensitive to pH and a corresponding polymer with opposite charges to the ionic monomer as a template, polymerizing in the presence of a cross-linking agent to obtain the structure of the product gel, wherein in addition to covalent bond cross-linking, ionic bond cross-linking formed by electrostatic bonding also exists, and the existence of the ionic bond cross-linking not only increases the strength of the gel, but also increases the response capability to pH; due to the fact that the copolymer has the ionic monomer unit sensitive to pH, the ion density inside the gel changes along with the change of the pH of the solution, when the ion density exceeds a certain value, the gel begins to swell, and due to the existence of the ionic template polymer with opposite charges in the gel, the response threshold of the gel to the pH can be changed. However, since the present invention employs a synthetic monomer for template polymerization, the biocompatibility of the hydrogel is poor compared to a monomer hydrogel derived from a natural polymer.
Chinese patent CN1995079A discloses a redispersible pH sensitive cationic polymer hydrogel submicron particle and a preparation method thereof, wherein the hydrogel submicron particle contains a hydrophilic nonionic polymer part, a cationic polymer part, an initiator part and a cross-linking agent part. The hydrogel submicron particles prepared by the method can be dispersed in pure water, normal saline, buffer solution and the like; when the pH value is less than 7, the hydrogel submicron particles swell, and when the pH value is more than 7, the particle size change of the hydrogel submicron particles is very small, so that the hydrogel submicron particles are an excellent drug controlled release carrier material. Due to the pH sensitive range of the hydrogel of the invention, the possibility of the hydrogel as a drug to be administered through the gastrointestinal tract is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a pH sensitive hydrogel.
Still another object of the present invention is to provide a method for preparing a pH sensitive hydrogel.
The invention further aims to provide application of the pH-sensitive hydrogel in the field of drug release.
The pH-sensitive hydrogel is prepared by taking vinyl-modified carboxymethyl chitosan, itaconic acid, maleic anhydride, diethylaminoethyl methacrylate, N-isopropyl acrylamide and a cross-linking agent as comonomers and adopting a specific aqueous solution type free radical polymerization method, and has the characteristics of pH sensitivity, high response speed and good biocompatibility, and the preparation method comprises the following steps:
a) preparing vinyl modified carboxymethyl chitosan: adding 10-20 parts of carboxymethyl chitosan, 2-5 parts of a catalyst and 30-50 parts of an organic solvent into a reaction kettle, stirring and dissolving uniformly, heating to 40-60 ℃, dropwise adding 5-10 parts of glycidyl methacrylate one by one, and reacting for 5-10 hours at 40-60 ℃; then adding methanol for dissolving and diluting, adding acetone for precipitating, carrying out suction filtration and precipitation, repeatedly dissolving and diluting with methanol, precipitating with acetone, and carrying out vacuum drying and precipitation to obtain the preparation of the vinyl modified carboxymethyl chitosan.
b) Aqueous solution polymerization to prepare hydrogel: adding 10-30 parts of the preparation of the vinyl modified carboxymethyl chitosan in the step a), 40 parts of itaconic acid, 5-10 parts of maleic anhydride, 20-30 parts of N-isopropylacrylamide, 5-10 parts of diethylaminoethyl methacrylate, 5-15 parts of a cross-linking agent and 300-400 parts of water into a reactor, fully dissolving and uniformly mixing, and adding an inorganic alkali solution to neutralize until the pH value is 6-8; heating to 60-100 ℃, dropwise adding an aqueous solution containing 0.5-10 parts of an initiator by using a dropwise adding device, continuously reacting for 24-96 hours at 50-100 ℃ after dropwise adding for 0.5-1 hour, and cooling to obtain a gel product; and taking out the gel product by a physical method, soaking the gel product in deionized water for one week, changing water every day, and removing unreacted raw materials to obtain the pH sensitive hydrogel.
The carboxymethyl chitosan is at least one of anionic chitosan, quaternary ammonium salt type chitosan and neutral chitosan.
The catalyst is at least one of 2, 4, 6-tri (dimethylaminomethyl) phenol, triethylamine, N-dimethyl-p-toluidine, triethanolamine, N-methylpyrrole, N-methylpiperidine and trimethylamine.
The organic solvent is at least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, hexamethylphosphoric triamide, nitromethane and acetonitrile.
The cross-linking agent is at least one of polyethylene glycol diacrylate, ethylene dimethacrylate, N- (1, 1-dimethyl-3-oxobutyl) acrylamide, N-methylene bisacrylamide, polyethylene glycol dimethacrylate and polyhexamethylene diacrylate.
The initiator is an inorganic peroxide initiator or an oxidation-reduction initiator system.
The inorganic peroxide initiator is at least one of ammonium persulfate, potassium ammonium persulfate and sodium persulfate.
The oxidation-reduction initiator system is benzoyl peroxide-sucrose, tert-butyl hydroperoxide-sodium pyrosulfite, benzoyl peroxide-N, N-dimethylaniline, ammonium persulfate-sodium bisulfite, potassium persulfate-sodium bisulfite, hydrogen peroxide-tartaric acid, hydrogen peroxide-rongalite, ammonium persulfate-ferrous sulfate, hydrogen peroxide-ferrous sulfate, benzoyl peroxide-N, at least one of N-diethylaniline, benzoyl peroxide-ferrous pyrophosphate, potassium persulfate-silver nitrate, persulfate-mercaptan, cumene hydroperoxide-ferrous chloride, potassium persulfate-ferric chloride, hydrogen peroxide-ferrous chloride or cumene hydroperoxide-tetraethylene imine.
The oxidation-reduction initiator system comprises the following oxidizing agents: the mass ratio of the reducing agent is 0.2 to 2, and the oxidizing agent and the reducing agent are respectively dripped into the reactor by a dripping device.
The inorganic alkali solution is an aqueous solution of inorganic alkali with the mass fraction of 30-40%, and the inorganic alkali is at least one of sodium hydroxide, potassium hydroxide, ammonia water, barium hydroxide, cesium hydroxide and lithium hydroxide.
The pH-sensitive hydrogel disclosed by the invention has the following pH responsiveness principle: the hydrogel disclosed by the invention contains a polyvinyl modified carboxymethyl chitosan unit, a polyitaconic acid unit and a poly-N-isopropylacrylamide unit, wherein carboxyl groups of the polyvinyl modified carboxymethyl chitosan unit and the polyitaconic acid unit are ionized at a high pH value, and amino groups of the polyvinyl modified carboxymethyl chitosan and the poly-N-isopropylacrylamide absorb hydrogen ions for ionization at a low pH value, and the hydrogel disclosed by the invention has pH sensitivity due to the existence of different polymer units as shown in the following (wherein 1 is a polymer main chain and 2 is a branched chain).
The pH sensitive hydrogel disclosed by the invention has the following advantages: (1) the pH response main polymerization monomer raw materials, namely carboxymethyl chitosan and itaconic acid, are selected from natural product compounds, and have the advantages of water-based environmental protection and good biocompatibility; (2) the vinyl of carboxymethyl chitosan is modified for the first time, and the vinyl of carboxymethyl chitosan participates in the aqueous free radical polymerization reaction, and forms a three-dimensional network structure with a polyitaconic acid unit and a poly N-isopropylacrylamide unit, so that the swelling and deswelling dynamics of the hydrogel are improved, and the hydrogel prepared by the method has the characteristic of quick response; (3) the hydrogel has high swelling rate at a relatively mild pH (6-8, pH range in human intestines) and low swelling rate at a relatively severe pH (1.5-3, pH in human stomachs), so that the hydrogel can be used for releasing medicaments and realizes the effectiveness of the medicaments for being administrated through gastrointestinal tracts.
Drawings
FIG. 1 is a schematic diagram showing the swelling ratios of hydrogels at 37. + -. 0.2 ℃ and different pH values in examples of the present invention
Detailed Description
The pH-sensitive hydrogel of the present invention, its preparation method and application are further described below with reference to examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
The pH-sensitive hydrogel is prepared by taking vinyl-modified carboxymethyl chitosan, itaconic acid, maleic anhydride, diethylaminoethyl methacrylate, N-isopropyl acrylamide and a cross-linking agent as comonomers and adopting a specific aqueous solution type free radical polymerization method, and has the characteristics of pH sensitivity, high response speed and good biocompatibility, and the preparation method comprises the following steps:
a) preparing vinyl modified carboxymethyl chitosan: adding 20 parts of anionic carboxymethyl chitosan, 2 parts of triethylamine and 30 parts of dimethyl sulfoxide into a reaction kettle, stirring and dissolving uniformly, heating to 50 ℃, dropwise adding 10 parts of glycidyl methacrylate, and reacting for 5 hours at 50 ℃; then adding methanol for dissolving and diluting, adding acetone for precipitating, carrying out suction filtration and precipitation, repeating methanol dissolving and diluting and acetone precipitating, and carrying out vacuum drying and precipitation to obtain the preparation of the vinyl modified carboxymethyl chitosan.
b) Aqueous solution polymerization to prepare hydrogel: 20 parts of preparation of vinyl modified carboxymethyl chitosan in a), 40 parts of itaconic acid, 5 parts of maleic anhydride, 25 parts of N-isopropyl acrylamide, 8 parts of diethylaminoethyl methacrylate, 10 parts of N, N-methylene-bis-acrylamide and 400 parts of water are added into a reactor, and after the materials are fully dissolved and uniformly mixed, a sodium hydroxide solution with the mass fraction of 30% is added to neutralize the mixture until the pH value is 7; heating to 70 ℃, dropwise adding an aqueous solution containing 2 parts of ammonium persulfate through a dropwise adding device, continuously reacting for 48 hours at 70 ℃ after the dropwise adding is finished for 0.5 hour, cooling to obtain a gel product, taking out the gel product by a physical method, soaking in deionized water for one week, changing water every day, and removing unreacted raw materials to obtain the pH-sensitive hydrogel.
Example 2
The pH-sensitive hydrogel is prepared by taking vinyl-modified carboxymethyl chitosan, itaconic acid, maleic anhydride, diethylaminoethyl methacrylate, N-isopropyl acrylamide and a cross-linking agent as comonomers and adopting a specific aqueous solution type free radical polymerization method, and has the characteristics of pH sensitivity, high response speed and good biocompatibility, and the preparation method comprises the following steps:
a) preparing vinyl modified carboxymethyl chitosan: adding 10 parts of carboxymethyl chitosan, 5 parts of 2, 4, 6-tris (dimethylaminomethyl) phenol and 30 parts of DMF (dimethyl formamide) into a reaction kettle, stirring and dissolving uniformly, heating to 60 ℃, dropwise adding 10 parts of glycidyl methacrylate, and reacting for 10 hours at 60 ℃; then adding methanol for dissolving and diluting, adding acetone for precipitating, carrying out suction filtration and precipitation, repeating the methanol for dissolving and diluting and the acetone for precipitating, and carrying out vacuum drying and precipitation to obtain the preparation of the vinyl modified carboxymethyl chitosan.
b) Aqueous solution polymerization to prepare hydrogel: adding 10 parts of the preparation of the vinyl modified carboxymethyl chitosan in the step a), 40 parts of itaconic acid, 8 parts of maleic anhydride, 30 parts of N-isopropyl acrylamide, 10 parts of dimethylaminoethyl methacrylate, 15 parts of N- (1, 1-dimethyl-3-oxobutyl) acrylamide and 300 parts of water into a reactor, fully dissolving and uniformly mixing, and adding a potassium hydroxide solution with the mass fraction of 30% to neutralize until the pH value is 7; and heating to 100 ℃, dropwise adding an aqueous solution containing 1 part of sodium persulfate through a dropwise adding device, continuing to react for 48 hours at 100 ℃ after the dropwise adding is finished for 1 hour, cooling to obtain a gel product, taking out the gel product by a physical method, soaking the gel product in deionized water for one week, changing water every day, and removing unreacted raw materials to obtain the pH-sensitive hydrogel.
Example 3
The pH-sensitive hydrogel is prepared by taking vinyl-modified carboxymethyl chitosan, itaconic acid, maleic anhydride, diethylaminoethyl methacrylate, N-isopropyl acrylamide and a cross-linking agent as comonomers and adopting a specific aqueous solution type free radical polymerization method, and has the characteristics of pH sensitivity, high response speed and good biocompatibility, and the preparation method comprises the following steps:
a) preparing vinyl modified carboxymethyl chitosan: adding 18 parts of carboxymethyl chitosan, 4 parts of N, N-dimethyl-p-aniline and 50 parts of DMF (dimethyl formamide) into a reaction kettle, stirring and dissolving uniformly, heating to 40 ℃, dropwise adding 10 parts of glycidyl methacrylate, and reacting for 8 hours at 40 ℃; then adding methanol for dissolving and diluting, adding acetone for precipitating, carrying out suction filtration and precipitation, repeating methanol dissolving and diluting and acetone precipitating, and carrying out vacuum drying and precipitation to obtain the preparation of the vinyl modified carboxymethyl chitosan.
b) Aqueous solution polymerization to prepare hydrogel: adding 25 parts of the preparation of the vinyl modified carboxymethyl chitosan in the step a), 40 parts of itaconic acid, 10 parts of maleic anhydride, 20 parts of N-isopropyl acrylamide, 8 parts of dimethylaminoethyl methacrylate, 10 parts of a cross-linking agent and 400 parts of water into a reactor, fully dissolving and uniformly mixing, adding a potassium hydroxide solution with the mass fraction of 30% and neutralizing until the pH value is 7; and then heating to 50 ℃, dropwise adding an aqueous solution containing 2 parts of hydrogen peroxide and an aqueous solution containing 4 parts of tartaric acid by a dropwise adding device, continuously reacting for 96 hours at 50 ℃ after 1 hour of dropwise adding is finished, cooling to obtain a gel product, taking out the gel product by a physical method, soaking in deionized water for one week, changing water every day, and removing unreacted raw materials to obtain the pH sensitive hydrogel.
The expansion ratios of the hydrogels of examples 1-3 at 37 + -0.2 deg.C and different pH's are shown in the figure of the specification.
Claims (9)
1. A preparation method of pH sensitive hydrogel is characterized by comprising the following steps:
a) preparing vinyl modified carboxymethyl chitosan: adding 10-20 parts of carboxymethyl chitosan, 2-5 parts of catalyst and 30-50 parts of organic solvent into a reaction kettle, stirring and dissolving uniformly, heating to 40-60 ℃, dropwise adding 5-10 parts of glycidyl methacrylate, and reacting for 5-10 hours at 40-60 ℃; then adding methanol for dissolving and diluting, adding acetone for precipitating, carrying out suction filtration and precipitation, repeating methanol dissolving and diluting and acetone precipitation, and carrying out vacuum drying and precipitation to obtain the preparation of the vinyl modified carboxymethyl chitosan;
b) aqueous solution polymerization to prepare hydrogel: adding 10-30 parts of vinyl modified carboxymethyl chitosan in a), 40 parts of itaconic acid, 5-10 parts of maleic anhydride, 20-30 parts of N-isopropylacrylamide, 5-10 parts of diethylaminoethyl methacrylate, 5-15 parts of a cross-linking agent and 300-400 parts of water into a reactor, fully dissolving and uniformly mixing, and adding an inorganic alkali solution to neutralize until the pH value is 6-8; heating to 60-100 ℃, dropwise adding an aqueous solution containing 0.5-10 parts of an initiator by using a dropwise adding device, continuously reacting for 24-96 hours at 50-100 ℃ after dropwise adding for 0.5-1 hour, and cooling to obtain a gel product; and taking out the gel product by a physical method, then soaking the gel product in deionized water for one week, changing water every day, and removing unreacted raw materials to obtain the pH sensitive hydrogel.
2. The method of claim 1, wherein the organic solvent is at least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, hexamethylphosphoric triamide, nitromethane, and acetonitrile.
3. The method of claim 1, wherein the initiator is an inorganic peroxide initiator or an oxidation-reduction initiator system, wherein the inorganic peroxide initiator is at least one of ammonium persulfate, potassium ammonium persulfate, and sodium persulfate, and the oxidation-reduction initiator system is benzoyl peroxide-sucrose, t-butyl hydroperoxide-sodium metabisulfite, benzoyl peroxide-N, N-dimethylaniline, ammonium persulfate-sodium bisulfite, potassium persulfate-sodium bisulfite, hydrogen peroxide-tartaric acid, hydrogen peroxide-sodium formaldehyde sulfoxylate, ammonium persulfate-ferrous sulfate, hydrogen peroxide-ferrous sulfate, benzoyl peroxide-N, N-diethylaniline, benzoyl peroxide-ferrous pyrophosphate, sodium persulfate, potassium persulfate, sodium hydrogen, At least one of potassium persulfate-silver nitrate, persulfate-mercaptan, cumene hydroperoxide-ferrous chloride, potassium persulfate-ferrous chloride, hydrogen peroxide-ferrous chloride or cumene hydroperoxide-tetraethylene imine.
4. The method of claim 1, wherein the catalyst is at least one of 2, 4, 6-tris (dimethylaminomethyl) phenol, triethylamine, N-dimethyl-p-toluidine, triethanolamine, N-methylpyrrole, N-methylpiperidine, and trimethylamine.
5. The method of claim 1, wherein the carboxymethyl chitosan is at least one of anionic chitosan, quaternary ammonium salt chitosan, and neutral chitosan.
6. The method of claim 1, wherein the cross-linking agent is at least one of polyethylene glycol diacrylate, vinyl dimethacrylate, N- (1, 1-dimethyl-3-oxobutyl) acrylamide, N-methylenebisacrylamide, polyethylene glycol dimethacrylate, and polyhexamethylene diacrylate.
7. The method of claim 1, wherein the oxidation-reduction initiator system comprises at least one of the following oxidizing agents: the ratio of the amount of the reducing agent is 0.2 to 2, and the oxidizing agent and the reducing agent are respectively added dropwise into the reactor by a dropping device.
8. The method according to claim 1, wherein the inorganic base solution is an aqueous solution of 30-40% inorganic base by weight, and the inorganic base is at least one of sodium hydroxide, potassium hydroxide, ammonia water, and lithium hydroxide.
9. The method of claim 1, wherein the pH sensitive hydrogel comprises a polyvinyl modified carboxymethyl chitosan unit, a polyitaconic acid unit, and a poly-N-isopropylacrylamide unit, wherein the carboxyl group of the polyvinyl modified carboxymethyl chitosan unit and the polyitaconic acid unit is ionized at a high pH value, and the amino group of the polyvinyl modified carboxymethyl chitosan and the poly-N-isopropylacrylamide unit absorbs hydrogen ions to be ionized at a low pH value, and the pH response process of the pH sensitive hydrogel is as follows:
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| CN110408053B (en) * | 2019-08-22 | 2022-04-19 | 广东工业大学 | High-toughness anti-freezing heat-resistant polyacrylamide organic hydrogel and preparation method thereof |
| CN111393675B (en) * | 2020-03-18 | 2022-09-27 | 武汉纺织大学 | Rapid-forming self-healing hydrogel and preparation method thereof |
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| CN113185718A (en) * | 2021-05-19 | 2021-07-30 | 河南工业大学 | PH/temperature double-sensitive type interpenetrating network hydrogel and preparation method thereof |
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| CN1206260C (en) * | 2002-12-06 | 2005-06-15 | 暨南大学 | Chitosan grafted polyvinylpyrrolidone and its prepn process and application in preparing biodegradable material |
| CN100556924C (en) * | 2007-04-02 | 2009-11-04 | 东华大学 | The preparation method of temperature and pH value valve sensitive nano microgel |
| EP2191007B1 (en) * | 2007-04-20 | 2019-06-05 | Becton, Dickinson and Company | Hydrogel compositions |
| CN100480291C (en) * | 2007-06-15 | 2009-04-22 | 北京化工大学 | Method for preparing temperature sensitive hydrogel with supramolecular structure |
| CN100567375C (en) * | 2007-06-26 | 2009-12-09 | 上海大学 | PH sensitive aqueous gel and preparation method thereof |
| CN102911381B (en) * | 2012-11-12 | 2014-03-26 | 天津工业大学 | Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof |
| CN103656745B (en) * | 2013-12-12 | 2015-02-18 | 天津大学 | Gel-poly(lactide-co-glycolide) (PLGA) two-phase gradient transition cartilage-bone repair material and preparation thereof |
| CN104558420A (en) * | 2015-01-24 | 2015-04-29 | 福州大学 | Temperature/pH-sensitive carboxymethyl chitosan hydrogel and preparation method thereof |
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2017
- 2017-09-08 CN CN201710807679.9A patent/CN107540851B/en active Active
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112300327A (en) * | 2020-09-16 | 2021-02-02 | 北京市燃气集团有限责任公司 | High polymer and preparation and application thereof |
| CN117047886A (en) * | 2023-07-24 | 2023-11-14 | 广西科学院 | Method for preparing non-adhesive fiber board through microwave hot pressing |
| CN117047886B (en) * | 2023-07-24 | 2024-05-03 | 广西科学院 | Method for preparing non-adhesive fiber board through microwave hot pressing |
Also Published As
| Publication number | Publication date |
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| CN107540851B (en) | 2021-04-09 |
| CN107936177A (en) | 2018-04-20 |
| CN107540851A (en) | 2018-01-05 |
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