CN110183570A - A kind of preparation method of thermo-sensitive gel - Google Patents

A kind of preparation method of thermo-sensitive gel Download PDF

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CN110183570A
CN110183570A CN201910416420.0A CN201910416420A CN110183570A CN 110183570 A CN110183570 A CN 110183570A CN 201910416420 A CN201910416420 A CN 201910416420A CN 110183570 A CN110183570 A CN 110183570A
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thermo
mass ratio
preparation
sensitive gel
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CN110183570B (en
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李日生
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SHANDONG ZHUSHI PHARMACEUTICAL GROUP Co.,Ltd.
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/44Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention relates to a kind of preparation methods of thermo-sensitive gel, belong to field of material technology.The present invention is with cod skin, fly maggot is eaten as raw material, it is crushed by milling, enzymatic hydrolysis, obtain polypeptide and ispol, it is mixed again with n-isopropyl acrylamide, in the course of the polymerization process, pass through the modified sensitive property improved to poly(N-isopropylacrylamide) of supernatant and additive, it is crosslinked simultaneously using crosslinking agent and supernatant, improve the swelling effect of thermo-sensitive gel, improve the biocompatibility of thermo-sensitive gel, and the anti-microbial property of gel can be effectively increased by antibacterial polypeptide substance therein, the present invention is by utilizing chlorophyll and hydroxyethyl methacrylate simultaneously, n-vinyl pyrrolidone is mixed, by carrying out de-magging processing in acid condition, initiator is recycled to cause graft polymerization polymer, form the reticular structure of crosslinking, pass through the increase to temperature and photosensitive property, into And improve the Thermo-sensitive of thermo-sensitive gel.

Description

A kind of preparation method of thermo-sensitive gel
Technical field
The present invention relates to a kind of preparation methods of thermo-sensitive gel, belong to field of material technology.
Background technique
Hydrogel is prevalent in nature by the tridimensional network that macromolecule is covalently cross-linked and is formed A kind of common physical form.Intelligent aqueous gel be it is a kind of can perceive chemical or physical stimulus small in ambient enviroment, and It makes and responding rapidly to, and a kind of special hydrogel of significant change can occur for many properties of itself.It can be in water The middle a large amount of moisture of swellable absorbent, but being not dissolved in water this many structure with living organism has similitude, in recent years water Gel has been directed to the numerous areas such as biomedicine, material science, agronomy, synthesis of many researchers to hydrogel, property And practical application conducts extensive research.
Temperature-sensitive hydrogel is that water suction (or solvent) amount in a certain temperature has a hydrogel of mutation, and swelling ratio mutates When temperature be sensitive temperature.Since its temperature sensitivity is big, there is biggish swelling ratio, and sensitive temperature and people are close, This make its feed separation, immobilised enzymes, immunoassay, in terms of have wide purposes.Thermo-sensitive gel at present Although easy to operate, preparation cost is lower, its temperature sensitivity is lower, be swollen it is relatively low, so that its application range is relatively narrow.
Summary of the invention
The technical problems to be solved by the invention: lower for current thermo-sensitive gel temperature sensitivity, swelling ratio is lower Problem, the present invention provides a kind of preparation methods of thermo-sensitive gel.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of preparation method of thermo-sensitive gel, the preparation method include the following steps:
(1) cod skin, edible fly maggot and mixed solvent 3~6:1 in mass ratio~3:10 are milled, collects object of milling, it will Object of milling is mixed with mixed enzyme 14~16:1~3 in mass ratio, adjusts pH, is stood, enzymatic hydrolysis;
(2) after wait digest, centrifugation collects supernatant and takes 120~130 parts of water, 30~40 parts of N- different according to parts by weight Propylacrylamide, 12~15 portions of supernatants, 7~9 parts of additives, 1~3 part of initiator, 1~2 part of crosslinking agent;
(3) water, n-isopropyl acrylamide, additive are put into reaction kettle, using nitrogen protection, heating adds initiation Agent is stirred, cooling, and supernatant and crosslinking agent is added, and is stirred, and is stood, and material is collected out in discharging;
(4) output mixture, surfactant 17:1~3 in mass ratio are uniformly mixed, adjust pH, be concentrated under reduced pressure, sterilization disappears Poison is to get thermo-sensitive gel.
Mixed solvent in the step (1) is by water, sodium acetate, glycerol and citric acid 9~11:1 in mass ratio~4:6 ~8:2 is mixed.
Mixed enzyme is papain in the step (1), serine protease 3:1~3 in mass ratio mix.
The additive the preparation method comprises the following steps:
A. chlorophyll, mixture and ether 3:2~4:17 in mass ratio are put into reaction kettle, are preheated at 50~55 DEG C, then rise Temperature adjusts pH to 3.0~3.5, heat preservation to 85~95 DEG C of heating;
B. wait keep the temperature after, be added mixture quality 1~1.5% catalyst and hydroxyethyl methacrylate quality 2~4% Initiator A, temperature reaction is cooling, adjusts pH to neutrality, stands, filter, washing is dry to get additive.
In the A mixture be hydroxyethyl methacrylate, n-vinyl pyrrolidone 1:1 in mass ratio~3 mixing and At.
Catalyst is dibutyltindilaurylmercaptide cinnamic acid in the B.
Initiator A is azo-bis-isobutyl cyanide in the B.
The initiator is potassium peroxydisulfate, any one in ammonium persulfate.
The crosslinking agent is by N, and N- methylene acrylamide, Geniposide 3:1~4 in mass ratio mix.
Surfactant is lecithin, sorbitan fatty acid ester 6:1 in mass ratio~5 mixing in the step (4) It forms.
The present invention is compared with other methods, and advantageous effects are:
The present invention is crushed using cod skin, edible fly maggot as raw material by milling, and enzymatic hydrolysis obtains polypeptide and ispol, It is mixed again with n-isopropyl acrylamide, by carrying out hybrid reaction with n-isopropyl acrylamide, forms poly- (N- isopropyl Base acrylamide), in the course of the polymerization process, improved by supernatant and the modified of additive to poly(N-isopropylacrylamide) Sensitive property, while being crosslinked using crosslinking agent and supernatant, the swelling effect of thermo-sensitive gel is improved, thermo-sensitive gel is improved Biocompatibility, and the anti-microbial property of gel, while the present invention can be effectively increased by antibacterial polypeptide substance therein By being mixed using chlorophyll with hydroxyethyl methacrylate, n-vinyl pyrrolidone, by acid condition into The processing of row de-magging, recycles initiator to cause graft polymerization polymer, forms the reticular structure of crosslinking, by temperature and photosensitive The increase of performance, and then improve the Thermo-sensitive of thermo-sensitive gel.
Specific embodiment
Mixed solvent is to mix water, sodium acetate, glycerol and citric acid 9~11:1 in mass ratio~4:6~8:2.
Mixed enzyme is papain, serine protease 3:1~3 in mass ratio mix.
Mixture is hydroxyethyl methacrylate, n-vinyl pyrrolidone 1:1~3 in mass ratio mix.
Catalyst is dibutyltindilaurylmercaptide cinnamic acid.
Initiator A is azo-bis-isobutyl cyanide.
Additive the preparation method comprises the following steps:
A. chlorophyll, mixture and ether 3:2~4:17 in mass ratio are put into reaction kettle, in 50~55 DEG C of preheating 30min, It is warming up to 85~95 DEG C of heating 2h again, adjusts pH to 3.0~3.5, heat preservation;
B. wait keep the temperature after, be added mixture quality 1~1.5% catalyst and hydroxyethyl methacrylate quality 2~4% Initiator A, be warming up to 110~115 DEG C of reaction 10h, be cooled to room temperature, adjust pH to neutrality, stand 5h, filtering, to filter residue It is washed, it is dry to get additive.
Initiator is potassium peroxydisulfate, any one in ammonium persulfate.
Crosslinking agent is by N, and N- methylene acrylamide, Geniposide 3:1~4 in mass ratio mix.
Surfactant is lecithin, sorbitan fatty acid ester 6:1~5 in mass ratio mix.
A kind of preparation method of thermo-sensitive gel, the preparation method include the following steps:
(1) cod skin, edible fly maggot and mixed solvent 3~6:1 in mass ratio~3:10 are milled, collects object of milling, it will Object of milling is mixed with mixed enzyme 14~16:1~3 in mass ratio, adjusts pH to 8.0, is stood, and 5h is digested;
(2) after wait digest, 10min is centrifuged with 6000r/min, supernatant is collected and takes 120~130 parts according to parts by weight Water, 30~40 parts of n-isopropyl acrylamide, 12~15 portions of supernatants, 7~9 parts of additives, 1~3 part of initiator, 1~2 part of friendship Join agent;
(3) water, n-isopropyl acrylamide, additive are put into reaction kettle, using nitrogen protection, are heated to 70~80 DEG C, Initiator is added, 6h is stirred, is cooled to 50~55 DEG C, supernatant and crosslinking agent is added, stirs 50min, stands 3h, is discharged, Collect out material;
(4) output mixture, surfactant 17:1~3 in mass ratio are uniformly mixed, obtain mixture, adjust pH to neutrality, The 60~70% of volume of mixture are concentrated under reduced pressure into, sterilizing is to get thermo-sensitive gel.
Embodiment 1
Mixed solvent is to mix water, sodium acetate, glycerol and citric acid 11:4:8:2 in mass ratio.
Mixed enzyme is papain, serine protease 3:3 in mass ratio is mixed.
Mixture is hydroxyethyl methacrylate, n-vinyl pyrrolidone 1:1 in mass ratio is mixed.
Catalyst is dibutyltindilaurylmercaptide cinnamic acid.
Initiator A is azo-bis-isobutyl cyanide.
Additive the preparation method comprises the following steps:
A. chlorophyll, mixture and ether 3:2:17 in mass ratio are put into reaction kettle, in 50 DEG C of preheating 30min, then are heated up To 85 DEG C of heating 2h, pH to 3.0 is adjusted, keeps the temperature 3h;
B. wait keep the temperature after, be added mixture quality 1% catalyst and hydroxyethyl methacrylate quality 2% initiator A is warming up to 110 DEG C of reaction 10h, is cooled to room temperature, and adjusts pH to neutrality, and standing 5h is filtered, washed to filter residue, dry, Up to additive.
Initiator is potassium peroxydisulfate.
Crosslinking agent is to mix N, N- methylene acrylamide, Geniposide 3:4 in mass ratio.
Surfactant is lecithin, sorbitan fatty acid ester 6:5 in mass ratio is mixed.
A kind of preparation method of thermo-sensitive gel, the preparation method include the following steps:
(1) cod skin, edible fly maggot and mixed solvent 6:3:10 in mass ratio are milled, object of milling is collected, by object of milling It is mixed with mixed enzyme 16:3 in mass ratio, adjusts pH to 8.0, stood, digest 5h;
(2) after wait digest, 10min is centrifuged with 6000r/min, supernatant is collected and takes 130 parts of water, 40 according to parts by weight Part n-isopropyl acrylamide, 15 portions of supernatants, 9 parts of additives, 3 parts of initiators, 2 parts of crosslinking agents;
(3) water, n-isopropyl acrylamide, additive are put into reaction kettle, using nitrogen protection, are heated to 80 DEG C, then plus Enter initiator, stir 6h, be cooled to 55 DEG C, supernatant and crosslinking agent is added, stir 50min, stand 3h, discharging is collected in discharging Object;
(4) output mixture, surfactant 17:3 in mass ratio are uniformly mixed, obtain mixture, adjust pH to neutrality, decompression It is concentrated into the 70% of volume of mixture, sterilizing is to get thermo-sensitive gel.
Embodiment 2
Mixed solvent is to mix water, sodium acetate, glycerol and citric acid 10:3:7:2 in mass ratio.
Mixed enzyme is papain, serine protease 3:2 in mass ratio is mixed.
Mixture is hydroxyethyl methacrylate, n-vinyl pyrrolidone 1:2 in mass ratio is mixed.
Catalyst is dibutyltindilaurylmercaptide cinnamic acid.
Initiator A is azo-bis-isobutyl cyanide.
Additive the preparation method comprises the following steps:
A. chlorophyll, mixture and ether 3:3:17 in mass ratio are put into reaction kettle, in 53 DEG C of preheating 30min, then are heated up To 90 DEG C of heating 2h, pH to 3.0 is adjusted, keeps the temperature 3h;
B. wait keep the temperature after, be added mixture quality 1.3% catalyst and hydroxyethyl methacrylate quality 3% initiation Agent A is warming up to 113 DEG C of reaction 10h, is cooled to room temperature, and adjusts pH to neutrality, stands 5h, filter residue is washed in filtering, does It is dry to get additive.
Initiator is ammonium persulfate.
Crosslinking agent is to mix N, N- methylene acrylamide, Geniposide 3:3 in mass ratio.
Surfactant is lecithin, sorbitan fatty acid ester 6:3 in mass ratio is mixed.
A kind of preparation method of thermo-sensitive gel, the preparation method include the following steps:
(1) cod skin, edible fly maggot and mixed solvent 5:2:10 in mass ratio are milled, object of milling is collected, by object of milling It is mixed with mixed enzyme 15:2 in mass ratio, adjusts pH to 8.0, stood, digest 5h;
(2) after wait digest, 10min is centrifuged with 6000r/min, supernatant is collected and takes 125 parts of water, 35 according to parts by weight Part n-isopropyl acrylamide, 14 portions of supernatants, 8 parts of additives, 2 parts of initiators, 1.5 parts of crosslinking agents;
(3) water, n-isopropyl acrylamide, additive are put into reaction kettle, using nitrogen protection, are heated to 75 DEG C, then plus Enter initiator, stir 6h, be cooled to 53 DEG C, supernatant and crosslinking agent is added, stir 50min, stand 3h, discharging is collected in discharging Object;
(4) output mixture, surfactant 17:2 in mass ratio are uniformly mixed, obtain mixture, adjust pH to neutrality, decompression It is concentrated into the 65% of volume of mixture, sterilizing is to get thermo-sensitive gel.
Embodiment 3
Mixed solvent is to mix water, sodium acetate, glycerol and citric acid 9:1:6:2 in mass ratio.
Mixed enzyme is papain, serine protease 3:1 in mass ratio is mixed.
Mixture is hydroxyethyl methacrylate, n-vinyl pyrrolidone 1:3 in mass ratio is mixed.
Catalyst is dibutyltindilaurylmercaptide cinnamic acid.
Initiator A is azo-bis-isobutyl cyanide.
Additive the preparation method comprises the following steps:
A. chlorophyll, mixture and ether 3:4:17 in mass ratio are put into reaction kettle, in 50~55 DEG C of preheating 30min, then 95 DEG C of heating 2h are warming up to, pH to 3.5 is adjusted, keep the temperature 3h;
B. wait keep the temperature after, be added mixture quality 1.5% catalyst and hydroxyethyl methacrylate quality 4% initiation Agent A is warming up to 115 DEG C of reaction 10h, is cooled to room temperature, and adjusts pH to neutrality, stands 5h, filter residue is washed in filtering, does It is dry to get additive.
Initiator is potassium peroxydisulfate.
Crosslinking agent is to mix N, N- methylene acrylamide, Geniposide 3:1 in mass ratio.
Surfactant is lecithin, sorbitan fatty acid ester 6:1 in mass ratio is mixed.
A kind of preparation method of thermo-sensitive gel, the preparation method include the following steps:
(1) cod skin, edible fly maggot and mixed solvent 3:1:10 in mass ratio are milled, object of milling is collected, by object of milling It is mixed with mixed enzyme 14:1 in mass ratio, adjusts pH to 8.0, stood, digest 5h;
(2) after wait digest, 10min is centrifuged with 6000r/min, supernatant is collected and takes 120 parts of water, 30 according to parts by weight Part n-isopropyl acrylamide, 12 portions of supernatants, 7 parts of additives, 1 part of initiator, 1 part of crosslinking agent;
(3) water, n-isopropyl acrylamide, additive are put into reaction kettle, using nitrogen protection, are heated to 70 DEG C, then plus Enter initiator, stir 6h, be cooled to 50 DEG C, supernatant and crosslinking agent is added, stir 50min, stand 3h, discharging is collected in discharging Object;
(4) output mixture, surfactant 17:1 in mass ratio are uniformly mixed, obtain mixture, adjust pH to neutrality, decompression It is concentrated into the 60% of volume of mixture, sterilizing is to get thermo-sensitive gel.
Comparative example 1
Mixed solvent is to mix water, sodium acetate, glycerol and citric acid 10:3:7:2 in mass ratio.
Mixed enzyme is papain, serine protease 3:2 in mass ratio is mixed.
Mixture is hydroxyethyl methacrylate, n-vinyl pyrrolidone 1:2 in mass ratio is mixed.
Catalyst is dibutyltindilaurylmercaptide cinnamic acid.
Initiator A is azo-bis-isobutyl cyanide.
Additive the preparation method comprises the following steps:
A. chlorophyll, mixture and ether 3:3:17 in mass ratio are put into reaction kettle, in 53 DEG C of preheating 30min, then are heated up To 90 DEG C of heating 2h, pH to 3.0 is adjusted, keeps the temperature 3h;
B. wait keep the temperature after, be added mixture quality 1.3% catalyst and hydroxyethyl methacrylate quality 3% initiation Agent A is warming up to 113 DEG C of reaction 10h, is cooled to room temperature, and adjusts pH to neutrality, stands 5h, filter residue is washed in filtering, does It is dry to get additive.
Initiator is ammonium persulfate.
Crosslinking agent is to mix N, N- methylene acrylamide, Geniposide 3:3 in mass ratio.
Surfactant is lecithin, sorbitan fatty acid ester 6:3 in mass ratio is mixed.
A kind of preparation method of thermo-sensitive gel, the preparation method include the following steps:
(1) cod skin, edible fly maggot and mixed solvent 5:2:10 in mass ratio are milled, object of milling is collected, by object of milling It is mixed with mixed enzyme 15:2 in mass ratio, adjusts pH to 8.0, stood, digest 5h;
(2) after wait digest, 10min is centrifuged with 6000r/min, supernatant is collected and takes 125 parts of water, 35 according to parts by weight Part n-isopropyl acrylamide, 8 parts of additives, 2 parts of initiators, 1.5 parts of crosslinking agents;
(3) water, n-isopropyl acrylamide, additive are put into reaction kettle, using nitrogen protection, are heated to 75 DEG C, then plus Enter initiator, stir 6h, be cooled to 53 DEG C, crosslinking agent is added, stir 50min, stand 3h, material is collected out in discharging;
(4) output mixture, surfactant 17:2 in mass ratio are uniformly mixed, obtain mixture, adjust pH to neutrality, decompression It is concentrated into the 65% of volume of mixture, sterilizing is to get thermo-sensitive gel.
Comparative example 2
It is substantially the same manner as Example 2, only the difference is that lacking supernatant.
Comparative example 3
Commercially available poly(N-isopropylacrylamide) thermo-sensitive gel.
Thermo-sensitive gel in embodiment and comparative example is detected.
At room temperature, colloidal sol is placed in the plastic centrifuge tube of 1.5mL, is put into 37 DEG C of water-bath, make its gelation, A period of time is irradiated under certain power with microwave therapy apparatus physiotherapy cervix, carries out thermometric with imported from America thermocouple wire, is surveyed Determine gel medium temperature, detects fringe time of the colloidal sol to gel;
The characterization of water absorption rate: the gel (n=5) after taking fritter to be lyophilized claims its quality, is denoted as W1, is immersed in distilled water For 24 hours, it then takes out, wipes excess surface moisture away, then claim its quality, be denoted as W2, water absorption rate calculation formula are as follows: E=(W2- W1)/W1*100%, testing result are as follows:
Fringe time (min) Water absorption rate (%)
Embodiment 1 2 568
Embodiment 2 1.2 593
Embodiment 3 1.8 572
Comparative example 1 3.8 521
Comparative example 2 3.2 558
Comparative example 3 2.3 547
Thermo-sensitive gel prepared by the present invention can to sum up be obtained with preferable performance.

Claims (10)

1. a kind of preparation method of thermo-sensitive gel, which is characterized in that the preparation method includes the following steps:
(1) cod skin, edible fly maggot and mixed solvent 3~6:1 in mass ratio~3:10 are milled, collects object of milling, it will Object of milling is mixed with mixed enzyme 14~16:1~3 in mass ratio, adjusts pH, is stood, enzymatic hydrolysis;
(2) after wait digest, centrifugation collects supernatant and takes 120~130 parts of water, 30~40 parts of N- different according to parts by weight Propylacrylamide, 12~15 portions of supernatants, 7~9 parts of additives, 1~3 part of initiator, 1~2 part of crosslinking agent;
(3) water, n-isopropyl acrylamide, additive are put into reaction kettle, using nitrogen protection, heating adds initiation Agent is stirred, cooling, and supernatant and crosslinking agent is added, and is stirred, and is stood, and material is collected out in discharging;
(4) output mixture, surfactant 17:1~3 in mass ratio are uniformly mixed, adjust pH, be concentrated under reduced pressure, sterilization disappears Poison is to get thermo-sensitive gel.
2. the preparation method of thermo-sensitive gel according to claim 1, which is characterized in that the mixed solvent in the step (1) For water, sodium acetate, glycerol and citric acid 9~11:1 in mass ratio~4:6~8:2 are mixed.
3. the preparation method of thermo-sensitive gel according to claim 1, which is characterized in that mixed enzyme is wood in the step (1) Melon protease, serine protease 3:1~3 in mass ratio mix.
4. the preparation method of thermo-sensitive gel according to claim 1, which is characterized in that the additive the preparation method comprises the following steps:
A. chlorophyll, mixture and ether 3:2~4:17 in mass ratio are put into reaction kettle, are preheated at 50~55 DEG C, then rise Temperature adjusts pH to 3.0~3.5, heat preservation to 85~95 DEG C of heating;
B. wait keep the temperature after, be added mixture quality 1~1.5% catalyst and hydroxyethyl methacrylate quality 2~4% Initiator A, temperature reaction is cooling, adjusts pH to neutrality, stands, filter, washing is dry to get additive.
5. the preparation method of thermo-sensitive gel according to claim 4, which is characterized in that mixture is metering system in the A Sour hydroxyl ethyl ester, n-vinyl pyrrolidone 1:1~3 in mass ratio mix.
6. the preparation method of thermo-sensitive gel according to claim 4, which is characterized in that catalyst is dibutyl tin in the B Tin dilaurate.
7. the preparation method of thermo-sensitive gel according to claim 4, which is characterized in that initiator A is that azo two is different in the B Fourth cyanogen.
8. the preparation method of thermo-sensitive gel according to claim 1, which is characterized in that the initiator is potassium peroxydisulfate, mistake Any one in ammonium sulfate.
9. the preparation method of thermo-sensitive gel according to claim 1, which is characterized in that the crosslinking agent is by N, N- methylene Acrylamide, Geniposide 3:1~4 in mass ratio mix.
10. the preparation method of thermo-sensitive gel according to claim 1, which is characterized in that surfactant in the step (4) It is mixed for lecithin, sorbitan fatty acid ester 6:1~5 in mass ratio.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001261845A (en) * 2000-03-14 2001-09-26 Mitsubishi Chemicals Corp Hydrogel particulate
CN102816340A (en) * 2012-09-06 2012-12-12 北京理工大学 Intelligent light adjusting film based on temperature-sensitive polymer hydrogel and preparation method of intelligent light adjusting film
CN107936177A (en) * 2017-09-03 2018-04-20 湖南七纬科技有限公司 A kind of temperature sensitive response type hydrogel based on chitosan and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001261845A (en) * 2000-03-14 2001-09-26 Mitsubishi Chemicals Corp Hydrogel particulate
CN102816340A (en) * 2012-09-06 2012-12-12 北京理工大学 Intelligent light adjusting film based on temperature-sensitive polymer hydrogel and preparation method of intelligent light adjusting film
CN107936177A (en) * 2017-09-03 2018-04-20 湖南七纬科技有限公司 A kind of temperature sensitive response type hydrogel based on chitosan and preparation method thereof

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