CN107936177A - A kind of temperature sensitive response type hydrogel based on chitosan and preparation method thereof - Google Patents
A kind of temperature sensitive response type hydrogel based on chitosan and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of temperature sensitive response type hydrogel based on chitosan and preparation method thereof, it is main polymerized monomer by N N-isopropylacrylamides of polymerized monomer, ensure that the temperature sensitive response performance of hydrogel, is conducive to simulate biotic environment；By to vinylation and Water-borne modification from natural chitosan, the response temperature of hydrogel is set to be more nearly human body temperature, simultaneously because the distinctive pliability of chitosan molecule structure and its tridimensional network formed after copolymerization, improve swelling and the deswelling dynamics of hydrogel so that hydrogel prepared by the present invention has the characteristics that quick response；In addition all excellent biocompatibility of the chitosan unit in hydrogel structure of the present invention, polyvinylpyrrolidone unit, does not form skin, mucous membrane, eye etc. any stimulation, therefore it is with a wide range of applications in biology, medical field.
Description
Technical field
The present invention relates to a kind of hydrogel, more particularly to a kind of temperature sensitive response type hydrogel and its system based on chitosan
Preparation Method and application, belong to technical field of hydrogel.
Technical background
Temperature-sensitive hydrogel is a kind of hydrophilic macromolecule cross-linked network, it can perceive the minor variations of ambient temperature,
And the stimulation in the external world is responded by the expansion of own vol and contraction.The These characteristics of temperature-sensitive hydrogel make it in medicine control
System release, material separating-purifying, light control material, tissue cultures, immobilised enzymes etc. have wide application prospects.
At present, the more poly-N-isopropyl acrylamide for being and its derivative are studied, PNIPAM class hydrogels are as one
The typical thermal shrinkage type temperature sensitive hydrogel of kind, its phase transition temperature are 32 DEG C or so, 37 DEG C of left sides of normal body temperature with human body
The right side is very close to when temperature is below or above 32 DEG C, PNIPAM hydrogels are respectively at swelling or deswelling state in water.It is molten
Swollen and deswelling speed is an important parameter for weighing thermosensitive aquagel temperature-sensitive property also referred to as the speed of response.
Chinese patent CN101712736A provides the side that a kind of ripple polymerization technique prepares fast responsive temperature-sensitive hydrogel
Method.Step is：(1) pre-gathering solutions are configured：It is molten that thermosensitive type monomer and crosslinking agent are dissolved in water/dimethyl sulfoxide mixing by a certain percentage
Agent, is made into homogeneous solution, wherein：Crosslinking agent N, N`- methylene-bisacrylamide, account for thermosensitive type monomer weight ratio for 1.2~
0.4%；The initiator for accounting for that thermosensitive type monomer weight ratio is 1.2~0.5% is added, obtains pre-gathering solutions.(2) will be above-mentioned pre-
The reaction mixture of poly solution is moved into reactor and heated, and is thermally decomposed initiator, polymerisation starts；(3) reaction is opened
After beginning, heat source is withdrawn, maintains reaction to carry out by polymerization exotherm, until all raw materials in whole reactor are completely converted into polymerization
Thing；(4) polymer obtained by step (3) is taken out, is rinsed with deionized water, obtains product.For industrial production fast responsive temperature-sensitive
Type hydrogel opens up new approach.But monomer etc. used in the invention is synthesis type industrial chemicals, and biocompatibility, the feature of environmental protection are poor,
It is limited in medicine, the application of biological field.
Chinese patent CN103122115A provides a kind of irreversible temperature-sensitive hydrogel and preparation method thereof, belongs to water-setting
Glue technical field, its is nontoxic, has a wide range of application, and holding time length (up to more than 1 year), denaturation temperature can be 60~65 DEG C of left sides
The right side, thermochromic zone are stablized, sharpness of border, and repeatability is strong；And preparation process is simple, suitable for producing in enormous quantities.The present invention is not
Reversible temperature-sensitive hydrogel contains (percentage by weight)：2% to 10% polyvinyl alcohol；5% to 40% temperature sensitivity refers to
Show agent；10% to 67.5% polyalcohol antifreeze；25% to 60% water.The irreversible temperature-sensitive hydrogel of the invention
Preparation method includes preparing above-mentioned irreversible temperature-sensitive hydrogel with freeze-thaw method.But due to its phase transition temperature is higher,
Phase in version limits the extensive use of the invention there are irreversibility.
The content of the invention
To overcome shortcoming and deficiency existing in the prior art, the purpose of the present invention aims to provide a kind of temperature based on chitosan
Quick response type hydrogel.
It is still another object of the present invention to provide a kind of preparation method of the temperature sensitive response type hydrogel based on chitosan.
It is still another object of the present invention to provide a kind of temperature sensitive response type hydrogel based on chitosan in biology, medicine neck
Application in domain.
A kind of temperature sensitive response type hydrogel based on chitosan of the present invention is with n-isopropyl acrylamide, Water-borne modification
Vinyl modified chitosan, vinyl pyrrolidone, crosslinking agent be comonomer, prepared using specific radical polymerization
Form, there is Thermo-sensitive, fast response time, good biocompatibility, its preparation method is as follows：
A) preparation of the vinyl modified chitosan of Water-borne modification：By 15~20 parts of chitosans, 1~3 part of catalyst, 30~50
Part organic solvent is added in reaction kettle, and 30~60 DEG C are heated to after stirring and dissolving is uniform, and 5~10 parts of metering systems are added dropwise dropwise
Acid glycidyl ester, 30~60 DEG C of 4~8h of reaction；5~10 parts of cyclic alkyl sultones is added, 30~60 DEG C the reaction was continued
3~5h postcoolings are to room temperature；Then addition acetone is precipitated after adding methanol dissolved dilution, filters precipitation, it is molten to repeat methanol
Solution dilution, acetone are precipitated, and vacuum drying precipitates the vinyl modified chitosan up to Water-borne modification.
B) preparation of hydrogel：By 10~30 parts a) in Water-borne modification vinyl modified chitosan, 100 parts of N- it is different
Propylacrylamide, 5~10 parts of vinyl pyrrolidones, 3~10 parts of crosslinking agent are dissolved in organic solvent, are sufficiently mixed uniformly
Afterwards, 60~100 DEG C are heated to by the way that the organic solvent solution containing 1~3 part of initiator is added dropwise dropwise, 0.5~1h is dripped
Finish, 60~100 DEG C of the reaction was continued 12~72h, jel product is obtained after cooling, is inserted after taking out jel product using physical method
Soaked one week in deionized water water, change water daily, remove unreacted raw material up to a kind of temperature sensitive response type based on chitosan
Hydrogel.
The chitosan number-average molecular weight is less than 500,000, is preferably chitosan, portion that natural chitin deacetylation obtains
Divide at least one of chitosan, chitosan oligosaccharide of hydrolysis.
The catalyst is 2,4,6- tri- (dimethylamino methyl) phenol, triethylamine, N, N- dimethyl-p-toluidines, three second
At least one of hydramine, N- methylpyrroles, N- methyl piperidines, trimethylamine.
The organic solvent is N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, hexamethyl phosphinylidyne
At least one of triamine, nitromethane, acetonitrile.
The cyclic alkyl sultones is 1,3- propane sultones, 1- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 2- methyl-
1,3- propane sultones, 3- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 1,4- butyl sultones, 1- methyl isophthalic acids, 4- butyl sultones, 2-
Methyl isophthalic acid, 4- butyl sultones, 3- methyl isophthalic acids, 4- butyl sultones, at least one of 4- methyl isophthalic acids, 4- butyl sultones.
The crosslinking agent is polyethyleneglycol diacrylate, dimethyl allene vinyl acetate, N- (1,1- dimethyl -3-
Oxo butyl) acrylamide, N, N- di-2-ethylhexylphosphine oxides acrylamide, polyethylene glycol double methyl methacrylate, gather double acrylic acid in oneself
At least one of ester.
The initiator is benzoyl peroxide, azodiisobutyronitrile, azobisisoheptonitrile, two isobutyric acid diformazan of azo
At least one of ester, diphenyl peroxide t-butyl formate, two tertiary butane of peroxidating, diisopropylbenzyl peroxide.
A kind of temperature sensitive response type hydrogel based on chitosan of the present invention, is gathered based on n-isopropyl acrylamide
Monomer is closed, ensure that the temperature sensitive response performance of hydrogel, is conducive to simulate biotic environment；By to from natural chitosan
Vinylation and Water-borne modification, make the response temperature of hydrogel be more nearly human body temperature, simultaneously because chitosan molecule structure is peculiar
Pliability and its tridimensional network that is formed after copolymerization, improve swelling and the deswelling dynamics of hydrogel so that
Hydrogel prepared by the present invention has the characteristics that quick response；In addition, the chitosan in hydrogel structure of the present invention
Unit, polyvinylpyrrolidone unit all have excellent biocompatibility, and any thorn is not formed to skin, mucous membrane, eye etc.
Swash；Therefore it is with a wide range of applications in biology, medical field, and energy large-scale application is in making food, medicine, biological material
Material or medical material.
Brief description of the drawings
Fig. 1 is the swelling ratio schematic diagram of hydrogel at different temperatures in the embodiment of the present invention
Fig. 2 is that hydrogel removes swelling ratio schematic diagram under different durations in the embodiment of the present invention
Embodiment
With reference to embodiment to a kind of temperature sensitive response type hydrogel based on chitosan of the present invention and preparation method thereof
It is further described with application.It is understood that specific embodiment described herein is used only for explaining related invention,
Rather than the restriction to the invention.
Embodiment 1
A kind of temperature sensitive response type hydrogel based on chitosan of the present invention is with n-isopropyl acrylamide, Water-borne modification
Vinyl modified chitosan, vinyl pyrrolidone, crosslinking agent be comonomer, prepared using specific radical polymerization
Form, there is Thermo-sensitive, fast response time, good biocompatibility, its preparation method is as follows：
A) preparation of the vinyl modified chitosan of Water-borne modification：By 15 parts of chitosans (number-average molecular weight 100000 ±
5000), 1 part of N, N- dimethyl-p-toluidine, 40 parts of dimethyl sulfoxides are added in reaction kettle, and 50 are heated to after stirring and dissolving is uniform
DEG C, 10 parts of glycidyl methacrylate, 50 DEG C of reaction 4h are added dropwise dropwise；Add 8 parts of 1,3-propane sultone, 60 DEG C after
Continuous 3h postcoolings of reacting are to room temperature；Then addition acetone is precipitated after adding methanol dissolved dilution, is filtered precipitation, is repeated methanol
Dissolved dilution, acetone are precipitated, and vacuum drying precipitates the vinyl modified chitosan up to Water-borne modification.
B) preparation of hydrogel：By 20 parts a) in Water-borne modification vinyl modified chitosan, 100 parts of N- isopropyls third
Acrylamide, 8 parts of vinyl pyrrolidones, 5 parts of polyethyleneglycol diacrylate are dissolved in DMF, after being sufficiently mixed uniformly, are added
Heat to 100 DEG C by being added dropwise the DMF solution containing 1 part of azodiisobutyronitrile dropwise, and 1h is added dropwise, and 100 DEG C the reaction was continued
36h, jel product is obtained after cooling, is taken out to insert after jel product using physical method and is soaked one week in deionized water water, often
It changes water, removes unreacted raw material up to the temperature sensitive response type hydrogel based on chitosan.Hydrogel in this example is different
At a temperature of expansion ratio see attached drawing 1, attached drawing 2.
Embodiment 2
A kind of temperature sensitive response type hydrogel based on chitosan of the present invention is with n-isopropyl acrylamide, Water-borne modification
Vinyl modified chitosan, vinyl pyrrolidone, crosslinking agent be comonomer, prepared using specific radical polymerization
Form, there is Thermo-sensitive, fast response time, good biocompatibility, its preparation method is as follows：
A) preparation of the vinyl modified chitosan of Water-borne modification：10 parts of chitosan oligosaccharides, 1 part of triethylamine, 40 parts of DMF are added
Into reaction kettle, 40 DEG C are heated to after stirring and dissolving is uniform, 5 parts of glycidyl methacrylate, 40 DEG C of reactions are added dropwise dropwise
8h；Add 5 parts of 3- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 40 DEG C of the reaction was continued 5h postcoolings to room temperature；Then it is molten to add methanol
Acetone is added after solution dilution to be precipitated, filters precipitation, repeats methanol dissolved dilution, acetone is precipitated, vacuum drying precipitation
Up to the vinyl modified chitosan of Water-borne modification.
B) preparation of hydrogel：By 20 parts a) in Water-borne modification vinyl modified chitosan, 100 parts of N- isopropyls third
Acrylamide, 10 parts of vinyl pyrrolidones, 10 parts of N, N- di-2-ethylhexylphosphine oxide acrylamides are dissolved in DMSO, are sufficiently mixed uniformly
Afterwards, be heated to 75 DEG C has DMSO solution by being added dropwise dropwise containing 1 part of dibenzoyl peroxide, and 0.5h is added dropwise, and 75
DEG C the reaction was continued 72h, jel product is obtained after cooling, is taken out to insert in deionized water water after jel product using physical method and is soaked
Bubble one week, changes water daily, removes unreacted raw material up to the temperature sensitive response type hydrogel based on chitosan.By water in this example
Expansion ratio under gel different temperatures is shown in attached drawing 1, attached drawing 2.
Embodiment 3
A kind of temperature sensitive response type hydrogel based on chitosan of the present invention is with n-isopropyl acrylamide, Water-borne modification
Vinyl modified chitosan, vinyl pyrrolidone, crosslinking agent be comonomer, prepared using specific radical polymerization
Form, there is Thermo-sensitive, fast response time, good biocompatibility, its preparation method is as follows：
A) preparation of the vinyl modified chitosan of Water-borne modification：By 20 parts of chitosans (number-average molecular weight 50000 ±
2000), 1.9 parts of N- methylpyrroles, 40 parts of hexamethylphosphoramide are added in reaction kettle, and 60 are heated to after stirring and dissolving is uniform
DEG C, 10 parts of glycidyl methacrylate, 60 DEG C of reaction 4h are added dropwise dropwise；Isosorbide-5-Nitrae-butyl sultone of 10 parts of addition, 60 DEG C
5h postcoolings that the reaction was continued are to room temperature；Then addition acetone is precipitated after adding methanol dissolved dilution, is filtered precipitation, is repeated first
Alcohol dissolved dilution, acetone are precipitated, and vacuum drying precipitates the vinyl modified chitosan up to Water-borne modification.
B) preparation of hydrogel：By 10~30 parts a) in Water-borne modification vinyl modified chitosan, 100 parts of N- it is different
Propylacrylamide, 8 parts of vinyl pyrrolidones, 3 parts of N- (1,1- dimethyl -3- oxos butyl) acrylamide are dissolved in DMF
In, after being sufficiently mixed uniformly, 85 DEG C are heated to by being added dropwise the DMF containing 3 parts of azo-bis-iso-dimethyl dropwise, 0.5
~1h is added dropwise, and 85 DEG C of the reaction was continued 48h, jel product is obtained after cooling, and jel product postposition is taken out using physical method
Enter in deionized water water and soak one week, change water daily, remove unreacted raw material up to the temperature sensitive response type water based on chitosan
Gel.Expansion ratio under hydrogel different temperatures in this example is shown in into attached drawing 1, attached drawing 2.
Claims (10)
1. a kind of preparation method of the temperature sensitive response type hydrogel based on chitosan, it is characterised in that include the following steps：
A) preparation of the vinyl modified chitosan of Water-borne modification：15~20 parts of chitosans, 1~3 part of catalyst, 30~50 parts are had
Solvent is added in reaction kettle, and 30~60 DEG C are heated to after stirring and dissolving is uniform, and 5~10 parts of methacrylic acid contractings are added dropwise dropwise
Water glyceride, 30~60 DEG C of 4~8h of reaction；Add 5~10 parts of cyclic alkyl sultones, 30~60 DEG C the reaction was continued 3~
5h postcoolings are to room temperature；Then addition acetone is precipitated after adding methanol dissolved dilution, filters precipitation, and it is dilute to repeat methanol dissolving
Release, acetone is precipitated, vacuum drying precipitates the vinyl modified chitosan up to Water-borne modification；
B) preparation of hydrogel：By 10~30 parts a) in Water-borne modification vinyl modified chitosan, 100 parts of N- isopropyls third
Acrylamide, 5~10 parts of vinyl pyrrolidones, 3~10 parts of crosslinking agent are dissolved in organic solvent, after being sufficiently mixed uniformly, are added
To 60~100 DEG C by the way that the organic solvent solution containing 1~3 part of initiator is added dropwise dropwise, 0.5~1h is added dropwise heat, and 60
~100 DEG C of the reaction was continued 12~72h, jel product is obtained after cooling, taken out using physical method insert after jel product from
Soaked one week in sub- water water, change water daily, remove unreacted raw material up to a kind of temperature sensitive response type water-setting based on chitosan
Glue.
2. a kind of preparation method of temperature sensitive response type hydrogel based on chitosan according to claim 1, its feature exist
In the chitosan number-average molecular weight is less than 500,000, chitosan, the shell of partial hydrolysis obtained for natural chitin deacetylation
At least one of glycan, chitosan oligosaccharide.
3. a kind of preparation method of temperature sensitive response type hydrogel based on chitosan according to claim 1, its feature exist
In, the catalyst be 2,4,6- tri- (dimethylamino methyl) phenol, triethylamine, N, N- dimethyl-p-toluidines, triethanolamine,
At least one of N- methylpyrroles, N- methyl piperidines, trimethylamine.
4. a kind of preparation method of temperature sensitive response type hydrogel based on chitosan according to claim 1, its feature exist
In, the organic solvent be n,N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, hexamethylphosphoramide,
At least one of nitromethane, acetonitrile.
5. a kind of preparation method of temperature sensitive response type hydrogel based on chitosan according to claim 1, its feature exist
In the cyclic alkyl sultones is 1,3-propane sultone, 1- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 2- methyl isophthalic acids, 3- third
Sultones, 3- methyl isophthalic acids, 3-N-morpholinopropanesulfonic acid lactone, 1,4- butyl sultones, 1- methyl isophthalic acids, 4- butyl sultones, 2- methyl isophthalic acids,
4- butyl sultones, 3- methyl isophthalic acids, 4- butyl sultones, at least one of 4- methyl isophthalic acids, 4- butyl sultones.
6. a kind of preparation method of temperature sensitive response type hydrogel based on chitosan according to claim 1, its feature exist
In the crosslinking agent is polyethyleneglycol diacrylate, dimethyl allene vinyl acetate, N- (1,1- dimethyl -3- oxo fourths
Base) acrylamide, N, N- di-2-ethylhexylphosphine oxides acrylamide, polyethylene glycol double methyl methacrylate, gather in oneself in double methacrylate
It is at least one.
7. a kind of preparation method of temperature sensitive response type hydrogel based on chitosan according to claim 1, its feature exist
In the initiator is benzoyl peroxide, azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, mistake
Aoxidize at least one of the dibenzoic acid tert-butyl ester, two tertiary butane of peroxidating, diisopropylbenzyl peroxide.
8. a kind of temperature sensitive response type hydrogel based on chitosan according to any one of claims 1 to 7, its feature exist
In：A kind of temperature sensitive response type hydrogel based on chitosan for preparing gained is with n-isopropyl acrylamide, the second of Water-borne modification
Alkenyl modification of chitosan, vinyl pyrrolidone, crosslinking agent are comonomer, using the preparation of specific radical polymerization
Into.
A kind of 9. temperature sensitive response type hydrogel based on chitosan according to claim 8, it is characterised in that：The water
Property vinyl modified chitosan, be chitosan, catalyst, after the heated stirring and dissolving of organic solvent, metering system be added dropwise
Acid glycidyl ester and the reaction of cyclic alkyl sultones, add methanol dissolved dilution, add acetone suction filtration precipitation gained
Product.
10. a kind of application process of temperature sensitive response type hydrogel based on chitosan according to claim 8, its feature exist
In the temperature sensitive response type hydrogel has Thermo-sensitive, fast response time, good biocompatibility, and energy large-scale application is in system
Make food, medicine, biomaterial or medical material.
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Also Published As
| Publication number | Publication date |
|---|---|
| CN111363169A (en) | 2020-07-03 |
| CN107540851B (en) | 2021-04-09 |
| CN107540851A (en) | 2018-01-05 |
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