CN106750030A - The preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel - Google Patents
The preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel Download PDFInfo
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- CN106750030A CN106750030A CN201611132144.8A CN201611132144A CN106750030A CN 106750030 A CN106750030 A CN 106750030A CN 201611132144 A CN201611132144 A CN 201611132144A CN 106750030 A CN106750030 A CN 106750030A
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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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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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
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
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Abstract
The present invention relates to a kind of preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The method is to make comonomer with MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methacrylic acid β hydroxypropyl acrylates, fumaric acid, PEGDMA-400 makees crosslinking agent, and potassium peroxydisulfate sodium hydrogensulfite makees initiator and carry out copolymerization in deionized water to obtain organic amphiprotic copolymerized macromolecule first network gel；The first network gel is in sorbic acid, xylitol, dimethylaminoethyl acrylate, dimethacrylate 1, it is swelling in the aqueous solution that 3 butanediol esters and deionized water are prepared, monomer, crosslinking agent in the aqueous solution are copolymerized conjunction, esterification through the effect of potassium peroxydisulfate, pyridoxine hydrochloride, finally obtain organic amphiprotic copolymerized macromolecule interpenetrating networks gel.
Description
Technical field
The present invention relates to a kind of preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel.
Background technology
Gel is a kind of special dispersion, and high-polymer molecular or colloidal solid interconnect, and to form three dimensions netted
Structure, can absorb substantial amounts of water-swellable and water insoluble, and definite shape can be kept in water, have solid and liquid duality concurrently
Matter.Macroscopically see, high-molecular gel has certain shape, applying certain external force can deform, can recover original after removal external force
Shape, the viscoplasticity with solid；Seen on microcosmic, high-molecular gel has three-dimensional net structure water insoluble, three-dimensional network point
Son can stretch in water, with liquid property.With soft, water content it is high and have the viscoelastic gel of rubber environmental protection, weaving,
All many-sides such as building materials, petrochemical industry, food, agricultural gardening, daily cosmetics have and are widely applied.
Organism including humans is all high-molecular gel composition, mostly with electrical, such as protein, amino acid.
Copolymerization Amphiphatic high polymer interpenetrating networks gel can obtain Protean specific performance, particularly height and contains with the change of copolymerization component
The similitude of the electrical and organization of human body in water and molecule, good biocompatibility, environmental stimulus response is cured in biology
The fields such as medicine controlled releasing, bio-sensing, the organizational project in medicine field have obtained some applications.
The problem that the preparation method of current organic amphiprotic copolymerized macromolecule interpenetrating networks gel is primarily present is monomer propylene
The toxic articles of acid amides category " carcinogenic, aberration inducing, mutagenesis ", crosslinking agent N, N methylene diacrylamine toxicity is larger, and gel is deposited
In unfavorable toxic effect；The interpenetrating networks gel stability that single crosslinking agent is formed is relatively low.Exploitation uses nontoxic or low toxicity
Monomer, crosslinking agent carry out combined polymerization to reduce gel toxicity, forming multiple interpenetrating networks using compounding crosslinking agent improves gel
The preparation method of the organic amphiprotic copolymerized macromolecule interpenetrating networks gel of stability has larger practical value.
The content of the invention
For the problem that the preparation method of current organic amphiprotic copolymerized macromolecule interpenetrating networks gel is present, mesh of the invention
Be to provide it is a kind of use nontoxic or low-toxicity monomer, the crosslinking agent to carry out combined polymerization to reduce gel toxicity, use and compound crosslinking agent
The preparation method that multiple interpenetrating networks improve the organic amphiprotic copolymerized macromolecule interpenetrating networks gel of gel stability is formed, it is special
It is that in closed reactor component A and deionized water stirring can added to prepare the aqueous solution to levy, and the weight concentration for controlling component A is
28%~62%；After the completion of prepared by solution, relative degree of vacuum is evacuated to for -0.02MPa~-0.08MPa, be passed through nitrogen and recover anti-
After answering device to normal pressure, add the aqueous solution prepared by B component and deionized water under agitation, the weight concentration of B component for 20%~
40%；After the aqueous solution charging of B component terminates, 35 DEG C~50 DEG C are warming up to, add matched somebody with somebody by component C and deionized water under agitation
The aqueous solution of system, the weight concentration of component C is 5%~15%；Control ph is 4~10, in 35 DEG C~50 DEG C constant temperature, continues to stir
Reaction 2h~3.5h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, in the case where nitrogen is passed through, will
The aqueous solution that first network gel input is prepared equipped with D components and deionized water can be swelling in closed reactor, D components
Weight concentration is 1.8%~11%, by weight, first network gel:Weight ratio=1 of D component deionized water solutions:（95~
155）, swelling 2h~6h；Add the aqueous solution prepared by component E and deionized water and continue swelling, the weight concentration of component E is
10%~20%, swelling 16 h~24 h；After the completion of swelling, 75 DEG C~95 DEG C are warming up to, control ph is 3~7,75 DEG C~95
DEG C constant temperature, reacts 4h~6h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The component A is by methacryloxypropyl
Ethyl-trimethyl salmiac, methacrylic acid-β-hydroxypropyl acrylate, fumaric acid composition, by the gauge of material, methylacryoyloxyethyl
Trimethyl ammonium chloride:Methacrylic acid-β-hydroxypropyl acrylate:The ratio between amount of material of fumaric acid=（0.5~1.2）:（0.3~1.6）:
（0.4~1.1）；B component is PEGDMA-400, and number-average molecular weight is 2000~20000, and its charged material weight is
The 2.5%~11% of component A gross weight；Component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, and its gross weight that feeds intake is component A gross weight
The 0.3%~1.8% of amount, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）；D components are by mountain
Pears acid, xylitol, dimethylaminoethyl acrylate and dimethacrylate -1,3-BDO ester composition, by the gauge of material, mountain
Pears acid:Xylitol:The ratio between amount of material of dimethylaminoethyl acrylate=（0.4~1.6）:（0.08~0.32）:（0.4~
1.1）, by weight, dimethacrylate -1,3-BDO ester charged material weight is sorbic acid, xylitol, acrylate
Three kinds the 1.8%~5.5% of total monomer weight of ethyl ester；Component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and potassium peroxydisulfate feeds intake
Weight is the 0.1%~1.2% of D component weights, and pyridoxine hydrochloride charged material weight is the 0.8%~5.6% of D component weights.
What technical method of the invention was realized in：Methylacryoyloxyethyl front three can be being prepared in closed reactor
Ammonium chloride CH2=C(CH3)COO(CH2)2N(CH3)3Cl, methacrylic acid-β-hydroxypropyl acrylate CH2=C(CH3)COOCH2CH(OH)
CH3, fumaric acid HOOCCH=CHCOOH comonomers the aqueous solution；After vacuumizing deoxidation, nitrogen protection is passed through, adds crosslinking agent
The aqueous solution of PEGDMA-400；After intensification, redox initiator potassium peroxydisulfate-sodium hydrogensulfite is added
K2S2O8-NaHSO3The aqueous solution, through trigger, combined polymerization chain propagation reaction, crosslinking agent PEGDMA-400 participate in
Copolyreaction and line style copolymerization macromolecular crosslink reaction and form cross-linked network structure, through chain termination reaction, obtain organic two
Property copolymerized macromolecule first network gel.Logical nitrogen protection, organic amphiprotic copolymerized macromolecule first network gel is in sorbic acid
CH3CH=CHCH=CHCOOH, xylitol HOCH2(CHOH)3CH2OH, dimethylaminoethyl acrylate CH2=CHCOO(C2H4)N
(CH3)2, dimethacrylate -1,3 butylene glycol ester CH2=C(CH3)COOCH(CH3)CH2CH2OOC(CH3)C=CH2The aqueous solution
It is swelling under effect, add initiator potassium persulfate K2S2O8, catalyst pyridoxine hydrochloride (CH3)(HOCH2)2(HO)C5HN·
Continue swelling in the presence of HCl/water solution, in swelling process, monomer, crosslinking agent, initiator, catalyst in the aqueous solution enter
To organic amphiprotic copolymerized macromolecule first network gel inside and be uniformly distributed；Line is formed through initiation, combined polymerization chain propagation reaction
Type copolymerization macromolecular, crosslinking agent dimethacrylate -1,3-BDO ester participates in copolyreaction and line style copolymerization macromolecular occurs
Cross-linking reaction, forms the molecule of cross-linked network structure, pyridoxine hydrochloride molecule of the catalysis with carboxylic group and hydroxyl group
Generation esterification, because xylitol will react to form cross-linked network knot with five OH groups with the molecule with carboxylic group
Structure；Further reaction, finally due to the chain termination and the completion of esterification of radical copolymerization macromolecular, forms organic amphiprotic
Copolymerized macromolecule interpenetrating networks gel.
Relative to art methods, outstanding advantages of the present invention are monomer methacryloxypropyl second used in technology of preparing
Base trimethyl ammonium chloride, methacrylic acid-β-hydroxypropyl acrylate, dimethylaminoethyl acrylate and crosslinking agent dimethacrylate -1,
3- butanediol ester low toxicities, monomer fumaric acid, sorbic acid and crosslinking agent PEGDMA-400, xylitol are nontoxic, drop
Low gel toxicity；The interpenetrating networks gel of preparation has radical crosslinking and esterification and crosslinking network structure, improves IPN net
The stability of network gel；Preparation method is simple, reaction condition is gentle, be suitable for production, with good environmental benefit and economic effect
Benefit.
Specific embodiment
Embodiment 1：124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 57.7g methacrylic acids-β-hydroxypropyl acrylate,
58g fumaric acid and 560.5ml deionized waters are added to volume can be uniformly mixed in closed reactor for 2L, the aqueous solution
Weight concentration be 30%；Relative degree of vacuum -0.03MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal pressure, added
The number-average molecular weight of 7.2g is the aqueous solution that 3000 PEGDMA-400 and 27.1ml deionized waters are prepared, should
The weight concentration of the aqueous solution is 21%；Then heat to 38 DEG C, add 0.92g potassium peroxydisulfates, 0.28g sodium hydrogensulfites and
The aqueous solution that 20.6ml deionized waters are prepared, the weight concentration of the aqueous solution is 5.5%, and in 38 DEG C of constant temperature, control ph is 4.5,
Continue stirring reaction 2.3h, obtain organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through nitrogen
Under, organic amphiprotic copolymerized macromolecule first network gel 72.9g input volumes can be swelling in closed reactor for 15L's, and this is anti-
Answer in device equipped with 56g sorbic acids, 15.2g xylitols, 71.6g dimethylaminoethyl acrylates, 2.9g dimethacrylates -1,3-
The aqueous solution that butanediol ester and 7140.6ml deionized waters are prepared, the weight concentration of the aqueous solution is 2%, first network gel
Weight（72.9g）:The weight of the aqueous solution（7286.4g）=1:100, swelling 3h；Add 0.29g potassium peroxydisulfates, 1.46g pyrroles
The aqueous solution that alcohol hydrochloride and the 14.9ml deionized waters of trembling are prepared continues swelling, and the weight concentration of the aqueous solution is 10.5%, swelling
17h；78 DEG C are warming up to after the completion of swelling, control ph is 3.4, in 78 DEG C of isothermal reaction 4.3h, obtain organic amphiprotic copolymerization high
Molecule interpenetration network gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=6531%（Deionized water）,
Gel swelling rate（ESR）=6397%（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：228.2g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 216.2g methacrylic acids-β-hydroxypropyl acrylate,
116.1g fumaric acid and 373.7ml deionized waters are added to volume for 1L can be uniformly mixed in closed reactor, and this is water-soluble
The weight concentration of liquid is 60%；Relative degree of vacuum -0.07MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal pressure, plus
The number-average molecular weight for entering 56.1g be 18000 PEGDMA-400 and 87.7ml deionized waters prepare it is water-soluble
Liquid, the weight concentration of the aqueous solution is 39%；Then heat to 48 DEG C, add 4.2g potassium peroxydisulfates, 4.2g sodium hydrogensulfites and
The aqueous solution that 49.6ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%, and in 48 DEG C of constant temperature, control ph is
9.6, continue stirring reaction 3.2h, obtain organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through nitrogen
Under gas, organic amphiprotic copolymerized macromolecule first network gel 25g inputs 5L can be swelling in closed reactor, is equipped with reactor
168.2g sorbic acids, 45.7g xylitols, 143.2g dimethylaminoethyl acrylates, 17.8g dimethacrylate -1,3- fourths two
The aqueous solution that alcohol ester and 3373.8ml deionized waters are prepared, the weight concentration of the aqueous solution is 10%, the weight of first network gel
（25g）:The weight of the aqueous solution（3748.7g）=1:150, swelling 5.6h；Add 0.75g potassium peroxydisulfates, 3.75g pyridoxols
The aqueous solution that hydrochloride and 18.6ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is 19.5%, swelling 23h；
92 DEG C are warming up to after the completion of swelling, control ph is 6.6, in 92 DEG C of isothermal reaction 5.5h, obtain organic amphiprotic copolymerized macromolecule
Interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=5275%（Deionized water）, gel
Swelling ratio（ESR）=5186%（The NaCl aqueous solution of weight concentration 1%）.
Claims (1)
1. a kind of preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel, it is characterized in that can in closed reactor plus
Enter component A and deionized water stirring prepares the aqueous solution, it is 28%~62% to control the weight concentration of component A, after the completion of prepared by solution,
Relative degree of vacuum is evacuated to for -0.02MPa~-0.08MPa, after being passed through nitrogen recovery reactor to normal pressure, is added under agitation
Enter the aqueous solution prepared by B component and deionized water, the weight concentration of B component is 20%~40%, the aqueous solution charging knot of B component
Shu Hou, is warming up to 35 DEG C~50 DEG C, and the aqueous solution prepared by component C and deionized water is added under agitation, and the weight of component C is dense
It is 5%~15% to spend, and control ph is 4~10, in 35 DEG C~50 DEG C constant temperature, continues stirring reaction 2h~3.5h, obtains organic two
Property copolymerized macromolecule first network gel, then cooled down, in the case where nitrogen is passed through, by the first network gel input be equipped with D
The aqueous solution that component and deionized water are prepared can be swelling in closed reactor, the weight concentration of D components is 1.8%~11%, is pressed
Weight meter, first network gel:Weight ratio=1 of D component deionized water solutions:（95~155）, swelling time is 2h~6h, then
The aqueous solution prepared by component E and deionized water is added to continue swelling, the weight concentration of component E is 10%~20%, swelling time
Be 16 h~24 h, it is swelling after the completion of, be warming up to 75 DEG C~95 DEG C, control ph is 3~7, in 75 DEG C~95 DEG C constant temperature, reaction
4h~6h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel；The component A is by methylacryoyloxyethyl trimethyl chlorine
Change ammonium, methacrylic acid-β-hydroxypropyl acrylate, fumaric acid composition, by the gauge of material, methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium:Methacrylic acid β-hydroxypropyl acrylate:The ratio between amount of material of fumaric acid=（0.5~1.2）:（0.3~1.6）:（0.4~1.1）, B
Component is PEGDMA-400, and number-average molecular weight is 2000~20000, and its charged material weight is component A gross weight
2.5%~11%, component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, its gross weight that feeds intake be component A gross weight 0.3%~
1.8%, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）, D components are by sorbic acid, xylose
Alcohol, dimethylaminoethyl acrylate and dimethacrylate -1,3-BDO ester composition, by the gauge of material, sorbic acid:Xylose
Alcohol:The ratio between amount of material of dimethylaminoethyl acrylate=（0.4~1.6）:（0.08~0.32）:（0.4~1.1）, by weight
Meter, dimethacrylate -1,3-BDO ester charged material weight is sorbic acid, xylitol, three kinds of lists of dimethylaminoethyl acrylate
The 1.8%~5.5% of body gross weight, component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and potassium peroxydisulfate charged material weight is D components
The 0.1%~1.2% of gross weight, pyridoxine hydrochloride charged material weight is the 0.8%~5.6% of D component weights.
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| US20070116765A1 (en) * | 2003-12-09 | 2007-05-24 | Zhibing Hu | Aqueous dispersion of hydrogel nanoparticles with inverse thermoreversible gelation |
| CN105289316A (en) * | 2015-09-28 | 2016-02-03 | 浙江大学 | Preparation method of composite separating film filled by interpenetrating polymer network hydrogel |
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