CN106750007A - 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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- CN106750007A CN106750007A CN201611126762.1A CN201611126762A CN106750007A CN 106750007 A CN106750007 A CN 106750007A CN 201611126762 A CN201611126762 A CN 201611126762A CN 106750007 A CN106750007 A CN 106750007A
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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
- C08F290/062—Polyethers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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, ethoxyethyl methacrylates, crotonic 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 swelling in the aqueous solution that itaconic acid, mannitol, vinyl pyrrolidone, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester 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, ethoxyethyl methacrylates, crotonic acid composition, by the gauge of material, methacryloxypropyl second
Base trimethyl ammonium chloride:Ethoxyethyl methacrylates:The ratio between amount of material of crotonic 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 it feeds intake
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 A groups
Divide the 0.3%~1.8% of gross weight, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）；D groups
Divide and be made up of itaconic acid, mannitol, vinyl pyrrolidone and trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, by the gauge of material, clothing
Health acid:Mannitol:The ratio between amount of material of vinyl pyrrolidone=（0.5~2.0）:（0.08~0.32）:（0.4~1.1）,
By weight, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester charged material weight is itaconic acid, mannitol, three kinds of monomers of vinyl pyrrolidone
The 1.8%~5.5% of gross weight；Component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and potassium peroxydisulfate charged material weight is that D components are total
The 0.1%~1.2% of weight, the pyridoxine hydrochloride gross weight that feeds intake 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, ethoxyethyl methacrylates CH2=C(CH3)
COOCH2CH2OCH2CH3, crotonic acid CH3CH=CHCOOH comonomers and deionized water are prepared into well mixed water under agitation
Solution；After vacuumizing deoxidation, nitrogen protection is passed through, adds the deionization of crosslinking agent PEGDMA-400 water-soluble
Liquid；After intensification, redox initiator potassium peroxydisulfate-sodium hydrogensulfite K is added2S2O8-NaHSO3Deionized water solution,
Through initiation, combined polymerization chain propagation reaction, crosslinking agent PEGDMA-400 participates in copolyreaction and line style copolymerization is big
Molecule crosslinks reaction and forms cross-linked network structure, through chain termination reaction, obtains organic amphiprotic copolymerized macromolecule first network
Gel.Nitrogen protection is passed through, organic amphiprotic copolymerized macromolecule first network gel is in itaconic acid H2C=C(COOH)CH2It is COOH, sweet
Dew alcohol HOCH2(CHOH)4CH2OH, vinyl pyrrolidone CH2=CH-(C4H6NO), trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester (CH2=
C(CH3)COOC2H4)3It is swelling under the aqueous solution effect of N, add initiator potassium persulfate K2S2O8, catalyst pyridoxine hydrochloric acid
Salt (CH3)(HOCH2)2(HO)C5Continue swelling in the presence of the HNHCl aqueous solution, in swelling process, monomer in the aqueous solution,
Crosslinking agent, initiator, catalyst and water enter into organic amphiprotic copolymerized macromolecule first network gel inside and are uniformly distributed；Rise
Wen Hou, line style copolymerization macromolecular, crosslinking agent trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester ginseng are formed through initiation, combined polymerization chain propagation reaction
Reaction is crosslinked with copolyreaction and line style copolymerization macromolecular, cross-linked network structure, pyridoxine hydrochloride catalysis band carboxylic is formed
The molecule of the molecule of base group and hydroxyl group carries out esterification, because mannitol is with six OH groups and band carboxyl base
The molecule of group reacts to form cross-linked network structure；Further reaction, finally due to radical copolymerization macromolecular chain termination and
The completion of esterification, 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, crotonic acid and crosslinking agent trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester low toxicity, monomer itaconic acid, methacrylic acid
Ethoxy ethyl ester, vinyl pyrrolidone and crosslinking agent PEGDMA-400, mannitol are nontoxic, reduce gel
Toxicity；The interpenetrating networks gel of preparation has radical crosslinking and esterification and crosslinking network structure, improves interpenetrating networks gel
Stability；Preparation method is simple, reaction condition is gentle, be suitable for production, with good environmental benefit and economic benefit.
Specific embodiment
Embodiment 1：By 124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 63.28g methacrylic acid ethyoxyl second
The deionized water of ester, 43g crotonic acids and 538ml is added to volume can be uniformly mixed in closed reactor for 2L, the water
The weight concentration of solution is 30%, is evacuated to relative degree of vacuum -0.035MPa, then passes to nitrogen and recovers reactor to normal pressure,
The PEGDMA-400 that 6.92g number-average molecular weights are 3000 and the aqueous solution that 26ml deionized waters are prepared are added,
The weight concentration of the aqueous solution is 21%；Then heat to 38 DEG C, add 0.89g potassium peroxydisulfates, 0.27g sodium hydrogensulfites and
The aqueous solution that 19.83ml deionized waters are prepared, the weight concentration of the aqueous solution is 5.5%；In 38 DEG C of constant temperature, control ph is
4.5, continue stirring reaction 2.4h, obtain organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through nitrogen
Under gas, organic amphiprotic copolymerized macromolecule first network gel 77.44g input volumes can be swelling in closed reactor for 15L's, should
78g itaconic acids, 18g mannitol, 55g vinyl pyrrolidones, 3.04g trimethacrylate triethylenetetraminehexaacetic acid alkanolamine esters are housed in reactor
The aqueous solution prepared with 7588ml deionized waters, the weight concentration of the aqueous solution is 2%, the weight of first network gel
（77.44g）：The weight of the aqueous solution（7743g）=1:100, swelling 2.5h；Add 0.31g potassium peroxydisulfates, 1.55g pyridoxols
The aqueous solution that hydrochloride and 16ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is 10.5%, swelling 17h；It is molten
78 DEG C are warming up to after the completion of swollen, control ph is 3.4, in 78 DEG C of isothermal reaction 4.3h, obtain organic amphiprotic copolymerized macromolecule mutual
Wear network gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=5382%（Deionized water）, gel is molten
Swollen rate（ESR）=5237%（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：By 228g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 237g ethoxyethyl methacrylates,
The deionized water of 86g crotonic acids and 368ml is added to volume can be uniformly mixed in closed reactor for 1L, the aqueous solution
Weight concentration be 60%, be evacuated to relative degree of vacuum -0.065MPa, then pass to nitrogen and recover reactor to normal pressure, add
55g number-average molecular weights are the aqueous solution that 11000 PEGDMA-400 and 86ml deionized waters are prepared, and this is water-soluble
The weight concentration of liquid is 39%；Then heat to 48 DEG C, add 4.14g potassium peroxydisulfates, 4.14g sodium hydrogensulfites and 49ml go from
The aqueous solution that sub- water is prepared, the weight concentration of the aqueous solution is 14.5%；In 48 DEG C of constant temperature, control ph is 9, continues to stir anti-
3.3h is answered, organic amphiprotic copolymerized macromolecule first network gel is obtained；Then cooled down, in the case where nitrogen is passed through, organic amphiprotic
Copolymerized macromolecule first network gel 28g input volumes can be swelling in closed reactor for 10L's, and 234g is housed in the reactor
Itaconic acid, 55g mannitol, 111.14g vinyl pyrrolidones, 20g trimethacrylate triethylenetetraminehexaacetic acid alkanolamine esters and 3780ml go from
The aqueous solution that sub- water is prepared, the weight concentration of the aqueous solution is 10%, the weight of first network gel（28g）：The weight of the aqueous solution
Amount（4200g）=1:150, swelling 5.5h, add 0.84g potassium peroxydisulfates, 4.2g pyridoxine hydrochlorides and 21ml deionized waters and match somebody with somebody
The aqueous solution of system continues swelling, and the weight concentration of the aqueous solution is 19.5%, swelling 23.5 h；92 DEG C are warming up to after the completion of swelling,
Control ph is 6.5, in 92 DEG C of isothermal reaction 5.6h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The gel is not
Water is dissolved in, can be swelling in water, gel swelling rate（ESR）=4193%（Deionized water）, gel swelling rate（ESR）=4075%（Weight
Measure the NaCl aqueous solution of 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, ethoxyethyl methacrylates, crotonic acid composition, by the gauge of material, methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium:Ethoxyethyl methacrylates:The ratio between amount of material of crotonic 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
The 2.5%~11% of gross weight, component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, and its gross weight that feeds intake is component A gross weight
0.3%~1.8%, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）, D components by itaconic acid,
Mannitol, vinyl pyrrolidone and trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester composition, by the gauge of material, itaconic acid:Mannitol:
The ratio between amount of material of vinyl pyrrolidone=（0.5~2.0）:（0.08~0.32）:（0.4~1.1）, by weight, front three
Base acrylic acid triethanolamine ester charged material weight is itaconic acid, mannitol, three kinds the 1.8% of total monomer weight of vinyl pyrrolidone
~5.5%, component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and the potassium peroxydisulfate gross weight that feeds intake is the 0.1% of D component weights
~1.2%, the pyridoxine hydrochloride gross weight that feeds intake 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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