CN106750005A - 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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- CN106750005A CN106750005A CN201611126758.5A CN201611126758A CN106750005A CN 106750005 A CN106750005 A CN 106750005A CN 201611126758 A CN201611126758 A CN 201611126758A CN 106750005 A CN106750005 A CN 106750005A
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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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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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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
- 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, vinyl pyrrolidone, abscisic 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, triethanolamine, hydroxyethyl methacrylate, dimethacrylate diglycol 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 28%~
62%；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, vinyl pyrrolidone, abscisic acid composition, by the gauge of material, methylacryoyloxyethyl front three
Ammonium chloride:Vinyl pyrrolidone:The ratio between amount of material of abscisic 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,
Triethanolamine, hydroxyethyl methacrylate and dimethacrylate diglycol ester composition, by the gauge of material, clothing health
Acid:Triethanolamine:The ratio between amount of material of hydroxyethyl methacrylate=（0.2~1.0）:（0.08~0.32）:（0.4~
1.1）, by weight, dimethacrylate diglycol ester charged material weight is itaconic acid, triethanolamine, methacrylic acid
Three kinds the 1.8%~5.5% of total monomer weight of hydroxyl ethyl ester；Component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and potassium peroxydisulfate is thrown
Material weight be the 0.1%~1.2% of D component weights, pyridoxine hydrochloride charged material weight be D component weights 0.8%~
5.6%。
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, vinyl pyrrolidone H2C=CH-(C4H6NO), abscisic acid
(C9H13O2)-CH=CHC(CH3The aqueous solution of)=CHCOOH comonomers；After vacuumizing deoxidation, nitrogen protection is passed through, adds crosslinking
The aqueous solution of agent PEGDMA-400；After intensification, redox initiator potassium peroxydisulfate-bisulfite is added
Sodium K2S2O8-NaHSO3The aqueous solution, through trigger, combined polymerization chain propagation reaction, crosslinking agent PEGDMA-400 ginseng
Crosslink reaction and form cross-linked network structure with copolyreaction and line style copolymerization macromolecular, through chain termination reaction, obtain organic
Both sexes copolymerized macromolecule first network gel.Nitrogen protection is passed through, organic amphiprotic copolymerized macromolecule first network gel is in clothing health
Sour H2C=C(COOH)CH2COOH, triethanolamine (HOCH2CH2)3N, hydroxyethyl methacrylate CH2=C(CH3)COO
CH2CH2OH, dimethacrylate diglycol ester CH2=C(CH3)COO-(C2H4OC2H4)-OOC(CH3)C=CH2It is water-soluble
It is swelling under liquid effect, add initiator potassium persulfate K2S2O8, catalyst pyridoxine hydrochloride (NC8H4)-(OH)3HCl/water is molten
Continue swelling in the presence of liquid, in swelling process, monomer, crosslinking agent in the aqueous solution, initiator, catalyst enter into organic two
Property copolymerized macromolecule first network gel inside and be uniformly distributed；After intensification, line style is formed through initiation, combined polymerization chain propagation reaction
Copolymerization macromolecular, crosslinking agent dimethacrylate diglycol ester participates in copolyreaction and line style copolymerization macromolecular is handed over
Connection reaction, forms the molecule hair of cross-linked network structure, pyridoxine hydrochloride molecule of the catalysis with carboxylic group and hydroxyl group
Raw esterification, because triethanolamine will react to form cross-linked network knot with three 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, hydroxyethyl methacrylate and crosslinking agent triethanolamine low toxicity, monomer abscisic acid, itaconic acid, vinyl
Pyrrolidones and crosslinking agent PEGDMA-400, dimethacrylate diglycol ester are nontoxic, reduce
Gel toxicity；The interpenetrating networks gel of preparation has radical crosslinking and esterification and crosslinking network structure, improves interpenetrating networks and coagulates
The stability of glue；Preparation method is simple, reaction condition is gentle, be suitable for production, with good environmental benefit and economic benefit.
Specific embodiment
Embodiment 1：124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 44.5g vinyl pyrrolidones, 132g take off
Acid and the 702.6ml deionized waters of falling are added to volume can be uniformly mixed in closed reactor for 2L, the weight of the aqueous solution
Amount concentration is 30%；Relative degree of vacuum -0.03MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal pressure, add 9g's
Number-average molecular weight is the aqueous solution that 3000 PEGDMA-400 and 34ml deionized waters are prepared, the aqueous solution
Weight concentration is 21%；38 DEG C are then heated to, 1.16g potassium peroxydisulfates, 0.35g sodium hydrogensulfites and 25.87ml deionizations is added
The aqueous solution that water is prepared, the weight concentration of the aqueous solution is 5.5%, and in 38 DEG C of constant temperature, control ph is 4.6, reacts 2.3h, is obtained
To organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, in the case where nitrogen is passed through, organic amphiprotic copolymerized macromolecule
First network gel 60.7g input volumes can be swelling in closed reactor for 10L's, in the reactor equipped with 39g itaconic acids,
15g triethanolamines, 65g hydroxyethyl methacrylates, 2.38g dimethacrylate diglycol esters and 5948ml deionizations
The aqueous solution that water is prepared, the weight concentration of the aqueous solution is 2%, the weight of first network gel（60.7g）:The weight of the aqueous solution
Amount（6070g）=1:100, swelling 2.5h；Add 0.24g potassium peroxydisulfates, 1.21g pyridoxine hydrochlorides and 12.42ml deionizations
The aqueous solution that water is prepared continues swelling, and the weight concentration of the aqueous solution is 10.5%, swelling 17h；78 are warming up to after the completion of swelling
DEG C, control ph is 3.5, in 78 DEG C of isothermal reaction 4.5h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The gel
It is water insoluble, can be swelling in water, gel swelling rate（ESR）=9752%（Deionized water）, gel swelling rate（ESR）=9586%
（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：228.25g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 166.71g vinyl pyrrolidones,
264.32g abscisic acids and 439.5ml 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 66g be 18000 PEGDMA-400 and 103.1ml deionized waters prepare it is water-soluble
Liquid, the weight concentration of the aqueous solution is 39%；Then heat to 47 DEG C, add 4.94g potassium peroxydisulfates, 4.94g sodium hydrogensulfites and
The aqueous solution that 58.31ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%, and in 47 DEG C of constant temperature, control ph is
8.9, 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 20.44g inputs 5L can be swelling in closed reactor, is filled in reactor
There are 117g itaconic acids, 44.75g triethanolamines, 130.14g hydroxyethyl methacrylates, the contracting diethyl of 14.6g dimethacrylates one
The aqueous solution that diol ester and 2759.14ml deionized waters are prepared, the weight concentration of the aqueous solution is 10%, first network gel
Weight（20.44g）:The weight of the aqueous solution（3065.71g）=1:150, swelling 5.6h；Add 0.61g potassium peroxydisulfates,
The aqueous solution that 3.07g pyridoxine hydrochlorides and 15.2ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is
19.5%, swelling time is 23 h；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, obtained
To organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=
7380%（Deionized water）, gel swelling rate（ESR）=7259%（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, vinyl pyrrolidone, abscisic acid composition, by the gauge of material, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride:Ethene
Base pyrrolidones:The ratio between amount of material of abscisic acid=（0.5~1.2）:（0.3~1.6）:（0.4~1.1）, B component is diformazan
Base polyalkylene glycol acrylate ester, number-average molecular weight be 2000~20000, its gross weight that feeds intake be component A weight 2.5%~
11%, component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, and its gross weight that feeds intake is the 0.3%~1.8% of component A gross weight, by weight
Gauge, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）, D components are by itaconic acid, triethanolamine, methyl-prop
Olefin(e) acid hydroxyl ethyl ester and dimethacrylate diglycol ester are constituted, by the gauge of material, itaconic acid:Triethanolamine:Methyl
The ratio between amount of material of hydroxy-ethyl acrylate=（0.2~1.0）:（0.08~0.32）:（0.4~1.1）, by weight, dimethyl
Diethylene glycol monoacrylate charged material weight is itaconic acid, triethanolamine, three kinds of total monomer weights of hydroxyethyl methacrylate
1.8%~5.5%, component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and potassium peroxydisulfate charged material weight is D component weights
0.1%~1.2%, 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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