CN106750028A - 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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- CN106750028A CN106750028A CN201611131109.4A CN201611131109A CN106750028A CN 106750028 A CN106750028 A CN 106750028A CN 201611131109 A CN201611131109 A CN 201611131109A CN 106750028 A CN106750028 A CN 106750028A
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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
- 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, the Octyl Nitrite of methacrylic acid 2, 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 fumaric acid, triethanolamine, methacrylic acid β hydroxypropyl acrylates, 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 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 -2- Octyl Nitrites, abscisic acid composition, by the gauge of material, methacryloxypropyl second
Base trimethyl ammonium chloride:Methacrylic acid -2- Octyl Nitrites: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 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:The weight ratio of sodium hydrogensulfite==1:（0.2~1.1）；D groups
Divide and be made up of fumaric acid, triethanolamine, methacrylic acid-β-hydroxypropyl acrylate and dimethacrylate diglycol ester, by thing
The gauge of matter, fumaric acid:Triethanolamine:The ratio between amount of material of methacrylic acid-β-hydroxypropyl acrylate=（0.2~1.0）:（0.08~
0.32）:（0.4~1.1）, by weight, dimethacrylate diglycol ester charged material weight is fumaric acid, three ethanol
Three kinds the 1.8%~5.5% of total monomer weight of amine, methacrylic acid-β-hydroxypropyl acrylate；Component E is by potassium peroxydisulfate, pyridoxine hydrochloride
Composition, potassium peroxydisulfate charged material weight is the 0.1%~1.2% of D component weights, and pyridoxine hydrochloride charged material weight is that D components are total
The 0.8%~5.6% of weight.
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 -2- Octyl Nitrites CH2=C(CH3)COOCH2CH
(C2H3) (CH2)3CH3, abscisic acid (C9H13O2)-CH=CHC(CH3The aqueous solution of)=CHCOOH comonomers；Vacuumize deoxidation
Afterwards, nitrogen protection is passed through, the aqueous solution of crosslinking agent PEGDMA-400 is added；After intensification, oxidation is added also
Former initiator potassium persulfate-sodium hydrogensulfite K2S2O8-NaHSO3The aqueous solution, through trigger, combined polymerization chain propagation reaction, crosslinking
Agent PEGDMA-400 participates in copolyreaction and line style copolymerization macromolecular crosslinks reaction and forms cross-linked network
Structure, through chain termination reaction, obtains organic amphiprotic copolymerized macromolecule first network gel.After cooling, nitrogen protection is passed through, it is organic
Both sexes copolymerized macromolecule first network gel is in fumaric acid HOOCCH=CHCOOH, triethanolamine (HOCH2CH2)3N, metering system
Acid-β-hydroxypropyl acrylate CH2=C(CH3)COOCH2CH(OH)CH3, dimethacrylate diglycol ester CH2=C(CH3)COO-
(C2H4OC2H4)-OOC(CH3)C=CH2The aqueous solution effect under it is swelling, add initiator potassium persulfate K2S2O8, catalyst pyrrole
Tremble alcohol hydrochloride (CH3)(HOCH2)2(HO)C5Continue swelling in the presence of the HNHCl aqueous solution, in swelling process, in the aqueous solution
Monomer, crosslinking agent, initiator, catalyst enter into organic amphiprotic copolymerized macromolecule first network gel inside and uniformly divide
Cloth；Line style copolymerization macromolecular, crosslinking agent dimethacrylate diglycol ester are formed through initiation, combined polymerization chain propagation reaction
Participate in copolyreaction and line style copolymerization macromolecular crosslinks reaction, form cross-linked network structure, pyridoxine hydrochloride catalysis band
There is esterification in the molecule of the molecule of carboxylic group and hydroxyl group, due to triethanolamine with three OH groups will and band
The molecule of carboxylic group reacts to form cross-linked network structure；Further reaction, finally due to the chain of radical copolymerization macromolecular
Terminate the completion with esterification, form 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 -2- Octyl Nitrites, methacrylic acid-β-hydroxypropyl acrylate and crosslinking agent triethanolamine low toxicity,
Monomer abscisic acid, fumaric acid and crosslinking agent PEGDMA-400, dimethacrylate diglycol ester without
Poison, reduces gel toxicity；The interpenetrating networks gel of preparation has radical crosslinking and esterification and crosslinking network structure, improves mutually
Wear the stability of network gel；Preparation method is simple, reaction condition is gentle, be suitable for production, with good environmental benefit and warp
Ji benefit.
Specific embodiment
Embodiment 1：124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 79.3g methacrylic acid -2- ethyl hexyls
Ester, 132.2g abscisic acids and 784ml deionized waters are added to volume can be uniformly mixed in closed reactor for 2L, the water
The weight concentration of solution is 30%；Relative degree of vacuum -0.03MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal pressure,
Add 10.1g number-average molecular weight be 3000 PEGDMA-400 and 38ml deionized waters prepare it is water-soluble
Liquid, the weight concentration of the aqueous solution is 21%；Then heat to 38 DEG C, add 1.29g potassium peroxydisulfates, 0.39g sodium hydrogensulfites and
The aqueous solution that 28.9ml 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 3.5,
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 62.1g input volumes can be swelling in closed reactor for 10L's, and this is anti-
Answer in device equipped with 34.8g fumaric acid, 14.9g triethanolamines, 72.1g methacrylic acids-β-hydroxypropyl acrylate, 2.4g dimethacrylates
The aqueous solution that diglycol ester and 6089ml deionized waters are prepared, the weight concentration of the aqueous solution is 2%, and first network coagulates
The weight of glue（62.1g）:The weight of the aqueous solution（6213g）=1:100, swelling 2.4h；Add 0.25g potassium peroxydisulfates,
The aqueous solution that 1.24g pyridoxine hydrochlorides and 12.7ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is
10.5%, swelling 18h；78 DEG C are warming up to after the completion of swelling, control ph is 4, in 78 DEG C of isothermal reaction 4.3h, obtain organic two
Property copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=9735%（Go
Ionized water）, gel swelling rate（ESR）=9613%（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：228.3g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 297.5g methacrylic acid -2- ethyl hexyls
Ester, 264.3g abscisic acids and 527ml deionized waters are added to volume for 2L 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 79g is the aqueous solution that 18000 PEGDMA-400 and 160ml deionized waters are prepared,
The weight concentration of the aqueous solution is 39%；Then heat to 47 DEG C, add 5.93g potassium peroxydisulfates, 5.93g sodium hydrogensulfites and
The aqueous solution that 69.9ml 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
9.5, 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 21g inputs 5L can be swelling in closed reactor, is equipped with reactor
104.5g fumaric acid, 44.8g triethanolamines, 144.2g methacrylic acids-β-hydroxypropyl acrylate, the contracting of 14.7g dimethacrylates one two
The aqueous solution that glycol ester and 2773ml deionized waters are prepared, the weight concentration of the aqueous solution is 10%, the weight of first network gel
Amount（21g）:The weight of the aqueous solution（3081g）=1:150, swelling 5h；Add 0.62g potassium peroxydisulfates, 3.08g pyridoxol salt
The aqueous solution that hydrochlorate and 15.3ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is 19.5%, swelling 23h；It is molten
92 DEG C are warming up to after the completion of swollen, control ph is 6.5, in 92 DEG C of isothermal reaction 5.5h, obtain organic amphiprotic copolymerized macromolecule mutual
Wear network gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=7863%（Deionized water）, gel is molten
Swollen rate（ESR）=7683%（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 -2- Octyl Nitrites, abscisic acid composition, by the gauge of material, methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium:Methacrylic acid -2- Octyl Nitrites: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 fumaric acid,
Triethanolamine, methacrylic acid-β-hydroxypropyl acrylate and dimethacrylate diglycol ester composition, it is rich by the gauge of material
Horse acid:Triethanolamine:The ratio between amount of material of methacrylic acid-β-hydroxypropyl acrylate=（0.2~1.0）:（0.08~0.32）:（0.4
~1.1）, by weight, dimethacrylate diglycol ester charged material weight is fumaric acid, triethanolamine, metering system
Three kinds the 1.8%~5.5% of total monomer weight of acid-β-hydroxypropyl acrylate, component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, persulfuric acid
Potassium charged material weight is the 0.1%~1.2% of D component weights, pyridoxine hydrochloride charged material weight be D component weights 0.8%~
5.6%。
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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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Application publication date: 20170531 |