CN106750032A - 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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- CN106750032A CN106750032A CN201611132279.4A CN201611132279A CN106750032A CN 106750032 A CN106750032 A CN 106750032A CN 201611132279 A CN201611132279 A CN 201611132279A CN 106750032 A CN106750032 A CN 106750032A
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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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- 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, hydroxyethyl methacrylate, 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 crotonic acid, xylitol, the Octyl Nitrite of methacrylic acid 2, 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
What the first network gel was put into the aqueous solution 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, hydroxyethyl methacrylate, fumaric acid composition, by the gauge of material, methylacryoyloxyethyl three
Ammonio methacrylate:Hydroxyethyl methacrylate: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 gross weight that feeds intake is A groups
Divide the 2.5%~11% of 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 crotonic acid,
Xylitol, methacrylic acid -2- Octyl Nitrites and dimethacrylate -1,3-BDO ester composition, by the gauge of material, crotons
Acid:Xylitol:The ratio between amount of material of methacrylic acid -2- Octyl Nitrites=（0.4~1.6）:（0.08~0.32）:（0.4~
1.1）, by weight, dimethacrylate -1,3-BDO ester charged material weight is crotonic acid, xylitol, methacrylic acid -2-
Three kinds the 1.8%~5.5% of total monomer weight of Octyl Nitrite；Component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, potassium peroxydisulfate
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%。
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, hydroxyethyl methacrylate CH2=C(CH3)COOCH2CH2OH, rich horse
Tri- kinds of comonomers of sour HOOCCH=CHCOOH and deionized water are prepared into the well mixed aqueous solution under agitation；Vacuumize
After oxygen, nitrogen protection is passed through, adds the aqueous solution of crosslinking agent PEGDMA-400；Add redox initiator
Potassium peroxydisulfate-sodium hydrogensulfite K2S2O8-NaHSO3The aqueous solution, through trigger, combined polymerization chain propagation reaction, crosslinking agent dimethyl
Polyalkylene glycol acrylate ester participates in copolyreaction and line style copolymerization macromolecular crosslinks reaction and forms cross-linked network structure, through chain
Terminating reaction, obtains organic amphiprotic copolymerized macromolecule first network gel.It is passed through nitrogen protection, organic amphiprotic copolymerized macromolecule the
One network gel is in crotonic acid CH3CH=CHCOOH, xylitol HOCH2(CHOH)3CH2OH, methacrylic acid -2- Octyl Nitrites CH2
=C(CH3)COOCH2CH(C2H5)(CH2)3CH3, dimethacrylate -1,3 butylene glycol ester CH2=C(CH3)COOCH(CH3)
C2H4OOC(CH3)C=CH2The aqueous solution effect under it is swelling, 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 enter into organic amphiprotic copolymerized macromolecule first network gel inside and are uniformly distributed；Heat up
Afterwards, line style copolymerization macromolecular, crosslinking agent dimethacrylate -1,3-BDO 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, because xylitol is with five OH groups and band carboxyl
The molecule of group reacts to form cross-linked network structure；Further reaction, finally due to the chain termination of radical copolymerization macromolecular
With the completion of esterification, organic amphiprotic copolymerized macromolecule interpenetrating networks gel is formed.
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, crotonic acid, methacrylic acid -2- Octyl Nitrites and crosslinking agent dimethyl propylene
Olefin(e) acid -1,3-BDO ester low toxicity, monomer fumaric 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：By 124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 52g hydroxyethyl methacrylates, 58g
The deionized water of fumaric acid and 547.4ml is added to volume can be uniformly mixed in closed reactor for 1L, the aqueous solution
Weight concentration be 30%, be evacuated to relative degree of vacuum -0.03MPa, then pass to nitrogen and recover reactor to normal pressure, add
7.04g number-average molecular weights are the aqueous solution that 4000 PEGDMA-400 and 26.5ml deionized waters are prepared, should
The weight concentration of the aqueous solution is 21%；36 DEG C are then heated to, 0.9g potassium peroxydisulfates, 0.27g sodium hydrogensulfites and 20.1ml is added
The aqueous solution that deionized water is prepared, the weight concentration of the aqueous solution is 5.5%；In 36 DEG C of constant temperature, control ph is 4.5, continues to stir
Reaction 2.4h is mixed, organic amphiprotic copolymerized macromolecule first network gel is obtained；Then cooled down, it is organic in the case where nitrogen is passed through
Both sexes copolymerized macromolecule first network gel 73.1g input volumes can be swelling in closed reactor for 15L's, is filled in the reactor
There are 43g crotonic acids, 15.2g xylitols, 85.1g methacrylic acid -2- Octyl Nitrites, dimethacrylate -1,3 butylene glycol ester
The aqueous solution that 2.87g and 7165.4ml deionized waters are prepared, the weight concentration of the aqueous solution is 2%, the weight of first network gel
（73.1g）：The weight of the aqueous solution（7311.6g）=1:100, swelling 2.5h；0.29g potassium peroxydisulfates, 1.46g pyrroles is added to tremble
The aqueous solution that alcohol hydrochloride and 15ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is 10.5%, swelling 18
h；76 DEG C are warming up to after the completion of swelling, control ph is 3.5, in 76 DEG C of isothermal reaction 4.3h, obtain organic amphiprotic copolymerization high score
Sub- interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=6583%（Deionized water）, coagulate
Glue swelling ratio（ESR）=6395%（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：By 228.2g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 166.7g hydroxyethyl methacrylates,
The deionized water of 116.1g fumaric acid and 340.7ml is added to volume can be uniformly mixed in closed reactor for 1L, should
The weight concentration of the aqueous solution is 60%, is evacuated to relative degree of vacuum -0.075MPa, then passes to nitrogen and recovers reactor to normal
Pressure, add 51.1g number-average molecular weights be 17000 PEGDMA-400 and 80ml deionized waters prepare it is water-soluble
Liquid, the weight concentration of the aqueous solution is 39%；Then heat to 48 DEG C, add 3.83g potassium peroxydisulfates, 3.83g sodium hydrogensulfites and
The aqueous solution that 45.2ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%；In 48 DEG C of constant temperature, control ph is 9,
Continue stirring reaction 3.2h, obtain organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through nitrogen
Under, organic amphiprotic copolymerized macromolecule first network gel 24.2g input volumes can be swelling in closed reactor for 10L's, reaction
129.1g crotonic acids, 45.6g xylitols, 170.2g methacrylic acid -2- Octyl Nitrites, dimethacrylate -1 are housed in device,
The aqueous solution that 3- butanediol ester 17.3g and 3260.2ml deionized water are prepared, the weight concentration of the aqueous solution is 10%, the first net
The weight of network gel（24.2g）：The weight of the aqueous solution（3622.4g）=1:150, swelling 5.7h, add 0.72g persulfuric acid
The aqueous solution that potassium, 3.62g pyridoxine hydrochlorides and 18ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is
19.5%, swelling 22.5h；92 DEG C are warming up to after the completion of swelling, control ph is 7, in 92 DEG C of isothermal reaction 5.7h, obtain organic
Both sexes copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=5354%
（Deionized water）, gel swelling rate（ESR）=5235%（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, hydroxyethyl methacrylate, fumaric acid composition, by the gauge of material, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride:First
Base hydroxy-ethyl 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, number-average molecular weight is 2000~20000, and its gross weight that feeds intake is the 2.5% of component A weight
~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, is pressed
Weight meter, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）, D components are by crotonic acid, xylitol, methyl-prop
Olefin(e) acid -2- Octyl Nitrites and dimethacrylate -1,3-BDO ester composition, by the gauge of material, crotonic acid:Xylitol:First
The ratio between amount of material of base acrylic acid-2-ethyl caproite=（0.4~1.6）:（0.08~0.32）:（0.4~1.1）, by weight
Meter, dimethacrylate -1,3-BDO ester charged material weight is crotonic acid, xylitol, three kinds of methacrylic acid -2- Octyl Nitrites
The 1.8%~5.5% of total monomer weight, component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and potassium peroxydisulfate charged material weight is D groups
Divide 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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