CN106699993A - Method for preparing organic amphiprotic copolymer interpenetrating polymer network gel - Google Patents
Method for preparing organic amphiprotic copolymer interpenetrating polymer network gel Download PDFInfo
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- CN106699993A CN106699993A CN201611130857.0A CN201611130857A CN106699993A CN 106699993 A CN106699993 A CN 106699993A CN 201611130857 A CN201611130857 A CN 201611130857A CN 106699993 A CN106699993 A CN 106699993A
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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 invention relates to a method for preparing organic amphiprotic copolymer interpenetrating polymer network gel. According to the method, methyl acrylyl ethyl trimethyl ammonium chloride, 2-ethylhexyl methacrylate and jasmonic acid are taken as comonomers, ethyleneglycol dimethacrylate serves as a cross-linking agent, potassium persulfate-sodium bisulfite serves as an initiator, copolymerized reaction is performed in deionized water to obtain organic amphiprotic copolymer first network gel; the first network gel is swollen in an aqueous solution prepared from itaconic acid, threose, beta-hydroxypropyl methacrylate, trimethylol propane trimethacrylate and deionized water, the monomers and the cross-linking agent in the aqueous solution undergo copolymerization and esterification reaction through effects of potassium sulfate and pyridoxine hydrochloride, and finally the organic amphiprotic copolymer interpenetrating polymer network gel is obtained.
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, methacrylic acid -2- Octyl Nitrites, jasmonic composition, by the gauge of material, methacryloxypropyl second
Base trimethyl ammonium chloride:Methacrylic acid -2- Octyl Nitrites:The ratio between amount of material of jasmonic=（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, threose, methacrylic acid-β-hydroxypropyl acrylate and trihydroxy methyl propane trimethyl acrylate, by material
Gauge, itaconic acid:Threose: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, trihydroxy methyl propane trimethyl acrylate charged material weight be itaconic acid, threose,
Three kinds the 1.8%~5.5% of total monomer weight of methacrylic acid-β-hydroxypropyl acrylate；Component E is by potassium peroxydisulfate, pyridoxine hydrochloride group
Into potassium peroxydisulfate charged material weight is the 0.1%~1.2% of D component weights, and pyridoxine hydrochloride charged material weight is D component gross weights
The 0.8%~5.6% of amount.
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, jasmonic HOOCCH2-(C5H6O)CH2CH=CHC2H5The aqueous solution of comonomer；After vacuumizing deoxidation,
Nitrogen protection is passed through, the aqueous solution of crosslinking agent PEGDMA-400 is added；After intensification, add redox and draw
Hair agent potassium peroxydisulfate-sodium hydrogensulfite K2S2O8-NaHSO3The aqueous solution, through trigger, combined polymerization chain propagation reaction, crosslinking agent two
Methacrylic acid macrogol ester participates in copolyreaction and line style copolymerization macromolecular crosslinks reaction and forms cross-linked network structure,
Through chain termination reaction, organic amphiprotic copolymerized macromolecule first network gel is obtained.It is passed through nitrogen protection, organic amphiprotic copolymerization high score
Sub- first network gel is in itaconic acid H2C=C(COOH)CH2COOH, threose HOCH2(CHOH)2CHO, methacrylic acid-β-hydroxyl
Propyl ester CH2=C(CH3)COOCH2CH(OH)CH3, trihydroxy methyl propane trimethyl acrylate C2H5C(CH2OOC(CH3)C=CH2)3
The aqueous solution effect under it is swelling, add initiator potassium persulfate K2S2O8, catalyst pyridoxine hydrochloride (CH3)(HOCH2)2
(HO)C5Continue swelling in the presence of the HNHCl aqueous solution, in swelling process, monomer, crosslinking agent, initiator in the aqueous solution,
Catalyst enters into organic amphiprotic copolymerized macromolecule first network gel inside and is uniformly distributed；Increase through initiation, combined polymerization chain
Reaction forms line style copolymerization macromolecular, and crosslinking agent trihydroxy methyl propane trimethyl acrylate participates in copolyreaction and line style copolymerization
Macromolecular crosslinks reaction, forms cross-linked network structure, pyridoxine hydrochloride molecule of the catalysis with carboxylic group and hydroxyl
There is esterification in the molecule of group, because threose will react to form friendship with three OH groups with the molecule with carboxylic group
Connection network 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 -2- Octyl Nitrites, jasmonic, methacrylic acid-β-hydroxypropyl acrylate and crosslinking agent trimethyl
Acrylic acid trihydroxymethylpropanyl ester low toxicity；Monomer itaconic acid and crosslinking agent PEGDMA-400, threose are nontoxic,
Reduce gel toxicity；The interpenetrating networks gel of preparation has radical crosslinking and esterification and crosslinking network structure, improves IPN
The stability of network gel；Preparation method is simple, reaction condition is gentle, be suitable for production, with good environmental benefit and economy
Benefit.
Specific embodiment
Embodiment 1：124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 79.32g methacrylic acid -2- ethyl hexyls
Ester, 105.1g jasmonics and 720.9ml deionized waters are added to volume can be uniformly mixed in closed reactor for 2L, should
The weight concentration of the aqueous solution is 30%；Relative degree of vacuum -0.03MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal
Pressure, the number-average molecular weight for adding 9.3g is the water that 3000 PEGDMA-400 and 34.9ml deionized waters are prepared
Solution, the weight concentration of the aqueous solution is 21%；38 DEG C are then heated to, 1.19g potassium peroxydisulfates, 0.36g sodium hydrogensulfites is added
The aqueous solution prepared with 26.5ml deionized waters, the weight concentration of the aqueous solution is 5.5%, and in 38 DEG C of constant temperature, control ph is
4.5,2.3h is reacted, obtain organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, in the case where nitrogen is passed through, had
Machine both sexes copolymerized macromolecule first network gel 62.8g input volumes can be swelling in closed reactor for 10L's, in the reactor
Equipped with 39g itaconic acids, 12g threoses, 72.1g methacrylic acids-β-hydroxypropyl acrylate, 2.46g trimethacrylates acid trihydroxy methyl third
The aqueous solution that alkyl ester and 6154ml deionized waters are prepared, the weight concentration of the aqueous solution is 2%, the weight of first network gel
（62.8g）:The weight of the aqueous solution（6279.1g）=1:100, swelling 3h；Add 0.25g potassium peroxydisulfates, 1.26g pyridoxols
The aqueous solution that hydrochloride and 12.9ml deionized waters 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 copolymerized macromolecule
Interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=9754%（Deionized water）, gel
Swelling ratio（ESR）=9643%（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：228.3g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 297.5g methacrylic acid -2- ethyl hexyls
Ester, 210.3g jasmonics and 490.7ml deionized waters are added to volume for 1.5L can be uniformly mixed in closed reactor, should
The weight concentration of the aqueous solution is 60%；Relative degree of vacuum -0.07MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal
Pressure, the number-average molecular weight for adding 73.6g is that 18000 PEGDMA-400 and 115.1ml deionized waters are prepared
The aqueous solution, the weight concentration of the aqueous solution is 39%；47 DEG C are then heated to, 5.52g potassium peroxydisulfates, 5.52g sulfurous acid is added
The aqueous solution that hydrogen sodium and 65.1ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%, in 47 DEG C of constant temperature, controls pH
It is 8 to be worth, and continues stirring reaction 3.2h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through
Under nitrogen, organic amphiprotic copolymerized macromolecule first network gel 20.8g inputs 5L can be swelling in closed reactor, is filled in reactor
There are 117.1g itaconic acids, 36g threoses, 144.2g methacrylic acids-β-hydroxypropyl acrylate, 14.9g trimethacrylates acid trihydroxy methyl
The aqueous solution that propane ester and 2809ml deionized waters are prepared, the weight concentration of the aqueous solution is 10%, the weight of first network gel
（20.8g）:The weight of the aqueous solution（3121.4g）=1:150, swelling 5.5h；0.62g potassium peroxydisulfates, 3.12g pyrroles is added to tremble
The aqueous solution that alcohol hydrochloride and 15.46ml 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 6.5, in 92 DEG C of isothermal reaction 5.6h, obtain organic amphiprotic copolymerization high
Molecule interpenetration network gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=7853%（Deionized water）,
Gel swelling rate（ESR）=7695%（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, is then cooled down, and in the case where nitrogen is passed through, the first network gel is put into 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, jasmonic composition, by the gauge of material, methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium:Methacrylic acid -2- Octyl Nitrites:The ratio between amount of material of jasmonic=（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,
Threose, methacrylic acid-β-hydroxypropyl acrylate and trihydroxy methyl propane trimethyl acrylate composition, by the gauge of material, clothing health
Acid:Threose: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, trihydroxy methyl propane trimethyl acrylate charged material weight be itaconic acid, threose, methacrylic acid-β-
Three kinds the 1.8%~5.5% of total monomer weight of hydroxypropyl acrylate, 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%。
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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: 20170524 |