CN106750033A - 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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- CN106750033A CN106750033A CN201611132280.7A CN201611132280A CN106750033A CN 106750033 A CN106750033 A CN 106750033A CN 201611132280 A CN201611132280 A CN 201611132280A CN 106750033 A CN106750033 A CN 106750033A
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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, chlorogenic 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 caffeic acid, chinic acid, the Octyl Nitrite of methacrylic acid 2, pentaerythritol tetramethacrylate 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, hydroxyethyl methacrylate, chlorogenic acid composition, by the gauge of material, methylacryoyloxyethyl three
Ammonio methacrylate:Hydroxyethyl methacrylate:The ratio between amount of material of chlorogenic 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 caffeic acid,
Chinic acid, methacrylic acid -2- Octyl Nitrites and pentaerythritol tetramethacrylate composition, by the gauge of material, caffeic acid:
Chinic acid:The ratio between amount of material of methacrylic acid -2- Octyl Nitrites=（0.3~1.3）:（0.08~0.32）:（0.4~
1.1）, by weight, pentaerythritol tetramethacrylate charged material weight is caffeic acid, chinic acid, methacrylic acid -2- ethyls
Three kinds the 1.8%~5.5% of total monomer weight of own ester；Component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, and potassium peroxydisulfate feeds intake
Weight is the 0.1%~1.2% of D component weights, and pyridoxine hydrochloride charged material weight 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, hydroxyethyl methacrylate CH2=C(CH3)COOCH2CH2OH, green original
Sour (HO)2C6H3CH=CHCOOCH(CH)2(OH)2(CH2)2C (OH) COOH comonomers and deionized water are prepared under agitation
The well mixed aqueous solution；After vacuumizing deoxidation, nitrogen protection is passed through, adds crosslinking agent PEGDMA-400
The aqueous solution；After intensification, redox initiator potassium peroxydisulfate-sodium hydrogensulfite K is added2S2O8-NaHSO3The aqueous solution, warp
Initiation, combined polymerization chain propagation reaction, crosslinking agent PEGDMA-400 participates in copolyreaction and line style copolymerization divides greatly
Son crosslinks reaction and forms cross-linked network structure, through chain termination reaction, obtains organic amphiprotic copolymerized macromolecule first network and coagulates
Glue.Nitrogen protection is passed through, organic amphiprotic copolymerized macromolecule first network gel is at caffeic acid (HO)2C6H3CH=CHCOOH, Kui Ni
Sour (HO)4C6H7COOH, methacrylic acid -2- Octyl Nitrites CH2=C(CH3)COOCH2CH(C2H3)(CH2)3CH3, tetramethyl propylene
Sour pentaerythritol ester (CH2=C(CH3)COOCH2)4It is swelling under the aqueous solution effect of C, 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 in the aqueous solution, initiator, catalyst enter into organic amphiprotic copolymerized macromolecule first network gel inside simultaneously
It is uniformly distributed；After intensification, line style copolymerization macromolecular, crosslinking agent tetramethyl acrylic acid are formed through initiation, combined polymerization chain propagation reaction
Pentaerythritol ester participates in copolyreaction and line style copolymerization macromolecular crosslinks reaction, forms cross-linked network structure, pyridoxol salt
Hydrochlorate is catalyzed the molecule with carboxylic group and the molecule of hydroxyl group occurs esterification, because chinic acid carries four OH bases
Group reacts to form cross-linked network structure with the molecule with carboxylic group；Further reaction, finally because radical copolymerization divides greatly
The chain termination of son and the completion of 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, hydroxyethyl methacrylate, methacrylic acid -2- Octyl Nitrites and crosslinking agent tetramethyl acrylic acid season penta
Four alcohol ester low toxicities, monomer chlorogenic acid, caffeic acid and crosslinking agent PEGDMA-400, chinic acid 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：By 124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 52g hydroxyethyl methacrylates,
The deionized water of 177.2g chlorogenic acids and 825.3ml is added to volume can be uniformly mixed in closed reactor for 2L, should
The weight concentration of the aqueous solution is 30%, is evacuated to relative degree of vacuum -0.03MPa, then passes to nitrogen and recovers reactor to normal
Pressure, adds the PEGDMA-400 that 10.6g number-average molecular weights are 3000 and the water that 39.9ml deionized waters are prepared
Solution, the weight concentration of the aqueous solution is 21%, then heats to 37 DEG C, adds 1.36g potassium peroxydisulfates, 0.41g sodium hydrogensulfites
The aqueous solution prepared with 30.4ml deionized waters, the weight concentration of the aqueous solution is 5.5%；In 37 DEG C of constant temperature, control ph is
4.4, continue stirring reaction 2.2h, obtain organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through nitrogen
Under gas, organic amphiprotic copolymerized macromolecule first network gel 90g be put into volume for 15L can be swelling in closed reactor, this is anti-
Answer in device equipped with 72g caffeic acids, 19.2g chinic acids, 85.1g methacrylic acid -2- Octyl Nitrites, 3.53g tetramethyl acrylic acid
The aqueous solution that pentaerythritol ester and 8815.6ml deionized waters are prepared, the weight concentration of the aqueous solution is 2%, first network gel
Weight（90g）：The weight of the aqueous solution（8995.5g）=1:100, swelling 2.7h；Add 0.36g potassium peroxydisulfates, 1.8g pyrroles
The aqueous solution that alcohol hydrochloride and the 18.4ml deionized waters of trembling are prepared continues swelling, and the weight concentration of the aqueous solution is 10.5%, swelling
17 h；77 DEG C are warming up to after the completion of swelling, control ph is 5, in 77 DEG C of isothermal reaction 4.2h, obtain organic amphiprotic copolymerization high score
Sub- interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=7381%（Deionized water）, coagulate
Glue swelling ratio（ESR）=7268%（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 354.3g chlorogenic acids and 499.5ml is added to volume can be uniformly mixed in closed reactor for 2L, should
The weight concentration of the aqueous solution is 60%, is evacuated to relative degree of vacuum -0.07MPa, then passes to nitrogen and recovers reactor to normal
Pressure, addition 74.9g number-average molecular weights are that 18000 PEGDMA-400 and 117.2ml deionized waters are prepared
The aqueous solution, the weight concentration of the aqueous solution is 39%；48 DEG C are then heated to, 5.62g potassium peroxydisulfates, 5.62g bisulfites is added
The aqueous solution that sodium and 66.3ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%；In 48 DEG C of constant temperature, control ph
It is 8.9, 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 31.1g input volumes are swelling in the closed reactor of 10L, are somebody's turn to do
216.2g caffeic acids, 57.6g chinic acids, 170.2g methacrylic acid -2- Octyl Nitrites, 22.2g tetramethyls are housed in reactor
The aqueous solution that acrylate, pentaerythritol and 4196.2ml deionized waters are prepared, the weight concentration of the aqueous solution is 43.3%, first
The weight of network gel（31.1g）：The weight of the aqueous solution（4662.4g）=1:150, swelling 5.5h；Add 0.93g over cures
The aqueous solution that sour potassium, 4.66g pyridoxine hydrochlorides and 23.1ml deionized waters are prepared continues swelling, the weight concentration of the aqueous solution
It is 19.5%, swelling 23 h；93 DEG C are warming up to after the completion of swelling, control ph is 6.5, in 93 DEG C of isothermal reaction 5.3h, are had
Machine both sexes copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=
6430%（Deionized water）, gel swelling rate（ESR）=6282%（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, chlorogenic acid composition, by the gauge of material, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride:First
Base hydroxy-ethyl acrylate:The ratio between amount of material of chlorogenic 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 charged material weight is the 2.5% of component A gross weight
~11%, component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, and its charged material weight 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 caffeic acid, chinic acid, metering system
Acid -2- Octyl Nitrites and pentaerythritol tetramethacrylate are constituted, by the gauge of material, caffeic acid:Chinic acid:Metering system
The ratio between amount of material of acid -2- Octyl Nitrites=（0.3~1.3）:（0.08~0.32）:（0.4~1.1）, by weight, tetramethyl
Base acrylate, pentaerythritol charged material weight is caffeic acid, chinic acid, three kinds of total monomer weights of methacrylic acid -2- Octyl Nitrites
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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