CN106749995A - 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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- CN106749995A CN106749995A CN201611124655.5A CN201611124655A CN106749995A CN 106749995 A CN106749995 A CN 106749995A CN 201611124655 A CN201611124655 A CN 201611124655A CN 106749995 A CN106749995 A CN 106749995A
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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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- 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
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- 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, methacrylic acid oxygen propyl group trimellitic anhydride ester, 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 the penetenoic acid of 2 methyl 4, xylitol, ethoxyethyl methacrylates, 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
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 oxygen propyl group trimellitic anhydride ester, fumaric acid composition, by the gauge of material, methyl-prop
Alkene acyloxyethyl trimethyl ammonium chloride:Methacrylic acid oxygen propyl group trimellitic anhydride ester: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, its charged material weight is the 2.5%~11% of component A gross weight；Component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, its throwing
Material gross weight is the 0.3%~1.8% of component A gross weight, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:
（0.2~1.1）；D components by 2- methyl -4- penetenoic acids, xylitol, ethoxyethyl methacrylates and dimethacrylate -
1,3-BDO ester is constituted, by the gauge of material, 2- methyl -4- penetenoic acids:Xylitol:The thing of ethoxyethyl methacrylates
The ratio between amount of matter=（0.4~1.6）:（0.08~0.32）:（0.4~1.1）, by weight, dimethacrylate -1,3- fourths two
Alcohol ester charged material weight is 2- methyl -4- penetenoic acids, xylitol, three kinds the 1.8% of total monomer weight of ethoxyethyl methacrylates
~5.5%；Component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, potassium peroxydisulfate charged material weight be D component weights 0.1%~
1.2%, 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, methacrylic acid oxygen propyl group trimellitic anhydride ester CH2=C(CH3)COO
(CH2)3OOCC6H3C2O3, that tri- kinds of comonomers of fumaric acid HOOCCH=CHCOOH and deionized water are prepared into mixing under agitation is equal
The even aqueous solution；After vacuumizing deoxidation, nitrogen protection is passed through, adds the water-soluble of crosslinking agent PEGDMA-400
Liquid；After intensification, redox initiator potassium peroxydisulfate-sodium hydrogensulfite K is added2S2O8-NaHSO3The aqueous solution, through trigger,
Combined polymerization chain propagation reaction, crosslinking agent PEGDMA-400 participates in copolyreaction and line style copolymerization macromolecular occurs
Cross-linking reaction forms cross-linked network structure, through chain termination reaction, obtains organic amphiprotic copolymerized macromolecule first network gel.It is passed through
Nitrogen is protected, and organic amphiprotic copolymerized macromolecule first network gel is in 2- methyl -4- penetenoic acids H2C=CHCH2CH(CH3)COOH、
Xylitol HOCH2(CHOH)3CH2OH, ethoxyethyl methacrylates CH2=C(CH3)COOCH2CH2OCH2CH3, dimethyl propylene
Olefin(e) acid -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 hydrochloride (CH3)(HOCH2)2(HO)C5In the presence of the HNHCl aqueous solution
Continue swelling, in swelling process, monomer, crosslinking agent in the aqueous solution, initiator, catalyst enter into organic amphiprotic copolymerization high score
Sub- first network gel inside is simultaneously uniformly distributed；After intensification, form line style copolymerization through initiation, combined polymerization chain propagation reaction and divide greatly
Son, crosslinking agent dimethacrylate -1,3-BDO ester participates in copolyreaction and line style copolymerization macromolecular crosslinks reaction, shape
Into cross-linked network structure, there is esterification instead in the molecule of pyridoxine hydrochloride molecule of the catalysis with carboxylic group and hydroxyl group
Should, because xylitol reacts to form cross-linked network structure with five OH groups and the molecule with carboxylic group；Further reaction,
Finally due to the chain termination and the completion of esterification of radical copolymerization macromolecular, organic amphiprotic copolymerized macromolecule IPN is formed
Network 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 oxygen propyl group trimellitic anhydride ester, 2- methyl -4- penetenoic acids and crosslinking agent dimethyl allene
Acid -1,3-BDO ester low toxicity, monomer fumaric acid, ethoxyethyl methacrylates and the poly- second two of crosslinking agent dimethacrylate
Alcohol ester, xylitol are nontoxic, reduce gel toxicity；The interpenetrating networks gel of preparation has radical crosslinking and esterification and crosslinking network
Structure, improves the stability of interpenetrating networks gel；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, the 116g methacrylic acid inclined benzene of oxygen propyl group
The deionized water of three acid anhydride esters, 58g fumaric acid and 696.6ml is added to volume and can stir mixing in closed reactor for 2L
Even, 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, PEGDMA-400 and the preparation of 33.7ml deionized waters that 8.96g number-average molecular weights are 3000 are added
The aqueous solution, the weight concentration of the aqueous solution is 21%；36 DEG C are then heated to, 1.15g potassium peroxydisulfates, 0.34g sulfurous acid is added
The aqueous solution that hydrogen sodium and 25.7ml deionized waters are prepared, the weight concentration of the aqueous solution is 5.5%；In 36 DEG C of constant temperature, control ph
It is 5, continues stirring reaction 3h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through nitrogen
Under, organic amphiprotic copolymerized macromolecule first network gel 77.1g input volumes can be swelling in closed reactor for 15L's, and this is anti-
Answer in device equipped with 57g 2- methyl -4- penetenoic acids, 15.2g xylitols, 79g ethoxyethyl methacrylates, dimethyl allene
The aqueous solution that acid -1,3-BDO ester 3g and 7557.7ml deionized water is prepared, the weight concentration of the aqueous solution is 20%, first
The weight of network gel（77.1g）：The weight of the aqueous solution（7712g）=1:100, swelling 2.3h；Add 0.31g persulfuric acid
The aqueous solution that potassium, 1.54g pyridoxine hydrochlorides and 15.8ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is
10.5%, 18 h when swelling；76 DEG C are warming up to after the completion of swelling, control ph is 4, in 76 DEG C of isothermal reaction 4.5h, obtain organic
Both sexes copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=6731%
（Deionized water）, gel swelling rate（ESR）=6558%（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：By 228.25g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 435g methacrylic acid oxygen propyl group is inclined
The deionized water of benzenetricarboxylic anhydride ester, 116.1g fumaric acid and 520ml is added to volume and can stir mixed in closed reactor for 2L
Close uniform, the weight concentration of the aqueous solution is 60%, is evacuated to relative degree of vacuum -0.075MPa, then pass to nitrogen and recover anti-
Device to normal pressure is answered, PEGDMA-400 and 121.9ml deionizations that 77.9g number-average molecular weights are 19000 is added
The aqueous solution that water is prepared, the weight concentration of the aqueous solution is 39%；45 DEG C are then heated to, 5.84g potassium peroxydisulfates, 5.84g is added
The aqueous solution that sodium hydrogensulfite and 69ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%；In 45 DEG C of constant temperature, control
PH value processed is 8, continues stirring reaction 3h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, logical
Enter under nitrogen, organic amphiprotic copolymerized macromolecule first network gel 26.23g input volumes can be molten in closed reactor for 10L's
It is swollen, in reactor equipped with 171g 2- methyl -4- penetenoic acids, 45.6g xylitols, 158g ethoxyethyl methacrylates,
The aqueous solution that 18.73g dimethacrylates -1,3-BDO ester and 3540.4ml deionized waters are prepared, the weight of the aqueous solution
Concentration is 10%, the weight of first network gel（26.23g）：The weight of the aqueous solution（3933.77g）=1:150, swelling 5.7h,
The aqueous solution for adding the preparation of 0.79g potassium peroxydisulfates, 3.93g pyridoxine hydrochlorides and 19.5ml deionized waters continues swelling, should
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 6.7, in 92 DEG C of constant temperature
Reaction 5.5h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel
Swelling ratio（ESR）=5217%（Deionized water）, gel swelling rate（ESR）=5173%（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 oxygen propyl group trimellitic anhydride ester, fumaric acid composition, by the gauge of material, methylacryoyloxyethyl three
Ammonio methacrylate:Methacrylic acid oxygen propyl group trimellitic anhydride ester: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, its throwing
Material weight is the 2.5%~11% of component A gross weight, and component C is made up of potassium peroxydisulfate-sodium hydrogensulfite, and its gross weight that feeds intake is A
The 0.3%~1.8% of component weight, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:（0.2~1.1）, D
Component is by 2- methyl -4- penetenoic acids, xylitol, ethoxyethyl methacrylates and dimethacrylate -1,3 butylene glycol ester
Composition, by the gauge of material, 2- methyl -4- penetenoic acids:Xylitol:The ratio between amount of material of ethoxyethyl methacrylates=
（0.4~1.6）:（0.08~0.32）:（0.4~1.1）, by weight, dimethacrylate -1,3-BDO ester charged material weight
It is 2- methyl -4- penetenoic acids, xylitol, three kinds the 1.8%~5.5% of total monomer weight of ethoxyethyl methacrylates, component E
It is made up of potassium peroxydisulfate, pyridoxine hydrochloride, potassium peroxydisulfate charged material weight is the 0.1%~1.2% of D component weights, pyridoxol
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 |
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Application publication date: 20170531 |