CN106750013A - 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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- CN106750013A CN106750013A CN201611128128.1A CN201611128128A CN106750013A CN 106750013 A CN106750013 A CN 106750013A CN 201611128128 A CN201611128128 A CN 201611128128A CN 106750013 A CN106750013 A CN 106750013A
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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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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
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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
- 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, vinyl pyrrolidone, itaconic 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 abscisic acid, D arabinoses, hydroxyethyl methacrylate, neopentyl glycol dimethacrylate 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, vinyl pyrrolidone, itaconic acid composition, by the gauge of material, methylacryoyloxyethyl front three
Ammonium chloride:Vinyl pyrrolidone:The ratio between amount of material of itaconic 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 abscisic acid,
D-R, hydroxyethyl methacrylate and neopentyl glycol dimethacrylate composition, by the gauge of material, abscisic acid:
D-R:The ratio between amount of material of hydroxyethyl methacrylate=(0.3~1.3):(0.08~0.32):(0.4~1.1),
By weight, neopentyl glycol dimethacrylate charged material weight is abscisic acid, D-R, hydroxyethyl methacrylate three
Plant 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
The 0.1%~1.2% of component weight, the pyridoxine hydrochloride gross weight that feeds intake 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, vinyl pyrrolidone H2C=CH-(C4H6NO), itaconic acid CH2=C
(COOH)CH2The aqueous solution of COOH comonomers;After vacuumizing deoxidation, nitrogen protection is passed through, adds crosslinking agent dimethyl allene
The aqueous solution of acid polyethylene glycol ester;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 participate in copolymerization it is anti-
Reaction should be crosslinked with line style copolymerization macromolecular and form cross-linked network structure, through chain termination reaction, obtain organic amphiprotic copolymerization
Macromolecule first network gel.Nitrogen protection is passed through, organic amphiprotic copolymerized macromolecule first network gel is in abscisic acid
(C9H13O2)-CH=CHC(CH3)=CHCOOH, D-R (HO)4C5H6O, hydroxyethyl methacrylate CH2=C(CH3)
COOCH2CH2OH, neopentyl glycol dimethacrylate CH2=C(CH3)COOCH2C(CH3)2CH2OOC(CH3)C=CH2It is water-soluble
It is swelling under liquid effect, 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, catalysis
Agent enters into organic amphiprotic copolymerized macromolecule first network gel inside and is uniformly distributed;After intensification, increase through initiation, combined polymerization chain
Reaction long forms line style copolymerization macromolecular, and crosslinking agent neopentyl glycol dimethacrylate participates in copolyreaction and line style copolymerization is big
Molecule crosslinks reaction, forms cross-linked network structure, pyridoxine hydrochloride the catalysis molecule with carboxylic group and hydroxyl base
There is esterification in the molecule of group, because D-R reacts to form friendship with four OH groups and 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, hydroxyethyl methacrylate and with crosslinking agent neopentyl glycol dimethacrylate low toxicity, monomer clothing health
Acid, abscisic acid, vinyl pyrrolidone and crosslinking agent PEGDMA-400, D-R 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 125g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 44g vinyl pyrrolidones, 65g clothing health
The deionized water of acid and 546ml is added to volume can be uniformly mixed in closed reactor for 2L, the weight of the aqueous solution
Concentration is 30%, is evacuated to relative degree of vacuum -0.035MPa, then passes to nitrogen and recovers reactor to normal pressure, adds 7g numbers equal
Molecular weight is the aqueous solution that 3000 PEGDMA-400 and 26ml deionized waters are prepared, the weight of the aqueous solution
Concentration is 21%;38 DEG C are then heated to, adds what 0.9g potassium peroxydisulfates, 0.27g sodium hydrogensulfites and 20ml deionized waters were prepared
The aqueous solution, the weight concentration of the aqueous solution is 5.5%;In 38 DEG C of constant temperature, control ph is 4.5, continues stirring reaction 2.4h, is obtained
To organic amphiprotic copolymerized macromolecule first network gel;Then cooled down, in the case where nitrogen is passed through, organic amphiprotic copolymerized macromolecule
First network gel 95g input volumes are swelling in the closed reactor of 20L, and 106g abscisic acids, 15g are housed in the reactor
What D-R, 65g hydroxyethyl methacrylates, 4g neopentyl glycol dimethacrylates and 9287ml deionized waters were prepared
The aqueous solution, the weight concentration of the aqueous solution is 2%, the weight of first network gel(95g):The weight of the aqueous solution(9476g)=
1:100, swelling 2.5h;Add the aqueous solution that 0.38g potassium peroxydisulfates, 1.9g pyridoxine hydrochlorides and 19ml deionized waters are prepared
Continue swelling, the weight concentration of the aqueous solution is 10.5%, swelling 17h;After the completion of swelling, 78 DEG C are warming up to, control ph is 4,
In 78 DEG C of isothermal reaction 4.4h, organic amphiprotic copolymerized macromolecule interpenetrating networks gel is obtained.The gel is water insoluble, can be in water
It is swelling, gel swelling rate(ESR)=7651%(Deionized water), gel swelling rate(ESR)=7585%(The NaCl water of weight concentration 1%
Solution).
Embodiment 2:By 228g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 167g vinyl pyrrolidones, 130g clothing
The deionized water of health acid and 350ml is added to volume 1L can be uniformly mixed in closed reactor, and the weight of the aqueous solution is dense
It is 60% to spend, and is evacuated to relative degree of vacuum -0.075MPa, then passes to nitrogen and recovers reactor to normal pressure, adds 53g numbers equal
Molecular weight is the aqueous solution that 18000 PEGDMA-400 and 82ml deionized waters are prepared, the weight of the aqueous solution
Amount concentration is 39%;48 DEG C are then heated to, adds 3.94g potassium peroxydisulfates, 3.94g sodium hydrogensulfites and 46ml deionized waters to match somebody with somebody
The aqueous solution of system, the weight concentration of the aqueous solution is 14.5%;In 48 DEG C of constant temperature, control ph is 9.5, continues stirring reaction
3.3h, obtains organic amphiprotic copolymerized macromolecule first network gel;Then cooled down, in the case where nitrogen is passed through, organic amphiprotic is common
Poly- macromolecule first network gel 34g input volume can be swelling in closed reactor for 10L's, de- equipped with 317g in the reactor
Fall acid, 45g D-Rs, 130g hydroxyethyl methacrylates, 25g neopentyl glycol dimethacrylates and 4653ml goes
The aqueous solution that ionized water is prepared, the weight concentration of the aqueous solution is 10%, the weight of first network gel(35g):The aqueous solution
Weight(5170g)=1:150, swelling 5.8h;Add 1.03g potassium peroxydisulfates, 5.17g pyridoxine hydrochlorides and 26ml deionizations
The aqueous solution that water is prepared continues swelling, and the weight concentration of the aqueous solution is 19.5%, swelling 23h;After the completion of swelling, 93 are warming up to
DEG C, control ph is 6.5, in 93 DEG C of isothermal reaction 5.4h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The gel
It is water insoluble, can be swelling in water, gel swelling rate(ESR)=6374%(Deionized water), gel swelling rate(ESR)=6293%
(The NaCl aqueous solution of weight concentration 1%).
Claims (1)
1. a kind of preparation method of organic copolymer Amphiphatic high polymer 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 common
Poly- Amphiphatic high polymer first network gel, is then cooled down, and in the case where nitrogen is passed through, first network gel input is equipped with into 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 copolymer Amphiphatic high polymer interpenetrating networks gel;The component A is by methylacryoyloxyethyl trimethyl chlorine
Change ammonium, vinyl pyrrolidone, itaconic acid composition, by the gauge of material, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride:Ethene
Base pyrrolidones:The ratio between amount of material of itaconic acid=(0.5~1.2):(0.3~1.6):(0.4~1.1), B component is diformazan
Base polyalkylene glycol acrylate ester, number-average molecular weight be 2000~20000, its gross weight that feeds intake be component A gross weight 2.5%~
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, by weight
Gauge, potassium peroxydisulfate:Weight ratio=1 of sodium hydrogensulfite:(0.2~1.1);D components are by abscisic acid, D-R, methyl
Hydroxy-ethyl acrylate and neopentyl glycol dimethacrylate are constituted, by the gauge of material, abscisic acid:D-R:Methyl
The ratio between amount of material of hydroxy-ethyl acrylate=(0.3~1.3):(0.08~0.32):(0.4~1.1), by weight, dimethyl
Acrylic acid DOPCP charged material weight is abscisic acid, D-R, three kinds of total monomer weights of hydroxyethyl methacrylate
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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