CN106749980A - 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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- 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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- 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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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, the Octyl Nitrite of methacrylic acid 2, 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 abscisic acid, xylitol, methacrylic acid β hydroxypropyl acrylates, 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, methacrylic acid -2- Octyl Nitrites, fumaric acid composition, by the gauge of material, methacryloxypropyl second
Base trimethyl ammonium chloride:Methacrylic acid -2- Octyl Nitrites: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 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 abscisic acid, xylitol, methacrylic acid-β-hydroxypropyl acrylate and dimethacrylate -1,3-BDO ester, by material
Gauge, abscisic acid:Xylitol:The ratio between amount of material of methacrylic acid-β-hydroxypropyl acrylate=（0.4~1.6）:（0.08~0.32）:
（0.4~1.1）, by weight, dimethacrylate -1,3-BDO ester charged material weight is abscisic acid, xylitol, metering system
Three kinds the 1.8%~5.5% of total monomer weight of acid-β-hydroxypropyl acrylate；Component E is made up of potassium peroxydisulfate, pyridoxine hydrochloride, persulfuric acid
Potassium 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, methacrylic acid -2- Octyl Nitrites CH2=C(CH3)COOCH2CH
(C2H3) (CH2)3CH3, fumaric acid HOOCCH=CHCOOH comonomers the aqueous solution；After vacuumizing deoxidation, nitrogen protection is passed through,
Add the aqueous solution of crosslinking agent PEGDMA-400；After intensification, add redox initiator potassium peroxydisulfate-
Sodium hydrogensulfite K2S2O8-NaHSO3The aqueous solution, through trigger, combined polymerization chain propagation reaction, the poly- second of crosslinking agent dimethacrylate
Diol ester participates in copolyreaction and line style copolymerization macromolecular crosslinks reaction and forms cross-linked network structure, through chain termination reaction,
Obtain organic amphiprotic copolymerized macromolecule first network gel.Nitrogen protection is passed through, organic amphiprotic copolymerized macromolecule first network coagulates
Glue is in abscisic acid (C9H13O2)-CH=CHC(CH3)=CHCOOH, xylitol HOCH2(CHOH)3CH2OH, methacrylic acid-β-hydroxypropyl
Ester CH2=C(CH3) COO CH2CH(OH)CH3, dimethacrylate -1,3 butylene glycol ester CH2=C(CH3)COOCH(CH3)
CH2CH2OOC(CH3)C=CH2Aqueous solution effect under it is swelling, then in 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；Through drawing
Hair, combined polymerization chain propagation reaction form line style copolymerization macromolecular, and crosslinking agent dimethacrylate -1,3-BDO ester participates in copolymerization
Reaction and line style copolymerization macromolecular crosslink reaction, form cross-linked network structure, pyridoxine hydrochloride catalysis band carboxylic group
Molecule and hydroxyl group molecule occur esterification, due to xylitol with five OH groups by with carboxylic group
Molecule forms cross-linked network structure；Further react, finally the chain termination due to radical copolymerization macromolecular and esterification
Completion, formed 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, methacrylic acid-β-hydroxypropyl acrylate and crosslinking agent dimethacrylate -
1,3-BDO ester low toxicity, monomer fumaric acid, abscisic acid and crosslinking agent PEGDMA-400, xylitol 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, 79.3g methacrylic acid -2- ethyl hexyls
Ester, 58g fumaric acid and 611ml deionized waters are added to volume can be uniformly mixed in closed reactor for 2L, and this is water-soluble
The weight concentration of liquid is 30%；Relative degree of vacuum -0.03MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal pressure, plus
The number-average molecular weight for entering 7.9g is the aqueous solution that 4000 PEGDMA-400 and 29.6ml deionized waters are prepared,
The weight concentration of the aqueous solution is 21%；Then heat to 36 DEG C, add 1.01g potassium peroxydisulfates, 0.3g sodium hydrogensulfites and
The aqueous solution that 22.5ml deionized waters are prepared, the weight concentration of the aqueous solution is 5.5%, and in 36 DEG C of constant temperature, control ph is 4.5,
Continue stirring reaction 2.3h, obtain organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through nitrogen
Under, organic amphiprotic copolymerized macromolecule first network gel 111.9g input volumes can be swelling in closed reactor for 20L's, and this is anti-
Answer in device equipped with 132.2g abscisic acids, 15.2g xylitols, 72.1g methacrylic acids-β-hydroxypropyl acrylate, 4.4g dimethacrylates-
The aqueous solution that 1,3-BDO ester and 10969ml deionized waters are prepared, the weight concentration of the aqueous solution is 2%, first network gel
Weight（111.9g）:The weight of the aqueous solution（11192.5g）=1:100, swelling 3h；Add 0.45g potassium peroxydisulfates,
The aqueous solution that 2.24g pyridoxine hydrochlorides and 22.9ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is
10.5%, swelling 18h；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
Both sexes copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=6753%
（Deionized water）, gel swelling rate（ESR）=6637%.
Embodiment 2：228.3g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 297.5g methacrylic acid -2- ethyl hexyls
Ester, 116.1g fumaric acid and 427.9ml 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 64.2g is that 18000 PEGDMA-400 and 100.4ml deionized waters are prepared
The aqueous solution, the weight concentration of the aqueous solution is 39%；47 DEG C are then heated to, 4.81g potassium peroxydisulfates, 4.81g sulfurous acid is added
The aqueous solution that hydrogen sodium 56.8ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%, in 47 DEG C of constant temperature, control ph
It is 9.2, 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 41g inputs 10L can be swelling in closed reactor, is filled in reactor
There are 396.5g abscisic acids, 45.6g xylitols, 144.2g methacrylic acids-β-hydroxypropyl acrylate, 29.3g dimethacrylate -1,3- fourths
The aqueous solution that diol ester and 5540ml deionized waters are prepared, the weight concentration of the aqueous solution is 10%, the weight of first network gel
（41g）:The weight of the aqueous solution（6156.1g）=1:150, swelling 5.3h；Add 1.23g potassium peroxydisulfates, 6.16g pyridoxols
The aqueous solution that hydrochloride and 30.5ml 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 6.3, in 92 DEG C of isothermal reaction 5.5h, obtain organic amphiprotic copolymerized macromolecule
Interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=5326%（Deionized water）, gel
Swelling ratio（ESR）=5267%.
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, fumaric acid composition, by the gauge of material, methylacryoyloxyethyl trimethyl ammonia chloride
Ammonium:Methacrylic acid -2- Octyl Nitrites: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 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,
Xylitol, methacrylic acid-β-hydroxypropyl acrylate and dimethacrylate -1,3-BDO ester composition, by the gauge of material, come off
Acid:Xylitol:The ratio between amount of material of methacrylic acid-β-hydroxypropyl acrylate=（0.4~1.6）:（0.08~0.32）:（0.4~
1.1）, by weight, dimethacrylate -1,3-BDO ester charged material weight be abscisic acid, xylitol, 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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Application publication date: 20170531 |