CN106589423A - Preparation method of organic amphiprotic interpenetrating copolymer network hydrogel - Google Patents

Preparation method of organic amphiprotic interpenetrating copolymer network hydrogel Download PDF

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CN106589423A
CN106589423A CN201611129043.5A CN201611129043A CN106589423A CN 106589423 A CN106589423 A CN 106589423A CN 201611129043 A CN201611129043 A CN 201611129043A CN 106589423 A CN106589423 A CN 106589423A
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weight
aqueous solution
deionized water
gel
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朱明�
石小阳
江燕妮
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Sichuan Normal University
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • 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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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks

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Abstract

The invention relates to a preparation method of organic amphiprotic interpenetrating copolymer network hydrogel. According to the method, methacryloyloxyethyl trimethyl ammonium chloride, beta-hydroxypropyl methacrylate and sorbic acid serving as a comonomer, poly(ethylene glycol) dimethacrylate serving as a crosslinking agent and potassium peroxydisulfate-sodium bisulfite serving as an initiator are subjected to a copolymerization reaction in deionized water, and organic amphiprotic first copolymer network hydrogel is obtained; the first network hydrogel swells in a water solution prepared from fumaric acid, inositol, N,N-dimethylaminoethyl acrylate, dibromoneopentyl glycol dimethacrylate and deionized water, the monomer and the crosslinking agent in the water solution are subjected to a copolymerization reaction and an esterification reaction under the action of potassium sulfate and pyridoxine hydrochloride, and finally, the organic amphiprotic interpenetrating copolymer network hydrogel is obtained.

Description

The preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel
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, to remove and can recover original after external force Shape, the viscoelasticity with solid；See 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 have again 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, aminoacid. Copolymerization Amphiphatic high polymer interpenetrating networks gel is obtained Protean specific performance, particularly height and contains with the change of copolymerization component The similarity of the electrical and organization of human body in the water yield and molecule, good biocompatibility, environmental stimuluses response, in biological doctor The fields such as medicine controlled releasing, bio-sensing, the organizational project in medicine field have obtained some applications.
The problem that at present preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel is primarily present is monomer propylene The toxic articles of amide category " carcinogenic, aberration inducing, mutagenesis ", cross-linking agent N, N methylene diacrylamine toxicity is larger, and gel is deposited In unfavorable toxic effect；The interpenetrating networks gel stability that single cross-linking agent is formed is relatively low.Exploitation adopts nontoxic or low toxicity Monomer, cross-linking agent carry out combined polymerization to reduce gel toxicity, form multiple interpenetrating networks using compounding cross-linking agent and improve 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, the mesh of the present invention Be to provide one kind adopt nontoxic or low-toxicity monomer, cross-linking agent to carry out combined polymerization to reduce gel toxicity, using compound cross-linking 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 in closed reactor component A and deionized water stirring can be added to prepare aqueous solution to levy, and the weight concentration for controlling component A is 28%～62%；After the completion of prepared by solution, it is -0.02MPa～-0.08MPa to be evacuated to relative degree of vacuum, is passed through nitrogen and recovers anti- Device is answered to add the aqueous solution prepared by B component and deionized water to normal pressure, under agitation, the weight concentration of B component is 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:The 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-β-hydroxypropyl acrylate, sorbic acid composition, by the gauge of material, methylacryoyloxyethyl Trimethyl ammonium chloride:Methacrylic acid-β-hydroxypropyl acrylate:The ratio of the amount of the material of sorbic 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 gross weight that feeds intake It is the 2.5%～11% of component A gross weight；Component C is made up of potassium peroxydisulfate-sodium sulfite, and its gross weight that feeds intake is that component A is total The 0.3%～1.8% of weight, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium sulfite:（0.2～1.1）；D components by Fumaric acid, cyclohexanhexanol, dimethylaminoethyl acrylate and the bromo DOPCP of dimethacrylate two composition, by material Gauge, fumaric acid:Cyclohexanhexanol:The ratio of the amount of the material of dimethylaminoethyl acrylate=（0.5～2.0）:（0.08～ 0.32）:（0.4～1.1）, by weight, the bromo DOPCP charged material weight of dimethacrylate two is fumaric acid, hexamethylene six The 1.8%～5.5% of alcohol, three kinds of total monomer weights of dimethylaminoethyl acrylate；Component E is by potassium peroxydisulfate, pyridoxine hydrochloride Composition, potassium peroxydisulfate charged material weight is the 0.1%～1.2% of D component weights, and pyridoxine hydrochloride charged material weight is that D components are total The 0.8%～5.6% of weight.
What the technical method of the present 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-β-hydroxypropyl acrylate CH2=C(CH3)COOCH2CH(OH) CH3, sorbic acid CH3The aqueous solution of CH=CHCH=CHCOOH comonomers；After evacuation is deoxygenated, nitrogen protection is passed through, adds crosslinking The aqueous solution of agent PEGDMA-400；After intensification, redox initiator potassium peroxydisulfate-bisulfite is added Sodium K2S2O8-NaHSO3Aqueous solution, Jing cause, combined polymerization chain propagation reaction, cross-linking agent PEGDMA-400 ginseng Reaction being crosslinked with copolyreaction and line style copolymerization macromole and forming cross-linked network structure, Jing chain termination reactions obtain organic Both sexes copolymerized macromolecule first network gel.Logical nitrogen protection, organic amphiprotic copolymerized macromolecule first network gel is in fumaric acid HOOCCH=CHCOOH, cyclohexanhexanol (CH)6(OH)6, dimethylaminoethyl acrylate CH2=CHCOO(C2H4)N(CH3)2, diformazan Bromo DOPCP CH of base acrylic acid two2=C(CH3)COOCH2C(CH2Br)2CH2OOC(CH3)C=CH2
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 HNHCl aqueous solutions, in swelling process, monomer, cross-linking agent in aqueous solution, Initiator, catalyst enter into organic amphiprotic copolymerized macromolecule first network gel inside and are uniformly distributed；Jing causes, combined polymerization Chain propagation reaction formed line style copolymerization macromole, the bromo DOPCP of cross-linking agent dimethacrylate two participate in copolyreaction and Line style copolymerization macromole crosslinks reaction, forms cross-linked network structure, pyridoxine hydrochloride molecule of the catalysis with carboxylic group There is esterification with the molecule of hydroxyl group, due to cyclohexanhexanol with six OH groups by with the molecule with carboxylic group Reaction forms cross-linked network structure；Further react, finally the chain termination due to radical copolymerization macromole and esterification Complete, 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-β-hydroxypropyl acrylate, dimethylaminoethyl acrylate and cross-linking agent dimethacrylate dibromo For DOPCP low toxicity, monomer sorbic acid, fumaric acid and cross-linking agent PEGDMA-400, cyclohexanhexanol without Poison, reduces gel toxicity；The interpenetrating networks gel of preparation has radical crosslinking and esterification and crosslinking network structure, improves mutually Wear the stability of network gel；Preparation method is simple, reaction condition is gentle, be suitable for production, with good environmental benefit and Jing Ji benefit.
Specific embodiment
Embodiment 1：124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 57.7g methacrylic acid-β-hydroxypropyl acrylate, 56g sorbic acid and 555.9ml deionized waters are added to volume can be uniformly mixed for 2L in closed reactor, the aqueous solution Weight concentration be 30%；Relative degree of vacuum -0.03MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal pressure, added The number-average molecular weight of 7.15g is the aqueous solution that 3000 PEGDMA-400 and 26.9ml deionized waters are prepared, The weight concentration of the aqueous solution is 21%；Then heat to 37 DEG C, add 0.92g potassium peroxydisulfates, 0.27g sodium sulfitees and The aqueous solution that 20.5ml deionized waters are prepared, the weight concentration of the aqueous solution is 5.5%, and in 37 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 81.5g input volumes for 15L can be swelling in closed reactor, this is anti- Answer and be equipped with device 69.6g fumaric acid, 18.6g cyclohexanhexanol, 71.6g dimethylaminoethyl acrylates, 3.2g dimethyl allenes The aqueous solution that sour two bromo DOPCP and 7989.4ml deionized waters are prepared, the weight concentration of the aqueous solution is 2%, first The weight of network gel（81.5g）:The weight of the aqueous solution（8152.4g）=1:100, swelling 3h；Add 0.33g persulfuric acid The aqueous solution that potassium, 1.63g pyridoxine hydrochloride and 16.7ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is 10.5%, swelling 17h；77 DEG C are warming up to after the completion of swelling, control ph is 3.4, in 77 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）=5327% （Deionized water）, gel swelling rate（ESR）=5276%（The NaCl aqueous solutions of weight concentration 1%）.
Embodiment 2：228.2g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 216.3g methacrylic acid-β-hydroxypropyl acrylate, 112.1g sorbic acid and 371.1ml deionized waters are added to volume and can be uniformly mixed in closed reactor for 1L, and this is water-soluble The weight concentration of liquid is 60%；Relative degree of vacuum -0.07MPa is evacuated to, nitrogen is then passed to and is recovered reactor to normal pressure, plus The number-average molecular weight for entering 55.7g is the aqueous solution that 19000 PEGDMA-400 and 87ml deionized waters are prepared, The weight concentration of the aqueous solution is 39%；Then heat to 47 DEG C, add 4.17g potassium peroxydisulfates, 4.17g sodium sulfitees and The aqueous solution that 49.2ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%, and in 47 DEG C of constant temperature, control ph is 9.6, continue stirring reaction 3.2h, obtain organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through nitrogen Under gas, organic amphiprotic copolymerized macromolecule first network gel 28.6g inputs 5L can be swelling in closed reactor, is equipped with reactor 208.9g fumaric acid, 55.9g cyclohexanhexanol, 143.2g dimethylaminoethyl acrylates, the bromo of 20.4g dimethacrylates two The aqueous solution that DOPCP and 3855.3ml deionized waters are prepared, the weight concentration of the aqueous solution is 10%, first network gel Weight（28.6g）:The weight of the aqueous solution（4283.6g）=1:150, swelling 5.4h；Add 0.86g potassium peroxydisulfates, The aqueous solution that 4.28g pyridoxine hydrochloride and 350ml deionized waters are prepared continues swelling, and the weight concentration of the aqueous solution is 19.5%, swelling 23h；93 DEG C are warming up to after the completion of swelling, control ph is 6.5, in 93 DEG C of isothermal reaction 5.6h, obtain organic Both sexes copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling rate（ESR）=4253% （Deionized water）, gel swelling rate（ESR）=4195%（The NaCl aqueous solutions of weight concentration 1%）.

Claims (1)

1. a kind of preparation method of organic amphiprotic copolymerized macromolecule interpenetrating networks gel, is characterized in that to add in closed reactor Enter component A and deionized water stirring prepares aqueous solution, the weight concentration for controlling component A is 28%～62%, after the completion of prepared by solution, It is -0.02MPa～-0.08MPa to be evacuated to relative degree of vacuum, is passed through nitrogen and recovers 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 Spend for 5%～15%, control ph is 4～10, in 35 DEG C～50 DEG C constant temperature, continue stirring reaction 2h～3.5h, obtain 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:The 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 For 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-β-hydroxypropyl acrylate, sorbic acid composition, by the gauge of material, methylacryoyloxyethyl trimethyl ammonia chloride Ammonium:Methacrylic acid-β-hydroxypropyl acrylate:The ratio of the amount of the material of sorbic 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 gross weight that feeds intake is component A gross weight The 2.5%～11% of amount, component C is made up of potassium peroxydisulfate-sodium sulfite, and its gross weight that feeds intake is the 0.3% of component A gross weight ～1.8%, by weight, potassium peroxydisulfate:Weight ratio=1 of sodium sulfite:（0.2～1.1）, D components are by fumaric acid, hexamethylene Six alcohol, dimethylaminoethyl acrylate and the bromo DOPCP of dimethacrylate two composition, by the gauge of material, rich horse Acid:Cyclohexanhexanol:The ratio of the amount of the material of dimethylaminoethyl acrylate=（0.5～2.0）:（0.08～0.32）:（0.4～ 1.1）, by weight, the bromo DOPCP charged material weight of dimethacrylate two is fumaric acid, cyclohexanhexanol, acrylic acid two The 1.8%～5.5% of three kinds of total monomer weights of methylamino ethyl ester, 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%。
CN201611129043.5A 2016-12-09 2016-12-09 Preparation method of organic amphiprotic interpenetrating copolymer network hydrogel Pending CN106589423A (en)

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