CN106750403A - 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 PDF

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CN106750403A
CN106750403A CN201611126580.4A CN201611126580A CN106750403A CN 106750403 A CN106750403 A CN 106750403A CN 201611126580 A CN201611126580 A CN 201611126580A CN 106750403 A CN106750403 A CN 106750403A
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component
weight
aqueous solution
gel
deionized water
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朱明�
江燕妮
王麒麟
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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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    • C08F222/00—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; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/10—Esters
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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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    • 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L35/02—Homopolymers or copolymers of esters
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    • C08F222/00—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; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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    • C08F222/00—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; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
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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 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 ethyl trimellitic anhydride ester, forulic 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 the penetenoic acid of 2 methyl 4, glycerine, methacrylic acid oxygen propyl group trimellitic anhydride ester, dimethacrylate cyclohexanediol ester 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

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, 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 ethyl trimellitic anhydride ester, forulic acid composition, by the gauge of material, methyl-prop Alkene acyloxyethyl trimethyl ammonium chloride:Methacrylic acid oxygen ethyl trimellitic anhydride ester:The ratio between amount of material of forulic 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 are by 2- methyl -4- penetenoic acids, glycerine, methacrylic acid oxygen propyl group trimellitic anhydride ester and dimethyl Acrylate diol ester is constituted, by the gauge of material, 2- methyl -4- penetenoic acids:Glycerine:The inclined benzene of methacrylic acid oxygen propyl group The ratio between amount of material of three acid anhydride esters=（0.2~1.0）:（0.08~0.32）:（0.4~1.1）, by weight, dimethyl allene Sour cyclohexanediol ester charged material weight is 2- methyl -4- penetenoic acids:Glycerine:Three kinds of methacrylic acid oxygen propyl group trimellitic anhydride ester 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 groups The 0.1%~1.2% of point gross 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, methacrylic acid oxygen ethyl trimellitic anhydride ester CH2=C(CH3)COO (CH2)2OOCC6H3C2O3, forulic acid (HO) (CH3O)C6H3The aqueous solution of CH=CHCOOH comonomers；After vacuumizing deoxidation, lead to Enter nitrogen protection, add the aqueous solution of crosslinking agent PEGDMA-400；After intensification, Redox Initiator is added Agent potassium peroxydisulfate-sodium hydrogensulfite K2S2O8-NaHSO3The aqueous solution, through trigger, combined polymerization chain propagation reaction, crosslinking agent diformazan Base polyalkylene glycol acrylate ester participates in copolyreaction and line style copolymerization macromolecular crosslinks reaction and forms cross-linked network structure, passes through Chain termination reaction, obtains organic amphiprotic copolymerized macromolecule first network gel.Logical nitrogen protection, organic amphiprotic copolymerized macromolecule the One network gel is in 2- methyl -4- penetenoic acids CH2=CHCH2CH(CH3) COOH, glycerine (HO) CH2CH(OH)CH2(OH), methyl Acrylic acid oxygen propyl group trimellitic anhydride ester CH2=C(CH3)COO(CH2)3OOCC6H3C2O3, dimethacrylate cyclohexanediol ester CH2 =C(CH3)COO-(C6H10)-OOC(CH3) C=CH the aqueous solution effect under it is swelling, add initiator potassium persulfate K2S2O8, urge Agent pyridoxine hydrochloride (CH3)(HOCH2)2(HO)C5Continue swelling in the presence of the HNHCl aqueous solution, in swelling process, water Monomer, crosslinking agent in solution, initiator, catalyst enter into organic amphiprotic copolymerized macromolecule first network gel inside simultaneously Even distribution；Line style copolymerization macromolecular, crosslinking agent dimethacrylate cyclohexanediol ester are formed through initiation, combined polymerization chain propagation reaction Participate in copolyreaction and line style copolymerization macromolecular crosslinks reaction, form cross-linked network structure, pyridoxine hydrochloride catalysis band There is esterification in the molecule of the molecule of carboxylic group and hydroxyl group, because glycerine will be with band carboxylic with three OH groups The molecule of base group reacts to form cross-linked network structure；Further reaction, finally due to the chain end of radical copolymerization macromolecular Only with the completion of esterification, organic amphiprotic copolymerized macromolecule interpenetrating networks gel is formed.
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 ethyl trimellitic anhydride ester, 2- methyl -4- penetenoic acids, methacrylic acid oxygen propyl group Trimellitic anhydride ester and crosslinking agent dimethacrylate cyclohexanediol ester low toxicity, monomer ferulic acid and crosslinking agent dimethacrylate Macrogol ester, glycerine are nontoxic, reduce gel toxicity；There is the interpenetrating networks gel of preparation radical crosslinking and esterification to hand over Connection network structure, improves the stability of interpenetrating networks gel；Preparation method is simple, reaction condition is gentle, be suitable for production, has Good environmental benefit and economic benefit.
Specific embodiment
Embodiment 1：124.5g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, the 110.5g methacrylic acid inclined benzene of oxygen ethyl Three acid anhydride esters, 97.1g forulic acids and 774.9ml deionized waters are added to volume and can stir mixing in closed reactor for 2L Even, the weight concentration of the aqueous solution is 30%；Relative degree of vacuum -0.03MPa is evacuated to, nitrogen is then passed to and is recovered reactor To normal pressure, the number-average molecular weight for adding 10g is that 3000 PEGDMA-400 and 37.5ml deionized waters are prepared The aqueous solution, the weight concentration of the aqueous solution is 21%；37 DEG C are then heated to, 1.28g potassium peroxydisulfates, 0.38g sulfurous acid is added The aqueous solution that hydrogen sodium and 28.5ml deionized waters are prepared, the weight concentration of the aqueous solution is 5.5%, in 37 DEG C of constant temperature, control ph It is 4.5, continues stirring reaction 2.3h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, be passed through Under nitrogen, organic amphiprotic copolymerized macromolecule first network gel 96.2g input volumes can be swelling in closed reactor for 15L's, 34.2g 2- methyl -4- penetenoic acids, 9.2g glycerine, 145.1g methacrylic acid oxygen propyl group trimellitic acids are housed in the reactor The aqueous solution that acid anhydride ester, 3.8g dimethacrylate cyclohexanediol esters and 9423.5ml deionized waters are prepared, the weight of the aqueous solution Concentration is 2%, the weight of first network gel（96.2g）:The weight of the aqueous solution（9615.8g）=1:100, swelling 3h；Again plus The aqueous solution for entering the preparation of 0.38g potassium peroxydisulfates, 1.92g pyridoxine hydrochlorides and 19.7ml deionized waters continues swelling, and this is water-soluble The weight concentration of liquid 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 reactions 4.3h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling Rate（ESR）=9758%（Deionized water）, gel swelling rate（ESR）=9682%（The NaCl aqueous solution of weight concentration 1%）.
Embodiment 2：228.3g MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, the 414.4g methacrylic acid inclined benzene of oxygen ethyl Three acid anhydride esters, 194.2g forulic acids and 557.9ml deionized waters are added to volume for 1L can stir mixing in closed reactor Even, 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 83.7g is 18000 PEGDMA-400 and 130.9ml deionized water The aqueous solution of preparation, the weight concentration of the aqueous solution is 39%；48 DEG C are then heated to, adds 6.28g potassium peroxydisulfates, 6.28g sub- The aqueous solution that niter cake and 74ml deionized waters are prepared, the weight concentration of the aqueous solution is 14.5%, in 48 DEG C of constant temperature, control PH value is 9.3, continues stirring reaction 3.2h, obtains organic amphiprotic copolymerized macromolecule first network gel；Then cooled down, It is passed through under nitrogen, organic amphiprotic copolymerized macromolecule first network gel 29.4g inputs 5L can swelling, reaction in closed reactor 102.6g 2- methyl -4- penetenoic acids, 27.6g glycerine, 290.3g methacrylic acid oxygen propyl group trimellitic anhydrides are housed in device The aqueous solution that ester, 21g dimethacrylate cyclohexanediol esters and 3973.8ml deionized waters are prepared, the weight concentration of the aqueous solution It is 10%, the weight of first network gel（29.4g）:The weight of the aqueous solution（4415.3g）=1:150, swelling 5.3h；Add The aqueous solution that 0.88g potassium peroxydisulfates, 4.42g pyridoxine hydrochlorides and 21.9ml deionized waters are prepared continues swelling, the aqueous solution Weight concentration be 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 reactions 5.6h, obtains organic amphiprotic copolymerized macromolecule interpenetrating networks gel.The gel is water insoluble, can be swelling in water, gel swelling Rate（ESR）=7637%（Deionized water）, gel swelling rate（ESR）=7549%（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 ethyl trimellitic anhydride ester, forulic acid composition, by the gauge of material, methylacryoyloxyethyl three Ammonio methacrylate:Methacrylic acid oxygen ethyl trimellitic anhydride ester:The ratio between amount of material of forulic 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, glycerine, methacrylic acid oxygen propyl group trimellitic anhydride ester and dimethacrylate hexamethylene two Alcohol ester is constituted, by the gauge of material, 2- methyl -4- penetenoic acids:Glycerine:The thing of methacrylic acid oxygen propyl group trimellitic anhydride ester The ratio between amount of matter=（0.2~1.0）:（0.08~0.32）:（0.4~1.1）, by weight, dimethacrylate cyclohexanediol ester Charged material weight is 2- methyl -4- penetenoic acids:Glycerine:Methacrylic acid oxygen propyl group trimellitic anhydride three kinds of total monomer weights of ester 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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CN105289316A (en) * 2015-09-28 2016-02-03 浙江大学 Preparation method of composite separating film filled by interpenetrating polymer network hydrogel

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