CN106220873A - A kind of synthetic method of microgel base composite aquogel - Google Patents

A kind of synthetic method of microgel base composite aquogel Download PDF

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CN106220873A
CN106220873A CN201610673077.4A CN201610673077A CN106220873A CN 106220873 A CN106220873 A CN 106220873A CN 201610673077 A CN201610673077 A CN 201610673077A CN 106220873 A CN106220873 A CN 106220873A
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microgel
poly
copolymer
bottle
maa
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潘忠宁
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • 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
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • 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
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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
    • 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
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/02—Applications for biomedical use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

A kind of synthetic method of microgel base composite aquogel, step includes synthesizing poly(MMA/MAA) microgel, prepare cation copolymer poly(HEMA-co-DMA+) and prepare composite aquogel.The invention has the beneficial effects as follows: synthesis technique is simple, reaction condition is gentle, and production cost is relatively low, favorable repeatability, and composite gel system structure interpenetrates between Kong Yukong, is more beneficial for the transmission of flow media, has the strain of higher threshold yield.

Description

A kind of synthetic method of microgel base composite aquogel
Technical field
The present invention relates to material synthesis method, the synthetic method of a kind of microgel base composite aquogel.
Background technology
Injection aquagel owing to having certain research value and the potential using value in terms of biomaterial, Receive significant attention all the time.In injection Macromolecule glue material, the polymer-network method microgranule of nanoscale is non-linear Polymer Systems, its special micrograined texture makes microgel dispersion system and has pole compared with the Polymer Systems of concentration Low stickiness, beneficially injection moulding.Therefore, based on microgel, utilize pH induction, electrostatic attraction or covalent linkage etc. Mode in-situ construction hydrogel becomes one of fast-developing research field of injection aquagel.PH response microgel is a kind of The polymeric colloid microgranule of crosslinking, after system pH reaches a certain marginal value, specific groups in micro-gel particles (as carboxyl, Amino) there is ionization or protonation reaction, granules swell, volume increases.The pH response that Vinyl-functionalization is modified is micro-solidifying Glue, the olefin group between swelling rear adjacent particle crosslinks under initiator effect, and the double cross connection forming covalent linkage is micro- Gel, the hydrogel of this kind of special construction has certain pliability.
Alkali swelling type polyacrylic microgel mixes, at electrostatic attraction mutually with acid-swellable type polyvinylpyridine microgel Effect is lower forms multi-phase aggregate structure, and microstructure changes with pH change, forms physical gel under relatively low or higher pH, The storage modulu of gel is affected by pH to change in hundreds of thousands Pascal thousand of.Linear polymer introduces pH response Microgel system, can increase the pliability of corresponding pluralgel to a certain extent, increases degree relevant with polymer architecture.
Summary of the invention
The technical problem to be solved is to provide the synthetic method of a kind of microgel base composite aquogel, it is provided that A kind of new synthetic method.
The synthetic method that the present invention uses, comprises the steps:
A, synthesis poly(MMA/MAA) microgel, equipped with tool agitator, condensing tube, constant current tube four-hole bottle in add SDS molten Liquid (1.3gSDS+270g deionized water), logical nitrogen 30min under 80 DEG C of water-baths.Take mix monomer (98gMMA+49gMA A+1gEGDMA) add in four-necked bottle, be added immediately 1.5964g10% K2PHO4 aqueous solution and 1.7920g 8.6%APS reactant aqueous solution 30min, is then added dropwise to residual monomer in four-hole bottle with the speed of 1.25g/min, treats monomer After dripping, add 1.5404g APS solution, continue reaction 2h, obtain milky emulsus dispersion liquid, then use deionized water Middle dialysis removes the materials such as surfactant, unreacted monomer and other little molecules, obtains poly(MMA/MAA)；
B, prepare cation copolymer poly(HEMA-co-DMA+) in bottle with two necks, add 5g Cu-lyt., 2,2 '-connection pyrrole Pyridine, the most logical nitrogen evacuation 3 times, rapidly by the 3g 2-isobutyl ethyl bromide of logical nitrogen 1h, 5mL methanol, 3.5g HEMA and 1.275g DMAM is transferred in bottle, under nitrogen protection 40 DEG C of reaction 24h, the sticky copolymer mixture that will obtain Through dilution, peroxidating aluminum post, precipitation, obtaining the copolymer of purification, the copolymer after purification is dissolved in the mixed solution of water and methanol, Adding potassium iodide regulation Ph is 8, and normal-temperature reaction 24h obtains the copolymer of cationization；
C, prepare composite aquogel, the poly(MMA/MAA by after purification) microgel and poly(HEMA-co-DMA+) by 2: 8-3:7 ratio is sufficiently mixed, and regulates mixed system pH=7-9 by NaOH solution, obtains the microgel base Compound Water of ionic crosslinking Gel.
The invention has the beneficial effects as follows: synthesis technique is simple, reaction condition is gentle, and production cost is relatively low, favorable repeatability, Interpenetrate between Kong Yukong in composite gel system structure, be more beneficial for the transmission of flow media, have higher critical in the wrong Clothes strain.
Detailed description of the invention
Further illustrating present disclosure below in conjunction with example, as known by the technical knowledge, the present invention also can pass through other The scheme without departing from the technology of the present invention feature describe, the most all within the scope of the present invention or equivalent the scope of the invention in Change and be all included in the invention.
Embodiment 1:
A, synthesis poly(MMA/MAA) microgel, equipped with tool agitator, condensing tube, constant current tube four-hole bottle in add SDS molten Liquid (1.3gSDS+270g deionized water), logical nitrogen 30min under 80 DEG C of water-baths.Take mix monomer (98gMMA+49gMA A+1gEGDMA) add in four-necked bottle, be added immediately 1.5964g10% K2PHO4 aqueous solution and 1.7920g 8.6%APS reactant aqueous solution 30min, is then added dropwise to residual monomer in four-hole bottle with the speed of 1.25g/min, treats monomer After dripping, add 1.5404g APS solution, continue reaction 2h, obtain milky emulsus dispersion liquid, then use deionized water Middle dialysis removes the materials such as surfactant, unreacted monomer and other little molecules, obtains poly(MMA/MAA)；
B, prepare cation copolymer poly(HEMA-co-DMA+) in bottle with two necks, add 5g Cu-lyt., 2,2 '-connection pyrrole Pyridine, the most logical nitrogen evacuation 3 times, rapidly by the 3g 2-isobutyl ethyl bromide of logical nitrogen 1h, 5mL methanol, 3.5g HEMA and 1.275g DMAM is transferred in bottle, under nitrogen protection 40 DEG C of reaction 24h, the sticky copolymer mixture that will obtain Through dilution, peroxidating aluminum post, precipitation, obtaining the copolymer of purification, the copolymer after purification is dissolved in the mixed solution of water and methanol, Adding potassium iodide regulation Ph is 8, and normal-temperature reaction 24h obtains the copolymer of cationization；
C, prepare composite aquogel, the poly(MMA/MAA by after purification) microgel and poly(HEMA-co-DMA+) press 2:8 Ratio is sufficiently mixed, and regulates mixed system pH=7 by NaOH solution, obtains the microgel base composite aquogel of ionic crosslinking.
Embodiment 2:
A, synthesis poly(MMA/MAA) microgel, equipped with tool agitator, condensing tube, constant current tube four-hole bottle in add SDS molten Liquid (1.3gSDS+270g deionized water), logical nitrogen 30min under 80 DEG C of water-baths.Take mix monomer (98gMMA+49gMA A+1gEGDMA) add in four-necked bottle, be added immediately 1.5964g10% K2PHO4 aqueous solution and 1.7920g 8.6%APS reactant aqueous solution 30min, is then added dropwise to residual monomer in four-hole bottle with the speed of 1.25g/min, treats monomer After dripping, add 1.5404g APS solution, continue reaction 2h, obtain milky emulsus dispersion liquid, then use deionized water Middle dialysis removes the materials such as surfactant, unreacted monomer and other little molecules, obtains poly(MMA/MAA)；
B, prepare cation copolymer poly(HEMA-co-DMA+) in bottle with two necks, add 5g Cu-lyt., 2,2 '-connection pyrrole Pyridine, the most logical nitrogen evacuation 3 times, rapidly by the 3g 2-isobutyl ethyl bromide of logical nitrogen 1h, 5mL methanol, 3.5g HEMA and 1.275g DMAM is transferred in bottle, under nitrogen protection 40 DEG C of reaction 24h, the sticky copolymer mixture that will obtain Through dilution, peroxidating aluminum post, precipitation, obtaining the copolymer of purification, the copolymer after purification is dissolved in the mixed solution of water and methanol, Adding potassium iodide regulation Ph is 8, and normal-temperature reaction 24h obtains the copolymer of cationization；
C, prepare composite aquogel, the poly(MMA/MAA by after purification) microgel and poly(HEMA-co-DMA+) press 3:7 Ratio is sufficiently mixed, and regulates mixed system pH=9 by NaOH solution, obtains the microgel base composite aquogel of ionic crosslinking.
Interpenetrate between Kong Yukong in composite gel system structure, be more beneficial for the transmission of flow media, according to this reality The composite aquogel that proved recipe method prepares, pluralgel has higher threshold yield strain (γ * ≈ 10.5-11.2), and with dense The gel γ * ≈ 1.75 that degree microgel is formed.This network structure has potential application valency in terms of biologic soft tissue reparation Value.

Claims (1)

1. a synthetic method for microgel base composite aquogel, comprises the steps:
A, synthesis poly(MMA/MAA) microgel, equipped with tool agitator, condensing tube, constant current tube four-hole bottle in add SDS Solution (1.3gSDS+270g deionized water), logical nitrogen 30min under 80 DEG C of water-baths；Take mix monomer (98gMMA+49gM AA+1gEGDMA) add in four-necked bottle, be added immediately 1.5964g10% K2PHO4 aqueous solution and 1.7920g 8.6%APS reactant aqueous solution 30min, is then added dropwise to residual monomer in four-hole bottle with the speed of 1.25g/min, treats monomer After dripping, add 1.5404g APS solution, continue reaction 2h, obtain milky emulsus dispersion liquid, then use deionized water Middle dialysis removes the materials such as surfactant, unreacted monomer and other little molecules, obtains poly(MMA/MAA)；
B, prepare cation copolymer poly(HEMA-co-DMA+), bottle with two necks adds 5g Cu-lyt., 2,2 '-connection Pyridine, the most logical nitrogen evacuation 3 times, rapidly by the 3g 2-isobutyl ethyl bromide of logical nitrogen 1h, 5mL methanol, 3.5g HEMA and 1.275g DMAM is transferred in bottle, under nitrogen protection 40 DEG C of reaction 24h, the sticky copolymer mixture that will obtain Through dilution, peroxidating aluminum post, precipitation, obtaining the copolymer of purification, the copolymer after purification is dissolved in the mixed solution of water and methanol, Adding potassium iodide regulation Ph is 8, and normal-temperature reaction 24h obtains the copolymer of cationization；
C, prepare composite aquogel, the poly(MMA/MAA by after purification) microgel and poly(HEMA-co-DMA+) by 2: 8-3:7 ratio is sufficiently mixed, and regulates mixed system pH=7-9 by NaOH solution, obtains the microgel base Compound Water of ionic crosslinking Gel.
CN201610673077.4A 2016-08-16 2016-08-16 A kind of synthetic method of microgel base composite aquogel Pending CN106220873A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250358A (en) * 2018-02-06 2018-07-06 西北师范大学 A kind of preparation method for the multiple response hydrogel for loading microgel

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CN101289541A (en) * 2008-05-30 2008-10-22 浙江大学 Organic-hybridization micro-hydrogels sensitive to pH value and temperature and method for preparing same
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Publication number Priority date Publication date Assignee Title
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CN101289541A (en) * 2008-05-30 2008-10-22 浙江大学 Organic-hybridization micro-hydrogels sensitive to pH value and temperature and method for preparing same
CN101531742A (en) * 2009-04-14 2009-09-16 东华大学 Method for preparing nanometer composite aquagel using nanometer microsphere as junction
CN101869727A (en) * 2009-04-24 2010-10-27 苏州博创同康生物工程有限公司 Reinforced anti-adhesion composite gel, preparation method and application
CN104707542A (en) * 2015-02-13 2015-06-17 大连工业大学 Photocatalyst/SiO2 composite aerogel material and preparation method thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108250358A (en) * 2018-02-06 2018-07-06 西北师范大学 A kind of preparation method for the multiple response hydrogel for loading microgel
CN108250358B (en) * 2018-02-06 2020-02-04 西北师范大学 Preparation method of microgel-loaded multi-responsiveness hydrogel

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Application publication date: 20161214