CN110183692A - Three-dimensional cross-linked soluble polymer microgel of one kind and preparation method thereof - Google Patents
Three-dimensional cross-linked soluble polymer microgel of one kind and preparation method thereof Download PDFInfo
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- CN110183692A CN110183692A CN201910494668.9A CN201910494668A CN110183692A CN 110183692 A CN110183692 A CN 110183692A CN 201910494668 A CN201910494668 A CN 201910494668A CN 110183692 A CN110183692 A CN 110183692A
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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
- C08F112/00—Homopolymers 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 an aromatic carbocyclic ring
- C08F112/34—Monomers containing two or more unsaturated aliphatic radicals
- C08F112/36—Divinylbenzene
-
- 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—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
- C08F220/12—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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- 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
-
- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- 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
- C08J2325/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
-
- 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
- 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
- C08J2333/06—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 only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
Abstract
The present invention relates to a kind of three-dimensional cross-linked soluble polymer microgels and preparation method thereof, monomer containing vinyl, anhydrous metal halide catalyst are added in solvent mix together, it is placed in reaction kettle and seals, higher than solvent boiling point and under 80-95 DEG C of bath temperature, reaction 2-48 hours, after the reaction was completed, products therefrom is washed, centrifugation, it is dry after, obtain three-dimensional cross-linked soluble polymer microgel, wherein, the weight ratio of the catalyst and the monomer containing vinyl is (2-100): 100；The volume ratio of the monomer containing vinyl and solvent is (0.5-10): 100.Three-dimensional cross-linked soluble polymer microgel of one kind of the invention and preparation method thereof, preparation process is simple, and reaction condition is safe and reliable, it is swift in response, the yield of microgel is up to 75%, is much higher than free radical solution polymerization method microgel yield obtained, is easy to industrialized production.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of three-dimensional cross-linked soluble polymer microgel
And preparation method thereof.
Background technique
Microgel (microgel) is a kind of three-dimensional cross-linked soluble polymer material.Microgel had both had three-dimensional cross-linked
Structure, under certain condition, have preferable physics and chemical stability, while " can also dissolve " in certain solvent
In, it is easy to process at various devices, in favor of heavy industrialization manufacture.Therefore, microgel is widely used in coating, absorption
The various fields such as agent, catalyst carrier and senser element.In recent years, the requirement of solar cell silk screen printing is continuously improved, and is
The transfer efficiency of solar battery is improved, filament printing needs constantly to reduce the sintered width of thin grid, it is necessary to improve
The ink excessively of silver paste of solar cells, the addition of microgel can greatly improve the ink excessively of silver paste.
Currently, the preparation method of microgel mainly includes emulsion polymerization and polymerisation in solution.Emulsion polymerization needs a large amount of table
Face activating agent stablizes the size of drop in polymerization process, and after completion of polymerization, these surfactants are generally difficult to remove, and have
The performance of product may be influenced.Solution polymerization system is relatively simple, generally contains only monomer, solvent and initiator, because
This products therefrom is more pure.However, in the polymerization of free radical weak solution, since monomer conversion is lower, the yield of microgel
Usually lower (being lower than 30%), constrain the large-scale production of microgel.
Summary of the invention
The present invention provides a kind of three-dimensional cross-linked soluble polymer microgels and preparation method thereof, and preparation process is simple,
Reaction condition is safe and reliable, is swift in response, and the yield of microgel is up to 75%, is obtained much higher than free radical solution polymerization method
Microgel yield, be easy to industrialized production.
The present invention provides a kind of preparation methods of three-dimensional cross-linked soluble polymer microgel, specifically according to the following steps
It carries out: the monomer containing vinyl, anhydrous metal halide catalyst being added in solvent mix together, reaction kettle is placed in
Middle sealing reacts 2-48 hours, after the reaction was completed, products therefrom higher than solvent boiling point and under 80-95 DEG C of bath temperature
Washed, centrifugation, it is dry after to get to particle diameter distribution 50-300nm three-dimensional cross-linked soluble polymer microgel,
Wherein, the weight ratio of the catalyst and the monomer containing vinyl is (2-100): 100；The monomer containing vinyl with
The volume ratio of solvent is (0.5-10): 100.
Preferably, the monomer containing vinyl includes but is not limited to divinylbenzene, ethyl acrylate, acrylic acid first
Ester, methyl methacrylate, n-BMA, Isobutyl methacrylate, benzyl methacrylate, styrene and 2-
The composition of one of (2- oxygen -1- imidazolidinyl) ethylmethyl acrylate or in which several arbitrary proportions.
Preferably, the anhydrous metal halide catalyst includes but is not limited to anhydrous ferric chloride, silver bromide, calcirm-fluoride.
Preferably, the solvent includes but is not limited to dichloroethanes, acetonitrile, isopropanol, tetrahydrofuran.
Preferably, the reaction time is 4-6 hours.
Preferably, the volume ratio of the monomer containing vinyl and solvent is (0.8-1.5): 100.
Preferably, the weight ratio of the catalyst and the monomer containing vinyl is (5-20): 100.
The present invention also provides a kind of three-dimensional cross-linked soluble polymer microgels, by any of the above-described preparation method
It is made.
Advantages of the present invention: three-dimensional cross-linked soluble polymer microgel of one kind of the invention and preparation method thereof, preparation
Process is simple, and reaction condition is safe and reliable, is swift in response, and the yield of microgel is up to 75%, is much higher than free radical solution polymerization
Method microgel yield obtained, is easy to industrialized production.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be described in further detail, the reality
It applies example for explaining only the invention, protection scope of the present invention is not constituted and limited.
Embodiment one
Present embodiments provide a kind of three-dimensional cross-linked soluble polymer microgel, by 3mL divinylbenzene monomers,
0.15g anhydrous ferric trichloride, 300mL tetrahydrofuran are prepared.
Preparation method: by 3mL divinylbenzene monomers, 0.15g anhydrous ferric trichloride, 300mL tetrahydrofuran in ice-water bath
Under conditions of it is miscible, be then added into the polytetrafluoroethyllining lining of stainless steel cauldron, seal；It is subsequently placed in water-bath, water
Bath temperature is set as 88 DEG C, reacts 6 hours, after the reaction was completed, wash with isopropanol, centrifugation, it is dry after to get arriving partial size
It is distributed in the three-dimensional cross-linked soluble polydivinylbenezene microgel of 50-300nm, yield 75% dissolves in conventional organic
Solvent.
Embodiment two
Present embodiments provide a kind of three-dimensional cross-linked soluble polymer microgel, by 3mL methyl methacrylate monomer,
0.6g silver bromide, 300mL acetonitrile are prepared.
Preparation method: by 3mL methyl methacrylate monomer, 0.6g silver bromide, 300mL acetonitrile under conditions of ice-water bath
It is miscible, it is then added into the polytetrafluoroethyllining lining of stainless steel cauldron, seals；It is subsequently placed in water-bath, bath temperature is set
Be set to 90 DEG C, react 5 hours, after the reaction was completed, with ethanol washing, centrifugation, it is dry after to get to particle diameter distribution in 50-
The three-dimensional cross-linked soluble polymethyl methacrylate microgel of 300nm, yield 73% dissolve in conventional organic solvent.
Embodiment two
Present embodiments provide a kind of three-dimensional cross-linked soluble polymer microgel, by 3mL methyl methacrylate monomer,
0.6g silver bromide, 300mL acetonitrile are prepared.
Preparation method: by 1.5mL methyl methacrylate monomer, 1.5mL n-BMA monomer, 0.55g chlorine
It is miscible under conditions of ice-water bath to change silver, 300mL acetonitrile, is then added into the polytetrafluoroethyllining lining of stainless steel cauldron,
Sealing；It is subsequently placed in water-bath, bath temperature is set as 90 DEG C, reacts 4 hours, after the reaction was completed, is washed, is centrifuged with isopropanol
Precipitating, it is dry after to get to particle diameter distribution 50-300nm three-dimensional cross-linked soluble methyl methacrylate and metering system
Sour N-butyl copolymer microgel, yield 71% dissolve in conventional organic solvent.
Polymer microgel of above embodiments and preparation method thereof, preparation process is simple, and reaction condition is safe and reliable, instead
Should rapidly, the yield of microgel may be up to 75%, is much higher than free radical solution polymerization method microgel yield obtained, is easy to
Industrialized production.
Above-described embodiment should not in any way limit the present invention, all to be obtained by the way of equivalent replacement or equivalency transform
Technical solution fall within the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of three-dimensional cross-linked soluble polymer microgel, it is characterised in that: be specifically according to the following steps into
Capable: the monomer containing vinyl, anhydrous metal halide catalyst are added in solvent mix together, is placed in reaction kettle
2-48 hours, after the reaction was completed, products therefrom warp higher than solvent boiling point and under 80-95 DEG C of bath temperature, are being reacted in sealing
Washing, centrifugation, it is dry after to get to particle diameter distribution 50-300nm three-dimensional cross-linked soluble polymer microgel,
In, the weight ratio of the catalyst and the monomer containing vinyl is (2-100): 100；The monomer containing vinyl with it is molten
The volume ratio of agent is (0.5-10): 100.
2. the preparation method of the three-dimensional cross-linked soluble polymer microgel of one kind according to claim 1, it is characterised in that:
The monomer containing vinyl includes but is not limited to divinylbenzene, ethyl acrylate, methyl acrylate, methyl methacrylate
Ester, n-BMA, Isobutyl methacrylate, benzyl methacrylate, styrene and 2- (2- oxygen -1- imidazolidine
Base) one of ethylmethyl acrylate or in which several arbitrary proportions composition.
3. the preparation method of the three-dimensional cross-linked soluble polymer microgel of one kind according to claim 1, it is characterised in that:
The anhydrous metal halide catalyst includes but is not limited to anhydrous ferric chloride, silver bromide, calcirm-fluoride.
4. the preparation method of the three-dimensional cross-linked soluble polymer microgel of one kind according to claim 1, it is characterised in that:
The solvent includes but is not limited to dichloroethanes, acetonitrile, isopropanol, tetrahydrofuran.
5. the preparation method of the three-dimensional cross-linked soluble polymer microgel of one kind according to claim 1, it is characterised in that:
The reaction time is 4-6 hours.
6. the preparation method of the three-dimensional cross-linked soluble polymer microgel of one kind according to claim 1, it is characterised in that:
The volume ratio of the monomer containing vinyl and solvent is (0.8-1.5): 100.
7. the preparation method of the three-dimensional cross-linked soluble polymer microgel of one kind according to claim 1, it is characterised in that:
The weight ratio of the catalyst and the monomer containing vinyl is (5-20): 100.
8. a kind of three-dimensional cross-linked soluble polymer microgel, it is characterised in that: by system of any of claims 1-7
Preparation Method is made.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910494668.9A CN110183692A (en) | 2019-06-10 | 2019-06-10 | Three-dimensional cross-linked soluble polymer microgel of one kind and preparation method thereof |
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| CN201910494668.9A CN110183692A (en) | 2019-06-10 | 2019-06-10 | Three-dimensional cross-linked soluble polymer microgel of one kind and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964593A (en) * | 2019-12-18 | 2020-04-07 | 中国科学院兰州化学物理研究所 | Polymerization-induced self-assembly oleogel and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2246135A1 (en) * | 2004-04-02 | 2006-02-01 | Universidad Complutense De Madrid | Set of microgel particles containing immobilised glucose oxidase consists of a glucose amperometric biosensor with a silver chloride reference electrode |
| CN107635655A (en) * | 2015-01-06 | 2018-01-26 | Lvmh研究公司 | PEG methacrylate microgel, preparation method and purposes |
| CN108976334A (en) * | 2018-06-22 | 2018-12-11 | 济南大学 | Three-dimensional cross-linked soluble polydivinylbenezene microgel of one kind and preparation method thereof |
-
2019
- 2019-06-10 CN CN201910494668.9A patent/CN110183692A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2246135A1 (en) * | 2004-04-02 | 2006-02-01 | Universidad Complutense De Madrid | Set of microgel particles containing immobilised glucose oxidase consists of a glucose amperometric biosensor with a silver chloride reference electrode |
| CN107635655A (en) * | 2015-01-06 | 2018-01-26 | Lvmh研究公司 | PEG methacrylate microgel, preparation method and purposes |
| CN108976334A (en) * | 2018-06-22 | 2018-12-11 | 济南大学 | Three-dimensional cross-linked soluble polydivinylbenezene microgel of one kind and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964593A (en) * | 2019-12-18 | 2020-04-07 | 中国科学院兰州化学物理研究所 | Polymerization-induced self-assembly oleogel and preparation method and application thereof |
| CN110964593B (en) * | 2019-12-18 | 2021-06-01 | 中国科学院兰州化学物理研究所 | Polymerization-induced self-assembly oleogel and preparation method and application thereof |
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Application publication date: 20190830 |