CN104926974A - Method for preparing styrene-acrylate copolymer - Google Patents
Method for preparing styrene-acrylate copolymer Download PDFInfo
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- CN104926974A CN104926974A CN201510411757.4A CN201510411757A CN104926974A CN 104926974 A CN104926974 A CN 104926974A CN 201510411757 A CN201510411757 A CN 201510411757A CN 104926974 A CN104926974 A CN 104926974A
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- acrylate
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Abstract
The invention provides a method for preparing a styrene-acrylate copolymer. The method comprises the steps that the temperature of a cellulose water solution is raised to be 60-90 DEG C, a mixing solution of styrene, acrylate and an initiator is added, the reaction is carried out for 2-12 hours, polymer beads are washed with water, filtered and dried, and the styrene-acrylate copolymer is obtained. According to the method, cellulose serves as a dispersing agent, the styrene-acrylate copolymer is prepared with the suspension polymerizing method, and the method has the advantages that the method is simple, cost is low, and the particles of the copolymer are even. The method has the practical application prospect.
Description
Technical field
The present invention relates to the preparation field of high-molecular copolymer, specifically belong to a kind of preparation method of copolymer in cinnamic acrylic ester.
Background technology
Copolymer in cinnamic acrylic ester has the two-fold advantage of polystyrene and acrylic ester polymer concurrently, not only there is good transparency, glossiness, weathering resistance and resistance to impact shock, and be easy to forming process, be widely used in the fields such as billboard, an illuminating material, material of construction.The synthetic method of copolymer in cinnamic acrylic ester, mainly contains bulk copolymerization method, emulsion copolymerization method and suspension copolymerization method.Due to bulk copolymerization method ubiquity gel effect, there will be automatic hastening phenomenon in reaction process, the controllability of reaction is poor, current less employing.And in emulsion copolymerization method, adopting a large amount of emulsifying agent to carry out stable reaction system, need breakdown of emulsion after reaction terminates, be separated multipolymer, subsequent technique is loaded down with trivial details.Suspension copolymerization method have reaction time short, equipment simple, be easy to industrialized advantage.
During suspension copolymerization synthesis copolymer in cinnamic acrylic ester, dispersion agent can be adopted to be divided into two classes: water-fast inorganic powder and water-soluble organic macromolecule material.Wherein, inorganic powder mainly contains calcium phosphate, magnesiumcarbonate, magnesium hydroxide etc., and this kind of dispersion agent often prepares use on the spot, such as magnesiumcarbonate by sodium carbonate solution and Adlerika formulated, calcium phosphate is made up of sodium radio-phosphate,P-32 solution and calcium chloride solution.Need to wash away inorganic powder dispersion agent with diluted acid after polymerization terminates.This makes complex manufacturing undoubtedly, adds production cost.In organic polymer material dispersion agent, applying more is polyvinyl alcohol, be widely used in the suspension polymerization of vinylbenzene, acrylate, vinylchlorid, but the price of polyvinyl alcohol is relatively costly.If the polyvinyl alcohol in polymkeric substance is not divisible, also safety problem may be brought.
Summary of the invention
The object of the invention is to for the complex manufacturing existed in current copolymer in cinnamic acrylic ester technology of preparing, the expensive problem of dispersion agent, as pectin/polyvinyl alcohol except bringing safe problem as far as possible, can not provide a kind of preparation method of copolymer in cinnamic acrylic ester in polymkeric substance.
The object of the invention is to be achieved through the following technical solutions: a kind of preparation method of copolymer in cinnamic acrylic ester, comprises the steps:
(1) in the reactor that reflux condensate device is housed, add Mierocrystalline cellulose and deionized water, heating in water bath is warming up to 60 ~ 90 DEG C, stirs and makes it to dissolve;
(2) take initiator, be placed in and clean and the container of drying, add monomer styrene and acrylate, join in the reactor of step (1) after dissolving;
(3) control stirring velocity 200 ~ 500 revs/min, isothermal reaction 2 ~ 12 hours, form copolymer bead;
(4) after stopped reaction, wash copolymer bead with water, filter, dry, obtain the copolymer in cinnamic acrylic ester of transparent pearl;
In described step (1), Mierocrystalline cellulose consumption is 0.05% ~ 20% of monomer styrene and acrylate total mass, and deionized water consumption is 2 ~ 10 times of monomer styrene and acrylate total mass;
In described step (2), initiator amount is 0.3% ~ 10% of monomer styrene and acrylate total mass;
In described step (2), monomer styrene and acrylate mass ratio are 1 ︰ 0.01-100.
In described step (1), Mierocrystalline cellulose is one or more in methylcellulose gum, ethyl cellulose, carboxymethyl cellulose, Natvosol, hydroxypropylcellulose, Vltra tears.
In described step (2), initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, dicumyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate.Preferred dibenzoyl peroxide.
In described step (2), acrylate is one or more in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, allyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, allyl methacrylate(AMA).
Beneficial effect of the present invention is:
(1) the present invention is directed to the expensive defect of dispersion agent in existing suspension polymerization, with Mierocrystalline cellulose as dispersion agent, prepare copolymer in cinnamic acrylic ester, greatly reduce production cost.
(2) implementation step of present method is simple, Mierocrystalline cellulose directly can be added reaction system, not need pre-treatment, improve production efficiency.
(3) the Mierocrystalline cellulose safety non-toxic selected of present method, improves the security of polymkeric substance.
Accompanying drawing explanation
Fig. 1 is the optical microscope photograph of the copolymer in cinnamic acrylic ester that the embodiment of the present invention 1 obtains
Fig. 2 is the optical microscope photograph of the copolymer in cinnamic acrylic ester that the embodiment of the present invention 2 obtains
Fig. 3 is the infrared spectrogram of the copolymer in cinnamic acrylic ester that the embodiment of the present invention 2 obtains
Embodiment
Below in conjunction with embodiment, set forth the present invention further.
Embodiment 1
(1) in the reactor that reflux condensate device is housed, add 0.5g carboxymethyl cellulose and 50g deionized water, heating in water bath is warming up to 80 DEG C, stirs and makes it to dissolve;
(2) take 0.3g initiator dibenzoyl peroxide, be placed in and clean and the container of drying, add monomer 2g vinylbenzene and 8g methyl methacrylate, join in the reactor of step (1) after dissolving;
(3) control stirring velocity 350 revs/min, isothermal reaction 4 hours, form copolymer bead;
(4) after stopped reaction, wash copolymer bead with water, filter, dry, obtain the copolymer in cinnamic acrylic ester of transparent pearl.The optical microscope photograph of copolymer in cinnamic acrylic ester is shown in Fig. 1.
Embodiment 2
(1) in the reactor that reflux condensate device is housed, add 0.5g Vltra tears and 50g deionized water, heating in water bath is warming up to 80 DEG C, stirs and makes it to dissolve;
(2) take 0.3g initiator dibenzoyl peroxide, be placed in and clean and the container of drying, add monomer 2g vinylbenzene and 8g methyl methacrylate, join in the reactor of step (1) after dissolving;
(3) control stirring velocity 350 revs/min, isothermal reaction 4 hours, form copolymer bead;
(4) after stopped reaction, wash copolymer bead with water, filter, dry, obtain the copolymer in cinnamic acrylic ester of transparent pearl.The optical microscope photograph of copolymer in cinnamic acrylic ester is shown in Fig. 2, and infrared spectrogram is shown in Fig. 3.
Embodiment 3
(1) in the reactor that reflux condensate device is housed, add 0.5g Vltra tears and 50g deionized water, heating in water bath is warming up to 80 DEG C, stirs and makes it to dissolve;
(2) take 0.3g initiator dibenzoyl peroxide, be placed in and clean and the container of drying, add monomer 10g vinylbenzene and 0.1g methyl methacrylate, join in the reactor of step (1) after dissolving;
(3) control stirring velocity 350 revs/min, isothermal reaction 4 hours, form copolymer bead;
(4) after stopped reaction, wash copolymer bead with water, filter, dry, obtain the copolymer in cinnamic acrylic ester of transparent pearl.
Embodiment 4
(1) in the reactor that reflux condensate device is housed, add 0.5g Vltra tears and 50g deionized water, heating in water bath is warming up to 80 DEG C, stirs and makes it to dissolve;
(2) take 0.3g initiator dibenzoyl peroxide, be placed in and clean and the container of drying, add monomer 0.1g vinylbenzene and 10g butyl acrylate, join in the reactor of step (1) after dissolving;
(3) control stirring velocity 350 revs/min, isothermal reaction 3 hours, form copolymer bead;
(4) after stopped reaction, wash copolymer bead with water, filter, dry, obtain the copolymer in cinnamic acrylic ester of transparent pearl.
Embodiment 5
(1) in the reactor that reflux condensate device is housed, add 0.5g Vltra tears and 50g deionized water, heating in water bath is warming up to 80 DEG C, stirs and makes it to dissolve;
(2) take 0.3g initiator Diisopropyl azodicarboxylate, be placed in and clean and the container of drying, add monomer 5g vinylbenzene and 5g methyl methacrylate, join in the reactor of step (1) after dissolving;
(3) control stirring velocity 350 revs/min, isothermal reaction 6 hours, form copolymer bead;
(4) after stopped reaction, wash copolymer bead with water, filter, dry, obtain the copolymer in cinnamic acrylic ester of transparent pearl.
Above-described embodiment further illustrates of the present invention, is not limiting the scope of the present invention.
Claims (4)
1. a preparation method for copolymer in cinnamic acrylic ester, is characterized in that, comprises the steps:
(1) in the reactor that reflux condensate device is housed, add Mierocrystalline cellulose and deionized water, heating in water bath is warming up to 60 ~ 90 DEG C, stirs and makes it to dissolve;
(2) take initiator, be placed in and clean and the container of drying, add monomer styrene and acrylate, join in the reactor of step (1) after dissolving;
(3) control stirring velocity 200 ~ 500 revs/min, isothermal reaction 2 ~ 12 hours, form copolymer bead;
(4) after stopped reaction, wash copolymer bead with water, filter, dry, obtain the copolymer in cinnamic acrylic ester of transparent pearl;
In described step (1), Mierocrystalline cellulose consumption is 0.05% ~ 20% of monomer styrene and acrylate total mass, and deionized water consumption is 2 ~ 10 times of monomer styrene and acrylate total mass;
In described step (2), initiator amount is 0.3% ~ 10% of monomer styrene and acrylate total mass;
In described step (2), monomer styrene and acrylate mass ratio are 1 ︰ 0.01-100.
2. the preparation method of a kind of copolymer in cinnamic acrylic ester as claimed in claim 1, it is characterized in that, in described step (1), Mierocrystalline cellulose is one or more in methylcellulose gum, ethyl cellulose, carboxymethyl cellulose, Natvosol, hydroxypropylcellulose, Vltra tears.
3. the preparation method of a kind of copolymer in cinnamic acrylic ester as claimed in claim 1, it is characterized in that, in described step (2), initiator is one or more in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, dilauroyl peroxide, isopropyl benzene hydroperoxide, tertbutyl peroxide, dicumyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, the peroxidation trimethylacetic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy dicarbonate.Preferred dibenzoyl peroxide.
4. the preparation method of a kind of copolymer in cinnamic acrylic ester as claimed in claim 1, it is characterized in that, in described step (2), acrylate is one or more in methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, allyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, allyl methacrylate(AMA).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510411757.4A CN104926974A (en) | 2015-07-14 | 2015-07-14 | Method for preparing styrene-acrylate copolymer |
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| CN201510411757.4A CN104926974A (en) | 2015-07-14 | 2015-07-14 | Method for preparing styrene-acrylate copolymer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575174A (en) * | 2018-12-20 | 2019-04-05 | 重庆颖锋兴瑞光电科技有限公司 | A kind of modified polystyrene resin |
| CN111629820A (en) * | 2017-11-20 | 2020-09-04 | 璐彩特国际特殊聚合物和树脂有限公司 | Hardenable multi-part acrylic composition |
| CN114716613A (en) * | 2022-05-11 | 2022-07-08 | 任丘市洁源化工有限公司 | Sand-fixing agent |
| CN115109404A (en) * | 2022-07-06 | 2022-09-27 | 浙江亘古电缆股份有限公司 | Phosphorus-nitrogen expansion type halogen-free cable material and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| JPS57149311A (en) * | 1981-03-11 | 1982-09-14 | Daicel Chem Ind Ltd | Production of styrene/methyl methacrylate copolymer |
| CN101891860A (en) * | 2010-07-13 | 2010-11-24 | 中国人民解放军空军油料研究所 | Porous high oil absorption resin and preparation method thereof |
| KR20150074599A (en) * | 2013-12-24 | 2015-07-02 | 경북대학교 산학협력단 | Styrene-Butylacrylate-Methylmetaacrylate copolymer resin |
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2015
- 2015-07-14 CN CN201510411757.4A patent/CN104926974A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57149311A (en) * | 1981-03-11 | 1982-09-14 | Daicel Chem Ind Ltd | Production of styrene/methyl methacrylate copolymer |
| CN101891860A (en) * | 2010-07-13 | 2010-11-24 | 中国人民解放军空军油料研究所 | Porous high oil absorption resin and preparation method thereof |
| KR20150074599A (en) * | 2013-12-24 | 2015-07-02 | 경북대학교 산학협력단 | Styrene-Butylacrylate-Methylmetaacrylate copolymer resin |
Non-Patent Citations (2)
| Title |
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| 吴红枚等: "苯乙烯-甲基丙烯酸酯系二元共聚树脂的吸油性能", 《南华大学学报（自然科学版）》 * |
| 闫福安等: "《涂料树脂合成及应用》", 30 September 2008 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111629820A (en) * | 2017-11-20 | 2020-09-04 | 璐彩特国际特殊聚合物和树脂有限公司 | Hardenable multi-part acrylic composition |
| US11548966B2 (en) | 2017-11-20 | 2023-01-10 | Lucite International Specialty Polymers And Resins Limited | Hardenable multi-part acrylic composition |
| CN109575174A (en) * | 2018-12-20 | 2019-04-05 | 重庆颖锋兴瑞光电科技有限公司 | A kind of modified polystyrene resin |
| CN114716613A (en) * | 2022-05-11 | 2022-07-08 | 任丘市洁源化工有限公司 | Sand-fixing agent |
| CN114716613B (en) * | 2022-05-11 | 2023-12-08 | 任丘市洁源化工有限公司 | Sand-fixing agent |
| CN115109404A (en) * | 2022-07-06 | 2022-09-27 | 浙江亘古电缆股份有限公司 | Phosphorus-nitrogen expansion type halogen-free cable material and preparation method thereof |
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