CN104926984A - Method for preparing high molecular weight modified polymethyl methacrylate - Google Patents
Method for preparing high molecular weight modified polymethyl methacrylate Download PDFInfo
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- CN104926984A CN104926984A CN201510412204.0A CN201510412204A CN104926984A CN 104926984 A CN104926984 A CN 104926984A CN 201510412204 A CN201510412204 A CN 201510412204A CN 104926984 A CN104926984 A CN 104926984A
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- methyl methacrylate
- high molecular
- modified poly
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Abstract
The invention relates to a method for preparing high molecular weight modified polymethyl methacrylate. The method includes the steps that firstly, the raw materials of 80-100 parts of monomer methyl methacrylate, 5-30 parts of copolymerization modified monomer, 10*10-4-150*10-4 parts of initiator and 0.1-0.5 part of chain transfer agent are taken and fully stirred so that the raw materials can be mixed evenly; the mixture is put into a reactor provided with a backflow condensing device, oil bath heating and temperature rising are conducted, the reaction temperature is controlled to range from 80 DEG C to 150 DEG C, a stirring reaction is conducted for 6-10 h under the rotating speed of 300-500 r/min, a viscous copolymerization product is formed, and finally the modified polymethyl methacrylate is prepared after aftertreatment. According to the method, polymerization is conducted in a one-time feeding mode, operation is simple, the polymerization reaction is easy to control, the polymerization rate is high, and the prepared polymer has high molecular weight.
Description
Technical field
The present invention relates to a kind of preparation method of high molecular modified poly (methyl methacrylate), belong to polymer preparing technical field.
Background technology
Polymethylmethacrylate, English abbreviation PMMA.PMMA has good light transmission, electrical insulating property, chemical-resistant reagent, solvent resistance, weather resistance and has certain heat-resisting winter hardiness, after post-treatment, can be applicable to liquid crystal light guide plate film, LED lamp, fiber optic materials, optical articles, automobile component, appliances parts and daily life requisite.
By the polyphosphazene polymer methyl methacrylate that methyl methacrylate is monomer synthesize, the properties of size to macromolecular material of its molecular weight has material impact, is one of principal element of its application performance of restriction.Polymethylmethacrylate generally adopts the free radical bulk polymerization of methyl methacrylate monomer to obtain, but its molecular weight fails the market product requirement of the polymethylmethacrylate meeting some high molecular.
Summary of the invention
The object of the invention is in order to solve be monomer synthesize polymethylmethacrylate by methacrylic acid in prior art time molecular weight little problem, provide a kind of method simple, the preparation method of the high molecular modified poly (methyl methacrylate) of easy handling.
The present invention adopts following technical scheme: a kind of preparation method of high molecular modified poly (methyl methacrylate), comprises the steps:
(1) prepare burden: take starting monomer methyl methacrylate 80 ~ 100 parts, modification by copolymerization monomer 5 ~ 30 parts, initiator 10 × 10 successively
-4~ 150 × 10
-4part, chain-transfer agent 0.1 ~ 0.5 part, fully stir and raw material mixed, add and be equipped with in the reactor of reflux condensate device;
(2) be polymerized: oil bath heat temperature raising, controlling temperature of reaction is 80 ~ 150 DEG C, and stirring reaction 6 ~ 10h under the rotating speed of 300 ~ 500r/min, forms thick copolymerization product;
(3) aftertreatment: take out step (2) gained copolymerization product, dissolve completely, then settle with methyl alcohol with acetone, filters, puts into baking oven and dry, and grinds, obtains fine particle shape methyl methacrylate-butyl acrylate multipolymer.
Further, described modification by copolymerization monomer is methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, Ethyl acrylate or Isooctyl acrylate monomer.
Further, described initiator is the peroxidation-2-ethyl acid tert-butyl ester, tert-butyl peroxy acetate, Diisopropyl azodicarboxylate, peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, 2, one in 5-dimethyl-2,5 di-t-butyl peroxy hexane, dilauroyl peroxide or ditertiary butyl peroxide.
Further, described chain-transfer agent is any one in n-butyl mercaptan, isobutyl mercaptan, positive hexylmercaptan, n-dodecyl mercaptan or tertiary lauryl mercaptan.
Further, the bake out temperature in described step (3) is 60 ~ 100 DEG C, and drying time is 3 ~ 8h.
Further, the relative molecular weight of methyl methacrylate-butyl acrylate multipolymer that described step (3) is prepared is 20 ~ 300,000.
The present invention adopts the mode once fed intake to be polymerized, simple to operate, and polymeric reaction temperature remains unchanged, only need to regulate stirring velocity in right amount, polyreaction is easy to control, and ensure that the polymkeric substance of higher percent polymerization and preparation has higher molecular weight, and the present invention adopts the mode of methyl methacrylate being carried out to modified copolymer, make polymerisate not only have the properties advantage of polymethylmethacrylate but also improve its molecular weight, meet the different demands of this product for market.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
In the 250mL flask that reflux condensate device is housed, add monomer 190g methyl methacrylate and 10g butyl acrylate, the 0.002g initiator peroxidation-2-ethyl acid tert-butyl ester and 0.5g chain-transfer agent octyl mercaptan; Stirring makes it to mix, and oil bath is heated to 100 DEG C; Control stirring velocity 300r/min, when polymerization system viscosity increases, the appropriate stirring velocity that improves is to 400r/min, and isothermal reaction 9h40min, forms thick copolymerization product; Stopped reaction, leave standstill, after system cooling, break flask into pieces take out copolymerization product, dissolve completely with acetone, then go out multipolymer with methyl alcohol sedimentation, filter, then be placed in baking oven and carry out drying, bake out temperature is 60 DEG C, and drying time is 8h, grind, obtain the high molecular modified poly (methyl methacrylate) product of fine particle shape.
Embodiment 2:
In the 250mL flask that reflux condensate device is housed, add monomer 160g methyl methacrylate and 60g ethyl propenoate, 0.01g initiator tert-butyl peroxy acetate and 1.0g chain-transfer agent n-butyl mercaptan; Stirring makes it to mix, and oil bath is heated to 95 DEG C; Control stirring velocity 300r/min, when polymerization system viscosity increases, the appropriate stirring velocity that improves is to 400r/min, and isothermal reaction 6h40min, forms thick copolymerization product; Stopped reaction, leave standstill, after system cooling, break flask into pieces take out copolymerization product, dissolve completely with acetone, then go out multipolymer with methyl alcohol sedimentation, filter, then be placed in baking oven and carry out drying, bake out temperature is 80 DEG C, and drying time is 4h, grind, obtain the high molecular modified poly (methyl methacrylate) product of fine particle shape.
Embodiment 3:
In the 250mL flask that reflux condensate device is housed, add monomer 200g methyl methacrylate and 10g methyl acrylate, 0.03g initiator peroxidized t-butyl perbenzoate and 0.8g chain-transfer agent octyl mercaptan; Stirring makes it to mix, and oil bath is heated to 110 DEG C; Control stirring velocity 300r/min, when polymerization system viscosity increases, the appropriate stirring velocity that improves is to 400r/min, and isothermal reaction 5h50min, forms thick copolymerization product; Stopped reaction, leave standstill, after system cooling, break flask into pieces take out copolymerization product, dissolve completely with acetone, then go out multipolymer with methyl alcohol sedimentation, filter, then be placed in baking oven and carry out drying, bake out temperature is 90 DEG C, and drying time is 4h, grind, obtain the high molecular modified poly (methyl methacrylate) product of fine particle shape.
Embodiment 4:
In the 250mL flask that reflux condensate device is housed, add monomer 180g methyl methacrylate and 40g isobutyl acrylate, 0.014g initiator dilauroyl peroxide and 0.6g chain-transfer agent n-dodecyl mercaptan; Stirring makes it to mix, and oil bath is heated to 80 DEG C; Control stirring velocity 300r/min, when polymerization system viscosity increases, the appropriate stirring velocity that improves is to 400r/min, and isothermal reaction 7h10min, forms thick copolymerization product; Stopped reaction, leave standstill, after system cooling, break flask into pieces take out copolymerization product, dissolve completely with acetone, then go out multipolymer with methyl alcohol sedimentation, then be placed in baking oven and carry out drying, bake out temperature is 100 DEG C, and drying time is 3h, dry, grind, obtain the high molecular modified poly (methyl methacrylate) product of fine particle shape.
Embodiment 5:
In the 250mL flask that reflux condensate device is housed, add monomer 190g methyl methacrylate and 50g Ethyl acrylate, 0.008g initiator benzoyl peroxide and the tertiary lauryl mercaptan of 0.4g chain-transfer agent; Stirring makes it to mix, and oil bath is heated to 90 DEG C; Control stirring velocity 300r/min, when polymerization system viscosity increases, the appropriate stirring velocity that improves is to 400r/min, and isothermal reaction 6h20min, forms thick copolymerization product; Stopped reaction, leave standstill, after system cooling, break flask into pieces take out copolymerization product, dissolve completely with acetone, then go out multipolymer with methyl alcohol sedimentation, filter, then be placed in baking oven and carry out drying, bake out temperature is 70 DEG C, and drying time is 5h, grind, obtain the high molecular modified poly (methyl methacrylate) product of fine particle shape.
Embodiment 6:
In the 250mL flask that reflux condensate device is housed, add monomer 185g methyl methacrylate and 15g Isooctyl acrylate monomer, 0.020g initiator 2,5-dimethyl-2,5 di-t-butyl peroxy hexane and the tertiary lauryl mercaptan of 0.9g chain-transfer agent; Stirring makes it to mix, and oil bath is heated to 120 DEG C; Control stirring velocity 300r/min, when polymerization system viscosity increases, the appropriate stirring velocity that improves is to 400r/min, and isothermal reaction 6h10min, forms thick copolymerization product; Stopped reaction, leave standstill, after system cooling, break flask into pieces take out copolymerization product, dissolve completely with acetone, then go out multipolymer with methyl alcohol sedimentation, then be placed in baking oven and carry out drying, bake out temperature is 80 DEG C, and drying time is 6h, dry, grind, obtain the high molecular modified poly (methyl methacrylate) product of fine particle shape.
Gel permeation chromatography (GPC) is adopted to carry out number-average molecular weight mensuration to the product in above-mentioned each example,
GPC tests underlying condition: stationary phase selects crosslinked polystyrene gel, moving phase Analysis about Selection pure tetrahydrofuran, and drip washing speed is 1ml/min, and sample size is 50 μ L, and strength of solution size is 0.01g/ml, and probe temperature is 25 DEG C, and result is as shown in table 1.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Number-average molecular weight | 254631 | 266813 | 235678 | 289564 | 275639 | 205422 |
As shown in Table 1, the relative molecular weight of the modified poly (methyl methacrylate) adopting preparation method of the present invention to prepare all is greater than 200000.
Claims (6)
1. a preparation method for high molecular modified poly (methyl methacrylate), is characterized in that: comprise the steps:
(1) prepare burden: take starting monomer methyl methacrylate 80 ~ 100 parts, modification by copolymerization monomer 5 ~ 30 parts, initiator 10 × 10 successively
-4~ 150 × 10
-4part, chain-transfer agent 0.1 ~ 0.5 part, fully stir and raw material mixed, add and be equipped with in the reactor of reflux condensate device;
(2) be polymerized: oil bath heat temperature raising, controlling temperature of reaction is 80 ~ 150 DEG C, and stirring reaction 6 ~ 10h under the rotating speed of 300 ~ 500r/min, forms thick copolymerization product;
(3) aftertreatment: take out step (2) gained copolymerization product, dissolve completely with acetone, sedimentation is carried out again with methyl alcohol, settling time is 1 ~ 4h, filter, then put into baking oven to dry, grind, obtain fine particle shape methyl methacrylate-butyl acrylate multipolymer and modified poly (methyl methacrylate).
2. the preparation method of high molecular modified poly (methyl methacrylate) as claimed in claim 1, is characterized in that: described modification by copolymerization monomer is methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, Ethyl acrylate or Isooctyl acrylate monomer.
3. the preparation method of high molecular modified poly (methyl methacrylate) as claimed in claim 1, it is characterized in that: described initiator is the peroxidation-2-ethyl acid tert-butyl ester, tert-butyl peroxy acetate, Diisopropyl azodicarboxylate, peroxidized t-butyl perbenzoate, benzoyl peroxide, peroxidation-2 ethyl hexanoic acid tert-pentyl ester, 2, one in 5-dimethyl-2,5 di-t-butyl peroxy hexane, dilauroyl peroxide or ditertiary butyl peroxide.
4. the preparation method of high molecular modified poly (methyl methacrylate) as claimed in claim 1, is characterized in that: described chain-transfer agent is any one in n-butyl mercaptan, isobutyl mercaptan, positive hexylmercaptan, n-dodecyl mercaptan or tertiary lauryl mercaptan.
5. the preparation method of high molecular modified poly (methyl methacrylate) as claimed in claim 1, it is characterized in that: the bake out temperature in described step (3) is 60 ~ 100 DEG C, drying time is 3 ~ 8h.
6. the preparation method of high molecular modified poly (methyl methacrylate) as claimed in claim 1, is characterized in that: the relative molecular weight of the modified poly (methyl methacrylate) that described step (3) is prepared is 20 ~ 300,000.
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|---|---|---|---|
| CN201510412204.0A CN104926984A (en) | 2015-07-14 | 2015-07-14 | Method for preparing high molecular weight modified polymethyl methacrylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109402758A (en) * | 2018-09-30 | 2019-03-01 | 镇江微芯光子科技有限公司 | The preparation method of polymer optical fiber |
| CN113336882A (en) * | 2021-05-24 | 2021-09-03 | 博立尔化工（扬州）有限公司 | Process for preparing PMMA resin with narrow molecular weight distribution by adopting intermittent bulk polymerization method |
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| US4239875A (en) * | 1977-01-24 | 1980-12-16 | Etlis Volf S | Method for producing prepolymers based on vinyl monomers |
| CN102070743A (en) * | 2009-11-20 | 2011-05-25 | 上海华明高技术（集团）有限公司 | Method for preparing polyacrylate copolymer resin for optical conduction |
| CN102336864A (en) * | 2011-06-16 | 2012-02-01 | 中国科学院长春应用化学研究所 | Preparation method for polymethyl methacrylate (PMMA) resin with high thermal stability |
| CN103145910A (en) * | 2013-03-27 | 2013-06-12 | 苏州双象光学材料有限公司 | Production process of polymethyl methacrylate (PMMA) through double-initiated polymerization |
| WO2014002503A1 (en) * | 2012-06-29 | 2014-01-03 | 株式会社クラレ | Manufacturing method for (meth)acrylic resin composition |
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2015
- 2015-07-14 CN CN201510412204.0A patent/CN104926984A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4239875A (en) * | 1977-01-24 | 1980-12-16 | Etlis Volf S | Method for producing prepolymers based on vinyl monomers |
| CN102070743A (en) * | 2009-11-20 | 2011-05-25 | 上海华明高技术（集团）有限公司 | Method for preparing polyacrylate copolymer resin for optical conduction |
| CN102336864A (en) * | 2011-06-16 | 2012-02-01 | 中国科学院长春应用化学研究所 | Preparation method for polymethyl methacrylate (PMMA) resin with high thermal stability |
| WO2014002503A1 (en) * | 2012-06-29 | 2014-01-03 | 株式会社クラレ | Manufacturing method for (meth)acrylic resin composition |
| CN103145910A (en) * | 2013-03-27 | 2013-06-12 | 苏州双象光学材料有限公司 | Production process of polymethyl methacrylate (PMMA) through double-initiated polymerization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109402758A (en) * | 2018-09-30 | 2019-03-01 | 镇江微芯光子科技有限公司 | The preparation method of polymer optical fiber |
| CN113336882A (en) * | 2021-05-24 | 2021-09-03 | 博立尔化工（扬州）有限公司 | Process for preparing PMMA resin with narrow molecular weight distribution by adopting intermittent bulk polymerization method |
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Application publication date: 20150923 |
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