CN102690386A - Method for preparing crosslinked copolymerized organic glass - Google Patents
Method for preparing crosslinked copolymerized organic glass Download PDFInfo
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- CN102690386A CN102690386A CN2012101860453A CN201210186045A CN102690386A CN 102690386 A CN102690386 A CN 102690386A CN 2012101860453 A CN2012101860453 A CN 2012101860453A CN 201210186045 A CN201210186045 A CN 201210186045A CN 102690386 A CN102690386 A CN 102690386A
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- organic glass
- macrogol ester
- dimethacrylate
- dimethacrylate macrogol
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Abstract
The invention discloses a method for preparing crosslinked copolymerized organic glass, and relates to the technical field of crosslinking-copolymerization modified organic glass. The crosslinked copolymerized organic glass is prepared from methyl methacrylate, comonomers and a crosslinking agent through bulk polymerization and a casting moulding process. The comonomers are butyl acrylates, including n-butyl acrylate or n-butyl methacrylate and the like; and the crosslinking agent is poly(ethylene glycol) dimethacrylates, including poly(ethylene glycol) dimethacrylate-330, poly(ethylene glycol) dimethacrylate-550, poly(ethylene glycol) dimethacrylate-875 and the like. A crosslinked organic glass cast plate with high impact strength, high light transmittance and scratch resistance is prepared. The crosslinking-copolymerization modified organic glass prepared by the method has the impact strength which is at least 30 percent higher than that of the unmodified organic glass, and has the scratch resistance which is at least 10 percent higher than that of the unmodified glass and 6-18 percent higher than polymerized organic glass not added with the crosslinking agent, and the light transmittance of the plate is not affected by adding the comonomers or the crosslinking agent.
Description
Technical field
The present invention relates to copolymerzation with cross-linking modified organic glass technical field, the especially a kind of high-impact high transmission rate of anti-scratch synthetic glass through the mass polymerization cast molding.
Background technology
Polymethylmethacrylate (PMMA) is the unformed thermoplastics of hard, is commonly called as synthetic glass, and light transmission is best in plastics, and all-optical transmittance surpasses 90%, and mist degree is less than 2%, and specific density is 1.19g/cm
3, being merely the half the of simple glass, toughness is more than 10 times of simple glass, and the tensile strength of polymethylmethacrylate and flexural strength reach the engineering plastics rank, is the organic transparent plastics of high-quality.Be mainly used in light fixture, opticglass, instrument dial plate, advertising show window and various medical, military, glass for building purposes.Condensing lens is the vitals of concentrating solar photovoltaic cell, we can say the quality and the price of condensing lens, with the victory or defeat of decision a few years from now on concentrating solar power station competition.Compare in light weight, excellent in cushion effect, advantages such as transmitance is high, moulding process is simple, low cost product that the synthetic glass condensing lens has with simple glass.Can greatly improve the electric weight that the unit cells sheet produces, greatly reduce cost of electricity-generating, improve the competitive power of solar energy power generating.
But, but synthetic glass also has it significantly not enough, and its elongation at break almost can't be measured; Belong to brittle plastic, and have notch sensitivity, easy to crack under stress; Produce crazing and crackle, under extraneous stress and low temperature environment effect, be prone in outdoor application, turn white easily and galled spots; So solve polymethylmethacrylate fragility problem, improve the toughness and the scuff resistance ability of synthetic glass, be research emphasis of the present invention and difficult point.
The present invention adopts and introduces the flexible structure unit, reduces synthetic glass macromole chain rigidity, adopts crosslinked method to improve the wear resisting property of material, preparation toughness anti scuffing synthetic glass.
Summary of the invention
The purpose of this invention is to provide the method that a kind of preparation has the crosslinked synthetic glass casting of the anti-scratch sheet material of high impact, high transmission rate.
A kind of preparation method of copolymerzation with cross-linking synthetic glass; By TEB 3K and comonomer and linking agent through mass polymerization; Casting molding process is prepared from, and reaction is carried out 1 hour time earlier at 75-85 ℃; Continue reaction 24 hours at 50 ℃ then, initiator is Diisopropyl azodicarboxylate (AIBN) in the polyreaction.
Wherein said comonomer is the Bing Xisuandingzhi class, specifically is selected from one or more of n-butyl acrylate, NSC 20949, n-BMA, Propenoic acid, 2-methyl, isobutyl ester.
Wherein said linking agent is a dimethacrylate macrogol ester class, specifically is selected from one or more of dimethacrylate macrogol ester-330, dimethacrylate macrogol ester-550, dimethacrylate macrogol ester-875.
The mass ratio of wherein said TEB 3K and comonomer and linking agent is 75:25:0.5 ~ 3; Optimum quality ratio is 75:25:2.5.
The mass ratio of wherein said initiator and TEB 3K is 0.1:75.
Wherein said Bing Xisuandingzhi class has: n-butyl acrylate, NSC 20949, n-BMA, Propenoic acid, 2-methyl, isobutyl ester.
Wherein said dimethacrylate macrogol ester class formation formula is:
;
Wherein n represents number of ethylene glycol repeat units, and for example, it is 4,9,16 that dimethacrylate macrogol ester-330, dimethacrylate macrogol ester-550, dimethacrylate macrogol ester-875 are represented number of ethylene glycol repeat units.
Advantage of the present invention: adopt the shock strength of the copolymerzation with cross-linking modified organic glass of the present invention's preparation to improve at least 30% than unmodified synthetic glass; Scuff resistance improves at least 10% than unmodified synthetic glass, improves 6-18% than the copolymerization synthetic glass that does not add linking agent, adds comonomer or linking agent to the not influence of sheet material transmittance.
The practical implementation method
The performance test methods of copolymerzation with cross-linking modified organic glass of the present invention:
Tensile strength: use Shenzhen triumphant strong profit WDT30 of mechanical ltd type microcomputer control electronics universal testing machine, press GB/T 1040-92 test material tensile strength, rate of extension 50mm/min test.
Shock strength: use Chengde XJJ-50 of trier ltd type impact experiment machine, press GB/T 1043-93 test material simple beam non-notch impact property, bob velocity is the 2.9m/s test.
Transmittance: the WGT-S of ltd of Nereid section type transmittance mist degree determinator in the use, press GB 2410-80 test material transmittance and mist degree, sample size 50x50x3mm test.
Rockwell hardness: use the Shanghai XHR-150 of material-testing machine factory plastic Rockwell hardometer, press GB9342-38 test sheet material Rockwell hardness, select the M scale, two 3mm plate stacks.
The scuff resistance ability: adopt the abrasive blasting trier that methacrylate sheet is polished, calculate transmittance by transmittance difference before and after testing and lose reflection scuff resistance ability, the sandblast material is AL
2O
3, pressure is 2Mpa.
Comparative Examples 1
Step 1: the silex glass of two 120x120x3mm is cleaned oven dry, with masking foil one square India-rubber strip is wrapped, inner die cavity size is 8x8x3mm; On the conglutinate silex glass of glass cement with India-rubber strip, cover another piece glass then, clip with clip; Process mould, for use.
Step 2: with the TEB 3K (MMA) of 100 gram process underpressure distillation and the initiator Diisopropyl azodicarboxylate (AIBN) of 0.10 gram; Behind the glass stick stirring and evenly mixing; Pour clean 100ml round-bottomed flask into, stir and be warmed up to 75 ℃, when solution becomes gets thickness, stop heating; Be cooled to room temperature, be performed polymer.
Step 3: performed polymer is poured in the mould of step 1 making, clip sealing, put into 50 ℃ of slow polymerization 24h of baking oven; When polymkeric substance becomes the solid glue, be warmed up to 100 ℃ of repolymerization 1 ~ 2h, make its abundant polymerization; Then gradually be chilled to room temperature, the demoulding promptly gets the thick clear sheet of 3mm.
Comparative Examples 2:
Operate identically with Comparative Examples 1, difference is to add comonomer n-butyl acrylate (BA), and initiator amount is constant.
Embodiment 1:
Operate identically with Comparative Examples, difference is to add linking agent dimethacrylate macrogol ester-550 (PEGDMA550), and comonomer and initiator are constant.
Embodiment 2 ~ 5:
Operate identically with instance 2, difference is that MMA is different with the mass ratio of BA and PEGDMA550.
Numbering | MMA/g | BA/g | AIBN/g | PEGDMA550/g |
Comparative Examples 1 | 100 | 0 | 0.10 | 0 |
Comparative Examples 2 | 75 | 25 | 0.10 | 0 |
Embodiment 1 | 75 | 25 | 0.10 | 1.0 |
Embodiment 2 | 75 | 25 | 0.10 | 1.5 |
Embodiment 3 | 75 | 25 | 0.10 | 2.0 |
Embodiment 4 | 75 | 25 | 0.10 | 2.5 |
Embodiment 5 | 75 | 25 | 0.10 | 3.0 |
The material proportion of table 1 instance 1 ~ 7
Numbering | Tensile strength/MPa | Shock strength/KJ/m 2 | Transmittance/% | Transmittance loss/% | Rockwell hardness (M) |
Comparative Examples 1 | 62.6 | 14.4 | 92.6 | 10.17 | 122 |
Comparative Examples 2 | 46.1 | 20.6 | 92.6 | 11.14 | 108 |
Embodiment 1 | 46.6 | 19.5 | 92.6 | 10.49 | 108 |
Embodiment 2 | 47.0 | 19.2 | 92.6 | 10.02 | 111 |
Embodiment 3 | 47.5 | 19.2 | 92.6 | 9.80 | 113 |
Embodiment 4 | 47.9 | 19.8 | 92.4 | 9.14 | 116 |
Embodiment 5 | 48.2 | 19.8 | 92.4 | 9.07 | 118 |
Table 2 plate property
Test data through in the table 2 is found out: Comparative Examples 2 is added the flexible comonomer n-butyl acrylate of 25g, and the sheet material shock strength is by 14.4KJ/m
2Be increased to 20.6KJ/m
2, having increased by 30% than Comparative Examples 1, shock strength significantly improves, transmittance is constant, but the loss of sheet material transmittance increases, but scuff resistance lowers.Embodiment 1-5 is owing to add linking agent PEGDMA550, and the sheet material shock strength is constant basically, and is high more a lot of than Comparative Examples 1; Transmittance is constant basically, but scuff resistance improves constantly, and explains that linking agent PEGDMA550 is to improving sheet material scuff resistance ability.Along with the increase of dosage of crosslinking agent, the sheet material tensile strength begins to increase, and shock strength and transmittance are constant basically; But scuff resistance can improve constantly, and is better than pure synthetic glass (Comparative Examples 1).In a word, the adding of toughness comonomer (n-butyl acrylate etc.) can significantly improve the sheet material shock strength, and the adding of linking agent PEGDMA550 improves the scratch performance of sheet material.
Claims (5)
1. the preparation method of a copolymerzation with cross-linking synthetic glass; It is characterized in that by TEB 3K and comonomer and linking agent through mass polymerization; Casting molding process is prepared from, and reaction is carried out 1 hour time earlier at 75 ℃; Continue reaction 24 hours at 50 ℃ then, initiator is a Diisopropyl azodicarboxylate in the polyreaction.
2. the preparation method of a kind of copolymerzation with cross-linking synthetic glass according to claim 1 is characterized in that wherein said comonomer is the Bing Xisuandingzhi class;
Wherein said linking agent is a dimethacrylate macrogol ester class;
The mass ratio of wherein said TEB 3K and comonomer and linking agent is 75:25:0.5 ~ 3;
The mass ratio of wherein said initiator and TEB 3K is 0.1:75.
3. the preparation method of a kind of copolymerzation with cross-linking synthetic glass according to claim 2 is characterized in that wherein said wherein said Bing Xisuandingzhi class is selected from one or more of n-butyl acrylate, NSC 20949, n-BMA, Propenoic acid, 2-methyl, isobutyl ester;
Wherein said dimethacrylate macrogol ester class is one or more of dimethacrylate macrogol ester-330, dimethacrylate macrogol ester-550, dimethacrylate macrogol ester-875;
The mass ratio of wherein said TEB 3K and comonomer and linking agent is for being 75:25:2.5.
5. the preparation method of a kind of copolymerzation with cross-linking synthetic glass according to claim 4 is characterized in that wherein said dimethacrylate macrogol ester class is dimethacrylate macrogol ester-330, dimethacrylate macrogol ester-550, dimethacrylate macrogol ester-875.
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104448643A (en) * | 2014-10-31 | 2015-03-25 | 田琳琳 | Glass capable of preventing static electricity |
CN106589733A (en) * | 2016-12-20 | 2017-04-26 | 安徽亚克力实业有限公司 | Modified organic glass with excellent impact resistance and preparation method thereof |
CN106589754A (en) * | 2016-12-20 | 2017-04-26 | 安徽亚克力实业有限公司 | Impact-resistant organic glass and preparation method thereof |
CN109134739A (en) * | 2018-08-13 | 2019-01-04 | 爱迪特(秦皇岛)科技股份有限公司 | A kind of machinable PMMA of dental CAD/CAM and preparation method thereof |
CN109134738A (en) * | 2018-07-13 | 2019-01-04 | 蚌埠承永玻璃制品有限公司 | A kind of shock resistance high temperature resistant organic glass |
CN109796548A (en) * | 2018-12-19 | 2019-05-24 | 锦西化工研究院有限公司 | A kind of preparation method of high performance turbine organic glass |
CN111875748A (en) * | 2020-08-14 | 2020-11-03 | 上海沪亮生物医药科技有限公司 | X-ray developing temporary crown-bridge resin and preparation method thereof |
CN112390905A (en) * | 2019-08-13 | 2021-02-23 | 中国石油化工股份有限公司 | Methyl methacrylate polymer and preparation method and application thereof |
CN112497778A (en) * | 2020-12-07 | 2021-03-16 | 锦西化工研究院有限公司 | Method for preparing aviation organic glass plate with special shape |
CN113248667A (en) * | 2021-04-30 | 2021-08-13 | 江苏可奥熙光学材料科技有限公司 | Super-tough acrylate resin and preparation process thereof |
CN113583161A (en) * | 2021-09-08 | 2021-11-02 | 安徽新涛光电科技有限公司 | Preparation method of PMMA casting plate with high bonding strength |
CN114806055A (en) * | 2022-05-19 | 2022-07-29 | 浙江华帅特新材料科技有限公司 | Reinforced and toughened PMMA plate and manufacturing method thereof |
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Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104448643A (en) * | 2014-10-31 | 2015-03-25 | 田琳琳 | Glass capable of preventing static electricity |
CN106589733A (en) * | 2016-12-20 | 2017-04-26 | 安徽亚克力实业有限公司 | Modified organic glass with excellent impact resistance and preparation method thereof |
CN106589754A (en) * | 2016-12-20 | 2017-04-26 | 安徽亚克力实业有限公司 | Impact-resistant organic glass and preparation method thereof |
CN109134738A (en) * | 2018-07-13 | 2019-01-04 | 蚌埠承永玻璃制品有限公司 | A kind of shock resistance high temperature resistant organic glass |
CN109134739A (en) * | 2018-08-13 | 2019-01-04 | 爱迪特(秦皇岛)科技股份有限公司 | A kind of machinable PMMA of dental CAD/CAM and preparation method thereof |
CN109796548A (en) * | 2018-12-19 | 2019-05-24 | 锦西化工研究院有限公司 | A kind of preparation method of high performance turbine organic glass |
CN112390905A (en) * | 2019-08-13 | 2021-02-23 | 中国石油化工股份有限公司 | Methyl methacrylate polymer and preparation method and application thereof |
CN111875748A (en) * | 2020-08-14 | 2020-11-03 | 上海沪亮生物医药科技有限公司 | X-ray developing temporary crown-bridge resin and preparation method thereof |
CN111875748B (en) * | 2020-08-14 | 2022-10-25 | 上海沪亮生物医药科技有限公司 | X-ray developing temporary crown-bridge resin and preparation method thereof |
CN112497778A (en) * | 2020-12-07 | 2021-03-16 | 锦西化工研究院有限公司 | Method for preparing aviation organic glass plate with special shape |
CN113248667A (en) * | 2021-04-30 | 2021-08-13 | 江苏可奥熙光学材料科技有限公司 | Super-tough acrylate resin and preparation process thereof |
CN113248667B (en) * | 2021-04-30 | 2022-04-12 | 江苏可奥熙光学材料科技有限公司 | Super-tough acrylate resin and preparation process thereof |
CN113583161A (en) * | 2021-09-08 | 2021-11-02 | 安徽新涛光电科技有限公司 | Preparation method of PMMA casting plate with high bonding strength |
CN114806055A (en) * | 2022-05-19 | 2022-07-29 | 浙江华帅特新材料科技有限公司 | Reinforced and toughened PMMA plate and manufacturing method thereof |
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Application publication date: 20120926 |