CN103421265B - Transparent PMMA flexibilizer - Google Patents
Transparent PMMA flexibilizer Download PDFInfo
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- CN103421265B CN103421265B CN201310155826.0A CN201310155826A CN103421265B CN 103421265 B CN103421265 B CN 103421265B CN 201310155826 A CN201310155826 A CN 201310155826A CN 103421265 B CN103421265 B CN 103421265B
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- polymkeric substance
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Abstract
The invention discloses a transparent PMMA (polymethyl methacrylate) flexibilizer. The transparent PMMA flexibilizer is characterized in that the transparent PMMA flexibilizer is prepared by the following raw materials in parts by mass: 70-85 parts of MAAS rubber elastomers, 14.5-29.9 parts of core-shell polymer and 0.1-0.5 part of an anti-oxygen 1010, wherein the content of acrylonitrile in the MAAS rubber elastomers is 10-30 parts in parts by mass, and the core-shell polymer is emulsion particles prepared by using seed emulsion butyl acrylate and a mixture of ethylene glycol dimethacrylate and allyl methacrylate as cross-linking agents. The transparent PMMA flexibilizer has the advantages that the additive amount is small during use, the cost is effectively lowered, and the environment is protected.
Description
Technical field
The present invention relates to the technical field of plastics additive, is the technology of transparent PMMA toughner specifically.
Background technology
PMMA is polymethylmethacrylate, is commonly called as synthetic glass, acryl or acrylic, has the transparency that crystal is general, and transmittance reaches more than 92%, has good color development effect.In addition, PMMA has splendid weathering resistance, higher surface hardness and surface luster and high-temperature behavior preferably.PMMA is widely used in industries such as aviation, automobile, electronics, medical treatment, chemical industry, building materials, bathroom and Advertisement labels.But ordinary PMMA resin is because extensibility is lower, easily split, frangible, limited it and further applied.Need the modification to PMMA, be generally to add auxiliary agent for this reason, i.e. toughner, to reduce matrix material fragility and to improve matrix material shock resistance.Toughner can be divided into endurable active toughener and nonactive toughner two classes, and endurable active toughener refers on its molecular chain and contain the active group that can react with matrix, and it can form network structure, increases a part of flexible chain, thereby improves the shock resistance of matrix material.To be that a class and matrix are fine mix but do not participate in the toughner of chemical reaction nonactive toughner.But existing toughner in use addition is large, generally need the addition of 10%-20%, cost is high like this, somewhat expensive.
Summary of the invention
The object of this invention is to provide a kind of in use addition little, effectively reduce costs, the transparent PMMA toughner of environmental protection.
The present invention is achieved through the following technical solutions.
A transparent PMMA toughner, is characterized in that described transparent PMMA toughner is formulated by the mass fraction of following raw materials according: 70 parts～85 parts of MAAS rubber elastomers; 14.5 parts～29.9 parts, nucleocapsid structure polymkeric substance; 0.1 part～0.5 part of antioxidant 1010; The fine content of propylene in described MAAS rubber elastomer is 10～30 parts by mass percentage, and described nucleocapsid structure polymkeric substance is the latex particle that linking agent makes by seed emulsion butyl acrylate with the mixture by Ethylene glycol dimethacrylate, methacrylic acid allyl alcohol ester.
The mass fraction ratio of described butyl acrylate, Ethylene glycol dimethacrylate, methacrylic acid allyl alcohol ester is: 80～90 parts: 0.5～2 part: 0.5～2 part, and adopt the method for letex polymerization to make described nucleocapsid structure polymkeric substance.
Or 70 parts of described MAAS rubber elastomers; 29.9 parts, nucleocapsid structure polymkeric substance; 0.1 part of antioxidant 1010.
Or 85 parts of described MAAS rubber elastomers; 14.5 parts, nucleocapsid structure polymkeric substance; 0.5 part of antioxidant 1010.
Or 71.6 parts of described MAAS rubber elastomers; 28 parts, nucleocapsid structure polymkeric substance; 0.4 part of antioxidant 1010.
Or 83 parts of described MAAS rubber elastomers; 16.5 parts, nucleocapsid structure polymkeric substance; 0.5 part of antioxidant 1010.
Or 80 parts of described MAAS rubber elastomers; 19.6 parts, nucleocapsid structure polymkeric substance; 0.4 part of antioxidant 1010.
Or 77 parts of described MAAS rubber elastomers; 22.7 parts, nucleocapsid structure polymkeric substance; 0.3 part of antioxidant 1010.
The present invention compared with prior art has the following advantages.
1) MAAS is dispersed in PMMA matrix with the form of caoutchouc elasticity particle, effectively improve PMMA resistance to impact shock, thereby improved the toughness of PMMA, acrylonitrile content in MAAS graft rubber body, not only affect it and carry out the effect of graft reaction, and affect the physical and mechanical properties of PMMA blend.Through test, when the content of vinyl cyanide is 15 parts, and when the content of MAAS in synthetic glass is 10 parts, to Improving Toughness of Organic Glass best results, resistance to impact shock can effectively promote 39.5 parts.
2) nucleocapsid structure polymkeric substance is to make latex particle by seed emulsion butyl acrylate and the method for the letex polymerization that is linking agent by the mixture of Ethylene glycol dimethacrylate, methacrylic acid allyl alcohol ester, the wherein existence of linking agent, one side has maintained form and the toughness of rubber. and can provide on the other hand activity to connect skill point.Described like this nucleocapsid structure polymkeric substance, can effectively control size, the degree of crosslinking of composite particles rubber phase, the nucleocapsid of composite particles than and introduce functional groups, thereby, the various impacts of the generation of rubber particles in toughened plastics;
3) antioxidant 1010 is the representative of polyphenol, is white crystalline powder, and chemistry four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester by name, has 4 structure of functional groups, and chemical property is stable, can significantly improve thermostability.
As can be seen here, cost of the present invention is low, environmental protection.Particularly in use addition is little, and after tested, addition only needs 1%-3%, greatly reduces cost.
Embodiment
A transparent PMMA toughner, is characterized in that described transparent PMMA toughner is formulated by the mass fraction of following raw materials according: 70 parts～85 parts of MAAS rubber elastomers; 14.5 parts～29.9 parts, nucleocapsid structure polymkeric substance; 0.1 part～0.5 part of antioxidant 1010; The fine content of propylene in described MAAS rubber elastomer is 10～30 parts by mass percentage, and described nucleocapsid structure polymkeric substance is the latex particle that linking agent makes by seed emulsion butyl acrylate with the mixture by Ethylene glycol dimethacrylate, methacrylic acid allyl alcohol ester.The present invention is configured and can obtains by aforementioned formula, can make as required powder or make liquid.Wherein the mass fraction ratio of butyl acrylate, Ethylene glycol dimethacrylate, methacrylic acid allyl alcohol ester is: 80～90 parts: 0.5～2 part: 0.5～2 part, and adopt the method for letex polymerization to make described nucleocapsid structure polymkeric substance.MAAS rubber elastomer is by the particle from the particle diameter of 70-150nm by methyl methacrylate, butyl acrylate, propylene is fine, vinylbenzene makes through emulsion copolymerization narrow wavelength-division cloth.
In the present invention, the method of the letex polymerization of described nucleocapsid structure polymkeric substance is to adopt traditional newborn drench polymerization process, step soap letex polymerization and hole enlargement, emulsifier-free emulsion polymerization and hole enlargement to make respectively each compared with the seed emulsion of small particle size and greater particle size, be that seed emulsion be take butyl acrylate as main monomer, the mixture of Ethylene glycol dimethacrylate or glycol ether allyl carbonate and methacrylic acid allyl alcohol ester of take is linking agent.By aforementioned ratio, get quantitative seed emulsion, supply moisture, stir, rise to certain temperature, add reduction components, drip continuously the monomer that contains a certain amount of oil-soluble initiator.Reaction finishes rear cooling, and copper mesh filters discharging.Composite emulsion is processed with anionite-exchange resin and spent ion exchange resin respectively, and then freezing breakdown of emulsion, washs suction filtration. and dry, stand-by in vacuum drying oven.Carry out the emulsion of shell and carry out grafting, along with nucleocapsid is than increasing, the particle diameter of composite particles reduces.When nucleocapsid is than from 20/80 during to 70/30 variation, newborn slag obtains white powder after breakdown of emulsion; Nucleocapsid has collection phenomenon also than equaling after 80/20 o'clock latex particle is dried.Rubber particles carries out the linking agent breast slag grafting of shell, and the size of the composite particles after grafting has increase in various degree.The impact of shell monomers content of crosslinking agent on composite particles form: along with the increase of linking agent proportion in shell monomers, the size well of composite particles is without too large variation.Adopt the method for letex polymerization, can effectively control size, the degree of crosslinking of composite particles rubber phase, the nucleocapsid of composite particles than and introduce functional groups.Like this, the various influence factors of rubber particles in toughened plastics can be investigated respectively.
The embodiment of each formula below:
Embodiment mono-: 70 parts of MAAS rubber elastomers; 29.9 parts, nucleocapsid structure polymkeric substance; 0.1 part of antioxidant 1010.
Embodiment bis-: 85 parts of MAAS rubber elastomers; 14.5 parts, nucleocapsid structure polymkeric substance; 0.5 part of antioxidant 1010.
Embodiment tri-: 71.6 parts of MAAS rubber elastomers; 28 parts, nucleocapsid structure polymkeric substance; 0.4 part of antioxidant 1010.
Embodiment tetra-: 83 parts of MAAS rubber elastomers; 16.5 parts, nucleocapsid structure polymkeric substance; 0.5 part of antioxidant 1010.
Embodiment five: 80 parts of MAAS rubber elastomers; 19.6 parts, nucleocapsid structure polymkeric substance; 0.4 part of antioxidant 1010.
Embodiment six: 77 parts of MAAS rubber elastomers; 22.7 parts, nucleocapsid structure polymkeric substance; 0.3 part of antioxidant 1010.
Claims (7)
1. a transparent PMMA toughner, is characterized in that described transparent PMMA toughner is formulated by the mass fraction of following raw materials according:
70 parts～85 parts of MAAS rubber elastomers;
14.5 parts～29.9 parts, nucleocapsid structure polymkeric substance;
0.1 part～0.5 part of antioxidant 1010;
The fine content of propylene in described MAAS rubber elastomer is 10～30% by mass percentage,
Described nucleocapsid structure polymkeric substance is the latex particle that linking agent makes by seed emulsion butyl acrylate with the mixture by Ethylene glycol dimethacrylate, methacrylic acid allyl alcohol ester,
The mass fraction ratio of described butyl acrylate, Ethylene glycol dimethacrylate, methacrylic acid allyl alcohol ester is: 80～90 parts: 0.5～2 part: 0.5～2 part, and adopt the method for letex polymerization to make described nucleocapsid structure polymkeric substance.
2. transparent PMMA toughner according to claim 1, is characterized in that: 70 parts of described MAAS rubber elastomers; 29.9 parts, nucleocapsid structure polymkeric substance; 0.1 part of antioxidant 1010.
3. transparent PMMA toughner according to claim 1, is characterized in that: 85 parts of described MAAS rubber elastomers; 14.5 parts, nucleocapsid structure polymkeric substance; 0.5 part of antioxidant 1010.
4. transparent PMMA toughner according to claim 1, is characterized in that: 71.6 parts of described MAAS rubber elastomers; 28 parts, nucleocapsid structure polymkeric substance; 0.4 part of antioxidant 1010.
5. transparent PMMA toughner according to claim 1, is characterized in that: 83 parts of described MAAS rubber elastomers; 16.5 parts, nucleocapsid structure polymkeric substance; 0.5 part of antioxidant 1010.
6. transparent PMMA toughner according to claim 1, is characterized in that: 80 parts of described MAAS rubber elastomers; 19.6 parts, nucleocapsid structure polymkeric substance; 0.4 part of antioxidant 1010.
7. transparent PMMA toughner according to claim 1, is characterized in that: 77 parts of described MAAS rubber elastomers; 22.7 parts, nucleocapsid structure polymkeric substance; 0.3 part of antioxidant 1010.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310155826.0A CN103421265B (en) | 2013-04-26 | 2013-04-26 | Transparent PMMA flexibilizer |
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| CN201310155826.0A CN103421265B (en) | 2013-04-26 | 2013-04-26 | Transparent PMMA flexibilizer |
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| CN103421265A CN103421265A (en) | 2013-12-04 |
| CN103421265B true CN103421265B (en) | 2014-12-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104448595A (en) * | 2014-12-19 | 2015-03-25 | 深圳市鑫恒力科技有限公司 | Gpps transparent liquid toughening agent |
| CN106496903A (en) * | 2016-12-20 | 2017-03-15 | 安徽亚克力实业有限公司 | A kind of cracking resistance lucite and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1902233A (en) * | 2003-12-30 | 2007-01-24 | Lg化学株式会社 | Polymer latex having excellent impact-resistance and powder flow property and method for preparing the same |
| CN102190846A (en) * | 2011-01-28 | 2011-09-21 | 上海锦湖日丽塑料有限公司 | Antiscratch resin and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10054053A1 (en) * | 2000-10-31 | 2002-05-29 | Roehm Gmbh | PMMA molding compounds with improved low-temperature impact strength |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1902233A (en) * | 2003-12-30 | 2007-01-24 | Lg化学株式会社 | Polymer latex having excellent impact-resistance and powder flow property and method for preparing the same |
| CN102190846A (en) * | 2011-01-28 | 2011-09-21 | 上海锦湖日丽塑料有限公司 | Antiscratch resin and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| PMMA增韧改性方法及机理;余林华等;《塑料科技》;20081031;第36卷(第10期);第96-99页 * |
| 伍雪强.有机玻璃的增韧改性研究.《中国优秀硕士学位论文全文数据库》.2009,第15页，第29页，第44页4.4 MAAS橡胶体对有机玻璃的增韧改性研究，第45页第1段，第49页最后一段. * |
| 余林华等.PMMA增韧改性方法及机理.《塑料科技》.2008,第36卷(第10期),第96-99页. * |
| 尹秀玲.浇铸型有机玻璃增韧改性研究.《化学工程师》.2007,第136卷(第1期),57-59. * |
| 有机玻璃的增韧改性研究;伍雪强;《中国优秀硕士学位论文全文数据库》;20091015;第15页，第29页，第44页4.4 MAAS橡胶体对有机玻璃的增韧改性研究，第45页第1段，第49页最后一段 * |
| 浇铸型有机玻璃增韧改性研究;尹秀玲;《化学工程师》;2007;第136卷(第1期);57-59 * |
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Owner name: SHENZHEN XINHENGLI TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: PENG ZHENCAI Effective date: 20150212 |
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Effective date of registration: 20150212 Address after: 518115 10 Longgang community road, Henggang District, Shenzhen City, Guangdong Province, No. 505, six Patentee after: SHENZHEN XIN HENGLI SCIENCE AND TECHNOLOGY Ltd. Address before: Henggang Longgang District of Shenzhen City, Guangdong province 518000 about six dragon shenhuiroad Village No. 433 Patentee before: Peng Zhencai |
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