CN101469117B - Hydrolysis resistant, high tenacity and uvioresistant polycarbonate composition - Google Patents
Hydrolysis resistant, high tenacity and uvioresistant polycarbonate composition Download PDFInfo
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- CN101469117B CN101469117B CN 200710172914 CN200710172914A CN101469117B CN 101469117 B CN101469117 B CN 101469117B CN 200710172914 CN200710172914 CN 200710172914 CN 200710172914 A CN200710172914 A CN 200710172914A CN 101469117 B CN101469117 B CN 101469117B
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Abstract
The invention discloses a polycarbonate composition with hydrolysis resistance, high toughness and ultraviolet resistance, which comprises the following components by weight proportion: 40 to 85 portions of polycarbonate, 10 to 55 portions of bulk polymerized acrylonitrile-butadiene-phenethylene graft copolymer (ABS), 2 to 10 portions of acrylate grafting rubber, 0.2 to 2 portions of titanium pigment or carbon soot, and 0.3 to 1 portion of oxidation-resistant stabilizing agent. The PC composition has high toughness, and simultaneously has good high-temperature hydrolysis resisting property and long-term ultraviolet radiation resisting property.
Description
Technical field
The present invention relates to a kind of polycarbonate compositions, be specially a kind of hydrolysis, H.T., uvioresistant polycarbonate composition, belong to the polymer composite field.
Background technology
Polycarbonate (PC) plastics have the thermotolerance height, and transparency is good, and gloss is high, advantages such as good toughness, but it is mobile poor, difficult forming; Goods are responsive to breach, are easy to generate stress cracking; Not anti-solvent, and cost an arm and a leg.
Have and manyly knownly improve these shortcomings through the method for preparing the PC polyblend; Wherein the PC/ABS polyblend is modal method; For example U.S. Pat 3130177, US4624986 etc. have obtained high impact toughness and have improved mobile low-cost PC/ABS polyblend compsn through the blending technology with ABS and PC.
When the PC/ABS blend composition being applied to long-term exposure under the occasion of hot and humid degree and/or the long-term direct irradiation of sunlight; Like Guangdong Coastal area, China Fujian and country in Southeast Asia; And during plastic items such as automobile such as tank shell, test board and electronic apparatus shell; When often requiring this material still to keep good comprehensive performances such as shock strength height, have excellent hydrolysis stability and good anti-ultraviolet radiation performance.Yet the thermostability of polycarbonate and anti-ultraviolet radiation performance are often owing to the ABS graft rubber that adds is affected.
Summary of the invention
The object of the invention provides a kind of H.T., has a polycarbonate compositions of good damp and hot and ultraviolet light stability simultaneously.
The object of the invention can be realized through following technical scheme:
A kind of hydrolysis, H.T., uvioresistant polycarbonate composition comprise acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), esters of acrylic acid graft rubber, white titanium pigment or the carbon black and the antioxidant stabilizer of polycarbonate, mass polymerization; Described polycarbonate is 40～85 weight parts; The acrylonitrile-butadiene-phenylethene grafted copolymer mixture of mass polymerization is 10～55 weight parts; The esters of acrylic acid graft rubber is 2～10 weight parts, and white titanium pigment or carbon black are 0.2～2 weight part, antioxidant stabilizer 0.3～1 weight part.
Described polycarbonate is the bisphenol A-type aromatic copolycarbonate.
In preferred embodiments, polycarbonate resin component of the present invention is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.
In preferred embodiments, the weight-average molecular weight of polycarbonate resin of the present invention is 20000-40000g/mol, and polycarbonate resin of the present invention is known and can obtains through a plurality of commercial source.
The ABS that the acrylonitrile-butadiene-phenylethene grafted copolymer of described mass polymerization (ABS) is produced for the continuous bulk polymerization method.
In preferred embodiments, mass polymerization ABS melting index of the present invention is 4～25g/10min, and mass polymerization ABS resin of the present invention is known and can obtains through a plurality of commercial source.
Described esters of acrylic acid graft rubber is selected from the esters of acrylic acid graft rubber ACR with nucleocapsid structure or the methacrylate butadi ene styrene copolymer with nucleocapsid structure and connects among the skill rubber MBS one or more.
Described antioxidant stabilizer is the mixture of Hinered phenols antioxidant and phosphite ester kind antioxidant.
Described compsn also can comprise tinting material, filler, thermo-stabilizer, static inhibitor, lubricant etc.
PC compsn of the present invention has H.T., has good high-temperature anti-hydrolytic performance and long-term ultraviolet radiation resisting performance simultaneously.Hydrolysis of the present invention, H.T., uvioresistant polycarbonate composition can be used under the mal-conditions such as hot and humid degree and/or the long-term direct irradiation of sunlight the various plastic parts that use, like fascia etc.
Embodiment
To combine specific embodiment below, the present invention is further specified, but said embodiment only is used to explain the present invention rather than restriction the present invention.
Embodiments of the invention adopt following material:
Polycarbonate-1, U.S. Dow chemical company, weight-average molecular weight is about 27,000, trade mark Calibre201-10;
Polycarbonate-2, U.S. Dow chemical company, weight-average molecular weight is about 30,000, trade mark Calibre301-5
Body ABS-1, U.S. Dow chemical company, melting index is 4.8g/10min, trade mark Magnum 3904;
Body ABS-2, U.S. Dow chemical company, melting index is 21g/10min, trade mark Magnum 342EZ;
Latex A BS, LG chemical company, melting index is 15g/10min, trade mark HI-130;
Esters of acrylic acid nucleocapsid structure graft rubber ACR, Rohm-Hass company, EXL-2330;
Methacrylate butadi ene styrene copolymer meets skill rubber MBS, Rohm-Hass company, EXL-2691A;
White titanium pigment, U.S. Dupont company, DLS-210;
Carbon black, Cabot company, BP800;
Oxidation inhibitor, Dover chemical company, Dovernox D-731, the mixture of hindered phenol antioxygen and phosphite ester kind antioxidant.
The product performance testing method:
Melting index: press ASTM D1238 method, 260 ℃, test under 5 kilograms of load
Bending property: press ASTM D790 method, trial speed 2 mm/min.
IZOD notched Izod impact strength: press ASTM D256 method, the sample of 3.2 mm thick.
Anti-hydrolytic performance: product pellet at 120 ℃, is handled under 100% the relative humidity after 48 hours, the variation percentage of test melting index, the more little anti-hydrolytic performance of velocity of variation is good more.
The xenon lamp accelerated deterioration: press SAE J1885 method, irradiation energy is 263kJ/m
2, measure aberration Δ E value.
Embodiment 1-3 and comparative example 1:
After mixing by proportion of composing in the table 1, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, ABS, esters of acrylic acid graft rubber, tinting material and other auxiliary agent.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.Said product is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result is seen table 1.
Table 1:
| Form | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| PC-1 | 65 | 40 | 65 | 85 |
| Body ABS-1 | 55 | 30 | 10 | |
| Latex A BS | 35 | |||
| MBS | 5 | 5 | 5 | |
| Carbon black | 1 | 1 | 1 | 1 |
| Oxidation inhibitor D-731 | 0.5 | 0.5 | 0.5 | |
| Test result | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Melting index (g/10min) | 28.6 | 22.7 | 12.8 | 10.6 |
| Modulus in flexure (MPa) | 2360 | 2160 | 2280 | 2070 |
| Notched Izod impact strength (J/m) | 520 | 676 | 617 | 561 |
| The variation of melting index after the hydrolysis | 110 | 18 | 26 | 29 |
| Xenon lamp aging performance (Δ E) | 4.2 | 2.1 | 1.8 | 1.7 |
Visible by table 1, very little by the variation of melting index before and after the PC/ABS composition material hydrolysis of the present invention's preparation, aberration Δ E≤3 behind the xenon lamp aging show that this alloy material has excellent hydrolysis stability and good anti-ultraviolet radiation performance simultaneously.
Embodiment 4-8:
After mixing by proportion of composing in the table 2, join in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel through exsiccant PC resin, body ABS, esters of acrylic acid graft rubber, tinting material and other auxiliary agent.Each section of main barrel controlled temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and the extruded stock bar obtains product through tank cooling back pelletizing.Said product is injection molded into standard batten with plastic-injection moulding machine in 85 ℃ of dryings after 5 hours in convection oven, 250 ℃ of injection temperatures.The batten of injection formed is in 50% relative humidity, and performance test is carried out in 23 ℃ of placements at least after 24 hours.Actual test result is seen table 2.
Table 2:
| Form | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| PC-2 | 60 | 80 | 40 | 65 | 85 |
| Body ABS-2 | 30 | 18 | 55 | 30 | 10 |
| MBS | 10 | 2 | |||
| ACR | 5 | 5 | 5 | ||
| White titanium pigment | 1 | 1 | 2 | 1 | 0.2 |
| Oxidation inhibitor D-731 | 0.3 | 0.9 | 0.5 | 0.5 | 0.5 |
| Test result | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Melting index (g/10min) | 23.6 | 22.7 | 12.8 | 10.6 | 11.2 |
| Modulus in flexure (MPa) | 2060 | 2160 | 2280 | 2070 | 2340 |
| Notched Izod impact strength (J/m) | 620 | 676 | 617 | 561 | 516 |
| The variation of melting index after the hydrolysis | 12 | 25 | 21 | 22 | 32 |
| Xenon lamp aging performance (Δ E) | 2.2 | 2.1 | 1.2 | 1.1 | 0.7 |
PC compsn of the present invention has H.T., has good high-temperature anti-hydrolytic performance and long-term ultraviolet radiation resisting performance simultaneously.Hydrolysis of the present invention, H.T., uvioresistant polycarbonate composition can be used under the mal-conditions such as hot and humid degree and/or the long-term direct irradiation of sunlight the various plastic parts that use, like fascia etc.
Claims (9)
1. a hydrolysis, H.T., uvioresistant polycarbonate composition comprise acrylonitrile-butadiene-phenylethene grafted copolymer, esters of acrylic acid graft rubber, white titanium pigment or the carbon black and the antioxidant stabilizer of polycarbonate, mass polymerization; Described polycarbonate is 40～85 weight parts; The acrylonitrile-butadiene-phenylethene grafted copolymer mixture of mass polymerization is 10～55 weight parts; The esters of acrylic acid graft rubber is 2～10 weight parts, and white titanium pigment or carbon black are 0.2～2 weight part, antioxidant stabilizer 0.3～1 weight part.
2. a kind of hydrolysis according to claim 1, H.T., uvioresistant polycarbonate composition is characterized in that: described polycarbonate is the bisphenol A-type aromatic copolycarbonate.
3. a kind of hydrolysis according to claim 2, H.T., uvioresistant polycarbonate composition is characterized in that: polycarbonate resin component is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.
4. a kind of hydrolysis according to claim 1, H.T., uvioresistant polycarbonate composition is characterized in that: the weight-average molecular weight of polycarbonate resin is 20000-40000.
5. a kind of hydrolysis according to claim 1, H.T., uvioresistant polycarbonate composition is characterized in that: the acrylonitrile-butadiene-phenylethene grafted copolymer that the acrylonitrile-butadiene-phenylethene grafted copolymer of described mass polymerization is produced for the continuous bulk polymerization method.
6. a kind of hydrolysis according to claim 1, H.T., uvioresistant polycarbonate composition is characterized in that: the acrylonitrile-butadiene-phenylethene grafted copolymer melting index of mass polymerization is 4～25g/10min.
7. a kind of hydrolysis according to claim 1, H.T., uvioresistant polycarbonate composition is characterized in that: one or more among the methacrylate butadi ene styrene copolymer graft rubber MBS that described esters of acrylic acid graft rubber is selected from the esters of acrylic acid graft rubber ACR with nucleocapsid structure or has nucleocapsid structure.
8. a kind of hydrolysis according to claim 1, H.T., uvioresistant polycarbonate composition is characterized in that: described antioxidant stabilizer is the mixture of Hinered phenols antioxidant and phosphite ester kind antioxidant.
9. a kind of hydrolysis according to claim 1, H.T., uvioresistant polycarbonate composition is characterized in that: described compsn also comprises tinting material, filler, thermo-stabilizer, static inhibitor, lubricant.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101787193B (en) * | 2009-10-20 | 2012-07-04 | 上海锦湖日丽塑料有限公司 | PC/ABS alloy with excellent hydrolysis resistance and preparation method thereof |
| CN102153850B (en) * | 2011-05-17 | 2012-12-26 | 天津戈瑞德新材料科技有限公司 | High-impact-resistance polyester composite material and preparation method thereof, manufacturing method of toe cap |
| CN103351591A (en) * | 2013-07-10 | 2013-10-16 | 深圳市兴盛迪新材料有限公司 | Cold-resistant polycarbonate/acrylonitrile-phenethylene-butadiene alloy and preparation method thereof |
| CN103804878A (en) * | 2014-02-26 | 2014-05-21 | 苏州市涵信塑业有限公司 | Shell for household appliance |
| CN104559116B (en) * | 2015-01-19 | 2017-01-04 | 苏州银禧科技有限公司 | A kind of controllable high whiteness PC/ABS alloy material and preparation method thereof |
| WO2017186663A1 (en) * | 2016-04-27 | 2017-11-02 | Covestro Deutschland Ag | Anti-static thermoplastic molding materials |
| KR102120397B1 (en) | 2016-08-31 | 2020-06-08 | 주식회사 엘지화학 | Method of preparation for polycarbonate |
| CN114634694B (en) * | 2022-02-18 | 2023-08-29 | 金发科技股份有限公司 | High-temperature-resistant well-cooked PC material, and preparation method and application thereof |
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| US20070137141A1 (en) * | 2005-11-30 | 2007-06-21 | Hirschmann Car Communication Gmbh | Integration of functional layers in or on transparent plastic parts for vehicle manufacture |
| CN101077925A (en) * | 2006-05-26 | 2007-11-28 | 佛山市顺德区汉达精密电子科技有限公司 | Modified formulation for high surface hardness PC-ABS resin |
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| US20070137141A1 (en) * | 2005-11-30 | 2007-06-21 | Hirschmann Car Communication Gmbh | Integration of functional layers in or on transparent plastic parts for vehicle manufacture |
| CN101077925A (en) * | 2006-05-26 | 2007-11-28 | 佛山市顺德区汉达精密电子科技有限公司 | Modified formulation for high surface hardness PC-ABS resin |
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| 陈燕 等.聚碳酸酯合成新方法的研究进展.《材料导报》.1997,第11卷(第1期),第57-61页. * |
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Effective date of registration: 20190212 Address after: 402560 No. 18 Longyun Road, Pulu Industrial Park, Tongliang District, Chongqing Co-patentee after: Shanghai Pret Compound Material Co., Ltd. Patentee after: CHONGQNG PRET NEW MATERIAL CO., LTD. Co-patentee after: ZHEJIANG PRET NEW MATERIAL CO., LTD. Address before: 200081 2nd Floor, 421 Lane, Siping Road, Hongkou District, Shanghai Patentee before: Shanghai Pret Compound Material Co., Ltd. |
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