CN101469120A - Low brightness, high impact and high flowablity polycarbonate composition - Google Patents
Low brightness, high impact and high flowablity polycarbonate composition Download PDFInfo
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- CN101469120A CN101469120A CNA2007101729216A CN200710172921A CN101469120A CN 101469120 A CN101469120 A CN 101469120A CN A2007101729216 A CNA2007101729216 A CN A2007101729216A CN 200710172921 A CN200710172921 A CN 200710172921A CN 101469120 A CN101469120 A CN 101469120A
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Abstract
The invention discloses a polycarbonate composition with low gloss, high impact resistance and high fluidity, which comprises the following components by weight portion: 40 to 85 portions of polycarbonate, 10 to 55 portions of phenethylene based resin, 2 to 5 portions of ethylene-acrylate copolymer elastomer, and 1 to 3 portions of gelated copolymer of phenethylene and acrylonitrile. The PC plastic alloy has the advantages of low gloss, high impact resistance, good heat resistance and good fluidity, is easy to fill and form large-sized moulds, and can be used for various internal decorative pieces of automobiles and the like.
Description
Technical field
The present invention relates to a kind of polycarbonate (PC) composition, especially is a kind of low gloss, high-impact, the high polycarbonate compositions that flows, and belongs to the polymer composite field.
Background technology
Polycarbonate (PC) plastics have the thermotolerance height, and transparency is good, the gloss height, and advantages such as good toughness, but it is mobile poor, difficult forming; Goods are easy to generate stress cracking to the breach sensitivity; Not anti-solvent, and cost an arm and a leg.
Have and manyly knownly improve these shortcomings by the method for preparing the PC polyblend, wherein the PC/ABS polyblend is modal method, and it is low that the PC/ABS alloy has melt viscosity, good processability, good comprehensive performances such as shock strength height.
In the various application scenarios of PC/ABS blend composition, the products appearance that often requires to be made by this material has low gloss.For example the gloss appearance of automobile plastic inner-decoration component is very big to the performance and the sensation influence of automotive upholstery, and in general, the automobile original equipment manufacturer (OEM) is ready to be provided with the glossiness target of 60 degree.
Reducing one of PC/ABS composition glossy method is the size of rubber grain in the control ABS resin, for example U.S. Pat 4677162 and US 4526926 pass through the use mass polymerization, and the ABS resin that contains big rubber grain reaches and reduces PC/ABS composition glossy purpose.It is limited to adopt this method to reduce effect for glossy.
Reduce other method of PC/ABS composition glossy and comprise introducing polyepoxides or the vinylbenzene of gelation and the multipolymer of vinyl cyanide etc.For example U.S. Pat 4761463, US 4835215 and US 5026277 disclose and have used the method that contains unsaturated acid glycidyl ester (GMA) and other epoxy compounds to obtain low gloss ABS method for compositions, but the shortcoming that adopts these methods is the melt viscosity that has increased composition, and is very unfavorable to the forming process of material.
Summary of the invention
The object of the invention provides a kind of low gloss, high-impact, the high polycarbonate compositions that flows.To solve above-mentioned defective of the prior art.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of low gloss, high-impact, the high polycarbonate compositions composition that flows comprise the vinylbenzene of polycarbonate, styrene base resin, ethylene-acrylate copolymer elastomerics and gelation and the multipolymer of vinyl cyanide.Described polycarbonate is 40～85 weight parts, and styrene resin is 10～55 weight parts, and the ethylene-acrylate copolymer elastomerics is 2～5 weight parts, and the vinylbenzene of gelation and the multipolymer of vinyl cyanide are 1～3 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 by a plurality of commercial source.
Described styrene base resin is selected from a kind of in the graft resin of the multipolymer of multipolymer, vinylbenzene or the vinylbenzene of vinylbenzene that mass polymerization obtains or vinylbenzene and vinyl monomer and vinyl monomer and diene rubber.
The typical example of used styrene base resin of the present invention comprises: mass polymerization ABS (third rare nitrile-butadiene-styrene copolymer), SAN (the rare lonitrile copolymer of vinylbenzene-third), and their miscellany.
It is in 16～30% ethylene-acrylate copolymers one or more that described ethylene-acrylic acid ester elastomer is selected from acrylate content.
Described ethylene-acrylate copolymer elastomerics is selected from ethylene-methyl acrylate multipolymer EMA, ethylene-acrylate butyl ester multipolymer EBA and their miscellany.
The multipolymer of described gelation styrene-acrylonitrile is selected from BMAT.
Described composition also can comprise tinting material, filler, thermo-stabilizer, static inhibitor, lubricant etc.
PC polyblend of the present invention has low gloss, high-impact and good thermotolerance; Simultaneously, mobile good, be easy to filling shaping large size mould.Can be used for various automotive upholsteries etc.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but described embodiment only is used to illustrate the present invention rather than restriction the present invention.
Embodiments of the invention adopt following material:
Polycarbonate, U.S. Dow chemical company, weight-average molecular weight is about 27,000, trade mark Calibre201-10;
ABS resin, continuous bulk production, U.S. Dow chemical company, trade mark Magnum 3904;
Ethylene-acrylate butyl ester multipolymer EBA, ARKAMA company, trade mark 17BA04, acrylate content is 16%;
Ethylene-methyl acrylate multipolymer EMA-1, Dupont company, trade mark AC1125, acrylate content is 25%;
Ethylene-methyl acrylate multipolymer EMA-1, Arkama company, trade mark 29MA03, acrylate content is 30%;
The multipolymer of gelation styrene-acrylonitrile, GE company, trade mark BMAT
Oxidation inhibitor, tetramethylolmethane stearic bicine diester bis-phosphite, GE plastics fine chemicals, Weston 619F.
Carbon black colorant, Cabot company, trade mark BP800
The product performance testing method:
Melting index: press ASTM D1238 method, 260 ℃, test under 5 kilograms of load
Tensile property: press ASTM D638 method, draw speed 50 mm/min.
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.
Vicat softening temperature: press ASTM D1525 method, 50 ℃/minute of temperature rise rates are tested under 5 kilograms of load.
Gloss: press ASTM D2457 method, diameter is 80 millimeters a disk.
Embodiment 1-3 and comparative example 1-2:
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, styrene copolymer resin, ethylene-acrylate copolymer elastomerics, 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.The said products 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 sees Table 1.
Table 1:
| Form | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| PC | 65 | 65 | 65 | 65 | 65 |
| Body ABS | 35 | 30 | 30 | 30 | 30 |
| EMA-1 | 4 | ||||
| EMA-2 | 4 | ||||
| EBA | 4 | ||||
| BMAT | 5 | 1 | 1 | 1 | |
| Carbon black colorant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Stablizer 619F | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Test result | Comparative example 1 | Comparative example 2 | Embodiment | Embodiment 2 | Embodiment 3 |
| Melting index | 18.2 | 9.7 | 20.5 | 26.6 | 22.7 |
| Tensile strength (MPa) | 54.3 | 53.5 | 52.3 | 50.6 | 52.6 |
| Flexural strength (MPa) | 82.5 | 86.2 | 78.3 | 75.8 | 79.1 |
| Modulus in flexure (MPa) | 2260 | 2370 | 2180 | 2020 | 2180 |
| Notched Izod impact strength | 520 | 536 | 667 | 726 | 627 |
| Vicat softening temperature | 124.4 | 120.1 | 123 | 120.2 | 123.3 |
| Gloss | 73 | 28 | 35 | 39 | 37 |
By table 1 as seen, with the disclosed technology of employing, compare (comparative example 1) by PC with the PC/ABS alloy material that substance law ABS produces, the PC/ABS alloy material that is prepared by the present invention can reach lower gloss, has still kept excellent mechanics and processing characteristics simultaneously; Simultaneously, when the addition of gelation styrene-acrylonitrile copolymer BMAT further strengthens (comparative example 2), though can reach lower luster effect, the melting index of composition sharply reduces, and shows that the processing flowability of material worsens.
Embodiment 4-7 and comparative example 3:
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, styrene copolymer resin, ethylene-acrylate copolymer elastomerics, 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.The said products 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 sees Table 2.
Table 2:
| Form | Comparative example 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| PC | 55 | 40 | 55 | 70 | 85 |
| Body ABS | 35 | 55 | 40 | 24 | 10 |
| EMA-1 | 8 | 2 | 3 | 5 | 3 |
| BMAT | 2 | 3 | 2 | 1 | 2 |
| Carbon black colorant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Stablizer 619F | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Test result | Comparative example 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Melting index | 29.7 | 26.2 | 25.1 | 24.9 | 20.5 |
| Tensile strength (MPa) | 46.5 | 47.8 | 51.6 | 56.2 | 58.6 |
| Flexural strength (MPa) | 72.2 | 75.3 | 76.5 | 83.1 | 88.4 |
| Modulus in flexure (MPa) | 2070 | 2280 | 2220 | 2240 | 2320 |
| Notched Izod impact strength | 736 | 646 | 668 | 743 | 656 |
| Vicat softening temperature | 110.1 | 109 | 117.2 | 125.2 | 134 |
| Gloss | 36 | 32 | 35 | 39 | 38 |
By table 2 as seen, when various different PC content, can both reach low luster effect, still keep excellent mechanics and processing characteristics simultaneously by the PC/ABS alloy material of the present invention's preparation; But when the addition of ethylene-acrylate copolymer elastomerics EMA further strengthens, though can reach low luster effect, the tensile strength of composition and vicat softening temperature but all sharply reduce, and show the mechanical mechanics property and the resistance toheat decline (comparative examples 3 and embodiment 5) of material.
The object of the invention provides a kind of low gloss, high-impact, the high polycarbonate compositions that flows.PC polyblend of the present invention has low gloss, high-impact and good thermotolerance; Simultaneously, mobile good, be easy to filling shaping large size mould.Can be used for various automotive upholsteries etc.
Claims (10)
1, a kind of low gloss, high-impact, the high polycarbonate compositions that flows comprise the vinylbenzene of polycarbonate, styrene base resin, ethylene-acrylate copolymer elastomerics and gelation and the multipolymer of vinyl cyanide.Described polycarbonate is 40～85 weight parts, and styrene resin is 10～55 weight parts, and the ethylene-acrylate copolymer elastomerics is 2～5 weight parts, and the vinylbenzene of gelation and the multipolymer of vinyl cyanide are 1～3 weight part.
2, a kind of low gloss according to claim 1, high-impact, the high polycarbonate compositions that flows, it is characterized in that: described polycarbonate is the bisphenol A-type aromatic copolycarbonate.
3, a kind of low gloss according to claim 2, high-impact, the high polycarbonate compositions that flows, it is characterized in that: in preferred embodiments, polycarbonate resin component of the present invention is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.
4, a kind of low gloss according to claim 1, high-impact, the high polycarbonate compositions that flows, it is characterized in that: the weight-average molecular weight of described polycarbonate resin is 20000-40000g/mol.
5, a kind of low gloss according to claim 1, high-impact, the high polycarbonate compositions that flows is characterized in that: described styrene base resin is selected from a kind of in the graft resin of the multipolymer of multipolymer, vinylbenzene or the vinylbenzene of vinylbenzene that mass polymerization obtains or vinylbenzene and vinyl monomer and vinyl monomer and diene rubber.
6, a kind of low gloss according to claim 5, high-impact, the high polycarbonate compositions that flows, it is characterized in that: used styrene base resin is: mass polymerization ABS, SAN and their miscellany.
7, a kind of low gloss according to claim 1, high-impact, the high polycarbonate compositions that flows is characterized in that: it is in 16～30% ethylene-acrylate copolymers one or more that described ethylene-acrylic acid ester elastomer is selected from acrylate content.
8, a kind of low gloss according to claim 7, high-impact, the high polycarbonate compositions that flows, it is characterized in that: described ethylene-acrylate copolymer elastomerics is selected from ethylene-methyl acrylate multipolymer EMA, ethylene-acrylate butyl ester multipolymer EBA and their miscellany.
9, a kind of low gloss according to claim 1, high-impact, the high polycarbonate compositions that flows, it is characterized in that: the multipolymer of described gelation styrene-acrylonitrile is selected from BMAT.
10, a kind of low gloss according to claim 1, high-impact, the high polycarbonate compositions that flows, it is characterized in that: described composition also comprises tinting material, filler, thermo-stabilizer, static inhibitor, lubricant.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120872A (en) * | 2011-01-31 | 2011-07-13 | 上海金发科技发展有限公司 | High-flowability easy-spraying high-heat-resistance polycarbonate (PC) composition and preparation method thereof |
| CN101787190B (en) * | 2009-09-21 | 2012-05-23 | 深圳市科聚新材料有限公司 | Flame-retarding environment-friendly high-intensity PC-AS composite material and preparation method thereof |
| CN102532737A (en) * | 2010-12-29 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Transparent high-hardness impact-resistant acrylonitrile butadiene styrene (ABS) plastic alloy composition |
| CN102108176B (en) * | 2009-12-25 | 2013-10-23 | 上海普利特复合材料股份有限公司 | ABS material with low gloss, high shock resistance, and high fluidity |
| CN103554867A (en) * | 2013-10-14 | 2014-02-05 | 上海俊尓新材料有限公司 | Low-VOC high-performance PC/ABS alloy material and its preparation and application |
| CN104403291A (en) * | 2014-11-28 | 2015-03-11 | 上海锦湖日丽塑料有限公司 | High-temperature and high-humidity resistant PC/ABS alloy composition and preparation method thereof |
| WO2016033992A1 (en) * | 2014-09-02 | 2016-03-10 | 金发科技股份有限公司 | Flame-retardant aromatic polycarbonate composition with low precipitate and favorable appearance |
| CN109836757A (en) * | 2017-11-27 | 2019-06-04 | 博富科技股份有限公司 | Low gloss low-density HI high impact high heat resistance PC/ABS alloy material and preparation method thereof |
| CN111138821A (en) * | 2018-11-06 | 2020-05-12 | 万华化学集团股份有限公司 | Thin-wall flame-retardant polycarbonate material and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2159351A1 (en) * | 1993-04-08 | 1994-10-27 | Henricus J.M. Van Dijk | Low gloss polymer blend compositions |
| EP0635547A3 (en) * | 1993-07-23 | 1995-05-10 | Gen Electric | Reduced gloss, flame retarded, high impact thermoplastic composition. |
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2007
- 2007-12-25 CN CN 200710172921 patent/CN101469120B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787190B (en) * | 2009-09-21 | 2012-05-23 | 深圳市科聚新材料有限公司 | Flame-retarding environment-friendly high-intensity PC-AS composite material and preparation method thereof |
| CN102108176B (en) * | 2009-12-25 | 2013-10-23 | 上海普利特复合材料股份有限公司 | ABS material with low gloss, high shock resistance, and high fluidity |
| CN102532737A (en) * | 2010-12-29 | 2012-07-04 | 上海普利特复合材料股份有限公司 | Transparent high-hardness impact-resistant acrylonitrile butadiene styrene (ABS) plastic alloy composition |
| CN102532737B (en) * | 2010-12-29 | 2014-01-08 | 上海普利特复合材料股份有限公司 | Transparent high-hardness impact-resistant acrylonitrile butadiene styrene (ABS) plastic alloy composition |
| CN102120872A (en) * | 2011-01-31 | 2011-07-13 | 上海金发科技发展有限公司 | High-flowability easy-spraying high-heat-resistance polycarbonate (PC) composition and preparation method thereof |
| CN103554867A (en) * | 2013-10-14 | 2014-02-05 | 上海俊尓新材料有限公司 | Low-VOC high-performance PC/ABS alloy material and its preparation and application |
| WO2016033992A1 (en) * | 2014-09-02 | 2016-03-10 | 金发科技股份有限公司 | Flame-retardant aromatic polycarbonate composition with low precipitate and favorable appearance |
| CN104403291A (en) * | 2014-11-28 | 2015-03-11 | 上海锦湖日丽塑料有限公司 | High-temperature and high-humidity resistant PC/ABS alloy composition and preparation method thereof |
| CN104403291B (en) * | 2014-11-28 | 2016-04-27 | 上海锦湖日丽塑料有限公司 | PC/ABS alloy composite of a kind of high-temp resisting high-humidity resisting and preparation method thereof |
| CN109836757A (en) * | 2017-11-27 | 2019-06-04 | 博富科技股份有限公司 | Low gloss low-density HI high impact high heat resistance PC/ABS alloy material and preparation method thereof |
| CN111138821A (en) * | 2018-11-06 | 2020-05-12 | 万华化学集团股份有限公司 | Thin-wall flame-retardant polycarbonate material and preparation method and application thereof |
| CN111138821B (en) * | 2018-11-06 | 2022-09-16 | 万华化学集团股份有限公司 | Thin-wall flame-retardant polycarbonate material and preparation method and application thereof |
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| CN101469120B (en) | 2012-10-17 |
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Effective date of registration: 20131113 Address after: 200081, building 20, No. 421, Siping Road, Siping Road, Shanghai, Hongkou District, 2 Patentee after: Shanghai Pret Compound Material Co., Ltd. Patentee after: CHONGQNG PRET NEW MATERIAL CO., LTD. Address before: 200081, building 20, No. 421, Siping Road, Siping Road, Shanghai, Hongkou District, 2 Patentee before: Shanghai Pret Compound Material Co., Ltd. |
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Address after: 402560 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. Address before: 200081 2nd Floor, 421 Lane, Siping Road, Hongkou District, Shanghai Co-patentee before: CHONGQNG PRET NEW MATERIAL CO., LTD. Patentee before: Shanghai Pret Compound Material Co., Ltd. |