CN102051034B - Polycarbonate composite with low gloss and high heat resistance - Google Patents
Polycarbonate composite with low gloss and high heat resistance Download PDFInfo
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- CN102051034B CN102051034B CN 200910198012 CN200910198012A CN102051034B CN 102051034 B CN102051034 B CN 102051034B CN 200910198012 CN200910198012 CN 200910198012 CN 200910198012 A CN200910198012 A CN 200910198012A CN 102051034 B CN102051034 B CN 102051034B
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Abstract
The invention discloses a polycarbonate composite, in particular to a polycarbonate composite with low gloss and high heat resistance, belonging to the macromolecular composite field. The polycarbonate composite with low gloss and high heat resistance comprises the following components in parts by weight: 35-85 parts of polycarbonate, 0-45 parts of acrylonitrile-butadiene-styrene (ABS) copolymer obtained through bulk polymerization, 5-25 parts of polyethylene terephthalate (PET) resin and 0.2-10 parts of epoxide. The polycarbonate composite prepared by the technical scheme of the invention has low gloss, high impact resistance and good heat resistance; and the composite has good fluidity and can be filled easily to form a large-size mould. The polycarbonate composite can be used for various automotive interior parts 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 heat polycarbonates composition, belongs to the polymer composite field.
Background technology
Polycarbonate (PC) plastics have the thermotolerance height, and transparency is good, and gloss is high, the advantages such as good toughness, but its poor fluidity, difficult forming; Goods are responsive to breach, produce easily stress cracking; Not anti-solvent, and expensive.
The method that has many known passing through to prepare the PC polyblend is improved these shortcomings, and wherein the PC/ABS polyblend is modal method, and it is low that the PC/ABS alloy has melt viscosity, good processability, the high good over-all properties of shock strength.
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 large on performance and the sensation impact of automotive upholstery, and in general, automobile original equipment manufacturer (OEM) is ready to arrange the glossiness target of 60 degree.
One of method that reduces PC/ABS composition gloss is the size of rubber grain in the control ABS resin, for example US Patent No. 4677162 and US 4526926 pass through the use mass polymerization, and the ABS resin that contains larger rubber grain reaches the purpose that reduces PC/ABS composition gloss.Adopt this method limited for the reduction effect of gloss.
Other method that reduces PC/ABS composition gloss comprises introduces polyepoxides or the vinylbenzene of gelation and the multipolymer of vinyl cyanide etc.For example US Patent No. 4761463, US 4835215 and US 5026277 disclose the method for having used the method that contains unsaturated acid glycidyl ester (GMA) and other epoxy compounds to obtain low gloss ABS composition, but when the addition of the styrene-acrylonitrile copolymer of polyepoxides or gelation was increased to a certain degree, resulting composition may produce demixing phenomenon.
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 heat polycarbonates composition, to solve defects of the prior art.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of low gloss, high heat polycarbonates composition comprise acrylonitrile-butadiene-styrene copolymer (ABS), pet resin (PET) and the epoxy compounds of polycarbonate, mass polymerization; Described polycarbonate is 35～85 weight parts, and the Acrylonitrile Butadiene—Styrene copolymer of mass polymerization is 0～45 weight part, and pet resin is 5～25 weight parts, and epoxide is 0.2～10 weight part.
Described polycarbonate is the bisphenol A-type aromatic copolycarbonate.In preferred embodiments, polycarbonate 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 of the present invention is 20000-40000g/mol, and polycarbonate of the present invention is known and can obtains by 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.
The limiting viscosity of described pet resin is 0.7-1.0.
Described composition also can comprise tinting material, filler, thermo-stabilizer, static inhibitor, lubricant etc.
The polycarbonate compositions for preparing by technical scheme 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
The present invention will be further described below in conjunction with specific embodiment, but described embodiment only is used for explanation 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;
Pet resin PET-1, Japanese Toyo Boseki K.K, limiting viscosity is 0.76, trade mark RT533;
Pet resin PET-2 far spins industrial (Shanghai) Co., Ltd., and limiting viscosity is 0.86, trade mark CB-608S;
Pet resin PET-3, Japanese Toyo Boseki K.K, limiting viscosity is 1.0, trade mark RT560;
Epoxide 1: contain the ethylene-acrylate copolymer of epoxy-functional, E.I.Du Pont Company, trade mark Elvaloy PTW;
Epoxide 2: contain the chainextender of epoxy-functional, BASF AG, trade mark 4370S;
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
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 ℃/hour of temperature rise rates are tested under 5 kilograms of load.
Gloss: press ASTM D2457 method, diameter is 80 millimeters disk.
Embodiment 1-3 and comparative example 1-2:
After the PC of super-dry resin, styrene copolymer resin, pet resin, tinting material and other auxiliary agent mix by proportion of composing in the table 1, joining in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel.Each section of main barrel control temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, extrude material strip through the tank cooling after pelletizing obtain product.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 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| PC | 60 | 60 | 60 | 60 |
| Body ABS-1 | 35 | 15 | 26.7 | 19.5 |
| PET-2 | 20 | 10 | 20 | |
| Elvaloy PTW | 5 | 3 | ||
| 4370S | 0.3 | 0.5 | ||
| BMAT | 5 | |||
| Carbon black colorant | 0.5 | 0.5 | 0.5 | 0.5 |
| Test result | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Melting index (g/10min) | 9.5 | 15.2 | 19.1 | 13.1 |
| Flexural strength (MPa) | 84.5 | 90.2 | 81.3 | 83.2 |
| Modulus in flexure (MPa) | 2260 | 2270 | 2280 | 2320 |
| Notched Izod impact strength (J/m) | 510 | 542 | 677 | 526 |
| Vicat softening temperature (℃) | 124 | 125 | 123 | 126 |
| Gloss | 24 | 28 | 25 | 29 |
By as seen from Table 1, can when reaching low gloss, still keep excellent mechanics and processing characteristics by the PC/ABS alloy material of the present invention's preparation; With adopt disclosed technology and compare, as the amount of adding matting agent gelation styrene-acrylonitrile copolymer BMAT is when strengthening (comparative example 1), although can reach low 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 the PC of super-dry resin, styrene copolymer resin, pet resin, tinting material and other auxiliary agent mix by proportion of composing in the table 2, joining in twin screw extruder (screw diameter 35mm, the length-to-diameter ratio L/D=36) main barrel.Each section of main barrel control temperature (exporting from charging opening to head) is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, extrude material strip through the tank cooling after pelletizing obtain product.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 2 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| PC | 50 | 35 | 50 | 65 | 85 |
| Body ABS | 38 | 45 | 24.5 | 14.8 | |
| PET-1 | 20 | 5 | |||
| PET-3 | 18 | 25 | |||
| 4370S | 0.5 | 0.2 | |||
| Elvaloy PTW | 12 | 2 | 10 | ||
| Carbon black colorant | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Test result | Comparative example 2 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Flexural strength (MPa) | Layering | 76.3 | 83.5 | 86.1 | 90.4 |
| Modulus in flexure (MPa) | 2380 | 2420 | 2440 | 2220 | |
| Notched Izod impact strength (J/m) | 426 | 518 | 721 | 656 | |
| Vicat softening temperature (℃) | 109 | 117 | 125 | 134 | |
| Gloss | 27 | 18 | 29 | 24 |
By as seen from Table 2, when various different PC content, the PC/ABS alloy material that is prepared by the present invention can both reach low luster effect, has still kept excellent mechanics and processing characteristics simultaneously; But when polyepoxides PTW addition when being increased to a certain degree, although can reach low luster effect, resulting composition produces demixing phenomenon, shows the mechanical mechanics property of material and resistance toheat descend (comparative example 2).
The object of the invention provides a kind of low gloss, high heat polycarbonates composition.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 (1)
1. a low gloss, high heat polycarbonates composition, it is characterized in that: the raw material by following weight part forms PC 60, body ABS-1 26.7, PET-2 10, Elvaloy PTW 3,4370S 0.3, carbon black colorant 0.5,
Described body ABS-1 is the ABS resin that continuous bulk is produced, U.S. Dow chemical company, trade mark Magnum 3904;
Described PET-2 produces for far spinning industrial (Shanghai) Co., Ltd., and limiting viscosity is 0.86, trade mark CB-608S;
Described Elvaloy PTW is the ethylene-acrylate copolymer that contains epoxy-functional, and E.I.Du Pont Company produces;
Join screw diameter 35mm after will mixing by proportion of composing through the raw material of super-dry, in the twin screw extruder main barrel of length-to-diameter ratio L/D=36; Each section of main barrel control temperature export from charging opening to head and is respectively 210 ℃, 240 ℃, 260 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins, and pelletizing obtains product after extruding material strip and cooling off through tank.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554883A (en) * | 2013-10-26 | 2014-02-05 | 安徽省富光实业股份有限公司 | ABS (acrylonitrile-butadiene-styrene) modified polycarbonate material for water cup shells and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863753B (en) * | 2012-09-13 | 2014-06-04 | 江苏安格特新材料科技有限公司 | Matte PCABS (polycarbonate acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN103059537B (en) * | 2012-11-20 | 2015-06-03 | 广东波斯科技股份有限公司 | High-rigidity high-fluidity PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) alloy and preparation method thereof |
| CN103525056A (en) * | 2013-10-25 | 2014-01-22 | 安徽省富光实业股份有限公司 | Composite polycarbonate material for water cup shell and preparation method of composite polycarbonate material |
| CN104559110B (en) * | 2014-12-29 | 2017-01-11 | 浙江俊尔新材料股份有限公司 | PC/PET (polycarbonate/polyethylene terephthalate) alloy material and preparation method thereof |
| CN107541040A (en) * | 2016-06-29 | 2018-01-05 | 中国石油天然气股份有限公司 | PC/ABS/PPET copolyester alloy and preparation method thereof |
| CN110088195B (en) | 2016-12-28 | 2022-09-06 | 科思创德国股份有限公司 | Compositions and thermoplastic moulding materials having good low-temperature toughness, high gloss and high processing stability |
| EP3562883B1 (en) * | 2016-12-28 | 2021-02-24 | Covestro Intellectual Property GmbH & Co. KG | Composition and thermoplastic molding compound having reduced gloss and good chemical resistance |
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| CN1106827A (en) * | 1993-12-10 | 1995-08-16 | 通用电气公司 | A multi-stage bulk process with grafting, phase inversion and crosslinking control for the preparation of ABS graft copolymers |
| CN101180364A (en) * | 2005-05-23 | 2008-05-14 | 通用电气公司 | Low gloss thermoplastic composition |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1106827A (en) * | 1993-12-10 | 1995-08-16 | 通用电气公司 | A multi-stage bulk process with grafting, phase inversion and crosslinking control for the preparation of ABS graft copolymers |
| CN101180364A (en) * | 2005-05-23 | 2008-05-14 | 通用电气公司 | Low gloss thermoplastic composition |
Non-Patent Citations (1)
| Title |
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| JP特开2008-88334A 2008.04.17 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554883A (en) * | 2013-10-26 | 2014-02-05 | 安徽省富光实业股份有限公司 | ABS (acrylonitrile-butadiene-styrene) modified polycarbonate material for water cup shells and preparation method thereof |
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Effective date of registration: 20190202 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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