CN1237115C - 耐冲击改性聚碳酸酯组合物 - Google Patents
耐冲击改性聚碳酸酯组合物 Download PDFInfo
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- CN1237115C CN1237115C CNB018215696A CN01821569A CN1237115C CN 1237115 C CN1237115 C CN 1237115C CN B018215696 A CNB018215696 A CN B018215696A CN 01821569 A CN01821569 A CN 01821569A CN 1237115 C CN1237115 C CN 1237115C
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- Prior art keywords
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- composition
- component
- rubber
- vinyl
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- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 28
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 28
- 229920001971 elastomer Polymers 0.000 claims abstract description 43
- 239000005060 rubber Substances 0.000 claims abstract description 41
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 14
- 239000003365 glass fiber Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- -1 acrylic ester Chemical class 0.000 claims description 50
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 229920001519 homopolymer Polymers 0.000 claims 2
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 15
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 14
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- 239000006085 branching agent Substances 0.000 description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
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- 239000000206 moulding compound Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
- 150000001263 acyl chlorides Chemical class 0.000 description 7
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- 239000001294 propane Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
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- 239000001257 hydrogen Substances 0.000 description 4
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- 239000012764 mineral filler Substances 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 125000005587 carbonate group Chemical group 0.000 description 3
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
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- 239000002964 rayon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
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- 239000002562 thickening agent Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
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- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
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Abstract
本发明涉及一种包含硅氧烷丙烯酸酯接枝橡胶、基于乙烯基单体的(共)聚合物以及无机填料,特别是玻璃纤维,的聚碳酸酯组合物。
Description
技术领域
本发明涉及一种包含硅氧烷丙烯酸酯接枝橡胶和基于乙烯基单体的(共)聚合物以及无机填料,特别是玻璃纤维,的聚碳酸酯组合物。
背景技术
EP-A 663 425公开一种改进,特别是在低温下,冲击强度的方法,包括在具有规定结构的聚碳酸酯树脂中加入两种特定类型橡胶。该特定类型橡胶由一种包含聚有机硅氧烷和聚(甲基)丙烯酸烷基酯的接枝橡胶-复合物构成。玻璃纤维被概括为常规添加剂。
US-A 5,807,914公开一种包含EP-A 663 423中已提到的特定橡胶-复合物的玻璃纤维增强聚碳酸酯混合物,其中该混合物的特征在于采用了一种由常规聚碳酸酯与1~20wt%低聚芳族聚碳酸酯制备的聚碳酸酯混合物。该树脂混合物不同于US-A 5,807,914之处在于加工性好、表面结构、挺度和冲击强度都好。
公开内容
本发明的目的是改进热塑性组合物和由它生产的模塑件的老化稳定性,特别是热稳定性和表面质量乃至加工性。
现已发现,包含聚碳酸酯、硅氧烷丙烯酸酯接枝橡胶和基于乙烯基单体的(共)聚合物乃至无机填料,特别是玻璃纤维的组合物具有所要求的综合性能。
因此,本发明提供一种聚碳酸酯组合物,它包含,
A)40~95,优选45~90,尤其是55~80重量份芳族聚碳酸酯和/或聚酯碳酸酯
B)0~45,优选5~40,尤其优选10~35,最优选15~30重量份基于乙烯基单体的(共)聚合物
C)1~25,优选2~20,尤其是3~15重量份硅氧烷丙烯酸酯接枝橡胶以及
D)0.4~40,优选1~30,尤其优选3~20,特别是5~18重量份无机填料,
其中组分A~D之和是100。
组分A
按照适合本发明的组分A的芳族聚碳酸酯和/或芳族聚酯碳酸酯在文献中是已知的或者可采用文献中已知的方法制备(为制备芳族聚碳酸酯,例如可参见,Schnell,《聚碳酸酯化学与物理》,国际科学出版社,1964,以及DE-AS 1 495 626、DE-A 2 232877,DE-A 2 703 376、DE-A 2 714 544,DE-A 3 000 610、DE-A3 832 396;以及,例如DE-A 3 077 934,用于制备芳族聚酯碳酸酯)。
芳族聚碳酸酯例如可通过二酚与碳酸酰卤,优选与光气和/或与芳族二羧酸二酰卤,优选苯二甲酸二酰卤,按照界面法进行反应来制备,任选地配合使用链终止剂如一元酚并任选地配合使用三官能或更高官能度支化剂如三元酚或四元酚。
制备芳族聚碳酸酯和/或芳族聚酯碳酸酯的二酚优选是例如对应于通式(I)的那些
其中
A是单键、C1~C5-亚烷基、C2~C5-烷叉、C5~C6-环烷叉(cycloakyliden)、-O-、-SO-、-CO-、-S-、-SO2-、C6~C12-亚芳基,其上还可进一步稠合上任选包含杂原子的芳环,
或者对应于通式(II)或(III)的基团
B,每种情况下是C1~C12-烷基,优选甲基,卤素,优选氯和/或溴,
x,每种情况下彼此独立地是0、1或2,
p,是1或0以及
R5和R6对每个X1可单独选择并彼此独立地代表氢或C1~C6-烷基,优选氢、甲基或乙基,
X1代表碳,以及
m代表4~7的整数,优选4或5,条件是,R5和R6在至少一个原子X1上同时是烷基。
优选的二酚是氢醌、间苯二酚、二羟基联苯酚、双(羟苯基)-C1~C5-链烷烃、双(羟苯基)-C5~C6-环烷烃、双(羟苯基)醚、双(羟苯基)亚砜、双(羟苯基)酮、双(羟苯基)砜和α,α-双(羟苯基)二异丙基苯,及其在环上可溴化和/或在环上可氯化的衍生物。
尤其优选的二酚是4,4’-二羟基联苯、双酚A、2,4-双(4-羟苯基)-2-甲基丁烷、1,1-双(4-羟苯基)环己烷、1,1-双(4-羟苯基)-3,3,5-三甲基环己烷、4,4’-二羟基联苯硫醚、4,4’-二羟基二苯砜及其可二-和四溴化或氯化的衍生物,例如,2,2-双(3-氯-4-羟苯基)丙烷、2,2-双(3,5-二氯-4-羟苯基)丙烷或2,2-双(3,5-二溴-4-羟苯基)丙烷。
2,2-双(4-羟苯基)丙烷(双酚A)是尤其优选的。
二酚可单独或以任意混合物形式使用。
该二酚从文献中可知或者可通过文献中已知的方法制备。
适合制备热塑性芳族聚碳酸酯的链终止剂例如是,苯酚、对氯苯酚、对叔丁基苯酚或2,4,6-三溴苯酚,但也包括长链烷基酚如按照DE-A 2 842 005的4-(1,3-四甲基丁基)苯酚,或烷基取代基中具有总共8~20个碳原子的单烷基苯酚或二烷基苯酚,如3,5-二叔丁基苯酚、对异辛基苯酚、对叔辛基苯酚、对十二烷基苯酚、2-(3,5-二甲基庚基)苯酚和4-(3,5-二甲基庚基)苯酚。链终止剂的用量一般介于0.5mol%~10mol%之间,相对于每种情况中使用的二酚总摩尔数而言。
热塑性芳族聚碳酸酯的重均分子量(Mw,例如按超离心或光散射测定)介于10000~200000,优选15000~80000。
热塑性芳族聚碳酸酯可按已知方式实现支化,具体地说优选通过结合进0.05~2.0mol%,相对于二酚总用量而言,三官能或更高官能度化合物,例如,具有3或更多酚羟基基团的那些。
不论均聚碳酸酯抑或共聚碳酸酯都适合。还可使用1~25wt%,优选2.5~25wt%(相对于要使用的二酚总量)以羟基-芳氧基基团为链端的聚二有机硅氧烷来制备对应于本发明组分A的共聚碳酸酯。它们是已知的(例如参见US-A 3 419 634)或可按文献中已知的方法制备。包含聚二有机硅氧烷的共聚碳酸酯的制备例如描述在DE-A 3 334 782中。
优选的聚碳酸酯是,除了双酚A均聚碳酸酯之外,具有最高15mol%,相对于二酚总摩尔数而言,除了上面作为优选或特别优选而举出的那些之外的二酚,特别是2,2-双(3,5-二溴-4-羟苯基)丙烷,的双酚A共聚碳酸酯。
用于制备芳族聚酯碳酸酯的芳族二羧酸二酰卤优选是间苯二甲酸、对苯二甲酸、联苯醚-4,4’-二羧酸和萘-2,6-二羧酸的二酰氯。
尤其优选间苯二甲酸和对苯二甲酸的二酰氯按1∶20~20∶1比例的混合物。
碳酸酰卤,优选光气,优选作为双官能酸衍生物另外共用于聚酯碳酸酯的制备中。
除了上面已经提到的一元酚之外,其氯碳酸酯以及芳族一元羧酸的酰氯,其上可任选地取代上C1~C22-烷基基团或卤素原子者,乃至脂族C2~C22一元羧酸酰氯,被考虑作为制备芳族聚酯碳酸酯用的链终止剂。
链终止剂的用量,每种情况下介于0.1~10mol%,相对于每种情况下二酚摩尔数而言,若采用的是酚链终止剂,或者相对于二羧酸二酰氯而言,若采用的是一元羧酸酰氯链终止剂的话。
芳族聚酯碳酸酯还可包含结合的芳族羟基羧酸。
该芳族聚酯碳酸酯既可以是线型也可以是按已知方式支化的(关于这一点还可参见DE-A 2 940 024和DE-A 3 007 934)。
下面的化合物可用作支化剂:例如,三官能或更高官能度羧酸酰氯如1,3,5-苯三酸三酰氯、氰尿酸三酰氯、3,3’,4,4’-二苯酮四甲酸四酰氯、1,4,5,8-萘四甲酸四酰氯或1,2,4,5-苯四酸四酰氯,其用量介于0.01~1.0mol%(相对于二羧酸二酰氯的用量而言)或三官能或更高官能度酚,如间苯三酚、4,6-二甲基-2,4,6-三(4-羟苯基)-庚-2-烯、4,4-二甲基-2,4,6-三(4-羟苯基)庚烷、1,3,5-三(4-羟苯基)苯、1,1,1-三(4-羟苯基)乙烷、三(4-羟苯基)苯基甲烷、2,2-双[4,4-双(4-羟苯基)-环己基]丙烷、2,4-双(4-羟苯基异丙基)苯酚、四(4-羟苯基)-甲烷、2,6-双(2-羟基-5-甲基苄基)-4-甲基苯酚、2-(4-羟苯基)-2-(2,4-二羟苯基)丙烷、四(4-[4-羟苯基异丙基]-苯氧基)甲烷、1,4-双(4,4’-二羟基三苯基)甲基)苯,其用量介于0.01~1.0mol%,相对于二酚的用量而言。酚类支化剂可在首次进料中与使用的二酚一起引入,而酰氯支化剂则可随二酰氯一起引入。
热塑性芳族聚酯碳酸酯的碳酸酯结构单元含量可任意改变。碳酸酯基团含量优选最高100mol%,特别是最高80mol%,尤其优选最高50mol%,相对于酯基团与碳酸酯基团之和而言。芳族聚酯碳酸酯的酯和碳酸酯单元都可以嵌段形式存在或无规地分布在缩聚物中。
芳族聚碳酸酯和聚酯碳酸酯的溶液相对粘度(ηrel)介于1.18~1.4,优选1.20~1.32的范围(按0.5g聚碳酸酯或聚酯碳酸酯在100mL二氯甲烷溶液中的溶液在25℃测定)。
热塑性芳族聚碳酸酯和聚酯碳酸酯可单独或以任意混合物使用。
组分B
下面的化合物适合作为乙烯基(共)聚合物B):由至少一种选自乙烯基芳烃、乙烯基氰(不饱和腈)、(甲基)丙烯酸-(C1~C8)-烷基酯、不饱和羧酸以及不饱和羧酸衍生物(例如,酸酐和酰亚胺)的单体所制备的聚合物。特别合适的是由以下组分制成的(共)聚合物:
B.150~99,优选60~80重量份乙烯基芳烃和/或环上取代的乙烯基芳烃,例如并优选,苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、对氯苯乙烯)和/或甲基丙烯酸-(C1~C8)-烷基酯,例如并优选,甲基丙烯酸甲酯、甲基丙烯酸乙酯),以及
B.21~50,优选20~40重量份乙烯基氰(不饱和腈),例如,丙烯腈和甲基丙烯腈和/或(甲基)丙烯酸-(C1~C8)-烷基酯(例如并优选,甲基丙烯酸甲酯、丙烯酸正丁酯、丙烯酸叔丁酯)和/或不饱和羧酸(例如,马来酸)和/或不饱和羧酸衍生物(例如,酸酐和酰亚胺)(例如并优选,马来酐和N-苯基马来酰亚胺)。
(共)聚合物B)是树脂状、热塑性和不含橡胶的。
B.1苯乙烯与B.2丙烯腈的共聚物是尤其优选的。
组分B)的(共)聚合物是已知的并可通过自由基聚合制备,尤其是通过乳液、悬浮、溶液或本体聚合。对应于组分C.1的(共)聚合物优选具有介于15000~200000的分子量Mw(重均,按光散射或沉降法测定)。
组分C
合适的本发明硅氧烷丙烯酸酯接枝橡胶C)通过芳族链烯基化合物和乙烯基酰胺在包含聚有机硅氧烷橡胶组分和聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯组分的复合橡胶上的接枝聚合来制备。该复合橡胶包含10~90wt%聚有机硅氧烷橡胶组分和90~10wt%聚丙烯酸烷基酯橡胶或聚甲基丙烯酸烷基酯橡胶,并且其结构中聚有机硅氧烷橡胶与聚丙烯酸烷基酯橡胶或聚甲基丙烯酸烷基酯橡胶互穿,以致各个橡胶组分实际上彼此无法分开。复合橡胶的平均粒度介于0.08~0.6μm。芳烃化合物和乙烯基氰化合物接枝到复合橡胶上,从而形成硅氧烷丙烯酸酯接枝橡胶C)。
该硅氧烷丙烯酸酯接枝橡胶是已知的,例如描述在EP-A663,452和US-A 5,807,914中。US-A 5,807,914中描述的橡胶优选作为适合本发明的硅氧烷丙烯酸酯接枝橡胶。聚有机硅氧烷橡胶组分可通过下面举出的有机硅氧烷与支化剂(I)的乳液聚合制备。
有机硅氧烷橡胶包含,作为单体结构单元,例如并优选,二甲基硅氧烷或至少三元环,优选3~6元环的环状有机硅氧烷,例如并优选,六甲基环三聚硅氧烷、八甲基环四聚硅氧烷、十甲基环五聚硅氧烷、十二甲基环六聚硅氧烷、三甲基三苯基环三聚硅氧烷、四甲基四苯基环四聚硅氧烷、八苯基环四聚硅氧烷。
有机硅氧烷单体可单独或以二或更多种单体的混合物形式使用。聚有机硅氧烷橡胶优选包含不少于50wt%,尤其优选不少于70wt%有机硅氧烷,相对于聚有机硅氧烷橡胶组分总重量而言。
官能度为3或4,尤其优选4的硅烷-基支化剂被优选用作支化剂(I)。例如并优选地,可举出下列化合物:
三甲氧基甲基硅烷、三乙氧基苯基硅烷、四甲氧基硅烷、四乙氧基硅烷、四正丙氧基硅烷、四丁氧基硅烷。
尤其优选四乙氧基硅烷。
支化剂可单独或以二或更多种的混合物形式使用。
能生成对应以下通式结构的接枝剂(II)适合用于接枝:
CH2=C(R2)-COO-(CH2)p-SiR1 nO(3-n)/2 (II-1)
CH2=CH-SiR1 nO(3-n)/2 (II-2)或
HS-(CH2)p-SiR1 nO(3-n)/2 (II-3),
其中
R1代表C1~C4-烷基,优选甲基、乙基或丙基或苯基,
R2代表氢或甲基,
n 代表0、1或2以及
p 代表1~6的数值。
丙烯酰氧基硅烷或甲基丙烯酰氧基硅烷特别适合用于生成上述结构(I-1),能高度有效地接枝。
例如并优选地,可举出以下化合物:
β-甲基丙烯酰氧基乙基二甲氧基甲基硅烷、γ-甲基丙烯酰氧基丙基甲氧基二甲基硅烷、γ-甲基丙烯酰氧基丙基二甲氧基甲基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基乙氧基二乙基硅烷、θ-甲基丙烯酰氧基丙基二乙氧基二乙基硅烷、δ-甲基丙烯酰氧基丁基二乙氧基二甲基硅烷或其混合物。
优选使用0~10wt%接枝剂,相对于聚有机硅氧烷橡胶总重量而言。
聚丙烯酸烷基酯橡胶或聚甲基丙烯酸烷基酯橡胶组分可由丙烯酸烷基酯或甲基丙烯酸烷基酯、支化剂(III)和接枝剂(IV)来制备。
丙烯酸烷基酯和甲基丙烯酸烷基酯例如并优选是丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸2-乙基己基酯、丙烯酸正丁酯、甲基丙烯酸己酯、甲基丙烯酸正-月桂酯或其混合物。丙烯酸正丁酯特别优选。支化剂(III)例如并优选是乙二醇的二甲基丙烯酸酯、丙二醇的二甲基丙烯酸酯、1,3-丁二醇的二甲基丙烯酸酯、1,4-丁二醇的二甲基丙烯酸酯或其混合物。
接枝剂(IV)例如并优选是甲基丙烯酸芳基酯、氰尿酸三芳基酯、异氰尿酸三芳基酯或其混合物。甲基丙烯酸芳基酯同样还可用作支化剂。芳基优选代表苯基。
支化剂(III)与接枝剂(IV)的总用量介于0.1~20wt%,以聚丙烯酸烷基酯橡胶或聚甲基丙烯酸酯橡胶的总重量为基准。
有机硅氧烷橡胶组分和聚丙烯酸烷基酯橡胶或聚甲基丙烯酸烷基酯橡胶组分按照US-A 5 807 914中的描述制备。
该复合橡胶的凝胶含量优选>80wt%,借助其可溶性组分在90℃甲苯中萃取12h来测定。
可接枝到复合橡胶上的乙烯基为基础的单体是芳族链烯基化合物,例如并优选,苯乙烯、α-甲基苯乙烯或乙烯基甲苯和/或乙烯基氰化合物,优选丙烯腈和/或甲基丙烯腈。
少量甲基丙烯酸酯如甲基丙烯酸甲酯或甲基丙烯酸2-乙基己基酯,或者丙烯酸酯如丙烯酸甲酯、丙烯酸乙酯或丙烯酸丁酯,可附加地共含于该乙烯基为基础的单体中。更特别优选苯乙烯与丙烯腈的组合物作为接枝单体。芳族链烯基化合物与乙烯基氰化合物之间的重量比优选介于5∶95~95∶5,尤其优选15∶75~75∶15,最优选20∶80~80∶20。
接枝复合橡胶的制备同样也描述在US-A 5 807 914中。
作为组分C提及的硅氧烷丙烯酸酯接枝橡胶有市售供应。可举出MetablenSRK 200和MetablenS2001,由三菱人造丝公司生产,作为例子。
组分D
本发明所指的无机填料是,例如能提高弹性模量和降低收缩的物质。它们特别是玻璃纤维、玻璃球、云母、硅酸盐、石英、滑石、二氧化钛、硅灰石,包括且尤其可使用表面处理的形式。优选的增强材料是市售玻璃纤维。玻璃纤维,其典型直径介于8~14μm,可以连续长丝形式或作为切碎丝或研磨的玻璃纤维形式使用,其中纤维可备有合适的上胶体系和基于硅烷的偶合剂或偶合剂体系。
组分E
另外还可使用分割得极细的无机粉末。
它们优选由至少一种极性化合物组成,该化合物又由一种或多种元素周期表第一~第五主族,或1-8副族、优选第二~第五主族或第四~第八副族,尤其优选第三~第五主族或第四~第八副族的金属组成,或者由这些金属的化合物与至少一种选自氧、氢、硫、磷、硼、碳、氮或硅的元素来制备。
优选的化合物例如是氧化物、氢氧化物、水合氧化物、硫酸盐、亚硫酸盐、硫化物、碳酸盐、碳化物、硝酸盐、亚硝酸盐、氮化物、硼酸盐、硅酸盐、磷酸盐、氢化物、亚磷酸盐或膦酸盐。
分割极细的无机粉末优选由氧化物、磷酸盐、氢氧化物组成,优选由TiO2、SiO2、SnO2、ZnO、ZnS、勃姆石、ZrO2、Al2O3、磷酸铝、氧化铁组成,还有TiN、WC、AlO(OH)、Sb2O3、氧化铁、Na2SO4、氧化钒、硼酸锌、硅酸盐如硅酸铝、硅酸镁,一-、二-、三-维硅酸盐。混合物和掺杂的化合物同样也可使用。
这些纳米级颗粒还可以用有机分子进行表面处理,以便实现与聚合物之间较高的相容性。疏水或亲水表面可用此种方式造成。
氧化铝的水合物如勃姆石或TiO2特别优选。
该纳米颗粒的平均颗粒直径小于或等于200nm,优选小于或等于150nm,尤其是1~100nm。
粒度和颗粒直径总是指按照W.Scholtan等人,Kolloid-ZundPolymere 250(1972),pp.782~796所描述的超离心测定法确定的平均颗粒直径d50。
该分割极细的无机化合物可以粉末、糊料、溶胶、分散体或悬浮体形式存在。粉末可由分散体、溶胶或悬浮体经沉淀获得。
粉末可通过常规方法结合到热塑性模塑组合物中,例如采用模塑组合物和分割极细的无机粉末的直接捏合或挤塑。优选的方法是制备母料,例如在阻燃添加剂中,以及至少一种本发明模塑组合物的组分在单体或溶剂中,或者热塑性组分与分割极细的无机粉末的共沉淀,例如通过水乳液与分割极细无机粉末,任选地以分割极细的无机材料的分散体、悬浮体、糊料或溶胶形式,的共沉淀。
玻璃纤维或玻璃球特别优选。
本发明组合物可包含至少一种常规添加剂如润滑剂和脱模剂,例如季戊四醇的四硬脂酸酯,成核剂、抗静电剂、组分D的稳定剂、各种填料和增强材料以及染料和颜料。
包含组分A~D和任选地添加剂的本发明组合物的制备过程是,各个组分按已知方式进行混合,并将它们在诸如密炼机、挤出机和双螺杆装置之类的常规装置中在200℃~300℃的温度熔融混炼和熔融挤出,其中组分F优选以上述沉淀混合物形式使用。
各个组分可按已知方式,既可先后也可同时地,特别是将可在约20℃(室温)也可在高温进行混合。
因此,本发明还提供一种制备模塑组合物的方法。
本发明模塑组合物可用于生产任何种类的模塑体。模塑体尤其可采用注塑生产。可生产的模塑体的例子是:任何类型的外壳零件,例如,家用电器的,例如,榨果汁机、咖啡机、混合机,以及办公机器,例如,显示器、打印机、复印机,或者建筑行业面板以及汽车行业零件,如仪表盘支架或护板。尤其优选气囊保护层的安全零件。由于其非常好的电气性能,它们另外还可用于电工领域。
本发明模塑组合物还可用于,例如,生产以下模塑体或模塑件:
轨道车辆的内部零配件、轮毂盖、装有小变压器的电器外壳、信息传播和传送的设备外壳、医疗器具的外壳和外罩、按摩设备以及后者的外壳,儿童玩具车、平壁元件、安全装置的外壳,车尾扰流板、隔热运输容器、住房或小宠物护理设备、卫生间模塑件和零配件、风扇通风罩盖、温室和棚子用模塑件、园艺设备外壳。
另一类加工形式是由预制好的片材或薄膜通过深冲进行模塑体的生产。
因此,本发明还提供本发明模塑组合物用于制备任何种类模塑体的应用,优选上面提到的那些,以及由本发明模塑组合物生产的模塑体。
实施例
组分A.1
基于双酚A的线型聚碳酸酯,溶液相对粘度1.272,以二氯甲烷为溶剂在25℃、0.5g/100mL浓度下测定。
组分A.2
基于双酚A的线型聚碳酸酯,溶液相对粘度1.202,以二氯甲烷为溶剂在25℃、0.5g/100mL浓度下测定。
组分B
苯乙烯/丙烯腈共聚物,苯乙烯/丙烯腈的重量比72∶28,特性粘度0.55dl/g(在20℃、二甲基甲酰胺中测定)。
组分C
C:1MetablenS2001(甲基丙烯酸甲酯-丙烯酸丁酯-二甲基硅氧烷共聚物)由三菱人造丝公司生产
C:2MetablenSRK 200(甲基丙烯酸甲酯-丙烯酸丁酯-二甲基硅氧烷共聚物)由三菱人造丝公司生产
对比组分C*
接枝聚合物,由40重量份由苯乙烯与丙烯腈按73∶27的比例制备的共聚物接枝到60重量份乳液聚合制备的粒状交联聚丁二烯橡胶(平均颗粒直径d50=0.28μm)上制成。
组分D
D-1:玻璃纤维CS 7942,由拜尔公司(Leverkusen)生产
添加剂
季戊四醇的四硬脂酸酯、亚磷酸盐稳定剂。
本发明模塑组合物的制备和试验
诸组分在3-立升密炼机中进行混炼。在260℃、Arburg 270E注塑机上制备模塑体。
本发明模塑组合物的组成与性能载于下表1:
表1 组成和性能
实例 | 1(对比) | 2 | 3 |
组分[份/wt] | |||
A1 | 68 | 20 | 20 |
A2 | - | 48 | 48 |
B | 16 | 26 | 26 |
C1 | - | 6 | - |
C2 | - | - | 6 |
C* | 16 | - | - |
D1 | 11 | 11 | 11 |
D2 | - | - | - |
季戊四醇四硬脂酸酯 | 0.5 | 0.5 | 0.5 |
稳定剂 | 0.12 | 0.12 | 0.12 |
性能: | |||
弹性模量 MpaISO 527 | 3590 | 3890 | 3850 |
维卡 BDIN 53460℃ | 131 | 135 | 135 |
伊佐德冲击强度0h/RTIzod ISO 180-1U | 26 | 25 | 25 |
冲击强度250h at 120℃ | 18 | 24 | 24 |
冲击强度750h at 120℃ | 11 | 23 | 24 |
冲击强度1250h at 120℃ | 9 | 23 | 24 |
剪切粘度260℃/1000/s-1ISO 11443 | 300 | 200 | 200 |
表面 | 0 | + | + |
Claims (10)
1.一种组合物,它包含,
A)40~95重量份,相对于100重量份总组合物而言,芳族聚碳酸酯和/或聚酯碳酸酯;
B)0~45重量份,相对于100重量份总组合物而言,基于乙烯基单体的均聚物或共聚物;它们是至少一种选自乙烯基芳烃、乙烯基氰、甲基丙烯酸-(C1-C8)-烷基酯、不饱和羧酸以及不饱和羧酸衍生物的单体的聚合物;
C)1~25重量份,相对于100重量份总组合物而言,硅氧烷丙烯酸酯接枝橡胶;以及
D)0.4~40重量份,相对于100重量份总组合物而言,玻璃纤维。
2.权利要求1的组合物,其中组分C通过芳族链烯基化合物与乙烯基氰接枝聚合到包含聚有机硅氧烷橡胶组分和聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯组分的复合橡胶上获得。
3.权利要求1或2的组合物,它包含,作为组分B,下列组分的均聚物或共聚物:
B.1 50~99重量份,相对于100重量份B而言,乙烯基芳烃和/或甲基丙烯酸-(C1~C8)-烷基酯和
B.2 1~50重量份,相对于100重量份B而言,乙烯基氰和/或甲基丙烯酸-(C1~C8)-烷基酯和/或不饱和羧酸和/或不饱和羧酸衍生物。
4.权利要求1或2的组合物,它包含1~30重量份玻璃纤维D。
5.权利要求1或2的组合物,它包含添加剂。
6.制备权利要求1~5中任何一项的组合物的方法,其中组分A~D进行混合并在高温混炼。
7.权利要求6的方法,其中含有添加剂。
8.权利要求1~5中任何一项的组合物用于生产模塑件的应用。
9.一种模塑件,它由权利要求1-5中任何一项的组合物制得。
10.外壳零件、建筑行业面板、汽车行业零件和气囊保护层的安全零件,它们由权利要求1~5中任何一项的组合物获得。
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DE10054275A DE10054275A1 (de) | 2000-11-02 | 2000-11-02 | Schlagzähmodifizierte Polycarbonat-Zusammensetzungen |
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CN (1) | CN1237115C (zh) |
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BR (1) | BR0115105A (zh) |
CA (1) | CA2427562A1 (zh) |
DE (2) | DE10054275A1 (zh) |
ES (1) | ES2274907T3 (zh) |
MX (1) | MXPA03003858A (zh) |
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CN109071951A (zh) * | 2016-05-27 | 2018-12-21 | 三菱化学株式会社 | 树脂组合物及其成形体 |
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US7799855B2 (en) * | 2001-11-12 | 2010-09-21 | Sabic Innovative Plastics Ip B.V. | Flame retardant thermoplastic polycarbonate compositions, use and method thereof |
US7365125B2 (en) * | 2004-08-16 | 2008-04-29 | General Electric Company | Polycarbonate compositions, articles, and method of manufacture |
JP4487689B2 (ja) | 2004-08-26 | 2010-06-23 | 日産自動車株式会社 | アルミナ粒子、アルミナ粒子の製造方法、樹脂組成物、及び樹脂組成物の製造方法 |
JP4940556B2 (ja) * | 2004-09-07 | 2012-05-30 | 日産自動車株式会社 | 樹脂組成物 |
KR100665806B1 (ko) * | 2005-06-30 | 2007-01-09 | 제일모직주식회사 | 광반사성이 우수한 폴리카보네이트 수지 조성물 |
KR100782265B1 (ko) * | 2005-12-30 | 2007-12-04 | 제일모직주식회사 | 광반사성 및 난연성이 우수한 폴리카보네이트 수지 조성물 |
DE102006012988A1 (de) * | 2006-03-22 | 2007-09-27 | Bayer Materialscience Ag | Flammgeschützte schlagzähmodifizierte Polycarbonat-Zusammensetzungen |
US8883878B2 (en) * | 2006-06-29 | 2014-11-11 | Sabic Global Technologies B.V. | Thermoplastic polycarbonate compositions |
US7928168B2 (en) | 2007-03-23 | 2011-04-19 | Sabic Innovative Plastics Ip B.V. | White light-shielding compositions and articles comprising same |
DE102008028571A1 (de) | 2008-06-16 | 2009-12-17 | Bayer Materialscience Ag | Schlagzähmodifizierte Polycarbonat-Zusammensetzungen |
JP5254816B2 (ja) * | 2008-08-27 | 2013-08-07 | 三菱レイヨン株式会社 | ポリカーボネート樹脂組成物、成形体の製造方法 |
KR101266294B1 (ko) * | 2008-12-19 | 2013-05-22 | 제일모직주식회사 | 폴리에스테르/폴리카보네이트 얼로이 수지 조성물 |
KR102547515B1 (ko) * | 2015-06-09 | 2023-06-26 | 코베스트로 도이칠란트 아게 | 향상된 인성을 갖는 유리-섬유-보강 폴리카르보네이트 성형 조성물 |
JP6678001B2 (ja) * | 2015-10-20 | 2020-04-08 | 旭ファイバーグラス株式会社 | ポリカーボネート樹脂組成物 |
CN114031923B (zh) * | 2021-12-16 | 2023-06-23 | 广东格瑞新材料股份有限公司 | 一种耐候、高韧性聚碳酸酯复合材料及其制备方法 |
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US4056504A (en) * | 1974-08-16 | 1977-11-01 | Bayer Aktiengesellschaft | Polycarbonate molding compositions |
DE2659357A1 (de) * | 1976-12-29 | 1978-07-13 | Basf Ag | Schlagzaehe thermoplastische formmassen |
US4888388A (en) * | 1987-09-21 | 1989-12-19 | Mitsubishi Rayon Company Limited | Polycarbonate resin composition |
US5840802A (en) * | 1991-10-11 | 1998-11-24 | General Electric Company | Dual graft stage and thermally stabilized polyorganosiloxane/polyvinyl-based graft copolymers and thermoplastic compositions containing the same |
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CN109071951A (zh) * | 2016-05-27 | 2018-12-21 | 三菱化学株式会社 | 树脂组合物及其成形体 |
CN109071951B (zh) * | 2016-05-27 | 2022-02-18 | 三菱化学株式会社 | 树脂组合物及其成形体 |
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CN1501960A (zh) | 2004-06-02 |
AU2002212333A1 (en) | 2002-05-15 |
DE50111571D1 (de) | 2007-01-11 |
BR0115105A (pt) | 2003-09-30 |
KR20030048106A (ko) | 2003-06-18 |
CA2427562A1 (en) | 2003-04-29 |
EP1334153A1 (de) | 2003-08-13 |
DE10054275A1 (de) | 2002-05-08 |
ATE346888T1 (de) | 2006-12-15 |
MXPA03003858A (es) | 2004-04-20 |
ES2274907T3 (es) | 2007-06-01 |
RU2003116512A (ru) | 2004-11-27 |
EP1334153B1 (de) | 2006-11-29 |
JP2004513205A (ja) | 2004-04-30 |
US20020147261A1 (en) | 2002-10-10 |
WO2002036686A1 (de) | 2002-05-10 |
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