CN1524102A - 具有改善的抗水解性的熔体聚碳酸酯 - Google Patents
具有改善的抗水解性的熔体聚碳酸酯 Download PDFInfo
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- CN1524102A CN1524102A CNA02807341XA CN02807341A CN1524102A CN 1524102 A CN1524102 A CN 1524102A CN A02807341X A CNA02807341X A CN A02807341XA CN 02807341 A CN02807341 A CN 02807341A CN 1524102 A CN1524102 A CN 1524102A
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- butyl
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
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- DMFXLIFZVRXRRR-UHFFFAOYSA-N octyl 3-[3-tert-butyl-5-(5-chlorobenzotriazol-2-yl)-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCCCCCCC)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O DMFXLIFZVRXRRR-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- ZPNJBTBYIHBSIG-UHFFFAOYSA-N phenyl-(2,2,6,6-tetramethylpiperidin-4-yl)methanone Chemical compound C1C(C)(C)NC(C)(C)CC1C(=O)C1=CC=CC=C1 ZPNJBTBYIHBSIG-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229940068886 polyethylene glycol 300 Drugs 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- INNSFNJTGFCSRN-UHFFFAOYSA-N tridecyl 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanyl]acetate Chemical compound CCCCCCCCCCCCCOC(=O)CSCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 INNSFNJTGFCSRN-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- YIKJXRBELCBNDP-UHFFFAOYSA-N tris(2,4,6-tritert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1OP(=O)(OC=1C(=CC(=CC=1C(C)(C)C)C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=C(C(C)(C)C)C=C1C(C)(C)C YIKJXRBELCBNDP-UHFFFAOYSA-N 0.000 description 1
- XZYAKNFKQSMBRX-UHFFFAOYSA-N tris(2,4,6-tritert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1OP(OC=1C(=CC(=CC=1C(C)(C)C)C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=C(C(C)(C)C)C=C1C(C)(C)C XZYAKNFKQSMBRX-UHFFFAOYSA-N 0.000 description 1
- AZSKHRTUXHLAHS-UHFFFAOYSA-N tris(2,4-di-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(=O)(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C AZSKHRTUXHLAHS-UHFFFAOYSA-N 0.000 description 1
- PULUPQRXGQULJP-UHFFFAOYSA-N tris(2,6-ditert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1OP(=O)(OC=1C(=CC=CC=1C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C PULUPQRXGQULJP-UHFFFAOYSA-N 0.000 description 1
- AJHKJOCIGPIJFZ-UHFFFAOYSA-N tris(2,6-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1OP(OC=1C(=CC=CC=1C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C AJHKJOCIGPIJFZ-UHFFFAOYSA-N 0.000 description 1
- SPUXJWDKFVXXBI-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphate Chemical compound CC(C)(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SPUXJWDKFVXXBI-UHFFFAOYSA-N 0.000 description 1
- SZPHBONKPMLMCA-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SZPHBONKPMLMCA-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- QEDNBHNWMHJNAB-UHFFFAOYSA-N tris(8-methylnonyl) phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OCCCCCCCC(C)C QEDNBHNWMHJNAB-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明涉及含有熔体聚碳酸酯和含磷有机化合物的组合物,该组合物显示改进的抗水解性。
Description
本发明涉及具有改善的抗水解性的熔体聚碳酸酯、含有其的组合物以及具有改善的抗水解性的模塑件。
在工业上聚碳酸酯采用界面法或通过在熔体中进行酯交换(熔融聚合物)来生产。熔融聚合法获得欢迎,这是因为它能够在不使用光气或氯化溶剂的条件下进行。界面法生产具有异常颜色的但抗水解性的聚碳酸酯。已知能够向这种聚碳酸酯中加入以磷为基础的添加剂,以便进一步改善色泽。但是,加入这些磷化合物会使通过界面法生产的聚碳酸酯的抗水解性降低。为了挽回一些抗水解性的损失,通常加入环氧类化合物。但是,环氧化合物和磷化合物的组合不能使聚碳酸酯产生比不加入这两类物质所得到的抗水解性有任何优越的抗水解性。加入环氧化物,最好不过是能够弥补因磷化合物引起的抗水解性的损失。
令人惊奇的是,已经发现,通过加入磷化物改善了通过熔融聚合生产的聚碳酸酯的抗水解性。这种效果即使在不加入以环氧化物为基础的水解稳定剂的条件下也会发生。
因此,本发明提供了通过熔融聚合得到的、含有有机磷化合物的聚碳酸酯、共聚碳酸酯和/或聚酯碳酸酯。本发明还提供含一种或多种前述聚合物的组合物。最后,本发明提供以有机磷化合物改善通过熔融聚合法生产的聚碳酸酯和聚酯碳酸酯的抗水解性的应用。
按照本发明的适宜有机磷化合物是,例如,膦类、氧化膦类、三价膦酸酯类、(phosphinites)亚膦酸酯类、亚磷酸酯类、二膦类、双三价膦酸酯类、二亚膦酸酯类、二亚磷酸酯类、次膦酸酯类、膦酸酯类、磷酸酯类、二次膦酸酯类、二膦酸酯类和二磷酸酯化合物以及上述磷化合物的低聚衍生物。
按照本发明的适宜的膦(PR3)和氧化膦(OPR3)化合物是,例如,其中R是氢、C1-C100烷基基团或者未取代或取代的C6-C14芳基基团者。基团R可以是相同的或不同的。最优选的基团R是苯基、2-叔丁基苯基、2,4-二叔丁基苯基、2,6-二叔丁基苯基、2,4,6-三叔丁基苯基、对壬基苯基和亚萘基。特别优选的膦是三苯基膦。
按照本发明的适宜的三价膦酸酯(P(OR)R2)、亚膦酸酯(P(OR)2R)和亚磷酸酯(P(OR)3)化合物是,例如,其中R是氢或C1-C100烷基基团,或者未取代的或取代的C6-C14芳基基团者。基团R可以是相同或不同的。最优选的基团R是苯基、2-叔丁基苯基、2,4-二叔丁基苯基、2,6-二叔丁基苯基、2,4,6-三叔丁基苯基、对壬基苯基和CH3至C18H37。
按照本发明的适宜的次膦酸酯(PO(OR)R2)、膦酸酯(PO(OR)2R)和磷酸酯(PO(OR)3)化合物是,例如,其中R是氢或C1-C100烷基基团、或者未取代的或取代的C6-C14芳基基团者。基团R可以是相同或不同的。最优选的基团R是苯基、2-叔丁基苯基、2,4-二叔丁基苯基、2,6-二叔丁基苯基、2,4,6-三叔丁基苯基、对壬基苯基和CH3至C18H37。
按照本发明的适宜的二膦化合物R2P-X-PR2是,例如,其中R是氢或C1-C100烷基基团,或者未取代的或取代的C6-C14芳基基团如下文式(2)相应的那些基团者。基团R可以是相同的或不同的。其它适宜的化合物是,其中X是二价的C1-C100烷基基团或者未取代的或取代的C6-C14芳基基团者。优选的二价基团是亚苯基、亚联苯基、2,2-二苯基丙烷和亚萘基。
按照本发明的适宜的双三价膦酸酯((RO)RP-X-PR(OR))、二亚膦酸酯((RO)2P-X-P(OR)2)和二亚磷酸酯((RO)2P-OXO-P(OR)2)化合物是,例如,其中R是C1-C100烷基基团或者未取代的或取代的C6-C14芳基基团者。基团R可以是相同的或不同的。基它适宜的化合物是,其中X是二价的C1-C100烷基基团或者未取代的或取代的C6-C14芳基基团者。特别优选的二价在团是亚苯基、亚联苯基和亚萘基。
尤其是,X可以是式(2)基团
或式(3)基团
其中,
R代表取代或未取代的苯基、甲基、丙基、乙基、丁基基团、Cl或Br,和n为0,1或2,和
Z代表C1-C8亚烷基或C5-C12亚环烷基基团,S、SO2或单键。
按照本发明适宜的二亚磷酸酯是下式者
其中,R是C1-C100烷基基团,或者未取代或取代的C6-C14芳基基团。Y是四价C1-C100烷氧基基团。最优选的四价化合物是季戊四醇。
最优选的亚磷酸酯是亚磷酸三苯酯、亚磷酸三(2-叔丁基苯)酯、亚磷酸三(2,4-二叔丁基苯)酯、亚磷酸三(2,6-二叔丁基苯)酯(Irganox 168:
亚磷酸三(2,4,6-三叔丁基苯)酯、(2,4,6-三叔丁基苯基)-(2-丁基-2-乙基-丙烷-1,3-二基)亚磷酸酯(Ultranox 641:
双(2,4-二枯基-苯基)季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双十八烷基季戊四醇二亚磷酸酯、亚磷酸三(对壬基苯)酯、亚磷酸二苯-异癸酯、亚磷酸二异癸-苯酯、亚磷酸三异癸酯、亚磷酸三月桂酯以及[三(3-乙氧基丁环(ethyloxethanyl)-3-基)-甲基]亚磷酸酯。最优选的膦是三苯基膦。最优选的亚膦酸酯是四(2,4-二叔丁基苯基)[1,1-联苯]-4,4’-二基二亚膦酸酯。
最优选的磷酸酯是磷酸三(2-乙基己)酯、磷酸三苯酯、磷酸三(2-叔丁基苯酯)、磷酸三(2,4-二叔丁基苯)酯、磷酸三(2,6-二叔丁基苯)酯和磷酸三(2,4,6-三叔丁基苯)酯。
这些磷化合物可市购,可以含有数量不定的杂质。优选使用高纯度的适当化合物以及仅仅具有数量微不足道的酸基。胺化合物和诸如碱金属盐和碱土金属盐等残余盐者。
磷化合物也可以以一种以上磷化合物的混合物的形式使用,以便使聚碳酸酯组合物的性能最佳化。这些磷化合物也可以以与另外的稳定剂和添加剂如紫外吸收剂、脱模剂、玻璃、其它聚合物、位阻酚和内酯等的混合物的形式市购。
设想按照本发明使用的磷化合物以与聚碳酸酯/聚酯碳酸酯的物理混合物的形式存在。按照本发明磷化合物显示效果的量为10ppm至30%,相对于熔体聚碳酸酯的量计。优选磷化合物的用量为10ppm至约1wt%,相对于聚碳酸酯的重量计,以便产生按照本发明的理想效果。
按照本发明加入的磷化合物可以在熔融聚合之前加入到前体或加入到催化剂溶液中。磷化合物也可以在熔融聚合过程中加入,或者在熔融聚合结束时直接加入到熔融物流中。最后,磷化合物可以与聚碳酸酯/聚酯碳酸酯在另外的步骤中混合,例如在混配料期间。
按照本发明使用的磷化合物的作用显示在通式(1)的熔体聚碳酸酯中
其中,方法号表示重复结构单元,
M可以是Ar或多官能基团A、B、C或基团D,其中Ar可以是由式(2)代表的基团
或特别优选由式(3)代表的基团
其中
Z代表C1-C8亚烷基或C5-C12亚环烷基、X、SO2或单键,
R代表取代的或未取代的苯基、甲基、丙基、乙基、丁基基团、Cl或Br,和n为0、1或2,
其中多官能基团A是下通式基团
其中多官能基团B是下通式基团
其中多官能基团C是下式通式基团
其中基团D是下通式基团
和多官能基团A、B、C和D之和>5ppm,其中Y=H或通式(4)基团
其中:
R相同或不同,代表H、C1-C20烷基、C6H5或C(CH3)2C6H5和N可以是0,1,2,或3,
其中X=Y或-(MOCOO)Y,
其中
M和Y以与上文所述相同方式限定。
特别优选具有假塑性特性(Y)的聚碳酸酯,(Y)由下方程的限定值所限定
(Q)c+axb>y>-c+axb
-尽管y≥1
-其中a、b和c为常数,和
-c=0.3-0.1,优选0.2-0.1和最优选约0.1,
-b=14.831±0.005至0.002,优选±0.004至0.002和最优选±约0.002和
-a=0.1262±0.005至0.003,优选±0.004至0.003和最优选±约0.003和
-x是聚碳酸酯的相对粘度。这些特别优选的聚碳酸酯及其制备叙述在具有内部提交号Le A 34 498的与本申请并列提交的申请中。
按照本发明的聚碳酸酯能够具有重均分子量5,000-80,000,优选10,000-60,000,最优选15,000-40,000,采用凝胶渗透色谱测定。
优选限定Ar如下:
多官能基团A优选为基团A1:
基团B优选为基团B1:
多官能基团C优选为基团Cl:
在基团(B1)和(C1)中,X按上文同样的方式限定。基团D优选是基团D1:
前述熔体聚碳酸酯仅以实例的形式叙述。成分A至D的比例在熔体聚碳酸酯中也可以以较大或较小的比例存在。
通过熔融酯交换法制备芳族聚碳酸酯现在已知,并叙述在,例如,Schnell,Chemistry and Physics of Polycarlonates(聚碳酸酯化学和物理),Polymer Reviews第9卷,Interscience Publishers,New York,London,Sydney 1964;参见:D.C.Prevorsek,B.T.Debona和Y.Kesten,Corporate Research Center,Allied ChemicalCorporation,Moristown,New Jersey 07960,“Synthesis of Poly(ester)carbonate Copolymers”(聚(酯)碳酸酯共聚物的合成),Journal of Polymer Science,Polymer Chemistry edition,第19卷,75-90(1980);D.Freitag,U.Grigo,P.R.Müller,N.Nouvertne,Bayer AG,“Polycarbonates”(聚碳酸酯),Encyclopedia of PolymereScience and Engineering,第11卷,第二版,1988,P648-718;和Des.U.Grigo,K.Kirchner和P.R.Müller“Poly carbonate”(聚碳酸酯),Becker/Braun,Kunststoff-Handbuch,第31卷,Polycarbonate,Polyacetale,Polyester,Celluloseester,CarlHanser Verlag,Munich,Vienna 1992,P117-299。
按照本发明的与磷化合物一起使用的聚碳酸酯/聚酯碳酸酯通过在适宜催化剂存在下适宜二酚和碳酸二芳酯的熔融酯交换反应来制备。所述聚碳酸酯也可以通过含有羟基或碳酸酯端基的碳酸酯低聚物和适宜二酚还有碳酸二芳酯的缩合来制备。
在本发明范围的适宜碳酸二芳酯是二C6-C14芳酯,优选苯酚或烷基取代苯酚的二酯,即,碳酸二苯酯、碳酸二(甲苯)酯和碳酸二(4-叔丁基苯)酯。碳酸二苯酯是最优选的。
适宜的碳酸酯低聚物由上文通式(1)所描述,其分子量为153-15,000。
在适宜的二C6-C14芳酯中还包括不对称二芳酯,其含有芳基取代基的混合物。碳酸苯-甲苯酯和碳酸-4-叔丁基苯-苯酯是最优选的。
在适宜的二芳酯中还包括一种以上二C6-C14芳酯的混合物。最优选的混合物是碳酸二苯酯、碳酸二甲苯酯和碳酸二(4-叔丁基苯)酯的混合物。
相对于1mol二酚计,碳酸二芳酯的用量可为1.00-1.30mol,特别优选的量为1.02-1.20mol,最优选的量为1.05-1.15mol。
在本发明范围中的适宜二羟基苯化合物是相当于通式(5)者:
其中:
R代表取代的或未取代的苯基、甲基、丙基、乙基、丁基基团、Cl或Br和
N为0,1或2。
最优选的二羟基苯化合物是1,3-二羟基苯、1,4-二羟基苯和1,2-二羟基苯。
在本发明范围内适宜的二酚是相当于通式(6)者:
其中:
Z是C1-C8亚烷基或C5-C12亚环烷基基团,S、SO2或单键,
R是取代的或未取代的苯基、甲基、丙基、乙基、丁基基团,Cl或Br和
N为0,1或2。
优选的二酚是4,4’-二羟基联苯、4,4’-二羟基二苯硫、1,1-双(4-羟基苯基)环己烷、1,2-双-(4-羟基苯基)苯、1,3-双(4-羟基苯基)苯、1,4-双(4-羟基苯基)苯、双(4-羟基苯基)甲烷、2,2-双(4-羟基苯基)丙烷、2,4-双(4-羟基苯基)-2-甲基丁烷、2,2-双(3-甲基-4-羟基苯基)丙烷、2,2-双(3-氯-4-羟基苯基)丙烷、双(3,5-二甲基-4-羟基苯基)甲烷、2,2-双(3,5-二甲基-4-羟基苯基)丙烷、双(3,5-二甲基-4-羟基苯基)砜、双(4-羟基苯基)砜、1,2-双[2-(4-羟基苯基)-异丙基]苯、1,3-双[2-(4-羟基苯基)-异丙基]苯、1,4-双[2-(4-羟基苯基)-异丙基]苯、1,1-双(4-羟基苯基)-1-苯基乙烷、2,4-双(4-羟基苯基)-2-甲基丁烷、2,2-双(3,5-二氯-4-羟基苯基)丙烷、2,2-双(3,5-二溴-4-羟基苯基)丙烷、1,1-双(4-羟基基)-3,3,5-三甲基环己烷。
最优选的二酚是1,1-双(4-羟基苯基)-1-苯基乙烷、2,2-双(4-羟基苯基)丙烷、4,4’-二羟基联苯、1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷、2,2-双(3,5-二溴-4-羟基苯基)丙烷和1,3-双[2-(4-羟基苯基)异丙基]苯。
在适宜的二酚中还包括-种以上的二酚的混合物,这样会得到共聚碳酸酯。最优选的混合成分是1,3-双[2-(4-羟基苯基)异丙基]苯、1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷、2,2-双(4-羟基苯基)丙烷、4,4’-二羟基联苯和2,2-双(3,5-二溴-4-羟基苯基)丙烷。
另外,可以加入支化剂,例如含有三官能酚羟基的化合物。显然,这些化合物会在聚合物中产生支化,会增加非牛顿流动特性。在适宜的支化剂中包括间苯三酚、3,3-双(3-甲基-4-羟基苯基)-2-氧代-2,3-二氢吲哚、4,6二甲基-2,4,6-三(4-羟基苯基)庚-2-烯、4,6-二甲基-2,4,6-三(4-羟基苯基)庚烷、1,3,5-三(4-羟基苯基)苯、1,1,1-三(4-羟基苯基)乙烷、三(4-羟基苯基)苯基甲烷、2,2-双[4,4-双(4-羟基苯基)环己基]丙烷、2,4-双(4-羟基苯基异丙基)苯酚、2,6-双(2-羟基-5’-甲基苄基)-4-甲基苯酚、2-(4-羟基苯基)-2-(2,4-二羟基苯基)丙烷、六(4-(4-羟基苯基异丙基)苯基)原对苯二甲酸酯、四(4-羟基苯基)甲烷、四(4-(4-羟基苯基-异丙基)-苯氧基)甲烷、1,4-双((4’,4”-二羟基-三苯基)甲基)苯,和靛红双甲酚、季戊四醇、2,4-二羟基苯甲酸、1,3,5-苯三酸、氰尿酸。
适用于制备按照本发明的聚碳酸酯的催化剂是,例如,具有通式(7)的那些
其中,
R1、R2、R3和R4,彼此无关,可以代表相同或不同的C1-C18亚烷基、
C6-C10芳基或C5-C6环烷基基团和
X-可以代表阴离子,其相应酸碱对H++X- HX具有pKb<11。
优选的催化剂是氟化四苯基鏻,四苯基鏻四苯基硼酸盐和四苯基鏻酚盐。最优选的是四苯基鏻酚盐。鏻盐催化剂的优选的量是,例如,每摩尔二酚10-2-10-8摩尔,最优选的催化剂量是每摩尔二酚10-4-10-6摩尔。除了鏻盐之外,可以任选使用其它助催化剂,以便增加聚合速度。助催化剂包括碱金属和碱土金属盐,例如,锂、钠和钾的氢氧化物、醇盐或酚盐,优选钠的氢氧化物、醇盐或酚盐。最优选氢氧化钠和苯酚钠。助催化剂的量可以是,例如,1-200ppb,优选5-150ppb,最优选10-125ppb,均按钠计算。
聚碳酸酯可以在下述条件下制备,反应在温度为150-400℃的步骤中进行,每步骤的停留时间可以为15min至5hr,压力为1000-0.01mbar。
按照本发明的组合物,除了聚碳酸酯或聚酯碳酸酯之外,可以含有其它聚合物组分和惯用添加剂。可能的聚合物组份是,例如,苯乙烯/丙烯腈共聚物(SAN)、丙烯腈/丁二烯/苯乙烯三元共聚物(ABS)、聚甲基丙烯酸甲酯(PMMA)、氟化聚烯烃(PTFE)、聚苯硫(PPS)、聚烯烃如聚乙烯、聚丙烯以及乙丙橡胶、环氧树脂、聚酯如聚对苯二甲酸丁二酯(PBT)、聚对苯二甲酸乙二酯(PET)、聚环己烯二甲醇(PCT)、两种成份的比例为1∶4的乙二醇和环己烯二甲醇对苯二甲酸的共聚酯(PCGT)、两种成份的比例为4∶1的乙二醇和环己烯二甲醇对苯二甲酸的共聚物(PETG),和其它通过界面法制备的聚碳酸酯以及前述组分的混合物。其它添加剂是脱模剂、稳定剂、抗氧剂、阻燃剂、着色剂和颜料、抗静电剂、核化剂、防滴剂、有机填料和另外的无机填料,以及增强剂。
按照本发明的聚碳酸酯可以以下述量存在于按照本发明的组合物中,优选5-95wt%,特别优选10-90wt%,最优选20-80wt%,相对于组合物的重量计。在按照本发明的组合物中其它聚合物组分可以以下述量存在,优选1-60wt%,特别优选1-40wt%,最优选2-30wt%,相对于组合物的重量计。
所述组合物可以最多含有60wt%,优选10-40wt%无机材料如填料和/或增强剂,相对于填充的或增强的模塑组合物计。阻燃剂可以以下述量存在于按照本发明的组合物中,最多为35wt%,优选为10-25wt%,相对于组合物的重量计。
对在按照本发明的组合物中可能存在的这些和其它组分或添加剂,除了聚碳酸酯/聚酯碳酸酯之外,以下文举例说明。
这些物质可见于许多出版物,例如,Additives for PlasticsHandbook(塑料添加剂手册),John Murphy,1999,并且是可市购的。
1.适宜的抗氧剂是,例如
1.1烷基化的一元酚,例如2,6-二叔丁基-4-甲基苯酚、2-叔丁基-4,6-二甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,6-二叔丁基-4-正丁基苯酚、2,6-二叔丁基-4-异丁基苯酚、2,6-二环戊基-4-甲基苯酚、2-(α-甲基环己基)-4,6-二甲基苯酚、2,6-二(十八烷基)-4-甲基苯酚、2,4,6-三环己基苯酚、2,6-二叔丁基-4-甲氧基甲基苯酚、壬基苯酚、其侧链是线性的或支化的,例如2,6-二壬基-4-甲基苯酚、2,4-二甲基-6-(1’-甲基十一烷-1’-基)苯酚、2,4-二甲基-6-(1’-甲基十七烷-1’-基)苯酚、2,4-二甲基-6’-(1’-甲基十三烷-1’-基)苯酚。
1.2烷硫基甲基苯酚,例如2,4-二辛硫基甲基-6-叔丁基苯酚、2,4-二辛硫基甲基-6-甲基苯酚、2,4-二辛硫基甲基-6-乙基苯酚、2,6-二(十二烷硫基甲基-4-壬基苯酚)。
1.3氢醌和烷基化氢醌,例如,2,6-二叔丁基-4-甲氧基苯酚、2,5-二叔丁基氢醌、2,5-二叔戊基氢醌、2,6-二苯基-4-十八烷氧基苯酚、2,6-二叔丁基氢醌、2,5-二叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、硬脂酸(3,5-二叔丁基-4-羟基苯)酯、己二酸双(3,5-二叔丁基-4-羟基苯)酯。
1.4生育酚,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚和其混合物(维生素E)。
1.5羟基化的二苯硫醚,例如2,2’-硫代双(6-叔丁基-4-甲基苯酚)、2,2’-硫代双(4-辛基苯酚)、4,4’-硫代双(6-叔丁基-3-甲基苯酚)、4,4’-硫代双(6-叔丁基-2-甲基苯酚)、4,4’-硫代双(3,6-二仲戊基苯酚)、4,4’-双(2,6-二甲基-4-羟基苯基)二硫化物。
1.6亚烷基双酚,例如2,2’-亚甲基双(6-叔丁基-4-甲基苯酚)、2,2’-亚甲基双(6-叔丁基-4-乙基苯酚)、2,2’-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚]、2,2’-亚甲基双[4-甲基-6-环己基苯酚]、2,2’-亚甲基双(6-壬基-4-甲基苯酚)、2,2’-亚甲基双(4,6-二叔丁基苯酚)、2,2’-亚乙基双(4,6-二叔丁基苯酚)、2,2’-亚乙基双(6-叔丁基-4-异丁基-苯酚)、2,2’-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚]、2,2’-亚甲基双[6-(α,α-二甲基苄基)-4-壬基苯酚]、4,4’-亚甲基双(2,6-二叔丁基苯酚)、4,4’-亚甲基双(6-叔丁基-2-甲基苯酚)、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷、2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚、1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷、乙二醇双[3,3-双(3’-叔丁基-4’-羟基苯基)丁酸酯]、双(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯、对苯二甲酸双[2-(3’-叔丁基-2’-羟基-5’-甲基苄基)-6-叔丁基-4-甲基苯]酯、1,1-双(3,5-二甲基-2-羟基苯基)丁烷、2,2-双(3,5-二叔丁基-4-羟基苯基)丙烷、2,2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷、1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7 O-、N-和S-苄基化合物,例如3,5,3’,5’-四叔丁基-4,4’-二羟基二苄基醚、十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯、十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯、三(3,5-二叔丁基-4-羟基苄基)胺、二硫代对苯二甲酸双(4-叔丁基-3-羟基-2,6-二甲基苄)酯、双(3,5-二叔丁基-4-羟苄基)硫化物、异辛基-3,5-二叔丁基-4-羟基苄基巯基乙酸酯。
1.8羟苄基化的丙二酸酯,例如双十八烷基-2,2-双(3,5-二叔丁基-2-羟苄基)丙二酸酯、双十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯、双十二烷基巯基乙基-2,2-双(3,5-二叔丁基-4-羟苄基)丙二酸酯、双[4-(1,1,3,3-四甲基丁基)苯基]-2,2-双(3,5-二叔丁基-4-羟苄基)丙二酸酯。
1.9芳族羟苄基化合物,例如1,3,5-三(3,5-二叔丁基-4-羟苄基)-2,4,6-三甲基苯、1,4-双(3,5-二叔丁基-4-羟苄基)-2,3,5,6-四甲基苯、2,4,6-三(3,5-二叔丁基-4-羟苄基)苯酚。
1.10三嗪化合物,例如2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟苯氧基)-1,3,5-三嗪、2,4,6-三(3,5-二叔丁基-4-羟苯氧基)-1,2,3-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、2,4,6-三(3,5-二叔丁基-4-羟苯基乙基)-1,3,5-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苯基丙酰)六氢-1,3,5-三嗪、1,3,5-三(3,5-二环己基-4-羟苄基)异氰脲酸酯。
1.11酰氨基酚,例如4-羟基-N-月桂酰苯胺、4-羟基-N-硬脂酰苯胺辛基-N-(3,5-二叔丁基-4-羟苯基)氨基甲酸酯。
1.12β-(3,5-二叔丁基-4-羟苯基)丙酸与一元醇或多元醇的酯,例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.13β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元醇或多元醇的酯,例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂二环[2,2,2]辛烷。
1.14β-(3,5-二环己基-4-羟苯基)丙酸与一元醇或多元醇的酯,例如与甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂二环[2,2,2]辛烷。
1.15 3,5-二叔丁基-4-羟基苯基乙酸与一元醇或多元醇的酯例如与甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N’-双(羟乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂二环[2,2,2]辛烷。
1.16β(3,5-二叔丁基-4-羟苯基)丙酸的酰胺,例如N,N’-双(3,5-二叔丁基-4-羟基苯基丙酰)六亚甲基二酰胺、N,N’-双(3,5-二叔丁基-4-羟基苯基丙酰)三亚甲基二胺、N,N’-双(3,5-二叔丁基-4-羟基苯基丙酰)肼、N,N’-双[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰氧基)乙基]草酰胺(NaugardXL-1,自Uniroyal).
1.17抗坏血酸(维生素C)
1.18胺基抗氧剂,例如N,N’-二异丙基-对苯二胺、N,N’-二仲丁基对苯二胺、N,N’-双(1,4-二甲基戊基)-对苯二胺、N,N’-双(1-乙基-3-甲基戊基)对苯二胺、N,N’-双(1-甲基-庚基)对苯二胺、N,N’-二环己基-对苯二胺、N,N’-二苯基-对苯二胺、N,N’-双(2-萘基)-对苯二胺、N-异丙基-N’-苯基-对苯二胺、N-(1,3-二甲基丁基)-N’-苯基-对苯二胺、N-(1-甲基-庚基)-N’-苯基-对苯二胺、N-环己基-N’-苯基-对苯二胺、4-(对甲苯氨磺酰)二苯胺、N,N’-二甲基-N,N’-二仲丁基-对苯二胺、二苯胺、N-烯丙基二苯胺、4-异丙氧基-二苯胺、N-苯基-1-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺、辛基化二苯胺如对,对’-二叔辛基二苯胺、4-正丁基-氨基苯酚、4-丁酰氨基苯酚、4-壬酰氨基苯酚、4-十二烷酰-氨基苯酚、4-十八烷酰氨基苯酚、对(4-甲氧基苯基)胺、2,6-二叔丁基-4-二甲基氨基甲基苯酚、2,4’-二氨基二苯基甲烷、4,4’-二氨基二苯基甲烷、N,N,N’,N’-四甲基-4,4’-二氨基二苯基甲烷、1,2-双[(2-甲基苯基)氨基]乙烷、1,2-双(苯基-氨基)丙烷、(邻-甲苯基)双胍、双[4-(1’,3’-二甲基丁基)苯基]胺、叔辛基化的N-苯基-1-萘胺、一和二烷基化的叔丁基/叔辛基二苯胺的混合物、一和二烷基化的壬基二苯胺的混合物、一和二烷基化的十二烷基二苯胺的混合物、一和二烷基化的异丙基/异己基二苯胺的混合物、一和二烷基化的叔丁基二苯胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、一和二烷基化的叔丁基/叔辛基吩噻嗪的混合物、一和二烷基化的叔辛基吩噻嗪的混合物、N-烯丙基吩噻嗪、N,N,N’,N’-四苯基-1,4-二氨基丁-2-烯、N,N-双(2,2,6,6-四甲基哌啶-4-基)六亚甲基二胺、双(2,2,6,6-四哌啶-4-基)癸二酸酯、2,2,6,6-四甲基哌啶-4-酮、2,2,6,6-四甲基哌啶-4-醇。这些化合物可以单独或以混合物的形式应用。
1.19.适宜的硫代增效化合物是,例如硫代二丙酸月桂酯和/或硫代二丙酸二硬脂酰酯。
2.紫外吸收剂和光稳定剂可以应用于按照本发明的组合物中,其量为0.1-15wt%,优选3-8wt%,相对于组合物的重量计。适宜的紫外吸收剂和光稳定剂是,例如:
2.12-(2’-羟基苯基)苯并三唑,例如:2-(2’-羟基-5’-甲基苯基)苯并三唑、2-(3’,5’-二叔丁基-2’-羟基苯基)苯并三唑、2-(5’-叔丁基-2’-羟基苯基)苯并三唑、2-(2’-羟基-5’-(1,1,3,3-四甲基-丁基)苯基)苯并三唑、2-(3’,5’-二叔丁基-2’-羟基苯基)-5-氯苯并三唑、2-(3’-叔丁基-2’-羟基-5’-甲基苯基)-5-氯苯并三唑、2-(3’-仲丁基-5’-叔丁基-2’-羟基苯基)苯并三唑、2-(2’-羟基-4’-辛氧基-苯基)苯并三唑、2-(3’,5’-二叔戊基-2’-羟苯基)苯并三唑、2-(3’,5’-双(α,α-二甲基苄基)-2’-羟基苯基)苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰基-乙基)苯基)-5-氯苯并三唑、2-(3’-(叔丁基)-5’-[2-(2-乙基-己氧基)羰基乙基]-2’-羟苯基)-5-氯苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰基乙基)苯基)-5-氯苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰基乙基)苯基)苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰基乙基)苯基)苯并三唑、2-(3’-叔丁基-5’-[2-(2-乙基己氧基)羰基乙基]-2’-羟基苯基)苯并三唑、2-(3’-十二烷基-2’-羟基-5’-甲基苯基)苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-异辛氧基羰基乙基)苯基苯并三唑、2,2’-亚甲基双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3’-叔丁基-5’-(2-甲氧基羰基乙基)-2’-羟基苯基]-2H-苯并三唑与聚乙二醇300,[R-CH2CH2-COO-CH2CH2]2的酯交换产物,其中R=3’-叔丁基-4’-羟基-5’-2H-苯并三唑-2-基苯基、2-[2’-羟基-3’-[α,α-二甲基苄基]-5’-(1,1,3,3-四甲基丁基)苯基]苯并三唑、2-[2’-羟基-3’-(1,1,3,3-四甲基丁基)-5’-(α,α-二甲基苄基)苯基]苯并三唑。
2.22-羟基二苯酮,例如4-羟基-、4-甲氧基、4-辛氧基-、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2’,4’-三羟基和2’-羟基-4,4’-二甲氧基衍生物。
2.3取代的和未取代的苯甲酸的酯,例如,水杨酸4-叔丁基苯酯、水杨酸苯酯、水杨酸辛基苯酯、联苯甲酰间苯二酚、联(4-叔丁基苯甲酰)是苯二酚、苯甲酰间苯二酚、2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯、十六烷基-3,5-二叔丁基-4-羟基苯甲酸酯、十八烷基-3,5-二叔丁基-4-羟基苯甲酸酯、2-甲基-4,6-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯。
2.4丙烯酸酯,例如乙基-α-氰基-β,β-二苯基丙烯酸酯、异辛基-α-氰基-β,β-二苯基丙烯酸酯、甲基-α-甲氧甲酰肉桂酸酯、甲基-α-氰基-β-甲基-对-甲氧基肉桂酸酯、丁基-α-氰基-β-甲基-对-甲氧基肉桂酸酯、甲基-α-甲氧甲酰-对-甲氧基肉桂酸酯和N(β-甲氧甲酰-β-氰乙烯基)-2-甲基二氢吲哚。
2.5镍化合物,例如2,2’-硫代双[4-(1,1,3,3-四甲基丁基)苯酚]的镍络合物,例如,1∶1或1∶2络全物,具有或不具有另外的配体,例如,正丁胺、三乙醇胺或N-环己基二乙醇胺、二丁基二硫代氨基甲酸镍、单烷基酯的镍盐如4-羟基-3,5-二叔丁基苄基磷酸的甲酯或乙酯的、酮肟的镍络合物如2-羟基-4-甲基苯基十一烷基酮肟的镍络合物,1-苯基-4-月桂酰-5-羟基吡唑的镍络合物,具有或不具有另外的配体。
2.6空间位阻胺,例如双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)丁二酸酯、双(2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双-(1,2,2,6,6-五甲基-4-哌啶基)、正丁基-3,5-二叔丁基-4-羟基-苄基丙二酸酯、1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和丁二酸的缩合物、N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三醋酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1’-(1,2-亚乙基)双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰基-2,2,6,6-四甲基哌啶、4-十八烷氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4,5]癸烷-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-哌啶基)丁二酸酯、N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨丙基-氨基)乙烷的缩合物、2-氯-4,6-双(4-正丁氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨丙基氨基)乙烷的缩合物、8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4,5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮、4-十六烷氧基-和4-十八烷氧基-2,2,6,6-四甲基哌啶的混合物、N,N’-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己氨基-2,6-二氯-1,3,5-三嗪的缩合产物、1,2-双(3-氨基丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合产物(CAS Reg.No.[136504-96-6]);N-(2,2,6,6-四甲基-4-哌啶基)-7-十二烷基-琥珀酰亚胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基-琥珀酰亚胺、2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4,5]-癸烷、7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4,5]癸烷和表氯醇的反应产物、1,1-双(1,2,2,6,6-五甲基-4-哌啶氧基羰基)-2-(4-甲氧苯基)乙烯、N,N’-双(甲酰基)-N,N’-双(2,2,6,6-四甲基-4-哌啶基)-六亚甲基二胺、4-甲氧基亚甲基丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯、聚[甲基丙基-3-氧代-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷、丙二酸酐-α-烯烃共聚物与2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
2.7草酰胺,例如4,4’-二辛氧基N,N’-草酰二苯胺、2,2’-二乙氧基N,N’-草酰二苯胺、2,2’-二辛氧基-5,5’-二叔丁基N,N’-草酰二苯胺、2,2’-二(十二烷氧基)-5,5’-二叔丁基N,N’-草酰二苯胺、2-乙氧基-2’-乙基N,N’-草酰二苯胺、N,N’-双(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2’-乙基N,N’-草酰二苯胺及其与2-乙氧基-2’-乙基-5,4’-二叔N,N’-草酰二苯胺的混合物、邻和对甲氧基-二取代的N,N’-草酰二苯胺的混合物以及邻和对乙氧基-二取代的N,N’-草酰二苯胺的混合物。
2.8 2-(2-羟基苯基)-1,3,5-三嗪,例如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基-4,6-双(2,4-二甲基苯基)1,3,5-三嗪、2-(2,4-二羟苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-三癸氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪、2-[4-(十二烷氧基/十三烷氧基-2-羟丙氧基)-2-羟苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基4-(2-羟基-3-十二烷氧基丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-己氧基)苯基-4,6-二苯基)-1,3,5-三嗪、2-(2-羟基-4-甲氧基-苯基)苯基-4,6-二苯基)-1,3,5-三嗪、2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基]-1,3,5-三嗪、2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪、2-{2-羟基-4-[3-(2-乙基己基-1-氧代)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪。
这些化合物可以单独或以混合物的形式应用。
3.适宜的金属去活化剂是,例如,N,N’-二苯基草酰胺、N-水杨醛-N’-水杨酰肼、N,N’-双(水杨酰)肼、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰)肼、3-水杨酰氨基-1,2,4-三唑、双(亚苄基)草二酰肼、N,N’-草酰二苯胺、间苯二酰肼、癸二酰双苯基肼、N,N’-二乙酰己二酰二肼、N,N’-双(水杨酰)草二酰肼、N,N’-双(水杨酰)硫代丙二酰二肼。可以应用其单一化合物或混合物。
5.适宜的过氧化物捕集剂是,例如:β-硫代二丙酸的酯、例如月桂酯、十八烷酯、肉豆蔻酯或十三烷酯、巯基苯并咪唑或2-巯基苯并咪唑的锌盐、二丁基二硫代氨基甲酸锌、二(十八烷基)二硫化物、季戊四醇四(十二烷基巯基)丙酸酯。可以应用其单一化合物或混合物。
6.适宜的碱性共稳定剂是,例如:三聚氰胺、聚乙烯基吡咯烷酮、双氰胺、三烯丙基氰脲酸酯、脲衍生物、肼衍生物、胺、聚酰胺、聚氨基甲酸酯、高级脂肪酸的碱金属盐、碱土金属盐,例如硬脂酸钙、硬脂酸锌、山嵛酸镁、硬脂酸镁、蓖麻油酸钠和棕榈酸钾、焦儿茶酚锑或焦儿茶酚锌。可以应用其单一化合物或其混合物。
7.适宜的成核剂是,例如无机物质如滑石、金属氧化物如二氧化钛或氧化镁、磷酸盐、碳酸盐或硫酸盐,优选其碱土金属盐;有机化合物如一元羧酸或多羧酸及其盐,例如4-叔丁基苯甲酸、己二酸、二苯基乙酸、丁二酸钠或苯甲酸钠;聚合物如离子共聚物(离聚物)。1,3:2,4-双(3’,4’-二甲基亚苄基)山梨糖醇、1,3:2,4-二(对甲基二亚苄基)山梨糖醇和1,3:2,4-二(亚苄基)山梨糖醇是特别优选的。
可以使用其单一化合物或其混合物。
8.适宜的填料和增强剂是,例如,碳酸钙、硅酸盐、玻璃纤维、玻璃珠、石棉、滑石、高岭土、云母、硫酸钡、金属氧化物和金属氢氧化物、碳黑、石墨、硅灰石、和木屑或其它天然产物的纤维、合成纤维。这些化合物可以单独或以混合物的形式应用。
9.适宜的其它活加剂是,例如,增塑剂、润滑剂、乳化剂、颜料、粘度改善剂、催化剂、流动控制剂、光学增白剂、阻燃剂、抗静电剂、和发泡剂。
10.适宜的苯并呋喃酮和吲哚满酮是,例如,在U.S.4,325,863;U.S.4,338,244;U.S.5,175,312;U.S.5,216,052;U.S.5,252,643;DE-A-4316611;DE-A-4316622;DE-A-4316876;EP-A-0589839或 EP-A-0591102中所公开的那些,或者3-[4-(2-乙酰氧基乙氧基)苯基]-5,7-二叔丁基-苯并呋喃-2-酮、5,7-二叔丁基-3-[4-(2-硬脂酰氧基乙氧基)苯基]苯并呋喃-2-酮、3,3’-双[5,7-二叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮]、5,7-二叔丁基-3-[4-乙氧基苯基]苯并呋喃-2-酮、3-(4-乙氧基-3,5-二甲苯苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,4-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(2,3-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、内酯抗氧剂如
这些化合物起诸如抗氧剂等作用。这些化合物可以单独或以混合物的形式应用。
11.适宜的荧光增塑剂是“Plastics Additives Handbook”(塑料添加剂手册),R.Gchter and H.Müller.编辑,Hanser Verlag,第三版,1990,P775~789,所列者。
12.适宜的模具分离剂是脂族酸和醇的酯,例如,四硬脂酸季戊四醇酯和甘油单硬脂酸酯。它们单独或以混合物形式应用,优选用量为0.02-1wt%,相对于组合物重量计。
13.适宜的阻燃添加剂是磷酸酯,即,磷酸三苯酯、间苯二酚二磷酸酯、含溴的化合物如溴化磷酸酯、溴化低聚碳酸酯和聚碳酸酯以及盐如C4F9SO3 -Na+。
14.适宜的抗冲改性剂是具有接枝苯乙烯/丙烯腈或甲基丙烯酸甲酯的丁二烯橡胶、具有接枝马来酸酐的乙烯/丙烯橡胶、具有接枝甲基丙烯酸甲酯或苯乙烯/丙烯腈的丙烯酸乙酯和丁酯橡胶、具有接枝甲基丙烯酸甲酯或苯乙烯/丙烯腈的互穿的硅氧烷和丙烯酸酯的网络。
15.适宜的聚合物是SAN、ABS、PMMA、PTFE、PSU、PPS、聚烯烃如聚乙烯、聚丙烯和乙烯/丙烯橡胶、环氧树脂、聚酯如PBT、PET、PCT、PCTG和PETG以及其它通过界面法生产的聚碳酸酯。
16.适宜的抗静电剂是磺酸盐,例如,C12H25SO3 -或C8F17SO3 -的四乙基铵盐。
17.适宜的着色剂是颜料以及有机染料和无机染料。
18.含环氧基团的化合物,例如,3,4-环氧环己基甲基-3,4-环氧环己基羧酸酯、甲基丙烯酸缩水甘油酯和环氧硅烷的共聚物。
19.含酐基团的化合物,例如,马来酸酐、丁二酸酐、苯甲酸酐和邻苯二甲酸酐。
第18和19类中的化合物起熔体稳定剂作用。它们可以单独或以混合物形式应用。
按照本发明的组合物(模塑料)通过下述方法来制备,包括按已知方法共混有关组分及在约300℃下如在200-400℃下采用传统设备如密闭配混机、挤出机和双轴螺杆进行熔融配混和熔体挤出。各个组分的共混可以按顺序进行或者同时进行,实际上可以在约20℃(室温)下或者在高温下进行。
按照本发明的模塑料可以用于制造任何类型的模塑件。这些模塑件可以通过注塑、挤塑和吹塑工艺来制造。加工的另一种成型方法是通过采用予先制备的板或薄膜经热成型制造模塑件。
按照本发明的模塑件的实例是各种类型的型材、薄膜、壳类部件,例如用于家庭应用如压汁机、咖啡机和混合器,用于办公设备如监视器、印刷机和复印机,用于建筑领域、室内装饰和室外应用的片材、管线、电气安装管道、窗、门和型材以及在电气工程领域中如用于开关和插座。另外,按照本发明的模塑件可以用于履带式车辆、船、飞机、汽车和其它车辆的内部构件和结构部件,还有可以用于汽车的车身制造构件。
按照本发明的模塑件可以是透明的或不透明的。尤其是,另外的模塑件是光学和磁光存储器如微盘、密盘(CD)或数字通用盘(DVD),用于食品和饮料的包装、光学透镜和棱镜、照明用灯玻璃、汽车灯玻璃、用于建筑和汽车的窗用玻璃、诸如用于温室等的各种类型的窗用玻璃、所谓的双壁片材或中空片材。
下述实施例用于更详细地解释本发明。
实施例
制备以两种熔体聚碳酸酯和一种通过界面法得到的线性聚碳酸酯为基础的聚碳酸酯组合物。将按照本发明使用的七种磷化合物采用ZSK33双螺杆挤出机与聚碳酸酯挤出配混。这意味着,能够直接比较将磷化合物加入到不同聚碳酸酯中的效果。
抗水解性通过将聚碳酸酯组合物置于300℃下Zwick MeltIndexer(茨维克熔体指数测定器)中按照ASTM方法D1238进行测定。首先将挤出的颗粒组合物在空气中进行调理,以得到0.12%含水量,然后进行熔体流动指数试验。挤出组合物的分子量和稳定性试验之后的组合物的分子量,通过与相对粘度的测定结果相关来求出。通过差来计算分子量下降。相对粘度采用在二氯甲烷中0.5%的溶液在20℃下进行测定。
黄度指数用厚度4mm的注塑试样使用CIELAB方法进行测定。
聚碳酸酯中的水含量采用卡尔·费歇尔滴定法测定。
表1
实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
PC1 | % | 100.00 | 99.97 | 99.99 | 99.9 | ||||
PC2 | % | 100.00 | 99.97 | 99.99 | 99.9 | ||||
磷化合物1 | % | 0.03 | 0.03 | ||||||
磷化合物2 | % | 0.01 | 0.01 | ||||||
磷化合物3 | % | 0.1 | 0.1 | ||||||
Mw | 28,949 | 28,561 | 28,432 | 28,561 | 28,820 | 28,561 | 28,561 | 28,561 | |
Mw,在抗水解性试验之后,水含量0.12% | 25,584 | 25,713 | 27,525 | 26,619 | 28,043 | 26,360 | 26,888 | 26,360 | |
Mw降低 | 3,366 | 2,848 | 906 | 1,942 | 777 | 2,201 | 1.673 | 2,201 | |
YI | 3.5 | 2.7 | 2.6 | 3.5 | 3.5 | 2.6 | 1.7 | 3.5 |
注:
PC1是采用256ppm化合物A、21ppm化合物B、59ppm化合物C和175ppm化合物D通过熔融聚合制备的双酚-A聚碳酸酯。
PC2是采用<5ppm化合物A、B、C和D通过界面法制备的双酚-A聚碳酸酯。
磷化合物1是亚磷酸三[(3-乙氧基丁环基-3)甲]酯。
磷化合物2是磷酸三[(2-乙基己)酯。
磷化合物3是三苯基膦。
表2给出具有不同氧化态磷的各种磷化合物的其它实例。
表2
实施例 | 9 | 10 | 11 | 14 | 15 | 16 | 17 | |
PC3 | % | 100.00 | 99.95 | 99.95 | 99.95 | 99.95 | 99.95 | 99.95 |
磷化合物4 | % | 0.05 | ||||||
磷化合物1 | % | 0.05 | ||||||
磷化合物5 | % | 0.05 | ||||||
磷化合物6 | % | 0.05 | ||||||
磷化合物7 | % | 0.05 | ||||||
磷化合物混合物8 | % | 0.05 | ||||||
Mw | 27,266 | 27,914 | 27,266 | 28,043 | 27,914 | 28,043 | 28,043 | |
Mw,在抗水解性试验之后,水含量0.12% | 25,066 | 27,266 | 25,584 | 27,137 | 25,842 | 26,878 | 26,490 | |
Mw降低 | 2,201 | 647 | 1,683 | 906 | 2,071 | 1,165 | 1,554 | |
YI | 4.3 | 4.2 | 3.6 | 3.3 | 3.2 | 3.3 | 3.0 |
注:
PC3是采用231ppm化合物A、10ppm化合物B、53ppm化合物C和144ppm化合物D通过熔融聚合制备的双酚-A聚碳酸酯。磷化合物4是亚磷酸三(2,4-二叔丁基苯)酯。磷化合物5是2,4,6-三叔丁基苯基-3-丁基-2-乙基-1,3-丙二醇亚磷酸酯。
磷化合物6是双(2,4-二枯基苯基)季戊四醇二亚磷酸酯
磷化合物7是四(2,4-二叔丁基苯基)[1,1-联苯]4,4’-二基二亚膦酸酯
磷化合物混合物8是57%亚磷酸三(2,4-二叔丁基苯)酯、28%十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯和15%通式(8)所代表的化合物
所得结果表明,由于向熔融混配聚合物中加入了磷化合物,所以分子量损失减小。这种效果与采用通过界面法制备的聚碳酸酯通常观察到的效果相反。所以认为,通过加入磷化合物改善了熔融聚合的聚碳酸酯的抗水解性,而通过界面法制备的聚碳酸酯的抗水解性降低。
Claims (13)
1.一种组合物,其含有通式1熔体聚碳酸酯
其中,方括号表示重复结构单元,
M可以是Ar或多官能基团A、B、C或基团D,其中Ar可以是由式
(2)代表的基团
或特别优选由式(3)代表的基团
其中
Z代表C1-C8亚烷基或C5-C12亚环烷基、X、SO2或单键,
R代表取代的或未取代的苯基、甲基、丙基、乙基、丁基基团、Cl或Br,和n为0、1或2,
其中多官能基团A是下通式基团
其中多官能基团B是下通式基团
其中多官能基团C是下式通式基团
其中基团D是下通式基团
和多官能基团A、B、C和D之和>5ppm,
其中Y=H或通式(4)基团
其中:
R相同或不同,代表H、C1-C20烷基、C6H5或C(CH3)2C6H5和
N可以是0,1,2,或3,
其中X=Y或-(MOCOO)Y,
其中
M和Y以与上文所述相同方式限定。
2.按照权利要求1的组合物,其中含磷(P)有机化合物是膦(PR3)、氧化膦(OPR3)、三价膦酸酯(P(OR)R2)、亚膦酸酯(P(OR)2R)、亚磷酸酯(P(OR)3)、次膦酸酯(PO(OR)R2)、膦酸酯(PO(OR)2R)和/或磷酸酯(PO(OR)3),和R可以是氢、C1-C100烷基基团或者未取代的或取代的C6-C14芳基基团,基团R可以是相同的或不同的。
3.按照权利要求1的组合物,其中含磷(P)有机化合物是二膦(R2P-X-PR2)、双三价膦酸酯((RO)RP-X-PR(OR))、二亚膦酸酯((RO)2P-X-P(OR)2)、二亚磷酸酯((RO)2-P-OXO-P(OR)2)、二次膦酸酯、二膦酸酯、二磷酸酯化合物或通式为(RO)mR2-mP-Xp(OR)mR2-m的化合物,和R为C1-C100烷基基团或者未取代的或取代的C6-C14芳基基团,n为0、1、2或3,m为0、1或2,和X为通式(2)或通式(3)基团
其中R代表取代的或未取代的苯基、甲基、丙基、乙基、丁基基团、Cl或Br,和n为0、1或2,
和Z是C1-C8亚烷基或C5-C12亚环烷基基团、S、SO2或单键。
4.按照权利要求1的组合物,其中含磷(P)有机化合物是下通式化合物
和R按与权利要求2和3中相同的方式限定,Y代表四价C1-C100烷氧基基团。
5.按照权利要求1-4之一的组合物,其中磷化合物存在量为10ppm-30wt%,相对于熔体聚合物的重量计。
6.按照权利要求1-5之一的组合物,其中磷化合物是下通式化合物
8.按照权利要求1-5之一的组合物,其中磷化合物是磷酸三苯酯。
9.一种模塑件,其含有按照权利要求1-5之一的组合物。
10.含磷化合物用来增加熔体聚碳酸酯和含有其的模塑件的抗水解性的应用。
11.按照权利要求7的应用,其中含磷化合物是权利要求2,3或4中所述的化合物之一。
12.按照权利要求7或8的应用,其中含磷化合物的量为10ppm-2wt%,相对于熔体聚碳酸酯的重量计。
13.按照权利要求9的应用,其中含磷化合物的量为10ppm-1wt%,相对于熔体聚碳酸酯的重量计。
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DE10114807.0 | 2001-03-26 | ||
DE10114807 | 2001-03-26 | ||
DE10122495A DE10122495A1 (de) | 2001-03-26 | 2001-05-10 | Schmelzepolycarbonat mit verbesserter Hydrolysebeständigkeit |
DE10122495.8 | 2001-05-10 | ||
PCT/EP2002/002720 WO2002077101A2 (de) | 2001-03-26 | 2002-03-13 | Schmelzepolycarbonat mit verbesserter hydrolysebeständigkeit |
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CN1320027C CN1320027C (zh) | 2007-06-06 |
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US (1) | US20030013788A1 (zh) |
EP (1) | EP1412412B1 (zh) |
JP (1) | JP4275949B2 (zh) |
KR (1) | KR100765040B1 (zh) |
CN (1) | CN1320027C (zh) |
AT (1) | ATE354602T1 (zh) |
AU (1) | AU2002238579A1 (zh) |
DE (2) | DE10122495A1 (zh) |
ES (1) | ES2279860T3 (zh) |
HK (1) | HK1068905A1 (zh) |
TW (1) | TWI300077B (zh) |
WO (1) | WO2002077101A2 (zh) |
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CN102030974A (zh) * | 2009-09-30 | 2011-04-27 | 拜尔材料科学股份公司 | 具有改进的熔流能力的聚碳酸酯组合物 |
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HK1068905A1 (en) | 2005-05-06 |
AU2002238579A1 (en) | 2002-10-08 |
CN1320027C (zh) | 2007-06-06 |
EP1412412A2 (de) | 2004-04-28 |
US20030013788A1 (en) | 2003-01-16 |
JP4275949B2 (ja) | 2009-06-10 |
ES2279860T3 (es) | 2007-09-01 |
WO2002077101A2 (de) | 2002-10-03 |
ATE354602T1 (de) | 2007-03-15 |
DE10122495A1 (de) | 2002-10-10 |
JP2004526843A (ja) | 2004-09-02 |
DE50209549D1 (de) | 2007-04-05 |
EP1412412B1 (de) | 2007-02-21 |
TWI300077B (en) | 2008-08-21 |
KR20030094296A (ko) | 2003-12-11 |
KR100765040B1 (ko) | 2007-10-09 |
WO2002077101A3 (de) | 2004-02-26 |
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