CN101472994A - 聚碳酸酯组合物以及由其形成的制品 - Google Patents
聚碳酸酯组合物以及由其形成的制品 Download PDFInfo
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- CN101472994A CN101472994A CNA2007800226947A CN200780022694A CN101472994A CN 101472994 A CN101472994 A CN 101472994A CN A2007800226947 A CNA2007800226947 A CN A2007800226947A CN 200780022694 A CN200780022694 A CN 200780022694A CN 101472994 A CN101472994 A CN 101472994A
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- composition
- polycarbonate
- bis
- phenyl
- group
- Prior art date
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 135
- 239000000203 mixture Substances 0.000 title claims abstract description 134
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 129
- 125000003118 aryl group Chemical group 0.000 claims abstract description 46
- 239000004609 Impact Modifier Substances 0.000 claims abstract description 34
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 11
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 9
- 125000004948 alkyl aryl alkyl group Chemical group 0.000 claims abstract description 5
- -1 siloxane repeat Chemical group 0.000 claims description 138
- 239000000126 substance Substances 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000000178 monomer Substances 0.000 claims description 48
- 239000000975 dye Substances 0.000 claims description 40
- 125000000217 alkyl group Chemical group 0.000 claims description 34
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 23
- 239000000654 additive Substances 0.000 claims description 23
- 229920000578 graft copolymer Polymers 0.000 claims description 23
- 239000000049 pigment Substances 0.000 claims description 23
- 230000000996 additive effect Effects 0.000 claims description 21
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000003381 stabilizer Substances 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 12
- 239000012745 toughening agent Substances 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 230000000007 visual effect Effects 0.000 claims description 10
- 125000005587 carbonate group Chemical group 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 150000003254 radicals Chemical group 0.000 claims description 4
- 239000004902 Softening Agent Substances 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 28
- 239000000463 material Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 150000002148 esters Chemical class 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 19
- 229920000728 polyester Polymers 0.000 description 18
- 150000001721 carbon Chemical group 0.000 description 17
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 17
- 229920001169 thermoplastic Polymers 0.000 description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 15
- 229960003742 phenol Drugs 0.000 description 15
- 239000004416 thermosoftening plastic Substances 0.000 description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- 238000000465 moulding Methods 0.000 description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 125000004122 cyclic group Chemical group 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 229920002313 fluoropolymer Polymers 0.000 description 9
- 239000004811 fluoropolymer Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229960001755 resorcinol Drugs 0.000 description 9
- 230000035882 stress Effects 0.000 description 9
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 8
- 229930185605 Bisphenol Natural products 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 235000012211 aluminium silicate Nutrition 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 125000001118 alkylidene group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 7
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- 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 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000013618 particulate matter Substances 0.000 description 5
- 239000003444 phase transfer catalyst Substances 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- AAOADXIHXYIOMT-UHFFFAOYSA-N 1,1'-biphenyl;phosphoric acid Chemical compound OP(O)(O)=O.C1=CC=CC=C1C1=CC=CC=C1 AAOADXIHXYIOMT-UHFFFAOYSA-N 0.000 description 4
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 4
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 238000010923 batch production Methods 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 4
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 3
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
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Abstract
本发明公开了具有改善的耐疲劳性的聚碳酸酯组合物。该组合物用于制造电子和机械制品,尤其是例如移动电话外壳。该组合物包括有效量的聚碳酸酯、抗冲改性剂和式(P-1)表示的季戊四醇二亚磷酸酯衍生物,m为整数,且1≤m≤5;n为整数,且1≤n≤5;R1和R2各自独立地选自芳基烷基、烷基芳基烷基、芳基、烷基芳基和它们的任意组合。
Description
背景技术
在各种示例性实施方式中,本公开内容涉及聚碳酸酯组合物和由该组合物制成的、展示出提高的耐疲劳性的制品,以及其用途。
在这一点上,耐疲劳性通常涉及耐受由重复应力所产生的材料局部变形的能力。通常将经受在挠曲、拉伸、压缩或扭曲方面的重复循环载荷的材料行为描述为疲劳。该重复循环载荷最终构成导致完全破坏的机械损伤和逐渐破裂。疲劳寿命被定义为在一组给定的振荡条件下产生试样破坏所需要的变形循环的数目。
由重复施加应力或应变发生的破坏适当地低于材料的表观极限强度。通常将疲劳数据记录为在给定的最大应力水平下破坏的循环数。耐疲劳性曲线,其表示应力对破坏的循环数的函数,也称之为S-N曲线,通常通过在循环应力下测试多个试样而产生,每个试样在不同的应力水平下进行。在高应力水平下,材料在相对小的循环数下趋于破坏。在低应力下,材料可以周期性耐受无限的次数,基本上不可能确定破坏点(failure point)。极限应力被称为耐疲劳极限,低于该极限应力则材料永远不会破坏。
耐疲劳性数据在设计将承受反复循环载荷的制品和部件方面具有实际重要性。这些产品的实例包括但不限于,齿轮、管道、铰链、在振动机械上的部件以及在循环压力下的压力容器。
聚碳酸酯和共聚碳酸酯组合物已经广泛应用于要求良好的耐疲劳性的大量重要的商业应用。例如,在移动电话外壳应用方面,耐疲劳性对于长期使用产品而不断裂是关键的。但是,目前,随着折叠电话设计变得比直板式电话(bar-phone)设计越来越普遍,问题就出现了。换言之,折叠电话设计更易于受材料疲劳损坏,因为在大量开-关循环使用之后铰链区更易于断裂。
为了增韧材料、降低疲劳期间的裂纹扩展和提高耐疲劳性和延性,以及其他目的,将诸如MBS(甲基丙烯酸甲酯/丁二烯/苯乙烯共聚物)和聚碳酸酯-聚硅氧烷(PC-Si)共聚物(例如 EXL级聚碳酸酯-聚硅氧烷共聚物-通用电气公司)等的抗冲改性剂加入到聚碳酸酯组合物中。也将各种亚磷酸酯化合物加入到聚碳酸酯组合物中,起稳定剂的作用。例如,授予Barren等的美国专利6,063,844披露了具有提高的热稳定性的聚碳酸酯/橡胶改性接枝共聚物树脂共混物。橡胶改性的接枝共聚物含有分散于连续的刚性热塑性相中的不连续的弹性体相,其中至少一部分刚性热塑性相化学接枝到弹性体相。该共混物也可以含有位阻酚稳定剂化合物,硫代酯稳定剂化合物和亚磷酸酯稳定剂化合物。该亚磷酸酯化合物具有如下结构式:
其中R6为(C1-C24)烷基或单环芳基,其任选地取代有最多三个(C1-C12)烷基;或者,该该亚磷酸酯具有根据如下的结构式:
其中R7、R8、R9、R10和R11各自独立地为(C1-C12)烷基。
授予Stevenson等的美国专利6,224,791披露了一种聚碳酸酯组合物,其包括亚磷酸酯(例如二(2,4-二枯基苯)季戊四醇二亚磷酸酯或2-丁基-2-乙基-1,3-丙二醇2,4,6-三-叔丁基苯酚亚磷酸酯)与下式的3-苯基苯并呋喃-2-酮衍生物的协同性共混物:
其中R1和R12独立地选自氢,1-20个碳原子的烷基,芳基,7-30个碳原子的芳基烷基和7-30个碳原子的烷基芳基。
授予Jaatinen等的美国专利6,649,677披露了具有提高的阻燃性的聚碳酸酯片材。该片材包括基于磷的稳定剂,例如三(2,4-二-叔丁基苯基)-亚磷酸酯;2,4,6-三-叔丁基苯基2-丁基-2-乙基-1,3-丙二醇亚磷酸酯;二(2,4-二枯基苯基)季戊四醇二亚磷酸酯;二苯基异癸基亚磷酸酯;和二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯。该片材也包括加工脱模剂,例如季戊四醇四硬脂酸酯(PETS)和季戊四醇酯。
授予Stein等的美国专利6,770,693披露了亚磷酸酯和抗氧化剂的共混物,用于制备具有提高的耐热氧化降解性的聚碳酸酯。亚磷酸酯的实例是二-(2,4-二枯基苯基)季戊四醇二亚磷酸酯。此外,授予Kishida等的美国专利5,008,313披露了一种抗冲改性剂,其包括100重量份通过将分子内具有乙烯基的单体接枝聚合到丁二烯聚合物形成的并且并入到其中的接枝共聚物,和0.01~5重量份亚磷酸酯类热稳定剂,以及其它热稳定剂。该抗冲改性剂可以用于饱和聚酯树脂、聚碳酸酯树脂、聚烯烃树脂、甲基丙烯酸类树脂和苯乙烯树脂。聚碳酸酯可以是双酚型聚碳酸酯,例如衍生于2,2′-(4,4′-二羟基二苯基)丙烷的那些。
但是,当含有诸如MBS和PC-Si共聚物等抗冲改性剂的聚碳酸酯组合物用于移动电话应用时,提高的耐疲劳性将是有益的。此外,随着移动电话外壳的厚度变得越来越薄,期待制备具有更好的耐疲劳性和优异的耐冲击性的材料的能力。
因此,在本领域仍然存在对于能够易于生产具有提高的耐疲劳性以及其它性质的制品的聚碳酸酯组合物的需求。
发明概述
本申请公开了一种组合物,其具有有效量的聚碳酸酯、季戊四醇二亚磷酸酯衍生物和抗冲改性剂,从而产生改善的耐疲劳性。该聚碳酸酯组合物可用于制造具有改善的耐疲劳性的制品,例如,移动电话部件,以及其它模制的电子和机械部件。
在另一方面,公开了一种耐疲劳性提高的组合物,其包括有效量的聚碳酸酯、季戊四醇二亚磷酸酯衍生物和抗冲改性剂,以生产根据ASTMD638-03破坏循环数(failure cycle rate)为至少8×104个循环的制品。参数“ASTM D638-03破坏循环”在压力为28.4MPa、频率为5Hz,根据ASTMD638-03型I进行测量,其中破坏点记录为破坏的循环数。
在另外的方面,公开了一种组合物,例如热塑性组合物,其具有改善的耐疲劳性。该组合物包括(i)100重量份聚碳酸酯;(ii)1.0重量份~约30重量份抗冲改性剂,和(iii)5.0×10-3重量份~约0.5重量份式(P-1)的季戊四醇二亚磷酸酯衍生物:
其中m为整数,且1≤m≤5;n为整数,且1≤n≤5;R1和R2各自独立地选自芳基烷基、烷基芳基烷基、芳基、烷基芳基及其任意组合。
在另一方面,公开了由该组合物制成的制品,例如电子或机械部件,例如移动电话外壳。例如,该组合物可以用于生产ASTM D638-03破坏循环数为至少8×104个循环的模制耐疲劳部件。
通过以下详细说明更加具体地示例各实施方式的这些和其它非限制性特征和/或性质。
发明详述
本申请公开了一种包括季戊四醇二亚磷酸酯衍生物和抗冲改性剂的聚碳酸酯组合物。该聚碳酸酯组合物表现出特别理想的性能,例如尤其是改善的耐疲劳特性。
如本申请使用的,术语“聚碳酸酯”是指含有相同或不同的碳酸酯单元的聚合物,或者含有相同或不同的碳酸酯单元以及不同于碳酸酯的一个或多个单元的共聚物(即,共聚碳酸酯);术语“脂族”是指这样的烃基,即其化合价至少为一,且含有不是环状的、线性或支化的碳原子排列;“芳族”是指含有至少一个芳基的、化合价至少为一的基团;“脂环族”是指这样的基团,即其化合价至少为一,且含有环状的但不是芳族的碳原子排列;“烷基”是指直链或支链的一价烃基;“烷撑”是指直链或支链的二价烃基;“烷叉”是指直链或支链的二价烃基,其具有在一个共同碳原子上的两个化合价;“链烯基”是指具有至少两个碳原子被碳-碳双键连接的、直链或支链的一价烃基;“环烷基”是指具有至少三个碳原子的非芳族的一价脂环烃基,其具有至少一个不饱和度;“环亚烷基”是指具有至少三个碳原子的非芳族的二价脂环烃基,其具有至少一个不饱和度;“芳基”是指一价芳族苯环基,或者是指稠合有至少一个任选取代苯环的任选取代的苯环体系基团;“芳族基团”是指含有至少一个芳基的、化合价至少为一的基团;芳族基团的实例包括:苯基、吡啶基、呋喃基、噻嗯基、萘基等;“亚芳基”是指苯环双基或者是指稠合有至少一个任选取代苯环的苯环体系双基;“酰基”是指与羰基碳原子连接的一价烃基,其中该羰基碳原子还与邻接基团相连接;“烷基芳基”是指将如上所定义的烷基取代到如上所定义的芳基上;“芳基烷基”是指将如上所定义的芳基取代到如上所定义的烷基上;“烷氧基”是指如上所定义的烷基通过氧基与邻接基团相连接;“芳氧基”是指如上所定义的芳基通过氧基与邻接基团相连接;所用的与量有关的修饰语“大约”包括设定值,具有本文所规定的含义(例如,包括与具体量的测量有关的误差度);“任选的”或“任选地”是指其后所描述的事件或情况可能发生或者可能不发生,该描述包括事件发生的情况以及事件不发生的情况;“直接键(direct bond)”,其中一部分结构变量说明,是指将在被称为“直接键”的变量之前以及之后的取代基直接连接。
在本申请中使用标准命名法来描述化合物。不在两个字母或符号之间的破折号(“-”)用来表示取代基的结合点。例如,-CHO是通过羰基(C=O)的碳原子进行结合。如果上下文没有清楚地相反规定,单数形式“a”、“an”和“the”包括复数对象。表示相同特征或组成的所有范围的端点都可独立地结合或包括该端点。所有的引用文献都并入本申请作为参考。本申请中术语“第一”、“第二”等不表示任何顺序、数量或重要性,而是被用来将一个元素与另一个元素区别开。
在一种实施方式中,本公开内容提供了一种耐疲劳的组合物例如热塑性组合物,其包括:
(i)100重量份聚碳酸酯;
(ii)约1.0重量份~约30重量份抗冲改性剂;和
(iii)约5.0×10-3重量份~约0.5重量份式(P-1)的季戊四醇二亚磷酸酯衍生物:
其中m为整数,且1≤m≤5;n为整数,且1≤n≤5;R1和R2各自独立地选自芳基烷基、烷基芳基烷基、芳基、烷基芳基及其任意组合。
该耐疲劳的组合物可以用于生产ASTM D638-03破坏循环数为至少8×104、优选至少1.0×105和更优选至少1.5×105的制品。
在优选的实施方式中,该季戊四醇二亚磷酸酯衍生物具有式(P-1),其中2≤m≤3;2≤n≤3;R1和R2各自独立地包括芳基烷基。
该季戊四醇二亚磷酸酯衍生物的实例包括但不限于以下具体化合物:
在具体的实施方式中,季戊四醇二亚磷酸酯衍生物为式(P-2)的化合物,或二(2,4-二枯基苯基)季戊四醇二亚磷酸酯。该化合物可以以名称 S-9228从Dover Chemical Corporation,Dover,Ohio购买。
虽然在该实施方式中,季戊四醇二亚磷酸酯的量通常为约5.0×10-3重量份~约0.5重量份,该量具体地可以为约1.0×10-2重量份~约0.1重量份,更具体地可以为约6.0×10-2重量份~约7.5×10-2重量份。例如,Doverphos S-9228的使用量可以为例如6.2×10-2重量份,6.3×10-2重量份,6.9×10-2重量份,和7.3×10-2重量份等。
在实施方式中,季戊四醇二亚磷酸酯可以起热稳定剂的作用,以及任选地,它可以与任何其它适宜的热稳定剂组合,条件是其它热稳定剂的性质和量不会有害地影响组合物的所需性质。适宜的热稳定剂包括,例如,有机亚磷酸酯例如三苯基亚磷酸酯、三-(2,6-二甲基苯基)亚磷酸酯、三-(混和的单-和二-壬基苯基)亚磷酸酯等;膦酸酯,例如二甲基苯膦酸酯(dimethylbenzene phosphonate)等,磷酸酯例如磷酸三甲酯等,或者含有至少一种前述热稳定剂的组合。例如,商品名为IRGAPHOSTM 168的三(2,4-二-叔丁基苯基)亚磷酸酯可以用作另外的热稳定剂。当存在时,任选的热稳定剂使用的量可以为0.0001~1wt%,基于用于组合物的聚碳酸酯的重量。
在各种示例性实施方式中,抗冲改性剂可以选自弹性体改性的接枝共聚物,聚硅氧烷-聚碳酸酯共聚物,和它们的任意组合。
虽然在该实施方式中,抗冲改性剂的量通常为约1.0重量份~约30重量份,该量具体地可以为约2.0重量份~约25重量份,更具体地可以为约2.6重量份~约22重量份。例如,弹性体改性的接枝共聚物的量可以为约2.6份~约9.98份,聚硅氧烷-聚碳酸酯共聚物的量可以为约14.2份~约21.2份。
该弹性体改性接枝共聚物可以包括:(i)弹性(即橡胶状)聚合物基体,其Tg低于10℃,更特别地低于-10℃,更加特别地为-40℃~-80℃;和(ii)接枝到弹性聚合物基体的刚性聚合物基体。
该弹性体改性接枝共聚物可以由以下方法来制备:首先,提供弹性聚合物;然后在弹性体存在下使刚性相的组成单体聚合,获得接枝共聚物。接枝物可以作为接枝支链或者作为壳而被连接到弹性体芯。该壳可以仅仅物理地包裹该芯,或者该壳可以部分地或者基本上完全地与该芯接枝。
用作弹性体相的适宜材料包括:例如,共轭二烯橡胶;共轭二烯与小于50wt%的可共聚单体的共聚物;C1-8烷基(甲基)丙烯酸酯与共轭二烯的弹性共聚物;烯烃橡胶例如乙烯-丙烯共聚物(EPR)或乙烯-丙烯-二烯单体橡胶(EPDM);乙烯-乙酸乙烯酯橡胶;硅橡胶;弹性的C1-8烷基(甲基)丙烯酸酯;C1-8烷基(甲基)丙烯酸酯与丁二烯和/或苯乙烯的弹性共聚物;或者含有至少一种前述弹性体的组合。
用于制备弹性体相的适宜共轭二烯单体为化学式(E-1):
其中R1各自独立地为氢、C1-C5烷基等。可以使用的共轭二烯单体的实例为:丁二烯、异戊二烯、1,3-庚二烯、甲基-1,3-戊二烯、2,3-二甲基-1,3-丁二烯、2-乙基-1,3-戊二烯、1,3-和2,4-己二烯等,以及含有至少一种前述共轭二烯单体的混合物。具体的共轭二烯均聚物包括聚丁二烯和聚异戊二烯。
也可以使用共轭二烯橡胶的共聚物,例如由共轭二烯和一种或多种可与其共聚合的单体的含水自由基乳液聚合而制备的那些共聚物。乙烯基芳族化合物可以与烯键式不饱和腈类单体共聚合而形成共聚物,其中乙烯基芳族化合物可以包括化学式(E-2)的单体:
其中R2各自独立地为氢、C1-C12烷基、C3-C12环烷基、C6-C12芳基、C7-C12芳基烷基、C7-C12烷基芳基、C1-C12烷氧基、C3-C12环烷氧基、C6-C12芳氧基、氯、溴或羟基;R3为氢、C1-C5烷基、溴或氯。可以使用的合适单乙烯基芳族单体的实例包括:苯乙烯、3-甲基苯乙烯、3,5-二乙基苯乙烯、4-正丙基苯乙烯、α-甲基苯乙烯、α-甲基乙烯基甲苯、α-氯苯乙烯、α-溴苯乙烯、二氯苯乙烯、二溴苯乙烯、四氯苯乙烯等,以及含有至少一种前述化合物的组合。苯乙烯和/或α-甲基苯乙烯可以用作与共轭二烯单体共聚合的单体。
可以与共轭二烯共聚合的其它单体是单乙烯基单体,例如衣康酸,丙烯酰胺,N-取代的丙烯酰胺或甲基丙烯酰胺,马来酸酐,马来酰亚胺,N-烷基、芳基-或卤代芳基取代的马来酰亚胺,(甲基)丙烯酸缩水甘油酯以及通式(E-3)的单体:
其中R4是氢、C1-C5烷基、溴或氯;R5是C1-C12烷氧基羰基、C1-C12芳氧基羰基、羟基羰基等。化学式(E-3)的单体的实例包括:丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸-2-乙基己酯等,以及含有至少一种前述单体的组合。通常使用诸如丙烯酸正丁酯、丙烯酸乙酯和丙烯酸-2-乙基己酯的单体作为可与共轭二烯单体共聚合的单体。也可以使用前述单乙烯基单体和单乙烯基芳族单体的组合。
适宜作为弹性体相的合适(甲基)丙烯酸酯类单体可以是C1-8烷基(甲基)丙烯酸酯、尤其是C4-6烷基(甲基)丙烯酸酯的交联的、颗粒状乳液均聚物或共聚物,例如:丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸-2-乙基己酯等以及含有至少一种前述单体的组合。C1-8烷基(甲基)丙烯酸酯单体可以任选地在具有最多15wt%的化学式(E-1)、(E-2)或(E-3)的共聚单体的混合物中进行聚合。示例性共聚单体包括但不限于:丁二烯、异戊二烯、苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸苯酯、甲基丙烯酸苯乙酯(penethylmethacrylate)、N-环己基丙烯酰胺、乙烯基·甲基醚以及含有至少一种前述共聚单体的混合物。任选地,可以存在最多5wt%的多官能交联共聚单体,例如二乙烯基苯,亚烷基二醇二(甲基)丙烯酸酯如乙二醇双丙烯酸酯,亚烷基三醇三(甲基)丙烯酸酯,聚酯二(甲基)丙烯酸酯、双丙烯酰胺、氰脲酸三烯丙酯、异氰脲酸三烯丙酯、(甲基)丙烯酸烯丙酯、马来酸二烯丙酯、富马酸二烯丙酯、己二酸二烯丙酯、柠檬酸的三烯丙酯、磷酸的三烯丙酯等,以及含有至少一种前述交联剂的组合。
弹性体相可以通过以下方法来聚合:本体、乳液、悬浮、溶液或者组合方法如本体-悬浮、乳液-本体、本体-溶液或其它技术,使用连续法、半分批法或分批法。弹性体基体的粒度不是关键性的。例如,0.001~25微米、特别是0.01~15微米或更特别是0.1~8微米的平均粒度可以用于基于乳液的聚合橡胶胶乳(emulsion based polymerized rubber lattice)。0.5~10微米、特别是0.6~1.5微米的粒度可以用于本体聚合的橡胶基体。可以通过简单的透光率法或毛细管体动力色谱法(capillary hydrodynamic chromatography,CHDF)来测量粒度。弹性体相可以是颗粒状的、适度交联的共轭丁二烯或C4-6烷基-丙烯酸酯橡胶,并且优选具有高于70wt%的凝胶含量。丁二烯与苯乙烯和/或C4-6烷基-丙烯酸酯橡胶的混合物也是适宜的。
弹性体相可以占全部接枝共聚物的5~95wt%,更特别是弹性体改性接枝共聚物的20~90wt%,更加特别是40~85wt%,余量为刚性接枝相。
弹性体改性接枝共聚物的刚性相可以通过以下方法来制备:在一种或多种弹性聚合物基体存在下,使含有(甲基)丙烯酸酯单体和任选的单乙烯基芳族单体的混合物进行接枝共聚。上述的化学式(E-2)的单乙烯基芳族单体可以用于刚性接枝相,包括:苯乙烯、α-甲基苯乙烯、卤代苯乙烯如二溴苯乙烯、乙烯基甲苯、乙烯基二甲苯、丁基苯乙烯、对羟基苯乙烯、甲氧基苯乙烯等,或者含有至少一种前述单乙烯基芳族单体的组合。适宜的共聚单体包括:例如,上述的单乙烯基芳族单体和/或通式(E-3)的单体。在一种实施方式中,R4是氢或C1-C2烷基,R5是氰基或C1-C12烷氧基羰基。用于刚性相的适宜共聚单体的具体实例包括:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯等,以及含有至少一种前述共聚单体的组合。
根据所存在的弹性体改性聚合物的量,未接枝的刚性聚合物或共聚物的分离基质或连续相可以与弹性体改性接枝共聚物一起同时获得。通常,基于抗冲改性剂的总重量,该抗冲改性剂包括40~95wt%弹性体改性接枝共聚物和5~60wt%接枝(共)聚合物。在另一实施方案中,基于抗冲改性剂的总重量,该抗冲改性剂包括50~85wt%、更特别是75~85wt%橡胶改性接枝共聚物和15~50wt%、更特别是15~25wt%接枝(共)聚合物。
另一具体类型的弹性体改性抗冲改性剂包括来源于以下的结构单元:至少一种硅橡胶单体,具有化学式H2C=C(Rd)C(O)OCH2CH2Re的支化丙烯酸酯类橡胶单体,其中Rd是氢或C1-C8直链或支链烷基,Re是支链C3-C16烷基;第一接枝连接单体;可聚合的、含链烯基的有机物;第二接枝连接单体。硅橡胶单体可以包括:例如,环状硅氧烷、四烷氧基硅烷、三烷氧基硅烷、(丙烯酰氧基)烷氧基硅烷、(巯基烷基)烷氧基硅烷、乙烯基烷氧基硅烷或烯丙基烷氧基硅烷(单独地或组合地),例如,十甲基环五硅氧烷、十二甲基环六硅氧烷、三甲基三苯基环三硅氧烷、四甲基四苯基环四硅氧烷、四甲基四乙烯基环四硅氧烷、八苯基环四硅氧烷、八甲基环四硅氧烷和/或四乙氧基硅烷。
示例的支化丙烯酸酯类橡胶单体包括:丙烯酸异辛酯、丙烯酸-6-甲基辛酯、丙烯酸-7-甲基辛酯、丙烯酸-6-甲基庚酯等(单独地或组合地)。可聚合的、含链烯基的有机物可以是:例如,化学式(E-2)或(E-3)的单体如苯乙烯、α-甲基苯乙烯,或者未支化的(甲基)丙烯酸酯如甲基丙烯酸甲酯、甲基丙烯酸-2-乙基己酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯等(单独地或组合地)。
至少一种第一接枝连接单体可以是:(丙烯酰氧基)烷氧基硅烷、(巯基烷基)烷氧基硅烷、乙烯基烷氧基硅烷或烯丙基烷氧基硅烷(单独地或组合地),例如,(γ-甲基丙烯酰氧基丙基)(二甲氧基)甲基硅烷和/或(3-巯基丙基)三甲氧基硅烷。至少一种第二接枝连接单体是具有至少一个烯丙基的多烯键式不饱和化合物,例如甲基丙烯酸烯丙酯、氰脲酸三烯丙酯或异氰脲酸三烯丙酯,单独地或组合地。
硅氧烷-丙烯酸酯类抗冲改性剂组合物可以通过乳液聚合来制备,其中例如在30℃~110℃的温度,在表面活性剂如十二烷基苯磺酸存在下,使至少一种硅橡胶单体与至少一种第一接枝连接单体进行反应,形成硅橡胶胶乳。可选择地,可以使环状硅氧烷(例如环八甲基四硅氧烷和正硅酸四乙氧基酯)与第一接枝连接单体(例如(γ-甲基丙烯酰氧基丙基)甲基二甲氧基硅烷)进行反应,以提供平均粒度为100纳米~2微米的硅橡胶。然后,任选地在交联单体如甲基丙烯酸烯丙酯存在下和/或在产生自由基的聚合催化剂如过氧化苯甲酰存在下,使至少一种支化丙烯酸酯类橡胶单体与该硅橡胶粒子进行聚合。然后,使该胶乳与可聚合的含链烯基有机物和第二接枝连接单体进行反应。通过凝结作用(通过用凝结剂处理)将接枝硅氧烷-丙烯酸酯类橡胶混合物的胶乳粒子从水相中分离出来,并干燥为细粉,以生产硅氧烷-丙烯酸酯类抗冲改性剂组合物。一般地,可以使用该方法来生产粒度为100纳米~2微米的硅氧烷-丙烯酸酯类抗冲改性剂。
用于制备前述弹性体改性接枝共聚物的已知方法包括:本体、乳液、悬浮、溶液或者组合方法如本体-悬浮、乳液-本体、本体-溶液或其它技术,使用连续法、半分批法或分批法。
前述类型的抗冲改性剂包括SAN共聚物,可以通过不含有碱性物质的乳液聚合法来制备,碱性物质是:例如,C6-30脂肪酸的碱金属盐,如硬脂酸钠、硬脂酸锂、油酸钠、油酸钾等;碱金属碳酸盐;胺如十二烷基二甲基胺、十二烷基胺等;胺的铵盐。这些物质通常用作乳液聚合的表面活性剂,可以催化聚碳酸酯的酯交换反应和/或降解。替代地,可以将离子型硫酸盐、磺酸盐或磷酸盐表面活性剂用于制备抗冲改性剂,尤其是抗冲改性剂的弹性基体部分。适宜的表面活性剂包括:例如,C1-22烷基或C7-25烷基芳基磺酸盐、C1-22烷基或C7-25烷基芳基硫酸盐、C1-22烷基或C7-25烷基芳基磷酸盐、取代的硅酸盐以及它们的混合物。具体的表面活性剂是C6-16烷基磺酸盐,特别地为C8-12烷基磺酸盐。实际上,任何上述抗冲改性剂都可以使用,只要它不含有脂肪酸的碱金属盐、碱金属碳酸盐和其它碱性物质。
在实施方式中,该弹性体改性接枝共聚物是甲基丙烯酸甲酯-丁二烯-苯乙烯(MBS)抗冲改性剂。除了MBS之外的弹性体改性接枝共聚物的其它实例包括但不限于:丙烯腈-丁二烯-苯乙烯(ABS)、丙烯腈-苯乙烯-丙烯酸丁酯(ASA)、甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯(MABS)和丙烯腈-乙烯-丙烯-二烯-苯乙烯(AES)。
在实施方式中,弹性体改性接枝共聚物包括橡胶状聚合物基体和接枝到该橡胶状聚合物基体上的刚性聚合物。橡胶状聚合物基体包括C1-8烷基(甲基)丙烯酸酯与共轭二烯的弹性共聚物;该刚性聚合物包括单乙烯基芳族单体的聚合物。弹性体改性接枝共聚物可以商业途径获得。在实施方式中,MBS共聚物可以以商品名ParaloidTM EXL2691A从Rohm & Haas获得,其是具有中性pH的稳定的MBS。
在实施方式中,抗冲改性剂可以包括聚硅氧烷-聚碳酸酯或聚碳酸酯-聚硅氧烷(PC-Si)共聚物,也被称为聚硅氧烷-聚碳酸酯。该共聚物的聚硅氧烷(在本申请中也被称为"聚二有机基硅氧烷")嵌段包括式(S-1)的硅氧烷重复单元(在本申请中也被称为“二有机基硅氧烷单元”):
其中R1在每次出现时相同或相异,为C1-13一价有机基团。例如,R1可以独立地为C1-C13烷基,C1-C13烷氧基,C2-C13链烯基,C2-C13链烯氧基,C3-C6环烷基,C3-C6环烷氧基,C6-C14芳基,C6-C10芳氧基,C7-C13芳基烷基,C7-C13芳基烷氧基,C7-C13烷基芳基,或者C7-C13烷基芳氧基。前述基团可以全部或部分被氟、氯、溴、碘或其组合卤化。在同一共聚物中,可以使用前述R1基团的组合。
在化学式(S-1)中的D值可以广泛地变化,这取决于热塑性组合物中各组分的类型和相对量、所需要的组合物性质以及其它需要考虑的事项。一般地,D的平均值可以为2~1000,特别是2~500,尤其是5~100。在一种实施方案中,D的平均值为10~75,在又一实施方案中,D的平均值为40~60。当D的值较低例如小于40时,可能需要使用相对较大量的聚碳酸酯-聚硅氧烷共聚物。相反,如果D的值较高例如大于40,可能需要使用相对较小量的聚碳酸酯-聚硅氧烷共聚物。
可以使用第一和第二(或更多)聚碳酸酯-聚硅氧烷共聚物的组合,其中第一共聚物的D平均值小于第二共聚物的D平均值。
在一种实施方式中,由化学式(S-2)的重复结构单元来提供聚二有机基硅氧烷嵌段:
其中D定义如上;每个R1可以独立地相同或不同,且定义如上;每个Ar可以独立地相同或不同,为取代或未取代的C6-C30亚芳基,其中价键直接地与芳族部分相连接。化学式(S-2)中适宜的Ar基团可以来源于C6-C30二羟基亚芳基化合物,或者两种或更多种二羟基亚芳基化合物的任意组合。适宜的二羟基亚芳基化合物的具体实例为:1,1-双(4-羟基苯基)甲烷、1,1-双(4-羟基苯基)乙烷、2,2-双(4-羟基苯基)丙烷、2,2-双(4-羟基苯基)丁烷、2,2-双(4-羟基苯基)辛烷、1,1-双(4-羟基苯基)丙烷、1,1-双(4-羟基苯基)正丁烷、2,2-双(4-羟基-1-甲基苯基)丙烷、1,1-双(4-羟基苯基)环己烷、双(4-羟基苯基)硫醚和1,1-双(4-羟基-叔丁基苯基)丙烷。也可以使用含有至少一种前述二羟基化合物的组合。
化学式(S-2)的单元可以衍生于化学式(S-3)的相应二羟基化合物:
其中R1、Ar和D描述如上。可以通过以下方法来得到化学式(S-3)的化合物:在相转移条件下,使二羟基亚芳基化合物与例如α,ω-二乙酰氧基聚二有机基硅氧烷反应。
在另一实施方式中,聚二有机基硅氧烷嵌段包括化学式(S-4)的单元:
其中R1和D描述如上,R2在每次出现时独立地为二价C1-C30亚烷基,并且其中聚合后的聚硅氧烷单元是其相应的二羟基化合物的反应残基。在具体的实施方式中,由化学式(S-5)的重复结构单元来提供聚二有机基硅氧烷嵌段:
其中R1和D定义如上。化学式(S-5)中R3各自独立地为二价C2-C8脂族基团。化学式(S-5)中每个M可以相同或不同,可以为:卤素、氰基、硝基、C1-C8烷基硫基、C1-C8烷基、C1-C8烷氧基、C2-C8链烯基、C2-C8链烯氧基、C3-C8环烷基、C3-C8环烷氧基、C6-C10芳基、C6-C10芳氧基、C7-C12芳基烷基、C7-C12芳基烷氧基、C7-C12烷基芳基或者C7-C12烷基芳氧基,其中n各自独立地为0、1、2、3或4。
在一种实施方案中,M为:溴或氯,烷基例如甲基、乙基或丙基,烷氧基例如甲氧基、乙氧基或丙氧基,或芳基例如苯基、氯苯基或甲苯基;R3为:二亚甲基、三亚甲基或四亚甲基;R1为:C1-8烷基,卤代烷基例如三氟丙基,氰基烷基或者芳基例如苯基、氯苯基或甲苯基。在另一实施方案中,R1是甲基,或者甲基与三氟丙基的混合物,或者甲基与苯基的混合物。在又一实施方案中,M为甲氧基,n为1,R3为二价C1-C3脂族基团,R1为甲基。
化学式(S-5)的单元可以衍生于相应的二羟基聚二有机基硅氧烷(S-6):
其中R、D、M、R3和n描述如上。该二羟基聚硅氧烷可以通过在化学式(S-7)的硅氧烷氢化物(siloxane hydride)与脂族不饱和一元酚之间的铂催化加成来制备:
其中R1和D定义如前。适宜的脂族不饱和一元酚包括:例如,丁子香酚、2-烯丙基苯酚、4-烯丙基-2-甲基苯酚、4-烯丙基-2-苯基苯酚、4-烯丙基-2-溴苯酚、4-烯丙基-2-叔丁氧基苯酚、4-苯基-2-苯基苯酚、2-甲基-4-丙基苯酚、2-烯丙基-4,6-二甲基苯酚、2-烯丙基-4-溴-6-甲基苯酚、2-烯丙基-6-甲氧基-4-甲基苯酚和2-烯丙基-4,6-二甲基苯酚。也可以使用含有至少一种前述化合物的混合物。
在另一实施方式中,聚硅氧烷-聚碳酸酯共聚物包括约50-约99wt%的碳酸酯单元和约1-约50wt%的硅氧烷单元。在该范围内,聚硅氧烷-聚碳酸酯共聚物可以包括约70-约98wt%、特别地约75-约97wt%的碳酸酯单元和约2-约30wt%、特别地约3-约25wt%的硅氧烷单元,例如约20wt%硅氧烷单元。
在一种具体的实施方式中,聚硅氧烷-聚碳酸酯共聚物包括聚硅氧烷单元和来源于双酚A的碳酸酯单元。聚硅氧烷-聚碳酸酯的重均分子量可以为2,000~100,000,具体地为5,000~50,000,如通过凝胶渗透色谱测定的:使用交联的苯乙烯-二乙烯基苯柱,样品浓度为1mg/ml,以聚碳酸酯标样来校准。
如在300℃/1.2kg测量的,聚硅氧烷-聚碳酸酯共聚物的熔体体积流速可以为1~35立方厘米/10分钟(cc/10min),特别地为2~30cc/10min。可以使用不同流动性的聚硅氧烷-聚碳酸酯的混合物来获得全部所需要的流动性。
在本申请中可以使用的适宜聚硅氧烷-聚碳酸酯共聚物的实例包括在美国专利6,657,018中所描述的那些,将其并入本申请作为参考。也包括聚硅氧烷单元数比美国专利6,657,018中具体提到的那些多的聚硅氧烷-聚碳酸酯共聚物。
在一种实施方式中,组合物包括聚硅氧烷-聚碳酸酯共聚物,例如General Electric Co.,C9030P。C9030P是具有20wt%硅氧烷片段的PC-硅氧烷共聚物。树脂组合物包括聚硅氧烷-聚碳酸酯,其量有效地保持在其它组分存在下、由其制成的热塑性组合物的至少一种机械性能。
在各种示例实施方式中,组合物包括约2.6份~约9.98份MBS,或者约14.2份~约21.2份C9030P。
在实施方式中,可以将MBS和不透明C9030P同聚碳酸酯预混,然后在通常的聚碳酸酯加工条件下,通过双螺杆挤出机将该混合物挤出。
本公开内容的聚碳酸酯可以包括式(1)的碳酸酯重复结构单元:
其中R1基团可以选自任何芳族基团、脂环族基团以及脂族基团。在实施方式中,至少60%的R1基团是芳族有机基团。
在另一实施方式中,R1是芳族有机基团,例如化学式(2)的基团:
——A1—Y1—A2— (2)
其中A1和A2各自是单环二价芳基,Y1是具有一个或两个将A1与A2隔开的原子的桥接基团。在示例实施方式中,一个原子将A1与A2隔开。该类基团的示例非限制性实例为:-O-,-S-,-S(O)-,-S(O)2-,-C(O)-,亚甲基,环己基亚甲基,2-[2.2.1]-二环庚叉,乙叉,异丙叉,新戊叉,环己叉,环十五烷叉,环十二烷叉,及金刚烷叉。桥接基团Y1可以为烃基或饱和烃基如亚甲基,环己叉,或异丙叉。
在另一实施方式中,聚碳酸酯可以包括化学式(A-1)的碳酸酯重复结构单元:
其中Y1、A1和A2描述如上。
在又一实施方式中,聚碳酸酯可以通过具有化学式HO-R1-OH的二羟基化合物的界面反应来制备,其包括式(3)的二羟基化合物:
HO-A1—Y1—A2-OH (3)
其中Y1、A1和A2描述如上。
在又一实施方式中,聚碳酸酯可以通过通式(4)的双酚化合物的界面反应来制备:
其中Ra和Rb各自代表卤原子或一价烃基,可以是相同的或不同的;p和q各自独立地是0~4的整数;Xa代表化学式(5)的基团之一:
其中Rc和Rd各自独立地代表氢原子或一价直链或环状的烃基,Re是二价烃基。
在又一实施方式中,聚碳酸酯可以通过一种或多种通式(B-1)的双酚化合物的界面反应来制备:
其中每个G1在每次出现时独立地是C6-C20芳族基团;E在每次出现时独立地是键、C3-C20脂环族基团、C3-C20芳族基团、C1-C20脂族基团、含硫连接基、含硒连接基、含磷连接基或氧原子;“t”是大于等于1的数;“s”为0或1;“u”是包括0的整数。
适宜二羟基化合物的一些示例性和非限制性实例包括:间苯二酚;C1-3烷基取代的间苯二酚;4-溴间苯二酚、氢醌、4,4′-二羟基联苯、1,6-二羟基萘、2,6-二羟基萘、1,1-双(4-羟基苯基)环戊烷;2,2-双(3-烯丙基-4-羟基苯基)丙烷;2,2-双(2-叔丁基-4-羟基-5-甲基苯基)丙烷;2,2-双(3-叔丁基-4-羟基-6-甲基苯基)丙烷;2,2-双(3-叔丁基-4-羟基-6-甲基苯基)丁烷;1,3-双[4-羟基苯基-1-(1-甲基亚乙基)]苯;1,4-双[4-羟基苯基-1-(1-甲基亚乙基)]苯;1,3-双[3-叔丁基-4-羟基-6-甲基苯基-1-(1-甲基亚乙基)]苯;1,4-双[3-叔丁基-4-羟基-6-甲基苯基-1-(1-甲基亚乙基)]苯;4,4′-联苯酚;2,2′,6,8-四甲基-3,3′,5,5′-四溴-4,4′-联苯酚;2,2′,6,6′-四甲基-3,3′,5-三溴-4,4′-联苯酚;1,1-双(4-羟基苯基)-2,2,2-三氯乙烷;1,1-双(4-羟基苯基)-1-氰基乙烷;1,1-双(4-羟基苯基)二氰基甲烷;1,1-双(4-羟基苯基)-1-氰基-1-苯基甲烷;2,2-双(3-甲基-4-羟基苯基)丙烷;1,1-双(4-羟基苯基)降冰片烷;3,3-双(4-羟基苯基)-2-苯并[c]呋喃酮;1,2-双(4-羟基苯基)乙烷;1,3-双(4-羟基苯基)丙烯酮(propenone);双(4-羟基苯基)硫醚;4,4′-二羟基二苯醚(4,4′-oxydiphenol);4,4-双(4-羟基苯基)戊酸;4,4-双(3,5-二甲基-4-羟基苯基)戊酸;2,2-双(4-羟基苯基)乙酸;2,4′-二羟基二苯基甲烷;2-双(2-羟基苯基)甲烷;双(4-羟基苯基)甲烷;双(4-羟基-5-硝基苯基)甲烷;双(4-羟基-2,6-二甲基-3-甲氧基苯基)甲烷;1,1-双(4-羟基苯基)乙烷;1,1-双(4-羟基-2-氯苯基)乙烷;2,2-双(4-羟基苯基)丙烷(双酚A);1,1-双(4-羟基苯基)丙烷;2,2-双(3-氯-4-羟基苯基)丙烷;2,2-双(3-溴-4-羟基苯基)丙烷;2,2-双(4-羟基-3-甲基苯基)丙烷;2,2-双(4-羟基-3-异丙基苯基)丙烷;2,2-双(3-叔丁基-4-羟基苯基)丙烷;2,2-双(3-苯基-4-羟基苯基)丙烷;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;2,2-双(3,5-二甲基-4-羟基苯基)丙烷;2,2-双(3-氯-4-羟基-5-甲基苯基)丙烷;2,2-双(3-溴-4-羟基-5-甲基苯基)丙烷;2,2-双(3-氯-4-羟基-5-异丙基苯基)丙烷;2,2-双(3-溴-4-羟基-5-异丙基苯基)丙烷;2,2-双(3-叔丁基-5-氯-4-羟基苯基)丙烷;2,2-双(3-溴-5-叔丁基-4-羟基苯基)丙烷;2,2-双(3-氯-5-苯基-4-羟基苯基)丙烷;2,2-双(3-溴-5-苯基-4-羟基苯基)丙烷;2,2-双(3,5-二异丙基-4-羟基苯基)丙烷;2,2-双(3,5-二叔丁基-4-羟基苯基)丙烷;2,2-双(3,5-二苯基-4-羟基苯基)丙烷;2,2-双(4-羟基-2,3,5,6-四氯苯基)丙烷;2,2-双(4-羟基-2,3,5,6-四溴苯基)丙烷;2,2-双(4-羟基-2,3,5,6-四甲基苯基)丙烷;2,2-双(2,6-二氯-3,5-二甲基-4-羟基苯基)丙烷;2,2-双(2,6-二溴-3,5-二甲基-4-羟基苯基)丙烷;2,2-双(4-羟基-3-乙基苯基)丙烷;2,2-双(4-羟基-3,5-二甲基苯基)丙烷;2,2-双(3,5,3’,5’-四氯-4,4’-二羟基苯基)丙烷;1,1-双(4-羟基苯基)环己基甲烷;2,2-双(4-羟基苯基)-1-苯基丙烷;1,1-双(4-羟基苯基)环己烷;1,1-双(3-氯-4-羟基苯基)环己烷;1,1-双(3-溴-4-羟基苯基)环己烷;1,1-双(4-羟基-3-甲基苯基)环己烷;1,1-双(4-羟基-3-异丙基苯基)环己烷;1,1-双(3-叔丁基-4-羟基苯基)环己烷;1,1-双(3-苯基-4-羟基苯基)环己烷;1,1-双(3,5-二氯-4-羟基苯基)环己烷;1,1-双(3,5-二溴-4-羟基苯基)环己烷;1,1-双(3,5-二甲基-4-羟基苯基)环己烷;4,4′-[1-甲基-4-(1-甲基-乙基)-1,3-环己二基]双酚(1,3 BHPM);4-[1-[3-(4-羟基苯基)-4-甲基环己基]-1-甲基-乙基]-苯酚(2,8 BHPM);3,8-二羟基-5a,10b-二苯基香豆冉基-2’,3’,2,3-香豆冉(3,8-dihydroxy-5a,10b-diphenylcoumarano-2’,3’,2,3-coumarane,DCBP);2-苯基-3,3-双(4-羟基苯基)苯并吡咯酮;1,1-双(3-氯-4-羟基-5-甲基苯基)环己烷;1,1-双(3-溴-4-羟基-5-甲基苯基)环己烷;1,1-双(3-氯-4-羟基-5-异丙基苯基)环己烷;1,1-双(3-溴-4-羟基-5-异丙基苯基)环己烷;1,1-双(3-叔丁基-5-氯-4-羟基苯基)环己烷;1,1-双(3-溴-5-叔丁基-4-羟基苯基)环己烷;1,1-双(3-氯-5-苯基-4-羟基苯基)环己烷;1,1-双(3-溴-5-苯基-4-羟基苯基)环己烷;1,1-双(3,5-二异丙基-4-羟基苯基)环己烷;1,1-双(3,5-二-叔丁基-4-羟基苯基)环己烷;1,1-双(3,5-二苯基-4-羟基苯基)环己烷;1,1-双(4-羟基-2,3,5,6-四氯苯基)环己烷;1,1-双(4-羟基-2,3,5,6-四溴苯基)环己烷;1,1-双(4-羟基-2,3,5,6-四甲基苯基)环己烷;1,1-双(2,6-二氯-3,5-二甲基-4-羟基苯基)环己烷;1,1-双(2,6-二溴-3,5-二甲基-4-羟基苯基)环己烷;1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3-氯-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3-溴-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(4-羟基-3-甲基苯基)-3,3,5-三甲基环己烷;1,1-双(4-羟基-3-异丙基苯基)-3,3,5-三甲基环己烷;1,1-双(3-叔丁基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3-苯基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3,5-二氯-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3,5-二溴-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3,5-二甲基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3-氯-4-羟基-5-甲基苯基)-3,3,5-三甲基环己烷;1,1-双(3-溴-4-羟基-5-甲基苯基)-3,3,5-三甲基环己烷;1,1-双(3-氯-4-羟基-5-异丙基苯基)-3,3,5-三甲基环己烷;1,1-双(3-溴-4-羟基-5-异丙基苯基)-3,3,5-三甲基环己烷;1,1-双(3-叔丁基-5-氯-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3-溴-5-叔丁基-4-羟基苯基)-3,3,5-三甲基环己烷;双(3-氯-5-苯基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3-溴-5-苯基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3,5-二异丙基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3,5-二叔丁基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(3,5-二苯基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(4-羟基-2,3,5,6-四氯苯基)-3,3,5-三甲基环己烷;1,1-双(4-羟基-2,3,5,6-四溴苯基)-3,3,5-三甲基环己烷;1,1-双(4-羟基-2,3,5,6-四甲基苯基)-3,3,5-三甲基环己烷;1,1-双(2,6-二氯-3,5-二甲基-4-羟基苯基)-3,3,5-三甲基环己烷;1,1-双(2,6-二溴-3,5-二甲基-4-羟基苯基)-3,3,5-三甲基环己烷;4,4-双(4-羟基苯基)庚烷;1,1-双(4-羟基苯基)癸烷;1,1-双(4-羟基苯基)环十二烷;1,1-双(3,5-二甲基-4-羟基苯基)环十二烷;4,4’二羟基-1,1-联苯;4,4’-二羟基-3,3’-二甲基-1,1-联苯;4,4’-二羟基-3,3’-二辛基-1,1-联苯;4,4′-(3,3,5-三甲基亚环己基)二酚;4,4′-双(3,5-二甲基)二酚;4,4’-二羟基二苯基醚;4,4’-二羟基二苯基硫醚;1,3-双(2-(4-羟基苯基)-2-丙基)苯;1,3-双(2-(4-羟基-3-甲基苯基)-2-丙基)苯;1,4-双(2-(4-羟基苯基)-2-丙基)苯;1,4-双(2-(4-羟基-3-甲基苯基)-2-丙基)苯;2,4′-二羟基苯基砜;4,4’-二羟基二苯基砜(BPS);双(4-羟基苯基)甲烷;2,6-二羟基萘;氢醌;3-(4-羟基苯基)-1,1,3-三甲基茚满基-5-醇;1-(4-羟基苯基)-1,3,3-三甲基茚满-5-醇;4,4-二羟基二苯基醚;4,4-二羟基-3,3-二氯二苯基醚;4,4-二羟基-2,5-二羟基二苯基醚;4,4-硫醇二酚;2,2,2′,2′-四氢-3,3,3′,3′-四甲基-1,1′-螺环双[1H-茚]-6,6′-二醇;双(4-羟基苯基)乙腈;双(4-羟基苯基)亚砜;双(4-羟基苯基)砜;9,9-双(4-羟基苯基)氟;2,7-二羟基芘;6,6′-二羟基-3,3,3′,3′-四甲基螺环(双)茚满("螺双茚满双酚");3,3-双(4-羟基苯基)-2-苯并[c]呋喃酮;2,6-二羟基二苯并-p-二氧芑;2,6-二羟基噻蒽;2,7-二羟基吩噻噁(2,7-dihydroxyphenoxathin);2,7-二羟基-9,10-二甲基吩嗪;3,6-二羟基二苯并呋喃;3,6-二羟基二苯并噻吩;2,7-二羟基卡唑等,以及含有至少一种前述二羟基化合物的组合。
以化学式(4)表示的双酚化合物类型的具体实例包括:1,1-双(4-羟基苯基)甲烷、1,1-双(4-羟基苯基)乙烷、2,2-双(4-羟基苯基)丙烷(以下称为“双酚A”或“BPA”)、2,2-双(4-羟基苯基)丁烷、2,2-双(4-羟基苯基)辛烷、1,1-双(4-羟基苯基)丙烷、1,1-双(4-羟基苯基)正丁烷、2,2-双(4-羟基-1-甲基苯基)丙烷、1,1-双(4-羟基-叔丁基苯基)丙烷、3,3-双(4-羟基苯基)苯并吡咯酮、2-苯基-3,3-双(4-羟基苯基)苯并吡咯酮(PPPBP)、1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷(BPI)和1,1-双(4-羟基-3-甲基苯基)环己烷(DMBPC)。也可以使用含有至少一种前述二羟基化合物的组合。
在一种实施方式中,聚碳酸酯可以包括式(A-2)的碳酸酯重复结构单元:
其中p、q、Ra、Rb和Xa描述如上。
在另一实施方式中,聚碳酸酯可以包括化学式(A-3)的碳酸酯重复结构单元,即BPA单元:
也可以使用支化聚碳酸酯,以及线性聚碳酸酯和支化聚碳酸酯的共混物。支化聚碳酸酯可通过在聚合期间加入支化剂来制备。这些支化剂包括多官能的有机化合物,其包含至少三个选自下列的官能团:羟基,羧基,羧酸酐,卤代甲酰基,及前述官能团的组合。具体实例包括偏苯三酸,偏苯三酸酐,偏苯三酰氯,三对羟基苯基乙烷,靛红-二酚,三酚TC(1,3,5-三((对-羟基苯基)异丙基)苯),三酚PA(4(4(1,1-二(对-羟基苯基)-乙基)α,α-二甲基苄基)苯酚),4-氯甲酰基邻苯二甲酸酐,均苯三酸,及二苯甲酮四羧酸。支化剂的添加量可以为聚碳酸酯的约0.05~2.0wt%。所有类型的聚碳酸酯端基均可用于聚碳酸酯组合物,只要这种端基不显著地影响所需要的聚碳酸酯产品的性质。
该聚碳酸酯的重均分子量(Mw)可以为约1500~约100,000,包括约5000~约50,000,最特别地为约10,000~约30,000,如通过以下的凝胶渗透色谱(GPC)测定的:使用交联的苯乙烯-二乙烯基苯柱,样品浓度为1mg/ml,以聚碳酸酯标样来校准。
在实施方式中,该聚碳酸酯具有适合于制造薄制品(例如移动电话外壳)的流动特性。熔体体积流动速率(通常简写为MVR)度量在规定的温度和载荷下热塑性材料通过喷嘴的挤出速率。根据ASTM D1238-04在300℃/1.2kg测量,适合于形成薄制品的聚碳酸酯的MVR可以为0.5~80立方厘米/10分钟(cc/10min)。在具体的实施方式中,根据ASTM D1238-04在300℃/1.2kg测量,合适的聚碳酸酯组合物的MVR为0.5~50cc/10min,特别地为0.5~25cc/10min,更特别地为1~15cc/10min。可以使用不同流动性的聚碳酸酯的混合物,以实现总体上所需要的流动性。
在实施方式中,聚碳酸酯或聚碳酸酯混合物的MVR值(在300℃/1.2kg)为约5~约13,例如约8~约12.5。
在另一实施方式中,阻燃组合物的组分(i)包括高流动性PC、常规流动性PC(100级PC(100 Grade PC)),或它们的混合物。高流动性PC可以包括,例如,分子量为约21,600~22,200的双酚A聚碳酸酯均聚物(分子量基于使用聚碳酸酯标样的凝胶渗透色谱测定法)。常规流动性PC可以包括,例如,分子量为约29,500~30,300的双酚A聚碳酸酯均聚物。
本公开内容的聚碳酸酯可以包括含有碳酸酯链单元和其他单元的共聚物。特别适宜的共聚物是聚酯-聚碳酸酯,也称为共聚酯-聚碳酸酯和聚酯-碳酸酯。也可以使用聚碳酸酯与聚酯-聚碳酸酯的组合。如在本申请中使用的,“组合”包括所有的混合物、共混物、合金、反应产物等。
不过,组合物中聚酯-聚碳酸酯和/或聚酯的量应该保持低含量,使得它不会有害地影响组合物的阻燃性。例如,聚酯-聚碳酸酯和/或聚酯的量可以为痕量,或者可以低到零。
在一种实施方式中,聚酯-聚碳酸酯含有式(6)的重复单元:
其中D是衍生自二羟基化合物的二价基团,可以是:例如,C2-10亚烷基、C6-20脂环族基团、C6-20芳族基团或者其中亚烷基含有2~6个碳原子,特别地2、3或4个碳原子的聚亚烷基氧化物基团;T是衍生自二羧酸的二价基团,可以是:例如,C2-10亚烷基、C6-20脂环族基团、C6-20烷基芳族基团或者C6-20芳族基团。
在一种实施方式中,D是C2-6亚烷基。在另一实施方式中,D衍生自化学式(7)的芳族二羟基化合物:
其中Rf各自独立地为卤原子、C1-10烃基或卤素取代的C1-10烃基;n为0~4。卤素通常为溴。可以以化学式(7)表示的化合物的实例包括:间苯二酚;取代的间苯二酚化合物,例如5-甲基间苯二酚、5-乙基间苯二酚、5-丙基间苯二酚、5-丁基间苯二酚、5-叔丁基间苯二酚、5-苯基间苯二酚、5-枯基间苯二酚、2,4,5,6-四氟间苯二酚、2,4,5,6-四溴间苯二酚等;邻苯二酚;氢醌;取代的氢醌,例如2-甲基氢醌、2-乙基氢醌、2-丙基氢醌、2-丁基氢醌、2-叔丁基氢醌、2-苯基氢醌、2-枯基氢醌、2,3,5,6-四甲基氢醌、2,3,5,6-四叔丁基氢醌、2,3,5,6-四氟氢醌、2,3,5,6-四溴氢醌等;或者包括至少一种前述化合物的组合。
可以用于制备聚酯的芳族二羧酸的实例包括:间苯二甲酸或对苯二甲酸、1,2-二(对羧基苯基)乙烷、4,4′-二羧基二苯醚(4,4′-dicarboxydiphenylether)、4,4′-联苯甲酸(4,4′-bisbenzoic acid)以及含有至少一种前述酸的混合物。也可以存在含有稠环的酸,例如1,4-萘二羧酸、1,5-萘二羧酸或2,6-萘二羧酸。具体的二羧酸是对苯二甲酸、间苯二甲酸、萘二羧酸、环己烷二羧酸或者它们的混合物。具体的二羧酸包括对苯二甲酸和间苯二甲酸的混合物(其中对苯二甲酸与间苯二甲酸的重量比为91:1~2:98)。在另一具体实施方式中,D是C2-6亚烷基,且T是对亚苯基、间亚苯基、亚萘基、二价脂环族基团或者它们的混合。这一类聚酯包括聚(对苯二甲酸亚烷基酯)。
在另一实施方式中,化学式(1)的碳酸酯单元可以衍生自化学式(7)的芳族二羟基化合物,其中具体的碳酸酯单元是间苯二酚碳酸酯单元。
特别地,聚酯-聚碳酸酯的聚酯单元可以通过以下方法来制备:使间苯二甲酸和对苯二甲酸(或其衍生物)的组合与间苯二酚、双酚A或含有间苯二酚、双酚A中的一种或多种的组合进行反应,其中间苯二甲酸酯单元与对苯二甲酸酯单元的摩尔比为91:9~2:98,特别地为85:15~3:97,更特别地为80:20~5:95,以及更加特别地为70:30~10:90。在聚碳酸酯包括来自间苯二酚和/或双酚A的单元的情况下,间苯二酚碳酸酯单元与双酚A碳酸酯单元的摩尔比为0:100~99:1,在聚酯-聚碳酸酯中,混合的间苯二甲酸酯-对苯二甲酸酯聚酯单元与聚碳酸酯单元的摩尔比可以为1:99~99:1,特别地为5:95~90:10,更特别地为10:90~80:20。当使用聚酯-聚碳酸酯与聚碳酸酯的共混物时,在共混物中聚碳酸酯与聚酯-聚碳酸酯的比例分别为1:99~99:1,特别地为10:90~90:10。
聚酯-聚碳酸酯的重均分子量(Mw)可以为1,500~100,000,特别地为1,700至50,000,更特别地为2,000至40,000。使用凝胶渗透色谱(GPC)来进行分子量测量:使用交联的苯乙烯-二乙烯基苯柱,以聚碳酸酯参照物来校准。将样品制备为约1mg/ml的浓度,在约1.0ml/min的流速下进行洗脱。
可以通过例如界面聚合和熔融聚合的方法来生产适用的聚碳酸酯。虽然界面聚合的反应条件可以变化,不过示例方法通常包括:将二元酚反应物溶解或分散于苛性钠或苛性钾的水溶液中,将所得到的混合物加入到合适的与水不混溶的溶剂介质中,然后,在受控的pH条件(例如8~11),在合适的催化剂例如三乙胺或相转移催化剂存在下,将反应物与碳酸酯前体接触。最常用的与水不混溶的溶剂包括:二氯甲烷、1,2-二氯乙烷、氯苯、甲苯等。适宜的碳酸酯前体包括:例如,碳酰卤如碳酰溴或碳酰氯,或者卤代甲酸酯(haloformate)如二元酚的双卤代甲酸酯(例如,双酚A、氢醌等的双卤代甲酸酯)或者二醇的双卤代甲酸酯(乙二醇、新戊二醇、聚乙二醇等的双卤代甲酸酯)。也可以使用含有至少一种前述类型的碳酸酯前体的组合。
聚合期间可以包括链终止剂(也称之为封端剂)。链终止剂限制分子量增长速度,因此控制聚碳酸酯的分子量。链终止剂可以是单酚化合物、单羧酸氯化物和/或单氯甲酸酯中的至少一种。
例如,适宜作为链终止剂的单酚化合物包括单环酚,如苯酚、C1-C22烷基取代的苯酚、对枯基-苯酚、对叔丁基苯酚、羟基联苯;二酚的单醚,例如对甲氧基苯酚。烷基取代的苯酚包括具有8~9个碳原子的支链烷基取代基的那些酚。单酚UV吸收剂可以用作封端剂。这些化合物包括:4-取代的-2-羟基二苯甲酮和它们的衍生物、水杨酸芳基酯、二酚的单酯(例如间苯二酚单苯甲酸酯)、2-(2-羟基芳基)-苯并***和它们的衍生物、2-(2-羟基芳基)-1,3,5-三嗪以及它们的衍生物等。特别地,单酚链终止剂包括苯酚、对枯基-苯酚和/或间苯二酚单苯甲酸酯。
单羧酸氯化物也可用作链终止剂。这包括单环的单羧酸氯化物如苯甲酰氯,C1-C22烷基取代的苯甲酰氯,甲苯甲酰氯,卤素取代的苯甲酰氯,溴苯甲酰氯,肉桂酰氯,4-桥亚甲基四氢化邻苯二甲酰胺苯甲酰氯,及其混合物;多环的单羧酸氯化物如偏苯三酸酐氯化物,及萘甲酰氯;以及单环和多环单羧酸氯化物的混合物。具有最多22个碳原子的脂族单羧酸的氯化物是合适的。官能化的脂族单羧酸氯化物如丙烯酰氯和甲基丙烯酰氯也是合适的。还合适的有单氯甲酸酯,包括单环的单氯甲酸酯如氯甲酸苯酯,烷基取代的氯甲酸苯酯,氯甲酸对枯基苯酯,甲苯氯甲酸酯,及其混合物。
在一种实施方案中,聚酯-聚碳酸酯可以通过界面聚合制备。不是采用二羧酸,可以使用并且有时甚至优选使用酸的反应性衍生物,如相应的酰卤,特别是酸的二氯化物和酸的二溴化物。这样,例如不是采用间苯二甲酸、对苯二甲酸或其混合物,而是可以采用间苯二酰氯、对苯二酰氯及其混合物。
在可以使用的相转移催化剂中,包括化学式(R3)4Q+X的催化剂,其中每个R3相同或不同,为C1-10烷基;Q是氮原子或磷原子;X为卤原子或C1-8烷氧基或C6-18芳氧基。适宜的相转移催化剂包括:例如,[CH3(CH2)3]4NX、[CH3(CH2)3]4PX、[CH3(CH2)5]4NX、[CH3(CH2)6]4NX、[CH3(CH2)4]4NX、CH3[CH3(CH2)3]3NX和CH3[CH3(CH2)2]3NX,其中X为Cl-、Br-、C1-8烷氧基或C6-18芳氧基。在一种实施方案中,基于光气化混合物中双酚的重量,相转移催化剂的有效量可以为0.1~10wt%。在另一实施方案中,基于光气化混合物中双酚的重量,相转移催化剂的有效量可以为0.5~2wt%。
作为选择,可以使用熔融法来制备聚碳酸酯。一般地,在熔融聚合法中,聚碳酸酯可以通过以下过程来制备:在熔融状态和酯交换催化剂存在下,在混合器、双螺杆挤出机等中使二羟基反应物和碳酸二芳基酯(如碳酸二苯酯)共反应,以形成均匀的分散体。通过蒸馏将挥发性一元酚从熔融反应物中除去,并以熔融的剩余物的形式分离聚合物。
除了如上所述的聚碳酸酯、聚酯-聚碳酸酯以及它们的组合之外,也可以使用聚碳酸酯和聚酯-聚碳酸酯与其他热塑性聚合物的组合,例如聚碳酸酯和/或聚碳酸酯共聚物与聚酯的组合。
适宜的聚酯包括化学式(6)的重复单元,可以是例如聚(亚烷基二羧酸酯)、液晶聚酯和聚酯共聚物。也可以使用其中引入了支化剂的支化聚酯,所述支化剂是例如具有三个或更多个羟基的醇或者三官能或多官能的羧酸。此外,有时也期望在聚酯上具有各种不同浓度的酸端基和羟端基,这取决于组合物的最终用途。
有用类别的聚酯的实例是聚(亚烷基对苯二甲酸酯)。聚(亚烷基对苯二甲酸酯)的具体实例包括,但不限于:聚(对苯二甲酸乙二醇酯)(PET)、聚(对苯二甲酸1,4-丁二醇酯)(PBT)、聚(萘二酸乙二醇酯)(PEN)、聚(萘二酸丁二醇酯)(PBN)、聚(对苯二甲酸丙二醇酯)(PPT)、聚(对苯二甲酸环己二甲醇酯)(PCT)以及含有至少一种前述聚酯的组合。聚(对苯二甲酸环己二甲醇酯)-共-聚(对苯二甲酸乙二醇酯)也是有用的:其中包括大于或等于50摩尔%的聚(对苯二甲酸乙二醇酯)的聚合物简称为PETG;其中包括大于或等于50摩尔%的聚(对苯二甲酸环己二甲醇酯)的聚合物简称为PCTG。以上聚酯可以包括类似的脂族聚酯例如聚(亚烷基环己二羧酸酯),其实例为聚(1,4-环己基二羧酸-1,4-环己烷二亚甲基酯)(PCCD)。还打算的有,上述聚酯与少量如约0.5~10%重量源于脂族二酸和/或脂族多元醇的单元制成的共聚酯。
在一种实施方式中,本公开内容提供了耐疲劳的组合物,例如热塑性组合物,其包括:
(i)100重量份聚碳酸酯;
(ii)约1.0重量份~约30重量份抗冲改性剂;
(iii)约5.0×10-3重量份~约0.5重量份式(P-1)的季戊四醇二亚磷酸酯衍生物:
其中m为整数,且1≤m≤5;n为整数,且1≤n≤5;R1和R2各自独立地选自芳基烷基、烷基芳基烷基、芳基、烷基芳基及其任意组合;以及
(iv)一种或多种任选的添加剂,该添加剂选自水解稳定剂、填料/增强剂、视觉效应增强剂、抗氧化剂、光稳定剂、紫外线吸收剂、增塑剂、脱模剂、润滑剂、抗静电剂、颜料、染料、阻燃剂、加工助剂、辐射稳定剂、防滴剂以及它们的组合。
在各种实施方式中,对常规加入热塑性组合物的添加剂进行选择,以使其不会对所期望的组合物性能产生有害影响。可以使用添加剂的混合物。可以在混合形成组合物的各组分的过程中在合适时间将这些添加剂混合。
本公开内容的组合物可以含有一种或多种水解稳定剂用于降低酯基和/或碳酸酯基的水解。典型的水解稳定剂可以包括基于碳二亚胺的添加剂,例如在位置2和2′取代的芳族和/或脂环族单碳二亚胺,例如2,2′,6,6′-四异丙基二苯基碳二亚胺。分子量超过500克/摩尔的聚碳二亚胺也是适合的。用作水解稳定剂的其它化合物包括环氧基改性的丙烯酸类低聚物或聚合物,以及基于脂环族环氧化物的低聚物。合适的环氧基功能化稳定剂的具体实例包括:由Union Carbide Corporation(Danbury,CT,Dow Chemical的子公司)生产的脂环族环氧树脂ERL-4221;以及购自Johnson Polymer Inc,Sturtevant,WI的 ADR-4300和 ADR-4368。当存在时,基于在热塑性组合物中使用的聚碳酸酯的重量,水解稳定剂的用量可以为0.05~1重量%,特别地0.1~0.5重量%,更特别地0.12~0.3重量%。
组合物可以包括着色剂例如颜料和/或染料添加剂。合适的颜料包括:例如,无机颜料如金属氧化物和混合的金属氧化物诸如氧化锌、二氧化钛、氧化铁等;硫化物诸如硫化锌等;铝酸盐;硫代硅酸钠、硫酸盐、铬酸盐等;炭黑;铁酸锌;群青;颜料棕24;颜料红101;颜料黄119;有机颜料例如偶氮类、重氮类、喹吖啶酮类、苝、萘四羧酸、黄烷士酮、异吲哚啉酮、四氯异吲哚啉酮、蒽醌、二苯并芘二酮、二噁嗪、酞青和偶氮色淀;颜料蓝60、颜料红122、颜料红149、颜料红177、颜料红179、颜料红202、颜料紫29、颜料蓝15、颜料绿7、颜料黄147和颜料黄150,或者含有至少一种前述颜料的组合。当存在时,颜料的用量可以为0.01~10重量%,基于在热塑性组合物中使用的聚碳酸酯的重量。
适宜的染料可以是有机材料,包括:例如香豆素染料例如香豆素460(蓝色)、香豆素6(绿色)、尼罗红等;镧系络合物;烃染料和取代的烃染料;多环芳烃染料;闪烁染料(scintillation dye)例如噁唑染料或噁二唑染料;芳基或杂芳基取代的聚(C2-8烯烃)染料;羰花青染料;阴丹酮染料;酞花青染料;噁嗪染料;喹诺酮染料(carbostyryl dye);萘四羧酸染料;卟啉染料;双(苯乙烯基)联苯染料;吖啶染料;蒽醌染料;花青染料;次甲染料;芳基甲烷染料;偶氮染料;靛类染料;硫靛染料;重氮鎓染料;硝基染料;醌亚胺染料;氨基酮类染料;四唑鎓染料;噻唑染料;苝染料;紫环酮染料(perinonedye);二苯并噁唑基噻吩(BBOT);三芳基甲烷染料;呫吨染料;噻吨染料;萘二甲酰亚胺染料(naphthalimide dye);内酯染料;荧光团例如在近红外波长吸收并且在可见光波长发射的抗斯托克斯漂移染料(anti-stokes shift dye)等;荧光染料,例如7-氨基-4-甲基香豆素、3-(2′-苯并噻唑基)-7-二乙基氨基香豆素、2-(4-联苯基)-5-(4-叔丁基苯基)-1,3,4-噁二唑、2,5-双(4-联苯基)-噁唑、2,2′-二甲基-对四联苯、2,2-二甲基-对三联苯、3,5,3"",5""-四叔丁基-对五联苯、2,5-二苯基呋喃、2,5-二苯基噁唑、4,4′-二苯基茋、4-二氰基亚甲基-2-甲基-6-(对-二甲氨基苯乙烯基)-4H-吡喃、1,1′-二乙基-2,2′-羰花青碘化物、3,3′-二乙基-4,4′,5,5′-二苯并硫杂三羰花青碘化物(dibenzothiatricarbocyanine)、7-二甲基氨基-1-甲基-4-甲氧基-8-氮杂喹诺酮-2、7-二甲基氨基-4-甲基喹诺酮-2、2-(4-(4-二甲氨基苯基)-1,3-丁二烯基)-3-乙基苯并噻唑鎓高氯酸盐、3-二乙基氨基-7-二乙基亚氨基吩噁嗪鎓高氯酸盐、2-(1-萘基)-5-苯基噁唑、2,2′-对亚苯基-双(5-苯基噁唑)、若丹明700、若丹明800、芘、(chrysene)、红荧烯、晕苯(coronene)等,或者含有至少一种前述染料的组合。当存在时,基于在热塑性组合物中使用的聚碳酸酯的总重量,可以以0.01~10重量%的用量来使用染料。
组合物可包括填料或增强剂。当使用时,适宜的填料或增强剂包括,例如,硅酸盐和硅石粉末如硅酸铝(莫来石),合成的硅酸钙,硅酸锆,熔凝硅石,结晶硅石,石墨,天然硅砂等;硼粉如硼-氮化物粉末,硼-硅酸盐粉末等;氧化物如TiO2,氧化铝,氧化镁等;硫酸钙(作为其无水物,二水合物或三水合物);碳酸钙如白垩,石灰石,大理石,合成沉淀的碳酸钙等;滑石,包括纤维状的,模块的(modular),针形,层状滑石等;硅灰石;表面处理的硅灰石;玻璃球如中空和实心玻璃球,硅酸盐球,空心煤胞,铝硅酸盐(armospheres)等;高岭土,包括硬高岭土,软高岭土,煅烧高岭土,包含本领域已知的用于促进与聚合物基质树脂的相容性的各种涂层的高岭土等;单晶纤维或"晶须"如碳化硅,氧化铝,碳化硼,铁,镍,铜等;纤维(包括连续的和切断的纤维)如石棉,碳纤维,玻璃纤维,如E,A,C,ECR,R,S,D,或NE玻璃等;硫化物如硫化钼,硫化锌等;钡化合物如钛酸钡,铁酸钡,硫酸钡,重晶石等;金属和金属氧化物如粒状或纤维状铝,青铜,锌,铜和镍等;薄片的填料如玻璃片,薄片碳化硅,二硼化铝,铝薄片,钢薄片等;纤维填料,例如,短的无机纤维如由包含硅酸铝、氧化铝、氧化镁和硫酸钙半水合物等中的至少一种的共混物获得的那些;天然填料和增强材料,如通过粉碎木材获得的木屑,纤维状产品如纤维素,棉花,剑麻,黄麻,淀粉,软木粉,木质素,花生壳,玉米,稻谷外壳等;有机填料如聚四氟乙烯;增强的有机纤维状填料,由能够形成纤维的有机聚合物形成,所述有机聚合物如聚(醚酮),聚酰亚胺,聚苯并噁唑,聚(亚苯基硫化物),聚酯,聚乙烯,芳族聚酰胺,芳族聚酰亚胺,聚醚酰亚胺,聚四氟乙烯,丙烯酸类树脂,聚(乙烯醇)等;以及其它填料和增强剂如云母,粘土,长石,烟灰,惰性硅酸盐微球,石英,石英岩,珍珠岩,硅藻石,硅藻土,炭黑等,或者包含至少一种前述填料或增强剂的组合。
可用金属材料层涂布填料和增强剂,以促进导电,或者用硅烷表面处理,以改进粘合性和与聚合物基体树脂的分散。另外,该增强填料可以以单丝或复丝纤维形式来提供,且可以单独地或者与其它类型纤维通过以下例举的方法组合地使用:共编织或芯/皮、并列(side-by-side)、橙型或矩阵和原纤维结构,或纤维制造技术领域的技术人员已知的其他方法。合适的共编织结构包括例如玻璃纤维-碳纤维、碳纤维-芳族聚酰亚胺(芳族聚酰胺)纤维,和芳族聚酰亚胺玻璃纤维或类似物。纤维状填料可以以下列形式来提供,例如,粗纱(rovings)、纺织的纤维状增强物,如0-90度织物等;无纺纤维增强材料,例如连续原丝片(continuous strand mat)、短切原丝片(chopped strand mat)、绢纱(tissue)、纸和毡等;或者三维增强材料如编带(braids)。当存在时,基于组合物中所用聚碳酸酯的重量,可以以0~90重量%的用量来使用填料。
视觉效应增强剂,有时也称为视觉效应添加剂或颜料,可以以胶囊化形式、非胶囊化形式存在,或者被层压到含有聚合物树脂的粒子。视觉效应添加剂的一些非限制性实例为:铝、金、银、铜、镍、钛、不锈钢、硫化镍、硫化钴、硫化锰、金属氧化物、白云母、黑云母、珍珠云母、合成云母、涂有二氧化钛的云母、涂覆金属的玻璃薄片,和着色剂(包括但不限于苝红)。视觉效应添加剂可以具有高的或低的长径比,可以包括不止1个小面(facet)。可以使用颜料诸如溶剂蓝(Solvent Blue)35、溶剂蓝36、分散紫26、溶剂绿3、Anaplast橙LFP、苝红和Morplas红36。也可以使用荧光染料,包括但不限于:永久粉红R(Permanent Pink R)(色指数颜料红181,购自Clariant Corporation)、霍斯塔佐红5B(Hostasol Red 5B)(色指数#73300,CAS # 522-75-8,购自Clariant Corporation)和Macrolex荧光黄10GN(色指数溶剂黄160:1,购自Bayer Corporation)。可以使用以下颜料,例如:二氧化钛、硫化锌、炭黑、铬酸钴、钛酸钴、硫化钙、氧化铁、硫代硅酸铝钠、硫代硅酸钠、铬锑钛金红石、镍锑钛金红石和氧化锌。包胶形式的视觉效应添加剂通常包括被聚合物所包裹的视觉效应材料,例如类似于薄铝片的高长径比材料。该包胶视觉效应添加剂具有珠状形状。当存在时,基于组合物中所用聚碳酸酯的重量,可以以0.01~10重量%的用量来使用视觉效应增强剂。
适宜的抗氧化剂添加剂包括:例如,有机亚磷酸酯如三(壬基苯基)亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯等;烷基化一元酚或多元酚;多元酚与二烯的烷基化反应产物,如四[亚甲基(3,5-二叔丁基-4-羟基氢化肉桂酸基)]甲烷(tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane)等;对甲酚或二环戊二烯的丁基化反应产物;烷基化氢醌;羟基化硫代联苯醚;次烷基双酚;苄基化合物;β-(3,5-二叔丁基-4-羟基苯基)丙酸与一元醇或多元醇的酯;β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元醇或多元醇的酯;硫代烷基或硫代芳基化合物的酯诸如二硬脂基硫代丙酸酯、二月桂基硫代丙酸酯、二(十三烷基)硫代二丙酸酯、十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、五(赤藓醇基)-四[3-(3,5-二叔丁基-4-羟基苯基)]丙酸酯等的酯;β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸等的酰胺,或者含有至少一种前述抗氧化剂的组合。当存在时,基于组合物中所用聚碳酸酯的重量,可以以0.0001~1重量%的用量来使用抗氧化剂。
也可以使用光稳定剂和/或吸收紫外线(UV)的添加剂。适宜的光稳定剂添加剂包括:例如,苯并***类如2-(2-羟基-5-甲基苯基)苯并***、2-(2-羟基-5-叔辛基苯基)苯并***和2-羟基-4-正辛氧基二苯甲酮等,或者含有至少一种前述光稳定剂的组合。当存在时,基于组合物中所用聚碳酸酯的重量,可以以0.0001~1重量%的用量来使用光稳定剂。
适宜的吸收UV的添加剂包括:例如,羟基二苯甲酮类、羟基苯并***类、羟基苯并三嗪类、氰基丙烯酸酯类、草酰二苯胺类、苯并噁嗪酮类、2-(2H-苯并***-2-基)-4-(1,1,3,3-四甲基丁基)苯酚(CYASORBTM 5411)、2-羟基-4-正辛氧基二苯甲酮(CYASORBTM 531)、2-[4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基]-5-(辛氧基)-苯酚(CYASORBTM 1164)、2,2’-(1,4-亚苯基)双(4H-3,1-苯并噁嗪-4-酮)(CYASORBTM UV-3638)、1,3-双[(2-氰基-3,3-二苯基丙烯酰基)氧基]-2,2-双[[(2-氰基-3,3-二苯基丙烯酰基)氧基]甲基]丙烷(UVINULTM3030)、2,2’-(1,4-亚苯基)双(4H-3,1-苯并噁嗪-4-酮)、1,3-双[(2-氰基-3,3-二苯基丙烯酰基)氧基]-2,2-双[[(2-氰基-3,3-二苯基丙烯酰基)氧基]甲基]丙烷;纳米尺寸的无机材料如氧化钛、氧化铈和氧化锌,均具有小于100纳米的粒度;等等;或者含有至少一种前述UV吸收剂的组合。当存在时,基于组合物中所用聚碳酸酯的重量,可以以0.0001~1重量%的用量来使用UV吸收剂。
也可以使用增塑剂、润滑剂和/或脱模剂添加剂。这些类型的材料存在显著的重叠,其中包括例如邻苯二甲酸酯,例如二辛基-4,5-环氧六氢邻苯二甲酸酯;三(辛氧基羰基乙基)异氰脲酸酯;三硬脂精;二-或多官能芳族磷酸酯,例如间苯二酚四苯基二磷酸酯(RDP)、氢醌的双(二苯基)磷酸酯和双酚A的双(二苯基)磷酸酯;聚-α-烯烃;环氧化豆油;硅氧烷类,其中包括硅油;酯,例如脂肪酸酯,例如烷基硬脂酯,例如硬脂酸甲酯;硬脂酸硬脂酯、四硬脂酸季戊四醇酯等;硬脂酸甲酯与含聚乙二醇聚合物、聚丙二醇聚合物及其共聚物的亲水和疏水非离子型表面活性剂的混合物,例如在合适溶剂内的硬脂酸甲酯和聚乙二醇-聚丙二醇共聚物;蜡,例如蜂蜡、褐煤蜡、石蜡等。当存在时,基于组合物中所用聚碳酸酯的重量,可以以0.001~1重量%、特别是0.01~0.75重量%、更特别是0.1~0.5重量%的用量来使用这些物质。
在实施方式中,十八烷基季戊四醇四硬脂酸酯(PETS),即购自于Henkel的Loxiol,用作脱模剂/润滑剂,其量为约0.3wt%,基于热塑性组合物中所用的组分(i)聚碳酸酯的重量。可以通过喷嘴将PETS注入到挤出机中。
术语“抗静电剂”是指可加工于聚合物树脂中和/或喷于材料或制品上以提高导电性和整体物理性能的单体、低聚或聚合材料。单体抗静电剂的实例包括单硬脂酸甘油酯,二硬脂酸甘油酯,三硬脂酸甘油酯,乙氧化胺,伯、仲、叔胺,乙氧基化醇,烷基硫酸盐或酯,烷基芳基硫酸盐或酯,烷基磷酸盐或酯,烷基胺硫酸盐或酯,烷基磺酸盐如硬脂基磺酸钠、十二烷基苯磺酸钠等,季铵盐,季铵树脂,咪唑啉衍生物,脱水山梨醇酯,乙醇胺,甜菜碱,等等,或者包含至少一种前述单体抗静电剂的组合。
示例性的聚合抗静电剂包括某些聚酯酰胺聚醚聚酰胺(聚醚酰胺)嵌段共聚物,聚醚酯酰胺嵌段共聚物,聚醚酯,或者聚氨酯,各自包含聚亚烷基二醇部分聚氧化烯单元如聚乙二醇,聚丙二醇,聚1,4-丁二醇等。这种聚合抗静电剂可从商业上得到,例如PelestatTM 6321(Sanyo)或PebaxTMMH1657(Atofina),IrgastatTM P18和P22(Ciba-Geigy)。可以用作抗静电剂的其它聚合材料是固有导电的聚合物如聚苯胺(商业上以得自Panipol),聚吡咯和聚噻吩(商业上得自Bayer),其在高温下熔体加工之后保持其一定的固有导电性。在一种实施方案中,可以在含化学抗静电剂的聚合树脂中使用碳纤维、碳纳米纤维、碳纳米管、炭黑或者前述材料的任意组合,以使组合物静电消散。当存在时,基于组合物中所用聚碳酸酯的重量,可以以0.0001~5重量%的用量来使用抗静电剂。
可以被加入的合适阻燃剂是含磷、溴和/或氯的有机化合物。由于法规上的原因,非溴化和非氯化的含磷阻燃剂在某些应用中是优选的,例如有机磷酸酯和含磷-氮键的有机化合物。
一类示例有机磷酸酯是化学式(GO)3P=O的芳族磷酸酯,其中G各自独立地为烷基、环烷基、芳基、烷基芳基或芳基烷基,条件是至少一个G是芳族基团。两个G基团可以被连接到一起形成环状基团,例如二苯基季戊四醇二磷酸酯。其他适用的芳族磷酸酯可以是:例如,苯基双(十二烷基)磷酸酯、苯基双(新戊基)磷酸酯、苯基双(3,5,5’-三甲基己基)磷酸酯、乙基二苯基磷酸酯、2-乙基己基二(对甲苯基)磷酸酯、双(2-乙基己基)对甲苯基磷酸酯、磷酸三甲苯酯、双(2-乙基己基)苯基磷酸酯、三(壬基苯基)磷酸酯、双(十二烷基)对甲苯基磷酸酯、二丁基苯基磷酸酯、2-氯乙基二苯基磷酸酯、对甲苯基双(2,5,5’-三甲基己基)磷酸酯、2-乙基己基二苯基磷酸酯等。特别的芳族磷酸酯是每个G均为芳族的磷酸酯,例如磷酸三苯酯、磷酸三甲苯酯、异丙基化的磷酸三苯酯等。
双或多官能的芳族含磷化合物也是有用的,例如,以下化学式的化合物:
其中G1各自独立地为具有1~30个碳原子的烃基;G2各自独立地为具有1~30个碳原子的烃基或烃氧基;Xa各自独立地为具有1~30个碳原子的烃基;X各自独立地为溴或氯;m为0~4,n为1~30。适宜的双或多官能芳族含磷化合物的实例包括:间苯二酚四苯基二磷酸酯(RDP)、氢醌的二(二苯基)磷酸酯和双酚A的二(二苯基)磷酸酯,它们的低聚和聚合的对应物(counterpart)等。
示例适用的含磷-氮键阻燃剂化合物包括:氯化磷腈、磷酯酰胺(phosphorus ester amides)、磷酰胺、膦酰胺、次膦酰胺、三(氮丙啶基)氧膦。当存在时,基于组合物中所用聚碳酸酯的重量,含磷阻燃剂可以以0.1~10重量%的用量存在。
卤化的材料也可以用作阻燃剂,例如,化学式(18)的卤化化合物和树脂:
其中R为烷撑、烷叉或脂环族的连接基(linkage),例如,亚甲基,乙撑,丙撑,异丙撑,异丙叉,丁撑,异丁撑,戊撑,环己撑,环戊叉等;或者氧醚,羰基,胺,或者含硫的连接基如硫醚、亚砜、砜等。R也可以由两个或多个连接有诸如芳族、氨基、醚、羰基、硫醚、亚砜、砜等基团的烷撑或烷叉连接基构成。
化学式(18)中Ar和Ar’各自独立地为单或多碳环的芳基,例如亚苯基、亚联苯基、亚三联苯基、亚萘基等。
Y是有机基、无机基或有机金属基,例如:卤素,如氯、溴、碘、氟;通式OE表示的醚基,其中E是类似于X的一价烃基;R所示类型的一价烃基;或者,其他取代基,如硝基、氰基等,所述的取代基基本是惰性的,条件是每个芳核上至少有一个,优选两个卤原子。
当存在时,X各自独立地为一价烃基,例如,烷基如甲基、乙基、丙基、异丙基、丁基、癸基等;芳基如苯基、萘基、联苯基、二甲苯基、甲苯基等;芳基烷基如苄基、乙基苯基等;脂环基如环戊基、环己基等。该一价烃基本身可以含有惰性取代基。
d各自独立地为1至最大相当于芳环(包括Ar或Ar’)上取代的可取代氢的数目。e各自独立地为0至最大相当于R上可取代氢的数目。a、b和c各自独立地为包括0的整数。当b不为0时,a和c都不为0。或者,a或c可以为0,但两者不同时为0。如果b为0,则芳族基团通过直接的碳-碳键结合。
芳族基团、Ar和Ar’上的羟基和Y取代基可以在芳环的邻位、间位或对位变化,并且这些基团可以相互处于任何可能的几何关系。
在上式范围内所包含的双酚中,下面是代表性的:2,2-二(3,5-二氯苯基)丙烷、二(2-氯苯基)-甲烷、二(2,6-二溴苯基)-甲烷、1,1-二(4-碘苯基)-乙烷、1,2-二(2,6-二氯苯基)-乙烷、1,1-二(2-氯-4-碘苯基)乙烷、1,1-二(2-氯-4-甲基苯基)-乙烷、1,1-二(3,5-二氯苯基)-乙烷、2,2-二(3-苯基-4-溴苯基)-乙烷、2,6-二(4,6-二氯萘基)-丙烷、2,2-二(2,6-二氯苯基)-戊烷、2,2-二(3,5-二溴苯基)-己烷、二(4-氯苯基)-苯基-甲烷、二(3,5-二氯苯基)-环己基甲烷、二(3-硝基-4-溴苯基)-甲烷、二(4-羟基-2,6-二氯-3-甲氧基苯基)-甲烷和2,2-二(3,5-二氯-4-羟基苯基)-丙烷、2,2-二(3-溴-4-羟基苯基)-丙烷。上述结构式还包括:1,3-二氯苯、1,4-二溴苯、1,3-二氯-4-羟基苯和联苯如2,2’-二氯联苯、多溴化1,4-二苯氧基苯、2,4’-二溴联苯和2,4’-二氯联苯,以及十溴二苯醚等。
低聚和聚合的卤代芳族化合物也是有用的,例如双酚A和四溴双酚A与碳酸酯前体如光气的共聚碳酸酯。金属增效剂如氧化锑也可以与阻燃剂一起使用。当存在时,基于组合物中所用聚碳酸酯的重量,含卤素的阻燃剂可以以0.1~10重量%的用量存在。
也可以使用无机阻燃剂,例如C2-16烷基磺酸的盐,如全氟丁烷磺酸钾(Rimar盐)、全氟辛烷磺酸钾、全氟己烷磺酸四乙铵和二苯砜磺酸钾等;通过反应形成的盐,例如碱金属或碱土金属(如锂、钠、钾、镁、钙和钡盐)与无机酸的复盐,例如含氧阴离子,如碳酸的碱金属和碱土金属盐(例如,Na2CO3、K2CO3、MgCO3、CaCO3和BaCO3),以及氟阴离子配合物(例如Li3AlF6、BaSiF6、KBF4、K3AlF6、KAlF4、K2SiF6和/或Na3AlF6等)。当存在时,基于组合物中所用聚碳酸酯的重量,无机阻燃剂可以以0.1~5重量%的用量存在。
也可以存在辐射稳定剂,特别是γ-射线稳定剂。适用的γ-射线稳定剂包括:二醇,如乙二醇、丙二醇,1,3-丙二醇、1,2-丁二醇、1,4-丁二醇、内消旋2,3-丁二醇(meso-2,3-butanediol)、1,2-戊二醇、2,3-戊二醇、1,4-戊二醇、1,4-己二醇等;脂环醇,如1,2-环戊二醇、1,2-环己二醇等;支化无环二醇,如2,3-二甲基-2,3-丁二醇(频哪醇)等;多元醇,以及烷氧基取代的环烷烃或无环烷烃。具有不饱和位点的链烯醇也是有用的醇类,其实例包括:4-甲基-4-戊烯-2-醇,3-甲基-戊烯-3-醇,2-甲基-4-戊烯-2-醇,2,4-二甲基-4-戊烯-2-醇(2,4-dimethyl-4-pene-2-ol)和9-癸烯-1-醇。另一类适用的醇是叔醇,其具有至少一个羟基取代的叔碳原子。它们的实例包括:2-甲基-2,4-戊二醇(己二醇)、2-苯基-2-丁醇、3-羟基-3-甲基-2-丁酮、2-苯基-2-丁醇等,脂环族叔碳原子如1-羟基-1-甲基环己烷。另一类适用的醇是羟甲基芳族化合物,其具有在与芳环的不饱和碳原子相连接的饱和碳原子上的羟基取代。该羟基取代的饱和碳原子可以是羟甲基(-CH2OH),或者它可以是更复杂的烃基的一部分,例如可以是(-CR4HOH)或(-CR4 2OH)的情况,其中R4是复杂的或简单的烃基。特别的羟基甲基芳族化合物可以是二苯基甲醇、1,3-苯二甲醇、苯甲醇、4-苄氧基苯甲醇和苄基苯甲醇。特别的醇是2-甲基-2,4-戊二醇(也称为己二醇)、聚乙二醇和聚丙二醇。当存在时,基于组合物中所用聚碳酸酯的重量,辐射稳定剂通常以0.001~1wt%,更特别地0.01~0.5wt%的用量使用。
也可以使用防滴剂,例如形成原纤维或不形成原纤维的含氟聚合物如聚四氟乙烯(PTFE)。该防滴剂可以被如上所述的刚性共聚物(例如苯乙烯-丙烯腈共聚物(SAN))所包胶。被包胶于SAN中的PTFE称为TSAN。包胶的含氟聚合物可以通过以下方法来制备:在含氟聚合物如水分散体存在下,使包胶聚合物进行聚合。TSAN可以提供显著优于PTFE的性能,因为TSAN更易于分散于组合物中。基于包胶的含氟聚合物的总重量,合适的TSAN可以包括例如50wt% PTFE和50wt% SAN。基于共聚物的总重量,SAN可以包括例如75wt%苯乙烯和25wt%丙烯腈。可选择地,可以以某种方式将含氟聚合物与第二聚合物(例如芳族聚碳酸酯树脂或SAN)预混,以形成用作防滴剂的聚集材料(agglomerated material)。任一方法也可以用于生产包胶的含氟聚合物。当存在时,基于组合物中所用聚碳酸酯的重量,防滴剂可以以0.1~5wt%的用量使用。
可以使用的加工助剂的非限制性实例包括: FL-599(购自Dover Chemical Corporation)、(购自Polychem Alloy Inc.)、Glycolube P(购自Lonza Chemical Company)、四硬脂酸季戊四醇酯、MetablenA-3000(购自Mitsubishi Rayon)、二苯甲酸新戊二醇酯等。当存在时,基于组合物中所用聚碳酸酯的重量,加工助剂可以以0.001~1wt%的用量使用。
可以通过本领域通用的方法来制备组合物,例如,在一种实施方案中,在一种加工方式下,将粉末状聚碳酸酯和任何任选的添加剂首先共混于HENSCHEL-高速搅拌机。其他低剪切方法(包括但不限于人工搅拌)也可以完成该共混。然后,将该共混物通过加料仓注入到挤出机的进料口中。可选择地,可以通过侧填充机(sidestuffer)在进料口和/或下游端直接注入到挤出机,将一种或多种组分加入到组合物中。也可以将添加剂混合到含有所需聚合物树脂的母料中,然后再送入到挤出机中。通常在比引起聚合物流动所必需的温度高的温度下操作挤出机。将挤出物在水浴中立即骤冷,然后制成颗粒物。当切割挤出物时根据需要,所制备的颗粒物可以为1/4英寸长或者更小。该颗粒物可以用于后续的模塑、成形或成型。
在具体的实施方案中,制备热塑性制品的方法包括使聚碳酸酯和任何任选的添加剂熔融组合以形成热塑性组合物。该熔融组合可以通过挤出来进行。在实施方案中,选择聚碳酸酯与任何任选的添加剂的比例,以使组合物的光学特性是最好的,而其机械性能处于所需要的水平。
在具体的实施方案中,挤出机是双螺杆挤出机。通常使该挤出机运行在180~385℃的温度,特别是200~330℃,更特别是220~300℃,其中模头温度可以不同。将挤出的组合物骤冷于水中,然后制成颗粒物。
本发明也提供了含有组合物的成形的、成型的或模塑的制品。可以通过各种方法将该组合物模塑成有用的成形制品,例如注塑、挤出、旋转模塑、吹塑和热成型。在具体的实施方案中,通过注塑来进行模塑。期望地,热塑性组合物具有优异的填模能力,可以用于形成机械部件和汽车部件,例如移动电话外壳、瓶、管、大口杯、离心管、吸移管、葡萄糖计、吸入器、盘、牙科器械等。
通过以下非限制性实施例来进一步说明本公开内容。
实施例
在以下实施例中,根据ASTM D1238-01对挤出的颗粒物测量熔体流动速率(MFR)。MFR定义为当将6~7g样品放置于1.2千克恒定载荷下,在300℃在10分钟,停留时间为6分钟时,通过带有活塞的喷嘴的样品的重量。结果以单位克/10分钟(g/10min)表示。
使用5磅锤根据ASTM D256-03对1/8英寸(3.2mm)试条测量不同温度的缺口伊佐德抗冲强度(简写为“NII”)。使用在室温老化24小时的试条测量NII 23℃;使用在-30℃老化24小时的试条测量NII-30℃。伊佐德抗冲强度ASTM D256(‘NII’)可以用于比较塑料材料的耐冲击性。结果可以计为J/m。
在压力为28.4MPa、频率为5Hz,根据ASTM D638-03型I,进行疲劳试验,其中破损点记录为至损坏的循环数。
根据ASTM D638方法测量伸长百分率。对进行20,000次疲劳循环和不进行疲劳循环的拉伸试条记录断裂伸长百分率。
根据ASTM D638方法测量伸长保留率。其定义为:进行20000次疲劳循环的拉伸试条的伸长百分率(E1)/不进行疲劳循环的拉伸试条的伸长百分率(E2)。
将所有原料预混,然后通过双螺杆挤出机在标准聚碳酸酯试条件下将混合物挤出。化合物Doverphos S9228(购自于Dover Chemical,Dover,Ohio)为:
化合物Ultranox 626(以商品名Ultranox 626购自于Chemtura)为:
化合物P-EPQ(以商品名Sandostab P-EPQ购自于Clariant)为:
以商品名PAO 166购自于Amoco Chemicals的聚α-烯烃用作润滑油。购自于GE塑料的PC1和PC2用作聚碳酸酯。
在表1中,配制物对照#1(MBS用作抗冲改性剂)和对照#2(PC-Si共聚物 EXL)用作抗冲改性剂)在过去已经用于具有可接受的耐疲劳性的移动电话设计。但是,申请人发现,当标准热稳定剂IrgaphosTM 168被二(2,4-二枯基苯基)季戊四醇二亚磷酸酯(记为Doverphos S9228)所代替时,对于MBS改性的(对照#1和实施例#1)和PC-Si共聚物改性的(对照#2和实施例#2)体系,在中等流动性配制物获得了好很多的耐疲劳性,而保持了优良的抗冲性能。
表1
通过替换稳定剂在抗冲改性的体系和EXL体系中耐疲劳性改善
此外,选择具有与Doverphos S9228类似的化学结构的三种其它亚磷酸酯,并且对比Doverphos S9228进行试验(表2)。这些亚磷酸酯为TNPP,Ultranox 626和Sandostab P-EPQ。
表2:亚磷酸酯对耐疲劳性的影响
如表2所示,与含有其它亚磷酸酯的配制物相比,含有Doverphos S9228的配制物,即配制物#1,是仅有的一种显示出极其高的耐疲劳性的配制物。这进一步证实由Doverphos S9228产生了耐疲劳性改善。尽管不期望被任何具体理论所限制,可以认为,该效果的可能机理是Doverphos S9228的优异的热稳定能力减缓了在疲劳试验和模塑加工过程中聚碳酸酯和抗冲改性剂的劣化。
设计另外的试验方法来研究在不同温度下模塑试条件对耐疲劳性的影响。在三个模塑温度285℃、305℃和325℃模制拉伸试条。将一些拉伸试条储存放置,其它进行20,000次拉伸疲劳循环。收集所有的样品,对存储/不进行疲劳的试条和进行疲劳的试条均进行标准拉伸试验。
此后,测量伸长保留率(进行疲劳的试条的拉伸伸长率/不进行疲劳的试条的伸长率),并用于研究模塑温度的影响。在该方法期间,并行测量含有Doverphos S9228和IrgaphosTM168(表1,实施例#1和对照#1)以及其它商品抗冲改性等级的配制物。
表3:模塑试条件对耐疲劳性的影响
配制物 | 对照#1 | 对照#1 | 对照#1 | 对照#2 | 对照#2 | 对照#2 | 实施例#1 | 实施例#1 | 实施例#1 | |
模塑温度 | 285 | 305 | 325 | 285 | 305 | 325 | 285 | 305 | 325 | |
20000次疲劳循环 | 伸长百分率,% | 13 | 82 | 16 | 41 | 12 | 26 | 77 | 83 | 59 |
无疲劳循环 | 伸长百分率,% | 88 | 63 | 130 | 57 | 62 | 140 | 64 | 100 | 140 |
伸长保留率 | 14.77273 | 130.1587 | 12.30769 | 71.92982 | 19.35484 | 18.57143 | 120.3125 | 83 | 42.14286 |
如表3所示,在20,000次疲劳循环之后对照#1和对照#2显示了显著的拉伸性能劣化,在所有的模塑试条件下具有较低的伸长百分率以及差的/不稳定的伸长保留率。对于实施例#1,虽然随着模塑温度升高,拉伸性能变差,但是绝对伸长率值和保留率仍然是最高的,这也证实Doverphos S9228在耐疲劳性方面的独特特性。
因此,已经发现,Doverphos S9228能够改善抗冲改性的聚碳酸酯的耐疲劳性,这尤其有益于移动电话应用。
已经参照代表性实施方式描述了示例性实施方式。显然地,对于阅读和理解前述详细说明的技术人员,将出现改进和变化。示例性实施方式应该理解为包括所有这些改进和变化,只要它们进入到所附权利要求或其等同方式的范围内。
Claims (21)
2.根据权利要求1的组合物,其中2≤m≤3;2≤n≤3;R1和R2各自为芳基烷基。
5.根据权利要求1的组合物,其中所述季戊四醇二亚磷酸酯衍生物的量为约1.0×10-2重量份~约0.1重量份。
6.根据权利要求1的组合物,其中所述季戊四醇二亚磷酸酯衍生物的量为约6.0×10-2重量份~约7.5×10-2重量份。
7.根据权利要求1的组合物,其中所述抗冲改性剂选自弹性体改性的接枝共聚物、聚硅氧烷-聚碳酸酯共聚物和它们的任意组合。
8.根据权利要求7的组合物,其中所述弹性体改性的接枝共聚物包括橡胶状聚合物基体和接枝到该橡胶状聚合物基体的刚性聚合物。
9.根据权利要求8的组合物,其中所述橡胶状聚合物基体包括单乙烯基芳族单体与共轭二烯的聚合物;所述刚性聚合物包括C1-8烷基(甲基)丙烯酸酯任选地与单乙烯基芳族单体的聚合物。
10.根据权利要求9的组合物,其中所述弹性体改性的接枝共聚物包括甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)。
11.根据权利要求7的组合物,其中所述抗冲改性剂为弹性体改性的接枝共聚物,其存在的量为约1份~约9.98份。
13.根据权利要求7的组合物,其中所述聚硅氧烷-聚碳酸酯共聚物包括约50~约99wt%碳酸酯单元,和约1~约50wt%硅氧烷单元。
14.根据权利要求7的组合物,其中所述聚硅氧烷-聚碳酸酯共聚物包括约2wt%~约30wt%硅氧烷单元。
18.根据权利要求1的组合物,还包括一种或多种任选的添加剂,所述添加剂选自:水解稳定剂、填料/增强剂、视觉效应增强剂、抗氧化剂、光稳定剂、紫外线吸收剂、增塑剂、脱模剂、润滑剂、抗静电剂、颜料、染料、阻燃剂、加工助剂、辐射稳定剂、防滴剂以及它们的组合。
19.由权利要求1的组合物制成的制品。
20.权利要求19的制品,其为电子或机械部件。
21.一种耐疲劳的制品,其由包括有效量的聚碳酸酯、季戊四醇二亚磷酸酯衍生物和抗冲改性剂的组合物模制而成,以耐受根据ASTM D638-03在8×104次循环的疲劳破坏。
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US11/424,929 US20070293608A1 (en) | 2006-06-19 | 2006-06-19 | Polycarbonate compositions and articles formed therefrom |
US11/424,929 | 2006-06-19 |
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US (1) | US20070293608A1 (zh) |
EP (1) | EP2029670A1 (zh) |
KR (1) | KR20090018827A (zh) |
CN (1) | CN101472994A (zh) |
WO (1) | WO2007149651A1 (zh) |
Cited By (1)
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CN109312149A (zh) * | 2016-10-31 | 2019-02-05 | 株式会社Lg化学 | 聚碳酸酯树脂组合物和使用该聚碳酸酯树脂组合物的光学模制品 |
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JP5379424B2 (ja) * | 2008-08-07 | 2013-12-25 | 出光興産株式会社 | 摺動用ポリカーボネート系樹脂組成物、および同樹脂組成物を用いた成形品 |
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KR101309808B1 (ko) | 2010-07-30 | 2013-09-23 | 제일모직주식회사 | 내스크래치성과 내충격성이 우수한 난연 폴리카보네이트 수지 조성물 및 이를 이용한 성형품 |
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- 2007-05-11 WO PCT/US2007/068719 patent/WO2007149651A1/en active Application Filing
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CN109312149A (zh) * | 2016-10-31 | 2019-02-05 | 株式会社Lg化学 | 聚碳酸酯树脂组合物和使用该聚碳酸酯树脂组合物的光学模制品 |
CN109312149B (zh) * | 2016-10-31 | 2021-01-29 | 株式会社Lg化学 | 聚碳酸酯树脂组合物和使用该聚碳酸酯树脂组合物的光学模制品 |
US10995214B2 (en) | 2016-10-31 | 2021-05-04 | Lg Chem, Ltd. | Polycarbonate resin composition and optical molded article using the same |
Also Published As
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WO2007149651A1 (en) | 2007-12-27 |
EP2029670A1 (en) | 2009-03-04 |
KR20090018827A (ko) | 2009-02-23 |
US20070293608A1 (en) | 2007-12-20 |
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