CN1516719A - 新型聚合物掺混物 - Google Patents
新型聚合物掺混物 Download PDFInfo
- Publication number
- CN1516719A CN1516719A CNA028073428A CN02807342A CN1516719A CN 1516719 A CN1516719 A CN 1516719A CN A028073428 A CNA028073428 A CN A028073428A CN 02807342 A CN02807342 A CN 02807342A CN 1516719 A CN1516719 A CN 1516719A
- Authority
- CN
- China
- Prior art keywords
- butyl
- phenyl
- ester
- alkyl
- polycarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002959 polymer blend Polymers 0.000 title abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 69
- 239000004417 polycarbonate Substances 0.000 claims abstract description 48
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 46
- 230000003287 optical effect Effects 0.000 claims abstract description 23
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 15
- -1 phosphorous acid ester Chemical class 0.000 claims description 123
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 150000002148 esters Chemical class 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229940059574 pentaerithrityl Drugs 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 6
- 239000000194 fatty acid Substances 0.000 claims description 6
- 229930195729 fatty acid Natural products 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000969 carrier Substances 0.000 abstract 3
- 239000006082 mold release agent Substances 0.000 abstract 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 65
- 150000001875 compounds Chemical class 0.000 description 28
- 239000002585 base Substances 0.000 description 23
- 229960003742 phenol Drugs 0.000 description 22
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 10
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 10
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- 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 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- 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 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000005030 aluminium foil Substances 0.000 description 7
- 239000012964 benzotriazole Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 5
- 125000002347 octyl 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])[H] 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- PMNGNPRHPYYVNM-UHFFFAOYSA-N 1-hydroxyundecane-3-sulfonic acid Chemical compound CCCCCCCCC(CCO)S(O)(=O)=O PMNGNPRHPYYVNM-UHFFFAOYSA-N 0.000 description 4
- ICHKVCYUNCKCGL-UHFFFAOYSA-N CN(C)C.OCCCCCCO Chemical compound CN(C)C.OCCCCCCO ICHKVCYUNCKCGL-UHFFFAOYSA-N 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- COVMBDWAODLWIB-UHFFFAOYSA-N n'-(2-hydroxyethyl)oxamide Chemical compound NC(=O)C(=O)NCCO COVMBDWAODLWIB-UHFFFAOYSA-N 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229940038384 octadecane Drugs 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000005501 phase interface Effects 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 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 description 3
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(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 JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 3
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- 238000002156 mixing Methods 0.000 description 3
- GXFQBBOZTNQHMW-UHFFFAOYSA-N n'-(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound CC1(C)CC(NCCCCCCN)CC(C)(C)N1 GXFQBBOZTNQHMW-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
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- 239000000843 powder Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
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- 230000003068 static effect Effects 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- JEFSTMHERNSDBC-UHFFFAOYSA-N 1,2-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC=CCC1(C)O JEFSTMHERNSDBC-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 2
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical class ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 2
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- HVDJXXVDNDLBQY-UHFFFAOYSA-N 5-butyl-5-ethyl-2-(2,4,6-tritert-butylphenoxy)-1,3,2-dioxaphosphinane Chemical compound O1CC(CCCC)(CC)COP1OC1=C(C(C)(C)C)C=C(C(C)(C)C)C=C1C(C)(C)C HVDJXXVDNDLBQY-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 2
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- 239000004902 Softening Agent Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 239000006096 absorbing agent Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 230000036760 body temperature Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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Abstract
本发明涉及一种含聚碳酸酯、脱模剂和特定的亚磷酸酯的新型热塑性聚合物混合物以及这种聚合物混合物在制备模制品,特别是光学数据载体的应用,如密盘、录象盘、数字通用盘以及其它的可一次或多次书写和删除的光学数据载体,本发明还涉及由此所制备的模制品。
Description
本申请涉及一种含聚碳酸酯、脱模剂和特定的亚磷酸酯的新型热塑性聚合物混合物,还涉及这些聚合物混合物用于制造模制品的应用,尤其是光学数据载体,例如,密盘、录象盘、数字通用盘以及可一次或多次书写和删除的其它光学数据载体,还涉及由此制造的模制品,见上。
聚碳酸酯鉴于其诸如透明度、耐热性和尺寸稳定性等性能的特殊组合,一般用作光学数据载体的注塑或注压成型的材料。为了改善一盘在300℃~400℃下进行的可加工性,将诸如脱模剂和稳定剂等添加剂加到聚碳酸酯中。
多元醇的脂族脂肪酸酯,如甘油与长链脂肪酸的酯及季戊四醇与长链脂肪酸的酯,优选用作脱模剂。这些酯也可以部分地酯化,在这种情况下,其具有明显有利于脱模作用的游离羟基,但是这些酯有损于混合物的热稳定性,所以必须加入稳定剂。但是,所述稳定剂必须是很有效的,即,必须在很低含量下是有效的,否则就有在模具中形成覆层的危险。在这种情况下,在加工中必须经常清洁模具和模头,这是不利的,并且产生劣质片材。相反,完全酯化的脱模剂虽然有较高稳定性,但是在低含量下这些酯的脱模作用比具有游离羟基的酯的脱模作用弱得多。所以,一般使用较大量的完全酯化的脱模剂这样会增加形成覆层的危险,相反,所加入的稳定剂的量可以是稍微较少的。
在文献中已经提出了许多混合物,例如:
为了稳定含有具有OH基的混合物,EP-A205192叙述了应用磷酸三甲酯和/或磷酸三乙酯与亚磷酸酯的混合物。单独的磷酸酯或亚磷酸酯的稳定作用是不充分的,并且这些磷酸酯在生态方面是有害的。
JP-A6218 4639叙述了用亚磷酸酯稳定的聚碳酸酯制造的光学数据存储器。优选是易挥发的亚磷酸酯,如亚磷酸三甲酯,它在生态方面是有害的,并且在形成覆层方面要求十分苛刻。
JP-A2000080261叙述了含有脱模剂、亚磷酸三(二叔丁基苯)酯和磷酸的聚碳酸酯混合物。因此,亚磷酸酯的稳定作用是不充分的,这样就使用了磷酸作另外的稳定剂,但是在高空气湿度和较高温下它能使光学数据载体的存储层发生腐蚀。
所以,本发明目的是开发一种含有聚碳酸酯、脱模剂和热稳定剂的热塑性聚合物混合物,它最适宜制备光学数据载体和其它模制品,换句话说,例如,采用较少量就具有良好脱模作用。尤其是,这种具有较高存储能力和任选较薄盘厚的新式如数字通用盘(DVD)要求有比CD更高的热稳定性。对在加工成模制品期间对材料的损伤和在模具中形成覆层有更严格的要求。
采用按照本发明的混合物,通过改进数据存储器的质量以及改进在注塑或注压成型期间材料的可加工性,令人惊异地实现了这个目的。
所以,本申请涉及一种含有至少一种聚碳酸酯、至少一种脱模剂和至少一种具有特殊化学结构的亚磷酸酯的热塑性聚合物混合物。这种亚磷酸酯即使在低浓度下也稳定所存在的脱模剂,所以能够降低具有相同脱模作用的脱模剂的配量。因此,覆层形成降低到令人惊异的低水平,其原因在于两方面,即,脱模剂的用量减少和脱模剂的稳定性令人惊异的增加。
本发明还涉及这些聚合物混合物在制造诸如密盘、录象盘、数字通用盘以及可以一次或多次书写和删除的其它光学数据载体等的光学数据载体中的应用,还涉及由该聚合物混合物制造的光学数据载体。
显然,所述聚合物混合物也适用于其它传统聚碳酸酯的应用,包括利用具有较高分子量的聚碳酸酯的那些应用。这些应用可以是透明的或不透明的,例如食品和饮料包装、光学透镜和棱镜、照明用透镜、汽车前灯透镜、建筑运输车和机动车窗用玻璃、诸如用于温室等各种类型窗用玻璃,所谓的桥接用双壁片材或中空腔片材。应用的其它例子是诸如用于医用仪器、家用设备如压汁机、咖啡机、混合器等、办公设备如计算机、监视器、印刷机、复印机等的各种类型的型材、薄膜、外壳,用于建筑工业、内装修和室外应用的片材、管材、电气设备管道、窗户、门和型材;用于电气工程领域如开关和插头。按照本发明的模制品也可以用于火车、轮船、飞机、公共汽车和其它运输车辆的内装饰和部件以及用于卡车车体零件。
本发明范围的热塑性聚合物混合物主要含有芳族聚碳酸酯。术语聚碳酸酯包括均聚碳酸酯和共聚碳酸酯;聚碳酸酯可以是已知意义的线形或支链的。它们的按凝胶渗透色谱测定的重均分子量为5,000~80,000,优选为10,000~40,000。特别优选的分子量为15,000~35,000,尤其为15,000~22,000。
这些聚碳酸酯以已知方法由二酚、碳酸衍生物、任选链终止剂和任选支化剂来制备。
约40年来,在许多专利中发表了关于制备聚碳酸酯的详述。参见,诸如Schnell,“Chemistry and Physics of Polycarbonates”(聚碳酸酯化学和物理学),Polymer Reviews(聚合物评论),第9卷,Interscience Publishers,New York,London,Sydney 1964;Dr.Freitag,U.Grigo,P.R. Müller,H.Nouvertne,BAYER AG,“Polycarbonates”(聚碳酸酯),发表在Encyclopedia of PolymerScience and Engineering(聚合物科学和工程大全),第11卷,第二版,1988,P 648~718,以及最后Dres.U.Grigo,K.Kirchner和P.R.Müller,“Polycabonate”(聚碳酸酯)发表在Becker/Braun,Kunststoff-Handbuch(塑料手册)第3/1卷,Polycarbonate,Polyacetate,Polyester,Celluloseester,Carl Hanser Verlag,Munich,Vienna 1992,P117~299。
适用于生产聚酸酯的二酚包括,例如,氢醌、间苯二酚、二羟基联苯、双(羟基苯基)烷、双(羟基苯基)环烷、双(羟基苯)硫化物、双(羟基苯基)醚、双(羟基苯基)酮、双(羟基苯基)砜、双(羟基苯基)亚砜、α-α’-双(羟基苯基)-二异丙基苯及其环上烷基化和环上卤代化合物。
优选的酚包括4,4’-二羟基联苯、2,2-双(4-羟基苯基)丙烷、2,4-双-(4-羟基苯基)-2-甲基丁烷、1,1-双-(4-羟基苯基)-对-二异丙基苯、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、2,4-双(3,5-二甲基-4-羟基苯基)-2-甲基丁烷、1,1-双(3,5-二甲基-4-羟基苯基)-对二异苯基苯、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-羟基苯基)-3,3,5-三甲基环己烷和4,4’-(间亚苯基二异亚丙基)-联苯。
特别优选的二酚是2,2-双(4-羟基苯基)丙烷(BPA)、2,2-双(3,5-二甲基-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、4,4’-(间亚苯基二异亚丙基)双酚(CAS-No 13595-25-0)(BPM)、1,1-双(4-羟基苯基)环己烷和1,1-双(4-羟基苯基)-3,3,5-三甲基环己烷(TMC)。
这些和其它适宜二酚叙述在,例如:US3028635,2999835,3148172,2991273,3271367,4982014和2999846、DE-A1570703,2063050,2036052,2211956和3832396、法国专利1 5611518,以及专论H.Schnell,Chemistry and Physics of Polycarbonates(聚碳酸酯的化学和物理学),Interscience Publishers,New York 1964,还有JP-A62039/1986,62040/1986和105550/1986。
在均聚碳酸酯情况下仅用一种二酚,在共聚碳酸酯情况下用多种二酚。
优选使用下述的聚合物混合物,它含至少一种具有由BPA和/或三甲基环己基双酚(TMC)组成的二醇单元的聚碳酸酯,所述二醇单元优选自BPA的均聚物、BPA和TMC的共聚物或具有5~60wt%TMC的共聚物。
适宜的碳酸衍生物包括例如光气或碳酸二苯酯。
适宜的链终止剂包括一元酚以及一元羧酸。
适宜的一元酚包括苯酚本身、烷基苯酚如对甲酚、对叔丁基酚、对正辛基酚、对异辛基酚、对正壬基酚和对异壬基酚、对枯基酚、卤代苯酚如对氯代苯酚、2,4-二氯代苯酚、对溴代苯酚戊基苯酚和2,4,6-三溴代苯酚及其混合物。
优选的链终止剂是通式(I)酚
其中
R代表氢、叔丁基或支链或非支链C8和/或C9烷基。但是,也可以优选使用对枯基酚。在酯交换过程中,链终止剂由所使用的碳酸二芳酯产生。
所使用的链终止剂的量,以应用的各双酚的摩尔计在相界面法中优选为0.1mol%~5mol%。链终止剂可以在光气化作用之前、之中或之后加入。
适宜的支化剂是自聚碳酸酯化学中已知的三官能或三官能以上的化合物,尤其是具有三个或三个以上的酚羟基的那些化合物。
适宜的支化剂包括,例如,间苯三酚、4,6-二甲基-2,4,6-三(4-羟苯基)-庚烯-2、4,6-二甲基-2,4,6-三(4-羟苯基)-庚烷、1,3,5-三(4-羟苯基)苯、1,1,1-三-(4-羟苯基)-乙烷、三(4-羟苯基)苯基甲烷、2,2-双[4,4-双(4-羟苯基)环己基]丙烷、2,4-双-(4-羟苯基-异丙基)苯酚、2,6-双(2-羟基-5’-甲基-苄基)-4-甲基苯酚、2-(4-羟苯基)-2-(2,4-二羟苯基)丙烷、六(4-(4-羟苯基-异丙基)-苯基-)邻对苯二甲酸酯、四(4-羟苯基)甲烷、四(4-(4-羟苯基-异丙基)-苯氧基)甲烷和1,4-双(4’,4”-二羟基三苯基)-甲基)苯以及2,4-双羟基苯甲酸、1,3,5-苯三酸、氰尿酰氯和,对于一些应用,甚至优选3,3-双(3-甲基-4-羟基-苯基)-2-氧代-2,3-二氢吲哚。
任选待用的支化剂量以应用的双酚的摩尔为0.01mol%~2mol%。
支化剂可以与在相界面法的碱性水相中的二酚和链终止剂一起存在,或者可以加入并溶解在有机溶剂中。在酯交换法中,支化剂可以与二酚一起应用。
本领域技术人员熟悉制备热塑性聚碳酸酯的所有这些方法。
作为脱模剂应用的化合物优选是多元醇与长链羧酸的酯。优选是未完全酯化的、因此具有游离OH基的脱模剂。特别优选具有16~22个碳原子的-价饱和脂肪酸与甘油、三羟甲基丙烷、季戊四醇或相似的多元醇的(部分)酯。尤其是甘油单硬脂酸酯和甘油单棕榈酸酯。
甘油的这些饱和一元脂肪酸酯可以单独应用或者以与两种或多种组分的混合物的形式应用。甘油的饱和单脂通常通过氢化的动物油或植物油与甘油的酯交换反应来制备。虽然反应产物也可能含有除了甘油酯之外的酯,但是应用它作为按照本发明的脱模剂。例如,所述混合物可含或多或少比例的甘油二酯和甘油三酯。
在制造CD和其它光学存储介质(DVD等)时脱模剂的最佳量,一方面由足够的脱模作用另一方面由模具中覆层的形成来决定。脱模剂的通常使用量为50~1,000ppm,更有利的是100~500ppm。对于聚碳酸酯的其它用途而言,含量为100~10,000ppm,优选为2,000~7,000ppm。
按照本发明的特殊亚磷酸酯是在分子中具有芳族自由基和脂族自由基两者。这些是具有下述结构的化合物:
其中:
n代表数0~5,优选1~3,特别优选3,
Y,在每种情况下是彼此无关的烷基或任选取代的芳基,优选C1~C4烷基,特别优选甲基、仲丁基和叔丁基,
m代表数字1~3,优选3和
X,在每种情况下是彼此无关的任选取代的亚甲基,其中至少一个亚甲基必须完全被取代,并且取代基彼此无关地选自C1~C20烷基,优选C1~C20烷基或在完全取代的亚甲基上的两个取代基一起代表基团:
其中
R1代表C1~C18烷基、C3~C12环烷基、C6~C30烷芳基和芳基,其中这些基团又可以取代上、1~4个O-亚烷基-O和/或羧酸酯-COO-基;含有2~10个羟基的C2~C18多羟基烷基;含2~10个酚羟基的C2~C18多苯基。
优选的化合物是通式如下:
其中
R2代表C1~C6烷基;
R3代表甲基或乙基和
R4选自C1~C18烷基、C3~C12环烷基、C6~C30烷芳基和芳基,其中这些基团又可以取代上1~4个O-亚烷基-O和/或羧酸酯-COO-基;含2-10个羟基的C2~C18多羟基烷基;含2~10个酚OH的C2~C18多苯基。
还优选下述通式化合物
其中
Y和n具有上述含义和
R5,彼此无关的选自氢和C3~C20烷基,优选至少一个R5代表烷基,
R6,彼此无关的代表C1~C10烷基。
下通式化合物是特别优选的。
其中,R1和R2代表甲基、仲丁基或叔丁基。
类似地,EP A1 0 038 876的第16~20页所限定的化合物和相同文件第21页的实施例也是特别优选的。
具有下述结构的亚磷酸(2,4,6-三叔丁基苯基)-(2-丁基-2-乙基-丙烷-1,3-二基)酯是颇特别优选的。
亚磷酸酯可以单独使用,但是也可以与其它磷化合物组合使用,其中,其它磷化合物也可以是具有不同磷氧化值的化合物。所以,诸如按照本发明的亚磷酸酯与其它亚磷酸酯、与膦如三苯基膦、与亚膦酸酯、与磷酸酯、与膦酸酯等的组合是可以使用的。
按照本发明使用的亚磷酸酯可以以通常已知的或相似已知的方法制备。亚磷酸(2,4,6-三叔丁基苯基)-(2-丁基-2-乙基-丙烷-1,3-二基)酯叙述在,例如,EP-A 702018和EP635514中。
按照本发明的聚合物混合物含有磷化合物的比例为10~5,000ppm,优选10~1,000ppm,特别优选20~500ppm,更特别优选50~250ppm。
优选、特别优选或更特别优选的含所述取代基的化合物是优选的、特别优选的或更特别优选的。
但是,上述一般的或在优选范围描述的基团的定义或解释和参数和使用量比也可以彼此组合,即在相应范围和优选范围当中进行组合。
将脱模剂和磷化合物加入到热塑性聚合物混合物中可如下进行,在聚碳酸酯制备之后和在加工聚碳酸酯期间加入,例如通过加入到聚碳酸酯聚合物溶液中或者加入到热塑性聚合物混合物的熔体中来实现。另外,也能够在各个操作步骤中将各成分彼此无关地加入,例如,例如在聚合物溶液加工期间加入一个成分,而其它成分加在熔体中,条件是在最终产物(模制品)生产期间包含所有成分。
按照本发明的热塑性聚合物混合物也可以含有已知量的适用于聚碳酸酯的常规添加剂,例如并优选,紫外辐射稳定剂、阻燃剂、染料、填料、发泡剂、荧光增白剂和抗静电剂。对于光学用途,优选使用对材料透明度无有害影响的成分。
这些物质可以在许多出版物中发现,例如在Additive forPlastics Handbook(塑料添加剂手册),John Murphy,1999,并且可市购。
1.适宜的抗氧剂包括,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。
1.12 β-(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,与十八烷醇的酯(IRGANOX 1076_,Ciba Spec制造)是更特别适宜的和优选的。
1.13 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,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。
1.14 β-(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。
1.16 β(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(Naugard_XL-1,自Uniroyal)。
1.17抗坏血酸(维生素C)
1.18胺的抗氧化剂,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、叔辛基吩噻嗪、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(2,2,6,6-四甲基哌啶-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。可以应用其单一化合物或混合物。
1.19适宜的硫代增效剂包括,例如硫代二丙酸月桂酯、硫代二丙酸二硬脂酰酯。
2.紫外吸收剂和光稳定剂可以以0.1~15wt%,优选3~8wt%。应用在按照本发明的组合物中,以组合物重量计。适宜的紫外吸收剂和光稳定剂是,例如:
2.1 2-(2’-羟基苯基)苯并***,例如:2-(2’-羟基-5’-甲基苯基)苯并***、2-(3’,5’-二叔丁基-2’-羟基苯基)苯并***、2-(5’-叔丁基-2’-羟基苯基)苯并***、2-(2’-羟基-5’-(1,1,3,3-四甲基-丁基)苯基)苯并***、2-(3’,5’-二叔丁基-2’-羟基苯基)-5-氯苯并***、2-(3’-叔丁基-2’-羟基-5’-甲基苯基)-5-氯苯并***、2-(3’-仲丁基-5’-叔丁基-2’-羟基苯基)苯并***、2-(2’-羟基-4’-辛氧基-苯基)苯并***、2-(3’,5’-二叔戊基-2’-羟苯基)苯并***、2-(3’,5’-双(α,α-二甲基苄基)-2’-羟基苯基)苯并***、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰基-乙基)苯基)-5-氯苯并***、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***、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰基乙基)苯基)-5-氯苯并***、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰基乙基)苯基)苯并***、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰基乙基)苯基)苯并***、2-(3’-叔丁基-5’-[2-(2-乙基己氧基)羰基乙基]-2’-羟基苯基)苯并***、2-(3’-十二烷基-2’-羟基-5’-甲基苯基)苯并***、2-(3’-叔丁基-2’-羟基-5’-(2-异辛氧基羰基乙基)苯基苯并***、2,2’-亚甲基双[4-(1,1,3,3-四甲基丁基)-6-苯并***-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***与聚乙二醇300,[R-CH2CH-COO-CH2CH2]2的酯交换产物,其中R=3’-叔丁基-4’-羟基-5’-2H-苯并***-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***、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***。
2.2 2-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)间苯二酚、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-甲氧基肉桂酸酯和、甲基-α-甲氧甲酰-对-甲氧基肉桂酸酯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络合物,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(2,2,6,6-四甲酯-4-哌啶基)丁二酸酯、双(1,2,2,6,6-五甲基-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。
其单一化合物或混合物均可以使用。
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-***、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。
4.适宜的过氧化物捕集剂包括,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。
5.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。
6.适宜的成核剂包括,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。
7.适宜的填料和增强剂包括,例如,碳酸钙、硅酸盐、玻璃纤维、玻璃珠、石棉、滑石、高岭土、去母、硫酸钡、金属氧化物和金属氢氧化物、碳黑、石墨、硅灰石、锯屑和其它天然产物的屑或纤维、合成纤维。可以应用其单一化合物或混合物。
8.适宜的其它添加剂包括,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。
9.适宜的苯并呋喃酮和吲哚满酮包括,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。可以应用其单一化合物或其混合物。
10.适宜的荧光增塑剂是“Plastics Additives Handbook”(塑料添加剂手册),R.G_chter and H.Müller.编辑,Hanser Verlag,第三版,1990,P775~789,所列者。
11.适宜的阻燃添加剂包括磷酸酯,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+。
12.适宜的增韧剂包括具有接枝苯乙烯/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。
13.适宜的聚合物包括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。
14.适宜的抗静电剂包括磺酸盐,例如,C12H25SO3-或C8F17SO3-的四乙基铵盐。
15.适宜的着色剂包括颜料以及有机染料和无机染料。
16.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。
17.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。
18.适宜作稳定剂的亚磷酸酯和亚膦酸酯包括,例如,三苯基亚磷酸酯、二苯基烷基亚磷酸酯、苯基二烷基亚磷酸酯、三(壬基苯基)亚磷酸酯、三月桂基亚磷酸酯、三(十八烷基)亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、二异癸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-(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、二异癸氧基季戊四醇二亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨糖醇三亚磷酸酯、四(2,4-二叔丁基苯基)-4,4’-二亚苯基二亚膦酸酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-dioxaphosphocine、6-氟-2,4,8,10-四叔丁基-12-甲基二苯并[d,g]-1,3,2-dioxaphosphocine、双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯、6-氟-2,4,8,10-四叔丁基-12-甲基二苯并[d,g]-1,3,2-dioxaphosphocine、2,2’,2”-次氮基[三乙基三(3,3’,5,5’-四叔丁基-1,1’-二苯基-2,2’-二基)亚磷酸酯、2-乙基-己基(3,3’,5,5’-四叔丁基-1,1’-二苯基-2,2’-二基]亚磷酸酯、5-丁基-5-乙基-2-(2,4,6-三叔丁苯氧基)-1,3,2-dioxaphosphirane。可以应用其单个化合物或者其混合物。
三(2,4-二叔丁基苯基)亚磷酸酯(Irgafos_168,Ciba-Geigy)或三苯基膦是特别优选的。
第16和17类中的化合物起熔体稳定剂作用。它们可以单个应用或者以混合物形式应用。
本领域技术人员显然会从上述添加剂中选择适用于CD、DVD和其它光学记录介质领域中应用的不损害其透明度的添加剂。
IRGANOX 1076_,参见上文,和2.1类的苯并***(所谓的延纳芬),尤其是其彼此混合是特别适宜的添加剂。
用本发明聚合物混合物以适于聚碳酸酯的已知方式来制造模制品,优选光学介质。尤其用于制造密盘和DVD以及可以一次或多次书写和删除的光学介质。可书写层尤其是由染料或金属层组成,后者利用从无定形态至结晶态的交换作为记录原理或者具有磁性性质。
光学介质的这种制造优选由已制成的本发明的例如以颗粒形式存在的聚合物混合物来进行。但是,光学介质的制造也可以通过把组分加工到纯的或常规市售聚碳酸酯和/或加到在由聚碳酸酯制造模制品时的常规添加剂中来进行。
此外,本发明还涉及由此得到的模制品,例如由本发明的热塑性聚合物混合物制得的光学数据载体,优选密盘和DVD。
本发明的热塑性聚合物混合物具有下述优点,在制造模制品期间具有更好的稳定性,以及得到的最终制品(模制品)易于从生产模具中脱模,并且不在模具中留下杂质。
以下实例用于举例说明本发明。本发明并不受限于这些实例。
实施例
通过相界面法制备的聚碳酸酯的实例
制备下述混合物
按照下表,将X重量份的、通过相界面方法制备的、具有叔丁基酚端基的、用BPA-PC制成的、平均溶液粘度1.195(在25℃下于二氯甲烷中测定,在100ml二氯甲烷中含量0.5g)的聚碳酸酯颗粒与y重量份的甘油单硬脂酸酯和Z重量份的磷化合物,在密闭容器中充分混合。然后所得混合物在本体温度约240℃下于Werner PfleidererZSK53型双螺杆捏合机中进行混配。
表1(组分)
聚碳酸酯 | 甘油单硬脂酸酯 | 亚磷酸酯1 | 亚磷酸酯2 | |
实施例1 | 99.955 | 0.04 | 0.005 | |
实施例2 | 99.95 | 0.04 | 0.01 | |
比较例1 | 99.955 | 0.04 | 0.005 | |
比较例2 | 99.95 | 0.04 | 0.01 | |
比较例3(无稳定剂) | 99.96 | 0.04 | 0 | 0 |
用Henke KgaA制造的产物Loxiol EP129作甘油单硬脂酸酯。亚磷酸酯1是(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,以商品名Ultranox 641_得自GE SpecialtyChemicals。亚磷酸酯-2是三(2,4-二叔丁基苯基)亚磷酸酯,以Irgafos_168得自Ciba-Geigy公司。
为测定CD的产品稳定性,采用Netstal Discjet 600型CD注塑机制造由上述材料制成的CD坯料。CD厚度为1.2mm,外径为120mm。借助在下文称为设定1~4的各种机器条件检验产品稳定性。
设定1:
料筒温度(进料/压缩/料筒头部/喷嘴):315/320/320/320℃,最大注射速率:130mm/sec,模具(预运行温度):55℃,循环时间:4.6sec
设定2:
料筒温度(进料/压缩/料筒头部/喷嘴):315/340/350/350℃,最大注射速率:110mm/sec,模具(预运行温度):55℃,循环时间:4.9sec
设定3:
料筒温度(进料/压缩/料筒头部/喷嘴):315/360/380/380℃,最大注射速率:100mm/sec,模具(预运行温度):55℃,循环时间:5.5sec
设定4:
如设定2,只是循环以5分钟停机而中断。注塑机重新起动之后的第五块板作如下测定。
然后测定CD坯料剩余甘油单硬脂酸酯含量和酚OH基含量。
表2(GMS测定)
(在各种条件下制备的CD中的GMS含量以ppm计)
设定1 | 设定2 | 设定3 | 设定4 | |
实施例1 | 305 | 285 | 280 | 255 |
实施例2 | 355 | 315 | 300 | 290 |
比较例1 | 290 | 270 | 255 | 195 |
比较例2 | 320 | 290 | 265 | 210 |
比较例3(无稳定剂) | 285 | 255 | 205 | 140 |
此外,在CD中酚OH含量也于各种条件下制备后进行测定。
表3(酚OH基测量定)
(在各种条件下制备的CD的酚OH基含量以ppm计)
设定1 | 设定2 | 设定3 | 设定4 | |
实施例1 | 120 | 130 | 130 | 140 |
实施例2 | 105 | 120 | 125 | 130 |
比较例1 | 120 | 135 | 135 | 150 |
比较例2 | 120 | 135 | 140 | 150 |
比较例3 | 125 | 145 | 155 | 175 |
表4(覆层检验)
覆层形成 | |
实施例1 | 轻微 |
实施例2 | 轻微 |
比较例1 | 轻微 |
比较例2 | 中等 |
比较例3 | 严重 |
覆层形成情况按下述测定:为测定在模具中的覆层,用具有Axxicon CD模具的Netstal Discjet 600型CD注塑机,在每种情况下均制造一千张部分填充的CD坯料。由于随与后压适配的计量流径减小产生了约80%的CD为部分填充。料筒温度在进料区为300℃、在压缩区为310℃,在料筒头和喷嘴为经常采用的330℃。循环时间为约5.5秒。在第一千次注射之后,肉眼检测模头表面和外区中的镜面以确定覆层形成情况,所谓外区即与聚碳酸酯熔体没有接触的区域。从而得到上述结果。
通过熔融酯交换法制造的聚碳酸酯的实例
按照下表,将x重量份的、通过熔融酯交换法生产的、具有酚端基的、用BPA-PC制成的、平均溶液粘度1,200(在25℃下于二氯甲烷中测定,在100ml二氯甲烷中含量0.5g)的聚碳酸酯颗粒与y重量份的甘油单硬脂酸酯和z重量份的磷化合物,在密闭容器中充分混合。然后将所得混合物在本体温度约240℃下于Werner Pfleiderer ZSK53型双螺杆捏合机中进行混配。
表1(组分)
聚碳酸酯 | 甘油单硬脂酸酯 | 亚磷酸酯1 | 亚磷酸酯2 | |
实施例1 | 99.06 | 0.03 | 0.01 | |
比较例1 | 99.06 | 0.03 | 0.01 | |
比较例2(无稳定剂) | 99.07 | 0.03 |
用Henke KgaA制造的产物Loxiol EP 129作甘油单硬脂酸酯。亚磷酸酯1是(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,以商品名Ultranox 641_得自GE SpecialtyChemicals.亚磷酸酯-2是三(2,4-二叔丁基苯基)亚磷酸酯,以Irgafos_168得自Ciba-Geigy公司。
为测定CD的产品稳定性,采用Netstal Discjet 600型CD注塑机制造由上述材料制成的CD坯料。CD厚度为1.2mm,外径为120mm。产物稳定性借助于上述加工程序的机器设定了进行检测。
在CD坯料上检测剩余的甘油单硬脂酸含量得到以下结果。
表2(GMS测定)
(在各种条件下制备的CD中的GMS含量以ppm计)
设定3 | |
实施例1 | 285 |
比较例1 | 195 |
比较例2(无热稳定剂) | 180 |
表3(覆层检验)
覆层形成(%) | |
实施例1 | 0.049 |
比较例1 | 0.099 |
比较例2 | 0.160 |
冷凝物量的测定
冷凝物的量按下述进行测定,称重具有和不具有覆层的铝箔。覆层的量按如下定义:
冷凝物量,%=(箔重量在检测后-箔重量在检测前)/样品重量×100%
方法详述
将干燥(120℃,4h)后的20g粒料倒入直径80mm、深15mm的铝盘中,使盘底均匀覆盖着粒料。将加粒料的盘放入一个专为此提供的、可电加热的金属设备的样品室(直径85mm、深50mm)中,并用0.03mm厚、100mm直径的铝箔封闭。为了使挥发性成分在铝箔上冷凝,在测定期间铝箔用冷却板冷却。冷却水温度调节至20℃。在进行测定时,应该保证铝箔良好密封样品室使其与外部隔离。
把金属设备在几分钟内加热至300℃。样品在该温度下持续4h,然后将检验设备冷却至室温。在达到室温之后,取下铝箔,并在微量天平上称量铝箔,按所述定义计算冷凝物量。
测定方法详述
甘油单硬酯酸
以气相色谱在毛细管柱上分离出甘油单硬脂酸酯,用火焰离子检测器检测。通过内标法求值。测定限为约10ppm。
酚OH基
使聚碳酸酯溶解于二氯甲烷中,加入氯化钛(IV)以形成橙红色络合物,在546mm下以光度分析测定后者的消光值。采用BPA作外标进行刻度。测定限为约20ppm OH。
Claims (10)
1.一种热塑性聚合物混合物,其含有至少一种聚碳酸酯、至少一种脱模剂和至少一种具有如下结构的亚磷酸酯,
其中:
n代表数0~5,优选1~3,特别优选3,
Y,在每种情况下是彼此无关的烷基或任选取代的芳基,优选C1~C4烷基,特别优选甲基、仲丁基和叔丁基,
m代表数字1~3,优选3和
X,在每种情况下是彼此无关的任选取代的亚甲基,其中至少一个亚甲基必须完全被取代,并且取代基彼此无关地选自C1~C20烷基,优选C1~C20烷基或在完全取代的亚甲基上的两个取代基一起代表基团:
其中
R1选自C1~C18烷基、C3~C12环烷基、C6~C30烷芳基和芳基,其中这些基团又可以取代上1~4个O-亚烷基-O和/或羧酸酯-COO-基;含有2~10个羟基的C2~C18多羟基烷基;含2~10个酚羟基的C2~C18多苯基。
2.按照权利要求1的热塑性聚合物混合物,其中,脱模剂是多元醇与长链羧酸的酯,并且该酯还含有至少一个游离OH基。
3.按照权利要求1的聚合物混合物,其中,脱模剂是含有16~22个碳原子的饱和一元脂肪酸与甘油、三羟甲基丙烷、季戊四醇或类似多元醇的部分酯。
4.按照前述权利要求的聚合物混合物,其中聚碳酸酯的分子量为15,000~35,000。
5.按照前述权利要求的聚合物混合物,其含有0.01~1.5wt%脱模剂和0.001~0.1wt%亚磷酸酯。
6.一种制造模制品的方法,其特征在于:应用按照前述权利要求之一的聚合物混合物。
7.一种由按照权利要求1~7的热塑性聚合物混合物生产的光学数据载体。
8.一种制造模制品的方法,其特征在于:应用在权利要求1~5中的混合物。
9.按照权利要求1~5中的混合物在制造热塑性聚合物和由其制造模制品中的应用。
10.按照前述权利要求界定的聚合物混合物在制造模制品中的应用。
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US7521505B2 (en) * | 2006-06-12 | 2009-04-21 | Sabic Innovative Plastics Ip B.V. | Method of stabilization of dihydric phenols |
DE102009007762A1 (de) * | 2009-02-06 | 2010-08-12 | Bayer Materialscience Ag | Folienmehrschichtverbund mit einer Schicht aus Polycarbonat |
DE102010033035A1 (de) * | 2010-08-02 | 2012-02-02 | Emery Oleochemicals Gmbh | Gleitmittelkombination für die Verarbeitung von thermoplastischen Kunststoffen |
US10081690B2 (en) * | 2016-06-23 | 2018-09-25 | Sunko Ink Co., Ltd. | Powdery diacetal clarifying agent and method of preparing the same |
KR102049577B1 (ko) * | 2016-10-31 | 2019-11-27 | 주식회사 엘지화학 | 폴리카보네이트 수지 조성물 및 이로 이루어진 광학 성형품 |
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US5244954A (en) * | 1990-12-21 | 1993-09-14 | Ecp Enichem Polimeri S.R.L. | Moulding thermoplastic compositions endowed with improved mould release characteristics |
DE4445544A1 (de) * | 1994-12-20 | 1996-06-27 | Bayer Ag | Stabilisierte Polycarbonate |
JPH1036645A (ja) * | 1996-07-22 | 1998-02-10 | Polyplastics Co | ポリブチレンテレフタレート樹脂組成物 |
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JPH11342510A (ja) * | 1998-04-03 | 1999-12-14 | Teijin Chem Ltd | 光学用成形材料 |
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US6649677B2 (en) * | 1998-11-03 | 2003-11-18 | General Electric Company | Polycarbonate sheet with improved fire retardant performance |
JP2000239510A (ja) * | 1999-02-25 | 2000-09-05 | Teijin Ltd | 安定化芳香族ポリカーボネート組成物及びそれよりの射出成型品 |
US6407199B1 (en) | 1999-05-27 | 2002-06-18 | Teijin Limited | Polycarbonate resin composition optical recording medium, and substrate therefor |
DE19925125A1 (de) * | 1999-06-01 | 2000-12-07 | Bayer Ag | Polycarbonatformmassen zur Herstellung von Artikeln mit verminderter Staubanlagerung |
US6492485B1 (en) * | 2000-04-11 | 2002-12-10 | General Electric Company | Redistributed polycarbonate resin |
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2001
- 2001-03-26 DE DE10114803A patent/DE10114803A1/de not_active Withdrawn
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2002
- 2002-03-13 EP EP02703634A patent/EP1379583B1/de not_active Expired - Lifetime
- 2002-03-13 CN CNB028073428A patent/CN1244619C/zh not_active Expired - Fee Related
- 2002-03-13 ES ES02703634T patent/ES2305202T3/es not_active Expired - Lifetime
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- 2002-03-13 JP JP2002576541A patent/JP4128874B2/ja not_active Expired - Fee Related
- 2002-03-13 KR KR1020037012459A patent/KR100839305B1/ko not_active IP Right Cessation
- 2002-03-13 AT AT02703634T patent/ATE397034T1/de not_active IP Right Cessation
- 2002-03-13 WO PCT/EP2002/002721 patent/WO2002077087A1/de active IP Right Grant
- 2002-03-22 US US10/104,748 patent/US6899939B2/en not_active Expired - Fee Related
- 2002-03-25 TW TW091105678A patent/TWI310778B/zh not_active IP Right Cessation
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102666702A (zh) * | 2009-09-30 | 2012-09-12 | 拜尔材料科学股份公司 | 具有改善的光学性能的聚碳酸酯组合物 |
CN102666702B (zh) * | 2009-09-30 | 2014-07-16 | 拜尔材料科学股份公司 | 具有改善的光学性能的聚碳酸酯组合物 |
CN102782033A (zh) * | 2009-12-05 | 2012-11-14 | 拜尔知识产权有限责任公司 | 具有酚取代的三嗪衍生物的聚碳酸酯组合物 |
CN102782033B (zh) * | 2009-12-05 | 2014-04-02 | 拜尔知识产权有限责任公司 | 具有酚取代的三嗪衍生物的聚碳酸酯组合物 |
Also Published As
Publication number | Publication date |
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US20020173566A1 (en) | 2002-11-21 |
TWI310778B (en) | 2009-06-11 |
DE50212321D1 (de) | 2008-07-10 |
US6899939B2 (en) | 2005-05-31 |
JP4128874B2 (ja) | 2008-07-30 |
ES2305202T3 (es) | 2008-11-01 |
EP1379583B1 (de) | 2008-05-28 |
EP1379583A1 (de) | 2004-01-14 |
JP2004526028A (ja) | 2004-08-26 |
KR20030088470A (ko) | 2003-11-19 |
CN1244619C (zh) | 2006-03-08 |
ATE397034T1 (de) | 2008-06-15 |
WO2002077087A1 (de) | 2002-10-03 |
DE10114803A1 (de) | 2002-10-10 |
KR100839305B1 (ko) | 2008-06-17 |
HK1068361A1 (en) | 2005-04-29 |
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