JP4053291B2 - Aromatic polycarbonate and method for producing the same - Google Patents
Aromatic polycarbonate and method for producing the same Download PDFInfo
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- JP4053291B2 JP4053291B2 JP2001388999A JP2001388999A JP4053291B2 JP 4053291 B2 JP4053291 B2 JP 4053291B2 JP 2001388999 A JP2001388999 A JP 2001388999A JP 2001388999 A JP2001388999 A JP 2001388999A JP 4053291 B2 JP4053291 B2 JP 4053291B2
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- JP
- Japan
- Prior art keywords
- aromatic polycarbonate
- polymerization
- compound
- polycarbonate
- aromatic
- 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.)
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- 125000003118 aryl group Chemical group 0.000 claims description 70
- 239000004417 polycarbonate Substances 0.000 claims description 69
- 229920000515 polycarbonate Polymers 0.000 claims description 67
- 238000006116 polymerization reaction Methods 0.000 claims description 50
- -1 diester compound Chemical class 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 12
- 150000007513 acids Chemical class 0.000 claims description 10
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 36
- 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 18
- 229920000642 polymer Polymers 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical class C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 238000006384 oligomerization reaction Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LVLNPXCISNPHLE-UHFFFAOYSA-N 2-[(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1O LVLNPXCISNPHLE-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 150000003868 ammonium compounds Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MPMIIBSWDJGKHH-UHFFFAOYSA-N (2,3,4-tributylphenyl)boron Chemical compound [B]C1=CC=C(CCCC)C(CCCC)=C1CCCC MPMIIBSWDJGKHH-UHFFFAOYSA-N 0.000 description 1
- VLCQYXZALXDPEV-UHFFFAOYSA-N (2,3,4-triethylphenyl)boron Chemical compound [B]C1=CC=C(CC)C(CC)=C1CC VLCQYXZALXDPEV-UHFFFAOYSA-N 0.000 description 1
- PJAWEFMLSSLAIM-UHFFFAOYSA-N (2,3,4-trimethylphenyl)boron Chemical compound [B]C1=CC=C(C)C(C)=C1C PJAWEFMLSSLAIM-UHFFFAOYSA-N 0.000 description 1
- IHPFDBSMYWRYHQ-UHFFFAOYSA-N (2-benzylphenyl)-diphenylborane Chemical compound C=1C=CC=C(B(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1CC1=CC=CC=C1 IHPFDBSMYWRYHQ-UHFFFAOYSA-N 0.000 description 1
- GCLVVFYKIZYIIL-UHFFFAOYSA-N (2-butylphenyl)-diphenylborane Chemical compound CCCCC1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 GCLVVFYKIZYIIL-UHFFFAOYSA-N 0.000 description 1
- KBIWOGUYLGWUTF-UHFFFAOYSA-N (2-methylphenyl)-diphenylborane Chemical compound CC1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 KBIWOGUYLGWUTF-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical compound SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 description 1
- HSNJERRVXUNQLS-UHFFFAOYSA-N 1-(4-tert-butylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C(C)(C)C)C=C1 HSNJERRVXUNQLS-UHFFFAOYSA-N 0.000 description 1
- XGVZPMZEBYEFAD-UHFFFAOYSA-N 2,2-dimethylpropylboron Chemical compound [B]CC(C)(C)C XGVZPMZEBYEFAD-UHFFFAOYSA-N 0.000 description 1
- QUMMIJOYXPIWKT-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-ylboron Chemical compound [B]C(C)(C)C1=CC=CC=C1C QUMMIJOYXPIWKT-UHFFFAOYSA-N 0.000 description 1
- LROZSPADHSXFJA-UHFFFAOYSA-N 2-(4-hydroxyphenyl)sulfonylphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=CC=C1O LROZSPADHSXFJA-UHFFFAOYSA-N 0.000 description 1
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- YQSPOXMPYQYCSI-UHFFFAOYSA-N 2-methoxy-1h-imidazole Chemical compound COC1=NC=CN1 YQSPOXMPYQYCSI-UHFFFAOYSA-N 0.000 description 1
- IWTFOFMTUOBLHG-UHFFFAOYSA-N 2-methoxypyridine Chemical compound COC1=CC=CC=N1 IWTFOFMTUOBLHG-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- VLUWLNIMIAFOSY-UHFFFAOYSA-N 2-methylbenzenesulfinic acid Chemical compound CC1=CC=CC=C1S(O)=O VLUWLNIMIAFOSY-UHFFFAOYSA-N 0.000 description 1
- PKRSYEPBQPFNRB-UHFFFAOYSA-N 2-phenoxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OC1=CC=CC=C1 PKRSYEPBQPFNRB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- CCZFANLSRKSNMX-UHFFFAOYSA-N 3-(2-ethylphenyl)pentan-3-ylboron Chemical compound CCC([B])(CC)C1=CC=CC=C1CC CCZFANLSRKSNMX-UHFFFAOYSA-N 0.000 description 1
- PQXOTHUSZUHPBK-UHFFFAOYSA-N 3-ethylpentan-3-ylboron Chemical compound CCC([B])(CC)CC PQXOTHUSZUHPBK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- DTOMAXGIWFLDMR-UHFFFAOYSA-N 4-[(4-hydroxy-3-nitrophenyl)methyl]-2-nitrophenol Chemical compound C1=C([N+]([O-])=O)C(O)=CC=C1CC1=CC=C(O)C([N+]([O-])=O)=C1 DTOMAXGIWFLDMR-UHFFFAOYSA-N 0.000 description 1
- XAIZOTQTRJYNHC-UHFFFAOYSA-N 4-[2-(3,5-diethyl-4-hydroxyphenyl)propan-2-yl]-2,6-diethylphenol Chemical compound CCC1=C(O)C(CC)=CC(C(C)(C)C=2C=C(CC)C(O)=C(CC)C=2)=C1 XAIZOTQTRJYNHC-UHFFFAOYSA-N 0.000 description 1
- ACWKCNYOCGALDS-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-diphenylphenyl)propan-2-yl]-2,6-diphenylphenol Chemical compound C=1C(C=2C=CC=CC=2)=C(O)C(C=2C=CC=CC=2)=CC=1C(C)(C)C(C=C(C=1O)C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 ACWKCNYOCGALDS-UHFFFAOYSA-N 0.000 description 1
- WCUDAIJOADOKAW-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)pentan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCC)C1=CC=C(O)C=C1 WCUDAIJOADOKAW-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XQABVLBGNWBWIV-UHFFFAOYSA-N 4-methoxypyridine Chemical compound COC1=CC=NC=C1 XQABVLBGNWBWIV-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 101100001674 Emericella variicolor andI gene Proteins 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000011101 absolute filtration Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000005010 aminoquinolines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 description 1
- QCRBMEFNXGBPLL-UHFFFAOYSA-M benzyl(triphenyl)azanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 QCRBMEFNXGBPLL-UHFFFAOYSA-M 0.000 description 1
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- 229910052790 beryllium Inorganic materials 0.000 description 1
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- 238000000071 blow moulding Methods 0.000 description 1
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- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
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- HPGJOUYGWKFYQW-UHFFFAOYSA-N diphenyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HPGJOUYGWKFYQW-UHFFFAOYSA-N 0.000 description 1
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- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
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- 150000004678 hydrides Chemical class 0.000 description 1
- IPJIKGJKMCILGV-UHFFFAOYSA-N imidazo[1,2-a]pyridin-6-ylboronic acid Chemical compound C1=C(B(O)O)C=CC2=NC=CN21 IPJIKGJKMCILGV-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPTPYMHWVGAEGG-UHFFFAOYSA-M methyl(triphenyl)azanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[N+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 KPTPYMHWVGAEGG-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- ODKLEQPZOCJQMT-UHFFFAOYSA-N n,n-diethylpyridin-4-amine Chemical compound CCN(CC)C1=CC=NC=C1 ODKLEQPZOCJQMT-UHFFFAOYSA-N 0.000 description 1
- WLFOHIVICZSIKG-UHFFFAOYSA-N n,n-dimethyl-1h-imidazol-2-amine Chemical compound CN(C)C1=NC=CN1 WLFOHIVICZSIKG-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- ZJKOMXZUJBYOOK-UHFFFAOYSA-M tetraphenylazanium;hydroxide Chemical compound [OH-].C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 ZJKOMXZUJBYOOK-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、芳香族ジヒドロキシ化合物及び炭酸ジエステル化合物の溶融重合によって得られた、透明性及び成形品外観に優れ、特に押出成形したときの成形品の表面外観に優れた品質の芳香族ポリカーボネート及びその製造方法を提供するものである。
【０００２】
【従来の技術】
ポリカーボネートは、耐衝撃性等の機械的特性に優れ、しかも耐熱性、透明性等にも優れており、各種機械部品、自動車部品等の用途に広く用いられている。特に、光ファイバー、レンズ等の光学用途への期待は大きく、種々の研究が盛んになされている。このような光学用途においては、不純物や異物含量の少ないポリカーボネートの出現が特に望まれている。
【０００３】
芳香族ポリカーボネートの製造方法としては、ビスフェノール等の芳香族ジオールとホスゲンとを界面重縮合法において反応させる、いわゆるホスゲン法が工業化されている。しかし、ホスゲン法は人体に有害なホスゲンを用いなければならないこと、環境に対する負荷の高いジクロロメタン等の溶剤を必要をすること、また多量に副生する塩化ナトリウムのポリマー中への混入により、これを電子部品に用いたときの腐食等の問題点が指摘されている。
一方、芳香族ジオール化合物と炭酸ジエステル化合物とを溶融状態でエステル交換し、副生するフェノール等の低分子量物を系外に取り除きながら芳香族ポリカーボネートを得る方法も、いわゆる溶融重合法又はエステル交換法として古くから知られている。溶融重合法は、界面重縮合法による上記のような問題点もなく、ポリカーボネートが製造できるという利点がある一方、ホスゲン法に比べて高温で重合を行うため、製品のポリカーボネート中にヤケ異物やゲル状異物等の異物が発生し易いという問題がある。
このような問題点を解決するために、芳香族ジヒドロキシ化合物及び炭酸ジエステル化合物の溶融重合によって得られる芳香族ポリカーボネートに、添加剤を添加し押出機等で溶融混練した後に、外部のダストや焼け異物を取る目的で、ポリマーフィルターを通過させる方法が提案されている（例えば、特開平５−２３９３３４号公報、特開平６−２３４８４５号公報、特開２０００−１７８３５５号公報、特許第３１０３６５２号公報等参照）。
【０００４】
ところが、本発明者等が検討したところ、ポリマーフィルターを通過させてもなお樹脂中に１０μｍ以上の透明異物がしばしば生成していることが判明した。また、この透明異物については、本質的にポリマー中に内在し、フィルターで濾過しようとしても捕集できないことが判明した。
【０００５】
さらに、もしこの透明異物が多発すると、特にＣＤ−ＲやＤＶＤ等の光学情報記録媒体の成形加工時において外観不良を起こすだけでなく、シート表面の肌荒れや芳香族ポリカーボネートの特徴である寸法安定性等の機能面にも影響してくることが判った。
一方、特開２０００−１５９８８０には、分岐成分を一定量以下に抑えた芳香族ポリカーボネートが提案されており、色相や耐熱性に優れることが示されているが、透明異物の低減という観点からは未だ不十分であった。
【０００６】
【発明が解決しようとする課題】
本発明は、芳香族ジヒドロキシ化合物及び炭酸ジエステル化合物の溶融重合時に生ずる透明異物の発生を少なくし、透明性及び成形外観に優れた芳香族ポリカーボネートを提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明者らは、透明性を低下させ、成形不良を起こし、記録エラーの誘因となる、透明異物の生成及び混入を防止するため、鋭意検討した結果、この透明異物はアルカリ金属化合物等のエステル交換触媒存在下、高温で溶融重合する段階で起こる副反応（架橋化反応）により生成することが判明した。この副反応を抑制しながら、触媒で活性化される主反応（重縮合反応）を進行させるべく、反応条件を特定触媒量、特定温度範囲等に制御することによって、芳香族ポリカーボネートへの透明異物の生成・混入を防止できることを見出し、本発明を完成するに至った。
【０００８】
即ち、本発明の要旨は、芳香族ジヒドロキシ化合物及び炭酸ジエステル化合物の溶融重合による芳香族ポリカーボネートの製造方法において、該溶融重合を芳香族ジヒドロキシ化合物１モルに対して、金属量として０．１μモル以上、０．９μモル以下のアルカリ金属化合物及び／又はアルカリ土類金属化合物の存在下に行い、第１竪型撹拌重合槽底より排出された重合液は、引き続き第２、第３及び第４の竪型撹拌重合槽に、逐次、連続供給され、反応の進行とともに高温、高真空に条件を設定して、ポリマー化工程の最終段階である第４の竪型撹拌重合槽では２００〜３２０℃、３００Ｐａ以下で、重合を行い、かつ、ポリカーボネート中に残存する触媒を中和するために、ポリカーボネートの重量に対して０．０１〜２０ｐｐｍの酸性化合物を添加することによって、１０μｍ以上の透明異物数（Ｎ：単位は個／ｇ）と粘度平均分子量（Ｍｖ）とが、下記（ａ）又は（ｂ）：
Ｍｖ≦２１０００の場合は、Ｎ≦ｅｘｐ（６．５２×１０-4×Ｍｖ−９．０８７） （ａ）
Ｍｖ＞２１０００の場合は、Ｎ≦ｅｘｐ（１．１１５×１０-4×Ｍｖ＋２．１７９） （ｂ）
で表される関係式を満足する芳香族ポリカーボネートを得ることを特徴とする芳香族ポリカーボネートの製造方法にある。
【０００９】
以下、本発明について具体的に説明する。
本発明に係わる芳香族ポリカーボネートを製造する溶融重合の原料として、炭酸ジエステル化合物と芳香族ジヒドロキシ化合物とが用いられる。
炭酸ジエステル化合物
原料の炭酸ジエステル化合物は、下記式（１）で示される。
【００１０】
【化１】
（式中、Ｒ及びＲ’は、炭素数１〜１８の、置換されていてもよい、脂肪族基又は芳香族基であり、ＲとＲ’とは、同一でも異なってもよい。）
【００１２】
式（１）で表される炭酸ジエステル化合物の具体例としては、例えば、ジメチルカーボネート、ジエチルカーボネート、ジ−ｔ−ブチルカーボネート、ジフェニルカーボネート及びジトリルカーボネート等の置換ジフェニルカーボネート等があるが、好ましくはジフェニルカーボネート、置換ジフェニルカーボネート、特にジフェニルカーボネートが好ましい。これらの炭酸ジエステル化合物は、単独でも、２種以上を混合して用いてもよい。
また、製法によって炭酸ジエステル化合物中に不純物として含まれることがある、ハロゲンイオンは、副反応である架橋構造生成反応を抑制しないだけでなく、触媒を被毒して主反応である重縮合反応を阻害するため、炭酸ジエステル化合物中のハロゲンイオンは、重量基準で、好ましくは３０ｐｐｂ以下、さらに好ましくは２０ｐｐｂ以下、中でも１０ｐｐｂ以下が好適である。
【００１３】
また、上記のような炭酸ジエステル化合物と共に、好ましくは５０モル％以下、さらに好ましくは３０モル％以下の量で、ジカルボン酸又はジカルボン酸エステルを使用してもよい。このようなジカルボン酸又はジカルボン酸エステルとしては、テレフタル酸、イソフタル酸、テレフタル酸ジフェニル、イソフタル酸ジフェニル等が用いられる。このようなカルボン酸又はカルボン酸エステルを炭酸ジエステル化合物と併用した場合には、ポリエステルカーボネートが得られる。
【００１４】
芳香族ジヒドロキシ化合物
もう一つの原料である芳香族ジヒドロキシ化合物は、下記式（２）で示される。
【００１５】
【化２】
（式中、Ｂは、１〜１５の炭素数を有する２価の炭化水素基、ハロゲン置換の２価の炭化水素基、−Ｓ−基、−ＳＯ2 −基、−ＳＯ−基、−Ｏ−基又は−ＣＯ−基を示し、Ｘは、ハロゲン原子、炭素数１〜１４のアルキル基、炭素数６〜１８のアリール基、炭素数１〜８のオキシアルキル基又は炭素数６〜１８のオキシアリール基を示す。ｍは、０又は１であり、ｙは、０〜４の整数である。）
【００１７】
式（２）で表される芳香族ジヒドロキシ化合物としては、例えば、２，２−ビス（４−ヒドロキシフェニル）プロパン［＝ビスフェノールＡ］、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジエチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−（３，５−ジフェニル）フェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシフェニル）ペンタン、２，４’−ジヒドロキシ−ジフェニルメタン、ビス（４−ヒドロキシフェニル）メタン、ビス（４−ヒドロキシ−５−ニトロフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、３，３−ビス（４−ヒドロキシフェニル）ペンタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、ビス（４−ヒドロキシフェニル）スルホン、２，４’−ジヒドロキシジフェニルスルホン、ビス（４−ヒドロキシフェニル）スルフィド、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシ−３，３’−ジクロロジフェニルエーテル、４，４’−ジヒドロキシ−２，５−ジエトキシジフェニルエーテル等が例示される。これらの中でも、２，２−ビス（４−ヒドロキシフェニル）プロパンが好ましい。また、これらの芳香族ジヒドロキシ化合物は、単独で又は２種以上を混合して、用いることができる。
【００１８】
炭酸ジエステル化合物と芳香族ジヒドロキシ化合物との混合比率は、所望する芳香族ポリカーボネートの分子量と末端ヒドロキシ基量により決められる。末端ヒドロキシ基量は、製品ポリカーボネートの熱安定性と加水分解安定性に大きな影響を及ぼし、実用的な物性を持たせるためには１０００ｐｐｍ以下にすることが必要となる。従って、芳香族ジヒドロキシ化合物１モルに対して炭酸ジエステル化合物を等モル量以上用いるのが一般的であり、１．０１〜１．３０モル、好ましくは１．０１〜１．２０モル、中でも１．０２〜１．１５の量で用いられるのが望ましい。
【００１９】
エステル交換触媒
溶融重合法により芳香族ポリカーボネートを製造する際には、通常エステル交換触媒が使用される。エステル交換触媒としては、主として、アルカリ金属化合物及び／又はアルカリ土類金属化合物が使用され、補助的に、塩基性ホウ素化合物、塩基性リン化合物、塩基性アンモニウム化合物又はアミン系化合物等の塩基性化合物を併用することも可能である。これらの触媒は、１種類で使用してもよく、２種以上を組み合わせて使用してもよい。
【００２０】
アルカリ金属化合物としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウムの水酸化物、炭酸水素塩、炭酸塩、酢酸塩、リン酸水素塩、フェニルリン酸塩等の無機アルカリ金属化合物や、ステアリン酸、安息香酸等の有機酸類、メタノール、エタノール等のアルコール類，石炭酸、ビスフェノールＡ等のフェノール類との塩等の有機アルカリ金属化合物等が挙げられる。アルカリ土類金属化合物としては、ベリリウム、カルシウム、マグネシウム、ストロンチウム、バリウムの水酸化物、炭酸水素塩、炭酸塩、酢酸塩等の無機アルカリ土類金属化合物や、有機酸類、アルコール類、フェノール類との塩等の有機アルカリ土類金属化合物等が挙げられる。
【００２１】
塩基性ホウ素化合物の具体例としては、テトラメチルホウ素、テトラエチルホウ素、テトラプロピルホウ素、テトラブチルホウ素、トリメチルエチルホウ素、トリメチルベンジルホウ素、トリメチルフェニルホウ素、トリエチルメチルホウ素、トリエチルベンジルホウ素、トリエチルフェニルホウ素、トリブチルベンジルホウ素、トリブチルフェニルホウ素、テトラフェニルホウ素、ベンジルトリフェニルホウ素、メチルトリフェニルホウ素、ブチルトリフェニルホウ素、等の水素化物、ナトリウム塩、カリウム塩、リチウム塩、カルシウム塩、マグネシウム塩、バリウム塩、或いはストロンチウム塩等が挙げられる。
【００２２】
塩基性リン化合物としては、例えば、トリエチルホスフィン、トリ−ｎ−プロピルホスフィン、トリイソプロピルホスフィン、トリ−ｎ−ブチルホスフィン、トリフェニルホスフィン、トリブチルホスフィン、又は四級ホスホニウム塩等が挙げられる。
【００２３】
塩基性アンモニウム化合物としては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルエチルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド、トリメチルフェニルアンモニウムヒドロキシド、トリエチルメチルアンモニウムヒドロキシド、トリエチルベンジルアンモニウムヒドロキシド、トリエチルフェニルアンモニウムヒドロキシド、トリブチルベンジルアンモニウムヒドロキシド、トリブチルフェニルアンモニウムヒドロキシド、テトラフェニルアンモニウムヒドロキシド、ベンジルトリフェニルアンモニウムヒドロキシド、メチルトリフェニルアンモニウムヒドロキシド、ブチルトリフェニルアンモニウムヒドロキシド等が挙げられる。
【００２４】
アミン系化合物としては、例えば、４−アミノピリジン、２−アミノピリジン、Ｎ，Ｎ−ジメチル−４−アミノピリジン、４−ジエチルアミノピリジン、２−ヒドロキシピリジン、２−メトキシピリジン、４−メトキシピリジン、２−ジメチルアミノイミダゾール、２−メトキシイミダゾール、イミダゾール、２−メルカプトイミダゾール、２−メチルイミダゾール、アミノキノリン等が挙げられる。
【００２５】
本発明の芳香族ポリカーボネートを得るためには、芳香族ジヒドロキシ化合物１モルに対して、金属量として０．１μモル以上０．９μモル以下、好ましくは０．２μモル以上０．９μモル以下、さらに好ましくは０．５μモル以上０．８μモル以下のアルカリ金属化合物及び／又はアルカリ土類金属化合物を触媒として使用する。アルカリ金属化合物及び／又はアルカリ土類金属化合物が０．１μモルより少なければ、必要な重合活性が得られず、所定の分子量の芳香族ポリカーボネートを得ようとすると、重合温度を上げたり、重合時間を長くしたりする必要が生じ、かえってポリマーの色調悪化や透明異物増大を招き、０．９μモルより多い場合もポリマーの色調悪化や透明異物増大を招く。
架橋化反応は、触媒量、反応温度、反応時間、ポリマー分子量、反応圧力に依存し、触媒量が多いほど、反応温度が高いほど、反応時間が長いほど、分子量が大きいほど、反応圧力が高いほど進む方向にある。従って、所定の分子量でかつ本発明に規定された透明異物量を有する芳香族ポリカーボネートを得るためには、分子量に応じて最適な触媒量、反応温度、反応時間、反応圧力を選択してやる必要がある。これらのパラメーターは相互に依存しているため、例えば所定分子量のポリマーを得ようとして、触媒量を下げると反応温度を上げたり反応時間を長くしたりする必要があり、反応温度を下げると、触媒量を増やしたり、反応時間を長くしたりする必要があるが、中でも触媒量の架橋構造生成反応への寄与は大きく、アルカリ金属化合物触媒を使用した場合、主反応には一次であるが、副反応（架橋構造生成）には多次で効いてくるため、高分子量ポリカーボネートの生産には、どちらかと言うと温度を上げ、触媒量は下げる手法を採ることが好ましい。
【００２６】
芳香族ポリカーボネート
［透明異物］
本発明の芳香族ポリカーボネートは、芳香族ジヒドロキシ化合物及び炭酸ジエステル化合物の溶融重合によって得られる芳香族ポリカーボネートにおいて、１０μｍ以上の透明異物数（Ｎ：単位は個／ｇ）と粘度平均分子量（Ｍｖ）とが、下記（ａ）又は（ｂ）：
Ｍｖ≦２１０００の場合は、
Ｎ≦ｅｘｐ（６．５２×１０-4×Ｍｖ−９．０８７） （ａ）
Ｍｖ＞２１０００の場合は、
Ｎ≦ｅｘｐ（１．１１５×１０-4×Ｍｖ＋２．１７９） （ｂ）
で表される関係式を満足するものである。
好ましくは、下記（ａ’）又は（ｂ’）：
Ｍｖ≦２１０００の場合は、
Ｎ≦ｅｘｐ（６．５２×１０-4×Ｍｖ−９．７８） （ａ’）
Ｍｖ＞２１０００の場合は、
Ｎ≦ｅｘｐ（９．７９６×１０-5×Ｍｖ＋１．８５５） （ｂ’）
で表される関係式を満足するものであることが好ましい。
【００２７】
本明細書において、「１０μｍ以上の透明異物数」は、次のようにして求める。
芳香族ポリカーボネートから製膜されたフィルム（厚み７０μｍ）につき、実体顕微鏡（倍率２００倍）を用いて、大きさが１０μｍ以上の透明異物の総数を数え、１ｇ当たりの異物数を算出し、「１０μｍ以上の透明異物数」とする。測定に際し、核のない透明異物の平面的境界は、周辺との屈折率が異なることによって定め、その大きさは、該平面的境界上の２点間の最大距離とする。
また、「粘度平均分子量」は、次のようにして求める。
芳香族ポリカーボネートの塩化メチレン中、温度２０℃の極限粘度［η］から、下記の式により「粘度平均分子量（Ｍｖ）」を算出する。
［η］＝１．２３×１０-4Ｍｖ0.83
【００２８】
［架橋構造単位］
溶融重合によって得られる芳香族ポリカーボネートは、その分子鎖上に、熱転移、脱炭酸、脱水縮合等の副反応によって生成した種々の架橋構造単位を有する。代表的なものを挙げれば、▲１▼下式（３）で示されるサリチル酸フェニル構造単位（以下、ＰＳＡ単位と略す）、▲２▼下式（４）で示されるフェノキシ安息香酸構造単位（以下、ＰＢＡ単位と略す）及び▲３▼下式（５）で示されるジフェニルエーテルジカルボン酸構造単位（以下、ＤＣＡ単位と略す）がある。
【００２９】
【化３】
本発明の芳香族ポリカーボネートでは、これら３種の架橋構造単位の総含有量が、ポリマー重量に対し２０００ｐｐｍ以下であることが好ましく、さらには１８００ｐｐｍ以下、特には１５００ｐｐｍ以下が好適である。これら３種の構造単位の総含有量が２０００ｐｐｍより多いと、芳香族ポリカーボネート中の透明異物量が増加するだけでなく色調も悪化する。
これらの架橋構造単位の含有量は、芳香族ポリカーボネートを重クロロホルム等の重水素化溶媒に溶解させて直接ＮＭＲで測定したり、芳香族ポリカーボネートを一旦加水分解し、主鎖のカーボネート結合を切断しモノマー単位にした後、ゲルパーミエーションクロマトグラフィー、液体クロマトグラフィー、ガスクロマトグラフィー等を測定したりすることにより求めることができる。
この様な架橋構造単位の総含有量と前述の１０μ以上の透明異物数（Ｎ：単位個／ｇ）とは、一定の関係を示すことから、透明異物の発生由来は、架橋化ポリマーであることが明解に判った。従って、透明異物を低減しようとすると、架橋化反応を抑制することがまず第一に必要なこととなる。
【００３１】
また、架橋構造単位の含有量は、樹脂の溶融特性（特に非ニュートン性）に直接影響を与えるため、本発明の芳香族ポリカーボネートは、ＪＩＳ Ｋ ７２１０に準拠し、下記式：
ＦＲＲ＝ＭＶＲ（２６０／２１．６）／ＭＶＲ（２６０／２．１６）
（式中、ＭＶＲ（２６０／２１．６）は、２６０℃、荷重２１．６ｋｇで測定したメルトボリュームフローレイト（Ｍｅｌｔ Ｖｏｌｕｍｅ−Ｆｌｏｗ Ｒａｔｅ）を示し、ＭＶＲ（２６０／２．１６）は、２６０℃、荷重２．１６ｋｇで測定したメルトボリュームフローレイトを示す。）
で表されるフローレイト比（ＦＲＲ）が１５以下であることが好ましく、更に好ましくは１４．５以下である。ＦＲＲが１５より大きいと、低剪断速度領域での流動性が低下し、ブロー成形等に向いた材料となるが、一般の射出成形には不向きで、射出による精密成形は困難になることがあるので好ましくない。
【００３２】
［溶融重合］
本発明の芳香族ポリカーボネートは、芳香族ジヒドロキシ化合物及び炭酸ジエステル化合物を原料とし、溶融重合により、二段階以上の多段工程で製造される。一般的には反応温度１４０〜３２０℃、反応時間０．１〜５時間、常圧より減圧度を上げながら、副生するモノフェノール化合物をラインから連続的に除去しながら反応を行う。必要に応じて窒素等の不活性ガスを流通させることもできる。また、モノフェノール化合物に同伴する原料を反応槽に戻すために分留塔を反応器に付設することもできる。オリゴマー化工程の反応温度は通常１００〜３００℃、好ましくは１８０〜２８０℃の範囲で、反応圧力は大気圧〜１３３Ｐａまでの範囲である。一方、ポリマー化工程の最終段階での反応温度は２００〜３２０℃であるが、芳香族ポリカーボネートの分子量、色調、透明異物量等、要求性能により決定され、前述の架橋構造生成反応は高温になるほど旺盛となるので、可能な限り低温で反応終了することが好ましい。
【００３３】
例えば、Ｍｖが２００００より小さい芳香族ポリカーボネートを得るには、最も反応温度が高い段階で、２５０〜３２０℃、好ましくは２６０℃〜３００℃、さらに好ましくは２６０〜２９０℃、特に好ましくは２６０〜２７５℃が好適である。さらに、外部加熱温度も架橋構造生成に影響を及ぼすため、好ましくは３２０℃以下、特に好ましくは３００℃以下、さらに好ましくは２９５℃以下、中でも２９０℃以下が好適である。
一方、Ｍｖ＝２００００以上の芳香族ポリカーボネートを得るには、ポリマー化工程の反応温度を高くする必要があるが、どちらかといえば、オリゴマー化工程の温度を上げ、ポリマー化工程の温度抑制する方向が好ましい。この場合もオリゴマー化工程の温度を上げすぎるとモノマー等の低分子量物の揮散による原料のモルバランスの崩れを招き、最終的に必要な分子量のポリマーが得られなくなるため、反応で生成するフェノールの半分以上が取り除かれる工程（通常は第１オリゴマー化工程）の温度は、１８０〜２５０℃、中でも１９０〜２４０℃、特には２１０〜２３０℃に保つことが好ましい。また、最も反応温度が高い段階は、好ましくは２５０〜３２０℃、より好ましくは２６０℃〜３００℃、さらに好ましくは２６０〜２９０℃であり、外部加熱温度は、好ましくは３２０℃以下、さらに好ましくは３００℃以下、特に好ましくは２９５℃以下である。
【００３４】
また、ポリマー化工程の最終段階での反応圧力も芳香族ポリカーボネートの分子量、色調、透明異物量等、要求性能により決定されるが、本発明の芳香族ポリカーボネートを得るためには３００Ｐａ以下であり、特にＭｖ＝２００００以上の芳香族ポリカーボネートを得るには、透明異物の生成を抑制するため樹脂が高温にさらされる時間を短くする必要があるので、好ましくは１００Ｐａ以下、さらに好ましくは７０Ｐａ以下、特には５０Ｐａ以下が好適である。各段階の反応時間は、反応の進行の程度により適宜定められるが、好ましくはオリゴマー化工程、ポリマー化工程トータルで０．１〜１０時間、中でも１〜６時間が最適であり、特に反応温度の最も高い段階での滞留時間は、透明異物生成に影響が大きいため、好ましくは０．１〜５時間、更に好ましくは０．２〜３時間、中でも０．３〜２時間が好適である。本発明の芳香族ポリカーボネートの分子量に特に制限はないが、実用上の物性を得るためには、通常、粘度平均分子量（Ｍｖ）が、１４０００〜６００００、中でも１５０００〜５００００が好ましく、特に耐衝撃性や機械的強度、成形性の観点からは、１５０００〜４００００、中でも１５０００〜３００００、特には１６０００〜３００００、さらには２００００〜３００００が好適である。
【００３５】
反応の方式は、バッチ式、連続式、又はバッチ式と連続式の組合せのいずれでもよい。使用する装置は、各種の撹拌翼を具備した竪型重合槽を使用する。反応は、実質的に無酸素下で行われることが好ましく、例えば、運転開始前に原料調整槽、反応器及び配管内を窒素ガス等の不活性ガスで置換しておく。通常、芳香族ジヒドロキシ化合物と炭酸ジエステル化合物との溶融混合物を、竪型反応器に供給する。触媒は、原料とは別のラインで第１反応槽に直接供給してもよいし、第１反応槽に入る手前の配管内で、スタティックミキサー等により原料と混合した状態で供給させてもよい。必要に応じて、触媒を溶解又は懸濁するための溶媒が用いられる。好ましい溶媒としては、水、アセトン、フェノール等が挙げられる。
【００３６】
重合液供給口は、反応槽側壁液相部にあり、抜き出し口は、反応槽底部にあるのが好ましい。また、各槽から反応液を連続して抜き出す方法は、落差を利用する方法、圧力差を利用する方法、ギアポンプ等の送液ポンプを用いる方法等、反応液の物性に適応した方法で行うのが好ましい。特に滞留部のある構造は最悪なので、極力回避できる構造とする。
【００３７】
添加剤
本発明に使用される添加剤として、溶融重合による芳香族ポリカーボネートの製造にアルカリ金属化合物等のエステル交換触媒を用いた場合には、ポリカーボネート中に残存する触媒を中和するために、酸性化合物、特にイオウ含有酸性化合物を、触媒金属１原子に対して０．５〜１０当量、好ましくは１〜５当量を添加することができる。すなわち、ポリカーボネートの重量に対して０．０１〜２０ｐｐｍ、好ましくは０．１〜１０ｐｐｍ、さらに好ましくは３〜７ｐｐｍ添加する。
【００３８】
イオウ含有酸性化合物の例としては、スルホン酸、スルフィン酸又はそれらのエステル誘導体であり、具体的には、ｐ−トルエンスルホン酸、ベンゼンスルホン酸及びドデシルベンゼンスルホン酸、それらのメチル、エチル、ブチル、ｔ−ブチル、オクチル、ドデシル、フェニル、ベンジル、フェネチル等のエステル類、ベンゼンスルフィン酸、トルエンスルフィン酸、ナフタレンスルホン酸等が挙げられる。これらの化合物の内、ｐ−トルエンスルホン酸のエステル又はベンゼンスルホン酸のエステルが好ましく、これらの化合物を２種以上使用してもよい。さらに、これらの化合物のアルカリ金属塩を、これらの化合物と併用すると、分散性が向上し失活効果が高まるので好ましい。併用する量としては、非アルカリ金属塩に対してアルカリ金属塩を、重量比で０．３〜３倍程度の量用いることが好ましい。
【００３９】
イオウ含有酸性化合物のポリカーボネートへの添加方法は、任意の方法により行うことができる。例えば、イオウ含有酸性化合物を、直接又は希釈剤で希釈して、溶融又は固体状態にあるポリカーボネートに添加し、分散させることができる。具体的には、重縮合反応器中、反応器からの移送ライン中、押出機中に供給して混合することができ、通常は押出機中に供給される。また、ミキサー等で、ポリカーボネートや、他種ポリマーのペレット、フレーク、粉末等と混合後、押出機に供給して混練することもできる。これらのうちポリカーボネートのフレークに、イオウ含有酸性化合物の原液を添加し、ミキサー等で混合後、マスターバッチとして添加することが好ましい。さらに、添加の際には、重量フィーダー等を用いて、添加量を精度良く制御することが好ましい。
【００４０】
また押出機で、ベントによる減圧処理を行う場合、又は水添加、熱安定剤、離型剤、染料、顔料、紫外線吸収剤、帯電防止剤、防曇剤、有機・無機充填剤等を添加する場合は、これらの添加及び処理は、酸性化合物と同時に行ってもよいが、酸性化合物を最初に添加、混練することが好ましい。
【００４１】
【実施例】
以下、本発明を実施例及び比較例を挙げて更に詳細に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。なお、以下の諸例で使用した原料及び得られた芳香族ポリカーボネートの分析は、下記の測定方法により行った。
【００４２】
（１）ジフェニルカーボネート中の塩素イオン含有量
ジフェニルカーボネート（ＤＰＣ）約５ｇを精秤してトルエン１０ｍＬに加え、６０℃で溶解後、超純水（塩素イオンを含有しないイオン交換水）１０ｍＬを添加し、２３℃の恒温室でマグネチックスターラーを用い１０００ｒｐｍで１０分間攪拌した後、水相を分離、水相中の塩素イオンをイオンクロマトグラフィーで定量した。分析結果はＤＰＣの重量に対する塩素イオンの重量を、ｐｐｂ単位で表した。
（２）粘度平均分子量（Ｍｖ）
ポリカーボネートを濃度（Ｃ）０．６ｇ／ｄｌ塩化メチレン溶液とし、ウベローデ粘度計を用いて、温度２０℃で測定した比粘度（ηｓｐ）から、下記の両式
ηｓｐ／Ｃ＝［η］（１＋０．２８ηｓｐ）
［η］＝１．２３×１０-4Ｍｖ0.83
を用いて算出した。
（３）フローレイト比（ＦＲＲ）
タカラ工業（株）製メルトインデクサーを用いて、芳香族ポリカーボネートの２６０℃、荷重２１．６ｋｇで測定した単位時間当たりの溶融流動体積ＭＶＲ（２６０／２１．６）と、２６０℃、荷重２．１６ｋｇで測定した単位時間当たりの溶融流動体積ＭＶＲ（２６０／２．１６）とを用い、下式で求めた。
ＦＲＲ＝ＭＶＲ（２６０／２１．６）／ＭＶＲ（２６０／２．１６）
【００４３】
（４）架橋構造単位
▲１▼ 加水分解処理：
芳香族ポリカーボネート１ｇを、塩化メチレン１００ｍｌに溶解した後、２８％ナトリウムメトキシドメタノール溶液１８ｍｌ、メタノール８０ｍｌを加え、さらに純水２５ｍｌを添加した後、室温で１時間攪拌して完全に加水分解した。その後、１規定塩酸を加え、塩化メチレン層を分離して、加水分解物を得た。
▲２▼ 液相クロマトグラフィー：
▲１▼で得られた加水分解物１ｇをアセトニトリル１０ｍｌに溶解し、逆相液体クロマトグラフィーにより測定した。逆相液体クロマトグラフィーは、溶離液としてアセトニトリルと１０ｍＭ酢酸アンモニウム水溶液とからなる混合溶媒を用い、アセトニトリル／１０ｍＭ酢酸アンモニウム水溶液比率を２０／８０からスタートし８０／２０までグラジュエントする条件下、カラム温度４０℃で測定を行い、検出は波長２８０ｎｍのＵＶ検出器（（株）島津製作所製、ＳＰＤ−６Ａ）を用い、定量はＢＰＡの検量線から各ピーク面積をＢＰＡ換算の重量に変換し加水分解前のポリマー重量に対する重量として求めた。
なお、ピークの同定は、Ａｇｉｌｅｎｔ（株）製ＬＣ−ＭＳ（Ａｇｉｌｅｎｔ−１１００）及び日本電子製ＮＭＲ（ＡＬ−４００）を用いて行った。
【００４４】
（５）１０μｍ以上の透明異物数（Ｎ：単位は個／ｇ）
芳香族ポリカーボネートを、窒素雰囲気下、１２０℃で６時間以上乾燥した後、（株）いすず化工製単軸３０ｍｍ押出機を用いて、厚み７０μｍのフィルムを製膜し、９ｃｍ×５０ｃｍ範囲（約４ｇ）のシート５枚を切り出し、実体顕微鏡を用いて、各シートの核のない透明異物（＝フィッシュアイ）をマーキングし、倍率２００倍で大きさと数を測定した。測定に際し、核のない透明異物の平面的境界は、周辺との屈折率が異なることによって定め、その大きさは、該平面的境界線上の２点間の最大距離とした。大きさが１０μｍ以上の透明異物の総数を数え、１ｇ当たりの異物数を算出し、「１０μｍ以上の透明異物数」とした。
（６）フィルム外観検査
上記（５）で得られたフィルムを目視で観察した。
【００４５】
（７）プレート色調
製造した芳香族ポリカーボネートを用いて６０×６０×３．２ｍｍの平板をバレル温度３６０℃、金型温度８０℃で射出成形した際の色調をミノルタ（株）製分光測色計ＣＭ−３７００ｄを用い測定し、イエローインデックス（ＹＩ）で評価した。値の小さい方が色調が良好であることを示す。
（８）熱滞留時プレート色調
製造した芳香族ポリカーボネートを用いて６０×６０×３．２ｍｍの平板をバレル温度３６０℃、金型温度８０℃、成形間隔１８０秒で、１０ショット連続射出成形した際の色調をミノルタ（株）製分光測色計ＣＭ−３７００ｄを用い測定し、１０ショット中の最大ＹＩ値で評価した。値の小さい方が熱滞留時の色調が良好であることを示す。
（９）熱滞留時色調悪化度
上記プレート色調と熱滞留時プレート色調の差（△ＹＩ）で評価した。値の小さい方が熱滞留時の安定性が良いことを示す。
【００４６】
実施例１１
窒素ガス雰囲気下、ビスフェノールＡとジフェニルカーボネートとを、一定のモル比（ＤＰＣ／ＢＰＡ＝１．０８０）で混合し、１４０℃に加熱して、溶融混合物を得た。これを、１４０℃に加熱した原料導入管を介して、窒素雰囲気下、２２０℃、１３３３２Ｐａに制御した第１竪型撹拌重合槽内に連続供給した。平均滞留時間が６０分になるように、槽底部のポリマー排出ラインに設けられたバルブ開度を制御しつつ、液面レベルを一定に保った。また、上記原料混合物の供給を開始すると同時に、触媒として炭酸セシウム水溶液を、ビスフェノールＡ１モルに対し、０．３５μモル（金属量として０．７０μモル）の割合で連続供給した。
【００４７】
槽底より排出された重合液は、引き続き第２、第３及びポリマー化工程の最終段階である第４の竪型撹拌重合槽に、逐次、連続供給された。反応の間、各槽の平均滞留時間が、それぞれ、６０分、６０分、１５０分になるように、液面レベルを制御し、また同時に副生するフェノールの留去も行った。第２〜４重合槽の重合条件は、それぞれ、第２重合槽（２６０℃、２０００Ｐａ）、第３重合槽（２７０℃、１３３Ｐａ）、第４重合槽（２８４℃、４０Ｐａ）で、反応の進行とともに高温、高真空、低撹拌速度に条件を設定した。ポリカーボネートの製造速度は、５０ｋｇ／Ｈｒである。こうして得られたポリカーボネートの粘度平均分子量は、２１０００であった。
【００４８】
次に、溶融状態のままで、このポリマーをギヤポンプにて２軸押出機（Ｌ／Ｄ＝４２、バレル温度２４０℃）に導入し、ｐ−トルエンスルホン酸ブチルを７ｐｐｍ添加した後、リーフディスク型ポリマーフィルターを通してペレット化した。このポリマーフィルターは、絶対濾過精度１０μｍの織金網製のリーフディスク１３５枚をセンターポストに装着したもので、ポリマー融液通液前に、流速５ｍｌ／ｍｉｎ、３６時間、窒素雰囲気下で２８０℃に昇温して、使用した。得られたペレットを用いてフィルムおよびプレートを成形し、フィルムの透明異物量と外観検査、およびプレートの色調評価の結果を表−２に示した。
【００５１】
実施例１２〜２０
ビスフェノールＡとジフェニルカーボネートとを、表−２のモル比で混合し、各重合槽の温度、圧力、滞留時間、触媒濃度を表−２の条件で行った以外は、実施例１１と同様な操作を行った。その結果を表−２に示した。
【００５２】
比較例４〜７
ビスフェノールＡとジフェニルカーボネートとを、表−２のモル比で混合し、各重合槽に於ける温度、圧力、滞留時間、触媒濃度を表−２のような条件とした以外は、実施例１１と同様な操作を行った。その結果を表−２に示した。
【００５４】
【表２】
【発明の効果】
本発明によれば、製品中への透明異物の混入を防止し、透明性と成形外観に優れたエステル交換法芳香族ポリカーボネートが得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aromatic polycarbonate obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound, excellent in transparency and appearance of a molded product, particularly excellent in surface appearance of the molded product when extruded. A manufacturing method is provided.
[0002]
[Prior art]
Polycarbonate is excellent in mechanical properties such as impact resistance, heat resistance, transparency and the like, and is widely used for various machine parts, automobile parts and the like. In particular, there are great expectations for optical applications such as optical fibers and lenses, and various studies have been actively conducted. In such optical applications, the appearance of polycarbonate with a low content of impurities and foreign matters is particularly desired.
[0003]
As a method for producing an aromatic polycarbonate, a so-called phosgene method in which an aromatic diol such as bisphenol and phosgene are reacted in an interfacial polycondensation method has been industrialized. However, the phosgene method requires the use of phosgene, which is harmful to the human body, requires a solvent such as dichloromethane, which has a high environmental impact, and mixes a large amount of by-product sodium chloride into the polymer. Problems such as corrosion when used in electronic parts have been pointed out.
On the other hand, an aromatic diol compound and a carbonic acid diester compound are transesterified in a molten state, and a method of obtaining an aromatic polycarbonate while removing low molecular weight substances such as phenol as a by-product from the system is also known as a melt polymerization method or a transesterification method. It has long been known as The melt polymerization method has the above-mentioned problems by the interfacial polycondensation method and has the advantage that polycarbonate can be produced. On the other hand, the polymerization is performed at a higher temperature than the phosgene method. There is a problem that foreign matter such as a shaped foreign matter is likely to be generated.
In order to solve such problems, after adding an additive to an aromatic polycarbonate obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound and melt-kneading with an extruder or the like, external dust or burnt foreign matter For the purpose of removing the polymer filter, methods for passing the polymer filter have been proposed (see, for example, JP-A-5-239334, JP-A-6-234845, JP-A 2000-178355, JP-A 3103652). ).
[0004]
However, as a result of studies by the present inventors, it has been found that transparent foreign matters of 10 μm or more are often generated in the resin even when the polymer filter is passed. Further, it has been found that this transparent foreign substance is inherently present in the polymer and cannot be collected even if it is filtered by a filter.
[0005]
In addition, if this transparent foreign matter occurs frequently, it not only causes poor appearance especially when molding optical information recording media such as CD-Rs and DVDs, but also the surface roughness of the sheet and the dimensional stability characteristic of aromatic polycarbonate. It was found that it also affects the functional aspects such as.
On the other hand, JP-A-2000-159880 proposes an aromatic polycarbonate in which the branching component is suppressed to a certain amount or less, and is shown to be excellent in hue and heat resistance, but from the viewpoint of reducing transparent foreign matter. It was still insufficient.
[0006]
[Problems to be solved by the invention]
It is an object of the present invention to provide an aromatic polycarbonate which is less likely to produce transparent foreign matters during melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound, and has excellent transparency and molded appearance.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have made extensive studies to prevent the generation and mixing of transparent foreign substances that reduce transparency, cause molding defects, and cause recording errors. As a result, the transparent foreign substances are esters such as alkali metal compounds. It was found to be produced by a side reaction (crosslinking reaction) that occurs at the stage of melt polymerization at a high temperature in the presence of an exchange catalyst. In order to advance the main reaction (polycondensation reaction) activated by the catalyst while suppressing this side reaction, by controlling the reaction conditions to a specific catalyst amount, a specific temperature range, etc., transparent foreign matter to the aromatic polycarbonate As a result, the present invention has been completed.
[0008]
That is, the gist of the present invention is the melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound.In the method for producing an aromatic polycarbonate by the method, the melt polymerization is performed.In the presence of an alkali metal compound and / or an alkaline earth metal compound having a metal content of 0.1 μmol or more and 0.9 μmol or less with respect to 1 mol of the aromatic dihydroxy compound.ConductThe polymerization liquid discharged from the bottom of the first vertical stirring polymerization tank is continuously continuously supplied to the second, third and fourth vertical stirring polymerization tanks, and the conditions are maintained at high temperature and high vacuum as the reaction proceeds. In the fourth vertical stirring polymerization tank which is the final stage of the polymerization step, polymerization is performed at 200 to 320 ° C. and 300 Pa or less, and the catalyst remaining in the polycarbonate is neutralized. By adding 0.01-20 ppm acidic compound to the weight of the polycarbonate.1The number of transparent foreign matters of 0 μm or more (N: unit / g) and viscosity average molecular weight (Mv) are the following (a) or (b):
In the case of Mv ≦ 21000, N ≦ exp (6.52 × 10-Four× Mv-9.087) (a)
In the case of Mv> 21000, N ≦ exp (1.115 × 10-Four× Mv + 2.179) (b)
Satisfies the relational expressionGet aromatic polycarbonateAromatic polycarbonate characterized byToIn the manufacturing method.
[0009]
Hereinafter, the present invention will be specifically described.
A carbonic acid diester compound and an aromatic dihydroxy compound are used as raw materials for melt polymerization for producing the aromatic polycarbonate according to the present invention.
Carbonic acid diester compound
The starting carbonic acid diester compound is represented by the following formula (1).
[0010]
[Chemical 1]
(In the formula, R and R ′ are each an aliphatic group or an aromatic group having 1 to 18 carbon atoms, which may be substituted, and R and R ′ may be the same or different.)
[0012]
Specific examples of the carbonic acid diester compound represented by the formula (1) include substituted diphenyl carbonates such as dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. Diphenyl carbonate and substituted diphenyl carbonate, particularly diphenyl carbonate are preferred. These carbonic acid diester compounds may be used alone or in admixture of two or more.
In addition, halogen ions, which may be included as impurities in the carbonic acid diester compound depending on the production method, not only inhibit the side-reaction cross-linking structure formation reaction, but also poison the catalyst to cause the main reaction polycondensation reaction. In order to inhibit, the halogen ion in the carbonic acid diester compound is preferably not more than 30 ppb, more preferably not more than 20 ppb, and most preferably not more than 10 ppb on a weight basis.
[0013]
Moreover, you may use dicarboxylic acid or dicarboxylic acid ester with the above carbonic acid diester compounds in the quantity of preferably 50 mol% or less, more preferably 30 mol% or less. Examples of such dicarboxylic acid or dicarboxylic acid ester include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate. When such a carboxylic acid or carboxylic acid ester is used in combination with a carbonic acid diester compound, polyester carbonate is obtained.
[0014]
Aromatic dihydroxy compounds
Another raw material, an aromatic dihydroxy compound, is represented by the following formula (2).
[0015]
[Chemical formula 2]
(In the formula, B is a divalent hydrocarbon group having 1 to 15 carbon atoms, a halogen-substituted divalent hydrocarbon group, an —S— group, —SO;2 -Group, -SO- group, -O- group or -CO- group, wherein X is a halogen atom, an alkyl group having 1 to 14 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. An oxyalkyl group or an oxyaryl group having 6 to 18 carbon atoms is shown. m is 0 or 1, and y is an integer of 0-4. )
[0017]
Examples of the aromatic dihydroxy compound represented by the formula (2) include 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A], 2,2-bis (4-hydroxy-3,5-dimethyl). Phenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy- 5-nitrophenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pen 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, 4,4′-dihydroxydiphenyl ether, Examples include 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether, 4,4′-dihydroxy-2,5-diethoxydiphenyl ether, and the like. Among these, 2,2-bis (4-hydroxyphenyl) propane is preferable. Moreover, these aromatic dihydroxy compounds can be used individually or in mixture of 2 or more types.
[0018]
The mixing ratio of the carbonic acid diester compound and the aromatic dihydroxy compound is determined by the molecular weight and the terminal hydroxy group amount of the desired aromatic polycarbonate. The amount of terminal hydroxy groups has a great influence on the thermal stability and hydrolysis stability of the product polycarbonate, and is required to be 1000 ppm or less in order to have practical physical properties. Therefore, it is common to use an equimolar amount or more of a carbonic acid diester compound with respect to 1 mol of the aromatic dihydroxy compound, and 1.01 to 1.30 mol, preferably 1.01 to 1.20 mol, especially 1. It is desirable to be used in an amount of 02 to 1.15.
[0019]
Transesterification catalyst
When producing an aromatic polycarbonate by a melt polymerization method, a transesterification catalyst is usually used. As the transesterification catalyst, alkali metal compounds and / or alkaline earth metal compounds are mainly used, and basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, or amine compounds are supplementarily used. It is also possible to use together. These catalysts may be used alone or in combination of two or more.
[0020]
Examples of the alkali metal compound include lithium, sodium, potassium, rubidium, cesium hydroxide, hydrogen carbonate, carbonate, acetate, hydrogen phosphate, and phenyl phosphate, stearic acid, Examples include organic acids such as benzoic acid, alcohols such as methanol and ethanol, organic alkali metal compounds such as salts with phenols such as carboxylic acid and bisphenol A, and the like. Examples of alkaline earth metal compounds include beryllium, calcium, magnesium, strontium, barium hydroxide, inorganic alkaline earth metal compounds such as hydrogen carbonate, carbonate, acetate, organic acids, alcohols, and phenols. And organic alkaline earth metal compounds such as salts thereof.
[0021]
Specific examples of basic boron compounds include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributyl. Hydride such as benzyl boron, tributyl phenyl boron, tetraphenyl boron, benzyl triphenyl boron, methyl triphenyl boron, butyl triphenyl boron, sodium salt, potassium salt, lithium salt, calcium salt, magnesium salt, barium salt, or Examples include strontium salts.
[0022]
Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salt, and the like.
[0023]
Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide Sid, butyl triphenyl ammonium hydroxide, and the like.
[0024]
Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.
[0025]
In order to obtain the aromatic polycarbonate of the present invention, the metal amount is 0.1 μmol or more and 0.9 μmol or less, preferably 0.2 μmol or more and 0.9 μmol or less, with respect to 1 mol of the aromatic dihydroxy compound. Preferably, an alkali metal compound and / or an alkaline earth metal compound of 0.5 μmol or more and 0.8 μmol or less is used as a catalyst. If the amount of the alkali metal compound and / or alkaline earth metal compound is less than 0.1 μmol, the required polymerization activity cannot be obtained, and when trying to obtain an aromatic polycarbonate having a predetermined molecular weight, the polymerization temperature is increased or the polymerization time is increased. The color tone of the polymer is deteriorated and the transparent foreign matter is increased, and if it is more than 0.9 μmol, the color tone of the polymer is deteriorated and the transparent foreign matter is increased.
The cross-linking reaction depends on the amount of catalyst, reaction temperature, reaction time, polymer molecular weight, and reaction pressure. The higher the amount of catalyst, the higher the reaction temperature, the longer the reaction time, the higher the molecular weight, the higher the reaction pressure. It is in the direction of progress. Therefore, in order to obtain an aromatic polycarbonate having a predetermined molecular weight and the amount of transparent foreign matter specified in the present invention, it is necessary to select an optimum catalyst amount, reaction temperature, reaction time, and reaction pressure according to the molecular weight. . Since these parameters are dependent on each other, for example, in order to obtain a polymer having a predetermined molecular weight, it is necessary to increase the reaction temperature or increase the reaction time if the catalyst amount is decreased. Although it is necessary to increase the amount or to increase the reaction time, the contribution of the catalytic amount to the cross-linked structure formation reaction is large, and when an alkali metal compound catalyst is used, the main reaction is primary, Since the reaction (crosslinking structure formation) is effective in multiple orders, it is preferable to take a method of raising the temperature and lowering the amount of catalyst to produce high molecular weight polycarbonate.
[0026]
Aromatic polycarbonate
[Transparent foreign matter]
The aromatic polycarbonate of the present invention is an aromatic polycarbonate obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester compound. The number of transparent foreign matters (N: units / g) of 10 μm or more, viscosity average molecular weight (Mv), Is the following (a) or (b):
When Mv ≦ 21000,
N ≦ exp (6.52 × 10-Four× Mv-9.087) (a)
If Mv> 21000,
N ≦ exp (1.115 × 10-Four× Mv + 2.179) (b)
Is satisfied.
Preferably, the following (a ′) or (b ′):
When Mv ≦ 21000,
N ≦ exp (6.52 × 10-Four× Mv-9.78) (a ')
If Mv> 21000,
N ≦ exp (9.796 × 10-Five× Mv + 1.855) (b ')
It is preferable that the relational expression represented by
[0027]
In this specification, “the number of transparent foreign matters of 10 μm or more” is obtained as follows.
For a film (thickness 70 μm) formed from an aromatic polycarbonate, the total number of transparent foreign matters having a size of 10 μm or more was counted using a stereomicroscope (magnification 200 times), and the number of foreign matters per 1 g was calculated. The number of transparent foreign matters above. In the measurement, the planar boundary of a transparent foreign substance without a nucleus is determined by a difference in refractive index from the periphery, and the size thereof is the maximum distance between two points on the planar boundary.
The “viscosity average molecular weight” is determined as follows.
From the intrinsic viscosity [η] at a temperature of 20 ° C. in methylene chloride of an aromatic polycarbonate, “viscosity average molecular weight (Mv)” is calculated by the following formula.
[Η] = 1.23 × 10-FourMv0.83
[0028]
[Crosslinked structural unit]
The aromatic polycarbonate obtained by melt polymerization has various cross-linking structural units generated by side reactions such as heat transfer, decarboxylation, and dehydration condensation on the molecular chain. Typical examples are (1) phenyl salicylate structural unit represented by the following formula (3) (hereinafter abbreviated as PSA unit), and (2) phenoxybenzoic acid structural unit represented by the following formula (4) (hereinafter referred to as “PSA unit”). And a diphenyl ether dicarboxylic acid structural unit (hereinafter abbreviated as DCA unit) represented by the following formula (5).
[0029]
[Chemical Formula 3]
In the aromatic polycarbonate of the present invention, the total content of these three kinds of crosslinked structural units is preferably 2000 ppm or less, more preferably 1800 ppm or less, particularly 1500 ppm or less, based on the polymer weight. When the total content of these three kinds of structural units is more than 2000 ppm, not only the amount of transparent foreign matter in the aromatic polycarbonate increases but also the color tone deteriorates.
The content of these crosslinked structural units can be measured directly by NMR by dissolving an aromatic polycarbonate in a deuterated solvent such as deuterated chloroform, or once the aromatic polycarbonate is hydrolyzed to cleave the carbonate bond in the main chain. After the monomer unit, it can be determined by measuring gel permeation chromatography, liquid chromatography, gas chromatography or the like.
Since the total content of such cross-linked structural units and the number of transparent foreign matters of 10 μm or more (N: units / g) show a certain relationship, the generation of transparent foreign matters originates from a crosslinked polymer. I understand it clearly. Therefore, in order to reduce the transparent foreign matter, first of all, it is necessary to suppress the crosslinking reaction.
[0031]
In addition, since the content of the crosslinked structural unit directly affects the melting characteristics (particularly non-Newtonian properties) of the resin, the aromatic polycarbonate of the present invention conforms to JIS K 7210 and has the following formula:
FRR = MVR (260 / 21.6) / MVR (260 / 2.16)
(In the formula, MVR (260 / 21.6) indicates a melt volume flow rate measured at 260 ° C. and a load of 21.6 kg, and MVR (260 / 2.16) indicates 260 ° C. The melt volume flow rate measured at a load of 2.16 kg is shown.)
It is preferable that the flow rate ratio (FRR) represented by these is 15 or less, More preferably, it is 14.5 or less. When the FRR is greater than 15, the fluidity in the low shear rate region is lowered, and the material is suitable for blow molding, etc., but is not suitable for general injection molding, and precision molding by injection may be difficult. Therefore, it is not preferable.
[0032]
[Melt polymerization]
The aromatic polycarbonate of the present invention is produced in a multistage process of two or more stages by melt polymerization using an aromatic dihydroxy compound and a carbonic acid diester compound as raw materials. In general, the reaction is carried out while continuously removing the monophenol compound produced as a by-product from the line while raising the degree of pressure reduction from normal pressure at a reaction temperature of 140 to 320 ° C. and a reaction time of 0.1 to 5 hours. An inert gas such as nitrogen can be circulated as necessary. Further, a fractionation tower can be attached to the reactor in order to return the raw material accompanying the monophenol compound to the reaction tank. The reaction temperature in the oligomerization step is usually in the range of 100 to 300 ° C., preferably 180 to 280 ° C., and the reaction pressure is in the range of atmospheric pressure to 133 Pa. On the other hand, the reaction temperature at the final stage of the polymerization process is200-320 ° C,It is determined by the required performance such as the molecular weight, color tone, and amount of transparent foreign matter of aromatic polycarbonate.,in frontSince the above-mentioned crosslinked structure formation reaction becomes more vigorous as the temperature becomes higher, the reaction is preferably completed at the lowest possible temperature.
[0033]
For example, in order to obtain an aromatic polycarbonate having an Mv of less than 20000, the reaction temperature is highest at 250 to 320 ° C, preferably 260 ° C to 300 ° C, more preferably 260 to 290 ° C, and particularly preferably 260 to 275. ° C is preferred. Furthermore, since the external heating temperature also affects the formation of a crosslinked structure, it is preferably 320 ° C. or less, particularly preferably 300 ° C. or less, more preferably 295 ° C. or less, and particularly preferably 290 ° C. or less.
On the other hand, in order to obtain an aromatic polycarbonate having Mv = 20000 or more, it is necessary to increase the reaction temperature in the polymerization step, but if anything, the temperature in the oligomerization step is increased to suppress the temperature in the polymerization step. Is preferred. In this case as well, if the temperature of the oligomerization step is raised too much, the molar balance of the raw material will be lost due to volatilization of low molecular weight substances such as monomers, and eventually the polymer with the required molecular weight will not be obtained. The temperature of the step in which more than half is removed (usually the first oligomerization step) is preferably maintained at 180 to 250 ° C, particularly 190 to 240 ° C, particularly 210 to 230 ° C. The stage with the highest reaction temperature is preferably 250 to 320 ° C, more preferably 260 ° C to 300 ° C, still more preferably 260 to 290 ° C, and the external heating temperature is preferably 320 ° C or less, more preferably 300 ° C. or lower, particularly preferably 295 ° C. or lower.
[0034]
The reaction pressure at the final stage of the polymerization step is also determined by the required performance such as the molecular weight, color tone, and amount of transparent foreign matter of the aromatic polycarbonate, but is 300 Pa or less to obtain the aromatic polycarbonate of the present invention.RIn particular, in order to obtain an aromatic polycarbonate having Mv = 20000 or more, it is necessary to shorten the time during which the resin is exposed to a high temperature in order to suppress the formation of transparent foreign matters. Therefore, it is preferably 100 Pa or less, more preferably 70 Pa or less, particularly Is preferably 50 Pa or less. The reaction time of each stage is appropriately determined depending on the degree of progress of the reaction, but preferably 0.1 to 10 hours in total in the oligomerization step and the polymerization step, and most preferably 1 to 6 hours. Since the residence time at the highest stage has a great influence on the generation of transparent foreign matter, it is preferably 0.1 to 5 hours, more preferably 0.2 to 3 hours, and particularly preferably 0.3 to 2 hours. The molecular weight of the aromatic polycarbonate of the present invention is not particularly limited, but in order to obtain practical physical properties, the viscosity average molecular weight (Mv) is usually 14,000 to 60,000, preferably 15,000 to 50,000, particularly impact resistance. From the viewpoint of mechanical strength and moldability, 15000 to 40000, 15000 to 30000, particularly 16000 to 30000, more preferably 20000 to 30000 are preferable.
[0035]
The reaction method may be any of a batch method, a continuous method, and a combination of a batch method and a continuous method. The equipment used is,eachVertical polymerization with various stirring bladesTankuseDo. The reaction is preferably carried out substantially in the absence of oxygen. For example, the inside of the raw material adjusting tank, the reactor and the piping is replaced with an inert gas such as nitrogen gas before the start of operation. Usually, a molten mixture of an aromatic dihydroxy compound and a carbonic acid diester compound is fed to a vertical reactor. The catalyst may be directly supplied to the first reaction tank through a line different from the raw material, or may be supplied in a state of being mixed with the raw material by a static mixer or the like in the pipe before entering the first reaction tank. . If necessary, a solvent for dissolving or suspending the catalyst is used. Preferable solvents include water, acetone, phenol and the like.
[0036]
It is preferable that the polymerization solution supply port is in the reaction vessel side wall liquid phase portion and the extraction port is in the reaction vessel bottom portion. In addition, the method of continuously extracting the reaction liquid from each tank is performed by a method suitable for the physical properties of the reaction liquid, such as a method using a drop, a method using a pressure difference, a method using a liquid feed pump such as a gear pump. Is preferred. In particular, the structure with the staying portion is the worst, so the structure should be avoided as much as possible.
[0037]
Additive
As an additive used in the present invention, when an ester exchange catalyst such as an alkali metal compound is used in the production of an aromatic polycarbonate by melt polymerization, an acidic compound, in order to neutralize the catalyst remaining in the polycarbonate, In particular, the sulfur-containing acidic compound can be added in an amount of 0.5 to 10 equivalents, preferably 1 to 5 equivalents, per 1 atom of the catalyst metal. That is, relative to the weight of the polycarbonate0. 01 to 20 ppm, preferably 0.1 to 10 ppm, more preferably 3 to 7 ppm is added.
[0038]
Examples of sulfur-containing acidic compounds are sulfonic acid, sulfinic acid or their ester derivatives, specifically p-toluenesulfonic acid, benzenesulfonic acid and dodecylbenzenesulfonic acid, their methyl, ethyl, butyl, Examples thereof include esters such as t-butyl, octyl, dodecyl, phenyl, benzyl and phenethyl, benzenesulfinic acid, toluenesulfinic acid, naphthalenesulfonic acid and the like. Of these compounds, esters of p-toluenesulfonic acid or esters of benzenesulfonic acid are preferred, and two or more of these compounds may be used. Furthermore, it is preferable to use alkali metal salts of these compounds in combination with these compounds because the dispersibility is improved and the deactivation effect is enhanced. As an amount to be used in combination, it is preferable to use an alkali metal salt in an amount of about 0.3 to 3 times by weight with respect to the non-alkali metal salt.
[0039]
The sulfur-containing acidic compound can be added to the polycarbonate by any method. For example, sulfur-containing acidic compounds can be added or dispersed directly or diluted with a diluent and added to a molten or solid polycarbonate. Specifically, in the polycondensation reactor, in the transfer line from the reactor, it can be fed into the extruder and mixed, and is usually fed into the extruder. Further, after mixing with polycarbonate, other polymer pellets, flakes, powders or the like with a mixer or the like, the mixture can be supplied to an extruder and kneaded. Of these, it is preferable to add a stock solution of a sulfur-containing acidic compound to polycarbonate flakes, mix with a mixer or the like, and then add as a master batch. Furthermore, when adding, it is preferable to control the addition amount with high accuracy using a weight feeder or the like.
[0040]
In addition, when decompressing by venting with an extruder, or adding water, heat stabilizer, mold release agent, dye, pigment, UV absorber, antistatic agent, antifogging agent, organic / inorganic filler, etc. In this case, these additions and treatments may be performed simultaneously with the acidic compound, but it is preferable to add and knead the acidic compound first.
[0041]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples, unless the summary is exceeded. The raw materials used in the following examples and the obtained aromatic polycarbonates were analyzed by the following measuring methods.
[0042]
(1) Chlorine ion content in diphenyl carbonate
About 5 g of diphenyl carbonate (DPC) is precisely weighed and added to 10 mL of toluene. After dissolution at 60 ° C., 10 mL of ultrapure water (ion-exchanged water not containing chlorine ions) is added, and a magnetic stirrer in a constant temperature room at 23 ° C. After stirring at 1000 rpm for 10 minutes, the aqueous phase was separated, and the chlorine ions in the aqueous phase were quantified by ion chromatography. As a result of the analysis, the weight of chloride ions relative to the weight of DPC was expressed in ppb units.
(2) Viscosity average molecular weight (Mv)
From the specific viscosity (ηsp) measured at a temperature of 20 ° C. using a Ubbelohde viscometer with a polycarbonate (concentration (C) 0.6 g / dl methylene chloride solution)
ηsp / C = [η] (1 + 0.28 ηsp)
[Η] = 1.23 × 10-FourMv0.83
It calculated using.
(3) Flow rate ratio (FRR)
Using a melt indexer manufactured by Takara Industries Co., Ltd., melt flow volume MVR (260 / 21.6) per unit time of aromatic polycarbonate measured at 260 ° C. and load 21.6 kg, 260 ° C. and load 2. Using the melt flow volume MVR (260 / 2.16) per unit time measured at 16 kg, the following formula was used.
FRR = MVR (260 / 21.6) / MVR (260 / 2.16)
[0043]
(4) Crosslinked structural unit
(1) Hydrolysis treatment:
After dissolving 1 g of aromatic polycarbonate in 100 ml of methylene chloride, 18 ml of 28% sodium methoxide methanol solution and 80 ml of methanol were added, and 25 ml of pure water was further added, followed by stirring at room temperature for 1 hour for complete hydrolysis. Thereafter, 1N hydrochloric acid was added, and the methylene chloride layer was separated to obtain a hydrolyzate.
(2) Liquid phase chromatography:
1 g of the hydrolyzate obtained in (1) was dissolved in 10 ml of acetonitrile and measured by reverse phase liquid chromatography. Reversed-phase liquid chromatography uses a mixed solvent consisting of acetonitrile and 10 mM ammonium acetate aqueous solution as an eluent, and starts at a ratio of acetonitrile / 10 mM ammonium acetate aqueous solution from 20/80 to a gradient of 80/20. Measured at ℃, detection is performed using a UV detector (SPD-6A, manufactured by Shimadzu Corporation) with a wavelength of 280 nm, and quantitative determination is performed by converting each peak area from a BPA calibration curve to a BPA equivalent weight before hydrolysis. Was determined as the weight relative to the polymer weight.
In addition, the identification of the peak was performed using Agilent Co., Ltd. LC-MS (Agilent-1100) and JEOL NMR (AL-400).
[0044]
(5) Number of transparent foreign matters of 10 μm or more (N: unit / g)
After drying the aromatic polycarbonate under a nitrogen atmosphere at 120 ° C. for 6 hours or more, a 70 μm-thick film was formed using a single-screw 30 mm extruder manufactured by Isuzu Chemical Co., Ltd., in a 9 cm × 50 cm range (about 4 g). 5) were cut out, and using a stereomicroscope, transparent foreign matters (= fish eyes) without nuclei of each sheet were marked, and the size and number were measured at a magnification of 200 times. In the measurement, the planar boundary of the transparent foreign substance without a nucleus was determined by the difference in refractive index from the periphery, and the size thereof was the maximum distance between two points on the planar boundary line. The total number of transparent foreign matters having a size of 10 μm or more was counted, and the number of foreign matters per gram was calculated as “number of transparent foreign matters of 10 μm or more”.
(6) Film appearance inspection
The film obtained in the above (5) was visually observed.
[0045]
(7) Plate color tone
Using the produced aromatic polycarbonate, a color tone when injection molding a flat plate of 60 × 60 × 3.2 mm at a barrel temperature of 360 ° C. and a mold temperature of 80 ° C. is performed using a spectral colorimeter CM-3700d manufactured by Minolta Co., Ltd. Measured and evaluated with a yellow index (YI). A smaller value indicates a better color tone.
(8) Plate color tone during heat retention
Minolta Co., Ltd. color tone when 10 shot continuous injection molding was performed on a 60 × 60 × 3.2 mm flat plate using a manufactured aromatic polycarbonate at a barrel temperature of 360 ° C., a mold temperature of 80 ° C., and a molding interval of 180 seconds. Measurement was performed using a spectrocolorimeter CM-3700d, and evaluation was performed using the maximum YI value in 10 shots. A smaller value indicates a better color tone during heat retention.
(9) Deterioration of color tone during heat retention
Evaluation was made by the difference (ΔYI) between the plate color tone and the plate color tone during heat retention. A smaller value indicates better stability during heat retention.
[0046]
Example11
Under a nitrogen gas atmosphere, bisphenol A and diphenyl carbonate are mixed at a certain molar ratio (DPC / BPA = 1.080) and heated to 140 ° C. to obtain a molten mixture. Through a raw material introduction tube heated to 140 ° C.Nitro220 ° C in an atmosphere13332 PaThe mixture was continuously fed into the first vertical stirring polymerization tank controlled in the above manner. The liquid level was kept constant while controlling the valve opening degree provided in the polymer discharge line at the bottom of the tank so that the average residence time was 60 minutes. Further, simultaneously with the start of the supply of the raw material mixture, an aqueous cesium carbonate solution as a catalyst was added in an amount of 0.35 μmol(As metal amount 0.70 μmol)Was continuously fed at a rate of.
[0047]
The polymerization liquid discharged from the bottom of the tank continues to be second, third andIs the final stage of the polymerization processFourth vertical stirring polymerizationIn the tankSequentially and continuously supplied. During the reaction, the average residence time of each tank,Respectively,60 minutes60 minutes, 150 minutesThen, the liquid level was controlled, and at the same time, by-product phenol was distilled off. 2nd to 2nd4The polymerization conditions of the polymerization tank were respectively the second polymerization tank (260 ° C,2000Pa), third polymerization tank (270 ° C,133Pa), fourth polymerization tank (284℃,40Pa)soThe conditions were set to high temperature, high vacuum, and low stirring speed as the reaction progressed. The production rate of polycarbonate is 50 kg / Hr. The viscosity average molecular weight of the polycarbonate thus obtained is21000.
[0048]
Next, in a molten state, this polymer was introduced into a twin-screw extruder (L / D = 42, barrel temperature 240 ° C.) with a gear pump, and 7 ppm of butyl p-toluenesulfonate was added. Pelletized through a polymer filter. This polymer filter is a woven wire mesh leaf disk with an absolute filtration accuracy of 10 μm attached to the center post. Before polymer melt flow, the flow rate is 5 ml / min for 36 hours at 280 ° C. in a nitrogen atmosphere. The temperature was raised and used. Films and plates are molded using the obtained pellets, and the amount of transparent foreign matter and visual inspection of the film, and the results of color tone evaluation of the plate are displayed.2It was shown to.
[0051]
Example 12~ 20
Bisphenol A and diphenyl carbonate−Mixed at a molar ratio of 2.,eachDisplays the temperature, pressure, residence time, and catalyst concentration in the polymerization tank−Example except that it was performed under the condition of 2.11The same operation was performed. The results are shown in Table-2.
[0052]
Comparative Examples 4-7
Bisphenol A and diphenyl carbonate are mixed at a molar ratio shown in Table-2.Displays the temperature, pressure, residence time, and catalyst concentration in each polymerization tank.−Like 2conditionsThe same operation as in Example 11 was performed except that. The results are shown in Table-2.
[0054]
[Table 2]
【The invention's effect】
According to the present invention, a transesterification aromatic polycarbonate excellent in transparency and molded appearance can be obtained by preventing the mixing of transparent foreign matters into the product.
Claims (3)
Ｍｖ≦２１０００の場合は、 Ｎ≦ｅｘｐ（６．５２×１０-4×Ｍｖ−９．０８７） （ａ）
Ｍｖ＞２１０００の場合は、 Ｎ≦ｅｘｐ（１．１１５×１０-4×Ｍｖ＋２．１７９） （ｂ）
で表される関係式を満足する芳香族ポリカーボネートを得ることを特徴とする芳香族ポリカーボネートの製造方法。 In the method for manufacturing by that an aromatic polycarbonate melt polymerization of an aromatic dihydroxy compound and a carbonic diester compound, the melt polymerization the aromatic dihydroxy compound to 1 mole, 0.1 [mu] mol or more as a metal amount, 0.9Myu mol The polymerization liquid carried out in the presence of the alkali metal compound and / or alkaline earth metal compound and discharged from the bottom of the first vertical stirring polymerization tank is continuously supplied to the second, third and fourth vertical stirring polymerization tanks. In the fourth vertical stirring polymerization tank, which is the final stage of the polymerization step, the polymerization is carried out at 200 to 320 ° C. and 300 Pa or less. In order to neutralize the catalyst remaining in the polycarbonate by adding 0.01 to 20 ppm of acidic compound relative to the weight of the polycarbonate. Tsu and, 10 [mu] m or more transparent the number of foreign matters (N: unit pieces / g) and viscosity average molecular weight (Mv), but the following (a) or (b):
In the case of Mv ≦ 21000, N ≦ exp (6.52 × 10 −4 × Mv−9.087) (a)
In the case of Mv> 21000, N ≦ exp (1.115 × 10 −4 × Mv + 2.179) (b)
A process for producing an aromatic polycarbonate , characterized by obtaining an aromatic polycarbonate satisfying the relational expression represented by :
ＦＲＲ＝ＭＶＲ（２６０／２１．６）／ＭＶＲ（２６０／２．１６） The method for producing an aromatic polycarbonate according to claim 1, wherein the aromatic polycarbonate has a flow rate ratio (FRR) represented by the following formula of 15 or less in accordance with JIS K 7210.
FRR = MVR (260 / 21.6) / MVR (260 / 2.16)
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| JP2005126494A (en) * | 2003-10-21 | 2005-05-19 | Mitsubishi Chemicals Corp | Aromatic polycarbonate |
| JP2005179497A (en) * | 2003-12-19 | 2005-07-07 | Mitsubishi Chemicals Corp | Aromatic polycarbonate |
| AU2005252556B2 (en) * | 2004-06-14 | 2007-11-01 | Asahi Kasei Chemicals Corporation | Process for efficiently producing aromatic polycarbonate |
| CN1946763B (en) * | 2004-06-14 | 2011-01-19 | 旭化成化学株式会社 | Improved process for producing aromatic polycarbonate |
| BRPI0515041B1 (en) | 2004-10-14 | 2015-06-09 | Asahi Kasei Chemicals Corporation | Process for the production of high purity diaryl carbonate and process for the production of aromatic polycarbonate by transesterification with an aromatic dihydroxy compound |
| JP5655495B2 (en) * | 2009-10-22 | 2015-01-21 | 三菱化学株式会社 | Polycarbonate resin and method for producing the same |
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