JP2006096959A - Production process of aromatic polycarbonate - Google Patents
Production process of aromatic polycarbonate Download PDFInfo
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- JP2006096959A JP2006096959A JP2004288045A JP2004288045A JP2006096959A JP 2006096959 A JP2006096959 A JP 2006096959A JP 2004288045 A JP2004288045 A JP 2004288045A JP 2004288045 A JP2004288045 A JP 2004288045A JP 2006096959 A JP2006096959 A JP 2006096959A
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- polymerization
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 65
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 47
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 117
- 229920000642 polymer Polymers 0.000 claims abstract description 52
- -1 diaryl carbonate Chemical compound 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 13
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 206010049040 Weight fluctuation Diseases 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 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 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 230000002411 adverse Effects 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003550 marker Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000003606 tin compounds Chemical class 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000005910 alkyl carbonate group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 125000002837 carbocyclic group Chemical group 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 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
- 238000009826 distribution Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000005551 pyridylene group Chemical group 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 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
- 239000010409 thin film Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- WDTYGAMSPKPQML-UHFFFAOYSA-N (2,3-ditert-butylphenyl) hydrogen carbonate Chemical compound CC(C)(C)C1=CC=CC(OC(O)=O)=C1C(C)(C)C WDTYGAMSPKPQML-UHFFFAOYSA-N 0.000 description 1
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical class CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-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
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- QGBLCIBATKETJC-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;manganese(2+) Chemical compound [Mn+2].O1B([O-])OB2OB([O-])OB1O2 QGBLCIBATKETJC-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 241000534000 Berula erecta Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 1
- ZKTFNWPPVIAFDC-UHFFFAOYSA-N OB(O)O.P.P.P Chemical class OB(O)O.P.P.P ZKTFNWPPVIAFDC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QFBYBEDCELVEAJ-UHFFFAOYSA-L [Ge+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 Chemical compound [Ge+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 QFBYBEDCELVEAJ-UHFFFAOYSA-L 0.000 description 1
- PZUDSCYHVMUKLX-UHFFFAOYSA-M [NH4+].[OH-].[OH-].C[N+](C)(C)CC1=CC=CC=C1 Chemical class [NH4+].[OH-].[OH-].C[N+](C)(C)CC1=CC=CC=C1 PZUDSCYHVMUKLX-UHFFFAOYSA-M 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- LLIZWEZMFYMWBC-UHFFFAOYSA-I antimony(3+) manganese(2+) pentaacetate Chemical class C(C)(=O)[O-].[Sb+3].[Mn+2].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-].C(C)(=O)[O-] LLIZWEZMFYMWBC-UHFFFAOYSA-I 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical group [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- FLLNLJJKHKZKMB-UHFFFAOYSA-N boron;tetramethylazanium Chemical compound [B].C[N+](C)(C)C FLLNLJJKHKZKMB-UHFFFAOYSA-N 0.000 description 1
- QYJXDIUNDMRLAO-UHFFFAOYSA-N butyl 4-methylbenzenesulfonate Chemical compound CCCCOS(=O)(=O)C1=CC=C(C)C=C1 QYJXDIUNDMRLAO-UHFFFAOYSA-N 0.000 description 1
- NIKBCKTWWPVAIC-UHFFFAOYSA-N butyl benzenesulfonate Chemical compound CCCCOS(=O)(=O)C1=CC=CC=C1 NIKBCKTWWPVAIC-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical class CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- VBVCYAZECWLFHP-UHFFFAOYSA-N dodecyl benzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 VBVCYAZECWLFHP-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- RAPJPBVRDGZZJI-UHFFFAOYSA-N ethoxy-ethyl-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](CC)(OCC)C1=CC=CC=C1 RAPJPBVRDGZZJI-UHFFFAOYSA-N 0.000 description 1
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 239000008188 pellet Substances 0.000 description 1
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- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- RGCLLPNLLBQHPF-HJWRWDBZSA-N phosphamidon Chemical compound CCN(CC)C(=O)C(\Cl)=C(/C)OP(=O)(OC)OC RGCLLPNLLBQHPF-HJWRWDBZSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
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- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical group [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- PEEVPXQMALOQSR-UHFFFAOYSA-N tributoxy(ethyl)stannane Chemical group CCCCO[Sn](CC)(OCCCC)OCCCC PEEVPXQMALOQSR-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Abstract
Description
本発明は、重合器を多段で用いて重合を行う際に、最終段重合器より前の段の重合器での分子量の変動を吸収し、最終段重合器から分子量の安定したポリマーを得る芳香族ポリカーボネートの製造方法に関する。 The present invention absorbs a change in molecular weight in a polymerization vessel in a stage prior to the final stage polymerization apparatus when performing polymerization using the polymerization apparatus in multiple stages, and obtains a polymer having a stable molecular weight from the final stage polymerization apparatus. The present invention relates to a method for producing a group polycarbonate.
近年、芳香族ポリカーボネートは、耐熱性、耐衝撃性、透明性などに優れたエンジニアリングプラスチックスとして、多くの分野において幅広く用いられている。この芳香族ポリカーボネートの製造方法については、従来種々の研究が行われ、その中で、芳香族ジヒドロキシ化合物、例えば２，２−ビス（４−ヒドロキシフェニル）プロパン（以下、ビスフェノールＡという。）とホスゲンとの界面重縮合法が工業化されている。
しかしながら、この界面重縮合法においては、有毒なホスゲンを用いなければならないこと、副生する塩化水素や塩化ナトリウム及び、溶媒として大量に用いる塩化メチレンなどの含塩素化合物により装置が腐食すること、ポリマー物性劣化に悪影響を及ぼす塩化ナトリウムなどの不純物や、残留塩化メチレンの分離が困難なことなどの問題があった。
In recent years, aromatic polycarbonate has been widely used in many fields as engineering plastics excellent in heat resistance, impact resistance, transparency and the like. Various methods have been conventionally studied for producing this aromatic polycarbonate, and among them, aromatic dihydroxy compounds such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) and phosgene. The interfacial polycondensation method is industrialized.
However, in this interfacial polycondensation method, toxic phosgene must be used, equipment is corroded by by-produced hydrogen chloride and sodium chloride, and chlorine-containing compounds such as methylene chloride used in large quantities as a solvent, polymer There have been problems such as impurities such as sodium chloride that adversely affect physical properties deterioration and difficulty in separating residual methylene chloride.
このような問題を解決するために、ホスゲンの替わりにジアリールカーボネートやジアルキルカーボネートを用いて芳香族ポリカーボネートを製造する方法が数多く提案されている。ジアルキルカーボネートを用いて芳香族ポリカーボネートを製造する方法として、ジアルキルカーボネートと芳香族ヒドロキシ化合物とのエステル交換反応による方法や（特許文献１、特許文献２、特許文献３参照）、ジアルキルカーボネートと芳香族ジヒドロキシ化合物の脂肪酸エステルとのエステル交換反応による方法（特許文献４参照）等が提案されている。このジアルキルカーボネートを用いる方法では、反応の際に、重合系内から脂肪族モノヒドロキシ化合物やその誘導体、及びジアルキルカーボネート等が蒸溜塔の塔頂溜分として溜出するが、これらは通常常温２５℃で液体であるため、上記ジアリールカーボネートを用いる方法に比べ、その取扱いは容易である。 In order to solve such a problem, many methods for producing an aromatic polycarbonate using diaryl carbonate or dialkyl carbonate instead of phosgene have been proposed. As a method for producing an aromatic polycarbonate using a dialkyl carbonate, a method by a transesterification reaction between a dialkyl carbonate and an aromatic hydroxy compound (see Patent Document 1, Patent Document 2, and Patent Document 3), dialkyl carbonate and aromatic dihydroxy A method of transesterification of a compound with a fatty acid ester (see Patent Document 4) has been proposed. In this method using a dialkyl carbonate, during the reaction, an aliphatic monohydroxy compound or a derivative thereof, a dialkyl carbonate, and the like are distilled from the polymerization system as a top distillate of a distillation column. Since it is liquid, it is easier to handle than the method using diaryl carbonate.
しかしながら、これらの方法においては、前者の方法は反応が遅くて、高分子量体を得るのが困難である等の欠点を有し、後者の方法は、原料製造時にケテンの様な不安定かつ有毒物質が生成する上に工程が複雑であって、工業プロセスとして満足しうる方法とはいえない。又、ジアルキルカーボネートを用いる方法では、得られる芳香族ポリカーボネートの末端にはアルキルカーボネート基が導入されるが、このアルキルカーボネートを有するポリマーは熱安定性に劣るという品質上の問題も有していた。
一方、ジアリールカーボネートと芳香族ジヒドロキシ化合物とからエステル交換反応により芳香族ポリカーボネートを製造する反応（以下しばしば本反応と略記する）は以前から知られており、例えばビスフェノールＡとジフェニルカーボネートを溶融状態で重合して、芳香族ポリカーボネートを得ることができる。この方法は、高粘度ポリカーボネートの溶融体中から、芳香族モノヒドロキシ化合物（フェノール等）を留去しなければ重合度が上がらないことから、（１）高温で重合するため、副反応によって分岐や架橋が起こりやすく、品質の良好なポリマーが得にくいこと、（２）着色を免れないこと等、種々の欠点を有していた（非特許文献１参照）。
However, in these methods, the former method has disadvantages such as a slow reaction and it is difficult to obtain a high molecular weight product, and the latter method is unstable and toxic like ketene during raw material production. In addition to the production of substances, the process is complicated, and it is not a satisfactory method as an industrial process. In the method using dialkyl carbonate, an alkyl carbonate group is introduced at the end of the obtained aromatic polycarbonate. However, the polymer having the alkyl carbonate has a quality problem that it is inferior in thermal stability.
On the other hand, a reaction for producing an aromatic polycarbonate by a transesterification reaction from a diaryl carbonate and an aromatic dihydroxy compound (hereinafter often abbreviated as this reaction) has been known for some time. For example, bisphenol A and diphenyl carbonate are polymerized in a molten state. Thus, an aromatic polycarbonate can be obtained. In this method, since the degree of polymerization cannot be increased unless an aromatic monohydroxy compound (phenol or the like) is distilled away from the melt of the high-viscosity polycarbonate, (1) the polymerization is carried out at a high temperature. There were various drawbacks such as cross-linking easily and difficulty in obtaining a polymer with good quality, and (2) inevitable coloring (see Non-Patent Document 1).
これらの欠点を克服するため、触媒や安定剤、重合方法等に関して数多くの試みがなされている。特に本出願人等は、特許文献５の明細書において、芳香族ジヒドロキシ化合物とジアリールカーボネートとの溶融混合物、または芳香族ジヒドロキシ化合物とジアリールカーボネートを反応して得られる重合中間体を、自由に落下させながら重合する方法を開示しており（以下しばしばワイヤー型重合器と略記する）、この方法によれば着色のない高品質のポリカーボネートを製造することが可能である。
このガイドに沿わせて落下させながら重合させる方法では、芳香族モノヒドロキシ化合物の除去が速やかに行われるため、従来の攪拌型反応器に比べて重合速度が高いのであるが、それでも、本反応は非常に遅い反応であり、１基の重合器で所望の分子量まで重合を進めるためには、工業的には実現の難しいほどに大きな重合器が必要となってしまい、実用上は重合器を２段以上用いて重合させる場合がほとんどである。実際、特許文献５やそれに続く特許文献６〜１５において本発明者らは、ワイヤー型重合器に関する詳細な技術開示を行っている訳であるが、いずれの技術開示においても、芳香族ジヒドロキシ化合物とジアリールカーボネートを予めある程度重合させたプレポリマーをまず製造し、このプレポリマーをワイヤー型重合器に供することによって、重合の進行が困難になる高分子量領域での重合を速やかに進めている。
In order to overcome these drawbacks, many attempts have been made regarding catalysts, stabilizers, polymerization methods and the like. In particular, the present applicants freely dropped a molten mixture of an aromatic dihydroxy compound and diaryl carbonate, or a polymerization intermediate obtained by reacting an aromatic dihydroxy compound and diaryl carbonate in the specification of Patent Document 5. However, a method for polymerizing is disclosed (hereinafter often abbreviated as a wire-type polymerizer), and according to this method, it is possible to produce a high-quality polycarbonate without coloring.
In the method of polymerizing while dropping along this guide, the aromatic monohydroxy compound is removed quickly, so the polymerization rate is higher than that of a conventional stirred reactor. This is a very slow reaction, and in order to proceed the polymerization to a desired molecular weight with one polymerization vessel, a large polymerization vessel that is difficult to realize industrially becomes necessary. In most cases, polymerization is carried out using more than one stage. In fact, in Patent Document 5 and Patent Documents 6 to 15 that follow, the present inventors have made detailed technical disclosures regarding wire-type polymerizers. In any of the technical disclosures, aromatic dihydroxy compounds and First, a prepolymer obtained by polymerizing a diaryl carbonate to some extent in advance is prepared, and this prepolymer is supplied to a wire-type polymerization vessel, whereby polymerization in a high molecular weight region where the progress of polymerization is difficult is rapidly advanced.
このように多段で重合を行う場合には、前の段から払い出される重合物の重合度、末端水酸基比率、払い出し量などの諸条件が決まらないと、後の段重合器の運転条件が決まらないし、前の段の諸条件が安定しないと、当然のことながら、引き続く後の段も安定して運転することができないことは言うまでもない。
しかしながら、本反応の場合、各段の重合時間は場合によっては数時間に及び、前段の反応条件を決めてから、後段で製品ポリマーの分子量を知るまでに、極めて長い時間が過ぎてしまい、後ろの重合器から払い出された重合物を分析してから前の重合器の運転条件を変更したのでは、遅きに失して重合反応を制御できなくなってしまう欠点があり、その対策が求められていた。
When polymerization is performed in multiple stages as described above, unless conditions such as the degree of polymerization of the polymer discharged from the previous stage, the ratio of terminal hydroxyl groups, and the amount of discharge are determined, the operating conditions of the subsequent stage polymerization apparatus cannot be determined. Needless to say, if the conditions of the previous stage are not stable, the subsequent stage cannot be operated stably.
However, in the case of this reaction, the polymerization time of each stage may be several hours depending on the case, and it takes a very long time to determine the molecular weight of the product polymer in the subsequent stage after determining the reaction conditions in the previous stage. Changing the operating conditions of the previous polymerization vessel after analyzing the polymer dispensed from the previous polymerization vessel has the disadvantage that the polymerization reaction cannot be controlled due to a delay, and countermeasures are required. It was.
本発明は、重合器を多段で用いて重合を行う際に、最終段重合器より前の段の重合器での分子量の変動を吸収し、最終段重合器から分子量の安定したポリマーを得る芳香族ポリカーボネートの製造方法を提供することを目的とする。 The present invention absorbs a change in molecular weight in a polymerization vessel in a stage prior to the final stage polymerization apparatus when performing polymerization using the polymerization apparatus in multiple stages, and obtains a polymer having a stable molecular weight from the final stage polymerization apparatus. An object of the present invention is to provide a method for producing a group polycarbonate.
本発明者らが、上記課題を解決するために鋭意検討を行った結果、例えば、２段重合器を用いて重合を行う場合、前段重合器と最終段重合器の間に中間タンクを設けることで、前段重合器の分子量変動を吸収できる（バッファー効果）ことが判り、本発明の端緒とした。さらに、該中間タンクの運転方法について検討を重ねた結果、中間タンクでの平均滞留時間を特定の範囲に絞ることで、適切なバッファー効果を得られることが判り、さらに機器や運転方法を改良して、本発明を完成させた。 As a result of intensive studies conducted by the present inventors to solve the above problems, for example, when polymerization is performed using a two-stage polymerization apparatus, an intermediate tank is provided between the preceding-stage polymerization apparatus and the final-stage polymerization apparatus. Thus, it was found that the molecular weight variation of the pre-stage polymerizer can be absorbed (buffer effect), and this is the beginning of the present invention. Furthermore, as a result of repeated studies on the operation method of the intermediate tank, it has been found that the appropriate buffer effect can be obtained by narrowing the average residence time in the intermediate tank to a specific range, and the equipment and operation method have been further improved. Thus, the present invention has been completed.
すなわち、本発明は、
１．芳香族ジヒドロキシ化合物とジアリールカーボネートを溶融状態で重合させて芳香族ポリカーボネートを製造する方法に用いる重合設備であって、該重合設備が、複数の重合器が直列につながった多段式であり、最終段重合器がガイドに沿わせて落下させながら重合させる重合器であり、最終段重合器とそれより一つ前の重合器の間に中間タンクを有する重合設備を用い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関わる。
２．該中間タンクにおけるポリマーの平均滞留時間Ｔ［ｈｒ］が、該最終段重合器におけるポリマーの落下時間ｔ［ｈｒ］に対して、０．５倍以上、２０倍以下である上記１記載の芳香族ポリカーボネートの製造方法に関わる。
３．該中間タンクが、攪拌設備を有することを特徴とする上記１あるいは２記載の芳香族ポリカーボネートの製造方法に関わる。
４．該最終段重合器より一つ前の重合器から該中間タンクへのポリマーの受け入れと、該中間タンクから最終段重合器へのポリマーの払い出しが連続的に行われることを特徴とする上記１から３のいずれか記載の芳香族ポリカーボネートの製造方法に関わる。
That is, the present invention
1. A polymerization facility used in a method for producing an aromatic polycarbonate by polymerizing an aromatic dihydroxy compound and diaryl carbonate in a molten state, wherein the polymerization facility is a multistage system in which a plurality of polymerization vessels are connected in series, and the final stage An aromatic polycarbonate characterized by using a polymerization equipment having an intermediate tank between a final stage polymerization apparatus and a polymerization apparatus immediately preceding the polymerization apparatus. Related to the manufacturing method.
2. 2. The aromatic according to 1 above, wherein the average residence time T [hr] of the polymer in the intermediate tank is 0.5 to 20 times the polymer fall time t [hr] in the final stage polymerization vessel. It is related to the manufacturing method of polycarbonate.
3. 3. The method for producing an aromatic polycarbonate according to 1 or 2 above, wherein the intermediate tank has a stirring facility.
4). From the above 1 characterized in that the polymer is continuously received from the polymerizer immediately before the final stage polymerizer into the intermediate tank and the polymer is discharged from the intermediate tank to the final stage polymerizer. 3. It relates to the manufacturing method of the aromatic polycarbonate in any one of 3.
本発明は、重合器を多段で用いて重合を行う際に、最終段重合器より前の段の重合器での分子量の変動を吸収し、最終段重合器から分子量の安定したポリマーを得る芳香族ポリカーボネートの製造方法を提供する。 The present invention absorbs a change in molecular weight in a polymerization vessel in a stage prior to the final stage polymerization apparatus when performing polymerization using the polymerization apparatus in multiple stages, and obtains a polymer having a stable molecular weight from the final stage polymerization apparatus. A method for producing a group polycarbonate is provided.
以下本発明を具体的に説明する。
本発明において、芳香族ジヒドロキシ化合物とは、ＨＯ−Ａｒ−ＯＨで示される化合物である（式中、Ａｒは２価の芳香族基を表す。）。芳香族基Ａｒは、例えば好ましくは−Ａｒ１−Ｙ−Ａｒ２−で示される２価の芳香族基である（式中、Ａｒ１及びＡｒ２は、各々独立にそれぞれ炭素数５〜７０を有する２価の炭素環式又は複素環式芳香族基を表し、Ｙは炭素数１〜３０を有する２価のアルカン基を表す。）。
２価の芳香族基Ａｒ１、Ａｒ２において、１つ以上の水素原子が、反応に悪影響を及ぼさない他の置換基、例えば、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、フェニル基、フェノキシ基、ビニル基、シアノ基、エステル基、アミド基、ニトロ基などによって置換されたものであっても良い。
複素環式芳香族基の好ましい具体例としては、１ないし複数の環形成窒素原子、酸素原子又は硫黄原子を有する芳香族基を挙げることができる。
２価の芳香族基Ａｒ１、Ａｒ２は、例えば、置換又は非置換のフェニレン、置換又は非置換のビフェニレン、置換または非置換のピリジレンなどの基を表す。ここでの置換基は前述のとおりである。
２価のアルカン基Ｙは、例えば、下記式（１）で示される有機基である。
The present invention will be specifically described below.
In the present invention, the aromatic dihydroxy compound is a compound represented by HO—Ar—OH (wherein Ar represents a divalent aromatic group). The aromatic group Ar is, for example, preferably a divalent aromatic group represented by —Ar 1 —Y—Ar 2 — (wherein Ar 1 and Ar 2 each independently has 5 to 70 carbon atoms, respectively). It represents a divalent carbocyclic or heterocyclic aromatic group, and Y represents a divalent alkane group having 1 to 30 carbon atoms.
In the divalent aromatic groups Ar 1 and Ar 2 , one or more hydrogen atoms have other substituents that do not adversely influence the reaction, for example, halogen atoms, alkyl groups having 1 to 10 carbon atoms, carbon atoms 1 to It may be substituted with 10 alkoxy groups, phenyl group, phenoxy group, vinyl group, cyano group, ester group, amide group, nitro group or the like.
Preferable specific examples of the heterocyclic aromatic group include aromatic groups having one or more ring-forming nitrogen atoms, oxygen atoms or sulfur atoms.
The divalent aromatic groups Ar 1 and Ar 2 represent groups such as substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted pyridylene, and the like. The substituents here are as described above.
The divalent alkane group Y is, for example, an organic group represented by the following formula (1).
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４は、各々独立に水素、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、環構成炭素数５〜１０のシクロアルキル基、環構成炭素数５〜１０の炭素環式芳香族基、炭素数６〜１０の炭素環式アラルキル基を表す。ｋは３〜１１の整数を表し、Ｒ５およびＲ６は、各Ｘについて個々に選択され、お互いに独立に、水素または炭素数１〜６のアルキル基を表し、Ｘは炭素を表す。また、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６において、一つ以上の水素原子が反応に悪影響を及ぼさない範囲で他の置換基、例えばハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、フェニル基、フェノキシ基、ビニル基、シアノ基、エステル基、アミド基、ニトロ基等によって置換されたものであっても良い。）
このような２価の芳香族基Ａｒとしては、例えば、下記式（２）で示されるものが挙げられる。
(Wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl having 5 to 10 carbon atoms in the ring structure. Group, a carbocyclic aromatic group having 5 to 10 ring carbon atoms, and a carbocyclic aralkyl group having 6 to 10 carbon atoms, k is an integer of 3 to 11, and R 5 and R 6 are each X Independently selected from each other, each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, X represents carbon, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 In the range where one or more hydrogen atoms do not adversely affect the reaction, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, vinyl Group, cyano group, ester group, amide group, nitro group, etc. Or it may be substituted.)
Examples of such a divalent aromatic group Ar include those represented by the following formula (2).
（式中、Ｒ７、Ｒ８は、各々独立に水素原子、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、環構成炭素数５〜１０のシクロアルキル基またはフェニル基であって、ｍおよびｎは１〜４の整数で、ｍが２〜４の場合には各Ｒ７はそれぞれ同一でも異なるものであってもよいし、ｎが２〜４の場合には各Ｒ８はそれぞれ同一でも異なるものであってもよい。）
さらに、２価の芳香族基Ａｒは、−Ａｒ１−Ｚ−Ａｒ２−で示されるものであっても良い。（式中、Ａｒ１、Ａｒ２は前述の通りで、Ｚは単結合又は−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ２−、−ＳＯ−、−ＣＯＯ−、−ＣＯＮ（Ｒ１）−などの２価の基を表す。ただし、Ｒ１は前述のとおりである。）
このような２価の芳香族基Ａｒとしては、例えば、下記式（３）で示されるものが挙げられる。
(Wherein R 7 and R 8 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 ring carbon atoms, or A phenyl group, m and n are integers of 1 to 4, and when m is 2 to 4, each R 7 may be the same or different, and when n is 2 to 4 Each R 8 may be the same or different.)
Furthermore, the divalent aromatic group Ar may be represented by —Ar 1 —Z—Ar 2 —. (In the formula, Ar 1 and Ar 2 are as described above, and Z is a single bond or —O—, —CO—, —S—, —SO 2 —, —SO—, —COO—, —CON (R 1 )-Represents a divalent group such as-, where R 1 is as described above.
Examples of such a divalent aromatic group Ar include those represented by the following formula (3).
（式中、Ｒ７、Ｒ８、ｍおよびｎは、前述のとおりである。）
さらに、２価の芳香族基Ａｒの具体例としては、置換または非置換のフェニレン、置換または非置換のナフチレン、置換または非置換のピリジレン等が挙げられる。ここでの置換基は前述のとおりである。
本発明で用いられる芳香族ジヒドロキシ化合物は、単一種類でも２種類以上でもかまわないが、製造される複数のポリカーボネートの内全てに共通で用いられる芳香族ジヒドロキシ化合物であることが必要である。現在は一般に、ビスフェノールＡポリカーボネートが主流であることから、ビスフェノールＡを単独で用いることが好ましい。
本発明で用いられるジアリールカーボネートは、下記式（４）で表される。
(Wherein R 7 , R 8 , m and n are as described above.)
Furthermore, specific examples of the divalent aromatic group Ar include substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted pyridylene, and the like. The substituents here are as described above.
The aromatic dihydroxy compound used in the present invention may be a single type or two or more types, but it is necessary to be an aromatic dihydroxy compound that is commonly used for all of a plurality of polycarbonates to be produced. Currently, bisphenol A polycarbonate is the mainstream, so it is preferable to use bisphenol A alone.
The diaryl carbonate used in the present invention is represented by the following formula (4).
（式中、Ａｒ３、Ａｒ４はそれぞれ１価の芳香族基を表す。）
Ａｒ３及びＡｒ４は、１価の炭素環式又は複素環式芳香族基を表すが、このＡｒ３、Ａｒ４において、１つ以上の水素原子が、反応に悪影響を及ぼさない他の置換基、例えば、ハロゲン原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、フェニル基、フェノキシ基、ビニル基、シアノ基、エステル基、アミド基、ニトロ基などによって置換されたものであっても良い。Ａｒ３とＡｒ４は同じものであっても良いし、異なるものであっても良い。
１価の芳香族基Ａｒ３及びＡｒ４の代表例としては、フェニル基、ナフチル基、ビフェニル基、ピリジル基を挙げることができる。これらは、上述の１種以上の置換基で置換されたものでも良い。
好ましいＡｒ３及びＡｒ４としては、それぞれ例えば、下記式（５）などが挙げられる。
(In the formula, Ar 3 and Ar 4 each represent a monovalent aromatic group.)
Ar 3 and Ar 4 represent a monovalent carbocyclic or heterocyclic aromatic group, and in this Ar 3 , Ar 4 , other substituents in which one or more hydrogen atoms do not adversely influence the reaction Substituted with, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, or a nitro group It may be. Ar 3 and Ar 4 may be the same or different.
Representative examples of the monovalent aromatic groups Ar 3 and Ar 4 include a phenyl group, a naphthyl group, a biphenyl group, and a pyridyl group. These may be substituted with one or more substituents as described above.
Preferred examples of Ar 3 and Ar 4 include the following formula (5).
ジアリールカーボネートの代表的な例としては、下記式（６）で示される置換または非置換のジフェニルカーボネート類を挙げることができる。 Representative examples of diaryl carbonates include substituted or unsubstituted diphenyl carbonates represented by the following formula (6).
（式中、Ｒ９及びＲ１０は、各々独立に水素原子、炭素数１〜１０を有するアルキル基、炭素数１〜１０を有するアルコキシ基、環構成炭素数５〜１０のシクロアルキル基又はフェニル基を示し、ｐ及びｑは１〜５の整数で、ｐが２以上の場合には、各Ｒ９はそれぞれ異なるものであっても良いし、ｑが２以上の場合には、各Ｒ１０は、それぞれ異なるものであっても良い。） (In the formula, R 9 and R 10 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 ring carbon atoms, or phenyl. P and q are integers of 1 to 5, and when p is 2 or more, each R 9 may be different, and when q is 2 or more, each R 10 May be different.)
このジフェニルカーボネート類の中でも、非置換のジフェニルカーボネートや、ジトリルカーボネート、ジ−ｔ−ブチルフェニルカーボネートのような低級アルキル置換ジフェニルカーボネートなどの対称型ジアリールカーボネートが好ましいが、特にもっとも簡単な構造のジアリールカーボネートである非置換のジフェニルカーボネートが好適である。
これらのジアリールカーボネート類は単独で用いても良いし、２種以上を組み合わせて用いても良い。
本発明における芳香族ジヒドロキシ化合物とジアリールカーボネートとの使用割合（仕込比率）は、目標とするポリカーボネートの分子量範囲や末端基比率、用いられる芳香族ジヒドロキシ化合物とジアリールカーボネートの種類、重合温度その他の重合条件によって異なるが、ジアリールカーボネートが、芳香族ジヒドロキシ化合物１モルに対して、通常上限は２．５モル、好ましくは２．０モル、さらに好ましくは１．５モルである。該モル比の下限は０．９モル、好ましくは０．９５モル、さらに好ましくは０．９８モルである。
得られる芳香族ポリカーボネートの数平均分子量は５００〜１０００００であり、好ましくは２０００〜３００００である。
Among these diphenyl carbonates, preferred are symmetric diaryl carbonates such as unsubstituted diphenyl carbonate, lower alkyl-substituted diphenyl carbonates such as ditolyl carbonate and di-t-butylphenyl carbonate, and particularly diaryls having the simplest structure. Unsubstituted diphenyl carbonate, which is carbonate, is preferred.
These diaryl carbonates may be used alone or in combination of two or more.
The use ratio (charge ratio) of the aromatic dihydroxy compound and diaryl carbonate in the present invention is the molecular weight range and end group ratio of the target polycarbonate, the type of aromatic dihydroxy compound and diaryl carbonate used, the polymerization temperature and other polymerization conditions. However, the upper limit of diaryl carbonate is usually 2.5 mol, preferably 2.0 mol, more preferably 1.5 mol, per 1 mol of the aromatic dihydroxy compound. The lower limit of the molar ratio is 0.9 mol, preferably 0.95 mol, more preferably 0.98 mol.
The number average molecular weight of the obtained aromatic polycarbonate is 500 to 100,000, preferably 2000 to 30,000.
本発明に用いる重合設備は、複数の重合器が直列につながったものである。なお、以下しばしば最終段重合器よりも前の重合器を総称して前段重合器と呼ぶ。
本発明における前段重合器は、ポリカーボネートの反応器として広く使用されているものが使用でき、例えば、攪拌槽型反応器、薄膜反応器、遠心式薄膜蒸発反応器、表面更新型二軸混練反応器、二軸横型攪拌反応器、濡れ壁式反応器、自由落下させながら重合する多孔板型反応器、ガイドとも呼ばれるワイヤーに沿わせて落下させながら重合するワイヤー付き多孔板型反応器等が用いられ、これらを組み合わせて用いることも好ましい。これらの反応器の材質は、鉄を２０％以上含む材質、例えばＳＵＳ３０４，ＳＵＳ３１６，ＳＵＳ３１６Ｌが、入手や加工が容易であり好ましく、また、鉄含有量が２０％以下の材質、例えば、ニッケルやチタン等の非鉄材料を用いた反応器も、着色を防止する効果が期待できて好ましい。
各段重合器での重合温度は、用いる芳香族ヒドロキシ化合物やジアリールカーボネートの種類、所望の分子量や水酸基末端比率、等によって異なり、通常上限は３５０℃、好ましくは２９０℃、さらに好ましくは２８０℃であり、通常下限は１００℃、好ましくは１５０℃、さらに好ましくは１８０℃である。
The polymerization equipment used in the present invention has a plurality of polymerization vessels connected in series. Hereinafter, the polymerization apparatus before the final stage polymerization apparatus is generally referred to as a front polymerization apparatus.
The pre-stage polymerizer in the present invention may be one widely used as a polycarbonate reactor, for example, a stirred tank reactor, a thin film reactor, a centrifugal thin film evaporation reactor, a surface renewal type twin screw kneading reactor , Biaxial horizontal stirring reactors, wet wall reactors, perforated plate reactors that polymerize while dropping freely, perforated plate reactors with wires that polymerize while dropping along wires called guides, etc. These are also preferably used in combination. As materials for these reactors, materials containing 20% or more of iron, such as SUS304, SUS316, and SUS316L, are preferable because they are easily available and processed, and materials having an iron content of 20% or less, such as nickel and titanium. A reactor using a non-ferrous material such as the like is also preferable because an effect of preventing coloring can be expected.
The polymerization temperature in each stage polymerization apparatus varies depending on the type of aromatic hydroxy compound or diaryl carbonate used, the desired molecular weight, the hydroxyl group terminal ratio, etc., and the upper limit is usually 350 ° C., preferably 290 ° C., more preferably 280 ° C. In general, the lower limit is 100 ° C, preferably 150 ° C, more preferably 180 ° C.
反応の進行にともなって、芳香族モノヒドロキシ化合物が生成してくるが、これを反応系外へ除去することによって反応速度が高められる。従って、窒素、アルゴン、ヘリウム、二酸化炭素や低級炭化水素ガスなど反応に悪影響を及ぼさない不活性なガスを導入して、生成してくる該芳香族モノヒドロキシ化合物をこれらのガスに同伴させて除去する方法や、減圧下に反応を行う方法などが好ましく用いられる。好ましい反応圧力は、分子量によっても異なり、比較的低分子量のポリマーを所望する場合には１０Ｔｏｒｒ〜常圧の範囲が好ましく、比較的高分子量のポリマーを所望する場合には、２０Ｔｏｒｒ以下、特に１０Ｔｏｒｒ以下が好ましく、２Ｔｏｒｒ以下とすることが更に好ましい。具体的には、例えばビスフェノールＡとジフェニルカーボネートから芳香族ポリカーボネートを製造する場合、数平均分子量が１０００以下の範囲では、５０Ｔｏｒｒ〜常圧の範囲が好ましく、数平均分子量が１０００〜２０００の範囲では、３Ｔｏｒｒ〜５０Ｔｏｒｒの範囲が好ましく、数平均分子量が２０００以上の範囲では、２０Ｔｏｒｒ以下が好ましく、１０Ｔｏｒｒ以下がより好ましく、特に２Ｔｏｒｒ以下が好ましい。
各段における重合は、不活性ガス存在下に行うことがほとんどで、該不活性ガスとしては、窒素、炭酸ガス、アルゴンやヘリウムなどの希ガス類、低級炭化水素ガスなど反応に悪影響を及ぼさない不活性なガスが挙げられるが、窒素が工業的に大量に容易に入手でき好ましい。
As the reaction proceeds, an aromatic monohydroxy compound is produced, and the reaction rate is increased by removing this from the reaction system. Therefore, an inert gas that does not adversely influence the reaction, such as nitrogen, argon, helium, carbon dioxide, and lower hydrocarbon gas, is introduced, and the generated aromatic monohydroxy compound is accompanied by these gases and removed. And a method of reacting under reduced pressure are preferably used. The preferred reaction pressure varies depending on the molecular weight, and is preferably in the range of 10 Torr to normal pressure when a relatively low molecular weight polymer is desired, and 20 Torr or less, particularly 10 Torr or less when a relatively high molecular weight polymer is desired. Is preferable, and 2 Torr or less is more preferable. Specifically, for example, when producing an aromatic polycarbonate from bisphenol A and diphenyl carbonate, the number average molecular weight is preferably 1000 or less, preferably 50 Torr to normal pressure, and the number average molecular weight is 1000 to 2000. The range of 3 Torr to 50 Torr is preferable, and when the number average molecular weight is 2000 or more, 20 Torr or less is preferable, 10 Torr or less is more preferable, and 2 Torr or less is particularly preferable.
The polymerization in each stage is mostly carried out in the presence of an inert gas, and the inert gas includes inert gases that do not adversely affect the reaction, such as nitrogen, carbon dioxide, rare gases such as argon and helium, and lower hydrocarbon gases. However, nitrogen is preferred because it can be easily obtained industrially in large quantities.
本発明で各段重合器に用いる触媒は、この分野で用いられているものであれば種々のものを例示でき、たとえば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化カルシウムなどのアルカリ金属またはアルカリ土類金属の水酸化物類；水素化アルミニウムリチウム、水素化ホウ素ナトリウム、水素化ホウ素テトラメチルアンモニウムなどのホウ素やアルミニウムの水素化物のアルカリ金属塩、アルカリ土類金属塩、第四級アンモニウム塩類；水素化リチウム、水素化ナトリウム、水素化カルシウムなどのアルカリ金属またはアルカリ土類金属の水素化合物類；リチウムメトキシド、ナトリウムエトキシド、カルシウムメトキシドなどのアルカリ金属またはアルカリ土類金属のアルコキシド類；リチウムフェノキシド、ナトリウムフェノキシド、マグネシウムフェノキシド、ＬｉＯ−Ａｒ−ＯＬｉ、ＮａＯ−Ａｒ−ＯＮａ（Ａｒはアリール基）などのアルカリ金属またはアルカリ土類金属のアリーロキシド類；酢酸リチウム、酢酸カルシウム、安息香酸ナトリウムなどのアルカリ金属またはアルカリ土類金属の有機酸塩類；酸化亜鉛、酢酸亜鉛、亜鉛フェノキシドなどの亜鉛化合物類；酸化ホウ素、ホウ酸、ホウ酸ナトリウム、ホウ酸トリメチル、ホウ酸トリブチル、ホウ酸トリフェニル、テトラメチルアンモニウムボロハイドライド、テトラブチルアンモニウムボロハイドライド、テトラブチルアンモニウムテトラフェニルボレート、テトラメチルアンモニウムテトラフェニルボレートなど（Ｒ１Ｒ２Ｒ３Ｒ４）ＮＢ（Ｒ１Ｒ２Ｒ３Ｒ４）で表されるアンモニウムボレート類、（Ｒ１Ｒ２Ｒ３Ｒ４）ＰＢ（Ｒ１Ｒ２Ｒ３Ｒ４）で表されるホスホニウムボレート類（Ｒ１、Ｒ２、Ｒ３、Ｒ４は前記式（１）の説明通りである。）などのホウ素の化合物類；酸化ケイ素、ケイ酸ナトリウム、テトラアルキルケイ素、テトラアリールケイ素、ジフェニル−エチル−エトキシケイ素などのケイ素の化合物類；酸化ゲルマニウム、四塩化ゲルマニウム、ゲルマニウムエトキシド、ゲルマニウムフェノキシドなどのゲルマニウムの化合物類；酸化スズ、ジアルキルスズオキシド、ジアルキルスズカルボキシレート、酢酸スズ、エチルスズトリブトキシドなどのアルコキシ基またはアリーロキシ基と結合したスズ化合物、有機スズ化合物などのスズの化合物類；酸化鉛、酢酸鉛、炭酸鉛、塩基性炭酸塩、鉛及び有機鉛のアルコキシドまたはアリーロキシドなどの鉛の化合物；第四級アンモニウム塩、第四級ホスホニウム塩、第四級アルソニウム塩などのオニウム化合物類；酸化アンチモン、酢酸アンチモンなどのアンチモンの化合物類；酢酸マンガン、炭酸マンガン、ホウ酸マンガンなどのマンガンの化合物類；酸化チタン、チタンのアルコキシドまたはアリーロキシドなどのチタンの化合物類；酢酸ジルコニウム、酸化ジルコニウム、ジルコニウムのアルコキシド又はアリーロキシド、ジルコニウムアセチルアセトンなどのジルコニウム化合物類；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、テトラブ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などのアルキル、アリール、アルキルアリール基などのアンモニウムヒドロオキシド類；トリメチルアミン、トリエチルアミン、ジメチルベンジルアミン、トリフェニルアミンなどの三級アミン類；ジメチルアミン、ジエチルアミン、ジフェニルアミン、エチルフェニルアミンなどの二級アミン類；メチルアミン、エチルアミン、フェニルアミン、トルイルなどの一級アミン類；２−メチルイミダゾール、２−フェニルイミダゾールなどの イミダゾール類などの触媒を挙げることができる。 As the catalyst used in each stage polymerization apparatus in the present invention, various catalysts can be exemplified as long as they are used in this field. For example, alkali such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like can be used. Metal or alkaline earth metal hydroxides; alkali metal salts, alkaline earth metal salts, quaternary of hydrides of boron and aluminum such as lithium aluminum hydride, sodium borohydride, tetramethylammonium borohydride Ammonium salts; alkali metal or alkaline earth metal hydrogen compounds such as lithium hydride, sodium hydride, calcium hydride; alkali metal or alkaline earth metal alkoxides such as lithium methoxide, sodium ethoxide, calcium methoxide Lithium phenoxide, sodium Alkali metal or alkaline earth metal aryloxides such as enoxide, magnesium phenoxide, LiO-Ar-OLi, NaO-Ar-ONa (Ar is an aryl group); alkali metals or alkalis such as lithium acetate, calcium acetate, sodium benzoate Organic acid salts of earth metals; zinc compounds such as zinc oxide, zinc acetate, zinc phenoxide; boron oxide, boric acid, sodium borate, trimethyl borate, tributyl borate, triphenyl borate, tetramethylammonium borohydride , ammonium represented by tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetramethylammonium tetraphenylborate, etc. (R 1 R 2 R 3 R 4) NB (R 1 R 2 R 3 R 4) Umuboreto such, the (R 1 R 2 R 3 R 4) PB (R 1 R 2 R 3 R 4) in phosphonium borates represented (R 1, R 2, R 3, R 4 is the formula (1) Boron compounds such as silicon oxide, sodium silicate, tetraalkyl silicon, tetraaryl silicon, diphenyl-ethyl-ethoxy silicon; germanium oxide, germanium tetrachloride, germanium ethoxy And germanium compounds such as germanium phenoxide; tin compounds such as tin oxide, dialkyltin oxide, dialkyltin carboxylate, tin acetate, ethyltin tributoxide, tin compounds bonded with aryloxy groups, tin compounds such as organic tin compounds Compounds: Lead oxide, lead acetate, lead carbonate, basic charcoal Lead compounds such as alkoxides, lead and organic lead alkoxides or aryloxides; Onium compounds such as quaternary ammonium salts, quaternary phosphonium salts and quaternary arsonium salts; antimony compounds such as antimony oxide and antimony acetate Manganese compounds such as manganese acetate, manganese carbonate, manganese borate; titanium compounds such as titanium oxide, titanium alkoxide or aryloxide; zirconium acetate, zirconium oxide, zirconium alkoxide or aryloxide, zirconium acetylacetone, zirconium, etc. Compounds; alkyls such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide Ammonium hydroxides such as aryl, alkylaryl groups; tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine; secondary amines such as dimethylamine, diethylamine, diphenylamine and ethylphenylamine; methylamine And primary amines such as ethylamine, phenylamine and toluyl; and catalysts such as imidazoles such as 2-methylimidazole and 2-phenylimidazole.
これらの触媒は１種だけで用いても良いし、２種以上を組み合わせて用いても良い。これらの中で、アルカリ金属塩やアルカリ土類金属塩類、アンモニウムヒドロオキシド類等の含窒素化合物、ホウ素化合物が単独もしくは併用で好ましく用いられる。また、これらの触媒の使用量は、原料の芳香族ジヒドロキシ化合物１００質量部に対して、通常１０−８〜１質量部、好ましくは１０−７〜１０−２質量部、特に好ましくは１０−６〜１０−４質量部の範囲で選ばれる。
本発明で用いる最終段重合器はガイドに沿わせて前段重合器の混合物を沿わせて落下させながら重合させるワイヤー型重合器である。
These catalysts may be used alone or in combination of two or more. Of these, alkali metal salts, alkaline earth metal salts, nitrogen-containing compounds such as ammonium hydroxides, and boron compounds are preferably used alone or in combination. Moreover, the usage-amount of these catalysts is 10 < -8 > -1 mass part normally with respect to 100 mass parts of aromatic dihydroxy compounds of a raw material, Preferably it is 10 < -7 > -10-2 mass part, Most preferably, it is 10 < -6>. It is chosen in the range of 10-4 mass parts.
The final-stage polymerization apparatus used in the present invention is a wire-type polymerization apparatus that performs polymerization while dropping a mixture of the previous-stage polymerization apparatus along a guide.
本発明では、内装物に沿わせて落下させながら重合させる重合器を最終段重合器に用いて芳香族ポリカーボネートを製造する。本発明において内装物とは、その内装物の表面に沿ってポリマーが落下できるものを言う。例えば内装物を重合器に固定するためのサポート類は、そのサポート表面に沿ってポリマーが落下できる場合は内装物とみなし、そのサポート表面に沿ってポリマーが落下できない場合は内装物とはみなさない。
内装物の中でも、特に重合器の上部から下部へ鉛直方向につながっている内装物が好ましい。この場合、つながっているというのは内装物が直接重合器上部及び下部に接していてもよいし、単に重合器上部の空間と重合器下部の空間をつなげているだけで、重合器に直接接していなくてもかまわない。このような内装物としては、例えば重合器の上部から下部へ鉛直方向につながって設置されているワイヤー、チューブ、チェーン、ワイヤーロープ、スプリング、平板等が挙げられる。このような内装物は、重合器内に複数設置されていることが好ましい。内装物に沿わせてポリマーを落下させるために、重合器上部にポリマーを供給するための多孔板を設け、多孔板の各孔と内装物を接続させておくことも好ましい方法である。その他の内装物としては、充填剤タイプのものが挙げられる。この様な内装物としては、例えばラシヒリング、レッシングリング、ポールリング、ベルルサドル、インタロックスサドル、ディクソンパッキング、マクマホンパッキング、ヘリパック、スルザーパッキング、メラパック等が挙げられる。
In the present invention, an aromatic polycarbonate is produced using a polymerizer that is polymerized while being dropped along the interior as the final-stage polymerizer. In the present invention, the term “interior” means that the polymer can fall along the surface of the interior. For example, the support for fixing the interior to the polymerization vessel is regarded as an interior when the polymer can fall along the support surface, and is not regarded as the interior when the polymer cannot fall along the support surface. .
Among the interior items, an interior item that is connected in a vertical direction from the upper part to the lower part of the polymerization vessel is particularly preferable. In this case, the term “connected” means that the interior may be in direct contact with the upper and lower portions of the polymerization vessel, or simply by connecting the space above the polymerization vessel and the space below the polymerization vessel. It does n’t matter if you do n’t. Examples of such an interior include a wire, a tube, a chain, a wire rope, a spring, and a flat plate that are connected in a vertical direction from the upper part to the lower part of the polymerization vessel. It is preferable that a plurality of such interior items are installed in the polymerization vessel. In order to drop the polymer along the interior, it is also preferable to provide a perforated plate for supplying the polymer at the upper part of the polymerization vessel and connect each hole of the perforated plate to the interior. Other interior items include those of the filler type. Examples of such interiors include Raschig rings, Lessing rings, pole rings, Berle saddles, Interlocks saddles, Dixon packing, McMahon packing, helipacks, sulzer packings, and melapacks.
前段重合器同様、最終段重合器の材質は、鉄を２０％以上含む材質、例えばＳＵＳ３０４，ＳＵＳ３１６，ＳＵＳ３１６Ｌが、入手や加工が容易であり好ましく、また、鉄含有量が２０％以下の材質、例えば、ニッケルやチタン等の非鉄材料を用いた反応器も、着色を防止する効果が期待できて好ましい。
本発明で用いる中間タンクは、上記前段重合器の場合の攪拌型重合器に準じる設備であって、最終段重合器の一つ前の重合器から重合物を受け入れる設備、および、最終段重合器に重合物を払い出す設備が必要である。
中間タンクの使用条件は、温度として５０℃〜３５０℃、好ましくは１００℃〜２９０℃の範囲から選ばれる場合が多く、最終段重合器の重合温度と同一の温度に制御しておくことは、温度変化を無くすることで、本発明の主旨である安定した重合反応を進める一助になることが期待できて好ましい。圧力は常圧で使用することが、設備が簡便で好ましいし、減圧で使用することも、本反応に伴って副生する芳香族モノヒドロキシ化合物を除去できて、少しでも重合を進めることが期待できるため好ましく、窒素などの不活性ガスによって微加圧条件で使用することも、空気などの漏れ込みを防げるために好ましい。
Like the former stage polymerization apparatus, the material of the final stage polymerization apparatus is preferably a material containing 20% or more of iron, for example, SUS304, SUS316, SUS316L, which is easy to obtain and process, and a material having an iron content of 20% or less. For example, a reactor using a non-ferrous material such as nickel or titanium is also preferable because an effect of preventing coloring can be expected.
The intermediate tank used in the present invention is an equipment according to the agitation type polymerizer in the case of the above-mentioned prepolymerizer, an equipment for receiving the polymer from the polymerizer immediately before the final polymerizer, and the final polymerizer It is necessary to provide equipment for discharging the polymer.
The use conditions of the intermediate tank are often selected from the range of 50 ° C. to 350 ° C., preferably 100 ° C. to 290 ° C., and the temperature is controlled to be the same as the polymerization temperature of the final stage polymerization vessel. Eliminating the temperature change is preferable because it can be expected to help promote a stable polymerization reaction that is the gist of the present invention. It is preferable to use the pressure at normal pressure because the equipment is simple and it is expected that the use of the reduced pressure can remove the aromatic monohydroxy compound produced as a by-product in this reaction and proceed the polymerization as much as possible. It is preferable because it can be used, and it is also preferable to use an inert gas such as nitrogen under slightly pressurized conditions in order to prevent leakage of air or the like.
本発明におけるバッファー効果とは、一定の分子量のポリマーを定常的に製造する場合に、原料の重合器への流量や反応温度が僅かに変動しても、製品の分子量が大きく変動しないようにする効果のことである。変動の許容幅は、樹脂を使用する目的によって異なるが、例えば、ポリカーボネート樹脂ハンドブックに拠れば（ポリカーボネート樹脂ハンドブック 本間 精一著 １９９２年８月２８日 日刊工業新聞社 ７５〜８５頁）、ハイフローグレードのポリカーボネート樹脂とは、数平均分子量として、１８０００〜２００００を指し、これが分子量変動の許容幅と考えることができる。他にも、同ハンドブックに拠れば、押出しグレードは２９０００〜３３０００、光ディスクグレードは１５０００〜１６０００となっている。これに倣い、本発明では、変動の幅を±５％まで許容する。 The buffer effect in the present invention means that, when a polymer having a constant molecular weight is constantly produced, the molecular weight of the product does not fluctuate greatly even if the flow rate of the raw material to the polymerization reactor or the reaction temperature slightly varies. It is an effect. The allowable range of fluctuation varies depending on the purpose of using the resin. For example, according to the polycarbonate resin handbook (Polycarbonate resin handbook by Seiichi Honma, August 28, 1992, Nikkan Kogyo Shimbun, pages 75-85) The polycarbonate resin refers to a number average molecular weight of 18000 to 20000, which can be considered as an allowable range of fluctuation in molecular weight. In addition, according to the handbook, the extrusion grade is 2900 to 33000, and the optical disc grade is 15000 to 16000. Following this, in the present invention, the fluctuation range is allowed up to ± 5%.
中間タンクにおける平均滞留時間Ｔは、適切なバッファー効果を得るために重要であり、最終段重合器におけるポリマーの落下時間ｔ（上記反応器内装物の上端から下端までの落下の時間）に対して、上限は２０倍以下、好ましくは１５倍以下、さらに好ましくは１０倍以下である。平均滞留時間Ｔがｔに対して２０倍よりも長い場合には、前段重合器の分子量変動が大きくても、中間タンクで充分に変動を吸収できるため好ましい面もあるのだが、ポリマーの着色やゲル状物の発生が顕著になったり、樹脂の粘度低下が見られる場合があったりするため好ましくない。平均滞留時間Ｔの下限は、０．５倍以上、好ましくは０．８倍以上、さらに好ましくは１．５倍以上である。平均滞留時間Ｔがｔに対して０．５倍よりも小さい場合には、適切なバッファー効果が得られないため好ましくない。 The average residence time T in the intermediate tank is important for obtaining an appropriate buffer effect, and is relative to the polymer fall time t in the final stage polymerization reactor (the time of fall from the upper end to the lower end of the reactor interior). The upper limit is 20 times or less, preferably 15 times or less, and more preferably 10 times or less. In the case where the average residence time T is longer than 20 times as much as t, even if the molecular weight fluctuation of the former stage polymerization vessel is large, there is a preferable aspect because the fluctuation can be sufficiently absorbed in the intermediate tank. This is not preferable because the generation of a gel-like substance becomes remarkable and the viscosity of the resin may be lowered. The lower limit of the average residence time T is 0.5 times or more, preferably 0.8 times or more, and more preferably 1.5 times or more. If the average residence time T is smaller than 0.5 times t, an appropriate buffer effect cannot be obtained, which is not preferable.
さらに、該中間タンクには攪拌設備を設けておくことが好ましい。本発明を工業的に実施する場合には、前段、最終段重合器、ならびに該中間タンクも含めて、設備が大きくなることは避けられず、中間タンク内で温度分布が生じて分子量分布が所定値よりも広がったり、タンク内に樹脂溜りが発生して、長期滞留した樹脂が異物になったりする場合があり、これらの障害を防ぐために、中間タンクを攪拌しておくことが好ましい。
該中間タンクは、バッチ式、連続式のいずれの方式でも運転することができる。
バッチ式で運転する場合には、前段重合器から一旦ポリマーを受け入れたのち、請求項３で規定する平均滞留時間内で保持し、好ましくは攪拌した状態で保持し、最終段重合器に払い出す。
Furthermore, it is preferable to provide a stirring facility in the intermediate tank. When the present invention is industrially implemented, it is inevitable that the equipment including the preceding stage, the final stage polymerization apparatus, and the intermediate tank will be large, and a temperature distribution is generated in the intermediate tank, so that the molecular weight distribution is predetermined. In order to prevent these obstacles, it is preferable to stir the intermediate tank in some cases.
The intermediate tank can be operated in either a batch type or a continuous type.
In the case of operating in a batch mode, after once receiving the polymer from the former stage polymerizer, the polymer is held within the average residence time defined in claim 3, preferably in a state of being stirred, and discharged to the final stage polymerizer. .
連続式で運転する場合には、受け入れ、払い出しとも連続して行い、本発明を工業的実施する場合には好ましい方式である。
連続式の場合、平均滞留時間の定義は、中間タンク内のポリマー溶融液部体積［ｍ３］を前段重合器からのポリマー受け入れ速度［ｍ３／ｈｒ］で割り返した値を以って定義する。
最終段重合器におけるポリマーの平均滞留時間は、公知の方法で測定することが可能であり、例えば、重合器入口において、投入ポリマーに色素や電解質などマーカーを微量パルス投入し、重合器出口でマーカーの色濃度やポリマーの電気伝導度を測定する方法、最終段重合器の運転開始時に、供給口に最初のポリマーを投入してから、排出口から最初にポリマーが出てくるまでの時間を測定する方法、最終段重合器の運転終了時に、ポリマーの投入を停止してから、最後にポリマーが出終わるまでの時間を測定する方法などが例示される。
In the case of continuous operation, both acceptance and withdrawal are performed continuously, which is a preferred method for industrial implementation of the present invention.
In the case of the continuous type, the definition of the average residence time is defined by a value obtained by dividing the polymer melt portion volume [m 3 ] in the intermediate tank by the polymer receiving speed [m 3 / hr] from the pre-stage polymerizer. To do.
The average residence time of the polymer in the final stage polymerization apparatus can be measured by a known method. For example, a marker or a small amount of a marker such as a dye or an electrolyte is injected into the input polymer at the inlet of the polymerization apparatus, and the marker is output at the outlet of the polymerization apparatus. Measure the color density and electrical conductivity of the polymer, and measure the time from the introduction of the first polymer to the supply port until the first polymer comes out from the discharge port at the start of the operation of the final stage polymerizer And a method of measuring the time from the end of the introduction of the polymer to the end of the end of the polymer at the end of the operation of the final stage polymerization apparatus.
いずれの測定方法でも、ある程度の誤差を含むことは避けられないし、測定方法間での値も違うことが懸念されるが、本発明者らが工夫を重ねて検討した結果では、それらの誤差や違いは思ったほど大きくはなく、１〜数時間の平均滞留時間に対して、高々２〜３分程度であり、中間タンクの設計上なんら問題とはならなかった。
本発明では、重合工程の温度や減圧度、平均滞留時間等を変更することで、分子量が異なるポリカーボネートを製造できる。また、重合工程に前述の芳香族ジヒドロキシ化合物や、水酸基末端のポリカーボネートプレポリマー（低重合度ポリカーボネート）、前述のジアリールカーボネート類やアリールカーボネート末端のポリカーボネートプレポリマー、ｔ−ブチルフェノールやｔ−オクチルフェノール等の単官能置換フェノール類等公知の末端調節剤を添加することで、水酸基末端比率や末端構造の異なるポリカーボネートを製造することができる。
さらに、重合工程に前述の芳香族ジヒドロキシ化合物類やそれらの重合体や、両末端にヒドロキシル基やカルボシキル基を有する化合物等の共重合成分を添加することで、繰り返し単位や比率の異なるポリカーボネートを製造することができる。
In any measurement method, it is unavoidable that some errors are included, and there is a concern that the values between the measurement methods may be different. The difference was not as great as expected, and it was at most about 2 to 3 minutes with respect to the average residence time of 1 to several hours, and there was no problem in designing the intermediate tank.
In the present invention, polycarbonates having different molecular weights can be produced by changing the polymerization step temperature, the degree of pressure reduction, the average residence time, and the like. In the polymerization step, the above-mentioned aromatic dihydroxy compound, a hydroxyl group-terminated polycarbonate prepolymer (low-polymerization polycarbonate), the aforementioned diaryl carbonates and aryl carbonate-terminated polycarbonate prepolymers, t-butylphenol, t-octylphenol, and the like By adding known terminal regulators such as functionally substituted phenols, polycarbonates having different hydroxyl terminal ratios and terminal structures can be produced.
Furthermore, polycarbonates with different repeating units and ratios are produced by adding copolymer components such as the above-mentioned aromatic dihydroxy compounds, their polymers, and compounds having hydroxyl groups or carboxy groups at both ends to the polymerization process. can do.
本発明で得られたポリカーボネートに触媒失活剤を添加することもできる。
本発明に使用する触媒失活剤としては、公知の触媒失活剤が有効に使用されるが、この中でもスルホン酸のアンモニウム塩、ホスホニウム塩が好ましく、更にドデシルベンゼンスルホン酸テトラブチルホスホニウム塩等のドデシルベンゼンスルホン酸の上記塩類やパラトルエンスルホン酸テトラブチルアンモニウム塩等のパラトルエンスルホン酸の上記塩類が好ましい。またスルホン酸のエステルとしてベンゼンスルホン酸メチル、ベンゼンスルホン酸エチル、ベンゼンスルホン酸ブチル、ベンゼンスルホン酸オクチル、ベンゼンスルホン酸フェニル、パラトルエンスルホン酸メチル、パラトルエンスルホン酸エチル、パラトルエンスルホン酸ブチル、パラトルエンスルホン酸オクチル、パラトルエンスルホン酸フェニル等が好ましく用いられ、就中、ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩が最も好ましく使用される。
A catalyst deactivator can also be added to the polycarbonate obtained in the present invention.
As the catalyst deactivator used in the present invention, known catalyst deactivators are effectively used. Among them, ammonium salts and phosphonium salts of sulfonic acid are preferable, and tetrabutylphosphonium salts of dodecylbenzene sulfonate and the like are more preferable. The above salts of dodecylbenzenesulfonic acid and the above salts of paratoluenesulfonic acid such as parabutylammonium tetrabutylammonium salt are preferred. As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, para Octyl toluenesulfonate, phenyl paratoluenesulfonate, and the like are preferably used, and among them, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used.
これらの触媒失活剤の使用量はアルカリ金属化合物および／またはアルカリ土類金属化合物より選ばれた前記重合触媒１モル当たり０．５〜５０モルの割合で、好ましくは０．５〜１０モルの割合で、更に好ましくは０．８〜５モルの割合で使用することができる。
更に、重合工程にＡＢＳやＰＥＴ等の他樹脂や、安定剤、酸化防止剤、紫外線吸収剤、離型剤、染顔料、難燃剤等の添加剤等を添加することで、さまざまな用途に合わせたポリカーボネート組成物を製造することができる。
更に、これらを組み合わせることで、多様なポリカーボネートを製造できる。
耐熱安定剤や酸化防止剤として、例えば、燐化合物、フェノール系安定剤、有機チオエーテル系安定剤、ヒンダードアミン系安定剤等を挙げることができ、光安定剤や紫外線吸収剤として、例えば、サリチル酸系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、シアノアクリレート系紫外線吸収剤等を挙げることができる。
These catalyst deactivators are used in an amount of 0.5 to 50 mol, preferably 0.5 to 10 mol, per mol of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds. It can be used in a proportion, more preferably in a proportion of 0.8 to 5 mol.
Furthermore, other resins such as ABS and PET, stabilizers, antioxidants, UV absorbers, mold release agents, dyes and pigments, flame retardants, and other additives can be added to the polymerization process to meet various applications. Polycarbonate compositions can be produced.
Furthermore, various polycarbonates can be manufactured by combining these.
Examples of heat stabilizers and antioxidants include phosphorus compounds, phenol stabilizers, organic thioether stabilizers, hindered amine stabilizers, and the like. Examples of light stabilizers and ultraviolet absorbers include salicylic acid ultraviolet rays. Examples thereof include absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.
離型剤としては一般的に知られた離型剤を用いることができ、例えば、パラフィン類などの炭化水素系離型剤、ステアリン酸等の脂肪酸系離型剤、ステアリン酸アミド等の脂肪酸アミド系離型剤、ステアリルアルコール、ペンタエリスリトール等のアルコール系離型剤、グリセリンモノステアレート等の脂肪酸エステル系離型剤、シリコーンオイル等のシリコーン系離型剤等を挙げることができる。
有機系や無機系の顔料や染料を使用することができる。
その他にも、金属不活性化剤、帯電防止剤、滑剤、造核剤など、目的に応じて使用することができる。
これらはいずれも２種以上組み合わせて使用することができる。
これらの添加剤は、直接に、または適当な溶剤またはポリマーに溶解または分散させて、あるいはマスターペレットとして、溶融状態のポリカーボネートに添加、混練する。このような操作を実施するのに用いられる設備に特に制限は無いが、例えば２軸押出機等が好ましく、添加剤を溶液の形で供給する場合はプランジャーポンプ等の定量ポンプが用いられ、添加剤をマスターポリマーの形で供給する場合はサイドフィーダー等が一般に使用される。添加剤を溶剤に溶解または分散させた場合はベント付きの２軸押出機が特に好ましく使用される。
次に、本発明を実施例および比較例によって説明する。
As the release agent, generally known release agents can be used. For example, hydrocarbon release agents such as paraffins, fatty acid release agents such as stearic acid, and fatty acid amides such as stearic acid amide. Examples thereof include alcohol release agents such as stearyl alcohol and pentaerythritol, fatty acid ester release agents such as glycerin monostearate, silicone release agents such as silicone oil, and the like.
Organic and inorganic pigments and dyes can be used.
In addition, a metal deactivator, an antistatic agent, a lubricant, a nucleating agent, and the like can be used depending on the purpose.
Any of these can be used in combination of two or more.
These additives are added or kneaded to the molten polycarbonate directly or dissolved or dispersed in a suitable solvent or polymer, or as master pellets. There are no particular restrictions on the equipment used to carry out such operations, but for example, a twin screw extruder or the like is preferable, and when supplying the additive in the form of a solution, a metering pump such as a plunger pump is used, When supplying an additive in the form of a master polymer, a side feeder or the like is generally used. When the additive is dissolved or dispersed in a solvent, a twin screw extruder with a vent is particularly preferably used.
Next, the present invention will be described with reference to examples and comparative examples.
数平均分子量（以下、Ｍｎと略す）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて行った。テトラヒドロフラン溶媒、ポリスチレンゲルを使用し、標準単分散ポリスチレンの構成曲線から下式による換算分子量較正曲線を用いて求めた。
ＭＰＣ＝０．３５９１ＭＰＳ １．０３８８
（ＭＰＣはポリカーボネートの分子量、ＭＰＳはポリスチレンの分子量）
水酸基末端比率の測定は、ポリカーボネートポリマー０．３ｇを５ｍｌの重水素置換クロロホルムに溶解し、２３℃で１Ｈ−ＮＭＲ（バルカー社製ＥＸ−４００）を用いて末端基を測定した。水酸基末端比率（モル％）は全末端数に対する水酸基の割合により計算した。
The number average molecular weight (hereinafter abbreviated as Mn) was performed using gel permeation chromatography (GPC). A tetrahydrofuran solvent and polystyrene gel were used, and the molecular weight was determined from the standard monodisperse polystyrene composition curve using a reduced molecular weight calibration curve according to the following formula.
M PC = 0.3591 M PS 1.0388
( MPC is the molecular weight of polycarbonate, MPS is the molecular weight of polystyrene)
The hydroxyl group terminal ratio was measured by dissolving 0.3 g of a polycarbonate polymer in 5 ml of deuterium-substituted chloroform and measuring the terminal group at 23 ° C. using 1H-NMR (EX-400 manufactured by VALQUA). The hydroxyl terminal ratio (mol%) was calculated by the ratio of hydroxyl groups to the total number of terminals.
次に、本発明を実施するプロセスの概略を図１に示す。
原料である芳香族ジヒドロキシ化合物とジアリールカーボネートと触媒は、調合槽に投入され混合される。ここまではバッチ操作で行った。混合された調合液は前段重合器に送られて重合し、さらに、ワイヤー型最終段重合器に送られて所望の分子量まで重合反応を進行させた後、ワイヤー型最終段重合器より取り出される。攪拌型前段重合器以降の操作は連続式で行った。
攪拌型重合器は攪拌槽型重合器で、前段攪拌型重合器は内液量２０リットルを維持するように運転する。ワイヤー型前段重合器はワイヤー付多孔板型重合器で、孔径５ｍｍの孔を２０個有する多孔板を備えており、孔の中心から鉛直に２ｍｍ径のＳＵＳ製ワイヤーを重合器下部の液溜めまで垂らしてあり、落下する高さは８ｍである。
Next, an outline of a process for carrying out the present invention is shown in FIG.
The aromatic dihydroxy compound, diaryl carbonate, and catalyst as raw materials are put into a mixing tank and mixed. Up to this point, a batch operation was performed. The mixed preparation liquid is sent to the former stage polymerizer to be polymerized, and further sent to the wire type last stage polymerizer to advance the polymerization reaction to a desired molecular weight, and then taken out from the wire type last stage polymerizer. The operation after the stirring type pre-stage polymerization apparatus was carried out continuously.
The stirring type polymerization apparatus is a stirring tank type polymerization apparatus, and the pre-stage stirring type polymerization apparatus is operated so as to maintain an internal liquid amount of 20 liters. The wire type pre-stage polymerizer is a perforated plate type polymerizer with wire, and is equipped with a perforated plate having 20 holes with a hole diameter of 5 mm. It is hung and the height to fall is 8m.
ワイヤー型最終段重合器は、重合器下部の液溜めの液量が２０リットルに達したら、液量２０リットルを保つように溶融ポリマーを払い出した。
本発明では、攪拌型前段重合器以降の温度圧力条件は以下のように決めて運転した。
攪拌型前段重合器は、反応温度２３５℃、反応圧力９８Ｔｏｒｒである。
ワイヤー型最終段重合器は、反応温度２７２℃、反応圧力０．８Ｔｏｒｒである。
用いた芳香族ジヒドロキシ化合物とジアリールカーボネートはそれぞれ、ビスフェノールＡとジフェニルカーボネートで、いずれも、５０Ｔｏｒｒで真空脱気し、窒素ガスで置換する不活性ガス処理を行った。
In the wire type final stage polymerization apparatus, when the liquid volume in the liquid reservoir at the lower part of the polymerization apparatus reached 20 liters, the molten polymer was discharged so as to maintain the liquid volume of 20 liters.
In the present invention, the temperature and pressure conditions after the stirring type pre-stage polymerization apparatus were determined and operated as follows.
The stirring type pre-stage polymerization reactor has a reaction temperature of 235 ° C. and a reaction pressure of 98 Torr.
The wire type final stage polymerization reactor has a reaction temperature of 272 ° C. and a reaction pressure of 0.8 Torr.
The aromatic dihydroxy compound and diaryl carbonate used were bisphenol A and diphenyl carbonate, respectively, and both were degassed at 50 Torr and treated with an inert gas that was replaced with nitrogen gas.
［実施例１］
調合槽の温度を１４０℃に設定し、窒素ガスを用いて常圧よりも５０Ｔｏｒｒ微加圧した。ジフェニルカーボネート粉体４０．８ｋｇを投入し、溶融させた。次に、ビスフェノールＡ粉体３９．２ｋｇを調合槽に投入した。投入したビスフェノールＡに対する投入したジフェニルカーボネートのモル比は１．１１であった。
このようにして調合した溶融ポリマーを、１０ｋｇ／ｈｒで前段攪拌型重合槽へ移送し、重合に供した。前段攪拌型重合器出口でのポリマーの分子量変動は、表１に示す通りであった。
この樹脂を連続的に中間タンクへ移送した。最終段ワイヤー型重合器の平均滞留時間は２時間だったので、中間タンクでの滞留時間は４ｈで設計した。タンクの温度は２７０℃、窒素で約５０Ｔｏｒｒに微加圧し、攪拌しながらポリマーを保持した。
中間タンクの樹脂は、連続的に最終段ワイヤー型重合器に送り、重合に供し、主に光ディスク向け射出成型グレード（数平均分子量１１，０００〜１３，０００）の芳香族ポリカーボネートを製造した。
製造の途中で意図的に調合槽の温度を１時間だけ１００℃に下げて、またもとの１４０℃に戻し、最終段反応器に供給するポリマーの分子量を変化させた。
前段重合器、および最終段ワイヤー型重合器出口の分子量の変動は表１に示した通りである。
前段重合器出口では、分子量の変動が５％を越えていたのに、最終段重合器の出口では、分子量変動が５％以内に収まっていた。
[Example 1]
The temperature of the compounding tank was set to 140 ° C., and the pressure was slightly increased by 50 Torr from the normal pressure using nitrogen gas. 40.8 kg of diphenyl carbonate powder was charged and melted. Next, 39.2 kg of bisphenol A powder was charged into the preparation tank. The molar ratio of charged diphenyl carbonate to charged bisphenol A was 1.11.
The molten polymer thus prepared was transferred to a pre-stage stirring type polymerization tank at 10 kg / hr and subjected to polymerization. The variation in molecular weight of the polymer at the outlet of the pre-stage agitation polymerizer was as shown in Table 1.
This resin was continuously transferred to an intermediate tank. Since the average residence time of the final-stage wire-type polymerizer was 2 hours, the residence time in the intermediate tank was designed to be 4 hours. The temperature of the tank was 270 ° C., slightly pressurized to about 50 Torr with nitrogen, and the polymer was held while stirring.
The resin in the intermediate tank was continuously sent to the final wire type polymerizer and used for polymerization to produce an injection polycarbonate (number average molecular weight 11,000 to 13,000) aromatic polycarbonate mainly for optical disks.
During the production, the temperature of the compounding tank was intentionally lowered to 100 ° C. for 1 hour and then returned to the original 140 ° C., and the molecular weight of the polymer supplied to the final stage reactor was changed.
The variation in molecular weight at the outlet of the former stage polymerization vessel and the final stage wire type polymerization vessel is as shown in Table 1.
The molecular weight variation at the outlet of the former stage polymerizer exceeded 5%, but the molecular weight variation at the outlet of the final stage polymerizer was within 5%.
［比較例１］
中間タンクを設置しなかった以外は、実施例１と同様の実験を行った。前段攪拌型反応器、最終段ワイヤー型反応器それぞれ出口での分子量変動を表１に示した。最終段重合器の出口でも、分子量変動は５％を越えて、さらに悪化していた。
[Comparative Example 1]
The same experiment as in Example 1 was performed except that no intermediate tank was installed. Table 1 shows the molecular weight fluctuations at the outlets of the front-stage stirred reactor and the final-stage wire reactor. Even at the outlet of the final stage polymerization apparatus, the molecular weight fluctuation exceeded 5% and was further deteriorated.
本発明は、多段重合における前段ポリマーの予期せぬ分子量変動に対しても、それを補償して分子量の変動の少ない芳香族ポリカーボネートを得る製造方法として好適である。 The present invention is suitable as a production method for obtaining an aromatic polycarbonate having a small molecular weight variation by compensating for an unexpected molecular weight variation of a preceding polymer in a multistage polymerization.
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