WO2006025478A1 - 高純度ジアリールカーボネートの工業的製造方法 - Google Patents
高純度ジアリールカーボネートの工業的製造方法 Download PDFInfo
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- WO2006025478A1 WO2006025478A1 PCT/JP2005/015980 JP2005015980W WO2006025478A1 WO 2006025478 A1 WO2006025478 A1 WO 2006025478A1 JP 2005015980 W JP2005015980 W JP 2005015980W WO 2006025478 A1 WO2006025478 A1 WO 2006025478A1
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- WIPO (PCT)
- Prior art keywords
- carbonate
- tower
- column
- distillation column
- boiling point
- Prior art date
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- -1 diaryl carbonate Chemical compound 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 101
- 238000009835 boiling Methods 0.000 claims abstract description 138
- 238000004821 distillation Methods 0.000 claims abstract description 126
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 103
- 238000000926 separation method Methods 0.000 claims abstract description 100
- 238000000066 reactive distillation Methods 0.000 claims abstract description 84
- 239000011541 reaction mixture Substances 0.000 claims abstract description 78
- 238000000746 purification Methods 0.000 claims abstract description 72
- 239000000126 substance Substances 0.000 claims abstract description 70
- 125000003118 aryl group Chemical group 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 36
- 238000001944 continuous distillation Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 72
- 239000003054 catalyst Substances 0.000 claims description 68
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical class C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 238000004519 manufacturing process Methods 0.000 claims description 63
- 238000012856 packing Methods 0.000 claims description 51
- 239000006227 byproduct Substances 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 33
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical class 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 10
- 239000002815 homogeneous catalyst Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 7
- XAQARUVJIHZGKB-UHFFFAOYSA-N COC1=C(C(=O)O)C=CC=C1.OC1=CC=CC=C1 Chemical compound COC1=C(C(=O)O)C=CC=C1.OC1=CC=CC=C1 XAQARUVJIHZGKB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 abstract description 25
- 229920000515 polycarbonate Polymers 0.000 abstract description 25
- 239000007858 starting material Substances 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 27
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 22
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 238000010992 reflux Methods 0.000 description 14
- 239000012535 impurity Substances 0.000 description 13
- ULSJTMWWIWWXIW-UHFFFAOYSA-N carbonic acid;phenol Chemical compound OC(O)=O.OC1=CC=CC=C1.OC1=CC=CC=C1 ULSJTMWWIWWXIW-UHFFFAOYSA-N 0.000 description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 150000002989 phenols Chemical class 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 230000007774 longterm Effects 0.000 description 7
- 239000010936 titanium Substances 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 5
- DHBPAQUDNKLCEJ-UHFFFAOYSA-N 2-hydroxybenzoic acid;phenol Chemical compound OC1=CC=CC=C1.OC(=O)C1=CC=CC=C1O DHBPAQUDNKLCEJ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004255 ion exchange chromatography Methods 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- BBSRDVDCIHLOTJ-UHFFFAOYSA-N benzoic acid phenol Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)C(=O)O BBSRDVDCIHLOTJ-UHFFFAOYSA-N 0.000 description 3
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007323 disproportionation reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- ILUJQPXNXACGAN-UHFFFAOYSA-N ortho-methoxybenzoic acid Natural products COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 3
- 229960000969 phenyl salicylate Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- MJKVTPMWOKAVMS-UHFFFAOYSA-N 3-hydroxy-1-benzopyran-2-one Chemical compound C1=CC=C2OC(=O)C(O)=CC2=C1 MJKVTPMWOKAVMS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- PXSSNPBEHHJLDH-UHFFFAOYSA-N 2,3,4,5-tetramethylphenol Chemical compound CC1=CC(O)=C(C)C(C)=C1C PXSSNPBEHHJLDH-UHFFFAOYSA-N 0.000 description 1
- XRUGBBIQLIVCSI-UHFFFAOYSA-N 2,3,4-trimethylphenol Chemical compound CC1=CC=C(O)C(C)=C1C XRUGBBIQLIVCSI-UHFFFAOYSA-N 0.000 description 1
- HRQPPTDGMMGDKC-UHFFFAOYSA-N 2,3-dipropylphenol Chemical compound CCCC1=CC=CC(O)=C1CCC HRQPPTDGMMGDKC-UHFFFAOYSA-N 0.000 description 1
- ASLNDVUAZOHADR-UHFFFAOYSA-N 2-butyl-3-methylphenol Chemical compound CCCCC1=C(C)C=CC=C1O ASLNDVUAZOHADR-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 description 1
- OCKYMBMCPOAFLL-UHFFFAOYSA-N 2-ethyl-3-methylphenol Chemical compound CCC1=C(C)C=CC=C1O OCKYMBMCPOAFLL-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical compound CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- FCUBUGPGVCEURB-UHFFFAOYSA-N 3-methyl-2-propylphenol Chemical compound CCCC1=C(C)C=CC=C1O FCUBUGPGVCEURB-UHFFFAOYSA-N 0.000 description 1
- 241000534000 Berula erecta Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010016717 Fistula Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- WQULVXNWEYLDJY-UHFFFAOYSA-N bis(2-chloroethyl) carbonate Chemical compound ClCCOC(=O)OCCCl WQULVXNWEYLDJY-UHFFFAOYSA-N 0.000 description 1
- GHBMZJNWOWVWCP-UHFFFAOYSA-N bis(2-cyanoethyl) carbonate Chemical compound N#CCCOC(=O)OCCC#N GHBMZJNWOWVWCP-UHFFFAOYSA-N 0.000 description 1
- STLGQBDVSTWGIP-UHFFFAOYSA-N bis(2-methoxyethyl) carbonate Chemical compound COCCOC(=O)OCCOC STLGQBDVSTWGIP-UHFFFAOYSA-N 0.000 description 1
- BUEBPZHICJLZNL-UHFFFAOYSA-N bis(methoxymethyl) carbonate Chemical compound COCOC(=O)OCOC BUEBPZHICJLZNL-UHFFFAOYSA-N 0.000 description 1
- AGAJWGOEYSXAFN-UHFFFAOYSA-N bis[methoxy(phenyl)methyl] carbonate Chemical compound C=1C=CC=CC=1C(OC)OC(=O)OC(OC)C1=CC=CC=C1 AGAJWGOEYSXAFN-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AJHQRWJZHVBYLU-UHFFFAOYSA-N dicyclopentyl carbonate Chemical compound C1CCCC1OC(=O)OC1CCCC1 AJHQRWJZHVBYLU-UHFFFAOYSA-N 0.000 description 1
- ZEBJPYUECLCDRQ-UHFFFAOYSA-N didecyl carbonate Chemical compound CCCCCCCCCCOC(=O)OCCCCCCCCCC ZEBJPYUECLCDRQ-UHFFFAOYSA-N 0.000 description 1
- ZYKOICDLSSOLAN-UHFFFAOYSA-N diheptyl carbonate Chemical compound CCCCCCCOC(=O)OCCCCCCC ZYKOICDLSSOLAN-UHFFFAOYSA-N 0.000 description 1
- OKQDSOXFNBWWJL-UHFFFAOYSA-N dihexyl carbonate Chemical compound CCCCCCOC(=O)OCCCCCC OKQDSOXFNBWWJL-UHFFFAOYSA-N 0.000 description 1
- FHWFURWDUGYUMA-UHFFFAOYSA-N dinonyl carbonate Chemical compound CCCCCCCCCOC(=O)OCCCCCCCCC FHWFURWDUGYUMA-UHFFFAOYSA-N 0.000 description 1
- PKPOVTYZGGYDIJ-UHFFFAOYSA-N dioctyl carbonate Chemical compound CCCCCCCCOC(=O)OCCCCCCCC PKPOVTYZGGYDIJ-UHFFFAOYSA-N 0.000 description 1
- HSNQKJVQUFYBBY-UHFFFAOYSA-N dipentyl carbonate Chemical compound CCCCCOC(=O)OCCCCC HSNQKJVQUFYBBY-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IZYBEMGNIUSSAX-UHFFFAOYSA-N methyl benzenecarboperoxoate Chemical compound COOC(=O)C1=CC=CC=C1 IZYBEMGNIUSSAX-UHFFFAOYSA-N 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical class OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical class O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/16—Fractionating columns in which vapour bubbles through liquid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Definitions
- the present invention relates to an industrial process for producing high-purity diaryl carbonate. More specifically, the reaction mixture containing alkylaryl carbonate obtained by transesterification of dialkyl carbonate and aromatic monohydroxy compound is used as a raw material, and transesterification is carried out in a reactive distillation column having a specific structure. The resulting reaction mixture containing diaryl carbonate was separated and purified using a continuous multistage distillation column having two specific structures, and high-purity diaryl carbonate useful as a raw material for transesterification polycarbonate was industrially produced. It relates to a method of manufacturing.
- High-purity diaryl carbonate is important as a raw material for producing aromatic polycarbonate, which is the most demanding engineering plastic, without using toxic phosgene.
- a method for producing an aromatic carbonate a method of reacting an aromatic monohydroxy compound with phosgene has been known for a long time, and various studies have been made recently.
- the aromatic carbonate produced by this method has chlorinated impurities that are difficult to separate, and cannot be used as a raw material for aromatic polycarbonate as it is. .
- Lewis acids such as transition metal halides or compounds that generate Lewis acids
- Patent Document 1 JP-A-51-105032, JP-A-56-123948, JP-A-56-123949
- Gazette West German Patent Publication No. 2528412, British Patent No. 1499530, US Patent No. 4182726
- Japanese Patent Laid-Open No. 51-75044 West German Patent Publication No. 2552907, US Patent No. 4045464) Description
- tin compounds such as organotin alkoxides and organic stanoxides
- Patent Document 2 JP 54-48733 A (West German Patent Publication No. 2736062), JP 54-63023 A, Kokai 60-169444 (U.S. Pat.
- Patent Documents JP-A-60-169445 (U.S. Pat. No. 4,552,704), JP-A-62-277345, JP-A-1- 265063), alkali metal or alkaline earth metal salts and alkoxides (Patent Documents) 3: JP-A-57-176932), lead compounds (Patent Document 4: JP-A-57-176932, JP-A-1-93560), copper, iron, zirconium and other metals Complexes (Patent Document 5: JP-A-57-183745), titanic acid esters (Patent Document 6: JP-A-58-185536 (US Pat. No.
- Patent Document 7 Japanese Patent Laid-Open No. 60-173016 (US Pat. No. 460 9501)), Sc, Mo, Mn, Bi, Te and other compounds (patents)
- Patent Document 8 JP-A-1-265 064
- ferric acetate Patent Document 9: JP-A-61-172852
- Patent Document 10 JP-A-54-48732 (West German Patent Publication No. 736). 063, US Pat. No. 4,252,737)
- Patent Document 11 Japanese Patent Laid-Open No. 58-185536 (US Pat. No. 410464)
- Patent Document 12 Examples of JP-A-56-123948 (US Pat. No. 4,182,726)), Examples of JP-A-56-25138, JP-A-60-169444 (US Pat. No. 4554110), Example of JP-A-60-169445 (U.S. Pat.No. 4,552,704), Example of JP-A-60-173016 (U.S. Pat.No. 4,609,501) Examples, Examples of JP-A 61-172852, Examples of JP-A 61-291545, Examples of JP-A 62-277345).
- the inventors of the present invention continuously supply dialkyl carbonate and aromatic hydroxy compound to a multistage distillation column, and continuously react in the column in the presence of a catalyst to produce by-produced alcohol.
- a low-boiling component containing nitrogen is continuously extracted by distillation, and a component containing the generated alkylaryl carbonate is extracted from the bottom of the column (Patent Document 13: Japanese Patent Publication No. Hei 3-291257), and alkylaryl carbonate is continuously extracted.
- Patent Document 14 Japanese Patent Laid-Open No. 4-9358. These reactions are carried out using two continuous multistage distillation columns to efficiently produce dialkyl carbonate as a by-product. Reactive distillation method for continuously producing diaryl carbonate while recycling it continuously (Patent Document 15: Japanese Patent Laid-Open No.
- Patent Document 17 International Publication No. 00Z18720 (US Pat. No. 5,362,901)
- Patent Document 18 Italian Patent No. 01255746
- Patent Document 19 Special Kaihei 6-9506 (European Patent No. 05 60159, US Pat. No. 5,282,965)
- Patent Document 20 Japanese Patent Laid-Open No. 6-41022 (European Patent 0572870, US Pat. No. 5,362,901)
- Patent Document 21 JP-A-6-157424 (European Patent 0582931, US Pat. No.
- Patent Document 23 Japanese Patent Laid-Open No. 9-40616
- Patent Document 24 Japanese Patent Laid-Open No. 9-59225
- Patent Document 25 Japanese Patent Laid-Open No. 9-110805
- Patent Document 26 Japanese Patent Laid-Open No. 9-165357
- Patent Document 27 JP-A-9-173819
- Patent Document 28 JP-A-9-176094, JP2000-191596, JP2000-191597
- Patent Document 29 JP-A-9- 194 436 (European Patent 0785184, US Pat. No.
- Patent Reference 30 International Publication No. 00Z18720 (US Patent No. 6093842), International Publication No. 01Z042187 (Special Table No. 2003-516376); Patent Reference 31: Japanese Unexamined Patent Publication No. 20-01-64234, Japanese Unexamined Patent Publication No. 2001-64235 gazette; Patent Document 32: International Publication No. 02Z4 0439 gazette (US Pat. No. 6,596,894, US Pat. No. 6596895, US Pat. No. 660,0061).
- the applicant of the present invention is a high-boiling point containing a catalyst component as a method for stably producing a high-purity aromatic carbonate for a long time without requiring a large amount of catalyst.
- a method of separating a substance after reacting with an active substance and recycling a catalyst component Patent Document 33: WO 97Z11049 (European Patent 0855384, US Pat. No. 58 72275))
- Patent Document 34 Japanese Patent Laid-Open No. 11-92429 (European Patent No. 1016648) US Pat. No. 6,622,210)
- Patent Document 35 JP-A-9-255772 (European Patent 0892001, US Pat. No. 5,747,609)).
- the reaction mixture containing the catalyst is flash-distilled with an evaporator, etc., and separated into a low-boiling substance and a high-boiling substance containing most of the catalyst, and then the low-boiling substance is distilled in a distillation column for recovering the raw material.
- a method for obtaining diphenyl carbonate containing a catalyst as a bottom substance and distilling it in a purification tower to obtain diphenyl carbonate as a top component Patent Document 37: JP-A-4 100824, Examples) 1; Patent Document 38: JP-A-9 169704
- the reaction mixture containing the catalyst is distilled in a distillation column (and an evaporator) and separated into a low-boiling substance and a high-boiling substance containing most of the catalyst.
- a distillation column and an evaporator
- Examples thereof include a method (Patent Document 25) in which distillate carbonate is obtained as a top component by sequentially performing continuous distillation using a distillation apparatus having a three-column power of a phenyl carbonate separation tower and a diphenyl carbonate separation tower.
- Another method is a method of obtaining diaryl carbonate as a bottom component of a distillation column, for example,
- the reaction mixture containing the catalyst is distilled in a distillation tower and separated into a low-boiling substance and a high-boiling substance containing most of the catalyst, and then the low-boiling substance is distilled in a distillation tower and diphenyl is used as a bottom component.
- Examples thereof include a method for obtaining carbonate (Patent Document 31).
- Another method is a method of obtaining diaryl carbonate as a side cut component of a distillation column.
- diphenyl carbonate is heated to a high temperature at the bottom of two distillation towers, a light boiling separation tower and a methylphenyl carbonate separation tower, and then exposed to a high temperature in a diphenyl carbonate separation tower.
- modification of diphenyl carbonate occurs, resulting in a decrease in purity and a decrease in yield.
- the method of obtaining diphenol carbonate from the bottom of the column of IV is not suitable because the target polycarbonate cannot be produced because of its low purity.
- a reaction mixture containing all of the catalyst, unreacted raw materials, impurities, and the like is introduced from the top of the third reactive distillation column from the bottom of the second reactive distillation column. Since the phenol carbonate is extracted, the purity of the diphenol carbonate from which the vapor and mist of catalyst, impurities and raw materials can be entrained is low.
- the production amount of diphenyl carbonate is 6.7 kgZhr (Patent Document 34, Example 3) and 3.9 kg / hr (Patent Document 35, Example 1), which is not an industrial scale.
- the method VII) is a preferable method, but the production amount of diphenyl carbonate is as small as 2 kgZhr (Patent Document 40, Example 8) and is not an industrial scale.
- the top pressure of the first purification column is high at 200 Pa, it is difficult to implement industrially because it requires a very large distillation column that can maintain a high vacuum.
- Patent Document 36 Example 2
- this example is produced by the phosgene method, and it is a purification method of diphenyl carbonate that always contains chlorine impurities. There is no mention of adverse effects. In this method, it is not sufficient to separate these chlorinated impurities, and it cannot be used as a raw material for polycarbonate. This is because Patent Document 41 (Japanese Patent Laid-Open No. 11-12230) filed more than one year after Patent Document 36.
- Comparative Example 1 Alkali Hot Water Washing 2 times then Hot Water Washing. Then, diphenyl carbonate dehydrated by distillation was passed through a solid alkali packed column and then distilled under reduced pressure in a multistage distillation column). Column not used).
- Patent Document 36 as a method for evaluating the purity of diphenol carbonate obtained by distillation, the temperature and time at which phenol reacts with bisphenol A and begins to distill is shown.
- the test method cannot evaluate diphenyl carbonate suitable for polymerization. This is because even in low-purity diphenyl carbonate, which cannot produce a polycarbonate having the required degree of polymerization, the reaction of eliminating the initial phenol is sufficient.
- this evaluation method uses a large amount of 2.3 ppm of NaOH relative to bisphenol A as the catalyst. For example, diphenol carbonate containing 1 ppm of chlorinated impurities has high purity. It will be mistakenly evaluated as suitable as a raw material for polycarbonate.
- the diphenyl carbonate having the necessary purity as a raw material for polycarbonate is obtained by the purification method of Patent Document 36.
- the purification amount of diphenyl carbonate disclosed in Patent Document 36 is 0.57 kgZhr, which is not an industrial scale.
- the reaction mixture obtained by the transesterification reaction using dialkyl carbonate and phenol as raw materials in the presence of a homogeneous catalyst usually contains various reaction by-products.
- High boiling point by-products such as salicylic acid phenol, xanthone, methoxybenzoic acid phenol, 1 phenoxy carboluene, 2-phenoxy power, lupoxy phenol, etc., which have a higher boiling point than carbonate, are reduced to a sufficient level.
- diphenol carbonate is used as a raw material for the transesterification polycarbonate, it may cause coloration and deterioration of physical properties. Therefore, it is preferable to reduce these impurities as much as possible.
- the problem to be solved by the present invention is to use a reaction mixture containing an alkylaryl carbonate obtained by transesterification of a dialkyl carbonate and an aromatic monohydroxy compound as a raw material, and as a raw material for a high-quality, high-performance polycarbonate.
- the purpose is to provide a specific method for producing a high-purity diaryl carbonate that can be used stably on an industrial scale of 1 ton Zhr or more for a long period of time.
- the present inventors disclosed a method for producing aromatic carbonates using a continuous multistage distillation column, there have been many proposals relating to a method for producing a reaction mixture containing aromatic carbonates by a reactive distillation method or the like. These are all small-scale and short-term laboratory levels, and therefore, the reaction mixture power is also high-quality high-performance polycarbonate that can be used as a raw material for high-performance polycarbonate on an industrial scale. We have not been able to disclose concrete methods and devices that can be mass-produced. Therefore, the present inventors are able to produce a high-purity diaryl carbonate, which is important as a raw material for high-quality and high-performance polycarbonate, on an industrial scale of 1 ton or more per hour. As a result of repeated studies to find a method, the present invention has been achieved.
- a reaction mixture containing an alkylaryl carbonate obtained by transesterification of a dialkyl carbonate and an aromatic monohydroxy compound is used as a raw material, and this raw material is composed of a continuous multistage distillation column in which a homogeneous catalyst exists. Continuously fed into the reactive distillation column The low-boiling point reaction mixture containing the dialkyl carbonate to be produced is simultaneously extracted in the column from the upper part of the column in a gaseous state, and the high-boiling point reaction mixture containing diaryl carbonate is removed from the lower part of the column.
- the liquid is continuously withdrawn, and the high-boiling reaction mixture is continuously introduced into the high-boiling-point material separation tower A, and is added to the top component (A) containing diaryl carbonate and the bottom component (A) containing catalyst. Continuously distilled off and then the top of the column
- Ingredient (A) is continuously fed to a diaryl carbonate purification tower B having a side cut outlet.
- the reactive distillation column is a continuous multi-stage distillation column satisfying the following formulas (1) to (6), having a length L (cm), an inner diameter D (cm), and an internal number n of stages.
- the diaryl carbonate purification tower B satisfies the following formulas (10) to (15), has a length of 1 ⁇ (cm), an inner diameter D (cm), and has an internal inside.
- To the middle of the tower There is a side cut outlet B2 between the inlet Bl and the inlet Bl and the bottom of the tower, the number of internal stages on the upper side from the inlet B1 is n, and between the inlet Bl and the side cut outlet B2 The number of internal stages is n, and the number of internal stages below the side cut outlet B2 is
- n is a continuous multi-stage distillation column in which the total number of plates (n + n + n) is n,
- T 190-240 o C
- P 2000-15000 Pa
- Dingka 190-240 o C
- P 2000-1
- the reactive distillation tower, the high-boiling point substance separation tower A, and the diaryl carbonate purification tower B are distillation towers each having a tray and Z or packing as the internal.
- a distillation column having a packing at the top and a tray at the bottom as the reactive distillation column force internal, and the internals of the high boiling point substance separation column A and the diaryl carbonate purification column B are respectively packed.
- tray of the reactive distillation column is a perforated plate tray having a perforated plate portion and a downcomer portion.
- the diaryl carbonate produced by the method according to any one of 1 to 9 above is an unsubstituted or lower hydrocarbon-substituted diphenol carbonate, wherein the halogen content of the diphenyl carbonate is 0. high-purity diphenyl carbonate having a content of by-products of not more than lppm and having a boiling point higher than that of diphenol carbonate of not more than lOOppm,
- the diphenyl carbonate is unsubstituted diphenyl carbonate, the halogen content is less than lOppb, and the by-products having higher boiling point than diphenyl carbonate, phenyl salicylate, xanthone, methoxybenzoic acid
- the halogen content is less than lppb and has a higher boiling point than diphenyl carbonate. 13.
- a reaction mixture containing an alkylaryl carbonate obtained by transesterification of a dialkyl carbonate and an aromatic monohydroxy compound is introduced as a raw material.
- the transesterification and distillation are simultaneously performed in the column, and the low boiling point reaction mixture containing the dialkyl carbonate to be produced is withdrawn in the form of gas from the top of the column, and the high boiling point reaction mixture containing the dialyl carbonate from the bottom of the column.
- Reactive distillation tower for extracting liquid in a liquid state
- the high-boiling point reaction mixture is introduced and contacted with the top component (A) containing diaryl carbonate.
- High-boiling substance separation connected to the reactive distillation column by distillation separation to the bottom component (A) containing the medium
- Diaryl Carbonate which is separated into three components, the Dokat component (B) and the bottom component (B).
- the reactive distillation column is a continuous multi-stage distillation column satisfying the following formulas (1) to (6), having a length L (cm), an inner diameter D (cm), and an internal number n of stages.
- n is a continuous multistage distillation column where the total number of plates (n + n + n) is n.
- the manufacturing apparatus according to 14 or 15 above which is 5000 Pa,
- the reactive distillation column, the high boiling point substance separation column A, and the diaryl carbonate purification column B are distillation columns each having a tray and Z or a packing as the internal, respectively, Thru
- a distillation column having a packing at the top and a tray at the bottom as the reactive distillation column force internal, and the internals of the high boiling point substance separation column A and the diaryl carbonate purification column B are respectively packed.
- the manufacturing apparatus according to any one of the preceding items 14 to 17, characterized in that:
- the filler is at least one kind of rule filler in which a mela pack, gem pack, techno bag, flexi pack, sulzer packing, good roll packing, and glitch grid force are also selected.
- tray of the reactive distillation column is a perforated plate tray having a perforated plate portion and a downcomer portion.
- a high-quality, high-performance polycarbonate raw material is obtained from a reaction mixture containing an alkylaryl carbonate obtained by a transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound.
- Purity dialyl power-Bonate on an industrial scale of over 1 ton per hour, preferably over 2 ton per hour, more preferably over 3 ton per hour, over 2000 hours, preferably over 3000 hours, It has been found that it can be produced stably for a long period of time, preferably 5000 hours or more.
- the dialkyl carbonate used in the present invention is represented by the general formula (16).
- R 1 represents an alkyl group having 1 to 10 carbon atoms, an alicyclic group having 3 to 10 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms.
- R 1 include methyl, ethyl, propyl (each isomer), allyl, butyl (each isomer), butenyl (each isomer), pentyl (each isomer), hexyl (each Isomers), heptyl (each isomer), octyl (each isomer), nonyl (each isomer), decyl (each isomer), alkyl group such as cyclohexylmethyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl Cycloheptyl and other alicyclic groups; aralkyl groups such as benzyl, phenethyl (each isomer), phenyl
- alkyl groups, alicyclic groups, and aralkyl groups may be substituted with other substituents such as a lower alkyl group, lower alkoxy group, cyan group, halogen, etc., or unsaturated. Have a bond.
- dialkyl carbonates having R 1 examples include dimethyl carbonate, jetyl carbonate, dipropyl carbonate (each isomer), diallyl carbonate, dibutenyl carbonate (each isomer), and dibutyl.
- R 1 is preferably a dialkyl carbonate composed of an alkyl group having 4 or less carbon atoms not containing halogen, particularly preferably! / Is dimethyl carbonate, which is preferably used in the present invention.
- dialkyl carbonates are preferred among the preferred dialkyl carbonates, more preferred are dialkyl carbonates produced in a state substantially free of halogen! /, For example, alkylene carbonates substantially free of halogen. Alcohol power substantially free of halogen and halogen is also produced.
- the aromatic monohydroxy compound used in the present invention is represented by the following general formula (17), and if the hydroxyl group is directly bonded to the aromatic group, It can be anything.
- Ar 1 represents an aromatic group having 5 to 30 carbon atoms.
- aromatic monohydroxy compounds having Ar 1 include phenol; talesol (each isomer), xylenol (each isomer), trimethylphenol (each isomer), tetramethylphenol (each isomer), Ethylphenol (each isomer), Propylphenol (each isomer), Butylphenol (each isomer), Jetylphenol (each isomer), Methylethylphenol (each isomer), Methylpropylphenol (each Isomers), dipropylphenol (each isomer), methylbutylphenol (each isomer), pentylphenol (each isomer), hexylphenol (each isomer), cyclohexylphenol (each isomer), etc.
- alkylphenols various alcohols such as methoxyphenol (each isomer) and ethoxyphenol (each isomer) Phenols; arylalkylphenols such as phenolpropylphenol (each isomer); naphthol (each isomer) and various substituted naphthols; hydroxypyridine (each isomer), hydroxycoumarin (each isomer), Heteroaromatic monohydroxy compounds such as hydroxyquinoline (each isomer) are used.
- aromatic monohydroxy compounds those preferably used in the present invention are unsubstituted and substituted phenols in which Ar 1 also has an aromatic group having 6 to 10 carbon atoms. Unsubstituted phenol.
- aromatic monohydroxy compounds those that are preferably used in the present invention are those that do not substantially contain halogen.
- the amount ratio of the dialkyl carbonate and the aromatic monohydroxy compound used in is required to be 0.5 to 3 in terms of molar ratio. Outside this range, the remaining amount of unreacted substances is increased relative to the required amount of alkylaryl carbonate, which is not efficient, and a large amount of energy is required to recover them. In this sense, the molar ratio is more preferably 0.5 to 5 force S, and more preferably 1 to 3.
- the catalyst used in the present invention contains a metal such as Pb, Cu, Zn, Fe, Co, Ni, Al, Ti, V, and Sn, and is homogeneously dissolved in the reaction system.
- System catalyst a catalyst species in which these metal components are combined with an organic group is preferably used.
- organic compounds in which these catalyst components are present in the reaction system such as aliphatic alcohols, aromatic monohydroxy compounds, alkylaryl carbonates, diaryl carbonates, dialkyl carbonates, etc. It may be one that has been reacted with, or one that has been heat-treated with raw materials or products prior to the reaction.
- the catalyst used in the present invention is preferably one having high solubility in the reaction solution under the reaction conditions.
- Preferred catalysts in this sense include, for example, PbO, Pb (OH), Pb (OPh); TiCl, Ti (OMe)
- a halogen-free raw material and a catalyst it is particularly preferable to use a halogen-free raw material and a catalyst.
- polycarbonate is used by the ester exchange method. It is important as a raw material for industrial production. This is because, even if the halogen power is present in the polymerization raw material even in an amount less than 1 ppm, the polymerization reaction is inhibited, the physical properties of the produced polycarbonate are lowered, and coloring is caused. is there.
- Any method for producing a reaction mixture containing an alkylaryl carbonate by a transesterification reaction between a dialkyl carbonate and an aromatic monohydroxy compound may be used.
- Particularly preferred for industrial implementation is a method using the continuous multistage distillation column previously proposed by the present inventors as a reactive distillation column.
- Particularly preferred among these methods is the use of dialkyl carbonate and aromatic compounds in the presence of a homogeneous catalyst. Perform transesterification with aromatic monohydroxy compound, continuously extract the reaction mixture containing alcohol at the top, and continuously extract the reaction mixture containing alkylaryl carbonate from the bottom. Is the method.
- the reaction mixture containing the alkylaryl carbonate thus obtained is continuously supplied into a reactive distillation column comprising a continuous multistage distillation column in which a homogeneous catalyst is present.
- the low-boiling reaction mixture containing the dialkyl carbonate produced is simultaneously extracted from the top of the tower in the form of a gas, and the high-boiling reaction mixture containing diaryl carbonate is liquidized from the bottom of the tower. Withdraw continuously.
- this ester exchange reaction the alkoxy group of the alkylaryl carbonate is exchanged with the aryloxy group of the aromatic monohydroxyl compound present in the system, and the alcohol is removed.
- the disproportionation reaction of alkylaryl carbonate occurs mainly.
- reaction mixture containing alkylaryl carbonate used as a raw material in the present invention may have a high purity or may contain other compounds. Including the dialkyl carbonate and Z or aromatic monohydroxy compound used to obtain the alkylaryl carbonate, and the compounds produced in this step and Z or other steps, It may contain reaction by-products such as alcohols, alkylaryl ethers, and diaryl carbonate. It is also a preferable method to use the raw material of the present invention as it is without separating unreacted substances and catalysts from the transesterification reaction mixture of dialkyl carbonate and aromatic monohydroxy compound.
- dialkyl carbonate and aromatic monohydroxy compound used to obtain the alkyl reel carbonate which is the raw material of the present invention is newly introduced into the reaction system.
- dialkyl carbonate and aromatic monohydroxy compound to be produced it is preferred to use those recovered from this step and z or other steps.
- Fig. 1 is a schematic view of a reactive distillation column carried out in one embodiment of the present invention.
- the reactive distillation column used in the above has an end plate part 5 above and below a cylindrical body having a length L (cm) and an inner diameter D (cm), and an internal 6 having n stages inside.
- first inlets 3 in the upper part of the tower and Z or in the middle part, and one or more second inlets 4 above the liquid outlet 2 and at the lower part of the tower It is necessary to be a continuous multistage distillation column, and not only distillation but also reaction is performed simultaneously.
- top of the tower or near the top of the tower used in the present invention means a portion of about 0.25 L downward from the top of the tower, and the term “bottom of the tower or near the bottom of the tower” It means the part up to about 0.25L from the bottom of the tower. “L” is as defined above.
- the reactive distillation column used in the present invention needs to have a specific structure.
- a high boiling point reaction mixture containing diaryl carbonate capable of providing 1 ton or more of high purity diaryl carbonate per hour while simultaneously performing not only distillation but also reaction is prolonged. It is necessary to satisfy various conditions to enable stable production over a period.
- the reactive distillation column is a combination of conditions necessary for advancing the reaction with a high selectivity in a stable manner, rather than just the conditions of the distillation functional power.
- the tower must satisfy the following formulas (1) and (6).
- L (cm) is less than 1500, the reaction rate decreases and the target production volume cannot be achieved.
- the force S is necessary to make L smaller than 8000.
- a more preferable range of L (cm) is 2000 ⁇ L ⁇ 6000, and more preferably 2500 ⁇ L ⁇ 5000.
- D (cm) is smaller than 100, the target production volume cannot be achieved, and D must be smaller than 2000 in order to reduce the equipment cost while achieving the target production volume. is there.
- the more preferable range of D (cm) is 150 ⁇ D ⁇ 1000, and more preferably 200 ⁇ D ⁇ 800.
- LZD When LZD is smaller than 2 or larger than 40, stable operation becomes difficult. Especially when LZD is larger than 40, the pressure difference between the top and bottom of the tower becomes too large, so that long-term stable operation becomes difficult. Since the temperature at the bottom must be increased, side reactions are likely to occur, leading to a decrease in selectivity.
- the more preferable range of LZD is 3 ⁇ LZD ⁇ 30, and more preferably 5 ⁇ LZD ⁇ 15.
- n is less than 10, the reaction rate decreases, the target production amount cannot be achieved, and the facility cost can be reduced while ensuring the reaction rate that can achieve the target production amount. It is necessary to make n smaller than 80. In addition, if n is greater than 80, the pressure difference between the top and bottom of the tower becomes too large, and it becomes difficult to perform long-term stable operation, and the temperature at the bottom of the tower must be increased. Resulting in a decline in rate.
- a more preferred range of n is 15 ⁇ n ⁇ 60, and more preferably 20 ⁇ n ⁇ 50.
- D / d force is smaller, not only will the equipment cost be increased, but also a large amount of gas components will be discharged out of the system, which makes stable operation difficult. The amount becomes relatively small, and the reaction rate is lowered just as stable operation becomes difficult.
- the more preferable range of D / d is 2.5 ⁇ D / d ⁇ 12, and more preferably 3 ⁇ D / d ⁇ 10.
- 2 is 7 ⁇ D / d ⁇ 25, more preferably 9 ⁇ D / d ⁇ 20.
- the long-term stable operation as used in the present invention means that the operation can be continued in a steady state based on the operating condition where there is no piping clogging or erosion for 1000 hours or more, preferably 3000 hours or more, more preferably 5000 hours or more. This means that a predetermined amount of jar reel carbonate is produced while maintaining high selectivity.
- the selectivity of dialyl carbonate in the reactive distillation step of the present invention refers to the reacted alkylaryl carbonate, and in the present invention, it is usually a high selectivity of 95% or more, preferably Can achieve a high selectivity of 97% or more, more preferably 99% or more.
- the continuous multistage distillation column used as the reactive distillation column in the present invention is preferably a distillation column having tray and Z or packing as internal.
- the term “internal” means a portion of the distillation column that actually makes gas-liquid contact.
- Such trays include foam trays, perforated plate trays, valve trays, countercurrent trays, super flack trays, max flack trays, etc.
- Irregular packing such as Berle saddle, Interlocks saddle, Dixon packing, McMahon packing, Helipac, etc. and regular packing such as Melapack, gem knock, Techno back, Flexi pack, Snow leather packing, Good roll packing, Glitch grid .
- n internal plate number used in the present invention means the number of trays in the case of trays, and the theoretical plate number in the case of packing. Therefore, a continuous multi-sheet that has both the tray portion and the portion filled with the filler. In the case of a plate distillation column, n is the sum of the number of trays and the number of theoretical plates.
- the reaction between the alkylaryl carbonate of the present invention and the aromatic monohydroxy compound present in the system has an extremely small equilibrium constant and a slow reaction rate, and is the main reaction.
- the disproportionation reaction of carbonate is also an equilibrium reaction with a small equilibrium constant and a slow reaction rate.
- the internal is a multistage distillation column having both a packing and a tray.
- the portion filled with the packing is installed at the upper part and the tray part is installed at the lower part.
- the packing is a regular packing. Further, it is preferable that one or two or more regular packings are used.
- the regular packing is preferably at least one selected from a mela pack, a gem pack, a techno bag, a flexi pack, a snow leather packing, a good roll packing, and a grip grid.
- the perforated plate tray in which the internal tray has a perforated plate portion and a downcomer portion is particularly excellent in terms of function and equipment cost. It was. It has also been found that it is preferred that the perforated plate tray has 100-: LOOO holes per area lm 2 of the perforated plate portion! More preferably! / The number of fistulas is 120-900 per lm 2 of the area, and more preferably 150-800. It has also been found that the cross-sectional area per hole of the perforated plate lay is preferably 0.5 to 5 cm 2 .
- the cross-sectional area per hole is more preferably 0.7 to 4 cm 2 , and further preferably 0.9 to 3 cm 2 .
- the perforated plate tray has 100 to: LOOO holes per area lm 2 of the perforated plate portion, and the cross-sectional area per hole is 0.5 to 5 cm 2 , It has been found to be particularly preferred.
- the regular packing is at least one selected from a mela pack, a gem pack, a techno bag, a flex pack, a sulza packing, a good roll packing, and a glitch grid, and the perforated plate tray has an area of the perforated plate portion.
- LO 00 has holes, and the cross-sectional area per hole of the perforated plate tray is 0.5 to 5 cm 2. It was. It has been found that by adding the above conditions to the reactive distillation column, the reactive distillation process of the present invention can be achieved more easily. [0050] When the reactive distillation step of the present invention is carried out, a raw material containing alkylaryl carbonate is continuously fed into a continuous multistage distillation column in which a homogeneous catalyst is present, and the reaction and distillation are simultaneously performed in the column.
- the low-boiling point reaction mixture containing dialkyl carbonate and alcohol produced is continuously withdrawn in the form of a gas from the top of the column, and the high-boiling point reaction mixture containing diaryl carbonate as the main reaction product is continuously in liquid form from the bottom of the column.
- diaryl carbonate is continuously produced.
- any method may be used for allowing the catalyst to be present in the reactive distillation column. However, since it is a homogeneous catalyst that dissolves in the raw material and the reaction solution, the position force above the middle portion of the distillation column is high. It is preferable to supply into the distillation column.
- the catalyst solution dissolved in the raw material or the reaction solution may be introduced together with the raw material, or the catalyst solution may be introduced into an introduction locus different from the raw material.
- the amount of catalyst used in the present invention is expressed as a ratio with respect to the total mass of raw materials, which varies depending on the type of catalyst used, the type and ratio of raw materials, the reaction temperature, and the reaction conditions such as reaction pressure. Usually, it is used at 0.0001 to 30% by mass, preferably 0.005 to 10% by mass, more preferably 0.001 to 1% by mass.
- the present invention in order to continuously supply the raw material containing alkylaryl carbonate into the reactive distillation column, it is below the gas outlet at the top of the distillation column, but at the top or middle of the column. Liquid and Z or gas from one or several inlets installed in the It is preferable to supply in the form of a slurry.
- at least one introduction port should be installed between the packed portion and the tray portion. Is preferred.
- the packing has a plurality of regular packing forces of two or more, it is also preferable to install introduction ports at intervals that constitute the plurality of regular packings.
- the reaction time of the transesterification reaction carried out in the present invention is considered to correspond to the average residence time of the reaction liquid in the reactive distillation column. This is because the internal shape and number of stages of the distillation column, the feed rate of the raw material, etc. Depending on the type and amount of the catalyst, reaction conditions, etc., it is usually from 0.01 to: LO time, preferably from 0.05 to 5 hours, more preferably from 0.1 to 3 hours.
- the reaction temperature is usually 100 to 350 ° C, although it varies depending on the type of raw material compound used and the type and amount of the catalyst. In order to increase the reaction rate, it is preferable to increase the reaction temperature. If the reaction temperature is high, side reactions are likely to occur. For example, alkylaryl ether is a fleece transfer product of diaryl carbonate and its ester compound. This is undesirable because by-products such as In this sense, the preferred reaction temperature is in the range of 130 to 280 ° C, more preferably 150 to 260 ° C, more preferably 180 to 240 ° C.
- the reaction pressure varies depending on the type and composition of the starting material used, the reaction temperature, etc., but the normal tower top pressure of 0.1 to 2 X 10 7 Pa can be used. Preferably, it is performed in the range of 10 3 to 10 6 Pa, more preferably 5 ⁇ 10 3 to 10 5 .
- the high boiling point reaction mixture containing diaryl carbonate continuously extracted from the lower part of the reactive distillation column usually contains a catalyst and dialkyl in addition to diaryl carbonate.
- a catalyst and dialkyl in addition to diaryl carbonate.
- By-products include relatively low boiling point by-products such as alkylaryl ethers, alkyl transferyl carbonates and free transition products of diaryl carbonates and their derivatives, diaryl carbonate metabolites, and structures.
- high-boiling by-products such as unknown high-boiling substances.
- reaction by-products are vinyl, methyl salicylate, salicylic acid phenol, xanthone, methoxybenzoic acid phenol, 1 phenolic carboxyl. 2-phenoxycarboxy phenol-ene etc. Usually, they contain a small amount of high-boiling by-products of unknown structure that are thought to have reacted further.
- the high boiling point reaction mixture containing diaryl carbonate continuously extracted from the lower part of the reactive distillation column is continuously introduced into the high boiling point substance separation column A, and the diaryl force-bonate is contained.
- the top component (A) and the bottom component (A) containing the catalyst are continuously separated.
- the tower top component (A) is added to the diaryl carbonate refined having a side cut outlet.
- point substance separation tower A and the diaryl carbonate purification tower B are continuous multistage distillation towers each having a specific structure, and they are used in combination.
- FIG. 2 is a schematic diagram showing an example of a continuous separation / purification apparatus in which a high boiling point substance separation tower A and a dialle carbonate purification tower B for carrying out the present invention are connected.
- Each of the high boiling point substance separation tower A and the diaryl carbonate purification tower B is composed of a continuous multistage distillation tower, and the inside thereof is not limited to the following, but in this example, a predetermined An internal consisting of a regular packing having the number of theoretical plates is installed.
- Each column A and B has the structure described later in order to carry out the purification method and the production method according to the present invention.
- the high boiling point substance separation column A used in the present invention satisfies the following formulas (7) to (9), and has a length L (
- the distillation conditions for the high-boiling point substance separation tower A are as follows: the bottom temperature (T) is 185 to 280 ° C.
- the pressure (P) force is preferably from 10000 to 20000 Pa.
- the diaryl carbonate purification tower B satisfies the following formulas (10) to (15), has a length L (cm), an inner diameter D (cm), and has an internal inside, In the middle of the tower There is a side cut extraction port B2 between the introduction port Bl and the introduction port Bl and the bottom of the tower, the number of internal stages on the upper side from the introduction port B1 is n, and between the introduction port Bl and the side cut extraction port B2 The number of internal stages is n, and the number of internal stages below the side cut outlet B2
- the temperature is ° C and the tower top pressure (P) is 1000 to 20000 Pa.
- the high boiling point reaction mixture containing the dialyl carbonate can be purified from the high purity dial. It has been found that reel carbonate can be stably produced on an industrial scale of 1 ton or more and 50 ton or less for 1 hour, for example, 2000 hours or more, preferably 3000 hours or more, more preferably 5 000 hours or more. It was issued.
- L (cm) is less than 800, the height of internal internals can be limited.
- the range is 1000 ⁇ L ⁇ 2500, more preferably 1200 ⁇ L ⁇ 2000.
- D (cm) is less than 100, the target production cannot be achieved, and the target production is It is necessary to make D smaller than 1000 to reduce the equipment cost while achieving the above.
- the more preferable range of D (cm) is 200 ⁇ D ⁇ 600, and more preferably 250 ⁇
- n is less than 20, the separation efficiency decreases, so that the desired high purity cannot be achieved,
- n should be less than 100.
- n force is greater than 100, the pressure difference between the top and bottom of the tower will increase.
- n is 30 ⁇ n ⁇ 70, and more preferably 35 ⁇ n ⁇ 60
- A is 1
- P is 2000 to 15000 Pa, and more preferably 3000 to 13000 Pa.
- L (cm) is less than 1000, the internal height that can be installed inside can be limited.
- Range is 1500 ⁇ L ⁇ 3000, more preferably 1700 ⁇ L ⁇ 2500
- a more preferred range of D (cm) is 150 ⁇ D ⁇ 500, and even more preferred is 200 ⁇ D
- n is smaller than 20, the separation efficiency of the entire column is lowered, so that the desired high purity is achieved.
- n In order to reduce the equipment cost while achieving the desired separation efficiency, n must be 70. It is necessary to make it smaller. Furthermore, if n is greater than 70, the pressure above and below the tower
- n 25 ⁇ n ⁇ 55, more preferably 3
- N, n, n are respectively 5 ⁇ n ⁇ 20, 12 ⁇ n ⁇ 40, 3 ⁇ n
- the temperature is higher than 280 ° C because a high-boiling by-product is produced during distillation. More preferred T is 19
- P is 2000 to 15000 Pa, and more preferably 3000 to 13000 Pa.
- D may have the same inner diameter from the top to the bottom of the tower.
- the inner diameter may be partially different.
- the inner diameter of the upper part of the column may be smaller or larger than the inner diameter of the lower part of the tower.
- the high boiling point substance separation tower A and the diaryl carbonate purification tower B used in the present invention are distillation towers each having a tray and Z or a packing as internal.
- the term “internal” as used in the present invention means a part of the distillation column that is actually brought into contact with gas and liquid, and is as described above.
- a multi-stage distillation column having both a tray part and a packed part can also be used.
- the high boiling point substance separation column A of the present invention preferably has a packing as an internal, and more preferably a regular packing as a packing. It has also been found that the dial reel carbonate purification tower B is preferably packed as an internal, and more preferably one or more ordered packings. [0074] In the present invention, it is preferable to supply the bottom liquid continuously extracted from the reactive distillation column to the high boiling point substance separation column A as it is.
- the high boiling point reaction mixture is continuously disconnect out from the bottom of the reactive distillation column, usually a dialkyl carbonate, from 0.05 to 2 wt%, an aromatic monohydroxy compound is 1 to 20 mass 0/0, Arukirua reel ether 0.5 0 5-2 mass 0/0, alkyl ⁇ reel carbonate 10 to 45 weight 0/0, di ⁇ reel carbonate Ne over preparative 50 to 80 wt%, 1 to a high boiling point by-products is 0.5 5% by mass, 0.001 to 5% by mass of catalyst is contained.
- the composition of the high boiling point reaction mixture varies depending on the reaction distillation conditions, the type and amount of the catalyst, etc.
- the high boiling point reaction mixture in order to continuously supply the high boiling point reaction mixture into the high boiling point substance separation tower A, one or several places installed below the middle part of the separation tower A It may be supplied in liquid form from the inlet, or it is also preferable to supply it into the tower through a reboiler from a pipe provided in the lower part of the reboiler of the separation tower A.
- the amount of the high-boiling point reaction mixture supplied to the high-boiling-point substance separation tower A depends on the production amount of high-purity diaryl carbonate to be produced, the concentration of diaryl carbonate in the high-boiling point reaction mixture, the separation tower A Varies depending on the separation conditions.
- diaryl carbonate is usually contained in an amount of 50 to 80% by mass, so that high purity diaryl carbonate of 1 ton or 50 ton or less per hour is obtained.
- the amount of the reaction mixture continuously introduced into the high boiling point substance separation tower A varies depending on the diaryl carbonate content, but is about 1.3 to 2 tons Zhr or more and 100 tons or less. .
- the high-boiling point reaction mixture continuously fed to the high-boiling-point substance separation column A is composed of most of the diaryl carbonate and unreacted raw materials, diaryl carbonates such as alkylaryl ether and alkylaryl carbonate.
- diaryl carbonates such as alkylaryl ether and alkylaryl carbonate.
- the top of the tower which is also a major force for compounds with low boiling points Ingredient (A), small amount of diaryl carbonate, catalyst and diaryl carbonate
- bottom component (A) containing point by-products.
- a small amount of Al is present in the bottom component (A).
- Kilaryl carbonate may be included. These organic substances in the bottom component are useful for dissolving the catalyst component and keeping it in a liquid state. The total amount of this bottom component (A) or
- a part of the catalyst is used as a catalyst component for the transesterification reaction and recycled to a transesterification reactor of dialkyl carbonate and aromatic monohydroxy compound and Z or a reactive distillation column as it is.
- an aromatic monohydroxy compound for example, an unsubstituted or low-grade hydrocarbon-substituted phenol
- phenyl salicylate for example, phenyl salicylate, xanthone, methoxybenzoic acid phenol
- Phenyloxycarbons 2-phenyloxycarboxyl-by-products such as phenols and higher boiling point by-products
- lower hydrocarbon-substituted dihydrocarbonates such as lower hydrocarbon-substituted compounds.
- the by-product having higher boiling point and the catalyst component are separated almost completely as the bottom component (A) in this high-boiling substance separation tower A.
- One of the characteristics of the present invention is that the content of the catalyst component can be easily adjusted to 200 ppm or less, preferably 10 ppm or less, more preferably 50 ppm or less.
- the high-boiling by-product is hardly contained in the top component (A), and the introduced reaction mixture
- the composition of the tower top component (A) is usually adjusted to 100% by weight of the tower top component.
- Alkyl carbonate is 0.05 to 2 mass 0/0
- the aromatic monohydroxy compound is 1 to 21 mass 0/0
- alkyl ⁇ reel ether from 0.05 to 2 mass%
- alkyl ⁇ reel carbonate Natick
- the content of high-boiling by-products is usually 200 ppm or less, preferably lOO ppm or less, and more preferably 50 ppm.
- the reflux ratio of the high-boiling point substance separation tower A is in the range of 0.01 to LO, preferably 0.0 to 5 and more preferably 0.1 to 3. It is.
- top component (B) All components having a boiling point lower than that of diaryl carbonate contained in the column are the top component (B).
- the tower top force is continuously extracted, and a small amount of liquid is continuously extracted from the tower bottom.
- the top component (B) contained a small amount of diaryl carbonate, which was supplied.
- the diaryl carbonate in the top component (B) is another distillation column that separates the top component (B).
- the tower bottom component (B) is diaryl carbonate and a small amount of high boiling point concentrated to several percent.
- the amount of the acid salt is very small, and the amount is usually 0.05 to 0.5% based on the supplied dianolate.
- high-purity diaryl carbonate is usually continuously extracted at a flow rate of 1 ton Zhr or more, preferably 3 ton Zhr or more, more preferably 5 ton Z or more and 50 ton or less. This amount usually corresponds to about 90 to 96% of the diaryl carbonate fed to the purification tower B.
- the purity of the diaryl carbonate obtained as the side cut component (B) in the present invention is as follows.
- the present invention is carried out using an alkylaryl carbonate obtained by transesterification of a dialkyl carbonate with phenol or a lower hydrocarbon-substituted phenol, the content of high-boiling impurities is phenyl salicylate or its lower hydrocarbon-substituted product.
- xanthone is 30 ppm or less, preferably 10 ppm or less, more preferably 1 ppm or less, and methoxybenzoic acid phenol or a lower hydrocarbon substitution product thereof.
- high-purity diaryl carbonate used in the present invention is a diaryl carbonate having a purity of 99.9% or more and obtained from dialkyl carbonate and phenol or lower hydrocarbon-substituted phenol as raw materials. In the case of carbonate, it refers to diaryl carbonate having a high boiling point by-product content of lOOppm or less.
- the halogen content of the obtained diaryl carbonate is 0.1 ppm or less, preferably 10 ppm or less, and more preferably. lppb or less.
- the reflux ratio of the diaryl carbonate purification column B is in the range of 0.01 to 10, preferably 0.1 to 8, and more preferably 0.5 to 5. is there.
- the materials constituting the reactive distillation column, the high boiling point substance separation column A, the diaryl carbonate purification column B, and the liquid contact part used in the present invention are mainly metal materials such as carbon steel and stainless steel. A certain force Stainless steel is preferred from the viewpoint of the quality of the dialyl carbonate to be produced.
- the purity and impurity content of diphenyl carbonate are determined by gas chromatography.
- the rogen content was measured by ion chromatography.
- a continuous multi-stage distillation column equipped with a melapack was used as the separation column A.
- Dimethyl carbonate / phenol 1.3 (weight ratio) A reaction mixture containing 18% by mass of methylphenol obtained by transesterification of a mixture of potassium carbonate was used as a raw material. This in raw materials, dimethyl carbonate of 26% by weight, Ryoji sole 6 mass 0/0, phenol 48 wt 0/0, Jifue - includes the Le carbonate 1 weight 0/0, more catalyst Pb (OPh) As about lOOppm was included. This raw material contains
- This raw material was introduced into the reactive distillation column in Fig. 1 at a flow rate of 66 ton Zhr from the raw material introduction port installed between the melapack and the perforated plate tray. Reactive distillation was continuously carried out under the conditions that the temperature at the bottom of the column was 210 ° C., the pressure at the top of the column was 3 ⁇ 10 4 Pa, and the reflux ratio was 0.3. After 24 hours, stable steady operation was achieved.
- composition of the high boiling point reaction mixture continuously withdrawn from the bottom of the tower at 13.1 ton Zhr was 0.1% by mass of dimethyl carbonate, Nord is 0.1 mass 0/0, phenol is 6.3 mass 0/0, Mechirufue - Le carbonate 32.2 wt%, Jifue two Le carbonate 58.6 wt%, the high boiling point by-products including the catalyst 2. 7% by mass.
- the reaction mixture obtained by the above-mentioned reactive distillation is transferred from inlet A1 to separation tower A. Ton Zhr continuously introduced.
- the temperature (T) at the bottom of the tower is set to 206.
- the pressure at the top of the column (P) was 3800Pa, and distillation was continuously performed at a reflux ratio of 0.6.
- the top component (A) is continuously withdrawn at 12.5 tons Zhr through
- the bottom component (A) was continuously extracted at 0.6 ton Zhr.
- the top component (A) is introduced as it is.
- the top component (B) was continuously withdrawn at 5.3 tons Zhr through conduit 26, and conduit 31 was
- the bottom component (B) is continuously withdrawn at 0.03 ton Zhr through the pipe 33 and the side force is
- composition of each component 24 hours after the system was completely stabilized was as follows.
- High-boiling substance containing a high-boiling by-product and a catalyst component such as benzoic acid phenol and 1-phenoxycarbo-l-2-phenoxycarboxy-phenol, higher boiling point by-products than diphenyl carbonate, and 59.0% by mass.
- Salicylic acid, xanthone, and methoxybenzoic acid in the side cut component The content was less than 1 ppm, and 1 phenoloxy 2-phenoxycarboxylene was 4 ppm.
- the halogen content was not more than lppb. From this, it was found that the purity of diphenyl carbonate obtained from the side cut was 99.999% or more. The production amount of this high-purity diphenyl carbonate was 7.17 tons per hour.
- Dimethyl carbonate Z phenol 1.9 (weight ratio)
- a mixture containing 21% by mass of methyl phenol obtained by subjecting the mixture to a transesterification reaction was used as a raw material.
- This raw material was introduced into the reactive distillation column in FIG. 1 at a flow rate of 80 ton Zhr from the raw material introduction port installed between the melapack and the perforated plate tray. Reactive distillation was carried out continuously under the conditions of a column bottom temperature of 205 ° C., a column top pressure of 2 ⁇ 10 4 Pa, and a reflux ratio of 0.5. After 24 hours, stable steady operation was achieved.
- Composition of the high boiling point reaction mixture continuously withdrawn in 11.3 tons Zhr from the bottom are dimethyl carbonate 0.1 wt%, Y two Nord is 0.1 mass 0/0, phenol is 2.5 mass 0/0, Mechirufue - Le carbonate 33.2 wt%, Jifue - Le carbonate 62.5 wt%, the high boiling point by-products including catalyst 1. was 6 wt%.
- the reaction mixture obtained by the above reactive distillation was transferred from the inlet A1 to the separation column A 11.3. Ton Zhr continuously introduced.
- the temperature (T) at the bottom of the tower is set to 205. Distillation was continuously performed at a reflux ratio of 0.7 at a temperature of ° C and the pressure (P) at the top of the column being 4000 Pa.
- the top component (A) was continuously withdrawn at 11.0 tons Zhr through 6,
- the bottom component (A) was continuously extracted at 0.3 ton Zhr.
- the top component (A) is introduced as it is.
- the top component (B) is continuously withdrawn at 4.7 ton Zhr through conduit 26, and conduit 31 is
- the bottom component (B) is continuously withdrawn at 0.03 ton Zhr through the pipe 33 and the side force is
- Ingredient (B) was continuously extracted at 6.27 tons Zhr.
- composition of each component 24 hours after the system was completely stabilized was as follows.
- High-boiling substances containing higher boiling point by-products and catalyst components than diphenyl carbonate such as benzoic acid phenol, 1-phenoxycarbon-2-phenol carboxy-phenol, etc. 59.8% by mass.
- Dimethyl carbonate Z phenol 1.4 (weight ratio)
- a mixture containing 16% by mass of methyl phenyl carbonate obtained by subjecting the mixture to a transesterification reaction was used as a raw material.
- dimethyl carbonate 27 wt%, Ma two ,, one Le 7 mass 0/0, phenol 49 mass 0/0, Jifue - Ri Contact contains Le carbonate 0.5 mass 0/0, further The catalyst power SPb (OPh) was about 200ppm.
- This raw material contains halogen
- This raw material was introduced into the above-mentioned continuous multistage distillation column at a flow rate of 94 ton Zhr from the raw material introduction port installed between the melapack and the perforated plate tray. Reactive distillation was continuously carried out under the conditions that the temperature at the bottom of the column was 215 ° C, the pressure at the top of the column was 2.5 X 10 4 Pa, and the reflux ratio was 0.4. After 24 hours, stable steady operation was achieved. Composition of the high boiling point reaction mixture withdrawn in continuous manner with 17.2 tons Zhr from the bottom are dimethyl carbonate 0.2 wt%, ⁇ - Nord is 0.1 mass 0/0, phenol 6. 6 weight 0/0, Mechirufue - Le carbonate force 2 wt%, diphenyl carbonate 60.1 wt%, the high boiling point by-products including catalyst 2. was 8 wt%.
- the reaction mixture obtained by the above reactive distillation was transferred from the inlet A1 to the separation column A 17.2. Ton Zhr continuously introduced.
- the temperature (T) at the bottom of the tower is 207.
- the top component (A) is continuously withdrawn through 16.4 at 16.4 tons Zhr, and the
- the bottom component (A) was continuously extracted at 0.8 ton Zhr.
- the top component (A) is introduced as it is.
- the bottom temperature (T) is 220 ° C
- the top pressure (P) is 6600 Pa
- distillation is continuously performed at a reflux ratio of 1.49.
- the top component (B) is continuously withdrawn at 7.1 tons Zhr through conduit 26, and conduit 31
- the bottom component (B) is continuously extracted at 0.05 tons Zhr through The cut component (B) was continuously extracted at 9.25 ton Zhr.
- composition of each component 24 hours after the system was completely stabilized was as follows.
- a high-boiling substance containing a by-product having a higher boiling point than diphenyl carbonate such as benzoic acid phenol, 1-phenoxycarbol-2-phenoloxycarboxy-phenylene, and a catalyst component 61.2% by mass.
- the present invention uses a reaction mixture containing an alkylaryl carbonate obtained by transesterification of a dialkyl carbonate and an aromatic monohydroxy compound as a raw material, and has a high purity that can be used as a raw material for a high-quality, high-performance polycarbonate.
- Diaryl carbonate can be suitably used as a specific method for stable production over a long period of time on an industrial scale of 1 ton Zhr or more.
- FIG. 1 is a schematic view showing an example of a reactive distillation column for carrying out the present invention.
- FIG. 2 is a schematic view showing an example of a high boiling point substance separation column A and a diaryl carbonate purification column B for carrying out the present invention, and a continuous separation / purification apparatus in which they are connected.
- an internal having a regular packing force having a predetermined number of theoretical plates is installed inside each continuous multistage distillation column.
- 1 Gas outlet
- 2 Liquid outlet
- 3 Inlet
- 4 Inlet
- 5 End plate
- 6 Internal
- L Body length (cm)
- D Body inner diameter (cm)
- d Gas outlet inner diameter (cm)
- d Liquid outlet inner diameter (cm)
- A1 and B1 Inlet
- B2 Inlet
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Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2005800295308A CN101010285B (zh) | 2004-09-03 | 2005-09-01 | 高纯度碳酸二芳基酯的工业制备方法 |
US11/661,605 US20080064846A1 (en) | 2004-09-03 | 2005-09-01 | Industrial Process for Production of High-Purity Diaryl Carbonate |
JP2006532776A JP4292211B2 (ja) | 2004-09-03 | 2005-09-01 | 高純度ジアリールカーボネートの工業的製造方法 |
BRPI0514693-3A BRPI0514693A (pt) | 2004-09-03 | 2005-09-01 | aperfeiçoamento em um processo industrial para a produção de carbonato de diarila de pureza elevada, carbonato de difenila de pureza elevada, e, aparelho para produzir o mesmo |
EP05776685A EP1787976A4 (en) | 2004-09-03 | 2005-09-01 | METHOD FOR THE PRODUCTION OF HIGH-PURITY DIARYLCARBONATE IN INDUSTRIAL STANDARD |
EA200700546A EA012179B1 (ru) | 2004-09-03 | 2005-09-01 | Промышленный способ получения высокочистого диарилкарбоната, высокочистый дифенилкарбонат и установка для получения высокочистого диарилкарбоната |
Applications Claiming Priority (2)
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JP2004256518 | 2004-09-03 | ||
JP2004-256518 | 2004-09-03 |
Publications (1)
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WO2006025478A1 true WO2006025478A1 (ja) | 2006-03-09 |
Family
ID=36000127
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2005/015980 WO2006025478A1 (ja) | 2004-09-03 | 2005-09-01 | 高純度ジアリールカーボネートの工業的製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20080064846A1 (ja) |
EP (1) | EP1787976A4 (ja) |
JP (1) | JP4292211B2 (ja) |
KR (1) | KR100880141B1 (ja) |
CN (1) | CN101010285B (ja) |
BR (1) | BRPI0514693A (ja) |
EA (1) | EA012179B1 (ja) |
WO (1) | WO2006025478A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009137952A (ja) * | 2007-11-20 | 2009-06-25 | Bayer Materialscience Ag | ジアリールカーボネートを精製する方法 |
US7777067B2 (en) | 2004-07-13 | 2010-08-17 | Asahi Kasei Chemicals Corporation | Industrial process for production of an aromatic carbonate |
US7812189B2 (en) | 2004-08-25 | 2010-10-12 | Asahi Kasei Chemicals Corporation | Industrial process for production of high-purity diphenyl carbonate |
US8044167B2 (en) | 2004-10-14 | 2011-10-25 | Asahi Kasei Chemicals Corporation | Process for production of high-purity diaryl carbonate |
WO2023058681A1 (ja) | 2021-10-05 | 2023-04-13 | 旭化成株式会社 | 高純度ジアリールカーボネートの製造方法 |
JP7566410B2 (ja) | 2021-10-15 | 2024-10-15 | エルジー・ケム・リミテッド | アクリル酸の製造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1762560A4 (en) * | 2004-06-25 | 2008-05-07 | Asahi Kasei Chemicals Corp | PROCESS FOR PRODUCING AROMATIC CARBONATE AT THE INDUSTRIAL SCALE |
US7803961B2 (en) | 2007-02-16 | 2010-09-28 | Sabic Innovative Plastics Ip B.V. | Process for manufacturing dimethyl carbonate |
IN2014DN07584A (ja) | 2007-02-16 | 2015-07-10 | Sabic Innovative Plastics Ip |
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- 2005-09-01 US US11/661,605 patent/US20080064846A1/en not_active Abandoned
- 2005-09-01 KR KR1020077004934A patent/KR100880141B1/ko not_active IP Right Cessation
- 2005-09-01 BR BRPI0514693-3A patent/BRPI0514693A/pt not_active IP Right Cessation
- 2005-09-01 EA EA200700546A patent/EA012179B1/ru not_active IP Right Cessation
- 2005-09-01 CN CN2005800295308A patent/CN101010285B/zh active Active
- 2005-09-01 EP EP05776685A patent/EP1787976A4/en not_active Withdrawn
- 2005-09-01 JP JP2006532776A patent/JP4292211B2/ja active Active
- 2005-09-01 WO PCT/JP2005/015980 patent/WO2006025478A1/ja active Application Filing
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7777067B2 (en) | 2004-07-13 | 2010-08-17 | Asahi Kasei Chemicals Corporation | Industrial process for production of an aromatic carbonate |
US7812189B2 (en) | 2004-08-25 | 2010-10-12 | Asahi Kasei Chemicals Corporation | Industrial process for production of high-purity diphenyl carbonate |
US8044167B2 (en) | 2004-10-14 | 2011-10-25 | Asahi Kasei Chemicals Corporation | Process for production of high-purity diaryl carbonate |
US8044226B2 (en) | 2004-10-14 | 2011-10-25 | Asahi Kasei Chemicals Corporation | Process for production of high-purity diaryl carbonate |
JP2009137952A (ja) * | 2007-11-20 | 2009-06-25 | Bayer Materialscience Ag | ジアリールカーボネートを精製する方法 |
WO2023058681A1 (ja) | 2021-10-05 | 2023-04-13 | 旭化成株式会社 | 高純度ジアリールカーボネートの製造方法 |
KR20240046762A (ko) | 2021-10-05 | 2024-04-09 | 아사히 가세이 가부시키가이샤 | 고순도 디아릴카르보네이트의 제조 방법 |
JP7566410B2 (ja) | 2021-10-15 | 2024-10-15 | エルジー・ケム・リミテッド | アクリル酸の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20070047334A (ko) | 2007-05-04 |
EP1787976A1 (en) | 2007-05-23 |
KR100880141B1 (ko) | 2009-01-23 |
JP4292211B2 (ja) | 2009-07-08 |
CN101010285A (zh) | 2007-08-01 |
EA012179B1 (ru) | 2009-08-28 |
EA200700546A1 (ru) | 2007-10-26 |
EP1787976A4 (en) | 2008-08-13 |
JPWO2006025478A1 (ja) | 2008-05-08 |
CN101010285B (zh) | 2011-03-16 |
BRPI0514693A (pt) | 2008-06-17 |
US20080064846A1 (en) | 2008-03-13 |
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