JP5480514B2 - High molecular weight halogenated polycarbonate compound and process for producing the same - Google Patents
High molecular weight halogenated polycarbonate compound and process for producing the same Download PDFInfo
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- JP5480514B2 JP5480514B2 JP2009074272A JP2009074272A JP5480514B2 JP 5480514 B2 JP5480514 B2 JP 5480514B2 JP 2009074272 A JP2009074272 A JP 2009074272A JP 2009074272 A JP2009074272 A JP 2009074272A JP 5480514 B2 JP5480514 B2 JP 5480514B2
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- 150000001875 compounds Chemical class 0.000 title claims description 36
- 239000004417 polycarbonate Substances 0.000 title claims description 32
- 229920000515 polycarbonate Polymers 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 73
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 48
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 37
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 19
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 18
- -1 halogenated carbonate compound Chemical class 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001246 bromo group Chemical group Br* 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000002619 bicyclic group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002346 iodo group Chemical group I* 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims 1
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 141
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 238000007664 blowing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 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 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 4
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical group OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 4
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- URFNSYWAGGETFK-UHFFFAOYSA-N 4,4'-Dihydroxybibenzyl Chemical compound C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- WPZJSWWEEJJSIZ-UHFFFAOYSA-N 2,6-dibromo-4-[(3,5-dibromo-4-hydroxyphenyl)methyl]phenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1CC1=CC(Br)=C(O)C(Br)=C1 WPZJSWWEEJJSIZ-UHFFFAOYSA-N 0.000 description 1
- WFQDPXQJWBLPPU-UHFFFAOYSA-N 2,6-dibromo-4-[1-(3,5-dibromo-4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)C1=CC(Br)=C(O)C(Br)=C1 WFQDPXQJWBLPPU-UHFFFAOYSA-N 0.000 description 1
- YYDJTJGFHTVGGF-UHFFFAOYSA-N 2,6-dichloro-4-(3,5-dichloro-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1S(=O)(=O)C1=CC(Cl)=C(O)C(Cl)=C1 YYDJTJGFHTVGGF-UHFFFAOYSA-N 0.000 description 1
- WIFDRXSVRSCMMY-UHFFFAOYSA-N 2,6-dichloro-4-[(3,5-dichloro-4-hydroxyphenyl)methyl]phenol Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1CC1=CC(Cl)=C(O)C(Cl)=C1 WIFDRXSVRSCMMY-UHFFFAOYSA-N 0.000 description 1
- BROGUPFIBZPXNW-UHFFFAOYSA-N 2,6-dichloro-4-[1-(3,5-dichloro-4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)C1=CC(Cl)=C(O)C(Cl)=C1 BROGUPFIBZPXNW-UHFFFAOYSA-N 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- XCUMMFDPFFDQEX-UHFFFAOYSA-N 2-butan-2-yl-4-[2-(3-butan-2-yl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=C(O)C(C(C)CC)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)CC)=C1 XCUMMFDPFFDQEX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- KULZKZCXEKWAFG-UHFFFAOYSA-N 2-tert-butyl-4-[2-(3-tert-butyl-4-hydroxyphenyl)propan-2-yl]phenol;2-cyclohexyl-4-[2-(3-cyclohexyl-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1.C=1C=C(O)C(C2CCCCC2)=CC=1C(C)(C)C(C=1)=CC=C(O)C=1C1CCCCC1 KULZKZCXEKWAFG-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- ZGZVGZCIFZBNCN-UHFFFAOYSA-N 4,4'-(2-Methylpropylidene)bisphenol Chemical compound C=1C=C(O)C=CC=1C(C(C)C)C1=CC=C(O)C=C1 ZGZVGZCIFZBNCN-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical group C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- KZMYFIUFUAOZHP-UHFFFAOYSA-N 4-(1-adamantyl)phenol Chemical compound C1=CC(O)=CC=C1C1(C2)CC(C3)CC2CC3C1 KZMYFIUFUAOZHP-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 1
- BHWMWBACMSEDTE-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclododecyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCCCCCCCC1 BHWMWBACMSEDTE-UHFFFAOYSA-N 0.000 description 1
- IJWIRZQYWANBMP-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-propan-2-ylphenyl)propan-2-yl]-2-propan-2-ylphenol Chemical compound C1=C(O)C(C(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)C)=C1 IJWIRZQYWANBMP-UHFFFAOYSA-N 0.000 description 1
- MUUFFRHLUZZMLK-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-propylphenyl)propan-2-yl]-2-propylphenol Chemical compound C1=C(O)C(CCC)=CC(C(C)(C)C=2C=C(CCC)C(O)=CC=2)=C1 MUUFFRHLUZZMLK-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- ZSKBUNLAPXSQAH-UHFFFAOYSA-M benzyl-diethyl-phenylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[N+](CC)(CC)CC1=CC=CC=C1 ZSKBUNLAPXSQAH-UHFFFAOYSA-M 0.000 description 1
- QLRKASHXFNIPLZ-UHFFFAOYSA-M benzyl-dimethyl-phenylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[N+](C)(C)CC1=CC=CC=C1 QLRKASHXFNIPLZ-UHFFFAOYSA-M 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- YXQMBBJITUIBDQ-UHFFFAOYSA-M dodecyl(triethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](CC)(CC)CC YXQMBBJITUIBDQ-UHFFFAOYSA-M 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- CHTGZWZVEFPJEQ-UHFFFAOYSA-N dodecyl-[2-(2-methylphenyl)propan-2-yl]azanium hydroxide Chemical compound [OH-].CC1=C(C([NH2+]CCCCCCCCCCCC)(C)C)C=CC=C1 CHTGZWZVEFPJEQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960004979 fampridine Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- SVHOVVJFOWGYJO-UHFFFAOYSA-N pentabromophenol Chemical compound OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br SVHOVVJFOWGYJO-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ABVVEAHYODGCLZ-UHFFFAOYSA-N tridecan-1-amine Chemical compound CCCCCCCCCCCCCN ABVVEAHYODGCLZ-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- ADZJWYULTMTLQZ-UHFFFAOYSA-N tritylphosphane;hydrobromide Chemical compound [Br-].C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 ADZJWYULTMTLQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、熱安定性の良好な高分子量ハロゲン化ポリカーボネート化合物、かかる高分子量ハロゲン化ポリカーボネート化合物をハロゲン置換二価フェノール及びホスゲンから、ホスゲン化反応終了時までアルカリの総使用量が該二価フェノールに対し、２．０倍モル以下に抑えた上で、アミン類触媒を用いて製造する方法に関する。 The present invention relates to a high molecular weight halogenated polycarbonate compound having good thermal stability, and the total amount of alkali used in the high molecular weight halogenated polycarbonate compound from the halogen-substituted dihydric phenol and phosgene until the end of the phosgenation reaction. On the other hand, the present invention relates to a method of producing using an amine catalyst after being suppressed to 2.0 times mol or less.
特許文献１には、テトラブロモビスフェノールAとホスゲンをアルカリ水溶液および塩化メチレン等の溶媒の存在下、ホスゲン化し、ホスゲン化後に第３級アミンを添加するハロゲン化ポリカーボネート樹脂を製造する方法が提案されている。この方法で報告された重量平均分子量は、最大で５０，０００である（特許文献２にも比較例として試験結果が報告されている）。また、この特許では、触媒としての第３級アミンは、ホスゲン化をはじめる前に添加すると、ホスゲンが分解して、得られるハロゲン化ポリカーボネートの平均分子量が低くなるため、ホスゲン化した後に添加することが好ましいとされている。 Patent Document 1 proposes a method for producing a halogenated polycarbonate resin in which tetrabromobisphenol A and phosgene are phosgenated in the presence of an alkaline aqueous solution and a solvent such as methylene chloride, and a tertiary amine is added after phosgenation. Yes. The maximum weight average molecular weight reported by this method is 50,000 (the test result is also reported as a comparative example in Patent Document 2). Further, in this patent, tertiary amine as a catalyst is added after phosgenation because phosgene is decomposed and the average molecular weight of the resulting halogenated polycarbonate is lowered when added before phosgenation. Is preferred.
２，２−ビス（３，５−ジブロム−４−ヒドロキシフェニル）プロパン（以下テトラブロムビスフェノールＡという）のようなハロゲン置換二価フェノールとホスゲンの反応は、一般のポリカーボネート樹脂の原料である２，２−ビス（４−ヒドロキシフェニル）プロパン（以下ビスフェノールＡという）とのホスゲンの反応に比べ、２個のブロムのオルト位置換による水酸基の立体障害によって反応性が低く、特に脂肪族３級アミンのようなアミン類触媒を使用する方法で、重量平均分子量５０，０００以上の高分子量ハロゲン化ポリカーボネートを製造した例は報告されてなく、これまで様々な研究が試みられているが、誰も成功していない。 The reaction of a halogen-substituted dihydric phenol such as 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (hereinafter referred to as tetrabromobisphenol A) with phosgene is a raw material for general polycarbonate resins. Compared with the reaction of phosgene with 2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), the reactivity is low due to the steric hindrance of the hydroxyl group due to ortho substitution of two bromines. No example of producing a high molecular weight halogenated polycarbonate having a weight average molecular weight of 50,000 or more by a method using such an amine catalyst has been reported, and various studies have been attempted so far. Not.
本発明は、ハロゲン置換二価フェノール及びホスゲンから、アミン類触媒を用いて熱安定性の良好な高分子量ハロゲン化ポリカーボネート化合物を安定して提供することを目的とする。本発明者は、上記目的を達成せんとして鋭意検討を重ねた結果、予想外にもホスゲン化をはじめる前のアルカリ化合物の使用量、および反応系のｐＨを特定の条件に満足させることで、ホスゲンのアルカリ化合物との分解反応が殆ど起こらないことが確認され、ホスゲンの使用量を必要最小限に抑えて、熱安定性の良好な重量平均分子量が５０，０００より大きく、且つ分子量分布（Ｍｗ／Ｍｎ）が４．５以下であることを特徴とした高分子量ハロゲン化ポリカーボネート化合物を製造できることを見出し、本発明に到達した。 An object of the present invention is to stably provide a high-molecular-weight halogenated polycarbonate compound having good thermal stability from a halogen-substituted dihydric phenol and phosgene using an amine catalyst. As a result of intensive investigations aimed at achieving the above object, the present inventor unexpectedly satisfied the use amount of the alkali compound before starting phosgenation and the pH of the reaction system to specific conditions. It is confirmed that the decomposition reaction with the alkali compound hardly occurs, the amount of phosgene used is minimized, the weight average molecular weight with good thermal stability is larger than 50,000, and the molecular weight distribution (Mw / The present inventors have found that a high molecular weight halogenated polycarbonate compound characterized in that Mn) is 4.5 or less has been achieved.
すなわち、本発明によれば、
１．下記一般式（１）で示されるハロゲン置換二価フェノールのアルカリ水溶液とホスゲンとを有機溶媒の存在下反応させてハロゲン化カーボネート化合物を製造するに当り、ホスゲン化反応終了時までのアルカリの総使用量が該二価フェノールに対し、１．０〜２．０倍モルの範囲に抑え続く重合反応に移行すること、且つアミン類触媒を一連の反応を通して使用することを特徴とした重量平均分子量が５０，０００より大きい高分子量ハロゲン化ポリカーボネート化合物の製造方法、
（II）各Ｘは独立的に、水素、Ｃ１−Ｃ１２の直鎖状または環状のアルキル、アルコキシ、アリール、もしくはアリールオキシ基であり；
（III）Ｄ１およびＤ２は同一かまたは異なるハロ基、たとえばフルオロ、クロロ、ブロモまたはヨードであり；
（IV）ａ，ｂ，ｃ，ｄは整数であり０＜ａ≦４および０＜ｂ≦４；かつｃ＝４−ａおよびｄ＝４−ｂである）
２．ホスゲン化反応終了時までのアルカリ化合物の総使用量をハロゲン置換二価フェノールに対して１．０倍モル以上２．０倍モル以下とし、且つアミン類触媒を存在させて、該二価フェノールに対して１．０〜１．５倍モルのホスゲンを添加しホスゲン化反応を行い、ホスゲン化後の反応液にアルカリ化合物を逐次添加し重合反応させることを特徴とする前項１記載の高分子量ハロゲン化ポリカーボネート化合物の製造方法、
３．アミン類触媒の添加時期が、
（Ｉ）ホスゲン化反応前、
（II）ホスゲン化反応時、
（III）ホスゲン化後、
（IV）重合反応時、
のうち少なくとも１点以上選択することを特徴とした前項１記載の高分子量ハロゲン化ポリカーボネート化合物の製造方法、
４．ハロゲン置換二価フェノールが、２，２−ビス（３，５−ジブロモ−４−ヒドロキシフェニル）プロパンである前項１記載の高分子量ハロゲン化ポリカーボネート化合物の製造方法、
５．ホスゲン化反応終了時までのアルカリの総使用量が、ハロゲン置換二価フェノールに対し１．２〜１．８倍モルである前項１記載の高分子量ハロゲン化ポリカーボネート化合物の製造方法、
６．アミン類触媒が、トリエチルアミンである前項１記載の高分子量ハロゲン化カーボネート化合物の製造方法、および
７．前記式（１）で示されるハロゲン置換二価フェノールから得られた、重量平均分子量が５０，０００より大きく、且つ分子量分布（Ｍｗ／Ｍｎ）が４．５以下であることを特徴とする高分子量ハロゲン化ポリカーボネート化合物、
が提供される。
That is, according to the present invention,
1. In producing a halogenated carbonate compound by reacting an alkali aqueous solution of a halogen-substituted dihydric phenol represented by the following general formula (1) with phosgene in the presence of an organic solvent, the total use of alkali until the end of the phosgenation reaction The weight average molecular weight is characterized in that the amount of the dihydric phenol is limited to a range of 1.0 to 2.0 times mole and the polymerization reaction is continued, and an amine catalyst is used through a series of reactions. A process for producing a high molecular weight halogenated polycarbonate compound of greater than 50,000,
(II) each X is, each independently, hydrogen, straight-chain or cyclic alkyl of C 1 -C 12, alkoxy, aryl, or an aryl group;
(III) D 1 and D 2 are the same or different halo groups, such as fluoro, chloro, bromo or iodo;
(IV) a, b, c, d are integers, 0 <a ≦ 4 and 0 <b ≦ 4; and c = 4-a and d = 4-b)
2. The total amount of the alkali compound used until the end of the phosgenation reaction is 1.0 to 2.0 times the mol of the halogen-substituted dihydric phenol, and an amine catalyst is present to the dihydric phenol. The high molecular weight halogen according to the above item 1, wherein 1.0 to 1.5-fold mol of phosgene is added to carry out a phosgenation reaction, and an alkali compound is sequentially added to the reaction solution after phosgenation to cause a polymerization reaction. A method for producing a polycarbonate compound,
3. When the amine catalyst is added,
(I) Before the phosgenation reaction,
(II) During the phosgenation reaction,
(III) After phosgenation,
(IV) During the polymerization reaction,
The method for producing a high-molecular-weight halogenated polycarbonate compound according to item 1 above, wherein at least one point is selected from
4). The method for producing a high-molecular-weight halogenated polycarbonate compound according to item 1, wherein the halogen-substituted dihydric phenol is 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane;
5. The method for producing a high-molecular-weight halogenated polycarbonate compound according to item 1 above, wherein the total amount of alkali used up to the end of the phosgenation reaction is 1.2 to 1.8 times mol of the halogen-substituted dihydric phenol;
6). 6. The method for producing a high molecular weight halogenated carbonate compound according to the above item 1, wherein the amine catalyst is triethylamine; A high molecular weight obtained from the halogen-substituted dihydric phenol represented by the formula (1), having a weight average molecular weight of more than 50,000 and a molecular weight distribution (Mw / Mn) of 4.5 or less. Halogenated polycarbonate compounds,
Is provided.
本発明によれば、ホスゲン化反応終了時までの塩基量をハロゲン置換二価フェノールに対して２．０倍モル以下に低減することで、該二価フェノール及びホスゲンから、熱安定性の良好な高分子量ハロゲン化ポリカーボネート化合物を製造する方法、さらにこれまで低い反応性により該二価フェノールに対して１．５倍モル以上という大過剰のホスゲンを用いていたが、ホスゲン必要量を大幅に低減した非常に安定かつ低コストで高分子量ハロゲン化ポリカーボネート化合物を製造する方法を確立出来、その奏する工業的効果は格別なものである。 According to the present invention, the amount of base until the end of the phosgenation reaction is reduced to 2.0 times mol or less with respect to the halogen-substituted dihydric phenol, so that the thermal stability of the dihydric phenol and phosgene is good. A method for producing a high molecular weight halogenated polycarbonate compound, and a large excess of phosgene of 1.5 times mol or more with respect to the dihydric phenol was used due to low reactivity so far, but the required amount of phosgene was greatly reduced. A method for producing a high-molecular-weight halogenated polycarbonate compound can be established at a very stable and low cost, and the industrial effect exerted by the method is exceptional.
本発明の製造方法で使用される二価フェノールは、前記一般式（１）で表されるハロゲン置換二価フェノールであり、特に好ましくは実質的に前記一般式（１）で表されるハロゲン置換二価フェノールからなる二価フェノールである。かかるハロゲン置換二価フェノールとしては、具体的には２，２−ビス（３，５−ジブロム−４−ヒドロキシフェニル）プロパン（通称テトラブロムビスフェノールＡ）、２，２−ビス（３，５−ジクロル−４−ヒドロキシフェニル）プロパン、１，１−ビス（３，５−ジブロム−４−ヒドロキシフェニル）エタン、１，１−ビス（３，５−ジクロル−４−ヒドロキシフェニル）エタン、１，１−ビス（３，５−ジブロム−４−ヒドロキシフェニル）メタン、１，１−ビス（３，５−ジクロル−４−ヒドロキシフェニル）メタン、ビス（３，５−ジブロム−４−ヒドロキシフェニル）スルホン、ビス（３，５−ジクロル−４−ヒドロキシフェニル）スルホン等が挙げられる。特にテトラブロムビスフェノールＡが好ましく使用される。これらは単独もしくは２種以上を混合して使用できる。 The dihydric phenol used in the production method of the present invention is a halogen-substituted dihydric phenol represented by the general formula (1), and particularly preferably a halogen-substituted phenol represented by the general formula (1). It is a dihydric phenol composed of a dihydric phenol. Specific examples of the halogen-substituted dihydric phenol include 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (commonly referred to as tetrabromobisphenol A) and 2,2-bis (3,5-dichloro). -4-hydroxyphenyl) propane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) ethane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) ethane, 1,1- Bis (3,5-dibromo-4-hydroxyphenyl) methane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) sulfone, bis (3,5-dichloro-4-hydroxyphenyl) sulfone and the like. In particular, tetrabromobisphenol A is preferably used. These can be used alone or in admixture of two or more.
また、必要に応じて一般的な二価フェノールを約５０モル％まで導入できる。かかる二価フェノールとしては、具体的には、レゾルシノール、ヒドロキノン、４，４′‐ジヒドロキシビフェニル、１，６‐ジヒドロキシナフタレン、ビス（４‐ヒドロキシフェニル）メタン、ビス（４‐ヒドロキシフェニル）ジフェニルメタン、１，１‐ビス（４‐ヒドロキシフェニル）エタン、１，２‐ビス（４‐ヒドロキシフェニル）エタン、１，１‐ビス（４‐ヒドロキシフェニル）‐１‐フェニルエタン、２，２‐ビス（４‐ヒドロキシフェニル）プロパン（すなわち、「ビスフェノールＡ」）、２，２‐ビス（４‐ヒドロキシフェニル）ブタン、１，１‐ビス（４‐ヒドロキシフェニル）イソブタン、１，１‐ビス（４‐ヒドロキシフェニル）シクロヘキサン、１，１‐ビス（４‐ヒドロキシフェニル）シクロドデカン、２，２‐ビス（４‐ヒドロキシフェニル）アダマンタン、２，２‐ビス（３‐メチル‐４‐ヒドロキシフェニル）プロパン、２，２‐ビス（３‐ｎ‐プロピル‐４‐ヒドロキシフェニル）プロパン、２，２‐ビス（３‐イソプロピル‐４‐ヒドロキシフェニル）プロパン、２，２‐ビス（３‐ｓｅｃ‐ブチル‐４‐ヒドロキシフェニル）プロパン、２，２‐ビス（３‐ｔｅｒｔ‐ブチル‐４‐ヒドロキシフェニル）プロパン、２，２‐ビス（３‐シクロヘキシル‐４‐ヒドロキシフェニル）プロパン、２，２‐ビス（４‐ヒドロキシフェニル）ヘキサフルオロプロパン、４，４′‐ジヒドロキシベンゾフェノン、３，３‐ビス（４‐ヒドロキシフェニル）‐２‐ブタノン、ビス（４‐ヒドロキシフェニル）エーテル、ビス（４‐ヒドロキシフェニル）スルフィド、ビス（４‐ヒドロキシフェニル）スルホキシド、ビス（４‐ヒドロキシフェニル）スルホン、９，９‐ビス（４‐ヒドロキシフェニル）フルオレン等が挙げられる。 Moreover, a general dihydric phenol can be introduce | transduced to about 50 mol% as needed. Specific examples of such dihydric phenols include resorcinol, hydroquinone, 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, 1 , 1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4- Hydroxyphenyl) propane (ie, “bisphenol A”), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) isobutane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 2, -Bis (4-hydroxyphenyl) adamantane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2,2- Bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxybenzophenone, 3,3-bis (4-hydroxy) Phenyl) -2-butanone, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ) Sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, 9,9-bis (4-hydroxyphenyl) fluorene, and the like.
本発明の製造方法で使用されるアルカリ化合物はアルカリ金属またはアルカリ土類金属の化合物であり、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化カルシウム等のアルカリ金属またはアルカリ土類金属の水酸化物が好ましく用いられ、なかでも水酸化ナトリウムおよび水酸化カリウムが特に好ましく用いられる。 The alkali compound used in the production method of the present invention is an alkali metal or alkaline earth metal compound, and an alkali metal or alkaline earth metal water such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or calcium hydroxide. Oxides are preferably used, and sodium hydroxide and potassium hydroxide are particularly preferably used.
本発明の製造方法で使用される有機溶媒は水に対して実質的に不溶で、反応に対して不活性で且つ反応によって生成するハロゲン化カーボネートオリゴマーを溶解する有機溶媒である。かかる有機溶媒としては例えば塩化メチレン、１，２−ジクロロエタン、テトラクロロエタン、クロロホルム等の塩素化脂肪族炭化水素、クロロベンゼン、ジクロロベンゼン、クロロトルエン等の塩素化芳香族炭化水素、アセトフェノン、シクロへキサノン、アニソール等があげられ、これらは単独又は２種以上混合して使用することができる。なかでも塩化メチレンが特に好ましく使用される。 The organic solvent used in the production method of the present invention is an organic solvent that is substantially insoluble in water, inert to the reaction, and dissolves the halogenated carbonate oligomer produced by the reaction. Examples of the organic solvent include chlorinated aliphatic hydrocarbons such as methylene chloride, 1,2-dichloroethane, tetrachloroethane, and chloroform, chlorinated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and chlorotoluene, acetophenone, cyclohexanone, Anisole etc. are mention | raise | lifted and these can be used individually or in mixture of 2 or more types. Of these, methylene chloride is particularly preferably used.
本発明の製造方法で使用されるアミン類触媒としては、例えばトリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリへキシルアミン、トリオクチルアミン、トリデシルアミン、ジメチル−ｎ−プロピルアミン、ジエチル−ｎ−プロピルアミン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、ピリジン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジメチル−４−アミノピリジン、Ｎ，Ｎ−ジエチル−４−アミノピリジン等の三級アミン、トリメチルドデシルアンモニウムクロリド、トリエチルドデシルアンモニウムクロリド、ジメチルベンジルフェニルアンモニウムクロリド、ジエチルベンジルフェニルアンモニウムクロリド、トリメチルドデシルベンジルアンモニウムヒドロキシド、トリエチルドデシルベンジルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムクロリド、トリエチルベンジルアンモニウムクロリド、テトラメチルアンモニウムクロリド、テトラエチルアンモニウムクロリド等の四級アンモニウム化合物が挙げられる。また、トリフェニル−ｎ−ブチルホスホニウムブロマイド、トリフェニルメチルホスホニウムブロマイド等の四級ホスホニウム塩を使用してもよく、なかでもトリエチルアミンが好ましい。これら触媒はホスゲン化反応時に存在させることも可能である。 Examples of the amine catalyst used in the production method of the present invention include trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, trioctylamine, tridecylamine, dimethyl-n-propylamine, diethyl-n- Tertiary amines such as propylamine, N, N-dimethylcyclohexylamine, pyridine, N, N-dimethylaniline, N, N-dimethyl-4-aminopyridine, N, N-diethyl-4-aminopyridine, trimethyldodecylammonium Chloride, triethyldodecylammonium chloride, dimethylbenzylphenylammonium chloride, diethylbenzylphenylammonium chloride, trimethyldodecylbenzylammonium hydroxide, triethyldodecylbenzylan Onium hydroxide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetramethylammonium chloride, quaternary ammonium compounds such as tetraethylammonium chloride. Further, a quaternary phosphonium salt such as triphenyl-n-butylphosphonium bromide or triphenylmethylphosphonium bromide may be used, and triethylamine is particularly preferable. These catalysts can also be present during the phosgenation reaction.
本発明の製造方法においては、まず上記二価フェノール、アルカリ化合物、水および有機溶媒からなる混合液を調製する。
ホスゲン化反応終了時までのアルカリ化合物の使用量は、二価フェノールに対して１．０〜２．０倍モル、好ましくは１．２〜１．８倍モル、より好ましくは１．４〜１．６倍モルの範囲とする。アルカリ化合物の使用量が１．０倍モルより少ないと、ホスゲン化反応においてクロロホーメートの生成が少なくなり、未反応二価フェノールが多くなる。
In the production method of the present invention, first, a mixed solution composed of the dihydric phenol, the alkali compound, water and an organic solvent is prepared.
The amount of the alkali compound used until the end of the phosgenation reaction is 1.0 to 2.0 times mol, preferably 1.2 to 1.8 times mol, more preferably 1.4 to 1 mol, relative to the dihydric phenol. The range is 6 moles. When the amount of the alkali compound used is less than 1.0 mole, the production of chloroformate is reduced in the phosgenation reaction, and the amount of unreacted dihydric phenol is increased.
アミン類触媒の使用量は、二価フェノールに対して０〜０．１倍モルが好ましく、０〜０．０７倍モルが更に好ましく、０〜０．０５倍モルがより好ましい。アミン類触媒の使用量が上記範囲より多いと一連の反応を通してクロロホーメート基とアミン類触媒が反応してウレタン結合（カルバモイル）が生成し、反応生成物の熱安定性が悪化することとなる。アミン類触媒は、ホスゲン化反応前、ホスゲン化反応時、ホスゲン化後、重合反応時のいずれの時期に添加しても良いが、ホスゲン化反応前やホスゲン化反応時に全量添加すると上記ウレタン結合（カルバモイル）が生成し易くなるため、ホスゲン化後や重合反応時に触媒の一部あるいは全部を添加もしくは逐次添加することがより好ましい。 The amount of the amine catalyst used is preferably 0 to 0.1 times mol, more preferably 0 to 0.07 times mol, and more preferably 0 to 0.05 times mol based on the dihydric phenol. If the amount of the amine catalyst used is larger than the above range, the chloroformate group and the amine catalyst react through a series of reactions to form urethane bonds (carbamoyl), which deteriorates the thermal stability of the reaction product. . The amine catalyst may be added before the phosgenation reaction, at the time of the phosgenation reaction, after the phosgenation, or at the time of the polymerization reaction. However, if the total amount of the amine catalyst is added before the phosgenation reaction or during the phosgenation reaction, the urethane bond ( It is more preferable to add a part or all of the catalyst after the phosgenation or during the polymerization reaction or to add them sequentially.
上記調製された二価フェノール、アルカリ化合物、水、有機溶媒およびアミン類触媒（無添加も可能）からなる混合液は、次いでホスゲン化反応を行う。ホスゲン化反応は、かかる混合液にホスゲンを添加し、且つ反応系のｐＨを７〜１２の範囲で反応させる。 The mixed liquid composed of the dihydric phenol, alkali compound, water, organic solvent and amine catalyst (addition is possible) is then performed for the phosgenation reaction. In the phosgenation reaction, phosgene is added to the mixed solution, and the pH of the reaction system is reacted in the range of 7-12.
かかるホスゲン化反応におけるホスゲンの使用量は、二価フェノールに対して１．０〜１．５倍モルが好ましく、１．０〜１．３倍モルがより好ましく、１．０〜１．１倍モルが更に好ましい。ホスゲンの使用量が上記範囲より少ないときはクロロホーメートの生成量が少なく、未反応二価フェノールが多くなり最終的な反応収率が低下し、上記範囲より多いときは、より過剰のアルカリ化合物が必要になって、ホスゲンや生成したクロロホーメートの分解が多くなり、更に水酸基やクロロホーメート基が残存して、得られる反応生成物の熱安定性が悪化するとともに重合度の調整が困難になる。 The amount of phosgene used in the phosgenation reaction is preferably 1.0 to 1.5 times mol, more preferably 1.0 to 1.3 times mol, and 1.0 to 1.1 times the dihydric phenol. Mole is more preferred. When the amount of phosgene used is less than the above range, the amount of chloroformate produced is small, the amount of unreacted dihydric phenol increases, and the final reaction yield decreases. Is required, the decomposition of phosgene and the generated chloroformate increases, and the hydroxyl and chloroformate groups remain, resulting in poor thermal stability of the resulting reaction product and difficulty in adjusting the degree of polymerization. become.
また、ホスゲン添加時に反応系の好ましくはｐＨを７〜１２、より好ましくはｐＨを９〜１２、更に好ましくはｐＨを１０〜１２の範囲に維持することが必要であり、ホスゲン化反応中にアルカリ化合物を添加することによっても上記ｐＨ範囲を維持することができる。かかるｐＨ範囲とすることによって過剰のアルカリ化合物によるホスゲンや生成したクロロホーメートの分解を抑制し、モノクロロホーメートの生成を促進する。また、ホスゲン添加時の反応系のｐＨが１２より高くなると、重合度の制御がし難くなり、また未反応二価フェノールも多くなり最終的な反応収率が低下することになる。 In addition, the pH of the reaction system is preferably 7 to 12, more preferably 9 to 12, and still more preferably 10 to 12 when phosgene is added. The pH range can also be maintained by adding a compound. By setting it as such pH range, decomposition | disassembly of the phosgene and the produced | generated chloroformate by an excess alkali compound is suppressed, and the production | generation of a monochloroformate is accelerated | stimulated. Moreover, when the pH of the reaction system at the time of phosgene addition becomes higher than 12, it becomes difficult to control the degree of polymerization, and the amount of unreacted dihydric phenol increases, resulting in a decrease in the final reaction yield.
また、ホスゲン化反応の際の反応温度は１０〜３０℃の範囲が好ましく、かかる範囲ではホスゲンの分解が少なくホスゲン化反応速度が適度で未反応二価フェノールが少なく反応収率が高くなり好ましい。 The reaction temperature during the phosgenation reaction is preferably in the range of 10 to 30 ° C. Within this range, the decomposition of phosgene is small, the phosgenation reaction rate is moderate, the amount of unreacted dihydric phenol is small, and the reaction yield is high.
本発明の製造方法において、ホスゲン化反応終了後、反応溶液にアルカリ化合物を加えて反応系のｐＨを１２以上にし、次いで反応温度３０〜４５℃の範囲でさらに重合反応させる。 In the production method of the present invention, after completion of the phosgenation reaction, an alkali compound is added to the reaction solution to bring the pH of the reaction system to 12 or more, and then the polymerization reaction is further carried out at a reaction temperature of 30 to 45 ° C.
ホスゲン化反応終了後、必要に応じて一価フェノールを添加することで分子量を調整することができる。一価フェノールとしては、例えばフェノール、クレゾール、ｓｅｃ−ブチルフェノール、ｔｅｒｔ−ブチルフェノール、ｔｅｒｔ−オクチルフェノール、ノニルフェノール、クミルフェノール、２，４，６−トリブロモフェノール、ペンタブロモフェノール、ヒドロキシクロマン類等が挙げられ、これらは単独で又は二種以上混合して使用してもよい。一価フェノールの使用量は目的とする反応生成物の重合度によって調整すればよい。 After completion of the phosgenation reaction, the molecular weight can be adjusted by adding monohydric phenol as necessary. Examples of the monohydric phenol include phenol, cresol, sec-butylphenol, tert-butylphenol, tert-octylphenol, nonylphenol, cumylphenol, 2,4,6-tribromophenol, pentabromophenol, hydroxychromans and the like. These may be used alone or in admixture of two or more. What is necessary is just to adjust the usage-amount of monohydric phenol with the polymerization degree of the target reaction product.
重合反応温度および重合反応時間は、３０〜４５℃の温度範囲で重合反応させる必要がある。反応温度が溶媒の沸点以上になる場合にはオートクレープ等圧力容器を用い加圧下で行うことが好ましい。重合反応温度が３０℃より低くいと、反応完結に長い時間を要すと共に、水酸基やクロロホーメート基が残存して、得られる反応生成物の熱安定性が悪化することとなり好ましくない。重合反応温度が４５℃を超えると反応生成物の分解反応が生じ好ましくない。 The polymerization reaction temperature and the polymerization reaction time need to be polymerized in a temperature range of 30 to 45 ° C. When the reaction temperature is equal to or higher than the boiling point of the solvent, it is preferably carried out under pressure using a pressure vessel such as autoclave. When the polymerization reaction temperature is lower than 30 ° C., it takes a long time to complete the reaction, and hydroxyl groups and chloroformate groups remain, which is not preferable because the thermal stability of the resulting reaction product deteriorates. When the polymerization reaction temperature exceeds 45 ° C., decomposition reaction of the reaction product occurs, which is not preferable.
重合反応時にはアルカリ化合物を逐次添加することが好ましい。重合反応時に添加するアルカリ化合物の使用量は、ホスゲン化反応時に使用したアルカリ化合物の量と合計して、二価フェノールに対して２．１〜４．５倍モルの範囲が好ましく、２．２〜３．５倍モルの範囲がより好ましく、２．３〜２．８倍モルの範囲がさらに好ましい。 It is preferable to add an alkali compound sequentially during the polymerization reaction. The amount of the alkali compound added during the polymerization reaction is preferably in the range of 2.1 to 4.5 times the molar amount of the dihydric phenol in total with the amount of the alkali compound used during the phosgenation reaction. The range of -3.5 times mol is more preferable, and the range of 2.3-2.8 times mol is further more preferable.
かかる重合反応によって得られる有機溶媒溶液から酸洗浄及び水洗等によって不純物を除去した後有機溶媒を除去することによって高分子量ハロゲン化カーボネート化合物が得られる。 A high molecular weight halogenated carbonate compound is obtained by removing impurities from an organic solvent solution obtained by such a polymerization reaction by acid washing, water washing or the like and then removing the organic solvent.
本発明の製造方法により、ハロゲン置換二価フェノール及びホスゲンから、熱安定性の良好な高分子量ハロゲン化ポリカーボネート化合物を安定して提供することができる。得られるハロゲン化カーボネート化合物は、末端停止剤として使用した一価フェノールの使用量を調整することにより、重量平均分子量が５０，０００を超えて５００，０００以下の範囲である。 According to the production method of the present invention, a high-molecular-weight halogenated polycarbonate compound having good thermal stability can be stably provided from a halogen-substituted dihydric phenol and phosgene. The obtained halogenated carbonate compound has a weight average molecular weight in the range of more than 50,000 to 500,000 or less by adjusting the amount of monohydric phenol used as a terminal terminator.
また、本発明の製造方法により得られるハロゲン化カーボネート化合物は、分子量分布（Ｍｗ／Ｍｎ）が４．５以下であることが好ましく、４．４以下であることがより好ましい。下限は１．０以上であるが、実用上２．０以上であってもよい。分子量分布（Ｍｗ／Ｍｎ）が４．５以下であるとハロゲン化カーボネート化合物の熱安定性が良好となる。 In addition, the halogenated carbonate compound obtained by the production method of the present invention preferably has a molecular weight distribution (Mw / Mn) of 4.5 or less, more preferably 4.4 or less. The lower limit is 1.0 or more, but may be 2.0 or more practically. When the molecular weight distribution (Mw / Mn) is 4.5 or less, the thermal stability of the halogenated carbonate compound is improved.
さらに、本発明の製造方法により得られるハロゲン化カーボネート化合物は、そのオリゴマー量が０．６％以下であることが好ましく、０．５５％以下であることがより好ましく、０．５％以下であることがさらに好ましい。下限は０％であるが、実用上０．１％以上であってもよい。そのオリゴマー量が０．６％以下であるとハロゲン化カーボネート化合物の熱安定性が良好となる。 Furthermore, the halogenated carbonate compound obtained by the production method of the present invention preferably has an oligomer amount of 0.6% or less, more preferably 0.55% or less, and 0.5% or less. More preferably. The lower limit is 0%, but may be practically 0.1% or more. When the amount of the oligomer is 0.6% or less, the thermal stability of the halogenated carbonate compound is improved.
以下に実施例をあげて更に説明する。なお、実施例中の重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）およびオリゴマー量の評価は下記の方法に従った。 Examples will be described further below. The weight average molecular weight (Mw), number average molecular weight (Mn) and oligomer amount in the examples were evaluated according to the following methods.
（１）重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）
乾燥した試料４０ｍｇをクロロホルム５ｍｌに溶解し、下記条件としたＧＰＣ（ゲル浸透クロマトグラフィー）装置に、２００μｌを導入して測定した。
装置；島津製作所（株）製ＧＰＣシステム（ＬＣ−１０Ａ）
検出器；ＲＩＤ−１０Ａ
カラム；Ｓｈｏｄｅｘ ＫＦ−８０１＋ＫＦ−８０２＋ＫＦ８０５Ｌ
標準物質；ＴＳＫ標準ポリスチレン
溶離液；クロロホルム、４０℃、１ｍｌ／ｍｉｎ
(1) Weight average molecular weight (Mw), number average molecular weight (Mn)
40 mg of the dried sample was dissolved in 5 ml of chloroform, and 200 μl was introduced into a GPC (gel permeation chromatography) apparatus under the following conditions for measurement.
Equipment: GPC system (LC-10A) manufactured by Shimadzu Corporation
Detector; RID-10A
Column; Shodex KF-801 + KF-802 + KF805L
Standard substance; TSK standard polystyrene Eluent: Chloroform, 40 ° C., 1 ml / min
（２）オリゴマー量
乾燥した試料５０ｍｇをクロロホルム５ｍｌに溶解し、下記条件としたＧＰＣ（ゲル浸透クロマトグラフィー）装置に、２０μｌを導入して測定した。尚、オリゴマー量を先測定方法で求めたＧＰＣチャートのリテンションタイムが１９ｍｉｎ以降に観測されるオリゴマー成分のピーク面積の全ピーク面積に対する割合（％）と定義した。
装置；Ｗａｔｅｒｓ（株）製ＧＰＣシステム（Ｗａｔｅｒｓ２６９５）
検出器；Ｗａｔｅｒｓ２４８７
カラム；ＴＳＫｇｅｌ Ｇ２０００ＨＸＬ＋Ｇ３０００ＨＸＬ
標準物質；ＴＳＫ標準ポリスチレン
溶離液；クロロホルム、４０℃、０．７ｍｌ／ｍｉｎ
(2) Oligomer amount 50 mg of a dried sample was dissolved in 5 ml of chloroform, and 20 μl was introduced into a GPC (gel permeation chromatography) apparatus under the following conditions for measurement. The oligomer amount was defined as the ratio (%) of the peak area of the oligomer component observed in the retention time of the GPC chart obtained by the previous measurement method after 19 min to the total peak area.
Apparatus: GPC system (Waters2695) manufactured by Waters Co., Ltd.
Detector; Waters 2487
Column; TSKgel G2000H XL + G3000H XL
Standard substance; TSK standard polystyrene Eluent: Chloroform, 40 ° C., 0.7 ml / min
各実施例および比較例におけるホスゲン使用量、ホスゲン化終了時までの総アルカリ添加量、ホスゲン化反応中のアルカリおよび触媒の添加の有無、重合中の触媒添加の有無、反応生成物の重量平均分子量、分散値（Ｍｗ／Ｍｎ）およびオリゴマー量については、下記の表１に示した。 The amount of phosgene used in each Example and Comparative Example, the total amount of alkali added until the end of phosgenation, the presence or absence of addition of alkali and catalyst during phosgenation reaction, the presence or absence of addition of catalyst during polymerization, the weight average molecular weight of the reaction product The dispersion value (Mw / Mn) and the amount of oligomer are shown in Table 1 below.
［実施例１］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、７．０％水酸化ナトリウム水溶液１６１ｍｌ（水酸化ナトリウム０．２９９モル）、塩化メチレン３９３ｍｌ及びトリエチルアミン０．２ｍｌ（０．００２モル）を仕込んで溶解し、攪拌下２０〜２５℃に保持し、ホスゲン２８．５ｇ（０．２８９モル）を６０分要して吹込み、ホスゲン吹き込み終盤には２５％水酸化ナトリウム水溶液５ｍｌ（水酸化ナトリウム０．０４１モル）を加えながら反応混合液のｐＨを、１０．５〜１１．０に維持してホスゲン化反応させた。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）を加え、トリエチルアミン０．８ｍｌ（０．００８モル）および２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を約６０分かけて加え、３５〜４０℃の温度で９０分間反応させた。反応終了後静置して水相と塩化メチレン相に分離し、水相中の炭酸ナトリウム量からホスゲン分解率を求めて結果を表１に示した。また、反応終了後の水相に濃塩酸を加えｐＨを３以下にしたところ、水相は白濁せず透明であり、未反応テトラブロムビスフェノールＡの析出は認められなかった。
分離した塩化メチレン相を無機塩類及びアミン類がなくなるまで酸洗浄及び水洗した後、塩化メチレンを除去してハロゲン化ポリカーボネートを得た。この際、重量平均分子量は２１４，０００、分散は４．１、オリゴマー量０．４１％であった。
[Example 1]
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 130 g (0.239 mol) of tetrabromobisphenol A, 161 ml of 7.0% aqueous sodium hydroxide solution (0.299 mol of sodium hydroxide), 393 ml of methylene chloride, and 0.3 ml of triethylamine were added. 2 ml (0.002 mol) was charged and dissolved, and maintained at 20 to 25 ° C. with stirring, and 28.5 g (0.289 mol) of phosgene was blown in for 60 minutes. While adding 5 ml of an aqueous sodium oxide solution (0.041 mol of sodium hydroxide), the pH of the reaction mixture was maintained at 10.5 to 11.0 for phosgenation reaction. After completion of the phosgenation reaction, 0.20 g (0.0013 mol) of p-tert-butylphenol was added, and 0.8 ml (0.008 mol) of triethylamine and 44 ml of 25% aqueous sodium hydroxide solution (0.363 mol of sodium hydroxide) were added. It added over about 60 minutes and made it react for 90 minutes at the temperature of 35-40 degreeC. After completion of the reaction, the mixture was allowed to stand and separated into an aqueous phase and a methylene chloride phase. The phosgene decomposition rate was determined from the amount of sodium carbonate in the aqueous phase, and the results are shown in Table 1. Further, when concentrated hydrochloric acid was added to the aqueous phase after completion of the reaction to adjust the pH to 3 or less, the aqueous phase was not cloudy and transparent, and no precipitation of unreacted tetrabromobisphenol A was observed.
The separated methylene chloride phase was acid washed and washed with water until inorganic salts and amines disappeared, and then methylene chloride was removed to obtain a halogenated polycarbonate. At this time, the weight average molecular weight was 214,000, the dispersion was 4.1, and the oligomer amount was 0.41%.
［実施例２］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、７．０％水酸化ナトリウム水溶液１６１ｍｌ（水酸化ナトリウム０．２９９モル）、塩化メチレン３９３ｍｌを仕込んで溶解し、攪拌下２０〜２５℃に保持し、ホスゲン２８．５ｇ（０．２８９モル）を６０分要して吹込み、ホスゲン吹き込み終盤には２５％水酸化ナトリウム水溶液５ｍｌ（水酸化ナトリウム０．０４１モル）を加えながら反応混合液のｐＨを、１０．５〜１１．０に維持してホスゲン化反応させた。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）、およびトリエチルアミン１．０３ｍｌ（０．０１モル）を加え、２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を約６０分かけて加え、以後実施例１と同様の操作を行ったところ、重量平均分子量２０８，０００、分散４．２、オリゴマー量０．４３％である高分子量ハロゲン化ポリカーボネートを得た。
[Example 2]
A flask equipped with a phosgene blowing tube, a thermometer and a stirrer was charged with 130 g (0.239 mol) of tetrabromobisphenol A, 161 ml of 7.0% aqueous sodium hydroxide solution (0.299 mol of sodium hydroxide), and 393 ml of methylene chloride. The mixture was kept at 20 to 25 ° C. with stirring, and 28.5 g (0.289 mol) of phosgene was blown in for 60 minutes. At the end of the phosgene blowing, 5 ml of 25% aqueous sodium hydroxide solution (0.041 sodium hydroxide) was added. The pH of the reaction mixture was maintained at 10.5 to 11.0 while adding (mol). After completion of the phosgenation reaction, 0.20 g (0.0013 mol) of p-tert-butylphenol and 1.03 ml (0.01 mol) of triethylamine were added, and 44 ml of 25% aqueous sodium hydroxide solution (0.363 mol of sodium hydroxide) Was added over about 60 minutes, and then the same operation as in Example 1 was performed to obtain a high molecular weight halogenated polycarbonate having a weight average molecular weight of 208,000, a dispersion of 4.2, and an oligomer amount of 0.43%.
［実施例３］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、７．０％水酸化ナトリウム水溶液２４２ｍｌ（水酸化ナトリウム０．３５９モル）、塩化メチレン３９３ｍｌ及びトリエチルアミン０．２ｍｌ（０．００２モル）を仕込んで溶解し、攪拌下２０〜２５℃に保持し、ホスゲン２８．５ｇ（０．２８９モル）を６０分要して吹込み、ホスゲン化反応させた。ホスゲン化反応時の反応混合液のｐＨは、１０．０〜１１．８であった。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）を加え、トリエチルアミン０．８ｍｌ（０．００８モル）および２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を約６０分かけて加え、以後実施例１と同様の操作を行ったところ、重量平均分子量２１３，０００、分散４．３、オリゴマー量０．４６％である高分子量ハロゲン化ポリカーボネートを得た。
[Example 3]
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 130 g (0.239 mol) of tetrabromobisphenol A, 242 ml of 7.0% sodium hydroxide aqueous solution (0.359 mol of sodium hydroxide), 393 ml of methylene chloride, and 0.3 ml of triethylamine were added. 2 ml (0.002 mol) was charged and dissolved, and kept at 20 to 25 ° C. with stirring, and 28.5 g (0.289 mol) of phosgene was blown in for 60 minutes to cause phosgenation reaction. The pH of the reaction mixture during the phosgenation reaction was 10.0 to 11.8. After completion of the phosgenation reaction, 0.20 g (0.0013 mol) of p-tert-butylphenol was added, and 0.8 ml (0.008 mol) of triethylamine and 44 ml of 25% aqueous sodium hydroxide solution (0.363 mol of sodium hydroxide) were added. The addition was carried out over about 60 minutes, and then the same operation as in Example 1 was carried out to obtain a high molecular weight halogenated polycarbonate having a weight average molecular weight of 213,000, a dispersion of 4.3 and an oligomer amount of 0.46%.
［実施例４］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、７．０％水酸化ナトリウム水溶液２４２ｍｌ（水酸化ナトリウム０．３５９モル）、塩化メチレン３９３ｍｌを仕込んで溶解し、攪拌下２０〜２５℃に保持し、ホスゲン２８．５ｇ（０．２８９モル）を６０分要して吹込み、ホスゲン化反応させた。ホスゲン化反応時の反応混合液のｐＨは、１０．０〜１１．８であった。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）およびトリエチルアミン１．０３ｍｌ（０．０１モル）を加え、２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を約６０分かけて加え、以後実施例１と同様の操作を行ったところ、重量平均分子量２０７，０００、分散４．２、オリゴマー量０．４５％である高分子量ハロゲン化ポリカーボネートを得た。
[Example 4]
A flask equipped with a phosgene blowing tube, a thermometer and a stirrer was charged with 130 g (0.239 mol) of tetrabromobisphenol A, 242 ml of 7.0% aqueous sodium hydroxide solution (0.359 mol of sodium hydroxide), and 393 ml of methylene chloride. The mixture was kept at 20 to 25 ° C. with stirring, and 28.5 g (0.289 mol) of phosgene was blown in for 60 minutes to cause phosgenation. The pH of the reaction mixture during the phosgenation reaction was 10.0 to 11.8. After completion of the phosgenation reaction, 0.20 g (0.0013 mol) of p-tert-butylphenol and 1.03 ml (0.01 mol) of triethylamine were added, and 44 ml of 25% aqueous sodium hydroxide solution (0.363 mol of sodium hydroxide) was added. The addition was carried out over about 60 minutes, and then the same operation as in Example 1 was carried out to obtain a high molecular weight halogenated polycarbonate having a weight average molecular weight of 207,000, a dispersion of 4.2, and an oligomer amount of 0.45%.
［実施例５］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、７．０％水酸化ナトリウム水溶液１６１ｍｌ（水酸化ナトリウム０．２９９モル）、塩化メチレン３９３ｍｌ及びトリエチルアミン１．０３ｍｌ（０．０１モル）を仕込んで溶解し、攪拌下２０〜２５℃に保持し、ホスゲン２８．５ｇ（０．２８９モル）を６０分要して吹込み、ホスゲン吹き込み終盤には２５％水酸化ナトリウム水溶液５ｍｌ（水酸化ナトリウム０．０４１モル）を加えながら反応混合液のｐＨを、１０．５〜１１．０に維持してホスゲン化反応させた。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）を加え、２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を約６０分かけて加え、以後実施例１と同様の操作を行ったところ、重量平均分子量２１２，０００、分散４．３、オリゴマー量０．４７％である高分子量ハロゲン化ポリカーボネートを得た。
[Example 5]
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 130 g (0.239 mol) of tetrabromobisphenol A, 161 ml of 7.0% aqueous sodium hydroxide solution (0.299 mol of sodium hydroxide), 393 ml of methylene chloride and 1. 03 ml (0.01 mol) was charged and dissolved, and maintained at 20 to 25 ° C. with stirring. 28.5 g (0.289 mol) of phosgene was blown in for 60 minutes, and 25% water was added at the end of phosgene blowing. While adding 5 ml of an aqueous sodium oxide solution (0.041 mol of sodium hydroxide), the pH of the reaction mixture was maintained at 10.5 to 11.0 for phosgenation reaction. After completion of the phosgenation reaction, 0.20 g (0.0013 mol) of p-tert-butylphenol was added, and 44 ml of 25% aqueous sodium hydroxide solution (0.363 mol of sodium hydroxide) was added over about 60 minutes. As a result of the same operation as described above, a high molecular weight halogenated polycarbonate having a weight average molecular weight of 212,000, a dispersion of 4.3, and an oligomer amount of 0.47% was obtained.
［実施例６］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、７．０％水酸化ナトリウム水溶液２４２ｍｌ（水酸化ナトリウム０．３５９モル）、塩化メチレン３９３ｍｌ及びトリエチルアミン１．０３ｍｌ（０．０１モル）を仕込んで溶解し、攪拌下２０〜２５℃に保持し、ホスゲン２８．５ｇ（０．２８９モル）を約６０分要して吹込み、ホスゲン化反応させた。ホスゲン化反応時の反応混合液のｐＨは、１０．０〜１１．８であった。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）を加え、２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を約６０分かけて加え、以後実施例１と同様の操作を行ったところ、重量平均分子量２１３，０００、分散４．４、オリゴマー量０．４９％である高分子量ハロゲン化ポリカーボネートを得た。
[Example 6]
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 130 g (0.239 mol) of tetrabromobisphenol A, 242 ml of 7.0% aqueous sodium hydroxide solution (0.359 mol of sodium hydroxide), 393 ml of methylene chloride and 1. 03 ml (0.01 mol) was charged and dissolved, and the mixture was kept at 20 to 25 ° C. with stirring, and 28.5 g (0.289 mol) of phosgene was blown in for about 60 minutes to cause a phosgenation reaction. The pH of the reaction mixture during the phosgenation reaction was 10.0 to 11.8. After completion of the phosgenation reaction, 0.20 g (0.0013 mol) of p-tert-butylphenol was added, and 44 ml of 25% aqueous sodium hydroxide solution (0.363 mol of sodium hydroxide) was added over about 60 minutes. As a result of the same operation, a high molecular weight halogenated polycarbonate having a weight average molecular weight of 213,000, a dispersion of 4.4, and an oligomer amount of 0.49% was obtained.
［比較例１］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、７．０％水酸化ナトリウム水溶液３２２ｍｌ（水酸化ナトリウム０．４７８モル）、塩化メチレン６４０ｍｌを仕込んで溶解し、攪拌下２０〜２５℃に保持し、ホスゲン３２．６ｇ（０．３２２モル）を約６０分要して吹込み、ホスゲン吹き込み中に適宜２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を加えながら反応混合液のｐＨ１０に維持してホスゲン化反応させた。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）及びトリエチルアミン１．０３ｍｌ（０．０１モル）を加え、２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を約６０分かけて加え、以後実施例１と同様の操作を行ったところ、重量平均分子量１０，０００未満のオリゴマーであるハロゲン化ポリカーボネートを得た。
[Comparative Example 1]
A flask equipped with a phosgene blowing tube, a thermometer and a stirrer was charged with 130 g (0.239 mol) of tetrabromobisphenol A, 322 ml of 7.0% aqueous sodium hydroxide solution (0.478 mol of sodium hydroxide), and 640 ml of methylene chloride. The mixture was kept at 20 to 25 ° C. with stirring, and 32.6 g (0.322 mol) of phosgene was blown in for about 60 minutes, and 44 ml of 25% aqueous sodium hydroxide solution was added appropriately during the phosgene blowing. 363 mol) was added and the reaction mixture was maintained at pH 10 for phosgenation reaction. After completion of the phosgenation reaction, 0.20 g (0.0013 mol) of p-tert-butylphenol and 1.03 ml (0.01 mol) of triethylamine were added, and 44 ml of 25% aqueous sodium hydroxide solution (0.363 mol of sodium hydroxide) was added. The addition was carried out over about 60 minutes, and then the same operation as in Example 1 was carried out to obtain a halogenated polycarbonate which was an oligomer having a weight average molecular weight of less than 10,000.
［比較例２］
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、７．０％水酸化ナトリウム水溶液３２２ｍｌ（水酸化ナトリウム０．４７８モル）、塩化メチレン６４０ｍｌ及びトリエチルアミン１．０３ｍｌ（０．０１モル）を仕込んで溶解し、攪拌下２０〜２５℃に保持し、ホスゲン３０．４ｇ（０．３０１モル）を約６０分を要して吹込み、ホスゲン吹き込み中に適宜２５％水酸化ナトリウム水溶液２９ｍｌ（水酸化ナトリウム０．２３９モル）を加えながら反応混合液のｐＨを９〜１０に維持してホスゲン化反応させた。ホスゲン化反応終了後ｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）を加え、２５％水酸化ナトリウム水溶液４４ｍｌ（水酸化ナトリウム０．３６３モル）を約６０分かけて加え、以後実施例１と同様の操作を行ったところ、重量平均分子量４１，０００であるハロゲン化ポリカーボネートを得た。
[Comparative Example 2]
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 130 g (0.239 mol) of tetrabromobisphenol A, 322 ml of 7.0% aqueous sodium hydroxide solution (0.478 mol of sodium hydroxide), 640 ml of methylene chloride and 1. 03 ml (0.01 mol) was charged and dissolved, and the mixture was kept at 20 to 25 ° C. with stirring, and 30.4 g (0.301 mol) of phosgene was blown in about 60 minutes. A phosgenation reaction was carried out while maintaining the pH of the reaction mixture at 9 to 10 while adding 29 ml of a sodium hydroxide aqueous solution (0.239 mol of sodium hydroxide). After completion of the phosgenation reaction, 0.20 g (0.0013 mol) of p-tert-butylphenol was added, and 44 ml of 25% aqueous sodium hydroxide solution (0.363 mol of sodium hydroxide) was added over about 60 minutes. As a result of the same operation as described above, a halogenated polycarbonate having a weight average molecular weight of 41,000 was obtained.
［比較例３］
米国特許第４，７９４，１５６号公報を参考に高分子量ハロゲン化ポリカーボネートの製造方法を追試した。
ホスゲン吹込管、温度計及び攪拌機を備えたフラスコにテトラブロムビスフェノールＡ１３０ｇ（０．２３９モル）、５０％水酸化ナトリウム水溶液３７．９ｇ（水酸化ナトリウム０．４７４モル）、水４８０ｍｌ、塩化メチレン３２０ｍｌ及びｐ−ｔｅｒｔ−ブチルフェノール０．２０ｇ（０．００１３モル）を仕込んで溶解し、攪拌下２２〜２８℃に保持し、ホスゲン３４．８ｇ（０．３５２モル）を約３０分要して吹込み、ホスゲン吹き込み中に適宜５０％水酸化ナトリウム水溶液４．７ｇ（水酸化ナトリウム０．０５９モル）を加えながら反応混合液のｐＨを１０に維持してホスゲン化反応させた。ホスゲン化反応終了後、塩化メチレン６３０ｍｌおよびＮ，Ｎ−ジメチルアミノピリジン６５ｍｇ（０．０００５３モル）を加え撹拌を開始し、ｐＨ１０を維持するように５０％水酸化ナトリウム水溶液３７．５ｇ（水酸化ナトリウム０．４６８モル）を約３０分かけて加えた後、ホスゲン３．２ｇ（０．０３２モル）を加えｐＨ７にして撹拌を停止した。以後実施例１と同様の操作を行ったところ、重量平均分子量２０１，０００、分散４．９、オリゴマー量０．６２％である高分子量ハロゲン化ポリカーボネートを得た。
[Comparative Example 3]
With reference to US Pat. No. 4,794,156, a method for producing a high molecular weight halogenated polycarbonate was additionally tested.
In a flask equipped with a phosgene blowing tube, a thermometer and a stirrer, 130 g (0.239 mol) of tetrabromobisphenol A, 37.9 g of 50% aqueous sodium hydroxide solution (0.474 mol of sodium hydroxide), 480 ml of water, 320 ml of methylene chloride and p-tert-Butylphenol 0.20 g (0.0013 mol) was charged and dissolved, maintained at 22-28 ° C. with stirring, and 34.8 g (0.352 mol) of phosgene was blown in over about 30 minutes, While the phosgene was being blown in, 4.7 g of a 50% aqueous sodium hydroxide solution (0.059 mol of sodium hydroxide) was added appropriately to maintain the pH of the reaction mixture at 10 for a phosgenation reaction. After completion of the phosgenation reaction, 630 ml of methylene chloride and 65 mg (0.00053 mol) of N, N-dimethylaminopyridine were added to start stirring, and 37.5 g of 50% aqueous sodium hydroxide solution (sodium hydroxide was maintained so as to maintain pH 10). 0.468 mol) was added over about 30 minutes, and then 3.2 g (0.032 mol) of phosgene was added to adjust the pH to 7 and stirring was stopped. Thereafter, the same operation as in Example 1 was performed to obtain a high molecular weight halogenated polycarbonate having a weight average molecular weight of 201,000, a dispersion of 4.9, and an oligomer amount of 0.62%.
本発明の高分子量ハロゲン化ポリカーボネートは、気体分離膜等の中空糸繊維用途として有用である。 The high molecular weight halogenated polycarbonate of the present invention is useful for use in hollow fiber fibers such as gas separation membranes.
Claims (6)
とを有機溶媒の存在下反応させてハロゲン化カーボネート化合物を製造するに当り、ホス
ゲン化反応終了時までのアルカリの総使用量が該二価フェノールに対し、１．０〜２．０
倍モルの範囲に抑え続く重合反応に移行すること、且つアミン類触媒を一連の反応を通し
て使用することを特徴とした重量平均分子量が５０，０００より大きい高分子量ハロゲン
化ポリカーボネート化合物の製造方法。
（III）Ｄ１およびＤ２は同一かまたは異なるハロ基、たとえばフルオロ、クロロ、ブロモまたはヨードであり；
（IV）ａ，ｂ，ｃ，ｄは整数であり０＜ａ≦４および０＜ｂ≦４；かつｃ＝４−ａおよびｄ＝４−ｂである） In producing a halogenated carbonate compound by reacting an alkali aqueous solution of a halogen-substituted dihydric phenol represented by the following general formula (1) with phosgene in the presence of an organic solvent, the total use of alkali until the end of the phosgenation reaction The amount is 1.0 to 2.0 with respect to the dihydric phenol.
A process for producing a high-molecular-weight halogenated polycarbonate compound having a weight average molecular weight of more than 50,000, characterized in that the polymerization reaction is continued in a range of double moles and an amine catalyst is used throughout a series of reactions.
(III) D1 and D2 are the same or different halo groups, such as fluoro, chloro, bromo or iodo;
(IV) a, b, c, d are integers, 0 <a ≦ 4 and 0 <b ≦ 4; and c = 4-a and d = 4-b)
に対して１．０倍モル以上２．０倍モル以下とし、且つアミン類触媒を存在させて、該二
価フェノールに対して１．０〜１．５倍モルのホスゲンを添加しホスゲン化反応を行い、
ホスゲン化後の反応液にアルカリ化合物を逐次添加し重合反応させることを特徴とする請
求項１記載の高分子量ハロゲン化ポリカーボネート化合物の製造方法。 The total amount of the alkali compound used until the end of the phosgenation reaction is 1.0 to 2.0 times the mol of the halogen-substituted dihydric phenol, and an amine catalyst is present to the dihydric phenol. The phosgenation reaction is performed by adding 1.0 to 1.5-fold moles of phosgene to
2. The method for producing a high molecular weight halogenated polycarbonate compound according to claim 1, wherein an alkali compound is sequentially added to the reaction solution after phosgenation to cause a polymerization reaction.
（Ｉ）ホスゲン化反応前、
（II）ホスゲン化反応時、
（III）ホスゲン化後、
（IV）重合反応時、
のうち少なくとも１点以上選択することを特徴とした請求項１記載の高分子量ハロゲン化
ポリカーボネート化合物の製造方法。 When the amine catalyst is added,
(I) Before the phosgenation reaction,
(II) During the phosgenation reaction,
(III) After phosgenation,
(IV) During the polymerization reaction,
2. The method for producing a high molecular weight halogenated polycarbonate compound according to claim 1, wherein at least one point is selected.
ェニル）プロパンである請求項１記載の高分子量ハロゲン化ポリカーボネート化合物の製
造方法。 The method for producing a high molecular weight halogenated polycarbonate compound according to claim 1, wherein the halogen-substituted dihydric phenol is 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
し１．２〜１．８倍モルである請求項１記載の高分子量ハロゲン化ポリカーボネート化合
物の製造方法。 The method for producing a high-molecular-weight halogenated polycarbonate compound according to claim 1, wherein the total amount of alkali used up to the end of the phosgenation reaction is 1.2 to 1.8 times mol of the halogen-substituted dihydric phenol.
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