CN1648153A - Purified polycarbonate organic solution and method for producing high-purity polycarbonate - Google Patents
Purified polycarbonate organic solution and method for producing high-purity polycarbonate Download PDFInfo
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- CN1648153A CN1648153A CN 200510005809 CN200510005809A CN1648153A CN 1648153 A CN1648153 A CN 1648153A CN 200510005809 CN200510005809 CN 200510005809 CN 200510005809 A CN200510005809 A CN 200510005809A CN 1648153 A CN1648153 A CN 1648153A
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- CN
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- Prior art keywords
- organic solution
- polycarbonate
- separation device
- water
- polycarbonate organic
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 172
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 172
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 135
- 238000005406 washing Methods 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000012074 organic phase Substances 0.000 claims abstract description 50
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 239000000839 emulsion Substances 0.000 claims abstract description 26
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims description 140
- 238000005054 agglomeration Methods 0.000 claims description 97
- 230000002776 aggregation Effects 0.000 claims description 97
- 239000007788 liquid Substances 0.000 claims description 52
- 238000007670 refining Methods 0.000 claims description 40
- -1 polytetrafluoroethylene Polymers 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 239000012071 phase Substances 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- 238000004945 emulsification Methods 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 5
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 8
- 238000012696 Interfacial polycondensation Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000008346 aqueous phase Substances 0.000 abstract description 6
- 230000001804 emulsifying effect Effects 0.000 abstract description 3
- 230000015271 coagulation Effects 0.000 abstract 6
- 238000005345 coagulation Methods 0.000 abstract 6
- 238000009825 accumulation Methods 0.000 abstract 1
- 230000005484 gravity Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000008676 import Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
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- 238000010828 elution Methods 0.000 description 5
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 3
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006085 branching agent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 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 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle 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
- 239000001294 propane Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 1
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-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
- XISFOXBYRQWDNK-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine;hydrochloride Chemical compound [Cl-].CC1=CC=CC=C1C(C)(C)[NH3+] XISFOXBYRQWDNK-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- PWDGALQKQJSBKU-UHFFFAOYSA-N 2-chloro-4-(3-chloro-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Cl)C(O)=CC=C1S(=O)(=O)C1=CC=C(O)C(Cl)=C1 PWDGALQKQJSBKU-UHFFFAOYSA-N 0.000 description 1
- WRLVTKZXVVEUPL-UHFFFAOYSA-N 2-chloro-4-propylphenol Chemical compound CCCC1=CC=C(O)C(Cl)=C1 WRLVTKZXVVEUPL-UHFFFAOYSA-N 0.000 description 1
- KMWKHQSAKNXIIW-UHFFFAOYSA-N 2-fluoro-4-propylphenol Chemical compound CCCC1=CC=C(O)C(F)=C1 KMWKHQSAKNXIIW-UHFFFAOYSA-N 0.000 description 1
- LDQYTDPXIMNESL-UHFFFAOYSA-N 2-methyl-4-propylphenol Chemical compound CCCC1=CC=C(O)C(C)=C1 LDQYTDPXIMNESL-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- LQOBMKYCRQDMTN-UHFFFAOYSA-N 3-(2-ethylphenyl)pentan-3-amine;hydrochloride Chemical compound Cl.CCC1=CC=CC=C1C(N)(CC)CC LQOBMKYCRQDMTN-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class 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 class C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- ASURBSPIYIISGI-UHFFFAOYSA-N 4-(3,3,5-trimethylcyclohexyl)phenol Chemical compound C1C(C)(C)CC(C)CC1C1=CC=C(O)C=C1 ASURBSPIYIISGI-UHFFFAOYSA-N 0.000 description 1
- KQSIVRHDEPHUII-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenoxy)-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(OC=2C=C(C)C(O)=C(C)C=2)=C1 KQSIVRHDEPHUII-UHFFFAOYSA-N 0.000 description 1
- SUCTVKDVODFXFX-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfonyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 SUCTVKDVODFXFX-UHFFFAOYSA-N 0.000 description 1
- IBNFPRMKLZDANU-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)sulfanyl-2-methylphenol Chemical compound C1=C(O)C(C)=CC(SC=2C=C(C)C(O)=CC=2)=C1 IBNFPRMKLZDANU-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical class C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)phenol Chemical class C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- OIFVQQSNDHJWTF-UHFFFAOYSA-N 4-(naphthalen-1-ylmethyl)phenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC2=CC=CC=C12 OIFVQQSNDHJWTF-UHFFFAOYSA-N 0.000 description 1
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-UHFFFAOYSA-N 0.000 description 1
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- KNDDEFBFJLKPFE-UHFFFAOYSA-N 4-n-Heptylphenol Chemical compound CCCCCCCC1=CC=C(O)C=C1 KNDDEFBFJLKPFE-UHFFFAOYSA-N 0.000 description 1
- SZWBRVPZWJYIHI-UHFFFAOYSA-N 4-n-Hexylphenol Chemical compound CCCCCCC1=CC=C(O)C=C1 SZWBRVPZWJYIHI-UHFFFAOYSA-N 0.000 description 1
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- 238000005299 abrasion Methods 0.000 description 1
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- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
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- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 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
- QOQHDJZWGSAHFL-UHFFFAOYSA-N butylphosphanium;bromide Chemical class [Br-].CCCC[PH3+] QOQHDJZWGSAHFL-UHFFFAOYSA-N 0.000 description 1
- CXUFAAUKTHVLAL-UHFFFAOYSA-N butylphosphanium;chloride Chemical compound [Cl-].CCCC[PH3+] CXUFAAUKTHVLAL-UHFFFAOYSA-N 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 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
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- PWAPCRSSMCLZHG-UHFFFAOYSA-N cyclopentylidene Chemical group [C]1CCCC1 PWAPCRSSMCLZHG-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001987 diarylethers Chemical class 0.000 description 1
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- HDVRLUFGYQYLFJ-UHFFFAOYSA-N flamenol Chemical compound COC1=CC(O)=CC(O)=C1 HDVRLUFGYQYLFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a method for producing a purified polycarbonate organic solution by mixing a crude polycarbonate organic solution containing water-soluble impurities after completion of a polycondensation reaction by an interfacial polycondensation method with an aqueous washing solution, emulsifying the mixture, and separating the emulsion into an organic phase and an aqueous phase by using a coagulation separator, wherein the polycarbonate organic solution and the aqueous washing solution are not formed into a substantial interface separating the organic phase and the aqueous phase in at least a part of the components in the coagulation separator, and the coagulation separator is operated to prevent the adhesion and accumulation of impurities of an intermediate specific gravity to at least a part of the components in the coagulation separator by controlling the amount of the polycarbonate organic solution from which water has been removed from the coagulation separator and the amount of the aqueous solution containing impurities including a part of the polycarbonate organic solution drawn from the top of the coagulation separator, and a process for producing a high-purity polycarbonate by using the purified polycarbonate organic solution.
Description
Technical field
The present invention relates to use the water-washing liquid washing to make with extra care the method for polycarbonate, and adopt this refining polycarbonate organic solution to make the method for highly purified polycarbonate by the rough polycarbonate organic solution preparation that contains water-soluble impurity that interface polycondensation obtains.Say in further detail, the rough polycarbonate organic solution that contains water-soluble impurity that the present invention relates to mix the water-washing liquid washing and obtain by interface polycondensation, emulsification, use agglomeration separation device (coalescer) that this separation of emulsions is organic phase and the water that contains impurity, make when making with extra care polycarbonate organic solution, this agglomeration separation device of running under specific operational condition, the impurity of proportion adheres in the middle of preventing on the part of parts at least in the agglomeration separation device, accumulate, can carry out stable lock out operation, make the method for refining polycarbonate organic solution simultaneously expeditiously, and use this refining polycarbonate organic solution to make the method for high-purity polycarbonate.
Background technology
As the manufacture method of polycarbonate, well-known to be to use halogen such as methylene dichloride be the interface polycondensation of organic solvent.When preparing polycarbonate, after finishing, polycondensation obtains containing the organic solution of polycarbonate and the mixture of the aqueous solution with this interface polycondensation.The organic solution that contains polycarbonate is made emulsion state usually, so need be the operation that contains the organic solution of polycarbonate and contain the aqueous solution of impurity to separation of emulsions.
In addition, in the polycarbonate organic solution after reaction finishes, because residual have influential sodium of pair quality or impurity such as unreacted monomer, catalyzer, so carry out adding the method for agitator treatings such as alkaline aqueous solution, acidic aqueous solution, pure water usually in polycarbonate organic solution.Further, in order to improve detersive efficiency, carry out the powerful mixture that stirs rough polycarbonate organic solution and washings, the emulsive operation.
In the past, as the isolating again method of the emulsion that will obtain like this, known had liquid liquid centrifugal separation, standing separation method or an agglomeration separation method.But centrifugal separation is installation cost, upkeep cost height not only, and burning of usually causing that buildup of resin produces such as the volatilization of the fault of rotating part, abrasion, reaction solvent methylene dichloride, separating machine fault such as stop, therefore needing to prepare pre-standby host.In addition because standing separation method settling velocity is also slow, the shortcoming that needs large-scale standing separation groove etc. is arranged.
Therefore, as the method that solves these shortcomings, developed the agglomeration separation method.For example, disclosing at the contact angle with water is the isolating method of polycarbonate resin liquid (the public clear 46-41622 communique of reference example such as spy) that feeds in the filtering layer below 40 °.But this method is owing to difficultly remove fine water droplet, so need repeatedly also to sneak into the pollutent from filtering layer in addition by filtering layer after separation, further by separating behind the filtering material, spended time for this reason is so need bigger standing separation groove.
There is report to disclose the water-based phase emulsification polycarbonate organic solution of the scope of use pH2～14, with the space velocity of 0.01-2cm/ second layer of fibers, be separated into the method (reference example such as spy open clear 55-104316 communique) of 2 phases by thickness 10-500mm, apparent density 0.2-0.7g/ml.But this method is because the thickness of filtering layer is big, takes place because the problem of the big pressure-losses that weighting material brings etc. so exist.
In addition, also disclose by using mixing tank mixed polycarbonate solution and water-washing liquid, after making the mixing solutions of oil-in-water type emulsion state, by filtering layer, be separated into the washing methods (reference example such as spy open flat 7-309940 communique) of polycarbonate solution phase and water-washing liquid polycarbonate solution mutually.But because this method is used the water-washing liquid phase more, so spend cost on its draining is handled, efficient is not high.
Further, method (reference example such as spy open the 2001-31755 communique) with metal filter material separating oil bag droplet-shaped emulsion is also disclosed.But it is also hard to say very abundant from its separation performance of amount of moisture.
There is report to disclose a kind of preparation method of the polycarbonate resin according to interface polycondensation, be the solution that contains polycarbonate by the water-washing liquid washing, during from this washings of solution separating of containing polycarbonate, in the agglomeration separation device that contains wetting ability filling material, carry out the washing in the 1st stage, be separated from each other the organic solution that contains polycarbonate and the method (reference example such as spy show the 2002-528580 communique) of washings.
But the lock out operation for use the agglomeration separation device under what kind of operational condition did not disclose, not about record of the present invention.
Summary of the invention
In such situation, the purpose of this invention is to provide the rough polycarbonate organic solution and the water-washing liquid mixing and emulsifying that contain water-soluble impurity after the polycondensation that will adopt interface polycondensation finishes, use the agglomeration separation device with this separation of emulsions during as the refining polycarbonate organic solution of organic phase and water manufacturing, by this agglomeration separation device of running under specific operational condition, the impurity of proportion adhered in the middle of parts at least (element) part in the agglomeration separation device prevented, accumulate, can carry out stable lock out operation, the efficient simultaneously method of refining polycarbonate organic solution and the manufacture method that adopts the high-purity polycarbonate of this refining polycarbonate organic solution made.
The inventor furthers investigate in order to solve above-mentioned problem.Found that, operational condition as this agglomeration separation device, by the part of the parts at least in the agglomeration separation device polycarbonate organic solution and water-washing liquid are separated into organic phase and water two-phase, make it not form the interface of essence, can reach above-mentioned purpose, finish the present invention based on this opinion.
The present invention is made of following.
(1) manufacture method of refining polycarbonate organic solution, be to mix with water-washing liquid by the rough polycarbonate organic solution after the polycondensation end that will adopt interface polycondensation, emulsification, obtain emulsion, this emulsion is imported in the agglomeration separation device, remove and anhydrate, obtain the method for refining polycarbonate organic solution thus, it is characterized in that, parts at least in this agglomeration separation device partly make polycarbonate organic solution and water-washing liquid be separated into the interface that organic phase and water two-phase do not form essence, the extraction amount of the extraction amount of the polycarbonate organic solution of having removed moisture of extracting out from the agglomeration separation device by control and the aqueous solution of extracting out from agglomeration separation device top that contains impurity that comprises a polycarbonate organic solution part, the polycarbonate organic solution of the moisture that is removed.
(2) manufacture method of above-mentioned (1) described refining polycarbonate organic solution, wherein, control comprises that from containing of agglomeration separation device top the extraction amount of the aqueous solution of the impurity of a polycarbonate organic solution part is the 1-1.5 amount doubly of the water-washing liquid amount supplied with.
(3) manufacture method of refining polycarbonate organic solution, be to mix with water-washing liquid by the rough polycarbonate organic solution after the polycondensation end that will adopt interface polycondensation, emulsification, obtain emulsion, this emulsion is imported in the agglomeration separation device, remove and anhydrate, obtain the method for refining polycarbonate organic solution thus, it is characterized in that, parts at least in this agglomeration separation device partly make polycarbonate organic solution and water-washing liquid be separated into organic phase and water two-phase, do not form the interface of essence, the total metering of amount that supplies to the water-washing liquid of the amount of organic solution of the rough polycarbonate in the agglomeration separation device and supply is retracted in the agglomeration separation device the standing separation groove that is arranged on the downstream, extracts polycarbonate organic solution layer out from this standing separation groove.
(4) manufacture method of each described refining polycarbonate organic solution of above-mentioned (1)-(3), wherein, the blending means of rough polycarbonate organic solution and water-washing liquid is to use the blending means of mixing tank in upright arrangement (inline mixer), static mixer (static mixer) or orifice mixer (orifice mixer).
(5) manufacture method of each described refining polycarbonate organic solution of above-mentioned (1)-(4), wherein, the material of the parts in the agglomeration separation device is glass fibre, carbon fiber, steel fiber, polytetrafluoroethylene fiber, polypropylene fibre, polyethylene fibre, paper pulp fiber or bombax cotton.
(6) manufacture method of each described refining polycarbonate organic solution of above-mentioned (1)-(5), wherein, the parts in the agglomeration separation device be shaped as tabular, cylindric or collapsed shape.
(7) manufacture method of each described refining polycarbonate organic solution of above-mentioned (1)-(6), wherein, the structure of the parts in the agglomeration separation device is that fibrolaminar structure has been installed in the cylindrical vessel.
(8) manufacture method of high-purity polycarbonate is characterized in that, the refining polycarbonate organic solution that adopts each described manufacture method of above-mentioned (1)-(7) to obtain.
The simple declaration of accompanying drawing
Fig. 1 represents not form organic phase and water for the part of the parts at least in the agglomeration separation device, extract water by the form that contains some organic phase out from the top, be recycled in the standing separation groove that is arranged on leading portion, extract the organic phase of having made with extra care out from the sidepiece of agglomeration separation device, be transported to 1 example of the embodiments of the present invention of subsequent processing.
Fig. 2 represents not form organic phase and water for the part of the parts at least in the agglomeration separation device, extract water by the form that contains some organic phase out from the top, import in the standing separation groove that is arranged on the downstream side, separate a part at back segment, extract the embodiment of the present invention of refining organic phase simultaneously from sidepiece out.
The agglomeration separation device that Fig. 3 represents to adopt series connection to be provided with is implemented the embodiments of the present invention of the washing operation of neutralizing treatment, acid elution, water washing in turn.
The parts at least that Fig. 4 is illustrated in the agglomeration separation device partly make polycarbonate organic solution and water-washing liquid be separated into organic phase and water two-phase, make it not form the interface of essence, the total metering of amount that supplies to the water-washing liquid of the amount of the rough polycarbonate organic solution in the agglomeration separation device and supply is retracted to the standing separation groove in the downstream that is arranged in the agglomeration separation device, with the embodiment of the present invention of this standing separation groove flash liberation.
Fig. 5 represents the mode chart of institute's facilities and equipments in the comparative example.
Embodiment
The present invention is rough polycarbonate organic solution and the water-washing liquid mixing and emulsifying that will contain water-soluble impurity after will adopting the polycondensation of interface polycondensation to finish, use the agglomeration separation device with this separation of emulsions during as the refining polycarbonate organic solution of organic phase and water manufacturing, by this agglomeration separation device of running under specific operational condition, the impurity of proportion adhered in the middle of parts at least in the agglomeration separation device partly prevented, accumulate, can carry out stable lock out operation, the efficient simultaneously method of refining polycarbonate organic solution and the manufacture method that adopts the high-purity polycarbonate of this refining polycarbonate organic solution made.
In this interface polycondensation, by being principal constituent with dihydric phenol, adding stops the caustic alkali of agent (being also referred to as " molecular weight regulator "), dihydric phenol and branch cladodification agent as required in order to dissolve a spot of end, by prepared in reaction in organic solvent with carbonyl chloride or phosgene derivatives, the rough polycarbonate organic solution and the water-washing liquid that obtain mix, wash water miscible impurity, separate then, prepare polycarbonate through recovery process.
In this interface polycondensation,, for example can enumerate the compound of general formula (I) expression as the employed dihydric phenol of raw material as polycarbonate.
In the above-mentioned general formula (I), X
1And X
2Represent straight chain, side chain or the cyclic alkyl of carbon number 1-6 separately,, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl etc. as concrete example.This X
1And X
2Mutually can be identical, also can be different.A and b represent X separately
1And X
2The replacement number, be the integer of 0-4.X
1When a plurality of, a plurality of X
1Mutually can be identical, also can be different, X
2When a plurality of, a plurality of X
2Mutually can be identical, also can be different.
Y is the alkylene base (for example methylene base, ethylene group, trimethylene base, fourth support base, pentamethylene base, hexamethylene base etc.) of singly-bound, carbon number 1-8, the ring alkylidene (for example cyclopentylidene base, cyclohexylidene base etc.) of the ring alkylene base of the alkylidene of carbon number 2-8 (for example ethidine, isopropylidene etc.), carbon number 5-15 (for example cyclopentylene base, cyclohexalene base etc.), carbon number 5-15 ,-S-,-SO-,-SO
2-,-O-,-key of CO-key or formula (II-1) or formula (II-2) expression.
Here, the dihydric phenol as aforementioned formula (I) expression has various materials, and specially suitable is 2, (the common name: dihydroxyphenyl propane) of 2-two (4-hydroxy phenyl) propane.As the dihydric phenol beyond the dihydroxyphenyl propane, for example can enumerate two (4-hydroxy phenyl) methane; Two (4-hydroxy phenyl) phenylmethane; Two (4-hydroxy phenyl) naphthyl methane; Two (4-hydroxy phenyls)-(4-isopropyl phenyl) methane; Two (3,5-two chloro-4-hydroxy phenyls) methane; Two (3,5-dimethyl-4-hydroxy phenyl) methane; 1,1-two (4-hydroxy phenyl) ethane; 1-naphthyl-1,1-two (4-hydroxy phenyl) ethane; 1-phenyl-1,1-two (4-hydroxy phenyl) ethane; 1,2-two (4-hydroxy phenyl) ethane; The 2-methyl isophthalic acid, 1-two (4-hydroxy phenyl) propane; 2,2-two (3,5-dimethyl-4-hydroxy phenyl) propane; 1-ethyl-1,1-two (4-hydroxy phenyl) propane; 2,2-two (3,5-two chloro-4-hydroxy phenyls) propane; 2,2-two (3,5-two bromo-4-hydroxy phenyls) propane; 2,2-two (3-chloro-4-hydroxy phenyl) propane; 2,2-two (3-methyl-4-hydroxy phenyl) propane; 2,2-two (3-fluoro-4-hydroxy phenyl) propane; 1,1-two (4-hydroxy phenyl) butane; 2,2-two (4-hydroxy phenyl) butane; 1,4-two (4-hydroxy phenyl) butane; 2,2-two (4-hydroxy phenyl) pentane; 4-methyl-2,2-two (4-hydroxy phenyl) pentane; 2,2-two (4-hydroxy phenyl) hexane; 4,4-two (4-hydroxy phenyl) heptane; 2,2-two (4-hydroxy phenyl) nonane; 1,10-two (4-hydroxy phenyl) decane; 1,1-two (4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane; 2,2-two (4-hydroxy phenyl)-1,1,1,3,3, dihydroxyl diaryl paraffinic such as 3-HFC-236fa, 1,1-two (4-hydroxy phenyl) hexanaphthene; 1,1-two (3,5-two chloro-4-hydroxy phenyls) hexanaphthene; 1, dihydroxyl diaryl loop chain alkanes, two (4-hydroxy phenyl) sulfones such as 1-two (4-hydroxy phenyl) cyclodecane; Two (3,5-dimethyl-4-hydroxy phenyl) sulfone; Dihydroxyl diaryl sulfone class, two (4-hydroxy phenyl) ethers such as two (3-chloro-4-hydroxy phenyl) sulfone; Dihydroxyl diaryl ethers, 4,4 '-dihydroxy benaophenonels such as two (3,5-dimethyl-4-hydroxy phenyl) ether; 3,3 ', 5,5 '-tetramethyl--4, dihydroxyl diaryl ketone, two (4-hydroxy phenyl) thioethers such as 4 '-dihydroxy benaophenonel; Two (3-methyl-4-hydroxy phenyl) thioether; Two (3,5-dimethyl-4-hydroxy phenyl) dihydroxyl diaryl sulphoxide classes, 4 such as dihydroxyl diaryl sulfide class, two (4-hydroxy phenyl) sulfoxide such as thioether, dihydroxyl hexichol base class, 9 such as 4 '-dihydroxyl phenylbenzene, dihydroxyl aryl fluorenes classes such as 9-two (4-hydroxy phenyl) fluorenes etc.In addition, except dihydric phenols, can enumerate dihydroxy-benzene classes, 1 such as quinhydrones, Resorcinol, toluhydroquinone, the 5-dihydroxy naphthlene with this general formula (I) expression; 2, dihydroxy naphthlene classes such as 6-dihydroxy naphthlene class etc.These dihydric phenols can be distinguished use separately, also can make up more than two kinds and use.
As molecular weight regulator,, can use various materials so long as be generally used for the polymeric material of polycarbonate.Particularly, as monohydric phenol, for example can enumerate phenol, p-cresol, p-tert-butylphenol, to tert-octyl phenol, to amyl phenol, bromophenol, tribromophenol, nonylphenol etc.Wherein, from economy, preferred p-tert-butylphenol in aspects such as easiness and the phenol bought.
Among the present invention, can use suitable branching agent with aforementioned dihydric phenol.As this branching agent, can enumerate the above polyphenol of ternary, particularly, can enumerate 1,1,1-three (4-hydroxy phenyl) ethane, α, α ', α "-three (4-hydroxy phenyls)-1,3; 5-triisopropylbenzene, 1-[Alpha-Methyl-α-(4 '-hydroxy phenyl) ethyl]-4-[α ', α '-two (4 "-hydroxy phenyl) ethyl] benzene, Phloroglucinol monomethyl ether, isatin two (ortho-cresol) etc.The usage quantity of these branching agents also can be different and different according to the degree of branching as purpose, usually with respect to dihydric phenol, for about 0.05-2 mole %.
During by interfacial polycondensation manufactured polycarbonate, use can generate the compound of carbonic acid ester bond in the polycarbonate main chain, for example use with carbonyl chloride as representative, three carbonyl chlorides, bromine carbonyl chloride, two (2,4, the 6-trichlorophenyl) carbonic ether, two (2,4 dichloro benzene base) carbonic ether, two (2-cyano-phenyl) carbonic ether, superpalite etc.
Manufacturing process as the polycarbonate in the interface polycondensation has no particular limits, and can use operation commonly used in the existing employing interfacial polycondensation manufactured polycarbonate.The for example polymerization process of the modulating process by implementing (A) dihydric phenol polycarbonate oligomer, (B) above-mentioned oligopolymer, (C) washing procedure and (D) separation, the recovery process of polycarbonate can be made expeditiously as the object polycarbonate.
In addition, among the present invention, do not separate aforementioned (A) operation and (B) operation, can be directly to the polymerization of polymkeric substance yet.In addition, the version of polycarbonate can be in batch-type and the continous way any, preferred continous way adopts the occasion of this continous way, connect carry out aforementioned (A) operation and (B) operation be favourable.
Below, each operation of simple declaration.
(A) operation:
Should (A) operation be to make dihydric phenol and carbonyl chloride or phosgene derivatives interfacial polycondensation, the operation of modulation dihydric phenol polycarbonate oligomer.
Modulator approach for this dihydric phenol polycarbonate oligomer has no particular limits, and for example can preferably use following method.
At first, modulation contains the alkaline aqueous solution of the aforementioned dihydric phenol of raw material, it is mixed with inert organic solvents, under the coexistence of alkaline aqueous solution that contains dihydric phenol and inert organic solvents, make it the reaction of carbonyl chloride or phosgene derivatives while stirring, obtain the dihydric phenol polycarbonate oligomer thus.
At this moment, as alkaline aqueous solution, preferably use the alkaline aqueous solution of its concentration usually as 1-15 quality %.In addition, the content of dihydric phenol is selected in 0.5-20 quality % scope usually in the alkaline aqueous solution.Further, the usage quantity of inert organic solvents, the volume ratio of wishing organic phase and water is 5/1-1/7, preferred 2/1-1/4 selectes like that.Temperature of reaction is generally 0-50 ℃, preferred 5-40 ℃ scope.
In this reaction, make the reaction of carbonyl chloride or phosgene derivatives after, can further add the alkaline aqueous solution that contains dihydric phenol, a part that end stops agent and required catalyzer, react.
As the used alkali of the modulation of the alkaline aqueous solution that contains above-mentioned dihydric phenol, for example can enumerate sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide etc., wherein, preferred sodium hydroxide and potassium hydroxide, preferred especially sodium hydroxide.In addition, as inert organic solvents, various solvents is arranged.For example, can enumerate methylene dichloride; Chloroform; Tetracol phenixin; 1, the 1-ethylene dichloride; 1, the 2-ethylene dichloride; 1; Vinyl trichloride; Unsym.-tetraehloroethane; Sym.-tetrachloroethane; Pentaline; Hydrochloric ethers such as chlorobenzene, toluene, methyl phenyl ketone etc.These organic solvents can be distinguished use separately, also can make up more than two kinds and use.Wherein preferred especially methylene dichloride.
As catalyzer, can preferably use alternate moving catalyst, for example tertiary amine or its salt, quaternary ammonium salt, quaternary alkylphosphonium salt etc.
As tertiary amine, can enumerate for example triethylamine, Tributylamine, N, N-dimethylcyclohexylamine, pyridine, xylidine, N-methyl piperidine etc. in addition as tertiary ammonium salt, for example can be enumerated hydrochloride, bromate of these tertiary amine etc.As quaternary ammonium salt, for example can enumerate trimethyl benzyl ammonia chloride, triethyl benzyl ammonia chloride, tributyl benzyl ammonium chloride, tri-n-octyl methyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide etc., as quaternary alkylphosphonium salt, for example can enumerate 4-butyl phosphonium chloride, four butyl phosphonium bromides etc.These catalyzer can be distinguished use separately, also can make up more than two kinds and use.In the aforementioned catalyzer, preferred tertiary amine, preferred especially triethylamine.
Reaction back is by leaving standstill or operation such as centrifugation, is separated into water and contains the organic phase of polycarbonate oligomer.Organic phase needn't be separated polycarbonate oligomer, can be used for next operation.
(B) operation;
It is the polymerization process of the polycarbonate oligomer that in aforementioned (A) operation, obtains, in the presence of the catalyzer used, alkaline aqueous solution and inert organic solvents, residual end is stopped agent, this polycarbonate oligomer and dihydric phenol interfacial polycondensation according to hope.
Particularly, polycarbonate oligomer solution, the residual end that aforementioned operation (A) is obtained stops agent, the alkaline aqueous solution of used catalyzer, inert organic solvents, alkaline aqueous solution, dihydric phenol mixes as required, carries out interfacial polycondensation under the temperature of 0-50 ℃ usually, preferred 5-40 ℃ scope.
Alkali, inert organic solvents and the catalyzer that use this moment, can enumerate with aforementioned (A) operation in the same material of material that illustrates.The occasion of the volume ratio of organic phase in this interfacial polycondensation and water and aforementioned (A) operation is same in addition.
In addition, in this polymerization process, polymerization is separately carried out in prepolymerization (pre-polymerization) and this polymerization (post polymerization).Promptly, first-selection stops polycarbonate oligomer solution, the residual end that obtains in aforementioned (A) operation agent, mixes according to the used catalyzer of hope, inert organic solvents, alkaline aqueous solution, in lower temperature, for example carry out prepolymerization (pre-polymerization) in the temperature that is lower than 20 ℃.Then, add the alkaline aqueous solution of dihydric phenol again, under the higher temperature for example the temperature about 20-40 ℃ carry out this polymerization (post polymerization).
After the reaction, with inert organic solvents suitably after the dilution,, be separated into water and contain the organic phase of polycarbonate by leaving standstill or operation such as centrifugation.
(C) operation:
Should (C) operation be the washing procedure of isolating rough polycarbonate organic solution in above-mentioned (B) operation.Obtain the method for the high polycarbonate organic solution of purity as removing residual monomer from the impurity of this polycarbonate organic solution, catalyzer, alkaline matter etc., by in this polycarbonate organic solution, adding washing water such as alkaline aqueous solution, acidic aqueous solution, pure water, mix, impurity is extracted into aqueous phase side carries out.Any of these washing operations can be only implemented in such washing, also can make up 2 kinds or the washing methods more than 3 kinds, also can set the number of times of these washing operations as required arbitrarily.
As the blending means of rough polycarbonate organic solution and water-washing liquid, can use liquid/liquid to be mixed into commercially available any instrument of purpose, for the stirring efficiency that obtains to wish, preference such as mixing tank in upright arrangement, static mixer or orifice mixer etc.As the stirring power of these mixing tanks, also relevant with the material of parts in the agglomeration separation device described later, be generally 0.1kW/m
3More than/the hr, preferred 0.2kW/m
3More than/the hr, further preferred 0.5kW/m
3More than/the hr.When stirring intensity is weak, not only can not wash fully, it is many that the moisture in the polycarbonate organic solution after the separation becomes, and the quality of the polycarbonate that the result obtains reduces.This shows on most qualities preferred material not in the organic phase side, but in aqueous phase side.
The water amount of the water-washing liquid the during mixing of rough polycarbonate organic solution and water-washing liquid usually below 50 volume %, preferred 30-3 volume %, more preferably 20-5 volume %.Even use water-washing liquid in a large number, expense on draining is handled, uneconomical.
In the washing of the present invention, constitute the organic phase (oil phase) of emulsion and the relation of water and can be useful in the occasion that W/O drips any in the oil droplet decentralized in decentralized, the water, but water droplet decentralized in the preferred oil.
For the present invention, in polymerization process, mix emulsification with water-washing liquid with the rough polycarbonate organic solution of aqueous phase separation.Use the agglomeration separation device that this emulsive separation of emulsions is organic phase and water.The agglomeration separation device is the utensil that promotes the cohesions such as water droplet in the emulsion, causes separating of organic phase and water when leading to liquid, separates in the groove (housing) of agglomeration separation device usually.At this moment, if in the agglomeration separation tank or the parts in groove parts carry out lock out operation with the state that the biphase interface of organic phase and water exists in fact, for example metal chloride, metal hydroxides, deterioration monomer and polymkeric substance etc. are put aside in this groove than heavy substance in the centre of impurity, for this reason, make the lost of life of agglomeration separation device inner part, not only lock out operation that can not be stable, and purified precision reduces, and can not obtain the high refining polycarbonate organic solution of purity.In addition, the parts part in the said here groove is meant the zone between two horizontal planes in the groove of the upper surface that comprises parts respectively and lower surface.Therefore, having passed through the organic phase and the separating with other separator tank of water of agglomeration separation device implements, need extract the aqueous solution that contains impurity like that out with a part that contains polycarbonate organic solution from the top of agglomeration separation device, make parts at least part in the groove of agglomeration separation device not form the biphase interface of organic phase and water in fact.Thus, the part of the parts at least in the groove of the agglomeration separation device biphase interface that forms organic phase and water in fact becomes and does not exist.At this moment, also can utilize this groove to separate (for example with reference to Fig. 1 and Fig. 3), also separator tank (for example with reference to Fig. 2) can be set in the downstream side of agglomeration separation device if separator tank is set in the leading portion operation.In addition, the extraction amount that comprises the aqueous solution that contains impurity of part polycarbonate organic solution has no particular limits, as long as it is just enough about doubly to control to the 1-1.5 of amount of water-washing liquid of supply.Further, total metering of the amount of the water-washing liquid by adopting the amount will supply to the polycarbonate organic solution in the agglomeration separation device and supply is retracted to the method for the standing separation groove that is arranged on the downstream in the agglomeration separation device, also can make the part of parts at least in the agglomeration separation tank form organic phase in fact and there be not (for example with reference to Fig. 4) in water biphase interface.
Used agglomeration separation device can use the agglomeration separation device of commercially available usually arbitrary form, for example can use the goods with emerging industry (strain), Japanese Port-Le (strain), the filter of Fuji (strain), Asahi Chemical Industry's fiber (strain) etc.
In the agglomeration separation device, install and have the parts that in fact promote the cohesion function, material as these parts has no particular limits, and porous materials such as organic fibre, porous matter carbon graphite such as the synthetic resin fiber of existing known glass fibre, carbon fiber, steel fiber, polytetrafluoroethylene (PTFE), polypropylene (PP) or polyethylene (PE) etc., paper pulp, kapok all can use.Wherein the separation after to the washing of polycarbonate organic solution of carbon fiber or glass fibre is better.
The shape of parts can be used tabular, cylindric or collapsed shape from operation, the easy degree that is provided with, can select the suitableeest shape in price, sees the parts of preferably drum shape from operating aspect.In addition, the structure of parts is fibrolaminar also passable, in order to keep intensity, also can be the structure of guard ring (retainer) etc., on performance and remove foreign matter the fluid and also can form multi-ply construction more than 2 layers or 2 layers.The wherein textural preferably fibrolaminar structure of arrangement in cylindrical vessel.The fibrolaminar thickness of component parts also can freely be set according to performance, for example can be from optimization on fibrolaminar thickness, pressure difference Δ P and the separation performance.
The either direction that is arranged on longitudinal direction, transverse direction of these parts can in addition.
Next, describe based on the example of accompanying drawing the embodiment of the lock out operation of the present invention of use agglomeration separation device.
Fig. 1 represents 1 example of embodiments of the present invention, promptly, the reaction solution that contains polycarbonate of the operation of auto-polymerization in the future imports in the standing separation groove of leading portion, rough polycarbonate organic solution with heavy lower floors of extraction such as pumps, add water-washing liquid halfway, (line mixer) mixes with mixing tank in upright arrangement, emulsification, this emulsion is passed through the agglomeration separation device, be separated into organic phase and water, simultaneously in order to make part organic phase of parts at least and water in the agglomeration separation device not form two-phase in fact, by extracting water out from the top with the form that contains some organic phase, be recycled in the aforementioned standing separation groove, extract the purified organic phase out, be transplanted in the subsequent processing from the sidepiece of agglomeration separation device.At this moment, there is no particular limitation for the amount of the water of extracting out from the top that contains some organic phase, as above-mentioned, as long as it is just enough about doubly to be controlled to be the 1-1.5 of amount of water-washing liquid of supply.Aqueous portion in the standing separation groove is extracted out by other approach, is transplanted on the draining treatment process.
Fig. 2 represent with emulsion import be separated into organic phase and water in the agglomeration separation device after, for part organic phase of parts at least and water at the agglomeration separation device do not form two-phase, by extracting water out from the top with the form that contains some organic phase, import in the standing separation groove of downstream side setting, separate in a back segment part, extract the mode of refining organic phase simultaneously from the sidepiece of agglomeration separation device out.As long as the amount of the water of extracting out from the top that contains some organic phase is with above-mentioned with degree.The aqueous portion that is arranged in the standing separation groove in downstream side is extracted out in addition, is transplanted on the draining treatment process.
The agglomeration separation device that Fig. 3 represents to adopt series connection to be provided with is implemented the embodiments of the present invention of neutralizing treatment, acid elution, water washing.Aqueous portion under this occasion in the standing separation groove also is other extraction, is transplanted on the draining treatment process.
Fig. 4 is illustrated in the part of parts at least in the agglomeration separation device in order polycarbonate organic solution and water-washing liquid not to be formed be separated into the interface of organic phase and water biphase essence, the total metering of amount that supplies to the water-washing liquid of the amount of organic solution of the rough polycarbonate in the agglomeration separation device and supply is retracted to the standing separation groove in the downstream that is arranged in the agglomeration separation device, carries out the embodiment of the present invention of lock out operation at this standing separation groove.Aqueous portion under this occasion in the standing separation groove is also extracted out in addition, is transplanted in the draining treatment process.
(D) operation
Should (D) operation be separation, the recovery process of polycarbonate.Particularly; after for example concentrating by the refining polycarbonate organic solution that above-mentioned (C) operation is obtained through carrying out washing treatment; pulverization process obtains fragment, this fragment is implemented the drying treatment of vacuum-drying etc.; obtain the high-purity polycarbonate goods; in addition, by with this polycarbonate of melting mixings such as forcing machine, extrude; granulating also can obtain coating of particles.
Polycarbonate sees that from aspects such as physical strength and formabilities preferred viscosities molecular-weight average (MV) is 10,000-100,000 scope.More preferably Mv is 12,000-40, and 000, preferred especially 13,000-30,000 scope.In addition, this viscosity-average molecular weight (Mv) is the viscosity that adopts in the dichloromethane solution of Ubbelohde type viscometer determining under 20 ℃, tries to achieve limiting viscosity [η] thus, according to [η]=1.23 * 10
-5The value that the formula of Mv 0.83 is calculated.
Embodiment
The present invention will be described in more detail to fetch down employing embodiment, but scope of the present invention is not limited by this.The mensuration of the amount of moisture in the polycarbonate organic solution (being called polymers soln) is measured according to Ka Er-Brigit Fischer (Schmidt) (Karl Fischer) method.
Production Example 1
(1) manufacturing of polycarbonate oligomer
Dihydroxyphenyl propane (BPA) is dissolved in the caustic soda that concentration is 6 quality % (NaOH) aqueous solution, obtains the BPA-NaOH solution of concentration 14.5 quality %.With the BPA-Na0H solution that obtains with 40L/hr, the p-tert-butylphenol of concentration 25 quality % (PTBP: molecular weight regulator)-dichloromethane solution is with 0.35L/hr, methylene chloride is with the flow of 18.5L/hr, be immersed in 20 ℃ the cooling tank, import in the tube-type reactor of internal diameter 6mm, length 30m, the flow with 3.8kg/hr is blown into carbonyl chloride then.The reaction mixture that will go out autoreactor imports in the separator tank, and water phase separated obtains containing the organic phase of the dichloromethane solution of polycarbonate oligomer.
The proterties of the polycarbonate oligomer that analysis obtains, the result is as follows.
Molecular-weight average: 860 (measuring number-average molecular weight) with vapor pressure osmometer (VPO)
Chloroformic acid ester group concentration: 0.68mol/L (as the organic solvent solution of oligopolymer)
(2) manufacturing of polycarbonate
The dichloromethane solution of the polycarbonate oligomer that (1) is obtained with the BPA-NaOH solution of 20L/hr, above-mentioned (1) synthetic concentration 14.5 quality % with 11.5L/hr, (TEA: catalyzer) aqueous solution is with 0.04L/hr for the triethylamine of concentration 4 quality %, the NaOH aqueous solution of concentration 25 quality % is with 0.8L/hr, and methylene chloride imports to the flow of 13L/hr and makes its reaction in the tower reactor.Residence time is 1 hour.Afterwards, slime flux comes out to obtain to contain the reaction mixture of polycarbonate.
Embodiment 1
Add methylene dichloride in the reaction mixture that contains polycarbonate that obtains according to above-mentioned Production Example 1, the polycarbonate concentration of adjusting the polycarbonate solution of organic phase side is 12 quality %, carry out 1 hour standing separation simultaneously, be separated into the dichloromethane solution (organic phase) and the water that contain polycarbonate.Measure the moisture in this isolating organic phase, the result is 7500 quality ppm.In addition, when the rough polycarbonate before the adding methylene dichloride is measured the viscosity-average molecular weight of polymkeric substance by other approach, MV=28700, when analyzing aqueous phase side, BPA is with the concentration dissolving of 21g/L, and NaOH concentration is 0.22mol/L.
With the dichloromethane solution that contains polycarbonate (organic phase) that obtains like this with 600L/hr, in addition with the caustic soda aqueous solution of NaOH synthetic pH=13 with 60L/hr with mixing tank in upright arrangement (special machine chemical industry system, pipeline mixing machine (pipe line homomixer) mixes under 2600rpm, implements washing.Confirm the phase state of the emulsion of outlet, for W/O drips type.In addition, be 0.53kW/m at this moment to stirring power with fluidic
3/ hr.Further, with the logical continuously liquid of this emulsion to the agglomeration separation device of the leveler that surperficial detection usefulness has been installed (with emerging industry system agglomeration separation device, part dimension: diameter 180mm, internal volume 700L, the material of parts: carbon fiber).Soon, obtain the polymers soln of transparent feel, obtain containing the aqueous solution of some polymers soln from top jet nozzle from the following side nozzle of agglomeration separation device.The aqueous solution flow at top is extracted out with 80L/hr continuously by under meter is set, and implements about 1 hour continuous operation.Confirm interface organic phase and water do not take place in agglomeration separation device inside by leveler.The temperature of the polymers soln of outlet is 32 ℃.Polymers soln for outlet is measured moisture, and the result is about 2000 quality ppm, in the agglomeration separation device, judges separable sufficient moisture by logical liquid.
In addition, in this method, implement 30 days continuous operation after, open agglomeration separation device main body, confirmed body interior and parts, not have to find to begin preceding different dirt the accumulating of foreign matter with running by range estimation.Its result is as shown in table 1.
Embodiment 2～11
Except the record of table 1 as described later changes polymers soln flow, water-washing liquid feed rate, stirs the parts material in power, the agglomeration separation device, other is implemented according to embodiment 1.The results are shown in table 1.
Embodiment 11-1～11-3
Except the record of table 1 as described later changes polymers soln flow, washings feed rate, stirs the parts material in power, the agglomeration separation device, other is implemented according to embodiment 1.The results are shown in table 1.
Embodiment 12～13
Use the polymers soln that obtains among the embodiment 1, in alkaline atmosphere, be through with washing, implement acid elution.Except use with hydrochloric acid adjust pH be 1 water as the water-washing liquid, other implements acid elution according to embodiment 1.The results are shown in table 1.
Embodiment 14～16-2
Except using the polymers soln that obtains among the embodiment 12～13, in acid atmosphere, be through with washing, next implement water washing, use pure water as beyond the water-washing liquid, other implements the washing of water according to embodiment 1.The results are shown in table 1.
Table 1
| Polymers soln flow (L/hr) | Water-washing liquid (L/hr) | Water is than (volume %) | Mixing tank stirs power (kw/m 3/hr) | The material of agglomeration separation device inner part | Polymers soln amount of moisture (* 1) (quality-ppm) | |
| Embodiment 1 | ?600 | ?60 | ?9.1 | ?0.53 | Carbon fiber (* 2) | 2000 |
| Embodiment 2 | ?600 | ?30 | ?4.8 | ?0.62 | ″ | 2100 |
| Embodiment 3 | ?600 | ?100 | ?14.3 | ?0.49 | ″ | 2000 |
| Embodiment 4 | ?600 | ?200 | ?25.0 | ?0.45 | ″ | 2400 |
| Embodiment 5 | ?400 | ?50 | ?11.1 | ?0.61 | ″ | 2000 |
| Embodiment 6 | ?950 | ?120 | ?11.2 | ?0.61 | ″ | 2100 |
| Embodiment 7 | ?600 | ?60 | ?9.1 | ?0.30 | ″ | 2200 |
| Embodiment 8 | ?600 | ?60 | ?9.1 | ?0.15 | ″ | 2300 |
| Embodiment 9 | ?600 | ?60 | ?9.1 | ?0.07 | ″ | 2600 |
| Embodiment 10 | ?700 | ?80 | ?10.3 | ?0.50 | SUS316(*2) | 2400 |
| Embodiment 11 | ?300 | ?60 | ?16.7 | ?0.30 | ″ | 2200 |
| Embodiment 11-1 | ?600 | ?60 | ?9.1 | ?0.03 | Carbon fiber (* 2) | 3700 |
| Embodiment 11-2 | ?300 | ?40 | ?11.8 | ?0.50 | Polypropylene (* 3) | 9800 |
| Embodiment 11-3 | ?300 | ?40 | ?11.8 | ?0.50 | PTFE system (* 4) | 13000 |
| Embodiment 12 | ?600 | ?70 | ?10.4 | ?0.53 | Glass fibre (* 2) | 2200 |
| Embodiment 13 | ?350 | ?50 | ?12.5 | ?0.70 | ″ | 2000 |
| Embodiment 14 | ?600 | ?70 | ?10.4 | ?0.45 | ″ | 2300 |
| Embodiment 15 | ?450 | ?50 | ?10.5 | ?0.55 | ″ | 2000 |
| Embodiment 16 | ?800 | ?120 | ?13.0 | ?0.30 | Carbon fiber (* 2) | 2100 |
| Embodiment 16-2 | ?800 | ?120 | ?13.0 | ?0.03 | ″ | 3400 |
* 1: measure with Ka Er-Brigit Fischer (Schmidt) method
* 2: and emerging industry (strain) inhibition and generation instrument agglomeration separation device
* 3: the filter of Fuji (strain) makes the filter separator VELCON of Fuji
* 4: Japanese Port-Le (strain) Off ェ-ズ セ Star プ agglomeration separation device
Comparative example 1
Among the embodiment 1,, in main body the interface is set and detects and use leveler, adjust the extraction amount of water side, formation separating interface turn round like that (with reference to Fig. 5) in the agglomeration separation device as the method for operation of agglomeration separation device.Like this, implement 120 days continuous operation.Regularly confirm the moisture in the polymers soln, the result shows that running beginning amount of moisture is 2000 quality ppm, but rises to 2600 quality ppm after 120 days.In addition, observe the pressure reduction of agglomeration separation device front and back, results verification begins to be Δ P=9.8kPa in running, but finds to rise to 26.46kPa after 120 days.Running is taken off liquid after finishing, and observes inside, and results verification is finding flatly to exist umbrinaceous sticking dirt settling with respect to the position of having set the interface in agglomeration separation device main body.This dirt settling is carried out metal analysis, found that Fe, Cr, Ni.This thinks a part of stripping of the stainless material that uses in the operation in front, and savings is in the result of near interface.In addition, on same position also chuck (cartridge), infer that this is the reason that causes that pressure rises or moisture rises attached to the agglomeration separation device.
Reference example 1
In the method for embodiment 1 record,,, implement same operation until use after the standing separation till the washing water of mixing tank mixing pH=13 in upright arrangement from modulating rough polycarbonate solution.The emulsion that obtains is collected in the graduated cylinder of 1000mL, carries out standing separation, confirm its velocity of separation and separate after the amount of moisture of polymers soln.As a result, amount of moisture is 5 quality % in the 1 hour standing separation post polymerization thing solution, and amount of moisture is 2 quality % in 2 hours standing separation post polymerization thing solution.
Embodiment 17 (adopting interface polycondensation to carry out full washing procedure)
Established and to have handled continuously as shown in Figure 3 according to the rough polycarbonate organic solution that embodiment 1 obtains, obtained the method for clarifying polycarbonate organic solution.Neutralizing treatment is carried out in the washing of polycarbonate organic solution at first, then carries out acid elution, carries out the pure water washing again, carries out separately 2 times.As polymers soln, use 600L/hr, make water be in a ratio of 12 volume % at whole washing procedures and modulate, agitator is adjusted into and stirs required drive Pv=0.5kW/m in addition
3/ hr.Measure representational impurity for the clarifying polycarbonate organic solution that obtains, results verification Na ion is below the 0.1 quality ppm, and the Fe ion is below the 0.1 quality ppm, and residual BPA is 3.2 quality ppm, efficient is good, and obtains clarifying polycarbonate organic solution.
Next; after the refining polycarbonate organic solution that embodiment 1～17 is obtained concentrates respectively; pulverization process; obtain fragment; this fragment is implemented vacuum drying treatment, obtain highly purified polycarbonate, further with this polycarbonate of melting mixings such as forcing machine; extrude granulating, obtain the particle of high-purity polycarbonate thus.
According to the present invention, rough polycarbonate organic solution and water-washing liquid that water-soluble impurity is provided after providing the polycondensation that will adopt interface polycondensation to finish mix, emulsification, use the agglomeration separation device that this separation of emulsions is organic phase and water, make when making with extra care polycarbonate organic solution, on the part of the parts at least in this agglomeration separation device, make polycarbonate organic solution and water-washing liquid this agglomeration separation device that under the operational condition that does not form the interface that is separated into organic phase and water biphase essence, turns round, the impurity of proportion adheres in the middle of preventing on the part of parts at least in the agglomeration separation device, accumulate, can carry out stable lock out operation, make the method for refining polycarbonate organic solution simultaneously expeditiously, and use this refining polycarbonate organic solution to make the method for high-purity polycarbonate.
Claims (12)
1. make with extra care the manufacture method of polycarbonate organic solution, be to mix with water-washing liquid by the rough polycarbonate organic solution after the polycondensation end that will adopt interface polycondensation, emulsification, obtain emulsion, this emulsion is imported in the agglomeration separation device, remove and anhydrate, obtain the method for refining polycarbonate organic solution thus, it is characterized in that, parts at least in this agglomeration separation device partly make polycarbonate organic solution and water-washing liquid be separated into organic phase and water two-phase, do not form the interface of essence, the extraction amount of the extraction amount of the polycarbonate organic solution of having removed moisture of extracting out from the agglomeration separation device by control and the aqueous solution of extracting out from agglomeration separation device top that contains impurity that comprises part polycarbonate organic solution, the polycarbonate organic solution of the moisture that has been removed.
2. the manufacture method of the described refining polycarbonate organic solution of claim 1, wherein, control is the 1-1.5 amount doubly of the water-washing liquid amount of supply from the extraction amount of the aqueous solution that contains impurity that comprises part polycarbonate organic solution of agglomeration separation device top extraction.
3. make with extra care the manufacture method of polycarbonate organic solution, be to mix with water-washing liquid by the rough polycarbonate organic solution after the polycondensation end that will adopt interface polycondensation, emulsification, obtain emulsion, this emulsion is imported in the agglomeration separation device, remove and anhydrate, obtain the method for refining polycarbonate organic solution thus, it is characterized in that, parts at least in this agglomeration separation device partly make polycarbonate organic solution and water-washing liquid be separated into organic phase and water two-phase, do not form the interface of essence, the total metering of amount that supplies to the water-washing liquid of the amount of the rough polycarbonate organic solution in the agglomeration separation device and supply is retracted in the agglomeration separation device the standing separation groove that is arranged on the downstream, extracts polycarbonate organic solution out from this standing separation groove.
4. the manufacture method of claim 1 or 2 described refining polycarbonate organic solutions, wherein, the blending means of rough polycarbonate organic solution and water-washing liquid is to use the blending means of mixing tank in upright arrangement, static mixer or orifice mixer.
5. the manufacture method of the described refining polycarbonate organic solution of claim 3, wherein, the blending means of rough polycarbonate organic solution and water-washing liquid is to use the blending means of mixing tank in upright arrangement, static mixer or orifice mixer.
6. the manufacture method of claim 1 or 2 described refining polycarbonate organic solutions, wherein, the material of the parts in the agglomeration separation device is glass fibre, carbon fiber, steel fiber, polytetrafluoroethylene fiber, polypropylene fibre, polyethylene fibre, paper pulp fiber or bombax cotton.
7. the manufacture method of the described refining polycarbonate organic solution of claim 3, wherein, the material of the parts in the agglomeration separation device is glass fibre, carbon fiber, steel fiber, polytetrafluoroethylene fiber, polypropylene fibre, polyethylene fibre, paper pulp fiber or bombax cotton.
8. the manufacture method of claim 1 or 2 described refining polycarbonate organic solutions, wherein, the parts in the agglomeration separation device be shaped as tabular, cylindric or collapsed shape.
9. the manufacture method of the described refining polycarbonate organic solution of claim 3, wherein, the parts in the agglomeration separation device be shaped as tabular, cylindric or collapsed shape.
10. the manufacture method of claim 1 or 2 described refining polycarbonate organic solution, wherein, the structure of the parts in the agglomeration separation device is to be provided with fibrolaminar structure in cylindrical vessel.
11. the manufacture method of the described refining polycarbonate organic solution of claim 3, wherein, the structure of the parts in the agglomeration separation device is to be provided with fibrolaminar structure in cylindrical vessel.
12. the manufacture method of high-purity polycarbonate is characterized in that, the refining polycarbonate organic solution that adopts aforesaid right to require the manufacture method of each described refining polycarbonate organic solution of 1-11 to obtain.
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| JP2004018276A JP4567981B2 (en) | 2004-01-27 | 2004-01-27 | Purified polycarbonate organic solution and method for producing high-purity polycarbonate |
| JP2004018276 | 2004-01-27 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604067A (en) * | 2012-03-16 | 2012-07-25 | 甘肃银光聚银化工有限公司 | Method for separating and purifying polycarbonate glue solution |
| CN102604068A (en) * | 2012-02-24 | 2012-07-25 | 青岛科技大学 | Washing and purifying method for polycarbonate adhesive solution |
| CN102775595A (en) * | 2012-03-12 | 2012-11-14 | 甘肃银光聚银化工有限公司 | Continuous purification method for polycarbonate emulsion |
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| KR102349078B1 (en) * | 2017-09-25 | 2022-01-07 | 주식회사 엘지화학 | Method for preparing polyalkylene carbonate resin |
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| IT1110267B (en) * | 1979-02-05 | 1985-12-23 | Montedison Spa | PURIFICATION PROCESS OF POLYCARONATE SOLUTIONS |
| JPH0317923Y2 (en) * | 1985-08-26 | 1991-04-16 | ||
| JPH109940A (en) * | 1996-06-19 | 1998-01-16 | Mitsubishi Heavy Ind Ltd | Measuring apparatus for radiant power |
| CN1233625A (en) * | 1998-04-30 | 1999-11-03 | 通用电气公司 | Method for recycling aromatic polycarbonates |
| DE19849004A1 (en) * | 1998-10-24 | 2000-04-27 | Bayer Ag | High purity polycarbonate is produced using coalescer with hydrophilic packing to separate wash liquid from organic product solution after first washing step |
| SG87068A1 (en) * | 1999-01-11 | 2002-03-19 | Mitsubishi Gas Chemical Co | Process for purifying polycarbonate resin solution |
| JP4280881B2 (en) * | 1999-07-23 | 2009-06-17 | 三菱瓦斯化学株式会社 | Purification method of polycarbonate resin solution |
| US6214892B1 (en) * | 1999-12-23 | 2001-04-10 | General Electric Company | Polycarbonate isolation through homogenization devolatization |
| US6620906B1 (en) * | 2000-02-07 | 2003-09-16 | Bayer Aktiengesellschaft | Method for the production of highly pure polycarbonate and ultrapure polycarbonate |
| CN100358934C (en) * | 2000-09-21 | 2008-01-02 | 通用电气公司 | Process for purification of polycarbonate-containing solutions by plate decantation |
| JP2003038902A (en) * | 2001-07-27 | 2003-02-12 | Yamaha Motor Co Ltd | Oil-water separation apparatus |
-
2004
- 2004-01-27 JP JP2004018276A patent/JP4567981B2/en not_active Expired - Lifetime
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604068A (en) * | 2012-02-24 | 2012-07-25 | 青岛科技大学 | Washing and purifying method for polycarbonate adhesive solution |
| CN102775595A (en) * | 2012-03-12 | 2012-11-14 | 甘肃银光聚银化工有限公司 | Continuous purification method for polycarbonate emulsion |
| CN102604067A (en) * | 2012-03-16 | 2012-07-25 | 甘肃银光聚银化工有限公司 | Method for separating and purifying polycarbonate glue solution |
| CN102604067B (en) * | 2012-03-16 | 2013-10-30 | 甘肃银光聚银化工有限公司 | Method for separating and purifying polycarbonate glue solution |
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| JP4567981B2 (en) | 2010-10-27 |
| TWI367225B (en) | 2012-07-01 |
| CN100451048C (en) | 2009-01-14 |
| TW200528488A (en) | 2005-09-01 |
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