CN1191290C - Process for production of polycarbonate - Google Patents
Process for production of polycarbonate Download PDFInfo
- Publication number
- CN1191290C CN1191290C CN 01802600 CN01802600A CN1191290C CN 1191290 C CN1191290 C CN 1191290C CN 01802600 CN01802600 CN 01802600 CN 01802600 A CN01802600 A CN 01802600A CN 1191290 C CN1191290 C CN 1191290C
- Authority
- CN
- China
- Prior art keywords
- polycarbonate
- chloroformate
- hydroxyl
- aryl
- aryl esters
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 65
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- -1 aryl chloroformate Chemical compound 0.000 claims abstract description 43
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 239000012074 organic phase Substances 0.000 claims abstract description 18
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012530 fluid Substances 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000002989 phenols Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 241001550224 Apha Species 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 125000005587 carbonate group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 20
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000005027 hydroxyaryl group Chemical group 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- 239000001294 propane Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- NFKJHAPTDLJRDP-UHFFFAOYSA-N 1,1'-biphenyl;urea Chemical compound NC(N)=O.C1=CC=CC=C1C1=CC=CC=C1 NFKJHAPTDLJRDP-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 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 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003822 preparative gas chromatography Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 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
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UFUBQDNODUUQTD-UHFFFAOYSA-N 2-bromo-4-propylphenol Chemical compound CCCC1=CC=C(O)C(Br)=C1 UFUBQDNODUUQTD-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
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- LXDMMLSDZKDEGI-UHFFFAOYSA-N 3-tert-butyl-4-propylphenol Chemical compound CCCC1=CC=C(O)C=C1C(C)(C)C LXDMMLSDZKDEGI-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
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- MNHKUCBXXMFQDM-UHFFFAOYSA-N 4-[(4-nitrophenyl)methyl]pyridine Chemical compound C1=CC([N+](=O)[O-])=CC=C1CC1=CC=NC=C1 MNHKUCBXXMFQDM-UHFFFAOYSA-N 0.000 description 1
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical class C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical class CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-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
- YBTCPHOMRXRZSB-UHFFFAOYSA-N C.OC1=CC=C(C=C1)C1=CC=CC2=CC=CC=C12 Chemical compound C.OC1=CC=C(C=C1)C1=CC=CC2=CC=CC=C12 YBTCPHOMRXRZSB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- WXLLKTLYGUILQD-UHFFFAOYSA-N OC1=CCC(C=C1)(CN)CCC Chemical compound OC1=CCC(C=C1)(CN)CCC WXLLKTLYGUILQD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YKOQAAJBYBTSBS-UHFFFAOYSA-N biphenyl-2,3-diol Chemical compound OC1=CC=CC(C=2C=CC=CC=2)=C1O YKOQAAJBYBTSBS-UHFFFAOYSA-N 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- HDVRLUFGYQYLFJ-UHFFFAOYSA-N flamenol Chemical compound COC1=CC(O)=CC(O)=C1 HDVRLUFGYQYLFJ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A process for production of polycarbonate improved in heat resistance, characterized by removing an aqueous phase from a polymerization fluid obtained by interfacial polymerization of a raw material comprising phosgene and a dihydric phenol as the main components and then adding a specified amount of an aryl chloroformate having a phosgene content of 150 ppm or below to the resulting organic phase to convert the terminal phenolic hydroxyl groups into aryl carbonate groups.
Description
Technical field
The present invention relates to the manufacture method of polycarbonate, in more detail, relate to the manufacture method of the polycarbonate of thermotolerance improvement.
Background technology
Polycarbonate resin has good physical strength (particularly shock-resistance), thermotolerance and electrology characteristic etc., is widely used in as engineering plastics in the various fields such as electric electronic Instrument field, automotive field.Yet to purposes such as thin slice, high temperature and high speed injection moulded products, some field needs better thermotolerance.Up to now, in order to improve the thermotolerance of polycarbonate, making the phenol in the polycarbonate is hydroxyl and aryl esters chloroformate reaction, and reduction phenol is that the method for the residual quantity of hydroxyl is known (spy opens clear 58-84822 communique).Yet its stable on heating raising can not be said so fully.
The present invention is in view of above-mentioned condition, and providing a kind of is hydroxyl and aryl esters chloroformate reaction by making the phenol in the polycarbonate, the method for the polycarbonate that the manufacturing thermotolerance fully improves.
The content of invention
What the inventor concentrated one's attention on to study found that, by using specific aryl esters chloroformate, is suitable for the purpose of the invention described above, so finished the present invention.
That is, main points of the present invention are as described below.
1. the manufacture method of a polycarbonate, this method is by with phosgene, the dihydric phenols method as the interfacial polymerization manufactured polycarbonate of main raw material, it is characterized in that, after the polymer fluid water phase separated, adding the aryl esters chloroformate of representing with following general formula (1) below the phosgene content 150ppm that terminal phenol with respect to the gained polycarbonate is mole～2 times of molar weights such as hydroxyl toward organic phase, is terminal phenol that hydroxyl is transformed into the aryl carbonates base.
(in the formula, Ar represents the aryl of 1 valency).
2. the polycarbonate manufacture method described in above-mentioned 1, wherein, the APHA of aryl esters chloroformate is below 30.
Implement preferred plan of the present invention
Describe the present invention below in detail.
The manufacture method of polycarbonate of the present invention is with phosgene, the dihydric phenols interfacial polymerization as main raw material.That is, the alkaline aqueous solution of phosgene, dihydric phenols, molecular weight regulator and organic solvent are supplied with polymerization reactor, carry out polycondensation.At first, raw materials in sequence is illustrated.
Have as described dihydric phenols multiple, yet, 2, two (4-hydroxy phenyl) propane (being commonly referred to as dihydroxyphenyl propane) of 2-are only.As the dihydric phenol beyond the dihydroxyphenyl propane, can enumerate, for example, two (4-hydroxyphenyl) methane, 1, two (4-hydroxyphenyl) ethane of 1-, 2, two (4-hydroxyphenyl) butane of 2-, 2, two (4-hydroxyphenyl) octanes of 2-, 2, two (4-hydroxyl-1-aminomethyl phenyl) propane of 2-, 1, two (4-hydroxyl-tert-butyl-phenyl) propane of 1-, 2, two (4-hydroxyl-3-bromophenyl) propane of 2-, 2, two (the 4-hydroxyls-3 of 2-, the 5-tetramethylphenyl) propane, 2, two (4-hydroxyl-3-chloro-phenyl-) propane of 2-, 2, two (4-hydroxyl-3, the 5-tetrachloro phenyl) propane of 2-, 2, two (hydroxyaryl) paraffinics such as two (4-hydroxyl-3, the 5-tetrabromo phenyl) propane of 2-; 2, two (hydroxyaryl) aryl paraffinics such as two (4-hydroxy phenyl) phenylmethanes of 2-, two (4-hydroxy phenyl) naphthalene methane; 1, two (4-hydroxyphenyl) pentamethylene, 1 of 1-, 1-bis(4-hydroxyphenyl) cyclohexane, 1, two (the 4-hydroxyphenyl)-3,5 of 1-, two (hydroxyaryl) cycloalkanes such as 5-trimethyl-cyclohexane; 4,4 '-dihydroxyl phenylate, 4,4 '-dihydroxyl-3,3 '-dihydroxyl aryl ethers such as dimethyl phenylate; 4,4 '-dihydroxyl diphenylsulfide, 4,4 '-dihydroxyl-3,3 '-dihydroxyl diaryl sulfide classes such as dimethyl diphenyl sulfide; 4,4 '-dihydroxyl diphenyl sulfoxide, 4,4 '-dihydroxyl-3,3 '-dihydroxyl diaryl sulphoxide classes such as dimethyl diphenyl sulfoxide; 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-dihydroxyl-3,3 '-dihydroxyl diaryl sulfone classes such as dimethyl diphenyl sulfone; 4,4 '-dihydroxyl hexichol base class such as dihydroxyl phenylbenzene etc.These dihydric phenols both can be used alone, can also be two or more kinds in combination separately.
Alkali as the alkaline aqueous solution of above-mentioned dihydric phenols can use sodium hydroxide, potassium hydroxide, yellow soda ash, yet sodium hydroxide is preferred.
In addition, in order to improve the flow characteristics of polycarbonate, suitable is that the above polyatomic phenol of the ternary of 0.05～2.0 mole of % of above-mentioned dihydric phenols is used with 2 yuan of phenols.
The polyatomic phenol that this ternary is above, generally be called branching agent, can enumerate 1,1,1-three (4-hydroxyphenyl) ethane, α, α ', α " three (4-hydroxyphenyl)-1; 3,5-triisopropylbenzene, 1-[Alpha-Methyl-α-(4 '-hydroxyphenyl) ethyl]-4-[α ', α '-two (4 " hydroxyphenyl) ethyl] benzene, Phloroglucinol monomethyl ether, trimellitic acid, isatin two (neighbour-cresols) etc.
Molecular weight regulator is also referred to as terminal terminator, generally can use phenol, p-Cresol, right-tert-butyl phenol, right-uncle's octyl phenol, p-cumylphenol, right-nonyl phenol, right-tert-pentyl phenol, right-monobasic phenols such as 4-dodecylphenol.
As above-mentioned organic solvent, can enumerate methylene dichloride, chloroform, chlorobenzene etc., and methylene dichloride is preferred.
And, in above-mentioned reaction, as required, can use three grades of fatty amines such as triethylamine, Tributylamine, N-ethylpiperidine to make catalyzer.
Above-mentioned polycondensation both can be put into polymeric kettle to above-mentioned starting material, carries out with one section, yet, also can make oligopolymer at the 1st section by the alkaline aqueous solution of phosgene and dihydric phenols, carry out good the 2nd section two-phase method of carrying out the polymerization materialization again.
Polycarbonate the organic phase after the polymer fluid that contains the polycarbonate made from aforesaid method is told water, the terminal phenol that generally contains 20～300ppm is hydroxyl.In addition, the residual thousands of ppm of organic phase neutral and alkali water.
In the present invention, the aryl esters chloroformate with following general formula (1) expression is added in the above-mentioned organic phase.
(in the formula, Ar represents the aryl of 1 valency).
As this aryl esters chloroformate, can enumerate phenol, right-tert-butyl phenol, 2,6-dimethyl phenol, 4-(1,1,3, the 3-tetramethyl butyl)-phenol etc.
Above-mentioned aryl esters chloroformate can be made by the phenols photoreactive gas.Phosgene amount in this aryl esters chloroformate must be below 150ppm.When surpassing 150ppm, the chloro-formic ester amount in the polycarbonate increases, and the thermotolerance of polycarbonate is not found to improve.Preferably below the 120ppm.In addition,, can breathe out standard color solution sequence number (APHA) 5～50 once, estimate the form and aspect that form and aspect are confirmed by visual method according to APHA[JIS K 2435 (1992) preparation to the form and aspect of this aryl esters chloroformate], preferred below 30.When surpassing 30, the thermotolerance of polycarbonate improves and diminishes sometimes.Also have, above-mentioned phosgene amount and form and aspect can be controlled by the underpressure distillation of aryl esters chloroformate.
About the addition of above-mentioned aryl esters chloroformate, be the amount that hydroxyl such as reaches at mole～2 times of moles with respect to the terminal phenol of the polycarbonate of organic phase.During less than equimolar amount, residual hydroxyl increases in the polycarbonate, does not find that the thermotolerance of polycarbonate improves, and when surpassing 2 times of molar weights, chloro-formic ester or diaryl carbonate and hydroxyaryl amount increase, and do not find that thermotolerance improves.1.2～1.7 times of molar weights preferably.
In addition, above-mentioned aryl esters chloroformate, what generally use is the solution that is dissolved in 1～4 quality % in the used organic solvent of polyreaction.
About the interpolation time of above-mentioned aryl esters chloroformate, both can add to from above-mentioned polymer fluid and isolate the organic phase of water and with in the organic phase behind the neutralizing treatment, also can add in the organic phase before the neutralizing treatment.Also have, the occasion in the organic phase before adding neutralizing treatment to when adding 0.01～0.08 normal alkene alkali aqueous solution (reaching 1～25 capacity % with respect to organic phase) simultaneously with aryl esters chloroformate, carries out also can with alkali cleaning simultaneously.In the occasion of not adding above-mentioned dilute alkaline aqueous solution, after the aryl esters chloroformate processing, must use the neutralizing treatment organic phase.
Handle with above-mentioned aryl esters chloroformate, also can in steel basin, carry out, yet, when employing has line mixer and carries out for the device of pipe arrangement of guaranteeing its downstream dwell time, the organic phase that contains polycarbonate is an external phase, and alkaline water is when being the outstanding turbid state of disperse phase, and its effect is better.In addition, with the processing of aryl esters chloroformate,, generally be 5～20 minutes as long as suitably select for use the residence time, can make terminal phenol in the polycarbonate is that the residual quantity of hydroxyl is less than 20ppm.
Pressing aforesaid operations, handle with aryl esters chloroformate, can be the terminal phenol of polycarbonate that hydroxyl is transformed into the aryl carbonates base.Aryl esters chloroformate will be isolated the organic phase of buck phase after handling, perhaps, and again with the organic phase after this organic phase of neutralizing treatment, with acid, water washing, till not becoming ionogen.Washing as required, is added poor solvents such as acetone, hexane, heptane after stopping in organic phase, carry out concentrate drying then, can obtain the polycarbonate section.
Resulting polycarbonate section, its viscosity-average molecular weight is 10000～100000, residual phenol be hydroxyl less than 20ppm, unreacted aryl esters chloroformate is below the 0.5ppm, is the product that thermotolerance has improved.Also have, its viscosity-average molecular weight (Mv) is with Ubbelohde type viscometer, in 20 ℃ of viscosity of measuring dichloromethane solution, obtains limiting viscosity [η] thus, from [η]=1.23 * 10
-5Mv
0.83The value that formula is calculated.
In the polycarbonate section that obtains in the present invention, as required, can cooperate additive or other synthetic resins, elastomerics etc.
At first, as additive, for example, can enumerate oxidation inhibitor such as hindered phenol system, phosphorus system (phosphorous acid ester system, phosphoric acid ester system etc.), amine system, for example internal lubricant, releasing agent, fire retardant, flame retardant, antistatic agent, tinting materials etc. such as photostabilizers such as benzotriazole system, benzophenone series UV light absorber, for example hindered amine system, for example aliphatic carboxylic acid esters, system, alkene hydrocarbon system, silicone oil, polyethylene wax.
As other synthetic resins, can enumerate various resins such as polyethylene, polypropylene, polystyrene, AS resin (acrylonitritrile-styrene resin), ABS resin (acrylonitrile-butadiene-styrene copolymer), polymethylmethacrylate.In addition, as elastomerics, can enumerate butyl rubber, styrene butadiene rubbers, second-third rubber, acrylic elastomer etc.
As cooperating above-mentioned each composition, carrying out mixing method, the employing usual method gets final product, for example, can adopt methods such as hurricane band mixing machine, rotary drum cylinder, Henschel mixing tank, Banbury mixing tank, single screw extrusion machine, twin screw extruder, kneading machine, multiple screw extruder to carry out.
The polycarbonate resin that obtains like this, adopt known various forming method, various goods are made in for example injection moulding, slush molding, extrusion moulding, compressed moulding, calendering formation, rotoforming etc.
In addition, by Production Example, embodiment and ratio are described more specifically the present invention, and the present invention is not subjected to the restriction of these examples.
Production Example
[manufacturing of polycarbonate oligomer]
In the aqueous sodium hydroxide solution of 5.6 quality %, dissolve dihydroxyphenyl propane, make bisphenol A concentration reach 13.5% (quality), the aqueous sodium hydroxide solution of preparation dihydroxyphenyl propane.
The aqueous sodium hydroxide solution of this dihydroxyphenyl propane with 41 l/ hours, methylene dichloride with 17 l/ hours flow, phosgene flow with 4.0kg/ hour, supply in the tube-type reactor of internal diameter 6mm, pipe range 30m.Tube-type reactor has the chuck part, toward the partly logical water coolant of chuck, reacting liquid temperature is remained on below 40 ℃.
Reaction solution from tube-type reactor, import continuously the tank reactor of the band dividing plate that has 40 liters of internal volumes that retreat the wing, toward wherein adding aqueous sodium hydroxide solution 0.07 l/hr of aqueous sodium hydroxide solution 2.8l/hr, the 25 quality % of dihydroxyphenyl propane, triethylamine aqueous solution 0.32 l/hr of water 17 l/hr, 1 quality %, react again.
Successive extracts the reaction solution that overflows from tank reactor, by leaving standstill, separates and removes water, obtains the methylene dichloride phase.
The polycarbonate oligomer concentration that obtains like this is 320g/l, and chloroformic acid ester group concentration is 0.70 mole/l.
[manufacturing of polycarbonate]
Above-mentioned oligomer solution 20l/hr, methylene dichloride 11 l/hr, 4.1 dichloromethane solution 4.3 l/hr of the p-tert-butylphenol of quality %, the triethylamine aqueous solution 0.2l/hr of 1 quality %, aqueous sodium hydroxide solution 12 l/hr of dihydroxyphenyl propane, aqueous sodium hydroxide solution 0.90 l/hr of 25 quality %, supply has diameter 43mm, in T.K. pipeline (パ イ プ ラ イ Application) the mixing tank 2SL of the turbine wing of diameter 48mm (special machine chemical industry society make), under the 3000rpm rotation, mixed, tower steel basin 5 sections paddles of 80 liters of the internal volumes of this mixed solution successive supply strap clamp cover carries out polyreaction.15 ℃ water coolant flows through chuck, makes the polymer fluid temperature reach 30 ℃.
The polymer fluid that overflows from tower reactor top after methylene dichloride 14 l/hr dilution, is removed water with centrifugal extractor (Kawasaki Heavy Industries industry society system), and the concentration that is contained dihydroxyphenyl propane continuously hardly is the dichloromethane solution A of the polycarbonate of 176g/l.It is hydroxyl 170ppm that this polycarbonate contains terminal phenol.
[embodiment 1]
The dichloromethane solution A48 l/hr of above-mentioned polycarbonate, contain dichloromethane solution 0.73 l/hr, 0.07 normal aqueous sodium hydroxide solution 8.0 l/hr of Phenyl Chloroformate 99 (a) of table 1 record of 2.0 quality %, mixed continuously with the pipeline stirrer, this mixed solution by behind the pipe arrangement of internal diameter 40mm, long 8m, remove water with centrifugal extractor, obtain the dichloromethane solution of polycarbonate continuously.In this occasion, the amount of Phenyl Chloroformate 99 is that the terminal phenol of polycarbonate is 1.4 times of moles of hydroxyl.
The dichloromethane solution of the polycarbonate that obtains like this, use 0.2 equivalent salt acid elution with respect to the dichloromethane solution 15 capacity % of polycarbonate, then, use pure water washing with respect to 15 capacity % of the dichloromethane solution of polycarbonate, and make specific conductivity after the washing,, reach below the 10 μ S/cm with the pure water washing by repeatedly.
Add the acetone of 20 capacity % of the dichloromethane solution be equivalent to wash the polycarbonate after the termination, then,, obtain the polycarbonate section by concentrate drying.Resulting polycarbonate section proterties is shown in table 2.
[embodiment 2]
In embodiment 1, except that the Phenyl Chloroformate 99 (b) with table 1 record replaced Phenyl Chloroformate 99 (a), same operation obtained the polycarbonate section.The proterties of resulting polycarbonate section is shown in table 2.
[embodiment 3]
In embodiment 1, except that the Phenyl Chloroformate 99 (c) with record in the table 1 replaced Phenyl Chloroformate 99 (a), all the other were operated equally, obtained the polycarbonate section.The proterties of resulting polycarbonate section is shown in table 2.
[embodiment 4]
In embodiment 1, except that the Phenyl Chloroformate 99 (d) with record in the table 1 replaced Phenyl Chloroformate 99 (a), all the other were operated equally, obtained the polycarbonate section.The proterties of resulting polycarbonate section is shown in table 2.
[comparative example 1]
In embodiment 1, except that obsolete Phenyl Chloroformate 99 (a), all the other are operated equally, obtain the polycarbonate section.The proterties of resulting polycarbonate section is shown in table 2.
[comparative example 2]
In embodiment 1, except that the Phenyl Chloroformate 99 (e) with record in the table 1 replaced Phenyl Chloroformate 99 (a), all the other were operated equally, obtained the polycarbonate section.Resulting polycarbonate section proterties is shown in table 2.
Table 1
| Phosgene content [ppm] | Form and aspect (APHA) | ||
| Embodiment 1 | Phenyl Chloroformate 99 (a) | 30 | 10 |
| Embodiment 2 | Phenyl Chloroformate 99 (b) | 100 | 20 |
| Embodiment 3 | Phenyl Chloroformate 99 (c) | 110 | 10 |
| Embodiment 4 | Phenyl Chloroformate 99 (d) | 50 | 40 |
| Comparative example 2 | Phenyl Chloroformate 99 (e) | 500 | 10 |
Table 2
| Residual hydroxyl amount [ppm] | Chloro-formic ester amount [ppm] | Initial form and aspect (YI) | Thermotolerance (Δ YI) | Insoluble one-tenth component | |
| Embodiment 1 | 20＞ | 0.4＞ | 0.7 | 1.1 | Do not have |
| Embodiment 2 | 20＞ | 0.4＞ | 0.8 | 1.1 | Do not have |
| Embodiment 3 | 20＞ | 0.4＞ | 0.8 | 1.2 | Do not have |
| Embodiment 4 | 20＞ | 0.4＞ | 1.0 | 1.9 | Slightly |
| Comparative example 1 | 170 | 0.4＞ | 0.8 | 2.4 | Slightly |
| Comparative example 2 | 20＞ | 1.0 | 0.8 | 3.4 | Many |
The various measuring methods of the proterties of record are as follows in above-mentioned table 1, the table 2.
(1) the phosgene amount in the Phenyl Chloroformate 99
This quantivative approach is that reference makes phosgene and aniline reaction by utilization, generates 1, and the quantivative approach of the health test method(s) of 3-phenylbenzene urea is implemented.
Concrete is as described below.
Sample 1.0ml is collected in the sample groove (10 * 10 * 60mm), with nitrogen as carrier gas, on one side divide with 30ml/ and to flow through on one side in 50 ℃ of heating 60 minutes.Carrier gas is fed the absorption bottle that absorption liquid 3ml is housed.
Absorption liquid with methanol constant volume to 10.0ml, contained 1 in this absorption liquid, 3-phenylbenzene urea is undertaken quantitatively by following condition with vapor-phase chromatography.
Add 100ml methyl alcohol in the distillatory aniline 0.25g and make the absorption liquid dissolving, add water 50ml and hydrochloric acid again, regulate pH6～7.
The condition of＜vapor-phase chromatography 〉
Chromatographic column: DB-1 (15m * 0.32mm φ, mould; 0.1 μ m)
Chromatogram column temperature: 180 ℃
Implantation temperature: 280 ℃
Detected temperatures: 430 ℃
Carrier gas: 40kPa (splitting ratio: 20)
Sample size: 2.5 μ l
(2) form and aspect of Phenyl Chloroformate 99
Breathe out standard color solution numbering (APHA) 5～50 once according to JIS K 2435 (1992) preparations, estimate the form and aspect of Phenyl Chloroformate 99 with visual method.
(3) amount of hydroxyl groups in the polycarbonate
1. accurately take by weighing sample 0.1g and put into the 25ml volumetric flask, make in the methylene dichloride that is dissolved in about 5ml.
2. add titanium tetrachloride solution 10ml and acetum 4ml again, use the methylene dichloride constant volume at 25ml.
3. the UV-240 that makes with society of Shimadzu Seisakusho Ltd. measures the absorbancy of 480nm (optical path length 10nm).
4. operate equally with dihydroxyphenyl propane, make typical curve, calculate the OH base unit weight from the absorbancy of test liquid.
And above-mentioned titanium tetrachloride solution is accurately to measure titanium tetrachloride 2.32ml, adds acetic acid 1.0ml, make with methylene dichloride 100ml dilution, and acetum is acetic acid 5ml, is diluted to 100ml with methylene dichloride and makes.
(4) chloro-formic ester amount
It is quantitative to open the method for putting down in writing in the flat 4-266925 communique with the spy.Concrete is as follows.
4-(4-nitrobenzyl) pyridine 1.0g is dissolved in the methylene dichloride, is settled to 100ml, be made into chromonic solution.Take test liquid 20ml, add the chromonic solution 2.0ml that has been made into inward, behind the thorough mixing, put into the silica glass pond of optical path length 10mm,, be determined at the absorbancy at 440nm place with the UV-240 that society of Shimadzu Seisakusho Ltd. makes.With methylene dichloride as reference substance.The Phenyl Chloroformate 99 typical curve is made in same operation, from the absorbancy and the polycarbonate concentration of test liquid, calculates the chloro-formic ester amount as cl concn.
(5) the initial stage form and aspect (YI) of polycarbonate
Polycarbonate section 3.0g is dissolved among the methylene dichloride 34.5g, the YI of this solution (yellowness index) be to use optical path length 57mm quartz cell, measure by colour meter one SM-3 (manufacturing of ス ガ trier society).With this measured value as YI
a, obtain YI according to following formula.
YI＝0.76(YI
a-YI
o)+0.11
(in the formula, YI
oBe the YI of methylene dichloride
aValue).
(6) thermotolerance of polycarbonate (Δ YI)
Weighing polycarbonate section 3.0g puts into aluminum dish, and it was heated 30 minutes in 340 ℃ in nitrogen atmosphere. after the cooling, make to be dissolved among the methylene dichloride 34.5g.Filter, remove undissolved composition, measure this YI as YI
b, calculate Δ TI according to following formula.
ΔYI＝0.76(YI
b-YI
a)
(7) insoluble one-tenth component
Weighing polycarbonate section 3.0g puts into aluminum dish, and it was heated 30 minutes in 340 ℃ in nitrogen atmosphere.After the cooling, be dissolved among the methylene dichloride 34.5g the not solvent components amount of generation.
Utilize the field on the industry
According to the present invention, providing a kind of is hydroxyl and aryl esters chloroformate reaction by making the phenol in the Merlon, the Merlon manufacture method that its heat resistance is fully enhanced. Resulting Merlon can be used for optical material, the high temperature and high speed injection-molded items such as thin slice, CD have requirements at the higher level to heat resistance field.
Claims (3)
1. the manufacture method of a polycarbonate, this method is by with phosgene, dihydric phenols is as the method for the interfacial polymerization manufactured polycarbonate of main raw material, it is characterized in that, after the polymer fluid water phase separated, adding terminal phenol with respect to resulting polycarbonate toward organic phase is mole～2 times of molar weights such as hydroxyl is, below the phosgene content 150ppm, represent with following general formula (1), APHA is the aryl esters chloroformate below 30, is terminal phenol that hydroxyl is transformed into the aryl carbonates base
In the formula, Ar represents the aryl of 1 valency,
And, terminal phenol be hydroxyl for being lower than 20ppm, the unreacted aryl esters chloroformate is below the 0.5ppm.
2. as the manufacture method of the polycarbonate of record in the claim 1, wherein, use the line mixer processing of aryl esters chloroformate.
3. as the manufacture method of the polycarbonate of record in claim 1 or 2, wherein, add 0.01～0.08 normal dilute alkaline aqueous solution 1～25 capacity % mutually with respect to organic solvent simultaneously with aryl esters chloroformate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP268152/2000 | 2000-09-05 | ||
| JP2000268152A JP2002080578A (en) | 2000-09-05 | 2000-09-05 | Method for manufacturing polycarbonate |
| JP268152/00 | 2000-09-05 |
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| Publication Number | Publication Date |
|---|---|
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| CN1191290C true CN1191290C (en) | 2005-03-02 |
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|---|---|---|---|
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| JP5775345B2 (en) * | 2011-03-31 | 2015-09-09 | 出光興産株式会社 | Control method for continuous production of polycarbonate oligomer |
| JP5775347B2 (en) * | 2011-03-31 | 2015-09-09 | 出光興産株式会社 | Control method for continuous production of polycarbonate oligomer |
| WO2018229730A1 (en) * | 2017-06-16 | 2018-12-20 | Sabic Global Technologies B.V. | Use of sulfonic acid as stabilizer in polycarbonate |
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