CN1795225A - Catalyst for polycarbonate production and method for producing polycarbonate - Google Patents
Catalyst for polycarbonate production and method for producing polycarbonate Download PDFInfo
- Publication number
- CN1795225A CN1795225A CN 200480014562 CN200480014562A CN1795225A CN 1795225 A CN1795225 A CN 1795225A CN 200480014562 CN200480014562 CN 200480014562 CN 200480014562 A CN200480014562 A CN 200480014562A CN 1795225 A CN1795225 A CN 1795225A
- Authority
- CN
- China
- Prior art keywords
- polycarbonate
- catalyzer
- catalyst
- phosphonium
- compound
- 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.)
- Granted
Links
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 167
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 167
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 125000003118 aryl group Chemical group 0.000 claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002941 palladium compounds Chemical class 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 229910052799 carbon Inorganic materials 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- 239000004793 Polystyrene Substances 0.000 claims description 27
- 229920002223 polystyrene Polymers 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 150000001350 alkyl halides Chemical group 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 229910000765 intermetallic Inorganic materials 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 claims description 5
- 150000001869 cobalt compounds Chemical class 0.000 claims description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 29
- 239000007790 solid phase Substances 0.000 abstract description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- 239000000460 chlorine Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000002411 adverse Effects 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 79
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 71
- -1 /halo compounds Chemical class 0.000 description 69
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 45
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 45
- 229910052763 palladium Inorganic materials 0.000 description 39
- 239000011572 manganese Substances 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 36
- 239000002904 solvent Substances 0.000 description 35
- 229910021536 Zeolite Inorganic materials 0.000 description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 31
- 239000010457 zeolite Substances 0.000 description 31
- 238000001035 drying Methods 0.000 description 24
- 206010013786 Dry skin Diseases 0.000 description 23
- 230000008961 swelling Effects 0.000 description 21
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 20
- 239000002585 base Substances 0.000 description 19
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 18
- 239000000843 powder Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 150000004054 benzoquinones Chemical class 0.000 description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 16
- 125000003963 dichloro group Chemical group Cl* 0.000 description 16
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 11
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000007306 turnover Effects 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 238000005810 carbonylation reaction Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000006315 carbonylation Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000004714 phosphonium salts Chemical class 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002265 redox agent Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- KUXIQKVLTGHSAN-UHFFFAOYSA-N (2-chlorophenyl)phosphane Chemical compound PC1=CC=CC=C1Cl KUXIQKVLTGHSAN-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- VMWGBWNAHAUQIO-UHFFFAOYSA-N 2-ethenyl-6-methylpyridine Chemical compound CC1=CC=CC(C=C)=N1 VMWGBWNAHAUQIO-UHFFFAOYSA-N 0.000 description 2
- DPZYLEIWHTWHCU-UHFFFAOYSA-N 3-ethenylpyridine Chemical compound C=CC1=CC=CN=C1 DPZYLEIWHTWHCU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical group C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZBBKCJXETVKDOI-UHFFFAOYSA-N butylphosphanium;hydroxide Chemical compound [OH-].CCCC[PH3+] ZBBKCJXETVKDOI-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- CMXKLPZLENDDMK-UHFFFAOYSA-M (2-chlorophenyl)-triphenylphosphanium;hydroxide Chemical compound [OH-].ClC1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CMXKLPZLENDDMK-UHFFFAOYSA-M 0.000 description 1
- OZXAJZJJKZYNCR-UHFFFAOYSA-M (2-phenoxyphenyl)-triphenylphosphanium;hydroxide Chemical compound [OH-].C=1C=CC=C([P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1OC1=CC=CC=C1 OZXAJZJJKZYNCR-UHFFFAOYSA-M 0.000 description 1
- KROPVFOECFKRIH-UHFFFAOYSA-N (4-phenylphenyl)phosphane Chemical compound C1=CC(P)=CC=C1C1=CC=CC=C1 KROPVFOECFKRIH-UHFFFAOYSA-N 0.000 description 1
- RUAFPCMISXUGHL-UHFFFAOYSA-N 1,1'-biphenyl;phosphane Chemical compound P.C1=CC=CC=C1C1=CC=CC=C1 RUAFPCMISXUGHL-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LCFYCLRCIJDYQD-UHFFFAOYSA-N 2-ethenyl-5-methylpyridine Chemical compound CC1=CC=C(C=C)N=C1 LCFYCLRCIJDYQD-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 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
- KCIVBLNHLBBZFE-UHFFFAOYSA-N 4-(9h-fluoren-1-yl)-2-methylphenol Chemical class C1=C(O)C(C)=CC(C=2C3=C(C4=CC=CC=C4C3)C=CC=2)=C1 KCIVBLNHLBBZFE-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
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- JRICUULAWRAUQJ-UHFFFAOYSA-M C(C)(=O)OC1=C(C=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C.[OH-] Chemical compound C(C)(=O)OC1=C(C=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C.[OH-] JRICUULAWRAUQJ-UHFFFAOYSA-M 0.000 description 1
- VEALVDWCBOPXQU-UHFFFAOYSA-M COC1=CC=C(C=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.[OH-] Chemical compound COC1=CC=C(C=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.[OH-] VEALVDWCBOPXQU-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- AJBXRBRVQMZREG-UHFFFAOYSA-N OC(CC)(C1=CC=CC=C1)O.OC1=CC=C(C=C1)CCC Chemical compound OC(CC)(C1=CC=CC=C1)O.OC1=CC=C(C=C1)CCC AJBXRBRVQMZREG-UHFFFAOYSA-N 0.000 description 1
- PFIMJZLHTUKTPH-UHFFFAOYSA-N OC1=CC=C([S])C=C1 Chemical compound OC1=CC=C([S])C=C1 PFIMJZLHTUKTPH-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- LAZNZXLUICBNFS-UHFFFAOYSA-M [OH-].C1=CC=CC=C1[P+](C=1C(=CC=CC=1)C=1C2=CC=CC=C2C=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [OH-].C1=CC=CC=C1[P+](C=1C(=CC=CC=1)C=1C2=CC=CC=C2C=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 LAZNZXLUICBNFS-UHFFFAOYSA-M 0.000 description 1
- GTHBNZAUZXLIAH-UHFFFAOYSA-M [OH-].C1=CC=CC=C1[P+](C=1C2=CC=CC=C2C=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound [OH-].C1=CC=CC=C1[P+](C=1C2=CC=CC=C2C=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GTHBNZAUZXLIAH-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- CBSRYWYICZRWMI-UHFFFAOYSA-M benzyl-(2-ethoxyphenyl)-diphenylphosphanium;hydroxide Chemical compound [OH-].CCOC1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 CBSRYWYICZRWMI-UHFFFAOYSA-M 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- BEVHTMLFDWFAQF-UHFFFAOYSA-N butyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 BEVHTMLFDWFAQF-UHFFFAOYSA-N 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- VLOHNGJRIFIHMO-UHFFFAOYSA-N chloromethane;hydrate Chemical compound O.ClC VLOHNGJRIFIHMO-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- MDUSRRSBTURCEN-UHFFFAOYSA-M cyclohexyl(triphenyl)phosphanium;hydroxide Chemical compound [OH-].C1CCCCC1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MDUSRRSBTURCEN-UHFFFAOYSA-M 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
- 230000002939 deleterious effect Effects 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- LJCVYBNBSCCSIG-UHFFFAOYSA-M methoxymethyl(triphenyl)phosphanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(COC)C1=CC=CC=C1 LJCVYBNBSCCSIG-UHFFFAOYSA-M 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- AZFQCTBZOPUVOW-UHFFFAOYSA-N methyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 AZFQCTBZOPUVOW-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NERGHQFTAZRNBS-UHFFFAOYSA-M phenacyl(triphenyl)phosphanium;hydroxide Chemical compound [OH-].C=1C=CC=CC=1C(=O)C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 NERGHQFTAZRNBS-UHFFFAOYSA-M 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- WNUPENMBHHEARK-UHFFFAOYSA-N silicon tungsten Chemical compound [Si].[W] WNUPENMBHHEARK-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-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
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
A catalyst for producing a polycarbonate, which comprises a reaction product obtained by reacting a nitrogen-or phosphorus-containing catalyst support with (b) a palladium compound and (c) a metal compound having redox catalytic ability, and a method for producing a polycarbonate, comprising: a first step of reacting an aromatic dihydroxy compound and a monovalent phenol with carbon monoxide and oxygen to produce a polycarbonate prepolymer; in the second step, the above polycarbonate prepolymer is subjected to solid phase polymerization to produce a polycarbonate, wherein the above catalyst is used in the above first step. The catalyst is easily separated from the polycarbonate and can be reused. The catalyst ensures efficient production of high quality polycarbonates without the use of harmful chlorine or phosgene or the use of any halogenated organic solvents such as methylene chloride and chloroform which are considered to have an adverse effect on the environment.
Description
Background of invention
The present invention relates to be used to produce the catalyzer of polycarbonate and the method for producing polycarbonate, particularly when paying attention to environmental protection, the method that is used for the catalyzer of the high-quality polycarbonate of High-efficient Production and produces polycarbonate, described polycarbonate can be used as electricity and resin material electronic applications, automotive field, optical element field and structured material field.
Association area
Usually, the method (solution methods) of aromatic dihydroxy compound (for example dihydroxyphenyl propane) and phosgene reaction is the method for known production polycarbonate in the presence of alkali.The problem that this method relates to is to use the phosgene of severe toxicity and produces stoichiometric alkali salt as by product.
In addition, also known such method (melting method) wherein uses carbonic diester (for example diphenyl carbonate) as carbonyl source, and by heating and melting with afterreaction.In this melting method, need heating to be used for producing and the fusion carbonic diester, owing to will at high temperature heat, the problem of being brought is that resulting polycarbonate is coloured.
Using palladium/redox agent/halogeno salt catalyzer is a kind of novel method (Japanese Patent Application Publication 68744/1978) of producing polycarbonate of proposing by the method for oxidation carbonylation.But the speed of this reaction is unsatisfactory, and has had to have the polycarbonate of low polymerization degree.
In order to solve above problem, the available method is that wherein oxidation carbonylation carries out under following catalyst system: palladium compound/inorganic oxide reducing catalyst/organic oxidation reducing catalyst/halo compounds/dewatering agent, to produce polycarbonate oligomer, obtain polycarbonate (Japanese Patent Application Publication 297148/2000) by transesterification reaction subsequently.
Though obtained having the polycarbonate of high-polymerization degree, above method needs two-step reaction.In addition, palladium compound is dissolved in (homogeneous catalyst) in the solvent, therefore form probably palladium (O) bunch with this catalyzer of passivation.Simultaneously, be difficult to separating catalyst, metal component easily remains in the polycarbonate.
Disclosure of the Invention
A target of the present invention is for solving the problem exist in the method for above-mentioned production polycarbonate, and provides and be easy to separate and the reusable catalyzer that is used to produce polycarbonate from polycarbonate.In addition, but use the high-quality polycarbonate of above-mentioned catalyzer High-efficient Production, think deleterious chlorine photoreactive gas and the halogenated organic solvent (for example methylene dichloride and chloroform) that environment is had a negative impact and need not to use.
The present inventor is by careful repeatedly research, the support of the catalyst of discovery by nitrogenous or phosphorus and palladium compound and have that catalyzer that the metallic compound reaction of redox catalysis ability makes is easy to separate and reusable from polycarbonate, and use above-mentioned catalyzer can be when paying attention to environmental protection the high-quality polycarbonate of High-efficient Production.Therefore, this catalyzer is used for the present invention.
That is to say, the invention provides catalyzer that is used to produce polycarbonate and the method for producing polycarbonate, be described below respectively:
(1) be used to produce the catalyzer of polycarbonate, described catalyzer comprises the support of the catalyst of or phosphorus nitrogenous by (a) and (b) palladium compound and (c) has the reaction product that the metallic compound reaction of redox catalysis ability obtains.
(2) as the described catalyzer that is used to produce polycarbonate of (1) bar, wherein said support of the catalyst nitrogenous or phosphorus is the vinylpyridine polymer with following formula (I) expression:
Wherein R is alkyl, the alkoxyl group with 1-20 carbon atom with 1-20 carbon atom, has the aryl of 6-20 carbon atom or have the aralkyl of 7-20 carbon atom; P is 0-4; N is 5-10000.
(3) as the described catalyzer that is used to produce polycarbonate of (1) bar, wherein said support of the catalyst (a) nitrogenous or phosphorus is the support of the catalyst that is selected from polyvinylpyrrolidone and diphenylphosphino-polystyrene.
(4) as the described catalyzer that is used to produce polycarbonate of (1) bar, the support of the catalyst (a) of wherein said nitrogenous or phosphorus is for the haloalkane part is quaternized to be contained in the compound that nitrogen in organic carrier or the inorganic carrier or phosphorus obtain by using.
(5) as the described catalyzer that is used to produce polycarbonate of (4) bar, wherein the described organic carrier in (a) is at least a organic carrier that is selected from diphenylphosphino-polystyrene, poly-(4-vinylpridine) or poly-(2-vinyl pyridine).
(6) as arbitrary described catalyzer that is used to produce polycarbonate in (1) bar-(3) bar, described catalyzer also comprises (d) salt.
(7) as arbitrary described catalyzer that is used to produce polycarbonate in (1) bar-(6) bar, described catalyzer also comprises (e) organic oxidation reductive agent.
(8) as arbitrary described catalyzer that is used to produce polycarbonate in (1) bar-(7) bar, described catalyzer also comprises (f) dewatering agent.
(9) as arbitrary described catalyzer that is used to produce polycarbonate in (1) bar-(8) bar, wherein said metallic compound (c) with redox catalysis ability is a cobalt compound.
(10) a kind of method of producing polycarbonate, described method comprises: the first step, with aromatic dihydroxy compound and monovalence phenol and carbon monoxide and oxygen reaction production polycarbonate prepolymer; Second step, above-mentioned polycarbonate prepolymer is carried out solid state polymerization produce polycarbonate, the arbitrary described catalyzer that is used for producing polycarbonate is used for the above-mentioned the first step wherein as in (1) bar-(9) bar.
Realize optimal mode of the present invention
To explain the present invention in more detail below.
At first, the catalyzer of the present invention that is used to produce polycarbonate is a kind of catalyzer of producing polycarbonate, described catalyzer comprises the support of the catalyst of or phosphorus nitrogenous by (a) with (b) palladium compound with (c) have a reaction product that the metallic compound reaction of redox catalysis ability obtains, and also comprise if desired, (d) salt, (e) organic oxidation reductive agent and (f) dewatering agent.
Typical catalyst component is explained as follows.
At the catalyzer that is used for producing polycarbonate, the specific examples of support of the catalyst of nitrogenous or phosphorus that is used for fixing palladium and has a metal of redox catalysis ability comprises: (a-1) vinylpyridine polymer, (a-2) are selected from the support of the catalyst of polyvinylpyrrolidone and diphenylphosphino-polystyrene and (a-3) the haloalkane part is quaternized to be contained in the compound that nitrogen in organic carrier or the inorganic carrier or phosphorus obtain by using.
(a-1) vinylpyridine polymer
Described vinylpyridine polymer is the polymkeric substance with following formula (I) expression:
Wherein R is alkyl, the alkoxyl group with 1-20 carbon atom with 1-20 carbon atom, has the aryl of 6-20 carbon atom or have the aralkyl of 7-20 carbon atom; P is 0-4; N is 5-10000.
The alkyl that has 1-20 carbon atom in the formula (I) for example has methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, methoxyl group and oxyethyl group with the alkoxyl group with 1-20 carbon atom.Aryl with 6-20 carbon atom comprises phenyl, naphthyl, tolyl, xylyl, mesityl and benzyl with the arylalkyl (aralkyl) with 7-20 carbon atom.
Be used for fixing palladium and carry out conventional radical polymerization with the derivative that the polymkeric substance with metal of redox catalysis ability derives from 2-vinyl pyridine, 3-vinyl pyridine, 4-vinylpridine and the replacement of its aromatic ring, the available polymkeric substance has poly-(2-vinyl pyridine), gather (3-vinyl pyridine), gather (4-vinylpridine), gather (6-methyl-2-vinyl pyridine), gather (5-methyl-2-vinyl pyridine) and poly-(5-ethyl-2-vinyl pyridine).Wherein, preferred poly-(4-vinylpridine).Above polymkeric substance can be linear or crosslinked.
Fixing (the formation complex compound) of palladium and the metal with redox catalysis ability finished by at room temperature stirring the solvent that is dissolved with metal-salt.For example can followingly make fixed catalyzer (complex compound): dissolving poly-(4-vinylpridine) in methylene dichloride, close the dichloromethane solution of palladium (II) to wherein adding dichloro two (benzonitrile), subsequently to the acetone soln that wherein adds cobalt chloride (II).Though do not confirm, supposition thinks that this fixed sturcture is as follows:
(a-2) being selected from polyethylene represents with following formula than the support of the catalyst polyvinylpyrrolidone of pyrrolidone and diphenylphosphino-polystyrene:
The molecular weight of above-mentioned polyvinylpyrrolidone does not limit especially, is generally 10,000-200,000.Polyvinylpyrrolidone can be linear or crosslinked.Number n represents the polymerization degree, and its numerical value will make the molecular weight of polyvinylpyrrolidone in above-mentioned scope.
Diphenylphosphino-polystyrene is represented with following formula:
In following formula, PS represents polystyrene.
As mentioned above, suppose that diphenylphosphino-polystyrene is such structure, wherein triphenylphosphine links to each other with various polystyrene beads (bead), can use every gram support of the catalyst to be connected with the polymkeric substance of 1-5 mmole diphenylphosphino.Argonaut Co., the product that Ltd. produces is commercially available product.Usually, polystyrene is by crosslinked with the copolymerization of Vinylstyrene.
Palladium can followingly be fixed with the metal with redox catalysis ability: for example usually at room temperature, polyvinylpyrrolidone or diphenylphosphino-polystyrene be dissolved or suspended in make solution in the appropriate solvent, this solution is mixed with the solution that is dissolved with palladium compound.When polyvinylpyrrolidone was used as support of the catalyst, though do not confirm, supposition thought that this structure is as follows:
(a-3) the haloalkane part is quaternized to be contained in the compound that nitrogen in organic carrier or the inorganic carrier or phosphorus obtain by using
Can use haloalkane quaternized wherein nitrogen or the organic carrier of phosphorus comprise: diphenylphosphino-polystyrene, poly-(4-vinylpridine), poly-(2-vinyl pyridine), polyvinylpyrrolidone, bipyridyl (bipyridino)-polystyrene, N, N-(di-isopropyl) aminomethylpolystyre.e, N-(methylated polystyrene)-4-(methylamino) pyridine and N, N-two hydroxyethylamino methyl-polystyrene.Inorganic carrier comprises diphenylphosphino-2-silicon-dioxide and pyridine subbase (pyridino)-2-silicon-dioxide, wherein preferred diphenylphosphino-polystyrene.
The haloalkane (R-X) that is used for quaterisation does not limit especially, and R comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl and benzyl.X comprises bromine, chlorine and iodine.Haloalkane can use or use two or more composition wherein separately.
Can use conventional method to carry out the quaterisation of organic carrier and inorganic carrier, for example can carry out quaterisation by heating carrier in solvent and haloalkane.In this case, employed solvent does not limit especially, can use methyl alcohol, ethanol, DMF and THF.Particular methanol.
Reaction under the situation of using the quaternized diphenylphosphino-polystyrene of n-butyl bromide can be represented by the formula as the example of quaterisation:
Under the situation of using haloalkane (R-X) quaternized poly-(4-vinylpridine), reaction can be represented by the formula:
In being dissolved with the solvent of metal-salt, stir the metal that fixes palladium and have the redox catalysis ability under the room temperature.For example can followingly make the fixed catalyzer: the quaternised diphenylphosphino-polystyrene of part (PS-TPP) is suspended in the acetone, close the dichloromethane solution of palladium (II) to wherein adding dichloro two (benzonitrile), this solution of stirring at room, after the color of the palladium in the acetone soln disappears subsequently to the acetone soln that wherein adds cobalt chloride (II), this solution of stirring at room.
When the haloalkane part is quaternized when being contained in compound that nitrogen in organic carrier or the inorganic carrier or phosphorus obtains as above-mentioned support of the catalyst, can be used in combination the dewatering agent that does not need solvent, do not use the organic oxidation reductive agent, thereby can obtain not having the polycarbonate of color.
(b) palladium compound
Make component (b) as long as can use any compound that contains the palladium atom.Concrete have common Palladous chloride (II), palladium bromide (II), chlorination carbonyl as above-mentioned palladium compound closes palladium and acid chloride, and available in addition dichloro two (acetonitrile) closes palladium (II) and dichloro two (benzonitrile) closes palladium (II).Above palladium compound can use or use two or more composition wherein separately.
(c) has the metallic compound of redox catalysis ability
Metal with redox catalysis ability comprises: the transition metal of family of the 5th family in lanthanon, the periodic table of elements-the 7th, chromium, manganese, iron, cobalt, nickel and copper, wherein preferred cobalt.Cobalt chloride (II) and cobaltous acetate (II) cobalt compound for being suitable for.Wherein preferred cobalt chloride (II).Its consumption is that every mole of palladium uses the 0.5-100 mole.The above metal with redox catalysis ability can use or use two or more composition wherein separately.
Can adopt the method for explanation described in the corresponding support of the catalyst fixedly palladium and metal with redox catalysis ability.
Above fixed catalyzer can use or use two or more composition wherein separately.In addition, can be used in combination the metallic compound that is carried on the inorganic layered compounds and without the fixed palladium compound.
(d) salt
If desired, can in the catalyzer of the present invention of producing polycarbonate, add and think the salt that can activate oxy-compound (condition is to get rid of following situation, promptly by using the quaternized situation that is contained in compound (a-3) that nitrogen in organic carrier or the inorganic carrier or phosphorus obtains as support of the catalyst of haloalkane part).
Described salt comprises: ammonium salt, salt, sulfonium salt, phosphonium salt and salt.Wherein preferred ammonium salt is with phosphonium salt.For example use bromination four (normal-butyl) ammonium and bis (triphenylphosphoranilidene) as ammonium salt.Bromination four (normal-butyl) Phosphonium and Xiuization tetraphenylphosphoniphenolate Zuo phosphonium salt.The consumption of salt can be about 0.1% mole or higher of oxy-compound.
(e) organic oxidation reductive agent
If desired, the organic oxidation reductive agent of adding comprises: quinhydrones, benzoquinones, α-Nai Kun, anthraquinone, catechol, 2,2 '-xenol and 4,4 '-xenol.Above redox agent can use or use two or more composition wherein separately.Its consumption is that every mole of palladium uses 0.5-100 mole redox agent.
(f) dewatering agent
If desired, add molecular sieve and zeolite, do not limit used dewatering agent especially as dewatering agent.The molecular sieve of wherein preferred synthetic zeolite.Preferred A-3 and A-4, more preferably A-3.
(g) promotor
In catalyzer of the present invention, in some cases selectivity, yield and work-ing life, can add promotor in order to improve catalytic activity, desired product.Only otherwise, can use any compound to make promotor, the suitable salt that heteropolyacid and heteropolyacid are arranged to having reacted side effect.
Described heteropolyacid comprises phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid, silicomolybdic acid, phosphotungstomolybdic acid, silicon tungsten molybdic acid and phosphovanadomolybdic acid.In addition, also can use its salt, an alkali metal salt, alkaline earth salt and transition metal salt.Can use or use two or more composition wherein separately.
Produce the method for polycarbonate
The method of production polycarbonate of the present invention comprises: the first step, with aromatic dihydroxy compound and monovalence phenol and carbon monoxide and oxygen reaction production polycarbonate prepolymer; Second step, above-mentioned polycarbonate prepolymer is carried out solid state polymerization produce polycarbonate, above-mentioned catalyzer is used for the above-mentioned the first step.
In the method for production polycarbonate of the present invention, can use the aromatic dihydroxy compound of known all cpds as raw material, can suitably select according to the kind of required polycarbonate.
Described aromatic dihydroxy compound comprises the aromatic dihydroxy compound (divalent phenol) with 12-37 carbon atom, available following formula (II) expression:
R wherein
1And R
2Respectively for containing the aryl that alkyl groups total has 6-20 carbon atom on halogen atom (for example chlorine, bromine, fluorine and iodine), alkoxyl group, ester group, carboxyl, hydroxyl, the alkyl with 1-8 carbon atom or the ring, they can be connected an ortho position or a position; Work as R
1And R
2Each R is all arranged when a plurality of
1And R
2Can be identical or different; A and b respectively are the integer of 0-4; And Y represent singly-bound, have 1-8 carbon atom alkylene base, have 2-8 carbon atom alkylidene, have 5-15 carbon atom the ring alkylene base, have 5-15 carbon atom the ring alkylidene ,-S-,-SO-,-SO
2-,-O-,-CO-key or the group represented with following formula:
In this case, available all cpds is as the aromatic dihydroxy compound of formula (II) expression, and preferred especially 2,2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane).Except dihydroxyphenyl propane, divalent phenol comprises two (4-hydroxy phenyl) compound, for example 1,1-two (4-hydroxy phenyl) methane, 1,1-two (4-hydroxy phenyl) ethane, 9,9-two (4-hydroxy phenyl) fluorenes, 9,9-two (3-methyl-4-hydroxy phenyl) fluorenes, two (4-hydroxy phenyl) naphthenic hydrocarbon, two (4-hydroxy phenyl) sulphur, two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) ether and two (4-hydroxy phenyl) ketone or halogenated bisphenol, for example 2,2-two (3,5-two bromo-4-hydroxy phenyls) propane and 2,2-two (3,5-two chloro-4-hydroxy phenyls) propane.When above-mentioned phenol contained alkyl and makes substituting group, preferred abovementioned alkyl was the alkyl with 1-8 carbon atom, especially preferably has the alkyl of 1-4 carbon atom.Above-mentioned aromatic dihydroxy compound can use or use two or more composition wherein separately.
The monovalence phenol that is used for the first step does not limit especially, comprises phenol, Ortho Cresol, m-cresol or p-cresol, p-tert-butylphenol, Pentaphen, to tert-octyl phenol, to cumyl phenol, p methoxy phenol and p-phenyl phenol.Wherein, preferred p-tert-butylphenol and phenol.Its consumption is generally the 5-70% mole of aromatic dihydroxy compound.Above-mentioned monovalence phenol can use or use two or more composition wherein separately.
Carbon monoxide with aromatic dihydroxy compound and the reaction of monovalence phenol in the first step can be single material or available inert gas dilution or can be the mixed gas that contains hydrogen.In addition, the oxygen of reaction usefulness also can be pure oxygen or available inert gas dilution in the first step, and for example oxygen containing gas is as air.
Be used to produce the qualification especially of solvent of prepolymer in the first step, comprise for example methylene dichloride, 1,2-ethylene dichloride, chloroform, acetone, gamma-butyrolactone, tetrahydrofuran (THF) and hexanaphthene are from the solvent of the preferred halogen of environmental angle.Solvent as the halogen solvent comprises the compound that contains carbonic acid ester bond.This kind solvent for example has methylcarbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, Texacar PC, carbonic acid diallyl, allyl carbonate methyl esters, carbonic acid two (2-methoxyl group phenyl ester), vinylene carbonate, dimethyl benzyl, carbonic acid two (O-methoxy phenyl ester) and methyl carbonate ethyl ester.Wherein preferred Texacar PC.Above carbonic ether basic solvent can use or use two or more composition wherein separately.
The temperature of reaction of producing prepolymer by oxidation carbonylation is 30-180 ℃, preferred 50-150 ℃, and more preferably 80-120 ℃.If temperature surpasses 180 ℃, then side reaction (for example decomposition reaction) increases, and is easy to produce color.On the other hand, if temperature is lower than 30 ℃, then speed of reaction reduces, and is unpractical.
Owing to use gaseous substance (for example carbon monoxide and oxygen), usually reaction pressure be made as pressurized state.The dividing potential drop of carbon monoxide is 1 * 10
-2-20Mpa, preferred 1 * 10
-2-10Mpa, and the dividing potential drop of oxygen is 1 * 10
-2-10Mpa, preferred 1 * 10
-2-5Mpa.The dividing potential drop of especially preferably controlling oxygen makes the gas composition in the reaction system depart from explosive range.If reaction pressure is too low, then speed of reaction reduces, and if pressure is too high, then reaction unit is wanted large-scale and has been increased laid down cost, is disadvantageous economically therefore.When using rare gas element and hydrogen is feasible, though do not limit its dividing potential drop especially, is adapted in the actual pressure range.
Under the situation of for example batch system, the reaction times is 1-48 hour, preferred 2-36 hour, and more preferably 3-24 hour.If the reaction times is less than 1 hour, then yield reduces, and if above 48 hours, then yield no longer raise.
Any batch system, semicontinuous system (wherein raw material, catalyzer etc. are introduced continuously) and continuous system (wherein raw material, catalyzer etc. are introduced continuously, and reaction product is taken out continuously) can be used for producing the reactive system of prepolymer.
In second step, the polycarbonate prepolymer that the first step is produced is produced polycarbonate through solid-phase polymerization.The ， quaternary alkylphosphonium salt is suitable for use as catalyzer in this case.
Be used for solid-phase polymerization De quaternary alkylphosphonium salt and do not limit especially, comprise all cpds, the compound of for example using following formula (III) or (IV) representing:
(PR
3 4)
+(X
2)
- (III)
(PR
3 4)
+ 2(Y
1)
2- (IV)
In above-mentioned formula (III) and formula (IV), R
3The expression organic group.This organic group represent straight chain, side chain or cyclic have containing of 1-20 carbon atom or do not contain substituent alkyl, have 6-20 carbon atom contain or do not contain substituent aryl or have a 7-20 carbon atom contain or do not contain substituent aralkyl.
In this case, the example with alkyl of 1-20 carbon atom comprises: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, just-or isopentyl, just-or isohexyl, just-or iso-octyl, just-or isodecyl, just-or different tetradecyl, cyclopentyl, cyclohexyl and methylcyclohexyl.The substituting group of abovementioned alkyl comprises for example halogen atom, alkoxyl group, aralkoxy and acyloxy.
Example with aryl of 6-20 carbon atom comprises: phenyl, naphthyl and xenyl.The substituting group of abovementioned alkyl for example has halogen atom, alkoxyl group, aralkoxy and acyloxy.Example with aralkyl of 7-20 carbon atom comprises: benzyl, styroyl, naphthyl methyl and 1,1,1-trityl group.The substituting group of above-mentioned aralkyl for example has halogen atom, alkoxyl group, aralkoxy and acyloxy.
4 above-mentioned R
3Can be identical or different, and two R
3Formation ring structure capable of being combined.
X
2Expression can form the group of univalent anion, for example halogen atom, hydroxyl, alkoxyl group, aryloxy, R ' COO, HCO
3, (R ' O)
2P (=O) O or BR "
4In this case, R ' represents alkyl (for example alkyl and aryl), and two R ' O can be identical or different.R " expression hydrogen atom or alkyl (for example alkyl and aryl), and 4 R " can be identical or different.Y
1Expression can form the group of dianion, for example CO
3
Above-mentioned X
2Concrete example comprises: oxyhydroxide, borohydride, tetraphenyl borate salts, alkyl triph-enylborate, formate, acetate, propionic salt, butyrates, fluorochemical, muriate and supercarbonate.Y
1Special example comprises carbonate.
The concrete example of above-mentioned formula (III) and formula (IV) expression De quaternary alkylphosphonium salt comprises hydroxide four (aryl or alkyl) Phosphonium, for example hydroxide tetraphenylphosphoniphenolate, hydroxide four Nai Ji Phosphonium, hydroxide four (chlorophenyl) Phosphonium, hydroxide four (phenylbenzene) Phosphonium, tetramethylphosphonihydroxide hydroxide Ben Ji Phosphonium, tetramethylphosphonihydroxide hydroxide Ji Phosphonium, hydroxide Si Yi Ji Phosphonium, hydroxide Si Yi Bing Ji Phosphonium, hydroxide 4-butyl-phosphonium, hydroxide Si Ji Ji Phosphonium and tetrahydrochysene oxidation Huan Ji Ji Phosphonium; Single (aryl or the alkyl) triphenyl phosphonium of hydroxide, for example hydroxide Jia base triphenyl phosphonium, hydroxide Yi base triphenyl phosphonium, hydroxide propyl group triphenyl phosphonium, hydroxide sec.-propyl triphenyl phosphonium, hydroxide Ding base triphenyl phosphonium, hydroxide octyl group triphenyl phosphonium, hydroxide four decyl triphenyl phosphoniums, hydroxide cyclohexyl triphenyl phosphonium, hydroxide Bian base triphenyl phosphonium, hydroxide ethoxy benzyl triphenyl phosphonium, hydroxide methoxymethyl triphenyl phosphonium, hydroxide acetoxy-methyl triphenyl phosphonium, hydroxide phenacyl triphenyl phosphonium, hydroxide chloromethane base triphenyl phosphonium, hydroxide brooethyl triphenyl phosphonium, hydroxide xenyl triphenyl phosphonium, hydroxide naphthyl triphenyl phosphonium, hydroxide chlorophenyl triphenyl phosphonium, hydroxide Phenoxyphenyl triphenyl phosphonium, hydroxide p-methoxy-phenyl triphenyl phosphonium, hydroxide acetoxyl group phenyl triphenyl phosphonium and hydroxide naphthyl phenyl triphenyl phosphonium; Single (aryl) San Wan of hydroxide Ji Phosphonium, for example hydroxide Ben base San Jia Ji Phosphonium, hydroxide xenyl San Jia Ji Phosphonium, hydroxide phenyl three Ji Ji Phosphonium and hydroxide xenyl three Ji Ji Phosphonium; Hydroxide diaryl Er Wan Ji Phosphonium, hydroxide Er methyldiphenyl Ji Phosphonium for example, single (alkyl or aralkyl) the San Wan Ji of hydroxide diethyl Er Ben Ji Phosphonium and hydroxide two (xenyl) Er Ben Ji Phosphonium and hydroxide Phosphonium, hydroxide sec.-propyl San Jia Ji Phosphonium for example, hydroxide sec.-propyl San Yi Ji Phosphonium, hydroxide sec.-propyl San Ding Ji Phosphonium, hydroxide cyclohexyl San Jia Ji Phosphonium, hydroxide cyclohexyl San Yi Ji Phosphonium, hydroxide cyclohexyl San Ding Ji Phosphonium, hydroxide 1,1,1-trityl group San Jia Ji Phosphonium, hydroxide 1,1,1-trityl group San Yi Ji Phosphonium and hydroxide 1,1,1-trityl group San Ding Ji Phosphonium.
In addition, also comprise tetraphenyl boric acid four (alkyl or aryl) Phosphonium, for example tetraphenyl boric acid tetramethyl phosphonium, tetraphenyl boric acid four second base Phosphonium, tetraphenyl boric acid tetraphenylphosphoniphenolate, tetraphenyl boric acid four naphthalene base Phosphonium, tetraphenyl boric acid four (chlorophenyl) Phosphonium, tetraphenyl boric acid four (xenyl) Phosphonium and tetraphenyl boric acid tetramethyl phenyl Phosphonium; Tetraphenyl boric acid list (aryl or alkyl) triphenyl phosphonium, for example tetraphenyl boron acid methyl triphenyl phosphonium, tetraphenyl boric acid Yi base triphenyl phosphonium, tetraphenyl boric acid propyl group triphenyl phosphonium, tetraphenyl boron acid butyl triphenyl phosphonium, tetraphenyl boric acid octyl group triphenyl phosphonium, tetraphenyl boric acid tetradecyl triphenyl phosphonium, tetraphenyl boric acid cyclopentyl triphenyl phosphonium, tetraphenyl boric acid cyclohexyl triphenyl phosphonium, tetraphenyl boric acid Bian base triphenyl phosphonium, tetraphenyl boric acid ethoxy benzyl triphenyl phosphonium, tetraphenyl boric acid methoxymethyl triphenyl phosphonium, tetraphenyl boric acid acetoxy-methyl triphenyl phosphonium, tetraphenyl boric acid phenacyl triphenyl phosphonium, tetraphenyl boric acid chloromethyl triphenyl phosphonium, tetraphenyl boric acid brooethyl triphenyl phosphonium, tetraphenyl boric acid xenyl triphenyl phosphonium, tetraphenyl boric acid naphthyl triphenyl phosphonium, tetraphenyl boric acid chlorophenyl triphenyl phosphonium, tetraphenyl boric acid Phenoxyphenyl triphenyl phosphonium, tetraphenyl boric acid acetoxyl group phenyl triphenyl phosphonium and tetraphenyl boric acid naphthyl phenyl triphenyl phosphonium; Tetraphenyl boric acid list aryl San Wan Ji Phosphonium, for example tetraphenyl boric acid Ben base San Jia Ji Phosphonium, tetraphenyl boric acid xenyl San Jia Ji Phosphonium, tetraphenyl boric acid phenyl three Ji Ji Phosphonium and tetraphenyl boric acid xenyl three Ji Ji Phosphonium and tetraphenyl boric acid diaryl Er Wan Ji Phosphonium, for example tetraphenyl boric acid Er methyldiphenyl Ji Phosphonium, tetraphenyl boric acid diethyl Er Ben Ji Phosphonium and tetraphenyl boric acid two (xenyl) Er Ben Ji Phosphonium.
In addition, the coupling negatively charged ion of replacing each above-mentioned oxyhydroxide and tetraphenyl borate salts comprises: alkyl triph-enylborate, aryloxy (for example phenoxy group), alkoxyl group (for example methylate and ethylate), alkyl-carbonyl oxygen base (for example formate, acetate, propionic salt and butyrates), aryl carbonyl oxygen base (for example benzoate) and use the above-mentioned De quaternary alkylphosphonium salt of halogen atom (for example chlorine and bromine).
Compound except above-mentioned formula (III) expression, also can use the divalence that has of formula (IV) expression to mate anionic compound, quaternary alkylphosphonium salt for example, for example carbonic acid two (tetraphenylphosphoniphenolate) and carbonic acid two (xenyl triphenyl phosphonium), 2, two (triphenyl phosphoniums) two (tetraphenyl borate salts) of two-tetraphenyl phosphonium salt, ethylenebis (triphenyl phosphonium) dibromo and the trimethylene of 2-two (4-hydroxy phenyl) propane.
From high catalytic activity and responsive and be difficult for remaining in angle the polymkeric substance to thermolysis, in above-mentioned quaternary alkylphosphonium salt, what be fit to is those quaternary alkylphosphonium salts that contain alkyl, specifically is for example methyl triphenyl boric acid tetramethyl phosphonium, ethyl triphenyl boric acid four second base Phosphonium, propyl group triphenyl boric acid 4 third basic Phosphonium, butyl triphenyl boric acid 4-butyl-phosphonium, tetraphenyl boric acid 4-butyl-phosphonium, tetraphenyl boric acid four second base Phosphonium, Three methyl Benzene ylboronic acid trimethylammonium second base Phosphonium and benzyl triphenyl boric acid three methyl benzyl base Phosphonium.
Si Wan Ji phosphonium salt, for example tetramethylphosphonihydroxide hydroxide Ji Phosphonium, hydroxide Si Yi Ji Phosphonium and hydroxide 4-butyl-phosphonium have lower decomposition temperature, so they are easy to decompose and are difficult for remaining in the product polycarbonate with the form of impurity.In addition, because less carbon atom makes required unit (unit) reduce, and also be favourable from cost consideration, say that from this angle they are preferred compounds.
Equally, from the angle of the quality of equilibrium catalyst effect and resulting polycarbonate, preferably use tetraphenyl boric acid tetraphenylphosphoniphenolate.
In addition, be extremely excellent angle from the quality of equilibrium catalyst effect and resulting polycarbonate, preferably use tetraphenyl boric acid cyclohexyl triphenyl phosphonium and tetraphenyl boric acid cyclopentyl triphenyl phosphonium.
Preferred quaternary alkylphosphonium salt and other catalyzer (if necessary) be as the catalysts of solid-phase polymerization, but add that prepolymer forms that remaining catalyzer former state after the step is used or above-mentioned catalyzer can powder, the form of liquid or gas adds once more.Carry out solid-phase polymerization temperature of reaction Tp (℃) and the reaction times can change according to following factor: the form of the prepolymer of (molecular structure, molecular weight etc.) kind and crystallization, in the prepolymer of crystallization the degree of crystallinity of the prepolymer of the kind of contained catalyzer existence, kind and content, the catalyzer that adds if desired or consumption, crystallization and its melt temperature Tm ' (℃) the required polymerization degree of the aromatic polycarbonate of difference, expection and other reaction conditions.Carry out solid-phase polymerization by heating, temperature of reaction preferably is not less than the second-order transition temperature of the aromatic polycarbonate of expection, and temperature range makes the prepolymer of crystallization in the solid-phase polymerization process keep solid phase and not have fusion, and more preferably temperature range is represented with following formula V:
Tm’-50≤Tp＜Tm’ (V)
Reaction times is 1 minute-100 hours, preferred 0.1-50 hour.
Under the situation of the polycarbonate of for example producing dihydroxyphenyl propane, preferably about 150-260 ℃ of above-mentioned temperature range, especially preferably about 180-245 ℃.Equally, the method for using at polymerization procedure is heated polymerizable thing and stir polymkeric substance as far as possible reposefully in polymerization process preferably, and reactor itself rotates or makes polymer flow in order to take out by product best by warm air.
Usually, the weight-average molecular weight of industrial available polycarbonate is 6,000-200, and 000, and the polycarbonate with this polymerization degree can be finished by above-mentioned solid phase polymerization step at an easy rate.The degree of crystallinity of the aromatic polycarbonate that the solid-phase polymerization of the prepolymer by crystallization obtains becomes bigger than the degree of crystallinity of prepolymer before the polymerization, has therefore obtained the aromatic polycarbonate powder of crystallization in the method for the invention.The aromatic polycarbonate powder of crystallization need not cooling can directly introduce forcing machine and granulation, perhaps need not cooling and can directly introduce mould machine and molding.Can suitably change the prepolymerization that influences polyreaction and the ratio of solid state polymerization if desired.
The swollen solid phase polymerization process passes through the solid-phase polymerization polymerization once more for the prepolymer by the aforesaid method crystallization, and state is by swelling gas swelling described later.In the process of producing polycarbonate by transesterification reaction, when removing low molecular compound (for example by-product phenol), use this method by the degassing or extraction, the rate of mass transfer of being removed under the situation of micromolecular compound from the polymkeric substance (oligo-ester carbonate) of swollen state by swelling gas by the degassing or extraction becomes faster than the rate of mass transfer under the situation of removing micromolecular compound by the degassing or extraction from the solid matter of high viscosity molten and crystallization, therefore can efficiently react.
The swelling solvent of Shi Yonging is included in down the mixture of the single swelling solvent of swellable polycarbonate under the reaction conditions that shows, single swelling solvent and by single swelling solvent or its mixture are mixed the solvent that obtains with the poor solvent of one or more polycarbonate in this case.
Swollen state in this step is meant such state, the volume or weight of raw material prepolymer thin slice becomes specific heat swelling value (heat swelling value) greatly under the reaction conditions that shows down, and swelling solvent is meant such compound, having the boiling temperature or the common vapour pressure of evaporating fully under following reaction conditions is 6.7kPa or higher simplification compound or its mixture, and described compound can form above-mentioned swelling phase.
As long as can satisfy above-mentioned swelling condition, do not limit this swelling solvent especially.For example, corresponding solubility parameter is 4-40 (cal/cm
3)
1/2, preferred 7-14 (caL/cm
3)
1/2Aromatic substance and oxygenatedchemicals.Described swelling solvent for example has aromatic hydrocarbon, for example benzene,toluene,xylene, ethylbenzene, diethylbenzene, propyl benzene and two propyl benzene; Ester, for example tetrahydrofuran (THF) is with diox; Ketone, for example methylethylketone and methyl iso-butyl ketone (MIBK).The simplification compound or its mixture that wherein preferably have the hydrocarbon of 6-20 carbon atom.
For with the situation of swelling solvent blended poor solvent, preferred saturated hydrocarbon compound with 4-18 carbon atom straight chain or side chain, be 0.1% weight or still less and be not easy to participate in reaction wherein, perhaps have 4-18 carbon atom and be the hydrocarbon compound of low-unsaturation-degree in the solubleness of polycarbonate in this solvent under the following reaction conditions.If the boiling point of swelling solvent and poor solvent all above 250 ℃, then is difficult to remove remaining solvent, and the quality of product easily descends, and is not preferred solvent therefore.
When using the mixture of this poor solvent and swelling solvent, comprise 1% weight or more swelling solvent in the suggestion mixed solvent, there are 5% weight or more swelling solvent in the preferred mixed solvent.In this swollen solid phase polymerization procedure, the preferred 100-240 of temperature of reaction ℃, the preferred 1330Pa-0.5MPaG of reaction pressure, special preferred atmosphere is pressed.If temperature of reaction is lower than above-mentioned scope, then do not carry out transesterification reaction.Can bring the melting phenomenon between the particle if temperature of reaction when surpassing the hot conditions of prepolymer fusing point, then can not keep solid phase, and operability reduces significantly.Therefore, temperature of reaction is necessary for fusing point or lower.
Swelling solvent gas can liquid state be dosed to reactor and evaporation or can be dosed in the reactor after the evaporation in advance by heat exchanger in reactor.About the feeding quantity of gas, preferably add to gas in the reactor and be every gram prepolymer reinforced 0.5 liter (under standard conditions)/hour.Therefore the flow and the speed of reaction of swelling solvent gas are closely related, and the effect that can be used as thermal barrier and remove phenol, along with the increase reaction rate accelerates of gas flow.The reactor that is used for this swollen solid phase polyreaction does not limit especially.
The catalyzer of the present invention that is used to produce polycarbonate can followingly make: palladium compound and metallic compound with redox catalysis ability are fixed in above-mentioned support of the catalyst, after finishing this reaction, can separate with dewatering agent by filtration, drying and regeneration at an easy rate.The content that remains in the metal in the resulting polycarbonate is considerably less.
In the method for production polycarbonate of the present invention, can obtain the polycarbonate of macromolecule according to the production stages in above-mentioned two steps, but the therefore high-quality polycarbonate of High-efficient Production.
Catalyst system of the present invention not only can be used for the carbonylation reaction of dihydroxy compound, also can be used for the carbonylation reaction of monohydroxy compound, but also can be used for the synthetic of diphenyl carbonate.
Explain the present invention in more detail below with reference to embodiment and comparing embodiment, but the present invention to be defined in these embodiment anything but.Reference example shows the situation that the catalyzer of recovery reuses.
In following embodiment, comparing embodiment and reference example, number-average molecular weight (Mn) and weight-average molecular weight (Mw) are by the GPC Instrument measuring.
Elutriant: chloroform
Pillar: Shodex K-804L
Calibration curve: polystyrene standard molecular weight: use 1050,5870,17100,98900 and 355,000 5 specimen preparations
Detector: ultraviolet ray (UV) detector
The calculating of the turnover number of palladium (TON) is the value with yield on duty that obtains divided by the mole number of reinforced palladium with the mole number of dihydroxyphenyl propane.
Embodiment 1
(1) produces the fixed catalyst A
With poly-(4-vinylpridine) (the molecular weight Mw:100000 of 1.26g, by Koei ChemicalInd.Co., Ltd. produce) be dissolved in the 40ml methylene dichloride, close the dichloromethane solution of palladium (II) (dichloro two (benzonitrile) closes palladium: 1.0mmol, methylene dichloride: 30ml) to wherein slowly adding dichloro two (benzonitrile) subsequently.Subsequently to the acetone soln that wherein adds cobalt chloride (II) (cobalt chloride (II): 5mmol, acetone: 70ml), and under room temperature, stirred 2 hours.Subsequently, filtering-depositing, with washing with acetone and under vacuum in 60 ℃ of dryings 24 hours.The fixed catalyst A that obtains expecting, output 1.90g.
(2) confirm catalyst performance
Reinforced in the autoclave of a 30ml volume: the fixed catalyst A that makes among 4.16mmol dihydroxyphenyl propane, the 52.5mg above-mentioned (1), 0.625mmol Tetrabutylammonium bromide, 0.125mmol benzoquinones, 1.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by WakoPure Chemicals Industries, Ltd. produce) and 10ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.Reinforced finishing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate prepolymer of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.The yield of resulting polycarbonate prepolymer and molecular weight (Mn, Mw) are shown in table 1.The amount of remaining palladium is 25ppm (measuring limit) or still less in the resulting polycarbonate prepolymer.
Embodiment 2
(1) produces the fixed catalyst B
Carry out same step among the embodiment 1 (1), be to use poly-(2-vinyl pyridine) (molecular weight Mw:18000, by Koei Chemical Ind.Co., Ltd. produces) to replace poly-(4-vinylpridine) with embodiment 1 (1) difference.The fixed catalyst B that obtains expecting, output 1.83g.
(2) confirm catalyst performance
Carry out same step among the embodiment 1 (2), be to use the fixed catalyst B that makes in above-mentioned (1) to replace the fixed catalyst A with embodiment 1 (2) difference.The yield of resulting polycarbonate prepolymer and molecular weight (Mn, Mw) are shown in table 1.
Embodiment 3
(1) produces fixed catalyzer C
Carry out same step among the embodiment 1 (1), be to use 1.43g to gather (6-methyl-2-vinyl pyridine) (molecular weight Mw:58000 with embodiment 1 (1) difference, by Koei ChemicalInd.Co., Ltd. produces) replace 1.26g to gather (4-vinylpridine).The fixed catalyzer C that obtains expecting, output 2.12g.
(2) confirm catalyst performance
Carry out same step among the embodiment 1 (2), be to use the 56.4mg fixed catalyzer C that makes in above-mentioned (1) to replace 52.5mg fixed catalyst A with embodiment 1 (2) difference.The yield of resulting polycarbonate prepolymer and molecular weight (Mn, Mw) are shown in table 1.
Reference example 1
Will be in embodiment 1 (2) isolating synthetic zeolite and fixed catalyzer under vacuum in 130 ℃ of dryings 24 hours.Reinforced in the autoclave of a 30ml volume: 4.16mmol dihydroxyphenyl propane, exsiccant synthetic zeolite and fixed catalyzer (total amount of recovery), 0.625mmol Tetrabutylammonium bromide, 0.125mmol benzoquinones and 10ml Texacar PC, subsequently in 25 ℃ to the wherein carbon monoxide of reinforced 6.0Mpa and the oxygen of 0.3Mpa.Reinforced finishing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction, separate synthetic zeolite and fixed catalyzer, make polycarbonate prepolymer by the methyl alcohol redeposition once more.Under the vacuum in 100 ℃ of dryings 24 hours.The yield of resulting polycarbonate prepolymer and molecular weight (Mn, Mw) are shown in table 1.
Table 1
| Yield (%) | Number-average molecular weight (Mn) | Weight-average molecular weight (Mw) | |
| Embodiment 1 | 69 | 3370 | 5690 |
| Embodiment 2 | 39 | 2560 | 3340 |
| Embodiment 3 | 51 | 2790 | 4070 |
| Reference example 1 | 45 | 2850 | 4920 |
Embodiment 4
The first step:
Reinforced in the autoclave of a 100ml volume: the fixed catalyst A that makes among 12.48mmol dihydroxyphenyl propane, 6.72mmol p-tert-butylphenol, the 157.5mg embodiment 1 (1), 1.875mmol Tetrabutylammonium bromide, 0.375mmol benzoquinones, 3.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by Wako Pure Chemicals Industries, Ltd. produce) and 30ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.Reinforced finishing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate prepolymer of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.
Second step:
300ppm tetraphenyl boric acid cyclohexyl triphenyl phosphonium is added in the polycarbonate prepolymer that makes in the 500mg the first step, and subsequently this mixture being placed internal diameter is the SUS pipe of 1.3cm.With 100ml/ minute speed introducing nitrogen, amount to 8 hours solid-phase polymerization to wherein:,, made the polycarbonate of expection in 210 ℃ of reactions 2 hours and in 230 ℃ of reactions 4 hours in 190 ℃ of reactions 2 hours.The amount of remaining palladium is 25ppm or still less in the polycarbonate.
The molecular weight (Mn, Mw) of the polycarbonate that obtains during the polycarbonate prepolymer that obtains in the first step and second goes on foot is shown in table 2.
Comparing embodiment 1
Carry out step same among the embodiment 4, difference from Example 4 is not use p-tert-butylphenol.The molecular weight (Mn, Mw) of the polycarbonate that obtains during the polycarbonate prepolymer that obtains in the first step and second goes on foot is shown in table 2.
Table 2
| The first step prepolymer | The second step polycarbonate | |||
| Mn | Mw | Mn | Mw | |
| Embodiment 4 | 2440 | 4040 | 11500 | 56000 |
| Comparing embodiment 1 | 3330 | 5680 | 3800 | 7030 |
Embodiment 5
(1) produces fixed catalyzer D
The 1.33g polyvinylpyrrolidone is (linear, K=30, molecular weight Mw:40000, by Tokyo Kasei Kogyo Co., Ltd. produce) be dissolved in the 100ml methylene dichloride, close the dichloromethane solution of palladium (II) (dichloro two (benzonitrile) closes palladium: 1.0mmol, methylene dichloride: 20ml) to wherein slowly adding dichloro two (benzonitrile) subsequently.Subsequently to the acetone soln that wherein adds cobalt chloride (II) (cobalt chloride (II): 5.0mmol, acetone: 70ml), and under room temperature, stirred 2 hours.Subsequently, filtering-depositing, with washing with acetone and under vacuum in 60 ℃ of dryings 24 hours.The fixed catalyzer D that obtains expecting, output 1.87g.
(2) confirm catalyst performance
Reinforced in the autoclave of a 30ml volume: the fixed catalyzer D that 4.16mmol dihydroxyphenyl propane, 27.0mg make in (1), 0.313mmol Tetrabutylammonium bromide, 0.313mmol benzoquinones, 1.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by Wako PureChemicals Industries, Ltd. produce) and 10ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.Reinforced finishing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.The turnover number (TON) of the yield of resulting polycarbonate, molecular weight (Mn, Mw) and palladium is shown in table 3.
Embodiment 6
(1) produces fixed catalyzer E
With 6.67g polyvinylpyrrolidone (cross-linking type, by Tokyo Kasei Kogyo Co., Ltd. produce) be suspended in the 50ml acetone, close the acetone soln of palladium (II) (dichloro two (benzonitrile) closes palladium: 1.0mmol to wherein adding dichloro two (benzonitrile) subsequently, acetone: 30ml), and under room temperature, stirred 2 hours.Subsequently to the acetone soln that wherein adds cobalt chloride (II) (cobalt chloride (II): 5mmol, acetone: 70ml), and under room temperature, stirred 17 hours.Filter resulting precipitation, with washing with acetone and under vacuum in 60 ℃ of dryings 24 hours.The fixed catalyzer E that obtains expecting, output 7.28g.
(2) confirm catalyst performance
Carry out same step among the embodiment 5 (2), be to be used in the 93.7mg fixed catalyzer E that makes in above-mentioned (1) with embodiment 5 (2) differences and replace 27.0mg fixed catalyzer D.
The turnover number (TON) of the yield of resulting polycarbonate, molecular weight (Mn, Mw) and palladium is shown in table 3.
Embodiment 7
Reinforced in the autoclave of a 100ml volume: the fixed catalyzer D that makes among 12.48mmol dihydroxyphenyl propane, the 16.2mg embodiment 5 (1), 0.938mmol Tetrabutylammonium bromide, 0.188mmol benzoquinones, 3.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by WakoPure Chemicals Industries, Ltd. produce) and 30ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.Reinforced finishing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.The turnover number (TON) of the yield of resulting polycarbonate, molecular weight (Mn, Mw) and palladium is shown in table 3.
Embodiment 8
Reinforced in the autoclave of a 100ml volume: the fixed catalyzer E that makes among 12.48mmol dihydroxyphenyl propane, the 45.0mg embodiment 6 (1), 0.938mmol Tetrabutylammonium bromide, 0.15mmol benzoquinones, 3.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by Wako PureChemicals Industries, Ltd. produce) and 30ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.Reinforced finishing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.The turnover number (TON) of the yield of resulting polycarbonate, molecular weight (Mn, Mw) and palladium is shown in table 3.
Table 3
| Yield (%) | Mn | Mw | TON | |
| Embodiment 5 | 83 | 4180 | 7300 | 276 |
| Embodiment 6 | 80 | 3870 | 6740 | 266 |
| Embodiment 7 | 78 | 3680 | 6580 | 1290 |
| Embodiment 8 | 70 | 3320 | 5510 | 1462 |
Embodiment 9
The first step:
Reinforced in the autoclave of a 100ml volume: the fixed catalyzer D that makes among 11.47mmol dihydroxyphenyl propane, 2.024mmol p-tert-butylphenol, the 81.0mg embodiment 5 (1), 0.937mmol Tetrabutylammonium bromide, 0.937mmol benzoquinones, 3.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by Wako Pure Chemicals Industries, Ltd. produce) and 30ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.After the sealing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate prepolymer of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.
Second step:
300ppm tetraphenyl boric acid cyclohexyl triphenyl phosphonium is added in the polycarbonate prepolymer that makes in the 500mg the first step, and subsequently this mixture being placed internal diameter is the SUS pipe of 1.3cm.With 100ml/ minute speed introducing nitrogen, amount to 8 hours solid-phase polymerization to wherein:,, made the polycarbonate of expection in 210 ℃ of reactions 2 hours and in 230 ℃ of reactions 4 hours in 190 ℃ of reactions 2 hours.The amount of remaining palladium is 25ppm (measuring limit) or still less in the polycarbonate.
The molecular weight (Mn, Mw) of the polycarbonate that obtains during the polycarbonate prepolymer that obtains in the first step and second goes on foot is shown in table 4.
Comparing embodiment 2
Carry out step same among the embodiment 9, be not use p-tert-butylphenol and use the 12.48mmol dihydroxyphenyl propane with the first step difference of embodiment 9.
The molecular weight (Mn, Mw) of the polycarbonate that obtains during the polycarbonate prepolymer that obtains in the first step and second goes on foot is shown in table 4.
Table 4
| The first step prepolymer | The second step polycarbonate | |||
| Mn | Mw | Mn | Mw | |
| Embodiment 9 | 3000 | 4600 | 12900 | 50000 |
| Comparing embodiment 2 | 4070 | 7210 | 5000 | 8100 |
Embodiment 10
(1) produces fixed catalyzer F
With 3.97g diphenylphosphino-polystyrene (PS-TPP, TPP:1.5mmol/g, lot number 01740, by Argonaut Co., Ltd. produce) be suspended in the 50ml acetone, close the acetone soln of palladium (II) (dichloro two (benzonitrile) closes palladium: 0.5mmol, acetone: 20ml), stirred under room temperature 4 hours to wherein adding dichloro two (benzonitrile) subsequently.Subsequently to the acetone soln that wherein adds cobalt chloride (II) (cobalt chloride (II): 2.5mmol, acetone: 35ml), and under room temperature, stirred 24 hours.Filtering-depositing, with acetone and methanol wash and under vacuum in 60 ℃ of dryings 24 hours.The fixed catalyzer F that obtains expecting, output 3.95g.
(2) confirm catalyst performance
Reinforced in the autoclave of a 30ml volume: the fixed catalyzer F that 4.16mmol dihydroxyphenyl propane, 219mg make in (1), 0.625mmol Tetrabutylammonium bromide, 0.625mmol benzoquinones, 1.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by Wako PureChemicals Industries, Ltd. produce) and 10ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.After the sealing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.The turnover number (TON) of the yield of resulting polycarbonate, molecular weight (Mn, Mw) and palladium is shown in table 5.The amount of remaining palladium is 25ppm (measuring limit) or still less in the resulting polycarbonate.
Embodiment 11
Carry out step same among the embodiment 10, difference from Example 10 is, the amount that the amount of fixed catalyzer F is reduced to 110mmol, Tetrabutylammonium bromide reduces to 0.313mmol and the amount of benzoquinones is reduced to 0.313mmol.
The turnover number (TON) of the yield of resulting polycarbonate, molecular weight (Mn, Mw) and palladium is shown in table 5.The amount of remaining palladium is 25ppm (measuring limit) or still less in the polycarbonate.
Embodiment 12
Carry out step same among the embodiment 10, difference from Example 10 is that the amount of fixed catalyzer F is reduced to 43.9mmol, and the amount of benzoquinones is reduced to 0.125mmol.
The turnover number (TON) of the yield of resulting polycarbonate, molecular weight (Mn, Mw) and palladium is shown in table 5.The amount of remaining palladium is 25ppm (measuring limit) or still less in the polycarbonate.
Reference example 2
With finish after the reaction of embodiment 10 isolating synthetic zeolite and fixed catalyzer under vacuum in 130 ℃ of dryings 24 hours.Reinforced in the autoclave of a 30ml volume: 4.16mmol dihydroxyphenyl propane, as above exsiccant synthetic zeolite and fixed catalyzer (total amount), 0.625mmol Tetrabutylammonium bromide, 0.625mmol benzoquinones and 10ml Texacar PC, subsequently in 25 ℃ to the wherein carbon monoxide of reinforced 6.0Mpa and the oxygen of 0.3Mpa.Reinforced finishing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.The turnover number (TON) of the yield of resulting polycarbonate, molecular weight (Mn, Mw) and palladium is shown in table 5.The amount of remaining palladium is 25ppm (measuring limit) or still less in the polycarbonate.
Table 5
| Yield (%) | Mn | Mw | TON | |
| Embodiment 10 | 61 | 3160 | 5120 | 101 |
| Embodiment 11 | 81 | 3990 | 7950 | 270 |
| Embodiment 12 | 78 | 4030 | 8950 | 647 |
| Reference example 2 | 59 | 3130 | 4980 | - |
Embodiment 13
The first step:
Reinforced in the autoclave of a 100ml volume: the fixed catalyzer F that makes among 11.46mmol dihydroxyphenyl propane, 2.024mmol p-tert-butylphenol, the 101.4mg embodiment 10 (1), 0.938mmol Tetrabutylammonium bromide, 0.938mmol benzoquinones, 3.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by Wako Pure Chemicals Industries, Ltd. produce) and 30ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.After reinforced, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction,, make the polycarbonate prepolymer of expection by the methyl alcohol redeposition by filtering separation synthetic zeolite and fixed catalyzer.Under the vacuum in 100 ℃ of dryings 24 hours.
Second step:
300ppm tetraphenyl boric acid cyclohexyl triphenyl phosphonium is added in the polycarbonate prepolymer that makes in the 500mg the first step, and subsequently this mixture being placed internal diameter is the SUS pipe of 1.3cm.With 100ml/ minute speed introducing nitrogen, amount to 8 hours solid-phase polymerization to wherein:,, made the polycarbonate of expection in 210 ℃ of reactions 2 hours and in 230 ℃ of reactions 4 hours in 190 ℃ of reactions 2 hours.The amount of remaining palladium is 25ppm (measuring limit) or still less in the polycarbonate.
The molecular weight (Mn, Mw) of the polycarbonate that obtains during the polycarbonate prepolymer that obtains in the first step and second goes on foot is shown in table 6.
Comparing embodiment 3
Carry out step same among the embodiment 13, be not use p-tert-butylphenol and use the 12.48mmol dihydroxyphenyl propane with embodiment 13 differences.
The molecular weight (Mn, Mw) of the polycarbonate that obtains during the polycarbonate prepolymer that obtains in the first step and second goes on foot is shown in table 6.
Table 6
| The first step prepolymer | The second step polycarbonate | |||
| Mn | Mw | Mn | Mw | |
| Embodiment 13 | 3280 | 5680 | 11900 | 56300 |
| Comparing embodiment 3 | 3530 | 5730 | 3900 | 7230 |
Embodiment 14
(1) quaterisation of diphenylphosphino-polystyrene
Reinforced in the autoclave of a 200ml volume: 5.00g diphenylphosphino-polystyrene (PS-TPP, TPP:2.22mmol/g, lot number 02689 is by Argonaut Co., Ltd. produce), 70ml methyl alcohol and 1.52g1-n-butyl bromide and use nitrogen bubble, be heated to 100 ℃ and stirred 48 hours.Subsequently, be cooled to room temperature.Filter solid matter and wash removing unreacted 1-n-butyl bromide with a large amount of butanols, and under vacuum in 80 ℃ of dryings 24 hours.Output is 6.25g.The scale that increases is bright to have 82% phosphine by quaternized.
(2) produce fixed catalyzer G
With above-mentioned 82% being suspended in the 60ml acetone of obtaining by quaternised diphenylphosphino-polystyrene 4.69g, close the acetone soln of palladium (II) (dichloro two (benzonitrile) closes palladium: 0.5mmol to wherein adding dichloro two (benzonitrile) subsequently, acetone: 20ml), under room temperature, stirred 1 hour.Subsequently to the acetone soln that wherein adds cobalt chloride (II) (cobalt chloride (II): 1.0mmol, acetone: 20ml), and under room temperature, stirred 12 hours.Subsequently, filtering-depositing, with washing with acetone and under vacuum in 80 ℃ of dryings 24 hours.The fixed catalyzer G that obtains expecting.
(3) confirm catalyst performance
Reinforced in the autoclave of a 30ml volume: the fixed catalyzer G that 4.16mmol dihydroxyphenyl propane, 245mg make in (1), 0.625mmol benzoquinones, 1.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by Wako Pure Chemicals Industries, Ltd. produce) and 10ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.After reinforced, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction, remove synthetic zeolite and fixed catalyzer, make the polycarbonate of expection by the methyl alcohol redeposition.Under the vacuum in 100 ℃ of dryings 24 hours.It is light yellow observing polycarbonate powder.The yield of resulting polycarbonate (%), number-average molecular weight (Mn) and weight-average molecular weight (Mw) are shown in table 7.
Embodiment 15
Carry out same step among the embodiment 14 (3), be not add benzoquinones with embodiment 14 (3) differences.Observing polycarbonate is white.The amount of remaining palladium is 25ppm or still less in the polycarbonate.The yield of resulting polycarbonate (%), number-average molecular weight (Mn) and weight-average molecular weight (Mw) are shown in table 7.
Embodiment 16
(1) quaterisation of diphenylphosphino-polystyrene
Carry out same step among the embodiment 14 (1), be that with embodiment 14 (1) differences the consumption of 1-n-butyl bromide becomes 1.29g.Output is 6.00g.The scale that increases is bright to have 66% phosphine by quaternized.
(2) produce fixed catalyzer H
With above-mentioned 66% being suspended in the 60ml acetone of obtaining by quaternised diphenylphosphino-polystyrene 4.77g, close the acetone soln of palladium (II) (dichloro two (benzonitrile) closes palladium: 2.5mmol to wherein adding dichloro two (benzonitrile) subsequently, acetone: 35ml), under room temperature, stirred 1 hour.Subsequently to the acetone soln that wherein adds cobalt chloride (II) (cobalt chloride (II): 1.0mmol, acetone: 20ml), and under room temperature, stirred 12 hours.Subsequently, filtering-depositing, with washing with acetone and under vacuum in 80 ℃ of dryings 24 hours.The fixed catalyzer H that obtains expecting.
(3) confirm catalyst performance
Carry out same step among the embodiment 14 (3), the fixed catalyzer G that the fixed catalyzer H that is to use 258mg to make with embodiment 14 (3) differences replaces 245mg to make in embodiment 14 (1) in above-mentioned (1).It is light yellow observing polycarbonate powder.The yield of resulting polycarbonate (%), number-average molecular weight (Mn) and weight-average molecular weight (Mw) are shown in table 7.
Embodiment 17
Carry out same step among the embodiment 16 (3), be not add benzoquinones with embodiment 16 (3) differences.Observing polycarbonate powder is white.The yield of resulting polycarbonate (%), number-average molecular weight (Mn) and weight-average molecular weight (Mw) are shown in table 7.
Reference example 3
With embodiment 14 (3) with after synthetic zeolite and fixed catalyzer G under vacuum in 130 ℃ of dryings 24 hours.Reinforced in the autoclave of a 30ml volume: 4.16mmol dihydroxyphenyl propane, exsiccant synthetic zeolite and fixed catalyzer (total amount of recovery) and 10ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.Reinforced finishing, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction, remove synthetic zeolite and fixed catalyzer, make polycarbonate by the methyl alcohol redeposition once more.Under the vacuum in 100 ℃ of dryings 24 hours.Observing polycarbonate powder is white.The yield of resulting polycarbonate (%), number-average molecular weight (Mn) and weight-average molecular weight (Mw) are shown in table 7.
Table 7
| Yield (%) | Mn | Mw | |
| Embodiment 14 | 49 | 2300 | 3830 |
| Embodiment 15 | 48 | 2200 | 3640 |
| Embodiment 16 | 48 | 2450 | 3850 |
| Embodiment 17 | 47 | 2400 | 3840 |
| Reference example 3 | 35 | 1980 | 3450 |
Embodiment 18
The first step:
Reinforced in the autoclave of a 100ml volume: the fixed catalyzer G that makes among 11.46mmol dihydroxyphenyl propane, 2.024mmol p-tert-butylphenol, the 735mg embodiment 14 (2), 3.0g synthetic zeolite A-3 powder (particle diameter: less than 75 μ m, by Wako Pure ChemicalsIndustries, Ltd. produce) and 30ml Texacar PC, subsequently in 25 ℃ to wherein the feed in raw material carbon monoxide of 6.0Mpa and the oxygen of 0.3Mpa.After reinforced, this container heated 24 hours in 100 ℃ in sealed structure.After finishing this reaction, remove synthetic zeolite and fixed catalyzer, make the polycarbonate prepolymer of expection by the methyl alcohol redeposition.Under the vacuum in 100 ℃ of dryings 24 hours.
Second step:
300ppm tetraphenyl boric acid cyclohexyl triphenyl phosphonium is added in the polycarbonate prepolymer that makes in the 500mg the first step, and subsequently this mixture being placed internal diameter is the SUS pipe of 1.3cm.With 100ml/ minute speed introducing nitrogen, amount to 8 hours solid-phase polymerization to wherein:,, made the polycarbonate of expection in 210 ℃ of reactions 2 hours and in 230 ℃ of reactions 4 hours in 190 ℃ of reactions 2 hours.The amount of remaining palladium is 25ppm or still less in the polycarbonate.
The number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the polycarbonate that obtains during the polycarbonate prepolymer that obtains in the first step and second goes on foot are shown in table 8.
Comparing embodiment 4
Carry out step same among the embodiment 18, be not use p-tert-butylphenol and use the 12.48mmol dihydroxyphenyl propane with embodiment 18 differences.The molecular weight (Mn) and the weight-average molecular weight (Mw) of the polycarbonate that obtains during the polycarbonate prepolymer that obtains in the first step and second goes on foot are shown in table 8.
Table 8
| The first step prepolymer | The second step polycarbonate | |||
| Mn | Mw | Mn | Mw | |
| Embodiment 18 | 2200 | 3400 | 9500 | 29900 |
| Comparing embodiment 4 | 2300 | 3650 | 3700 | 6500 |
Industrial usability
Make by palladium compound and metallic compound with redox catalysis ability are fixed on the specific polymer for the production of the catalyst of the present invention of Merlon, and do not form palladium bunch, but so that steady production Merlon.
Catalyst of the present invention for the production of Merlon can pass through isolated by filtration at an easy rate after reaction is finished, and the metal that remains in the Merlon after above-mentioned catalyst separation exists hardly.
Therefore, reusable and keep high catalytic efficiency for the production of the catalyst of the present invention of Merlon, so that turnover number that can be high (TON) is produced Merlon.
In addition, in the method for the present invention of producing Merlon, by the production stages in above-mentioned two steps, do not use think harmful chlorine photoreactive gas that environment is had a negative impact and halogenated organic solvent (for example carrene and chloroform) but High-efficient Production has macromolecule and high-quality Merlon.
The carbonylation that not only can be used for dihydroxy compounds for the production of the catalyst of the present invention of Merlon also can be used for the carbonylation of monohydroxy compound, but also can be used for the dipheryl carbonate ester synthesis.
Claims (10)
1. catalyzer that is used to produce polycarbonate, described catalyzer comprise the support of the catalyst of or phosphorus nitrogenous by (a) and (b) palladium compound and (c) have the reaction product that the metallic compound reaction of redox catalysis ability obtains.
2. the catalyzer that is used to produce polycarbonate of claim 1, wherein said support of the catalyst (a) nitrogenous or phosphorus are the vinylpyridine polymer of following formula (I) expression:
Wherein R is alkyl, the alkoxyl group with 1-20 carbon atom with 1-20 carbon atom, has the aryl of 6-20 carbon atom or have the aralkyl of 7-20 carbon atom; P is 0-4; N is 5-10000.
3. the catalyzer that is used to produce polycarbonate of claim 1, the support of the catalyst (a) of wherein said nitrogenous or phosphorus is for being selected from the support of the catalyst of polyvinylpyrrolidone and diphenylphosphino-polystyrene.
4. the catalyzer that is used to produce polycarbonate of claim 1, the support of the catalyst (a) of wherein said nitrogenous or phosphorus is for the haloalkane part is quaternized to be contained in the compound that nitrogen in organic carrier or the inorganic carrier or phosphorus obtain by using.
5. the catalyzer that is used to produce polycarbonate of claim 4, wherein the described organic carrier in (a) is at least a organic carrier that is selected from diphenylphosphino-polystyrene, poly-(4-vinylpridine) or poly-(2-vinyl pyridine).
6. each the catalyzer that is used to produce polycarbonate among the claim 1-3, described catalyzer also comprises (d) salt.
7. each the catalyzer that is used to produce polycarbonate among the claim 1-6, described catalyzer also comprises (e) organic oxidation reductive agent.
8. each the catalyzer that is used to produce polycarbonate among the claim 1-7, described catalyzer also comprises (f) dewatering agent.
9. each the catalyzer that is used to produce polycarbonate among the claim 1-8, wherein said metallic compound (c) with redox catalysis ability is a cobalt compound.
10. method of producing polycarbonate, described method comprises: the first step, aromatic dihydroxy compound and monovalence phenol and carbon monoxide and oxygen reaction are produced polycarbonate prepolymer; Second step, above-mentioned polycarbonate prepolymer is carried out solid state polymerization produce polycarbonate, wherein be used for the above-mentioned the first step as each described catalyzer that is used for producing polycarbonate among the claim 1-9.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP152783/2003 | 2003-05-29 | ||
| JP2003152783A JP4326838B2 (en) | 2003-05-29 | 2003-05-29 | Catalyst for producing polycarbonate and method for producing polycarbonate |
| JP290326/2003 | 2003-08-08 | ||
| JP398743/2003 | 2003-11-28 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100952019A Division CN101311202B (en) | 2003-05-29 | 2004-05-26 | Catalyst for polycarbonate production and method for producing polycarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1795225A true CN1795225A (en) | 2006-06-28 |
| CN100445317C CN100445317C (en) | 2008-12-24 |
Family
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100952019A Expired - Fee Related CN101311202B (en) | 2003-05-29 | 2004-05-26 | Catalyst for polycarbonate production and method for producing polycarbonate |
| CNB2004800145626A Expired - Fee Related CN100445317C (en) | 2003-05-29 | 2004-05-26 | Catalyst for polycarbonate production and method for producing polycarbonate |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100952019A Expired - Fee Related CN101311202B (en) | 2003-05-29 | 2004-05-26 | Catalyst for polycarbonate production and method for producing polycarbonate |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4326838B2 (en) |
| CN (2) | CN101311202B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841485A (en) * | 2015-04-24 | 2015-08-19 | 南京大学扬州化学化工研究院 | Poly(4-vinylpyridine) supported cobalt carbonyl, and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4667053A (en) * | 1986-06-30 | 1987-05-19 | Texaco Inc. | Process for oxidative carbonylation using a catalyst having a novel support |
| US5281359A (en) * | 1992-08-31 | 1994-01-25 | Hoechst Celanese Corporation | Polymeric carbonylation catalyst system |
| TW272949B (en) * | 1994-07-22 | 1996-03-21 | Taishal Kagaku Kogyo Kk | |
| JP4195145B2 (en) * | 1999-04-01 | 2008-12-10 | 出光興産株式会社 | Method for producing polycarbonate |
| JP4081519B2 (en) * | 1999-04-14 | 2008-04-30 | 独立行政法人産業技術総合研究所 | Method for producing polycarbonate |
-
2003
- 2003-05-29 JP JP2003152783A patent/JP4326838B2/en not_active Expired - Lifetime
-
2004
- 2004-05-26 CN CN2008100952019A patent/CN101311202B/en not_active Expired - Fee Related
- 2004-05-26 CN CNB2004800145626A patent/CN100445317C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841485A (en) * | 2015-04-24 | 2015-08-19 | 南京大学扬州化学化工研究院 | Poly(4-vinylpyridine) supported cobalt carbonyl, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100445317C (en) | 2008-12-24 |
| JP2004352878A (en) | 2004-12-16 |
| CN101311202B (en) | 2011-06-22 |
| JP4326838B2 (en) | 2009-09-09 |
| CN101311202A (en) | 2008-11-26 |
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