CN107417719A - 一种用于合成碳酸苯甲酯和碳酸二苯酯的钛螯合物催化剂 - Google Patents
一种用于合成碳酸苯甲酯和碳酸二苯酯的钛螯合物催化剂 Download PDFInfo
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- CN107417719A CN107417719A CN201710317769.XA CN201710317769A CN107417719A CN 107417719 A CN107417719 A CN 107417719A CN 201710317769 A CN201710317769 A CN 201710317769A CN 107417719 A CN107417719 A CN 107417719A
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- Prior art keywords
- ester
- methyl
- acetate
- propyl
- butyl
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 title claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000010936 titanium Substances 0.000 title claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 15
- 239000013522 chelant Substances 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 150000002148 esters Chemical group 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- -1 substituted-phenyl Chemical group 0.000 claims description 94
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 16
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 14
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 14
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 claims description 11
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 9
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 9
- 229940090181 propyl acetate Drugs 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl ester butanoic acid Natural products CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 5
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 5
- 150000004702 methyl esters Chemical class 0.000 claims description 5
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 5
- REIYHFWZISXFKU-UHFFFAOYSA-N Butyl acetoacetate Chemical compound CCCCOC(=O)CC(C)=O REIYHFWZISXFKU-UHFFFAOYSA-N 0.000 claims description 4
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 4
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 4
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 claims description 4
- 229940017219 methyl propionate Drugs 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- GKKZMYDNDDMXSE-UHFFFAOYSA-N Ethyl 3-oxo-3-phenylpropanoate Chemical compound CCOC(=O)CC(=O)C1=CC=CC=C1 GKKZMYDNDDMXSE-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 2
- NKXMBTKMOVMBPH-UHFFFAOYSA-N 1-phenylpentane-1,3-dione Chemical compound CCC(=O)CC(=O)C1=CC=CC=C1 NKXMBTKMOVMBPH-UHFFFAOYSA-N 0.000 claims description 2
- KYZVJFJOZPKDEF-UHFFFAOYSA-N 2,6-dimethylheptane-3,4-dione Chemical compound CC(C)CC(=O)C(=O)C(C)C KYZVJFJOZPKDEF-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 2
- KHZGUWAFFHXZLC-UHFFFAOYSA-N 5-methylhexane-2,4-dione Chemical compound CC(C)C(=O)CC(C)=O KHZGUWAFFHXZLC-UHFFFAOYSA-N 0.000 claims description 2
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- ZIWPCBJTNFTIAJ-UHFFFAOYSA-N butyl 2-isocyanatopropanoate Chemical compound CCCCOC(=O)C(C)N=C=O ZIWPCBJTNFTIAJ-UHFFFAOYSA-N 0.000 claims description 2
- WZUQMOGWPIRDHH-UHFFFAOYSA-N butyl 2-methyl-3-oxobutanoate Chemical compound CCCCOC(=O)C(C)C(C)=O WZUQMOGWPIRDHH-UHFFFAOYSA-N 0.000 claims description 2
- HOELPKLZHACYPW-UHFFFAOYSA-N butyl 3-oxo-3-phenylpropanoate Chemical compound CCCCOC(=O)CC(=O)C1=CC=CC=C1 HOELPKLZHACYPW-UHFFFAOYSA-N 0.000 claims description 2
- GBCGEXQYERFWNO-UHFFFAOYSA-N butyl 3-oxopropanoate Chemical compound CCCCOC(=O)CC=O GBCGEXQYERFWNO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- PFIQRPNWLUAMOF-UHFFFAOYSA-N ethyl 2-isocyanatopropanoate Chemical compound CCOC(=O)C(C)N=C=O PFIQRPNWLUAMOF-UHFFFAOYSA-N 0.000 claims description 2
- KQWWVLVLVYYYDT-UHFFFAOYSA-N ethyl 3-oxohexanoate Chemical compound CCCC(=O)CC(=O)OCC KQWWVLVLVYYYDT-UHFFFAOYSA-N 0.000 claims description 2
- UDRCONFHWYGWFI-UHFFFAOYSA-N ethyl 3-oxopentanoate Chemical compound CCOC(=O)CC(=O)CC UDRCONFHWYGWFI-UHFFFAOYSA-N 0.000 claims description 2
- SYFFHRPDTQNMQB-UHFFFAOYSA-N ethyl 3-oxopropanoate Chemical compound CCOC(=O)CC=O SYFFHRPDTQNMQB-UHFFFAOYSA-N 0.000 claims description 2
- FATAVLOOLIRUNA-UHFFFAOYSA-N formylmethyl Chemical group [CH2]C=O FATAVLOOLIRUNA-UHFFFAOYSA-N 0.000 claims description 2
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940058352 levulinate Drugs 0.000 claims description 2
- WRGLZAJBHUOPFO-UHFFFAOYSA-N methyl 3-oxo-3-phenylpropanoate Chemical compound COC(=O)CC(=O)C1=CC=CC=C1 WRGLZAJBHUOPFO-UHFFFAOYSA-N 0.000 claims description 2
- AGADEVQOWQDDFX-UHFFFAOYSA-N methyl 3-oxopropanoate Chemical class COC(=O)CC=O AGADEVQOWQDDFX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- QHVLCOWDGCCMRF-UHFFFAOYSA-N propyl 2-isocyanatopropanoate Chemical compound CCCOC(=O)C(C)N=C=O QHVLCOWDGCCMRF-UHFFFAOYSA-N 0.000 claims description 2
- UDVTUIQSPYLVPT-UHFFFAOYSA-N propyl 3-oxo-3-phenylpropanoate Chemical compound CCCOC(=O)CC(=O)C1=CC=CC=C1 UDVTUIQSPYLVPT-UHFFFAOYSA-N 0.000 claims description 2
- DWQOUEWATKLTTC-UHFFFAOYSA-N propyl 3-oxopropanoate Chemical compound CCCOC(=O)CC=O DWQOUEWATKLTTC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- QSARSHXEQJHWCO-UHFFFAOYSA-N 2-chloro-3-oxo-3-phenylpropanoic acid Chemical compound OC(=O)C(Cl)C(=O)C1=CC=CC=C1 QSARSHXEQJHWCO-UHFFFAOYSA-N 0.000 claims 1
- QQWACHGKILUHGB-UHFFFAOYSA-N 2-isocyanatopropanoic acid Chemical compound OC(=O)C(C)N=C=O QQWACHGKILUHGB-UHFFFAOYSA-N 0.000 claims 1
- FHSUFDYFOHSYHI-UHFFFAOYSA-N 3-oxopentanoic acid Chemical compound CCC(=O)CC(O)=O FHSUFDYFOHSYHI-UHFFFAOYSA-N 0.000 claims 1
- NEFLHMABGJPULT-UHFFFAOYSA-N C(C)(=O)OCCCC.C(C)(=O)F Chemical compound C(C)(=O)OCCCC.C(C)(=O)F NEFLHMABGJPULT-UHFFFAOYSA-N 0.000 claims 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims 1
- QXWVORHITDDPOT-UHFFFAOYSA-N propyl 2-methyl-3-oxohexanoate Chemical compound CCCOC(=O)C(C)C(=O)CCC QXWVORHITDDPOT-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 8
- 239000004425 Makrolon Substances 0.000 abstract description 4
- 229920000515 polycarbonate Polymers 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NHZZUJIRMHDTKR-UHFFFAOYSA-N carbonic acid;toluene Chemical compound OC(O)=O.CC1=CC=CC=C1 NHZZUJIRMHDTKR-UHFFFAOYSA-N 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229940093858 ethyl acetoacetate Drugs 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- DKHKWOWKZHBBGV-UHFFFAOYSA-N 2-ethyl-3-oxohexanoic acid Chemical compound CCCC(=O)C(CC)C(O)=O DKHKWOWKZHBBGV-UHFFFAOYSA-N 0.000 description 1
- BDCLDNALSPBWPQ-UHFFFAOYSA-N 3-oxohexanoic acid Chemical compound CCCC(=O)CC(O)=O BDCLDNALSPBWPQ-UHFFFAOYSA-N 0.000 description 1
- LIQBKSIZAXKCPA-UHFFFAOYSA-N 4,4,4-trifluoro-3-oxobutanoic acid Chemical compound OC(=O)CC(=O)C(F)(F)F LIQBKSIZAXKCPA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- QGMRQYFBGABWDR-UHFFFAOYSA-M Pentobarbital sodium Chemical group [Na+].CCCC(C)C1(CC)C(=O)NC(=O)[N-]C1=O QGMRQYFBGABWDR-UHFFFAOYSA-M 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FPHBHTKYNMFZOB-UHFFFAOYSA-N [Ti].C(CC)OC(C)=O Chemical compound [Ti].C(CC)OC(C)=O FPHBHTKYNMFZOB-UHFFFAOYSA-N 0.000 description 1
- LTYAEWRGZNEFLG-UHFFFAOYSA-N [Ti].C(CCC)(=O)OCC.C(=O)(C)C(=O)C Chemical compound [Ti].C(CCC)(=O)OCC.C(=O)(C)C(=O)C LTYAEWRGZNEFLG-UHFFFAOYSA-N 0.000 description 1
- KPZUWETZTXCDED-UHFFFAOYSA-N [V].[Cu] Chemical compound [V].[Cu] KPZUWETZTXCDED-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- AOMUALOCHQKUCD-UHFFFAOYSA-N dodecyl 4-chloro-3-[[3-(4-methoxyphenyl)-3-oxopropanoyl]amino]benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=C(Cl)C(NC(=O)CC(=O)C=2C=CC(OC)=CC=2)=C1 AOMUALOCHQKUCD-UHFFFAOYSA-N 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UVLHVOLSVZIDSG-UHFFFAOYSA-N ethyl 2,2-dimethoxy-3-oxo-3-phenylpropanoate Chemical compound C(C)OC(C(C(C1=CC=CC=C1)=O)(OC)OC)=O UVLHVOLSVZIDSG-UHFFFAOYSA-N 0.000 description 1
- WIEGKKSLPGLWRN-UHFFFAOYSA-N ethyl 3-oxobutanoate;titanium Chemical compound [Ti].CCOC(=O)CC(C)=O WIEGKKSLPGLWRN-UHFFFAOYSA-N 0.000 description 1
- NVPXEWPKAICFCQ-UHFFFAOYSA-N ethyl acetate;titanium Chemical compound [Ti].CCOC(C)=O NVPXEWPKAICFCQ-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- ZPZCREMGFMRIRR-UHFFFAOYSA-N molybdenum titanium Chemical compound [Ti].[Mo] ZPZCREMGFMRIRR-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000005677 organic carbonates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 229960005222 phenazone Drugs 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
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种用于酯交换合成碳酸苯甲酯和碳酸二苯酯的钛螯合物催化剂,主要克服现有催化剂活性差、选择性差的问题。该催化剂以有机钛酸酯为原料,与具有
Description
技术领域
本发明属于化学反应工程领域,涉及碳酸苯甲酯(分子结构式为,也称甲基苯基碳酸酯)和碳酸二苯酯(分子结构式为)的生产方法,更具体地说,涉及一种用于苯酚与碳酸二甲酯酯交换合成碳酸苯甲酯和碳酸二苯酯的钛螯合物催化剂制备的方法。
背景技术
碳酸二苯酯(DPC)是一种用途十分广泛的有机碳酸酯,可用来合成许多有机中间体。DPC本身无毒、无污染,是一种重要的绿色环保化工产品,可通过卤化、硝化、水解、氨解等反应来合成许多有机化合物和高分子材料,如单异氰酸酯、二异氰酸酯、聚碳酸酯、聚对羟基苯甲酸酯、聚芳基碳酸酯等。还可以作为聚酰胺和聚酯的增塑剂、高沸点有机溶剂和载热体等。近年来,随着环境友好的以DPC和双酚A为原料合成高品质的聚碳酸酯新工艺的开发,使DPC成为特别引人注目的化合物。
合成DPC传统的方法以光气和苯酚为原料,在碱性介质中进行反应,如CN8610765所公开的方法。但光气有剧毒且腐蚀性大,安全及环境问题突出,而且所生产的DPC中会残留氯离子,影响了由该碳酸二苯酯与双酚A反应所得的聚碳酸酯的质量。因此采用非光气法合成DPC备受关注,在非光气法合成DPC的制备方法中,目前研究的重点是氧化羰基化法和酯交换法。
氧化羰基化法以苯酚、一氧化碳、氧气为原料,在催化剂作用下反应生成碳酸二苯酯。该工艺具有无污染、不需溶剂、无有毒盐生成的优点,但是由于催化剂体系比较复杂,包括主催化剂、助催化剂和助剂等,而且活性较低,同时反应生成的水难于除去。如在EP0350700中,反应5小时苯酚转化率仅为14%,加入一定量的3A分子筛以除水,5小时后转化率升至34%。Ho Young Song等[Journal of Molecular Catalysis A: Chemical 154,2000,243~250]开发的羰基钯催化剂在300K下反应7小时,苯酚的转化率为30%,DPC产率为21.1%。CN1391985公开了用负载型Cu(OAc)2/沸石作为催化剂,碳酸二苯酯的收率为14.2%。CN1391986进一步改进催化剂,用双组分负载型PdCl2-Cu(OAc)2/沸石作为催化剂,碳酸二苯酯的收率也才提高到53.7%。
为此,国内外研究者又开发了苯酚和碳酸二甲酯(DMC)为原料直接合成碳酸二苯酯的酯交换工艺路线。
目前苯酚与碳酸二甲酯在催化剂下的酯交换反应是唯一工业化的非光气合成路线。该方法有两种工艺路径可以选择,一种是一步法,在一个反应器中碳酸二甲酯和苯酚通过酯交换反应直接合成,产物中包括碳酸二苯酯、碳酸苯甲酯(或称甲基苯基碳酸酯)以及苯甲醚等,再通过进一步分离得到碳酸二苯酯;另一种方法是两步法,即碳酸二甲酯和苯酚先酯交换反应得到中间体碳酸苯甲酯,然后把中间体碳酸苯甲酯分馏出来单独进行歧化反应,或再次与苯酚酯交换反应,得到碳酸二苯酯。目前,该工艺已开发出了有机锡化合物、茂钛类络合物、钛酸酯类化合物等新型催化剂,使碳酸二苯酯的收率有所提高。但由于碳酸二甲酯的羰基化反应活性低于光气,能产生副产物苯甲醚,因此能否开发出高转化率、高选择性的催化剂是该路线的关键。现有催化剂体系主要有多相催化剂和均相催化剂两种,多相催化剂具有催化剂容易分离的特点,但存在催化剂活性差、苯酚转化率低,产物选择性差等缺点,如CN1803282采用了钒-铜的复合氧化物作为催化剂,碳酸二苯酯的收率为30%。CN1915504采用了钼-铜的复合氧化物作为催化剂,碳酸二苯酯的收率达到了40.6%;在CN1128664中,采用了PbO-ZnO的复合金属氧化物作为催化剂,碳酸二苯酯的收率达到了45.6%,但酯交换选择性只有72%。在CN101905155A中,采用了钼-钛复合氧化物为催化剂,酯交换总选择性也只达到96%左右。均相催化剂的活性较高,但存在催化剂与产物分离困难、催化剂不稳定等缺点。在高俊杰等人的论文中(催化学报,2001,22(4):405-407),采用了钛酸丁酯和钛酸苯酯作为催化剂,催化苯酚和碳酸二甲酯的反应,但苯酚的转化率小于30%,而且钛酸酯类的稳定性较差,在空气中易吸湿潮解,生成TiO2,在工业应用中收到了一定的限制。
综上所述,研究开发高活性、高选择性和高稳定性的催化剂是提高碳酸苯甲酯或碳酸二苯酯生产效率的关键。
发明内容
本发明的目的在于克服现有技术中均相催化剂稳定性差、多相催化剂中苯酚转化率不高和碳酸二苯酯或碳酸苯甲酯选择性不高的问题,提出了一种稳定性好、苯酚转化率高、碳酸二苯酯或碳酸苯甲酯选择性高的催化剂及制备方法。
实现本发明目的的技术方案:
本发明提供了一种用于酯交换合成碳酸二苯酯或碳酸苯甲酯的催化剂体系,即钛螯合物催化剂体系,该催化剂由有机钛酸酯与具有分子结构的化合物反应而成,R1为烷基、卤代烷基、苯基和取代苯基中的一种;R2为烷基-CH2-、、和中的一种;R3为-CH3、-CH2-CH3、烷氧基中的一种。本发明的催化剂结构如通式(1)~(5)所示:
(1) (2)
(3) (4)
(5)
本发明的催化剂具体制备步骤如下:
(1)将钛酸酯与在0.03MPa~1.0MPa下混合,在40-140℃下搅拌0.5~5小时;
(2)逐步升温至60-190℃,减压下蒸馏,直至没有馏出物;
(3)冷却至室温后,制备得钛螯合物催化剂。
所述的钛酸酯分子式表示为CnH2n+4O4Ti,n=4~16;及(CnHn-1O)4Ti,n=6。具体地,钛酸酯为钛酸四甲酯、钛酸正丁酯、钛酸四异丙酯、钛酸四乙酯、钛酸正丙酯、钛酸叔丁基酯、及钛酸苯酯等中的一种、两种或两种以上。
所述的分子结构中,R1为烷基、卤代烷基、苯基和取代苯基中的一种;R2为烷基-CH2-、、和中的一种;R3为-CH3、-CH2-CH3、烷氧基中的一种。具体地,为乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰乙酸丙酯、乙酰乙酸丁酯、丙酰乙酸甲酯、丙酰乙酸乙酯、丙酰乙酸丙酯、丙酰乙酸丁酯、甲酰乙酸甲酯、甲酰乙酸乙酯、甲酰乙酸丙酯、甲酰乙酸丁酯、丁酰乙酸甲酯、丁酰乙酸乙酯、丁酰乙酸丙酯、丁酰乙酸丁酯、苯甲酰乙酸甲酯、苯甲酰乙酸乙酯、苯甲酰乙酸丙酯、苯甲酰乙酸丁酯、4,4-二氟乙酰乙酸甲酯、4,4-二氟乙酰乙酸乙酯、4,4-二氟乙酰乙酸丙酯、4,4-二氟乙酰乙酸丁酯、4-氯乙酰乙酸甲酯、4-氯乙酰乙酸乙酯、4-氯乙酰乙酸丙酯、4-氯乙酰乙酸丁酯、4,4-二氯乙酰乙酸甲酯、4,4-二氯乙酰乙酸乙酯、4,4-二氯乙酰乙酸丙酯、4,4-二氯乙酰乙酸丁酯、三氟乙酰乙酸甲酯、三氟乙酰乙酸乙酯、三氟乙酰乙酸丙酯、三氟乙酰乙酸丁酯、对甲氧基苯甲酰乙酸甲酯、对甲氧基苯甲酰乙酸乙酯、对甲氧基苯甲酰乙酸丙酯、对甲氧基苯甲酰乙酸丁酯、二甲氧基苯甲酰乙酸甲酯、二甲氧基苯甲酰乙酸乙酯、二甲氧基苯甲酰乙酸丙酯、二甲氧基苯甲酰乙酸丁酯、氯苯甲酰乙酸甲酯、氯苯甲酰乙酸乙酯、氯苯甲酰乙酸丙酯、氯苯甲酰乙酸丁酯、乙酰丙酸甲酯、乙酰丙酸乙酯、乙酰丙酸丙酯、乙酰丙酸丁酯、丙酰丙酸甲酯、丙酰丙酸乙酯、丙酰丙酸丙酯、丙酰丙酸丁酯、甲酰丙酸甲酯、甲酰丙酸乙酯、甲酰丙酸丙酯、甲酰丙酸丁酯、丁酰丙酸甲酯、丁酰丙酸乙酯、丁酰丙酸丙酯、丁酰丙酸丁酯、乙酰丁酸甲酯、乙酰丁酸乙酯、乙酰丁酸丙酯、乙酰丁酸丁酯、丙酰丁酸甲酯、丙酰丁酸乙酯、丙酰丁酸丙酯、丙酰丁酸丁酯、甲酰丁酸甲酯、甲酰丁酸乙酯、甲酰丁酸丙酯、甲酰丁酸丁酯、丁酰丁酸甲酯、丁酰丁酸乙酯、丁酰丁酸丙酯、丁酰丁酸丁酯、乙酰丙酮、乙酰丁酮、苯甲酰丙酮、苯甲酰丁酮、丙酰丙酮、丙酰丁酮、异丁酰丙酮、异丁酰丁酮、异丁酰异丁酮中的一种、两种或两种以上。
钛酸酯与的摩尔比为1:1~1:4。
由上述公开的技术方案可见,按照本发明的方法可以制备出高活性、高稳定性的催化剂,可以高效地制取碳酸二苯酯或碳酸苯甲酯,苯酚转化率可达71%以上,碳酸苯甲酯的选择性大于99%,且催化剂具有较长的使用寿命。
这无疑为碳酸二苯酯的产业带来良好的发展前景和巨大的经济效益。
具体实施方式:
以下结合实施例对本发明作进一步阐述,但这些实施例并不限制本发明得到保护范围。
实施例1
将0.1mol乙酰乙酸乙酯缓慢滴加入0.05mol钛酸异丙酯中,搅拌回流2小时,升温减压,脱除异丙醇得到螯合物二异丙氧基双乙酰乙酸乙酯钛。
实施例2
将0.124mol乙酰乙酸乙酯缓慢滴加入0.062mol钛酸正丁酯中,搅拌回流2小时,升温减压,脱除正丁醇得到螯合物二正丁氧基双乙酰乙酸乙酯钛。
实施例3
将0.26mol乙酰乙酸丙酯缓慢滴加入0.13mol钛酸正丁酯中,搅拌回流2小时,升温减压,脱除正丁醇得到螯合物二正丁氧基双乙酰乙酸丙酯钛。
实施例4
将0.1mol乙酰乙酸乙酯缓慢滴加入0.025mol钛酸异丙酯中,搅拌回流2小时,升温减压,脱除异丙醇得到螯合物四乙酰乙酸乙酯钛。
实施例5
将0.1mol乙酰丙酮缓慢滴加入0.05mol钛酸异丙酯中,搅拌回流2小时,升温减压,脱除异丙醇得到二异丙氧基双乙酰丙酮钛。
实施例6
将0.1mol 乙酰丁酸乙酯缓慢滴加入0.05mol 钛酸四苯酯中,搅拌回流2小时,升温减压,脱除苯酚得到螯合物二苯氧基双乙酰丁酸乙酯钛。
实施例7
将0.136mol苯甲酰乙酸乙酯缓慢滴加入0.068mol钛酸正丁酯中,搅拌回流2小时,升温减压,脱除正丁醇得到鳌合物二苯甲酰乙酸乙酯钛。
实施例8
以实施例1-7制备的样品为催化剂,进行碳酸二甲酯与苯酚的酯交换反应。
在连有氮气、热电偶和精馏塔的高压反应釜中加入苯酚316.9g,碳酸二甲酯33.1g,催化剂0.00269 mol;通入氮气,升温至190℃,开始计时,反应5小时,反应中不断由精馏柱蒸出甲醇和碳酸二甲酯的混合物;混合馏分和含主产物甲基苯基碳酸酯的反应液均用GC7800气相色谱仪分析,均未检测到明显的副产物,其催化性能如表1.
表1 样品1-7的催化剂性能对比
催化剂 | 苯酚转化率(%) | 酯交换选择性(%) |
样品1 | 71.19 | 99.77 |
样品2 | 74.43 | 99.66 |
样品3 | 73.50 | 99.87 |
样品4 | 72.10 | 99.43 |
样品5 | 72.19 | 99.59 |
样品6 | 71.28 | 99.64 |
样品7 | 72.31 | 99.59 |
由上表可知,实例催化剂均对碳酸二甲酯与苯酚的酯交换反应有很好的催化性能。
Claims (6)
1.一种用于酯交换反应制备碳酸苯甲酯或碳酸二苯酯的钛螯合物催化剂的制备方法,其特征在于该催化剂是由钛酸酯与具有分子结构的化合物反应而成,具体制备步骤如下:
(1) 将钛酸酯与在0.03MPa~1.0MPa下混合,在40-140℃下搅拌0.5~5小时;
(2) 逐步升温至60-190℃,减压下蒸馏,直至没有馏出物;
(3) 冷却至室温后,制备得钛螯合物催化剂。
2.根据权利要求1所述的方法,其特征在于,所述的钛酸酯分子式表示为CnH2n+4O4Ti,n=4~16;及(CnHn-1O)4Ti,n=6。
3.根据权利要求1所述的方法,其特征在于,所述的分子结构中,R1为烷基、卤代烷基、苯基和取代苯基中的一种;R2为烷基-CH2-、、和中的一种;R3为-CH3、-CH2-CH3、烷氧基中的一种。
4.根据权利要求1、2所述的方法,钛酸酯为钛酸四甲酯、钛酸正丁酯、钛酸四异丙酯、钛酸四乙酯、钛酸正丙酯、钛酸叔丁基酯、及钛酸苯酯等中的一种、两种或两种以上。
5.根据权利要求1、3所述的方法,为乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰乙酸丙酯、乙酰乙酸丁酯、丙酰乙酸甲酯、丙酰乙酸乙酯、丙酰乙酸丙酯、丙酰乙酸丁酯、甲酰乙酸甲酯、甲酰乙酸乙酯、甲酰乙酸丙酯、甲酰乙酸丁酯、丁酰乙酸甲酯、丁酰乙酸乙酯、丁酰乙酸丙酯、丁酰乙酸丁酯、苯甲酰乙酸甲酯、苯甲酰乙酸乙酯、苯甲酰乙酸丙酯、苯甲酰乙酸丁酯、4,4-二氟乙酰乙酸甲酯、4,4-二氟乙酰乙酸乙酯、4,4-二氟乙酰乙酸丙酯、4,4-二氟乙酰乙酸丁酯、4-氯乙酰乙酸甲酯、4-氯乙酰乙酸乙酯、4-氯乙酰乙酸丙酯、4-氯乙酰乙酸丁酯、4,4-二氯乙酰乙酸甲酯、4,4-二氯乙酰乙酸乙酯、4,4-二氯乙酰乙酸丙酯、4,4-二氯乙酰乙酸丁酯、三氟乙酰乙酸甲酯、三氟乙酰乙酸乙酯、三氟乙酰乙酸丙酯、三氟乙酰乙酸丁酯、对甲氧基苯甲酰乙酸甲酯、对甲氧基苯甲酰乙酸乙酯、对甲氧基苯甲酰乙酸丙酯、对甲氧基苯甲酰乙酸丁酯、二甲氧基苯甲酰乙酸甲酯、二甲氧基苯甲酰乙酸乙酯、二甲氧基苯甲酰乙酸丙酯、二甲氧基苯甲酰乙酸丁酯、氯苯甲酰乙酸甲酯、氯苯甲酰乙酸乙酯、氯苯甲酰乙酸丙酯、氯苯甲酰乙酸丁酯、乙酰丙酸甲酯、乙酰丙酸乙酯、乙酰丙酸丙酯、乙酰丙酸丁酯、丙酰丙酸甲酯、丙酰丙酸乙酯、丙酰丙酸丙酯、丙酰丙酸丁酯、甲酰丙酸甲酯、甲酰丙酸乙酯、甲酰丙酸丙酯、甲酰丙酸丁酯、丁酰丙酸甲酯、丁酰丙酸乙酯、丁酰丙酸丙酯、丁酰丙酸丁酯、乙酰丁酸甲酯、乙酰丁酸乙酯、乙酰丁酸丙酯、乙酰丁酸丁酯、丙酰丁酸甲酯、丙酰丁酸乙酯、丙酰丁酸丙酯、丙酰丁酸丁酯、甲酰丁酸甲酯、甲酰丁酸乙酯、甲酰丁酸丙酯、甲酰丁酸丁酯、丁酰丁酸甲酯、丁酰丁酸乙酯、丁酰丁酸丙酯、丁酰丁酸丁酯、乙酰丙酮、乙酰丁酮、苯甲酰丙酮、苯甲酰丁酮、丙酰丙酮、丙酰丁酮、异丁酰丙酮、异丁酰丁酮、异丁酰异丁酮中的一种、两种或两种以上。
6.根据权利要求1所述的方法,其特征在于钛酸酯与的摩尔比为1:1~1:4。
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