CN108160116B - 催化剂及以此催化剂合成环状碳酸酯的方法 - Google Patents
催化剂及以此催化剂合成环状碳酸酯的方法 Download PDFInfo
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- CN108160116B CN108160116B CN201710131402.9A CN201710131402A CN108160116B CN 108160116 B CN108160116 B CN 108160116B CN 201710131402 A CN201710131402 A CN 201710131402A CN 108160116 B CN108160116 B CN 108160116B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- -1 Hydrogen Chemical class 0.000 claims abstract description 103
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 10
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 239000010936 titanium Chemical group 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052719 titanium Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 150000001334 alicyclic compounds Chemical class 0.000 claims description 2
- 150000007824 aliphatic compounds Chemical group 0.000 claims description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- BWGVEMBFNIKUJU-UHFFFAOYSA-N 2-[2-(3-methoxyphenyl)ethynyl]-6-methylpyridine;hydrochloride Chemical compound Cl.COC1=CC=CC(C#CC=2N=C(C)C=CC=2)=C1 BWGVEMBFNIKUJU-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical compound [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 3
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 2
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical group ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 229910020923 Sn-O Inorganic materials 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 2
- 231100000171 higher toxicity Toxicity 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 238000011160 research 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
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- FMUYQRFTLHAARI-UHFFFAOYSA-N 2,4-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 FMUYQRFTLHAARI-UHFFFAOYSA-N 0.000 description 1
- 125000006183 2,4-dimethyl benzyl group Chemical group [H]C1=C(C([H])=C(C(=C1[H])C([H])([H])*)C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006179 2-methyl benzyl group Chemical group [H]C1=C([H])C(=C(C([H])=C1[H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000006180 3-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1[H])C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000003352 4-tert-butyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
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- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011630 iodine Substances 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
- 239000002649 leather substitute Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 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
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
Description
技术领域
本发明涉及催化剂领域,特别涉及一种催化剂及以此催化剂合成环状碳酸酯的方法。
背景技术
聚氨酯(Polyurethane,PU)主要应用于交通、建筑、纺织、机电、航空、医疗、涂料、合成皮革等领域,产品种类众多,应用领域广,需求不断提升。但由于聚氨酯是由高毒性多异氰酸酯(isocyanate)与多元醇制备而得,多异氰酸酯的原料为光气(phosgene),其毒性更大,在原材料生产过程和涂料加工、涂装过程中,容易对人体带来具大的伤害,且异氰酸酯对环境中湿气敏感,与水反应生成二氧化碳气体,导致涂层气泡和封闭性降低,进而影响其使用性质。
因此,目前已有研究投入非异氰酸酯体系的聚氨酯材料的开发。在众多的研究中,以环状碳酸酯与胺基化合物制备的非异氰酸酯的聚氨酯(Non-isocyanate polyurethane,NIPU)材料最受注目。
非异氰酸酯聚氨酯主要是以环状碳酸酯与胺基化合物反应制备而得,其合成方法因可避免使用毒性较高的异氰酸酯类化合物,所得产品为日益受到重视的绿色材料。
前述非异氰酸酯材料的关键原料为环状碳酸酯化合物,该化合物可在催化剂的催化下由二氧化碳与环氧化合物反应制备。目前用于合成环状碳酸酯化合物的催化剂存在严苛的反应条件与低反应转化率,提高了环状碳酸酯的生产难度及非异氰酸酯聚氨酯材料的商业化量产门槛,因此如何有效提高环氧化合物与二氧化碳反应效率,开发活性更高,可在温和条件下制备多环状碳酸酯的催化剂系统,成了近年来相继投入的重点研究。
发明内容
为了解决上述技术问题,本发明目的在于提供一种催化剂及以此催化剂合成环状碳酸酯的方法,以提高环碳酸酯生产效率,并提高生产过程中的安全性。
具体地说,本发明公开了一种催化剂,其包括如式(I)所示的金属络合物:
其中,R1、R2、R4及R5独立地为C1~C25烷基、C1~C25烷氧基、C3~C8环烷基、C6~C25芳基、C6~C25芳氧基、C7~C25芳烷基、C7~C25芳烷氧基、或卤素;R3为氢、C1~C25烷基、C3~C8环烷基、C6~C25芳基、C6~C25芳氧基、C7~C25芳烷基或C7~C25芳烷氧基;M为锡或钛;X为Cl、Br、I或OAc;以及L为醚或呋喃。
该催化剂,还包括如式(II)所示的四级铵盐:
HN(R6)(R7)(R8)+X- (II)
其中,R6、R7及R8独立地为C1~C25烷基或C6~C25芳基;以及X为Cl、Br、I或OAc。
该催化剂,其中该四级铵盐与该金属络合物的摩尔比介于0.01至5。
该催化剂,其中该式(I)中的M为锡,且X为Cl或Br。
该催化剂,其中该式(I)中的R1、R2、R4及R5独立地为C1~C4烷基、C1~C4烷氧基、C5~C6环烷基、C6~C10芳基、C6~C7芳氧基或C7~C9芳烷基;R3为氢、C1~C4烷基、C5~C6环烷基、C6~C10芳基、C6~C7芳氧基或C7~C9芳烷基。
一种环状碳酸酯的合成方法,其中包括:
在上述任意该催化剂存在的条件下,使环氧化合物与二氧化碳反应形成环状碳酸酯化合物。
该环状碳酸酯的合成方法,其中该环氧化合物以式(III)表示:
其中,d为1至6的整数;以及R9为脂肪族化合物、脂环族化合物、芳香族化合物、烷基取代芳香族化合物、聚醚寡聚物或聚酯寡聚物的可被取代的官能团,或其组合物。
该环状碳酸酯的合成方法,其中该催化剂的浓度为1×10-6mol%至1mol%。
该环状碳酸酯的合成方法,其中该二氧化碳的压力为0.1atm至100atm。
该环状碳酸酯的合成方法,其中反应形成该环状碳酸酯化合物的温度为50℃至200℃。
该环状碳酸酯的合成方法,其中反应形成该环状碳酸酯化合物的时间为2小时至30小时。
该环状碳酸酯的合成方法,其中该环氧化合物为聚丙二醇二缩水甘油醚、间苯二酚二缩水甘油醚、双酚A二缩水甘油醚或1,4-丁二醇二缩水甘油醚。
本发明技术效果在于,本发明的催化剂具有较强的催化活性,且不需严苛的反应条件即可具有更良好的环碳酸酯转化率。
附图说明
图1为本发明的合成例2中的催化剂C-2的结构立体示意图。
具体实施方式
在本发明的一实施例中,催化剂包括如式(I)所示的金属络合物(metalcomplex)。
在式(I)中,M为锡(Sn)或钛(Ti);较佳为锡。
在式(I)中,X为Cl、Br、I或OAc;较佳为Cl或Br。
在式(I)中,L为醚或呋喃。
醚或呋喃的具体例,不限于但可列举有甲醚、乙醚、甲乙醚、二丙醚、甲丙醚、乙丙醚、二丁醚、异二丁醚、异丙醚、呋喃、四氢呋喃、二氢吡喃、四氢吡喃。其中,以乙醚、四氢呋喃较佳。
在式(I)中,R1、R2、R4及R5独立地为C1~C25烷基、C1~C25烷氧基、C3~C8环烷基、C6~C25芳基、C6~C25芳氧基、C7~C25芳烷基、C7~C25芳烷氧基、或卤素;R3为氢、C1~C25烷基、C3~C8环烷基、C6~C25芳基、C6~C25芳氧基、C7~C25芳烷基或C7~C25芳烷氧基。
C1~C25烷基可以是未取代的或任选地被一个或多个取代基所取代的,具体例不限于但可列举有甲基、乙基、正丙基、1-甲基乙基、正丁基、1-甲基丙基、2-甲基丙基、1,1’-二甲基乙基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、2,2’-二甲基丙基、1-乙基丙基、正己基、1,1’-二甲基丙基、1,2-二甲基丙基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1’-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2’-二甲基丁基、2,3-二甲基丁基、3,3’-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1’,2-三甲基丙基、1,2,2’-三甲基丙基、1-乙基-1-甲基丙基、1-乙基-2-甲基丙基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基或正二十烷基。其中,以C1~C4烷基较佳,如甲基、乙基、1-甲基乙基、正丙基、1-甲基丙基、2-甲基丙基、1,1’-二甲基乙基或正丁基。
C1~C25烷氧基可以是未取代的或任选地被一个或多个取代基所取代的,具体例不限于但可列举有甲氧基、乙氧基、异丙氧基、正丙氧基、1-甲基丙氧基、正丁氧基、正戊氧基、2-甲基丙氧基、3-甲基丁氧基、1,1’-二甲基丙氧基、2,2’-二甲基丙氧基、己氧基、1-甲基-1-乙基丙氧基、庚氧基、辛氧基或2-乙基己氧基。其中,以C1~C4烷氧基较佳,如甲氧基、乙氧基、正丙氧基、异丙氧基、1-甲基丙氧基或正丁氧基。
C3~C8环烷基可以是未取代的或任选地被一个或多个取代基所取代的,具体例不限于但可列举环丙基、环丁基、环戊基、环己基、环庚基、1-甲基环丙基、1-乙基环丙基、1-丙基环丙基、1-丁基环丙基、1-戊基环丙基、1-甲基-1-丁基环丙基、1,2-二甲基环丙基、1-甲基-2-乙基环丙基或环辛基。其中,以C5~C6环烷基较佳,如环戊基或环己基。
C6~C25芳基可以是未取代的或任选地被一个或多个取代基所取代的,具体例不限于但可列举有苯基、萘基、2-甲基苯基、3-甲基苯基、4-甲基苯基、2-乙基苯基、1,1’-二甲基苯基、2-叔丁基苯基、3-叔丁基苯基、4-叔丁基苯基、3-乙基苯基、4-乙基苯基、2,4-二叔丁基苯基、3-甲基-6-叔丁基苯基、2,4-二叔丁基苯基、2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基、2,4-二甲氧基苯基、2-乙氧基苯基、3-乙氧基苯基、4-乙氧基苯基、2,4-二乙氧基苯基、3-甲氧基-6-叔丁基苯基或对金刚烷基苯基。其中,以C6~C10芳基较佳,如苯基、2-甲基苯基、3-甲基苯基或4-甲基苯基、2-叔丁基苯基、3-叔丁基苯基、4-叔丁基苯基、2-甲氧基苯基、3-甲氧基苯基、4-甲氧基苯基、2-乙氧基苯基、3-乙氧基苯基或4-乙氧基苯基。
C6~C25芳氧基可以是未取代的或任选地被一个或多个取代基所取代的,具体例不限于但可列举有苯氧基、2-甲基苯氧基、3-甲基苯氧基、4-甲基苯氧基、4-甲氧基苯氧基或4-叔丁基苯氧基。其中,以C6~C7芳氧基较佳,如苯氧基、2-甲基苯氧基、3-甲基苯氧基、4-甲基苯氧基或4-甲氧基苯氧基。
C7~C25芳烷基可以是未取代的或任选地被一个或多个取代基所取代的,具体例不限于但可列举有苄基、α-甲基苄基、α,α-二甲基苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、2,4-二甲基苄基、2,6-二甲基苄基或4-叔丁基苄基。其中,以C7~C9芳烷基较佳,如苄基、α-甲基苄基或α,α-二甲基苄基。
C7~C25芳烷氧基可以是未取代的或任选地被一个或多个取代基所取代的,具体例不限于但可列举有苄氧基、4-甲基苄氧基、4-甲氧基苄氧基或3-苯氧基苄氧基。
卤素例如是氟、氯、溴或碘。
上述式(I)所示的金属络合物可利用双酚化合物与含氧原子配体,在胺基化合物存在下与锡(IV)化合物或钛化合物反应制备,其反应式(1)如下所示:
在式(1)中,R1、R2、R3、R4、R5、M、X以及L如上式(I)所定义。R6、R7及R8则独立地为C1~C25烷基或C6~C25芳基。
因此,在本发明的一实施例中,上述催化剂还可包括如式(II)所示的四级铵盐。
HN(R6)(R7)(R8)+X- (II)
在式(II)中,R6、R7及R8与上述式(1)定义的相同;X则如上式(I)所定义。
另外,由于本发明的催化剂的合成如上式(1)所示,所以四级胺盐与金属络合物的摩尔(mol)比介于0.01至2,例如1至2,但本发明并不限于此。在另一实施例中,可另外添加其它四级铵盐,以进一步提升催化剂的转化率,其中四级胺盐与金属络合物的摩尔比介于0.01至5,例如0.5至3或1至2,若四级胺盐添加过高,可能造成后续产物不易分离。
在一实施例的制造方法中,在上述催化剂存在的条件下,使环氧化合物与二氧化碳反应(CO2)形成环状碳酸酯化合物(cyclic carbonate compound)。其中,环氧化合物可以式(III)表示:
在式(III)中,d为1至6的整数;R9为脂肪族化合物、脂环族化合物、芳香族化合物、烷基取代芳香族化合物、聚醚寡聚物(低聚物)或聚酯寡聚物的可被取代的官能团,或其组合物。
上述环氧化合物的具体例,不限于但可列举有环氧化合物为聚丙二醇二缩水甘油醚(Poly(propylene glycol)diglycidyl ether,PPGDG)、间苯二酚二缩水甘油醚(resorcinol diglycidyl ether,RDCE)、双酚A二缩水甘油醚(diglycidyl ether ofbisphenol-A,DGEBA)或1,4-丁二醇二缩水甘油醚(1,4-butanediol diglycidyl ether,BDGE)。
此外,以环氧化合物的用量为计算基准,上述催化剂的浓度可在1×10-6mol%至1mol%之间,例如1×10-2mol%至0.5mol%之间或4×10-3mol%至16×10-3mol%之间。当浓度在1mol%以上,易产生产品黄料问题,且过多催化剂残留于产品中易影响后续应用性质;若浓度在1×10-6mol%以下,反应效率不佳,反应时间过长问题。在这个实施例中,压力(CO2)例如在0.1atm(标准大气压)至100atm之间,较佳是在0.5atm至20atm之间,若压力过高,则设备规格需求严苛而使环状碳酸酯化合物生产方式不具经济效益。反应的温度例如在50℃至200℃之间,较佳是在100℃至140℃之间。当温度在200℃以上,系统温度易失控并突升;当温度在50℃以下,反应效率差,转化率不佳。至于反应时间可在2至30小时之间,较佳是在2至24小时之间,若时间过长,对于环状碳酸酯化合物的转化率并没有帮助。
由于上述实施例的催化剂是五配位型催化剂(coordinate catalyst),以五配位锡为例,其中O(1)-Sn-O(2)的键角、O(1)-Sn-Cl的键角与O(2)-Sn-Cl的键角的总和接近360度,这就表示与锡相接的3个键所构成的面几乎为平面,催化反应进行时,醚或呋喃配体脱去并于Sn金属中心提供极大立体空间,将有利环氧单体接近并配位活化,加速催化反应进行,相较于四配位型催化剂,其四面体结构无法提供足够立体空间给予环氧单体接近并配位活化,所以上述五配位型催化剂能于温和的反应条件下得到高转化率的环状碳酸酯化合物。
以下列举数个实验来验证本发明的效果,但并不以此限定本发明的范围。
催化剂C-1的合成
取EDBP(2,2’-ethylidene-bis(4,6-di-tert-butylphenol),50mmol,21.9g)置入250mL三角瓶中,以氮气置换,加入乙醚(Et2O,50ml)并充份搅拌溶解,再加入SnCl4(Tin(IV)tetrachloride,50mmol,5.85mL),于冰浴下加入三丁胺(Tributylamine,又称NBu3,100mmol,23.8ml),搅拌10分钟后,移开冰浴并于室温下持续反应1小时,反应后将Et2O抽干,可获得催化剂C-1:(EDBP)SnCl2(Et2O)/HNBu3Cl,产率>99%。
催化剂C-2的合成
在催化剂C-1加入Et2O溶解后缓慢加入己烷(Hexane)搅拌(Hexane/Et2O=100mL/10mL),可析出大量黄色固体,获得催化剂C-2:(EDBP)SnCl2(Et2O),产率81%。
催化剂C-2的1H NMR(CDCl3,ppm):δ7.34,7.18(dd,4H,Ph,J=2.4Hz);4.44(q,1H,CH,J=6.4Hz);3.47(q,4H,OCH2CH3,J=6.8Hz);1.69(d,3H,J=6.8Hz);1.41(s,18H,C(CH3)3);1.33-1.27(m,24H,C(CH3)3+OCH2CH3)。
图1是经X-Ray晶体绕射分析所得到的催化剂C-2的结构立体示意图。在图1中,经分析得到的O(1)-Sn-O(2)的键角为121.8度、O(1)-Sn-Cl(1)的键角为112.05度为与O(2)-Sn-Cl(1)的键角为119.59度,所以催化剂C-2为五配位型的锡催化剂。
催化剂C-3的合成
取EDBP(2,2′-Ethylidene-bis(4,6-di-tert-butylphenol),50mmol,21.9g)置入250mL三角瓶中,以氮气置换,加入乙醚(Et2O,50ml)并充份搅拌溶解,再加入SnBr4(Tin(IV)tetrabromide,50mmol,6.56mL),于冰浴下加入三丁胺(NBu3,100mmol,23.8ml),搅拌10分钟后,移开冰浴并于室温下持续反应1小时,反应后将Et2O抽干,可获得催化剂C-3:(EDBP)SnBr2(Et2O)/HNBu3 Br,产率>99%。
催化剂C-4的合成
在催化剂C-3加入Et2O溶解后缓慢加入己烷(Hexane)搅拌(Hexane/Et2O=50mL/10mL),可析出大量橘黄色固体,获得催化剂C-4:(EDBP)SnBr2(Et2O),产率88%。
催化剂C-4的1H NMR(CDCl3,ppm):δ7.34,7.18(dd,4H,Ph,J=2.4Hz);4.64(q,1H,CH,J=6.4Hz);3.74(q,4H,OCH2CH3,J=6.8Hz);1.67(d,3H,J=6.8Hz);1.41(s,18H,C(CH3)3);1.33-1.27(m,24H,C(CH3)3+OCH2CH3)。
催化剂C-5的合成
取MMPEP(2,2’-Methylenebis(4,6-di(1-methyl-1-phenyl-ethyl)-phenol),20mmol,13.5g,制作方法如Macromolecules2001,34,6196-6201所记载的内容,置入250mL三角瓶中,以氮气置换,加入乙醚(Et2O,50ml)并充份搅拌溶解,再加入SnBr4(Tin(IV)tetrabromide,50mmol,6.56mL),于冰浴下加入三丁胺(NBu3,100mmol,23.8ml),搅拌10分钟后,移开冰浴并于室温下持续反应1小时,反应后将Et2O抽干,可获得催化剂C-5:(MMPEP)SnBr2(Et2O)/HNBu3 Br,产率>99%。
催化剂C-6的合成
在催化剂C-5以甲苯(Toluene)搅拌溶解后,浓缩至饱和,再置入-18℃环境再结晶,可析出大量橘黄色固体,获得催化剂C-6:(MMPEP)SnBr2(Et2O),产率62%。
催化剂C-6的1H NMR(CDCl3,ppm):1HNMR(CDCl3,ppm):δ6.97-7.36(m,24H,Ph);3.48(d,1H,CH2,J=13.6Hz);3.07-3.01(m,5H,CH2+OCH2CH3);1.67,1.63(m,12H,CH3),1.39-1.33(m,18H,CH3+OCH2CH3)。
实验例1
取环氧化合物BDGE(1,4-Butanediol diglycidyl ether,100g)及催化剂C-1(0.457g,0.4×10-2M,0.08mol%)置于反应槽中,待催化剂充份溶解后,通入CO2(1atm)并升温至100℃,持续搅拌反应24小时,以1HNMR光谱分析反应转化率为99%。详细参数与结果列于下表1。
实验例2~6
按照实验例1的方式合成环状碳酸酯化合物,但使用的催化剂分别为催化剂C-2(实验例2)、催化剂C-3(实验例3)、催化剂C-4(实验例4)、催化剂C-5(实验例5)和催化剂C-6(实验例6)。详细参数与1H NMR光谱分析的转化率列于下表1。
实验例7
按照实验例4的方式合成环状碳酸酯化合物,但使用的催化剂C-4的浓度是0.8×10-2M(0.631g,0.16mol%)。详细参数与1H NMR光谱分析的转化率列于下表1。
实验例8~10
按照实验例4的方式合成环状碳酸酯化合物,但使用的催化剂C-4的浓度是1.6×10-2M(1.263g,0.32mol%)。另外,反应温度与时间分别为100℃和8小时(实验例8)、120℃和5小时(实验例9)、140℃和3小时(实验例10)。详细参数与1H NMR光谱分析的转化率列于下表1。
实验例11~13
按照实验例8的方式合成环状碳酸酯化合物,但使用的环氧化合物改为PPGDG(Poly(propylene glycol)diglycidyl ether,100g)(实验例11)、RDCE(Resorcinoldiglycidyl ether,100g)(实验例12)以及DGEBA(Diglycidyl etherof bisphenol-A,100g)(实验例13)。另外,反应温度与时间分别为100℃和8小时(实验例11)、100℃和24小时(实验例12)、100℃和24小时(实验例13)。详细参数与1H NMR光谱分析的转化率列于下表1。
实验例14~15
按照实验例8的方式合成环状碳酸酯化合物,但另添加共催化剂TBAB(Tetrabutylammonium bromide,0.516g,1.6×10-2M,0.32mol%,Sigma-Aldrich),且反应温度与时间分别为100℃和5小时(实验例14)、140℃和2小时(实验例15)。详细参数与1HNMR光谱分析的转化率列于下表1。
比较例1
取环氧化合物BDGE(100g)及催化剂SnBr4(0.175g,1.6×10-2M,0.32mol%,Sigma-Aldrich)置于反应槽中,待催化剂充份溶解后,通入CO2(1atm)并升温至100℃,持续搅拌反应24小时,以1H NMR光谱分析反应转化率列于下表1。
比较例2
按照比较例1的方式合成环状碳酸酯化合物,但再添加另一催化剂TBAB(0.516g,1.6×10-2M,0.32mol%)。详细参数与1H NMR光谱分析的转化率列于下表1。
比较例3
按照比较例2的方式合成环状碳酸酯化合物,但不使用催化剂SnBr4。详细参数与1HNMR光谱分析的转化率列于下表1。
表1
由表1可知,本发明的催化剂不需严苛的反应条件即可具有更良好的环碳酸酯转化率。
另外,比较使用相同浓度但不同催化剂的实验例8、比较例1与比较例3的催化活性(turnover frequency,TOF),结果如下表2所示。其中,TOF=[(环氧官能基摩尔数/催化剂摩尔数)×反应转化率]/反应时间)。
表2
由表2可知,本发明的催化剂在催化活性方面较目前的商用催化剂要高5倍以上。
综上所述,本发明开发五配位型催化剂,提高温室气体二氧化碳环化加成反应活性,降低反应活化能,提高环碳酸酯生产效率。
虽然本发明以上述实施例公开,但具体实施例仅用以解释本发明,并不用于限定本发明,任何本技术领域技术人员,在不脱离本发明的构思和范围内,可作一些的变更和完善,故本发明的权利保护范围以权利要求书为准。
Claims (12)
2.如权利要求1所述的催化剂,其特征在于,还包括如式(II)所示的四级铵盐:
HN(R6)(R7)(R8)+X- (II)
其中,R6、R7及R8独立地为C1~C25烷基或C6~C25芳基;以及X为Cl、Br、I或OAc。
3.如权利要求2所述的催化剂,其特征在于,该四级铵盐与该金属络合物的摩尔比介于0.01至5。
4.如权利要求1所述的催化剂,其特征在于,该式(I)中的M为锡,且X为Cl或Br。
5.如权利要求1所述的催化剂,其特征在于,该式(I)中的R1、R2、R4及R5独立地为C1~C4烷基、C1~C4烷氧基、C5~C6环烷基、C6~C10芳基、C6~C7芳氧基或C7~C9芳烷基;R3为氢、C1~C4烷基、C5~C6环烷基、C6~C10芳基、C6~C7芳氧基或C7~C9芳烷基。
6.一种环状碳酸酯的合成方法,其特征在于,包括:
在权利要求1~5中任一项所述的催化剂存在的条件下,使环氧化合物与二氧化碳反应形成环状碳酸酯化合物。
8.如权利要求6所述的环状碳酸酯的合成方法,其特征在于,该催化剂的浓度为1×10- 6mol%至1mol%。
9.如权利要求6所述的环状碳酸酯的合成方法,其特征在于,该二氧化碳的压力为0.1atm至100atm。
10.如权利要求6所述的环状碳酸酯的合成方法,其特征在于,反应形成该环状碳酸酯化合物的温度为50℃至200℃。
11.如权利要求6所述的环状碳酸酯的合成方法,其特征在于,反应形成该环状碳酸酯化合物的时间为2小时至30小时。
12.如权利要求6所述的环状碳酸酯的合成方法,其特征在于,该环氧化合物为聚丙二醇二缩水甘油醚、间苯二酚二缩水甘油醚、双酚A二缩水甘油醚或1,4-丁二醇二缩水甘油醚。
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