CN1138811C - 用于制备聚醚多元醇的双金属氰化物催化剂 - Google Patents
用于制备聚醚多元醇的双金属氰化物催化剂 Download PDFInfo
- Publication number
- CN1138811C CN1138811C CNB008035660A CN00803566A CN1138811C CN 1138811 C CN1138811 C CN 1138811C CN B008035660 A CNB008035660 A CN B008035660A CN 00803566 A CN00803566 A CN 00803566A CN 1138811 C CN1138811 C CN 1138811C
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- Prior art keywords
- acid
- salt
- dmc
- catalyst
- dmc catalyst
- Prior art date
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- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229920000570 polyether Polymers 0.000 title claims description 31
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 29
- 229920005862 polyol Polymers 0.000 title 1
- 150000003077 polyols Chemical class 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 150000001408 amides Chemical class 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 239000007858 starting material Substances 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 55
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 claims description 29
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 claims description 28
- 239000004380 Cholic acid Substances 0.000 claims description 28
- 229960002471 cholic acid Drugs 0.000 claims description 28
- 235000019416 cholic acid Nutrition 0.000 claims description 28
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 19
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 235000013495 cobalt Nutrition 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 206010004542 Bezoar Diseases 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- RUDATBOHQWOJDD-BSWAIDMHSA-N chenodeoxycholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-BSWAIDMHSA-N 0.000 claims description 8
- 229960001091 chenodeoxycholic acid Drugs 0.000 claims description 8
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- DGABKXLVXPYZII-UHFFFAOYSA-N Hyodeoxycholic acid Natural products C1C(O)C2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)CC2 DGABKXLVXPYZII-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- DKPMWHFRUGMUKF-KWXDGCAGSA-N hyocholic acid Chemical compound C([C@H]1[C@@H](O)[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 DKPMWHFRUGMUKF-KWXDGCAGSA-N 0.000 claims description 6
- DGABKXLVXPYZII-SIBKNCMHSA-N hyodeoxycholic acid Chemical compound C([C@H]1[C@@H](O)C2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 DGABKXLVXPYZII-SIBKNCMHSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- SMEROWZSTRWXGI-UHFFFAOYSA-N Lithocholsaeure Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)CC2 SMEROWZSTRWXGI-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- SMEROWZSTRWXGI-HVATVPOCSA-N lithocholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 SMEROWZSTRWXGI-HVATVPOCSA-N 0.000 claims description 5
- 241000272814 Anser sp. Species 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- WBWWGRHZICKQGZ-UHFFFAOYSA-N Taurocholic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(=O)NCCS(O)(=O)=O)C)C1(C)C(O)C2 WBWWGRHZICKQGZ-UHFFFAOYSA-N 0.000 claims description 3
- WBWWGRHZICKQGZ-HZAMXZRMSA-N taurocholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCCS(O)(=O)=O)C)[C@@]2(C)[C@@H](O)C1 WBWWGRHZICKQGZ-HZAMXZRMSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229940099352 cholate Drugs 0.000 claims 1
- RFDAIACWWDREDC-YUHACDEOSA-N n-cholylglycine Chemical compound C([C@@H]1C[C@H]2O)[C@@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@@H]([C@@H](CCC(=O)NCC(O)=O)C)[C@@]2(C)[C@H](O)C1 RFDAIACWWDREDC-YUHACDEOSA-N 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003613 bile acid Substances 0.000 abstract 1
- -1 halogen ion Chemical class 0.000 description 20
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 230000006698 induction Effects 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000011592 zinc chloride Substances 0.000 description 5
- 235000005074 zinc chloride Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LGRDAQPMSDIUQJ-UHFFFAOYSA-N tripotassium;cobalt(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] LGRDAQPMSDIUQJ-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 3
- DUYSCILLIVEITB-ADQIWYCWSA-M sodium;(4r)-4-[(3r,5r,6s,8s,9s,10r,13r,14s,17r)-3,6-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]pentanoate Chemical compound [Na+].C([C@H]1[C@@H](O)C2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)CC1 DUYSCILLIVEITB-ADQIWYCWSA-M 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- WXBFPUDKHADDKC-UHFFFAOYSA-N [Co+3].N#CC#N Chemical compound [Co+3].N#CC#N WXBFPUDKHADDKC-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- RFDAIACWWDREDC-FRVQLJSFSA-N glycocholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 RFDAIACWWDREDC-FRVQLJSFSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- FHHPUSMSKHSNKW-SMOYURAASA-M sodium deoxycholate Chemical compound [Na+].C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 FHHPUSMSKHSNKW-SMOYURAASA-M 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- DXOCDBGWDZAYRQ-UHFFFAOYSA-N (3alpha,5beta)-3-Hydroxy-7-oxocholan-24 -oic acid Natural products C1CC(O)CC2CC(=O)C3C4CCC(C(CCC(O)=O)C)C4(C)CCC3C21C DXOCDBGWDZAYRQ-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- DXOCDBGWDZAYRQ-AURDAFMXSA-N 7-oxolithocholic acid Chemical compound C1C[C@@H](O)C[C@H]2CC(=O)[C@H]3[C@@H]4CC[C@H]([C@@H](CCC(O)=O)C)[C@@]4(C)CC[C@@H]3[C@]21C DXOCDBGWDZAYRQ-AURDAFMXSA-N 0.000 description 1
- 241000208199 Buxus sempervirens Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DLYVTEULDNMQAR-SRNOMOOLSA-N Cholic Acid Methyl Ester Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@H](C)CCC(=O)OC)[C@@]2(C)[C@@H](O)C1 DLYVTEULDNMQAR-SRNOMOOLSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 108010007979 Glycocholic Acid Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- RFDAIACWWDREDC-UHFFFAOYSA-N Na salt-Glycocholic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(=O)NCC(O)=O)C)C1(C)C(O)C2 RFDAIACWWDREDC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
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Abstract
本发明涉及新型的双金属氰化物(DMC)催化剂,用于将烯化氧聚加成到包含活性氢原子的起始化合物上,以制备聚醚多元醇,其中催化剂包含a)双金属氰化合物,b)胆酸或其盐、酯或酰胺,和c)有机络合配位体。本发明的催化剂表明,在制备聚醚多元醇的过程中,其活性大大地增加。
Description
本发明提供新型的双金属氰化物(DMC)催化剂,用于将烯化氧聚加成到包含活性氢原子的起始化合物上,以制备聚醚多元醇。
将烯化氧聚加成到包含活性氢原子的起始化合物上使用的双金属氰化物(DMC)催化剂是熟知的(例如从美国专利-A 3 404 109、3829 505、3 941 849和5 158 922中得知)。特别是,采用这些DMC催化剂制备聚醚多元醇,与采用碱金属催化剂如碱金属氢氧化物并使用常规方法制备聚醚多元醇相比,能引起具有末端双键即所谓一元醇的单官能聚醚部分还原。以这种方法制备的聚醚多元醇,经过加工可以生产高质量的聚氨酯(例如弹性体、泡沫体和涂料)。DMC催化剂通常是使金属盐水溶液与金属氰化物盐水溶液在有机络合配位体如醚存在下发生反应制备的。在典型的催化剂制备过程中,例如,将氯化锌(过量)水溶液与六氰钴酸钾混合,然后将二甲氧基乙烷(甘醇二甲醚)加入生成的悬浮液中。在过滤和用甘醇二甲醚水溶液洗涤催化剂以后,获得的活性催化剂(见欧洲专利-A 700 949)通式如下:
Zn3[Co(CN)6]2·xZnCl2·yH2O·z甘醇二甲醚
日本专利-A 4145123、美国专利-A 5 470 813、欧洲专利-A 700949、欧洲专利-743 093、欧洲专利-A 761 708、和WO97/40086公开了DMC催化剂,它通过采用叔丁醇作为有机络合配位体(单独或与聚醚组合(欧洲专利-A 700 949、761 708、WO97/40086))在制备聚醚多元醇的过程中进一步还原具有末端双键的单官能聚醚部分。此外,在烯化氧与相应的起始化合物进行聚加成反应的过程中,诱导时间缩短,而且采用这些DMC催化剂,提高了催化剂活性。
本发明的目的是提供进一步改进的DMC催化剂,用于将烯化氧聚加成到相应的起始化合物上,与目前已知类型的催化剂相比,这种催化剂提高了催化剂的活性。由于这种催化剂缩短了烷氧化的时间,所以提高了制备聚醚多元醇方法的经济性。确实,由于活性的增加,催化剂的使用浓度是如此之低(≤25ppm),以致不再需要分离催化剂和产品的费钱步骤,产品可直接用于聚氨酯的生产。
令人意外的是,现已发现,在生产聚醚多元醇的过程中,DMC催化剂含有用作络合配位体的胆酸或其盐、酯或酰胺能大大地提高催化剂的活性。
因此本发明提供一种双金属氰化物(DMC)催化剂,其中包含
a)一种或多种,优选一种双金属氰化合物,
b)一种或多种,优选一种胆酸或其盐、酯或酰胺,和
c)一种或多种,优选一种与b)不同的有机络合配位体。
在根据本发明的催化剂中,还包含d)水,优选1-10%(重量),和/或e)来自制备双金属氰化合物a)的,具有通式(I)M(X)n的一种或多种水溶性金属盐,优选5-25%(重量)。在通式(I)中,M选自金属Zn(II)、Fe(II)、Ni(II)、Mn(II)、Co(II)、Sn(II)、Pb(II)、Fe(III)、Mo(IV)、Mo(VI)、Al(III)、V(V)、V(IV)、Sr(II)、W(IV)、W(VI)、Cu(II)和Cr(III)。Zn(II)、Fe(II)、Co(II)和Ni(II)是特别优选的。阴离子X可以相同或不同,优选相同,X优选自卤离子、氢氧根、硫酸根、碳酸根、氰酸根、硫氰酸根、异氰酸根、异硫氰酸根、羧酸根、草酸根或硝酸根。n值为1,2或3。
在根据本发明的催化剂中包含的双金属氰化合物a)是水溶性金属盐和水溶性金属氰化物盐反应的产物。
为了制备双金属氰化合物a),适宜的水溶性金属盐优选具有通式(I)M(X)n,其中M选自金属Zn(II)、Fe(II)、Ni(II)、Mn(II)、Co(II)、Sn(II)、Pb(II)、Fe(III)、Mo(IV)、Mo(VI)、Al(III)、V(V)、V(IV)、Sr(II)、W(IV)、W(VI)、Cu(II)和Cr(III)。Zn(II)、Fe(II)、Co(II)和Ni(II)是特别优选的。阴离子X可以相同或不同,优选相同,X优选自卤离子、氢氧根、硫酸根、碳酸根、氰酸根、硫氰酸根、异氰酸根、异硫氰酸根、羧酸根、草酸根或硝酸根。n值为1,2或3。
适宜的水溶性金属盐的实例是氯化锌、溴化锌、乙酸锌、乙酰基丙酮锌、苯甲酸锌、硝酸锌、硫酸铁(II)、溴化铁(II)、氯化铁(II)、氯化钴(II)、硫氰酸钴(II)、氯化镍(II)、和硝酸镍(II)。也可以使用不同的水溶性金属盐的混合物。
为了制备双金属氰化合物a),适宜的水溶性金属氰化物盐优选具有通式(II)(Y)aM′(CN)b(A)c,其中M′选自金属Fe(II)、Fe(III)、Co(II)、Co(III)、Cr(II)、Cr(III)、Mn(II)、Mn(III)、Ir(III)、Ni(II)、Rh(III)、Ru(II)、V(IV)和V(V)。M′特别优选选自金属Co(II)、Co(III)、Fe(II)、Fe(III)、Cr(III)、Ir(III)和Ni(II)。水溶性的金属氰化物盐可以包含这些金属中的一种或多种。阳离子Y可以相同或不同,优选相同,Y选自碱金属离子和碱土金属离子。阴离子A可以相同或不同,优选相同,A选自卤离子、氢氧根、硫酸根、碳酸根、氰酸根、硫氰酸根、异氰酸根、异硫氰酸根、羧酸根、草酸根或硝酸根。下标a、b和c是整数,其中a、b和c值是如此选择的,使金属氰化物盐是电中性的:a优选1、2、3或4;b优选4、5或6;c优选0值。适宜的水溶性金属氰化物盐的实例是六氰钴(III)酸钾、六氰亚铁(II)酸钾、六氰铁(III)酸钾、六氰钴(III)酸钙、和六氰钴(III)酸锂。
在根据本发明的催化剂中包含的优选的双金属氰化合物a)是具有下列通式(III)的化合物:
Mx[M′x′(CN)y]z其中M的定义与通式(I)相同,M′的定义与通式(II)相同,x、x′、y和z是整数,它们的选择以使双金属氰化合物是电中性的。
优选x=3、x′=1、y=6和z=2,
M=Zn(II)、Fe(II)、Co(II)或Ni(II)和
M′=Co(III)、Fe(III)、Cr(III)或Ir(III)。
适宜的双金属氰化合物a)的实例是六氰钴(III)酸锌、六氰铱(III)酸锌、六氰铁(III)酸锌、和六氰钴(III)酸亚钴(II)。例如在美国专利-A 5 158 922中给出另一些适宜的双金属氰化合物的实例。六氰钴(III)酸锌是特别优选采用的。
在根据本发明的DMC催化剂中包含的有机络合配位体c)基本上是已知的,在现有技术中已有详细地叙述(例如见美国专利-A 5 158922、3 404 109、3 829 505、3 941 849、欧洲专利-A 700 949、761 708、日本专利-A 4145123、美国专利-A 5 470 813、欧洲专利-A 743 093、和WO97/40086)。优选的有机络合配位体是水溶性的、具有氧、氮、磷或硫之类杂原子的有机化合物,它能与双金属氰化合物a)生成络合物。适宜的有机络合配位体是例如醇、醛、酮、醚、酯、酰胺、尿、腈、硫化物、和它们的混合物。优选的有机络合配位体,是水溶性的脂肪醇例如乙醇、异丙醇、正丁醇、异丁醇、仲丁醇、和叔丁醇。叔丁醇是特别优选的。
有机络合配位体可在催化剂制备过程中加入,也可在双金属氰化合物a)沉淀之后马上加入。有机络合配位体通常以过量的形式使用。
根据本发明的DMC催化剂包含双金属氰化合物a)和有机络合配位体c),前者的量为成品催化剂量的25-90%(重量),优选30-85%(重量),后者的量为成品催化剂量的0.5-30%(重量),优选1-25%(重量)。根据本发明,DMC催化剂通常包含成品催化剂量的1-80%(重量)的胆酸或其盐、酯或酰胺,优选1-40%(重量)。
适合制备根据本发明的催化剂的胆酸,是C24-甾族羧酸,C24-甾族羧酸是胆甾醇的降解产物,一般是通过在C3、C6、C7和C12上加入α位-羟基,从5β-胆烷-24-酸衍生的。
优选的胆酸具有下列通式:其中,R1、R2、R3和R4分别为H或OH,R5为OH、NH-CH2-COOH、NH-CH2-CH2-SO3H、NH-(CH2)3-N+(CH3)2-CH2-CHOH-CH2-SO3 -或NH-(CH2)3-N+(CH3)2-(CH2)3-SO3 -。
呈酸和盐形式的游离酸和其盐,优选碱金属或碱土金属盐是合适的,还有其酯,优选具有2-30个碳原子烷基的酯类,和其酰胺,优选具有烷基或磺烷基、磺烷基氨基烷基、磺基羟烷基氨基烷基、和羧烷基的酰胺。
适宜的胆酸或它们的盐、酯或酰胺的实例,是胆酸(3α,7α,12α-三羟基-5β-胆烷-24-酸;R1=R3=R4=R5=OH,R2=H),胆酸钠盐(胆酸钠)、胆酸锂、胆酸钾、甘氨胆酸(3α,7α,12α-三羟基-5β-胆烷-24-酸-N-[羧甲基]-酰胺;R1=R3=R4=OH、R2=H、R5=NH-CH2-COOH)、甘氨胆酸钠、牛黄胆酸(3α,7α,12α-三羟基-5β-胆烷-24-酸-N-[2-磺乙基]-酰胺;R1=R3=R4=OH、R2=H、R5=NH-CH2-CH2-SO3H)、牛黄胆酸钠、脱氧胆酸(3α,12α-二羟基-5β-胆烷-24-酸;R1=R4=R5=OH、R2=R3=H)、脱氧胆酸钠、脱氧胆酸钾、脱氧胆酸锂、脱氧甘胆酸(3α,12α-二羟基-5β-胆烷-24-酸-N[羧甲基]-酰胺;R1=R4=OH、R2=R3=H、R5=NH-CH2-COOH)、甘氨脱氧胆酸钠、牛黄脱氧胆酸(3α,12α-二羟基-5β-胆烷-24-酸-N-[2-磺乙基]-酰胺;R1=R4=OH、R2=R3=H、R5=NH-CH2-CH2-SO3H)、牛黄脱氧胆酸钠、鹅脱氧胆酸(3α,7α-二羟基-5β-胆烷-24-酸;R1=R3=R5=OH、R2=R4=H)、鹅脱氧胆酸钠、鹅脱氧甘胆酸(3α,7α-二羟基-5β-胆烷-24-酸-N-[羧甲基]-酰胺;R1=R3=OH、R2=R4=H、R5=NH-CH2-COOH)、鹅脱氧甘胆酸钠、牛黄鹅脱氧胆酸(3α,7α-二羟基-5β-胆烷-24-酸-N-[2-磺乙基]-酰胺;R1=R3=OH、R2=R4=H、R5=NH-CH2-CH2-SO3H)、牛黄鹅脱氧胆酸钠、石胆酸(3α-羟基-5β-胆烷-24-酸;R1=R5=OH、R2=R3=R4=H)、石胆酸钠、石胆酸钾、猪胆酸(3α,6α,7α-三羟基-5β-胆烷-24-酸;R1=R2=R3=R5=OH、R4=H)、猪胆酸钠、猪胆酸锂、猪胆酸钾、猪脱氧胆酸(3α,6α,-二羟基-5β-胆烷-24-酸;R1=R2=R5=OH、R3=R4=H)、猪脱氧胆酸钠、猪脱氧胆酸锂、猪脱氧胆酸钾、胆酸甲酯、胆酸乙酯、脱氧胆酸乙酯、和猪胆酸甲酯。
胆酸或它们的盐、酯或酰胺可以单独使用,也可以以混合物的形式使用。
胆酸、甘胆酸、牛黄胆酸、脱氧胆酸、脱氧甘胆酸、牛黄脱氧胆酸、鹅脱氧胆酸、鹅脱氧甘胆酸、牛黄鹅脱氧胆酸、石胆酸、猪胆酸、猪脱氧胆酸的钠盐、锂盐或钾盐、或甲基酯或乙基酯、或它们的混合物,是特别优选使用的。
乌索脱氧胆酸(3α,7α-二羟基-5β-胆烷-24-酸)、7-氧代-石胆酸(3α-羟基-7-氧代-5β-胆烷-24-酸)、石胆酸-3-硫酸盐(3α-羟基-5β-胆烷-24-酸-3-硫酸盐)、降胆酸和双降胆酸,或它们的盐、酯或酰胺之类的胆酸,也是适宜的。
胆酸和它们的盐、酯或酰胺一般是众所周知的,例如在化学工艺实验室通讯(Nachr.Chem.Tech.Lab.)43(1995)1047和“伦普斯天然材料大全”(Rmpp-Lexikon Naturstoffe),斯图加特,纽约,1997,p.248等中有详细的叙述。
也可以采用前述所有胆酸或它们的盐、酯或酰胺的任一混合物。
催化剂组成的分析通常是采用元素分析、热重分析,和在胆酸或其盐、酯或酰胺的萃取分离后采用重量分析进行的。
根据本发明的催化剂可以是结晶的、部分结晶的或无定形的。结晶度的分析,通常是采用粉末X-射线衍射方法进行的。
根据本发明的催化剂优选包含:
a)六氰钴(III)酸锌
b)胆酸或其盐、酯或酰胺,和
c)叔丁醇。
根据本发明的DMC催化剂通常是使α)金属盐,特别是带有(II)式的金属氰化物盐的(I)式的金属盐、β)与胆酸或其盐、酯或酰胺不同的有机配位体c)、和γ)胆酸或其盐、酯或酰胺反应,在水溶液中制备的。
优选首先使金属盐(例如采用超过化学计算量的氯化锌(为金属氰化物盐的至少50%(摩尔))和金属氰化物盐(例如六氰钴酸钾)的水溶液,在有机络合配位体c)(例如叔丁醇)存在下进行反应,其中生成包含双金属氰化合物a)(例如六氰钴酸锌)、水d)、过量金属盐e)、和有机络合配位体c)的悬浮液。
有机络合配位体c),可以以金属盐和/或金属氰化物盐水溶液的形式存在,或可将其直接加入在双金属氰化合物a)沉淀后获得的悬浮液中。已经证明,在强烈搅拌下混合水溶液和有机络合配位体c)是有利的。然后,一般采用胆酸或其盐、酯、或酰胺b)处理生成的悬浮液。在具有水和有机络合配位体c)的混合物中,优选采用胆酸或其盐、酯或酰胺b)。
然后采用已知的技术,例如离心或过滤,从悬浮液中分离催化剂。在一个优选实施方案中,被分离的催化剂采用有机络合配位体c)的水溶液洗涤(例如重新制备悬浮液,在过滤或离心后重新分离)。采用这种方法,例如可从根据本发明的催化剂中除去水溶性的副产物,例如氯化钾。
有机络合配位体c)在洗涤水溶液中的量,优选为溶液总量的40-80%(重量)。此外,在洗涤水溶液中加入一些胆酸或其盐、酯或酰胺是有利的,优选加入溶液总量的0.5-5%(重量)。
此外,洗涤催化剂一次以上是有利的。在这种情况下,例如可以重复第一次洗涤过程。然而,进一步的洗涤过程优选采用非水溶液,例如有机络合配位体与胆酸或其盐、酯或酰胺的混合物。
然后任选在制成粉末以后,在温度一般为20-100℃和压力一般为0.1mbar至标准压力(1013mbar)下,干燥洗涤后的催化剂。
本发明还涉及根据本发明的DMC催化剂在烯化氧聚加成到包含活性氢原子的起始化合物上以制备聚醚多元醇过程中的应用。
所采用的烯化氧,优选环氧乙烷、环氧丙烷、环氧丁烷和它们的混合物。通过烷氧基化作用建立聚醚链,例如可仅采用一种单体环氧化物来进行,也可无规地或嵌段地用二种或三种不同的单体环氧化物来完成。更详细的资料可从“厄尔曼工业化学百科全书”(UllmansEncyclopdie der industriellen Chemie),第A21卷,1992,670页等找到。
包含活性氢原子的起始化合物,优选分子量(数均)为18-2000并具有1-8个羟基的化合物。作为实例,可列举下列化合物:乙二醇、二甘醇、三甘醇、1,2-丙二醇、1,4-丁二醇、己二醇、双酚A、三羟甲基丙烷、甘油、季戊四醇、山梨糖醇、蔗糖、降解淀粉或水。
采用这种包含活性氢原子的起始化合物是有利的,例如以常规的碱金属催化方法由上述的低分子量起始物来制备,它是分子量(数均)为200-2000的低聚的烷氧基化产物。
采用根据本发明的催化剂催化的烯化氧在包含活性氢原子的起始化合物上的聚加成,一般是在温度20-200℃下进行的,优选40-180℃,特别优选50-150℃。反应可在总压为0.001-20bar下进行。聚加成可本体地,或在惰性有机溶剂如甲苯和/或THF中进行。溶剂量通常为所制备的聚醚多元醇量的10-30%(重量)。
选择催化剂的浓度,使在给定的反应条件下,能有效地控制聚加成反应。催化剂浓度一般为待制备的聚醚多元醇量的0.0005%(重量)-1%(重量),优选0.001%(重量)-0.1%(重量),特别优选0.001-0.0025%(重量)。
根据本发明的方法制备的聚醚多元醇的数均分子量为500-100000g/mol,优选1000-50000g/mol,特别优选2000-20000g/mol。
聚加成反应可以连续地进行,也可以间歇地进行,例如以间歇或半间歇的方法进行。
根据本发明的催化剂,由于其明显高的活性,所以可以采用非常低的浓度(相对待制备的多元醇量,≤25ppm)。如果采用在根据本发明的催化剂存在下制备的聚醚多元醇制备聚氨酯(塑料手册(Kunststoffhandbuch),第七卷,聚氨酯,第三版,1993,25-32页和57-67页),不需要从聚醚多元醇中除去催化剂,这对所制备的聚氨酯产品的质量没有不利的影响。
.
实施例 催化剂的制备 实施例A 采用胆酸钠盐制备DMC催化剂(催化剂A)
将6.2g(45.75mmol)氯化锌的10ml蒸馏水溶液,在强烈搅拌(24000rpm)下加入到2g(6mmol)六氰钴酸钾的35ml蒸馏水溶液中。然后立即将25g叔丁醇和25g蒸馏水的混合物加入所生成的悬浮液中,接着强烈搅拌(24000rpm)10分钟。然后加入0.5g胆酸钠盐(Fluka化学股份公司,CH-9471 Buchs)、0.5g叔丁醇和50g蒸馏水的混合物,继续搅拌(1000rpm)3分钟。采用过滤分离固体,然后将固体与35g叔丁醇、15g蒸馏水和0.5g胆酸钠盐的混合物搅拌(10000rpm)10分钟,再次过滤。然后再将产品与50g叔丁醇和0.25g胆酸钠盐的混合物搅拌(10000rpm)10分钟。过滤后,在50℃和大气压下将催化剂干燥至恒重。
干燥的粉末状催化剂产量:2.1g
元素分析、热重分析和萃取:
钴=12.6%(重量),锌=27.3%(重量),叔丁醇=10.9%(重量),
胆酸钠盐=4.3%(重量)。实施例B 采用猪脱氧胆酸钠盐制备DMC催化剂(催化剂B)
采用与实施例A所述相同的方法,但采用猪脱氧胆酸钠盐(Sigma-Aldrich化学有限公司,D-82041 Deisenhofen)代替实施例A的胆酸钠盐。
干燥的粉末状催化剂产量:2.0g
元素分析、热重分析和萃取:
钴=13.8%(重量),锌=28.3%(重量),叔丁醇=7.3%(重量),猪脱氧胆酸钠盐=6.2%(重量)。实施例C(对比例)
在没有胆酸或其盐、酯或酰胺的情况下,采用叔丁醇制备DMC催化剂(催化剂C,按照日本专利-A 4145123合成)
将10g(73.3mmol)氯化锌的15ml蒸馏水溶液,在强烈搅拌(24000rpm)下,加入到4g(12mmol)六氰钴酸钾的75ml蒸馏水溶液中。然后立即将50g叔丁醇与50g蒸馏水的混合物加入所生成的悬浮液中,强烈搅拌(24000rpm)10分钟min。采用过滤分离固体,然后将固体与125g叔丁醇和蒸馏水的混合物(70/30(重量/重量))搅拌(10000rpm)10分钟,再次过滤。然后再将产品与125g叔丁醇搅拌(10000rpm)10分钟。过滤后,在50℃和大气压下下将催化剂干燥至恒重。
干燥的粉末状催化剂产量:3.08g
元素分析:
钴=13.6%(重量),锌=27.4%(重量),叔丁醇=14.2%(重量)。制备聚醚多元醇 方法概要
首先将50g聚丙二醇起始化合物(分子量=1,000g/mol)和3-5mg催化剂(相对待制备的聚醚多元醇量为15-25ppm),加入到有保护性气体(氩)的500ml加压反应器中,在搅拌下加热到105℃。然后剂量加入环氧丙烷(约5g),直到总压增加到2.5bar为止。在观察到反应器中的压力加速下降时,才加入另一些环氧丙烷。这种压力加速下降表明,催化剂已被活化。然后在总压恒定为2.5bar的情况下,连续地加入其余的环氧丙烷(145g)。在加入所有的环氧丙烷并在105℃下反应2小时后,在90℃下(1mbar)蒸馏出挥发性成分,然后将混合物冷却到室温。
测定所制聚醚多元醇特征的OH值、双键含量和粘度。
利用时间/转化率曲线(环氧丙烷的耗量[g]对反应时间[min])跟踪反应。诱导时间是根据时间/转化率曲线最陡点的切线与曲线的延长基线的交点确定的。对催化剂活性很重要的丙氧基化时间相应于催化剂活化(诱导期结束)和环氧丙烷剂量加入结束之间的时间间隔。总反应时间是诱导时间和丙氧基化时间的总合。实施例1 用催化剂A(25ppm)制备聚醚多元醇
诱导时间: 217分钟
丙氧基化时间: 33分钟
总反应时间: 250分钟
聚醚多元醇:OH值(mg KOH/g): 29.6
双键含量(mmol/kg): 6
在25℃下的粘度(mPa): 855
实施例2 采用催化剂A(15ppm)制备聚醚多元醇
诱导时间: 387分钟
丙氧基化时间: 168分钟
总反应时间: 555分钟
聚醚多元醇: OH值(mg KOH/g): 30.1
双键含量(mmol/kg): 6
在25℃下的粘度(mPa): 993
在不除去催化剂的情况下,多元醇中的金属含量为:Zn=4ppm,Co=2ppm。实施例3 采用催化剂B(25ppm)制备聚醚多元醇
诱导时间: 371分钟
丙氧基化时间: 40分钟
总反应时间: 411分钟
聚醚多元醇: OH值(mg KOH/g): 30.2
双键含量(mmol/kg): 6
在25℃下的粘度(mPa): 902实施例4(对比例)
在上述的反应条件下,即使在14小时诱导时间以后,催化剂C(15ppm)根本没有任何活性。
在采用50ppm的催化剂C时,诱导时间约9小时。丙氧基化时间大于12小时,其中在反应过程中催化剂发生去活作用。
实施例1-3表明,由于新型的本发明的催化剂有明显高的活性,所以在制备聚醚多元醇的过程中,可以采用很低的浓度,以致不需要将催化剂与多元醇分离。
Claims (9)
1.一种双金属氰化物(DMC)催化剂,其中包括
a)一种或多种双金属氰化合物,
b)一种或多种胆酸或其盐、酯或酰胺,和
c)一种或多种与b)不同的有机络合配位体。
2.根据权利要求1的DMC催化剂,其中还包括d)水,和/或e)水溶性的金属盐。
3.根据权利要求1或2的DMC催化剂,其中双金属氰化合物a)是六氰钴(III)酸锌。
4.根据权利要求1或2的DMC催化剂,其中有机络合配位体c)是叔丁醇。
5.根据权利要求1或2的DMC催化剂,其中包括1-80重量%的胆酸或其盐、酯或酰胺。
6.根据权利要求1或2的DMC催化剂,其中胆酸具有下列通式:其中
R1、R2、R3、R4分别为H或OH,和
R5为OH、NH-CH2-CH2-SO3H、NH-(CH2)3-N+(CH3)2-(CH2)3-SO3、NH-(CH2)3-N+(CH3)2-CH2-CHOH-CH2-SO3 -或NH-CH2-COOH。
7.根据权利要求1或2的DMC催化剂,其中催化剂以胆酸盐的形式包括,胆酸、甘胆酸、牛黄胆酸、脱氧胆酸、脱氧甘胆酸、牛黄脱氧胆酸、鹅脱氧胆酸、鹅脱氧甘胆酸、牛黄鹅脱氧胆酸、石胆酸、猪胆酸、和猪脱氧胆酸的钠、锂或钾盐,或它们的混合物。
8.一种制备聚醚多元醇的方法,它通过在权利要求1-7任一项的一种或多种DMC催化剂的存在下,将烯化氧聚加成到包含活性氢原子的起始化合物上。
9.根据权利要求1-7任一项的一种或多种DMC催化剂在通过烯化氧聚加成到包含活性氢原子的原料化合物上以制备聚醚多元醇中的应用。
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BR0008108A (pt) * | 1999-02-11 | 2001-11-13 | Bayer Ag | Catalisadores de cianeto de duplo metal paraprodução de polióis poliéter |
DE19958355A1 (de) * | 1999-12-03 | 2001-06-07 | Bayer Ag | Verfahren zur Herstellung von DMC-Katalysatoren |
HU226653B1 (en) * | 2000-04-20 | 2009-05-28 | Bayer Ag | Method for producing double metal cyanide (dmc) catalysts |
DE10122019A1 (de) * | 2001-05-07 | 2002-11-14 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
US6797665B2 (en) * | 2002-05-10 | 2004-09-28 | Bayer Antwerpen | Double-metal cyanide catalysts for preparing polyether polyols |
US6764978B2 (en) * | 2002-08-28 | 2004-07-20 | Basf Aktiengesellschaft | Multimetal cyanide compounds |
US6696383B1 (en) * | 2002-09-20 | 2004-02-24 | Bayer Polymers Llc | Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto |
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1999
- 1999-02-11 DE DE19905611A patent/DE19905611A1/de not_active Withdrawn
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2000
- 2000-01-31 KR KR1020017010106A patent/KR100599355B1/ko active IP Right Grant
- 2000-01-31 US US09/890,889 patent/US7008900B1/en not_active Expired - Lifetime
- 2000-01-31 JP JP2000598563A patent/JP4523170B2/ja not_active Expired - Fee Related
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- 2000-01-31 CN CNB008035660A patent/CN1138811C/zh not_active Expired - Lifetime
- 2000-01-31 AT AT00901607T patent/ATE273340T1/de not_active IP Right Cessation
- 2000-01-31 BR BRPI0008106-0A patent/BR0008106B1/pt not_active IP Right Cessation
- 2000-01-31 AU AU22943/00A patent/AU2294300A/en not_active Abandoned
- 2000-01-31 HU HU0200197A patent/HUP0200197A3/hu unknown
- 2000-01-31 DE DE50007385T patent/DE50007385D1/de not_active Expired - Lifetime
- 2000-01-31 ID IDW00200101907A patent/ID30028A/id unknown
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- 2000-01-31 WO PCT/EP2000/000727 patent/WO2000047649A1/de active IP Right Grant
- 2000-01-31 RU RU2001124862/04A patent/RU2235589C2/ru not_active IP Right Cessation
- 2000-01-31 PT PT00901607T patent/PT1165657E/pt unknown
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CZ296405B6 (cs) | 2006-03-15 |
AU2294300A (en) | 2000-08-29 |
PL349858A1 (en) | 2002-09-23 |
DE50007385D1 (de) | 2004-09-16 |
KR100599355B1 (ko) | 2006-07-12 |
HK1044959A1 (en) | 2002-11-08 |
ES2226774T3 (es) | 2005-04-01 |
ATE273340T1 (de) | 2004-08-15 |
JP2002536177A (ja) | 2002-10-29 |
EP1165657B1 (de) | 2004-08-11 |
HUP0200197A2 (hu) | 2002-05-29 |
EP1165657A1 (de) | 2002-01-02 |
US7008900B1 (en) | 2006-03-07 |
PT1165657E (pt) | 2004-11-30 |
CN1340071A (zh) | 2002-03-13 |
ID30028A (id) | 2001-11-01 |
WO2000047649A1 (de) | 2000-08-17 |
JP4523170B2 (ja) | 2010-08-11 |
DE19905611A1 (de) | 2000-08-17 |
CA2362503C (en) | 2009-12-01 |
HUP0200197A3 (en) | 2003-08-28 |
RU2235589C2 (ru) | 2004-09-10 |
TWI227248B (en) | 2005-02-01 |
HK1044959B (zh) | 2004-12-17 |
BR0008106A (pt) | 2001-11-13 |
CA2362503A1 (en) | 2000-08-17 |
BR0008106B1 (pt) | 2010-02-09 |
CZ20012882A3 (cs) | 2001-10-17 |
KR20010102029A (ko) | 2001-11-15 |
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