CA2441185C - Double metal cyanide catalysts which can be used to prepare polyols and the processes related thereto - Google Patents
Double metal cyanide catalysts which can be used to prepare polyols and the processes related thereto Download PDFInfo
- Publication number
- CA2441185C CA2441185C CA2441185A CA2441185A CA2441185C CA 2441185 C CA2441185 C CA 2441185C CA 2441185 A CA2441185 A CA 2441185A CA 2441185 A CA2441185 A CA 2441185A CA 2441185 C CA2441185 C CA 2441185C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- zinc
- iii
- poly
- metal cyanide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 74
- 239000002184 metal Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229920005862 polyol Polymers 0.000 title claims abstract description 36
- 150000003077 polyols Chemical class 0.000 title claims abstract description 36
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 53
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 230000000536 complexating effect Effects 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 150000002825 nitriles Chemical class 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 105
- -1 alkali metal salt Chemical class 0.000 claims description 44
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 34
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 27
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 22
- 239000011780 sodium chloride Substances 0.000 claims description 18
- 239000011592 zinc chloride Substances 0.000 claims description 15
- 235000005074 zinc chloride Nutrition 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- SZAVHWMCBDFDCM-KTTJZPQESA-N cobalt-60(3+);hexacyanide Chemical compound [60Co+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] SZAVHWMCBDFDCM-KTTJZPQESA-N 0.000 claims description 11
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 claims description 11
- 239000001103 potassium chloride Substances 0.000 claims description 11
- 235000011164 potassium chloride Nutrition 0.000 claims description 11
- 239000007858 starting material Substances 0.000 claims description 11
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 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 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 4
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 claims description 4
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 claims description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- 229920000858 Cyclodextrin Polymers 0.000 claims description 3
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000003613 bile acid Substances 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 claims description 3
- 229930182470 glycoside Natural products 0.000 claims description 3
- 150000002338 glycosides Chemical class 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 3
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 4
- 229910052783 alkali metal Inorganic materials 0.000 claims 4
- HSINOMROUCMIEA-FGVHQWLLSA-N (2s,4r)-4-[(3r,5s,6r,7r,8s,9s,10s,13r,14s,17r)-6-ethyl-3,7-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]-2-methylpentanoic acid Chemical compound C([C@@]12C)C[C@@H](O)C[C@H]1[C@@H](CC)[C@@H](O)[C@@H]1[C@@H]2CC[C@]2(C)[C@@H]([C@H](C)C[C@H](C)C(O)=O)CC[C@H]21 HSINOMROUCMIEA-FGVHQWLLSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 2
- 229930182556 Polyacetal Natural products 0.000 claims 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims 2
- 239000011976 maleic acid Substances 0.000 claims 2
- 229920001446 poly(acrylic acid-co-maleic acid) Polymers 0.000 claims 2
- 239000004584 polyacrylic acid Substances 0.000 claims 2
- 239000011118 polyvinyl acetate Substances 0.000 claims 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims 2
- 239000004094 surface-active agent Substances 0.000 claims 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229920005906 polyester polyol Polymers 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 3
- 229910001507 metal halide Inorganic materials 0.000 abstract description 3
- 150000005309 metal halides Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 44
- 238000002156 mixing Methods 0.000 description 38
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- 150000002009 diols Chemical class 0.000 description 28
- 229920001451 polypropylene glycol Polymers 0.000 description 22
- 239000011701 zinc Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 238000000921 elemental analysis Methods 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 239000004677 Nylon Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical group CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- 101000952936 Homo sapiens Ubiquinone biosynthesis monooxygenase COQ6, mitochondrial Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 102100037292 Ubiquinone biosynthesis monooxygenase COQ6, mitochondrial Human genes 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004808 allyl alcohols Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ZAEAYFVVHCPYDI-UHFFFAOYSA-N dizinc;iron(2+);hexacyanide Chemical compound [Fe+2].[Zn+2].[Zn+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZAEAYFVVHCPYDI-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YJUIKPXYIJCUQP-UHFFFAOYSA-N trizinc;iron(3+);dodecacyanide Chemical compound [Fe+3].[Fe+3].[Zn+2].[Zn+2].[Zn+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YJUIKPXYIJCUQP-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
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
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
-
- 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
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention is directed to double metal cyanide catalysts ("DMC") which can be used to prepare polyols. DMC catalysts of the present invention are prepared by combining i) at least one metal salt; ii) at least one metal cyanide salt; iii) at least one organic complexing ligand; iv) at least one alkaline metal salt; and, optionally, v) at least one functionalized polymer. The present invention is also directed to a process for preparing a polyol in the presence of a DMC catalyst of or prepared according to the present invention. Surprisingly, DMC catalysts of the present invention, which are preferably prepared with at least one alkaline metal halide, have acceptable activity and can be used to catalyze oxyalkylation reactions. Additionally, DMC catalysts produced by the process of the present invention can be used to prepare polyols which have reduced levels of high molecular weight tail.
Description
Mo-6961 DOUBLE-METAL CYANIDE CATALYSTS WHICH CAN BE USED TO
PREPARE POLYOLS AND THE PROCESSES RELATED THERETO
TECHNICAL FIELD OF THE INVENTION
The present invention is directed to double-metal cyanide ( DMC") catalysts which can be used to prepare polyols. The present invention is also directed to a process for preparing DMC catalysts. The present invention is further directed to a process for polymerizing an alkylene. oxide in the presence of a DMC catalyst prepared according to the process of the present invention.
BACKGROUND OF THE INVENTION
In the preparation of polyoxyalkylene polyols, starter compounds having active hydrogen atoms are oxyalkylated with alkylene oxides in the presence of a suitable catalyst. For many years, basic as well as DMC
catalysts have been used in oxyalkylation reactions to prepare polyoxyalkylene polyols. Base-catalyzed oxyalkylation involves oxyalkylating a low molecular weight starter compound (such as propylene glycol or glycerine) with an alkylene oxide (such as ethylene oxide or propylene oxide) in the presence of a basic catalyst (such as potassium hydroxide (KOH)) to form a polyoxyalkylene polyol.
In base-catalyzed oxyalkylation reactions, propylene oxide and certain other alkylene oxides are subject to a competing internal rearrangement which generates unsaturated alcohols. For example, when KOH is used to catalyze an oxyalkylation reaction using propylene oxide, the resulting product will contain allyl alcohol-initiated, monofunctional impurities. As the molecular weight of the polyol increases, the isomerization reaction becomes more prevalent. As a result, 800 or higher equivalent weight poly(propylene oxide) products prepared using KOH
tend to have significant quantities of monofunctional impurities.
Monofunctional impurities tend to reduce the average functionality and broaden the molecular weight distribution of the polyol.
Mo-6961 Unlike basic catalysts, DMC catalysts do not significantly promote the isomerization of propylene oxide. As a result, DMC catalysts can be used to prepare polyols which have low unsaturation values and relatively high molecular weights. DMC catalysts can be used to produce polyether, polyester and polyetherester polyols which are useful in applications such as polyurethane coatings, elastomers, sealants, foams and adhesives.
DMC-catalyzed oxyalkylation reactions, however, are known to produce small amounts of high molecular weight polyol impurities (typically, molecular weights in excess of 100,000 Da). These high molecular weight impurities are often referred to as the "high molecular weight tail". In elastomers and other systems, the high molecular weight tail may interfere with hard segment phase out as well as with the alignment of hard segments responsible for strength and modulus properties. In polyurethane foam systems, for example, polyols which have a high molecular weight tail produce course foam cells, very tight foams or weak foams or contribute to foam collapse.
DMC catalysts are known and are described in, for example, United States Patent Nos. 3,278,457, 3,278,459, 3,289,505, 3,427,256, 4,477,589, 5,158,922, 5,470,813, 5,482,908, 5,545,601, 5,627,122 and 6,423,662 as well as in WO 01104180 and WO 02/09875. DMC catalysts are typically prepared by mixing an aqueous solution of a metal salt with an aqueous solution of a metal cyanide salt in the presence of an organic complexing ligand. A precipitate forms when these two solutions are mixed together. The resulting precipitate is isolated and then washed.
The art teaches that, during the preparation of a DMC catalyst, alkaline metal salts are incorporated into the catalyst. See Huang et al., "Controlled Ring-Opening Polymerization of Propylene Oxide Catalyzed by Double Metal-Cyanide Complex,", Journal of Polymer Science, Vol. 40, page 1144 (2002); United States Patent No. 3,278,457, column 5, lines 40-44; and WO 02/09875, page 5, lines 5-12. The art also teaches that these occluded ions must be removed during the preparation of a DMC
catalyst. See Huang et al., page 1144; United States Patent No.
Mo-6961 3,278,457, column 5, lines 57-58; and WO 02/09875, page 5, lines 5-12.
United States Patent No. 6,423,662 (at column 6, lines 47-50) , WO/01/04180 (at page 8, lines 17-19), and United States Patent No. 3,278,457 (at column 5, lines 45-58), for example, teach those skilled in the art to wash the precipitate formed during the preparation of a DMC catalyst as thoroughly as possible in order to remove essentially all of these occluded ions.
SUMMARY OF THE INVENTION
The present invention is directed to process for preparing a DMC
catalyst which involves combining: i) at least one metal salt selected from the group consisting of zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, zinc propionate, zinc formate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate and mixtures thereof; ii) at least one metal cyanide salt selected from the group consisting of potassium hexacyanocobaltate (III), potassium hexacyanoferrate(II), lithium hexacyanoiridate(III), lithium hexacyanocobaltate(III), sodium hexacyanocobaltate(III) and cesium hexacyanocobaltate(III); iii) at least one organic complexing ligand; and iv) at least one alkaline metal salt. In an optional embodiment, the process additionally comprises combining v) at least one functionalized polymer with component i), ii), iii) and iv) as set forth above. In accordance with the present invention, the alkaline metal salt is added to the catalyst in an amount such that the catalyst contains from 0.4 to 6 wt. %, based on the total weight of the catalyst.
The present invention is also directed to a DMC catalyst which is produced by the process of the invention described hereinbefore.
The present invention is also directed to a process for preparing a polyol in the presence of a DMC catalyst prepared according to the process of the present invention.
DOCSMTL: 3979416\1 Mo-6961 -3a-The present invention is also directed to a DMC catalyst which is represented by the following general formula (I) M1 x([M2x.(CN)y],.[M3(x)(y)]) L1'I-2.M4Z (I) Surprisingly, DMC catalysts of and produced by the process of the present invention, which are preferably prepared with at least one alkaline metal halide, have acceptable activity and can be used to catalyze oxyalkylation reactions.
Additionally, DMC catalysts produced by the process of the present invention can be used to produce polyols which have reduced levels of high molecular weight tail.
DESCRIPTION OF THE INVENTION
In a first aspect, the present invention is a process for preparing a DMC catalyst comprising combining: i) at least one metal salt; ii) at least one metal cyanide salt; iii) at least one organic complexing ligand; iv) at least one alkaline metal salt; and, optionally, v) at least one functionalized polymer, under conditions sufficient to form a catalyst.
In a second aspect, the present invention is a process for preparing a DOCSMTL: 3979416\1 Mo-6961 polyol comprising reacting i) at least one starter compound having active hydrogen atoms with ii) at least one oxide in the presence of iii) at least one DMC catalyst which is prepared according to the process of the present invention, under conditions sufficient to form a polyol.
In another aspect, the present invention is a DMC catalyst which is represented by the general formula M'x([M2x.(CN)y]z.[M3(x)(Y)]) L',L2,M4Z, wherein M1 represents at least one metal salt;
M2 represents at least one metal cyanide salt;
M3 represents at least one transition metal salt;
M4 represents at least one alkaline metal salt;
L' represents at least one organic complexing ligand;
L2 is optional and can represent at least one functionalized polymer;
and x, x', y and z are integers and are chosen such that electroneutrality of the DMC catalyst exists.
in yet another aspect, the present invention is a process for preparing a polyol comprising reacting i) at least one starter compound having active hydrogen atoms with ii) at least one oxide in the presence of iii) at least one DMC catalyst which is represented by the general formula M'x([M2x,(CN)y]z-[M3(x)(Y)])-L'' L2' M4z.
wherein M1 represents at least one metal salt;
M2 represents at least one metal cyanide salt;
M3 represents at least one transition metal salt;
M4 represents at least one alkaline metal salt;
L' represents at least one organic complexing ligand;
L2 is optional and can represent at least one functionalized polymer;
and x, x', y and z are integers and are chosen such that electroneutrality of the DMC catalyst exists.
Any metal salt can be used in the present invention. Preferably, Mo-6961 water soluble metal salts which are known in the art are used in the present invention. Examples of metal salts which are useful in the present invention include, for example, zinc chloride, zinc bromide, zinc acetate, zinc cetylacetonate, zinc benzoate, zinc nitrate, zinc propionate, zinc formate, iron(!!) sulfate, iron(!!) bromide, cobalt(!!) chloride, cobalt(!!) thiocyanate, nickel(!!) formate, nickel(!!) nitrate and mixtures thereof.
Any metal cyanide salt can be used in the present invention.
Examples of metal cyanide salts which can be used in the present invention include, for example, cyanometalic acids and water-soluble metal cyanide salts. Preferably, water soluble metal cyanide salts which are known in the art are used in the present invention. Metal cyanide salts which are useful in the invention include, for example,potassium hexacyanocobaltate(lll), potassium hexacyanoferrate(lI), potassium hexacyanoferrate(III), lithium hexacyanoiridate(lll), lithium hexacyanocobaltate(III), sodium hexacyanocobaltate(lll) and cesium hexacyanocobaltate(lil) are used in the present invention.
Metal salts of the present invention are preferably combined with metal cyanide salts of the present invention to form DMC compounds. DMC
compounds which are useful in the present invention include, for example, zinc hexacyanocobaltate(lll), zinc hexacyanoiridate(lIl), zinc hexacyanoferrate(II), zinc hexacyanoferrate(III), zinc hexacyanocolbaltic acid, cobalt(II) hexacyanocobaltate(III) and nickel(lI) hexacyanoferrate(II).
Zinc hexacyanocobaltate is particularly preferred.
Any organic complexing ligand can be used in the present invention.
Organic complexing ligands useful in the present invention are known and are described in, for example, United States Patent Nos. 3,404,109, 3,829,505, 3,941,849, 5,158,922 and 5,470,813, as well as in EP 700 949, EP 761 708, EP 743 093, WO 97/40086 and JP 4145123. Organic complexing ligands useful in the present invention include, for example, water-soluble organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the DMC
compound.
Mo-6961 Suitable organic complexing ligands useful in the present invention include, for example, alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof. Preferred organic complexing ligands useful in the present invention include water-soluble aliphatic alcohols, such as, for example, ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol and tert-butanol. Tert-butanol is particularly preferred.
Any alkaline metal salt can be used in the present invention.
Preferably, alkaline metal halides are used in the present invention.
More preferably, sodium chloride, sodium bromide, sodium iodide, lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide and mixtures thereof are used in the present invention.
The relative amounts of organic complexing ligand and alkaline metal salt used in the present invention can vary. A skilled person can control catalyst activity, polyol viscosity and the like by varying these amounts. Preferably, DMC catalysts produced by the process of the present invention are composed of at least one alkaline metal salt which is present in an amount within the range of from about 0.1 to about 10 wt.%, more preferably, from about 0.4 to about 6 wt.%, most preferably, from about 1 to about 3 wt.%, based on the total weight of the DMC catalyst.
DMC catalysts of the present invention can optionally include at least one functionalized polymer. "Functionalized polymer" is defined as a polymer or its salt which contains one or more functional groups including oxygen, nitrogen, sulfur, phosphorus or halogen. Examples of functionalized polymers useful in the present invention include, for example: polyethers; polyesters; polycarbonates; polyalkylene glycol sorbitan esters; polyalkylene glycol glycidyl ethers; polyacrylamides;
poly(acrylamide-co-acrylic acids), polyacrylic acids, poly(acrylic acid-co-maleic acids), poly(N-vinylpyrrolidone-co-acrylic acids), poly(acrylic acid-co-styrenes) and their salts; maleic acids, styrenes and maleic anhydride copolymers and their salts; block copolymers which are composed of branched chain ethoxylated alcohols; alkoxylated alcohols such as Mo-6961 NEODOL* which is sold commercially by Shell Chemical Company;
polyether; polyacrylonitriles; polyalkyl acrylates; polyalkyl methacrylates;
polyvinyl methyl ethers; polyvinyl ethyl ethers; polyvinyl acetates; polyvinyl alcohols; poly-N-vinylpyrrolidones; polyvinyl methyl ketones; poly(4-vinylphenols); oxazoline polymers; polyalkyleneimines;
hyd roxyethylcel I u loses; polyacetals; glycidyl ethers; glycosides;
carboxylic acid esters of polyhydric alcohols; bile acids and their salts, esters or amides; cyclodextrins; phosphorus compounds; unsaturated carboxylic acid esters; and ionic surface- or interface-active compounds. Polyether polyols are preferably used.
When used, functionalized polymers are present in the DMC
catalyst in an amount within the range of from about 2 to about 80 wt. %, preferably, within the range of from about 5 to about 70 wt. %, more preferably, within the range of from about 10 to about 60 wt. %, based on the total weight of DMC catalyst.
The combination of metal salt, metal cyanide salt, organic complexing ligand, alkaline metal salt and, optionally, functionalized polymer, can be accomplished by any of the methods known in the art. Such methods include, for example, precipitation, dispersion and incipient wetness.
Preferably, the process of the present invention involves using a precipitation method in which an aqueous solution of at least one metal salt employed in a stoichiometric excess, i.e., at least 50 mol. %, based on the molar amount of metal cyanide salt, is mixed with an aqueous solution of at least one metal cyanide salt, at least one alkaline metal salt and, optionally, at least one functionalized polymer, in the presence of at least one organic complexing ligand.
The alkaline metal salt can be added to either the aqueous solution of metal salt or to the aqueous solution of metal cyanide salt or to both solutions or to the mixture after the two solutions are combined. Preferably, the alkaline metal salt is added to the aqueous solution of metal salt. The organic complexing ligand can be added to either the aqueous solution of metal salt or to the aqueous solution of metal cyanide salt or to both *trade-mark Mo-6961 solutions or to the mixture after the two solutions are combined or it can be added after formation of the precipitate. The functionalized polymer can be added to either the aqueous solution of metal salt or to the aqueous solution of metal cyanide salt or to both solutions or to the mixture after the two solutions are combined or it can be added after formation of the precipitate.
The reactants are mixed using any of the mixing methods known in the art, such as, for example, by simple mixing, high-shear mixing or homogenization. Preferably, the reactants are combined with simple mixing at a temperature within the range of from about room temperature to about 80 C. A precipitate forms when the reactants are mixed.
The resulting precipitate is isolated from suspension by known techniques such as, for example, by centrifugation, filtration, filtration under pressure, decanting, phase separation or aqueous separation.
The isolated precipitate is preferably washed at least once with water and/or with a mixture which is preferably composed of water and at least one organic complexing ligand. More preferably, this mixture is composed of water, at least one organic complexing ligand and at least one alkaline metal salt. Most preferably, this mixture is composed of water, at least one organic complexing ligand, at least one alkaline metal salt and at least one functionalized polymer.
Preferably, the isolated precipitate is filtered from the wash mixture by known techniques such as, for example, centrifugation, filtration, filtration under pressure, decanting, phase separation or aqueous separation. The filtered precipitate is preferably washed at least once with a mixture which is preferably composed of at least one organic complexing ligand. More preferably, this mixture is composed of water, at least one organic complexing ligand and at least one alkaline metal salt. Most preferably, this mixture is composed of water, at least one organic complexing ligand, at least one alkaline metal salt and at least one functionalized polymer.
The present invention is also directed to a process for preparing a polyol in the presence of a DMC catalyst of or prepared according to the present invention.
Mo-6961 Any starter compound which has active hydrogen atoms can be used in the present invention. Starter compounds which are useful in the present invention include compounds having number average molecular weights between 18 to 2,000, preferably, between 32 to 2,000, and which have from I to 8 hydroxyl groups. Examples of starter compounds which can be used in the present invention include, for example, polyoxypropylene polyols, polyoxyethylene polyols, polytetatramethylene ether glycols, glycerol, propoxylated glycerols, tripropylene glycol, alkoxylated allylic alcohols, bisphenol A, pentaerythritol, sorbitol, sucrose, degraded starch, water and mixtures thereof.
Monomers or polymers which will copolymerize with an oxide in the presence of a DMC catalyst can be included in the process of the present invention to produce various types of polyols. The build-up of the polymer chains by alkoxylation can be accomplished randomly or blockwise.
Additionally, any copolymer known in the art made using a conventional DMC catalyst can be made with the DMC catalyst prepared according to the process of the present invention.
Any alkylene oxide can be used in the present invention. Alkylene oxides preferably used in the present invention include, for example, ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
Oxyalkylation of the starter compound can be accomplished by any of the methods known in the art, such as, for example, in a batch, semi-batch or continuous process. Oxyalkylation is carried out at a temperature in the range of from about 20 and 200 C, preferably, from about 40 and 180 C, more preferably, from about 50 and 150 C and under an overall pressure of from about 0.0001 to about 20 bar. The amount of DMC catalyst used in the oxyalkylation reaction is chosen such that sufficient control of the reaction is possible under the given reaction conditions. The DMC catalyst concentration of an oxyalkylation reaction is typically in the range of from about 0.0005 wt.% to about I wt.%, preferably, from about 0 0.001 wt.% to about 0.1 wt.%, more preferably, from about 0.001 to about 0.0025 wt.%, based on the total weight of polyol to be prepared.
Mo-6961 -10-The number average molecular weight of the polyol prepared by the process of the present invention is in the range of from about 500 to about 100,000 g/mol, preferably, from about 1,000 to about 12,000 g/mol, more preferably, from about 2,000 to about 8,000 g/mol. Polyols prepared by the process of the present invention have average hydroxyl functionalities of from about 1 to 8, preferably, from about 2 to 6, and more preferably, from about 2 to 3.
DMC catalysts of the present invention can be used to produce polyols which have reduced levels of high molecular weight tail (greater than 400 K). The amount of high molecular weight tail is quantified by any suitable method. A particularly convenient way to measure the amount of high molecular weight tail is by gel permeation chromatography (GPC). A
suitable technique for measuring high molecular weight tail is described below as well as in, for example, United States Patent No. 6,013,596.
Those skilled in the art will recognize many variations in the illustrative examples, that are within the invention.
Examples A DMC catalyst which was prepared according to any one of Examples 1-16 set forth below was used to prepare a 6000 MW
polyoxypropylene triol by adding propylene oxide over 4 hours to an activated mixture composed of the DMC and a propoxylated glycerin starter (hydroxyl number = 240 mg KOH/g). Catalyst levels of 30 ppm were used.
The hydroxyl number, viscosity and unsaturation of each product were measured by standard methods. A gel permeation chromatography (GPC) technique as described in United States Patent No. 6,013,596, was used to measure the amount of polyol component having a number average molecular weight (Mn) from 40,000 to > 400,000. The amount present (in ppm) is recorded and the percent of high molecular weight (HMW) tail reduction of the catalyst for each range of molecular DOCSMTL: 4436718\1 Mo-6961 weight is calculated using the following formula (hereinafter referred to as "Formula I"):
% Reduction*
(HMW tail of comparative example - HMW tail of polyol prepared with a DMC catalyst of the present invention) X 100%/
HMW tail of comparative control * no reduction of HMW tail is obtained if the % reduction is less than zero.
Example 1 Preparation of a DMC catalyst using sodium chloride and a polyoxypropylene diol:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnCI2) was diluted with deionized water (230 g.) and tert-butyl alcohol (38 g.) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and sodium chloride (4 g.) were dissolved in a 500-ml beaker with deionized water (100 g) and tert-butyl alcohol (15.5 g.) (Solution 2).
Solution 3 was prepared by dissolving a 1000 mol. wt. polyoxypropylene diol (8 g.) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 1,500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 1,500 rpm for 20 min. The mixing was stopped. Solution 3 was then added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 t nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g) and sodium chloride (2 g) and mixed at 1,500 rpm for 20 min. The mixing was stopped. 1000 mol. wt.
polyoxypropylene diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was filtered as described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and mixed as described above. 1000 mol. wt. polyoxypropylene diol (1 g.) was added and the product was Mo-6961 filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Cobalt = 9 wt.%; Zinc = 21.7 wt.%; Sodium = 0.75 wt.%;
Cl = 6.1 wt.%
Example 2 Preparation of a DMC catalyst using lithium chloride and a polyoxypropylene diol:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnCl2) was diluted with deionized water (230 g.) and tert-butyl-alcohol (38 g.) in a one-liter stirred reactor. Lithium chloride (0.3 g.) was added to this solution (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-m1 beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 3 was prepared by dissolving a 1000 mol. wt.
polyoxypropylene diol (8 g.) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 1,500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling.
Following the addition, mixing continued at 1,500 rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g..), deionized water (55 g.) and lithium chloride (2 g.) and mixed at 1,500 rpm for 20 min. The mixing was stopped. 1000 mol. wt.
polyoxypropylene diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was filtered as described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and lithium chloride (0.5 g.) and mixed as described above. 1000 mol. wt. polyoxypropylene diol (1 g.) was added and the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Cobalt = 9.1 wt.%; Zinc = 21.9 wt. / ;
Mo-6961 Lithium = 0.15 wt.%; Cl = 4.8 wt.%
Example 3 Preparation of a DMC catalyst using sodium bromide and a polyoxypropylene diol:
The procedure of Example 2 was followed, except that NaBr was used in lieu of LiCI.
Elemental analysis: Cobalt = 8.1 wt.%; Zinc = 21.9 wt.%;
Sodium = 0.48 wt.%; CI = 3.8 wt.%; Br = 3.8 wt.%
Example 4 Preparation of a DMC catalyst using lithium bromide and a polyoxypropylene diol:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnCl2) was diluted with deionized water (230 g.) and tent-butyl alcohol (38 g.) in a one-liter stirred reactor. Lithium bromide (4 g.) was added to this solution (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-ml beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 3 was prepared by dissolving a 1000 mol. wt.
polyoxypropylene diol (8 g.) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 1,500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling.
Following the addition, mixing continued at 1,500 rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 nylon membrane. The catalyst cake was re-slurried in a mixture of tent-butyl alcohol (100 g.) and deionized water (55 g) and mixed at 1,500 rpm for 20 min. The mixing was stopped. 1000 mol. wt. polyoxypropylene diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was filtered as described above. The cake was re-slurried in tent-butyl alcohol (144 g.) and mixed as described above. 1000 rnol. wt. polyoxypropylene Mo-6961 diol (1 g.) was added and the product was filtered as described above.
The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in.
(Hg) to constant weight.
Elemental Analysis Zn = 23.4 wt.% ; Co = 10.8 wt.%; Li = <0.02 wt.%;
Br: 0.4 wt.%; Cl = 3.6 wt.%
Example 5 Preparation of a DMC catalyst using sodium chloride and a diol of propylene oxide and ethylene oxide copolymer:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnC12) was diluted with deionized water (230 g.) and tert-butyl alcohol (38 g.) in a one-liter stirred reactor. Sodium chloride (0.3 g.) was added to this solution (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-m1 beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 3 was prepared by dissolving 8 g. of a 4000 mol. wt.
diol of propylene oxide and ethylene oxide copolymer (80:20 wt. ratio) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 900 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 900 rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 p nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g.) and sodium chloride (2 g.) and mixed at 900 rpm for 20 min. The mixing was stopped. 4000 mol. wt. diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was filtered as described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and sodium chloride (1 g.) and mixed as described above.
4000 mol. wt. diol (1 g.) was added and the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Cobalt = 8.8 wt.%; Zinc = 20.3 wt.%; Sodium = 2.4 wt.%
Mo-6961 Example 6 Preparation of a DMC catalyst using potassium chloride and a polyoxypropylene diol:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnCl2) was diluted with deionized water (230 g.) and tent-butyl alcohol (38 g.) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and potassium chloride (4.0 g) were dissolved in a 500-ml beaker with deionized water (100 g.) and tent-butyl alcohol (15.5 g.) (Solution 2).
Solution 3 was prepared by dissolving 8 g. of a 1000 mol. wt.
polyoxypropylene diol (8 g.) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling.
Following the addition, mixing continued at 500 rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 [t nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g.) and mixed at 500 rpm for 20 min.
The mixing was stopped. 1000 mol. wt. diol (2 g.) and potassium chloride (2 g) were added and the mixture was stirred slowly for 3 min. The catalyst was isolated as described above. The cake was re-slurried in tent-butyl alcohol (125 g) and deionized water (30 g) and was mixed at 500 rpm for 20 min. The mixing was stopped. 1000 mol. wt. diol (2 g) and potassium chloride (2 g) were added and the mixture was stirred slowly for 3 min. The catalyst was filtered as-described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and mixed as described above.
1000 mol. wt. diol (1 g.) was added and the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Co = 9.4 wt. %; Zn = 20 wt. %; K = 6.1 wt. %.
Mo-6961 Example 7 Preparation of a DMC catalyst using potassium chloride, a polyoxypropylene diol and a polystyrene-alt-maleic acid, sodium salt) (30 wt % in water):
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnC12) was diluted with deionized water (230 g.) and tent-butyl alcohol (38 g.) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and potassium chloride (4.0 g.) were dissolved in a 500-ml beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2).
Solution 3 was prepared by dissolving 8 g. of a 1000 mol. wt.
polyoxypropylene diol in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution I over 45 min. while mixing at 500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 500 rpm for 20 min. The mixing was stopped.
Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 , nylon membrane. The catalyst cake was re-slurried in a mixture of potassium chloride (2 g.), tert-butyl alcohol (100 g.), poly(styrene-alt-maleic acid, sodium salt) solution (7 g.) and deionized water (55 g.) and mixed at 800 rpm for 20 min. The mixing was stopped. 1000 mol. wt. diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was isolated as described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and mixed as described above. More 1000 mol. wt. diol (1 g.) was added and the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Co = 10.1 wt. %; Zn = 22.4 wt. %; K = 1.86 wt. %.
Example 8 Preparation of a DMC catalyst using potassium chloride, a polyoxypropylene diol and a poly(methacrylic acid, sodium salt) (30 wt % solution in water):
Mo-6961 The procedure of Example 7 was followed, except that poly(methacrylic acid, sodium salt) (30 wt % solution in water) was used in lieu of poly(styrene-alt-maleic acid, sodium salt) (30 wt % solution in water).
Elemental analysis: Co = 8 wt. %; Zn = 21.6 wt. %; K = 4.3 wt. %.
Example 9 Preparation of a DMC catalyst using sodium chloride but no functionalized polymer:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnC12) was diluted with deionized water (230 g.) and tert-butyl alcohol (38 g.) in a one-liter stirred reactor. Sodium chloride (0.3 g.) was added to this solution (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-m1 beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 2 was added to Solution I over 45 min. while mixing at 800 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 800 rpm for 20 min. The mixing was stopped.
The reaction mixture was filtered at 40 psig through a 0.65 nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g.) and sodium chloride (2 g.) and mixed at 800 rpm for 20 min. The mixing was stopped. The catalyst was isolated as described above. The cake was re-slurried in tent-butyl alcohol (144 g.) and sodium chloride and mixed as described above. The product was isolated as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental Analysis: Zn = 25.9 wt. %; Co = 12 wt. %; Na = 1.29 wt. %.
Example 10 (Comparative) Preparation of a DMC catalyst using a functionalized polymer but no salt:
The procedure of Example 1 was followed, except that no NaCl was added.
Elemental analysis: Cobalt = 9 wt. %; Zinc = 21.6 wt. %; CI = 4.1 wt.%
Mo-6961 Examples 11, 12 and 13 (all Comparative) Preparation of a DMC catalyst using a functionalized polymer but no salt:
For Comparative Examples 11, 12 and 13, DMC catalysts were prepared according to the procedure of Example 1, except that no NaCl was added.
Elemental analysis: Cobalt = 10.3 wt. %; Zinc = 23.2 wt. %; Cl = 4.0 wt.%;
K= 0.21 wt. %
Example 14 (Comparative) Preparation of a DMC catalyst using no functionalized polymer and no salt:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnC12) was diluted with deionized water (230 g.) and tert-butyl alcohol (38 g.) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-m1 beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 2 was added to Solution 1 over 45 min. while mixing at 800 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 800 rpm for min. The mixing was stopped.
The reaction mixture was filtered at 40 psig through a 0.65 nylon 20 membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g.) and mixed at 800 rpm for 20 min.
The mixing was stopped. The catalyst was isolated as described above.
The cake was re-slurried in tert-butyl alcohol (144 g.) and mixed as described above. The product was isolated as described above.
The resulting catalyst residue was dried in a vacuum oven at 60 C, in. (Hg) to constant weight.
Elemental Analysis: Co = 12.4 wt. %; Zn = 26.8 wt. %.
Example 15 Preparation of a DMC catalyst using sodium chloride and a block copolymer 30 of NEODOL-(EO)m-IBO:
The procedure of Example 5 was followed except that a block copolymer of NEODOL-(EO)m-IBO was used in lieu of the 1000 mol. wt.
*trade-mark Mo-6961 - 19 -diol. The block copolymer was prepared using NEODOL* (which is available commercially from Shell Chemical Company) as a starter and a DMC catalyst prepared essentially by the method of United States Patent No. 5,482,908 to produce a polyoxyethylene having a molecular weight of about 1000. This di-blockcopolymer was end-capped by 1-2 units of isobutylene oxide.
Example 16 (Comparative) Preparation of a DMC catalyst using zinc hexacyanocobaltate/t-butyl alcohol and a polyoxypropylene diol:
The procedure of Example 1 was followed, except that no NaCl was added.
Elemental analysis: Cobalt = 9 wt. %; Zinc = 21.6 wt. %
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PREPARE POLYOLS AND THE PROCESSES RELATED THERETO
TECHNICAL FIELD OF THE INVENTION
The present invention is directed to double-metal cyanide ( DMC") catalysts which can be used to prepare polyols. The present invention is also directed to a process for preparing DMC catalysts. The present invention is further directed to a process for polymerizing an alkylene. oxide in the presence of a DMC catalyst prepared according to the process of the present invention.
BACKGROUND OF THE INVENTION
In the preparation of polyoxyalkylene polyols, starter compounds having active hydrogen atoms are oxyalkylated with alkylene oxides in the presence of a suitable catalyst. For many years, basic as well as DMC
catalysts have been used in oxyalkylation reactions to prepare polyoxyalkylene polyols. Base-catalyzed oxyalkylation involves oxyalkylating a low molecular weight starter compound (such as propylene glycol or glycerine) with an alkylene oxide (such as ethylene oxide or propylene oxide) in the presence of a basic catalyst (such as potassium hydroxide (KOH)) to form a polyoxyalkylene polyol.
In base-catalyzed oxyalkylation reactions, propylene oxide and certain other alkylene oxides are subject to a competing internal rearrangement which generates unsaturated alcohols. For example, when KOH is used to catalyze an oxyalkylation reaction using propylene oxide, the resulting product will contain allyl alcohol-initiated, monofunctional impurities. As the molecular weight of the polyol increases, the isomerization reaction becomes more prevalent. As a result, 800 or higher equivalent weight poly(propylene oxide) products prepared using KOH
tend to have significant quantities of monofunctional impurities.
Monofunctional impurities tend to reduce the average functionality and broaden the molecular weight distribution of the polyol.
Mo-6961 Unlike basic catalysts, DMC catalysts do not significantly promote the isomerization of propylene oxide. As a result, DMC catalysts can be used to prepare polyols which have low unsaturation values and relatively high molecular weights. DMC catalysts can be used to produce polyether, polyester and polyetherester polyols which are useful in applications such as polyurethane coatings, elastomers, sealants, foams and adhesives.
DMC-catalyzed oxyalkylation reactions, however, are known to produce small amounts of high molecular weight polyol impurities (typically, molecular weights in excess of 100,000 Da). These high molecular weight impurities are often referred to as the "high molecular weight tail". In elastomers and other systems, the high molecular weight tail may interfere with hard segment phase out as well as with the alignment of hard segments responsible for strength and modulus properties. In polyurethane foam systems, for example, polyols which have a high molecular weight tail produce course foam cells, very tight foams or weak foams or contribute to foam collapse.
DMC catalysts are known and are described in, for example, United States Patent Nos. 3,278,457, 3,278,459, 3,289,505, 3,427,256, 4,477,589, 5,158,922, 5,470,813, 5,482,908, 5,545,601, 5,627,122 and 6,423,662 as well as in WO 01104180 and WO 02/09875. DMC catalysts are typically prepared by mixing an aqueous solution of a metal salt with an aqueous solution of a metal cyanide salt in the presence of an organic complexing ligand. A precipitate forms when these two solutions are mixed together. The resulting precipitate is isolated and then washed.
The art teaches that, during the preparation of a DMC catalyst, alkaline metal salts are incorporated into the catalyst. See Huang et al., "Controlled Ring-Opening Polymerization of Propylene Oxide Catalyzed by Double Metal-Cyanide Complex,", Journal of Polymer Science, Vol. 40, page 1144 (2002); United States Patent No. 3,278,457, column 5, lines 40-44; and WO 02/09875, page 5, lines 5-12. The art also teaches that these occluded ions must be removed during the preparation of a DMC
catalyst. See Huang et al., page 1144; United States Patent No.
Mo-6961 3,278,457, column 5, lines 57-58; and WO 02/09875, page 5, lines 5-12.
United States Patent No. 6,423,662 (at column 6, lines 47-50) , WO/01/04180 (at page 8, lines 17-19), and United States Patent No. 3,278,457 (at column 5, lines 45-58), for example, teach those skilled in the art to wash the precipitate formed during the preparation of a DMC catalyst as thoroughly as possible in order to remove essentially all of these occluded ions.
SUMMARY OF THE INVENTION
The present invention is directed to process for preparing a DMC
catalyst which involves combining: i) at least one metal salt selected from the group consisting of zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, zinc propionate, zinc formate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate and mixtures thereof; ii) at least one metal cyanide salt selected from the group consisting of potassium hexacyanocobaltate (III), potassium hexacyanoferrate(II), lithium hexacyanoiridate(III), lithium hexacyanocobaltate(III), sodium hexacyanocobaltate(III) and cesium hexacyanocobaltate(III); iii) at least one organic complexing ligand; and iv) at least one alkaline metal salt. In an optional embodiment, the process additionally comprises combining v) at least one functionalized polymer with component i), ii), iii) and iv) as set forth above. In accordance with the present invention, the alkaline metal salt is added to the catalyst in an amount such that the catalyst contains from 0.4 to 6 wt. %, based on the total weight of the catalyst.
The present invention is also directed to a DMC catalyst which is produced by the process of the invention described hereinbefore.
The present invention is also directed to a process for preparing a polyol in the presence of a DMC catalyst prepared according to the process of the present invention.
DOCSMTL: 3979416\1 Mo-6961 -3a-The present invention is also directed to a DMC catalyst which is represented by the following general formula (I) M1 x([M2x.(CN)y],.[M3(x)(y)]) L1'I-2.M4Z (I) Surprisingly, DMC catalysts of and produced by the process of the present invention, which are preferably prepared with at least one alkaline metal halide, have acceptable activity and can be used to catalyze oxyalkylation reactions.
Additionally, DMC catalysts produced by the process of the present invention can be used to produce polyols which have reduced levels of high molecular weight tail.
DESCRIPTION OF THE INVENTION
In a first aspect, the present invention is a process for preparing a DMC catalyst comprising combining: i) at least one metal salt; ii) at least one metal cyanide salt; iii) at least one organic complexing ligand; iv) at least one alkaline metal salt; and, optionally, v) at least one functionalized polymer, under conditions sufficient to form a catalyst.
In a second aspect, the present invention is a process for preparing a DOCSMTL: 3979416\1 Mo-6961 polyol comprising reacting i) at least one starter compound having active hydrogen atoms with ii) at least one oxide in the presence of iii) at least one DMC catalyst which is prepared according to the process of the present invention, under conditions sufficient to form a polyol.
In another aspect, the present invention is a DMC catalyst which is represented by the general formula M'x([M2x.(CN)y]z.[M3(x)(Y)]) L',L2,M4Z, wherein M1 represents at least one metal salt;
M2 represents at least one metal cyanide salt;
M3 represents at least one transition metal salt;
M4 represents at least one alkaline metal salt;
L' represents at least one organic complexing ligand;
L2 is optional and can represent at least one functionalized polymer;
and x, x', y and z are integers and are chosen such that electroneutrality of the DMC catalyst exists.
in yet another aspect, the present invention is a process for preparing a polyol comprising reacting i) at least one starter compound having active hydrogen atoms with ii) at least one oxide in the presence of iii) at least one DMC catalyst which is represented by the general formula M'x([M2x,(CN)y]z-[M3(x)(Y)])-L'' L2' M4z.
wherein M1 represents at least one metal salt;
M2 represents at least one metal cyanide salt;
M3 represents at least one transition metal salt;
M4 represents at least one alkaline metal salt;
L' represents at least one organic complexing ligand;
L2 is optional and can represent at least one functionalized polymer;
and x, x', y and z are integers and are chosen such that electroneutrality of the DMC catalyst exists.
Any metal salt can be used in the present invention. Preferably, Mo-6961 water soluble metal salts which are known in the art are used in the present invention. Examples of metal salts which are useful in the present invention include, for example, zinc chloride, zinc bromide, zinc acetate, zinc cetylacetonate, zinc benzoate, zinc nitrate, zinc propionate, zinc formate, iron(!!) sulfate, iron(!!) bromide, cobalt(!!) chloride, cobalt(!!) thiocyanate, nickel(!!) formate, nickel(!!) nitrate and mixtures thereof.
Any metal cyanide salt can be used in the present invention.
Examples of metal cyanide salts which can be used in the present invention include, for example, cyanometalic acids and water-soluble metal cyanide salts. Preferably, water soluble metal cyanide salts which are known in the art are used in the present invention. Metal cyanide salts which are useful in the invention include, for example,potassium hexacyanocobaltate(lll), potassium hexacyanoferrate(lI), potassium hexacyanoferrate(III), lithium hexacyanoiridate(lll), lithium hexacyanocobaltate(III), sodium hexacyanocobaltate(lll) and cesium hexacyanocobaltate(lil) are used in the present invention.
Metal salts of the present invention are preferably combined with metal cyanide salts of the present invention to form DMC compounds. DMC
compounds which are useful in the present invention include, for example, zinc hexacyanocobaltate(lll), zinc hexacyanoiridate(lIl), zinc hexacyanoferrate(II), zinc hexacyanoferrate(III), zinc hexacyanocolbaltic acid, cobalt(II) hexacyanocobaltate(III) and nickel(lI) hexacyanoferrate(II).
Zinc hexacyanocobaltate is particularly preferred.
Any organic complexing ligand can be used in the present invention.
Organic complexing ligands useful in the present invention are known and are described in, for example, United States Patent Nos. 3,404,109, 3,829,505, 3,941,849, 5,158,922 and 5,470,813, as well as in EP 700 949, EP 761 708, EP 743 093, WO 97/40086 and JP 4145123. Organic complexing ligands useful in the present invention include, for example, water-soluble organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the DMC
compound.
Mo-6961 Suitable organic complexing ligands useful in the present invention include, for example, alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof. Preferred organic complexing ligands useful in the present invention include water-soluble aliphatic alcohols, such as, for example, ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol and tert-butanol. Tert-butanol is particularly preferred.
Any alkaline metal salt can be used in the present invention.
Preferably, alkaline metal halides are used in the present invention.
More preferably, sodium chloride, sodium bromide, sodium iodide, lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide and mixtures thereof are used in the present invention.
The relative amounts of organic complexing ligand and alkaline metal salt used in the present invention can vary. A skilled person can control catalyst activity, polyol viscosity and the like by varying these amounts. Preferably, DMC catalysts produced by the process of the present invention are composed of at least one alkaline metal salt which is present in an amount within the range of from about 0.1 to about 10 wt.%, more preferably, from about 0.4 to about 6 wt.%, most preferably, from about 1 to about 3 wt.%, based on the total weight of the DMC catalyst.
DMC catalysts of the present invention can optionally include at least one functionalized polymer. "Functionalized polymer" is defined as a polymer or its salt which contains one or more functional groups including oxygen, nitrogen, sulfur, phosphorus or halogen. Examples of functionalized polymers useful in the present invention include, for example: polyethers; polyesters; polycarbonates; polyalkylene glycol sorbitan esters; polyalkylene glycol glycidyl ethers; polyacrylamides;
poly(acrylamide-co-acrylic acids), polyacrylic acids, poly(acrylic acid-co-maleic acids), poly(N-vinylpyrrolidone-co-acrylic acids), poly(acrylic acid-co-styrenes) and their salts; maleic acids, styrenes and maleic anhydride copolymers and their salts; block copolymers which are composed of branched chain ethoxylated alcohols; alkoxylated alcohols such as Mo-6961 NEODOL* which is sold commercially by Shell Chemical Company;
polyether; polyacrylonitriles; polyalkyl acrylates; polyalkyl methacrylates;
polyvinyl methyl ethers; polyvinyl ethyl ethers; polyvinyl acetates; polyvinyl alcohols; poly-N-vinylpyrrolidones; polyvinyl methyl ketones; poly(4-vinylphenols); oxazoline polymers; polyalkyleneimines;
hyd roxyethylcel I u loses; polyacetals; glycidyl ethers; glycosides;
carboxylic acid esters of polyhydric alcohols; bile acids and their salts, esters or amides; cyclodextrins; phosphorus compounds; unsaturated carboxylic acid esters; and ionic surface- or interface-active compounds. Polyether polyols are preferably used.
When used, functionalized polymers are present in the DMC
catalyst in an amount within the range of from about 2 to about 80 wt. %, preferably, within the range of from about 5 to about 70 wt. %, more preferably, within the range of from about 10 to about 60 wt. %, based on the total weight of DMC catalyst.
The combination of metal salt, metal cyanide salt, organic complexing ligand, alkaline metal salt and, optionally, functionalized polymer, can be accomplished by any of the methods known in the art. Such methods include, for example, precipitation, dispersion and incipient wetness.
Preferably, the process of the present invention involves using a precipitation method in which an aqueous solution of at least one metal salt employed in a stoichiometric excess, i.e., at least 50 mol. %, based on the molar amount of metal cyanide salt, is mixed with an aqueous solution of at least one metal cyanide salt, at least one alkaline metal salt and, optionally, at least one functionalized polymer, in the presence of at least one organic complexing ligand.
The alkaline metal salt can be added to either the aqueous solution of metal salt or to the aqueous solution of metal cyanide salt or to both solutions or to the mixture after the two solutions are combined. Preferably, the alkaline metal salt is added to the aqueous solution of metal salt. The organic complexing ligand can be added to either the aqueous solution of metal salt or to the aqueous solution of metal cyanide salt or to both *trade-mark Mo-6961 solutions or to the mixture after the two solutions are combined or it can be added after formation of the precipitate. The functionalized polymer can be added to either the aqueous solution of metal salt or to the aqueous solution of metal cyanide salt or to both solutions or to the mixture after the two solutions are combined or it can be added after formation of the precipitate.
The reactants are mixed using any of the mixing methods known in the art, such as, for example, by simple mixing, high-shear mixing or homogenization. Preferably, the reactants are combined with simple mixing at a temperature within the range of from about room temperature to about 80 C. A precipitate forms when the reactants are mixed.
The resulting precipitate is isolated from suspension by known techniques such as, for example, by centrifugation, filtration, filtration under pressure, decanting, phase separation or aqueous separation.
The isolated precipitate is preferably washed at least once with water and/or with a mixture which is preferably composed of water and at least one organic complexing ligand. More preferably, this mixture is composed of water, at least one organic complexing ligand and at least one alkaline metal salt. Most preferably, this mixture is composed of water, at least one organic complexing ligand, at least one alkaline metal salt and at least one functionalized polymer.
Preferably, the isolated precipitate is filtered from the wash mixture by known techniques such as, for example, centrifugation, filtration, filtration under pressure, decanting, phase separation or aqueous separation. The filtered precipitate is preferably washed at least once with a mixture which is preferably composed of at least one organic complexing ligand. More preferably, this mixture is composed of water, at least one organic complexing ligand and at least one alkaline metal salt. Most preferably, this mixture is composed of water, at least one organic complexing ligand, at least one alkaline metal salt and at least one functionalized polymer.
The present invention is also directed to a process for preparing a polyol in the presence of a DMC catalyst of or prepared according to the present invention.
Mo-6961 Any starter compound which has active hydrogen atoms can be used in the present invention. Starter compounds which are useful in the present invention include compounds having number average molecular weights between 18 to 2,000, preferably, between 32 to 2,000, and which have from I to 8 hydroxyl groups. Examples of starter compounds which can be used in the present invention include, for example, polyoxypropylene polyols, polyoxyethylene polyols, polytetatramethylene ether glycols, glycerol, propoxylated glycerols, tripropylene glycol, alkoxylated allylic alcohols, bisphenol A, pentaerythritol, sorbitol, sucrose, degraded starch, water and mixtures thereof.
Monomers or polymers which will copolymerize with an oxide in the presence of a DMC catalyst can be included in the process of the present invention to produce various types of polyols. The build-up of the polymer chains by alkoxylation can be accomplished randomly or blockwise.
Additionally, any copolymer known in the art made using a conventional DMC catalyst can be made with the DMC catalyst prepared according to the process of the present invention.
Any alkylene oxide can be used in the present invention. Alkylene oxides preferably used in the present invention include, for example, ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
Oxyalkylation of the starter compound can be accomplished by any of the methods known in the art, such as, for example, in a batch, semi-batch or continuous process. Oxyalkylation is carried out at a temperature in the range of from about 20 and 200 C, preferably, from about 40 and 180 C, more preferably, from about 50 and 150 C and under an overall pressure of from about 0.0001 to about 20 bar. The amount of DMC catalyst used in the oxyalkylation reaction is chosen such that sufficient control of the reaction is possible under the given reaction conditions. The DMC catalyst concentration of an oxyalkylation reaction is typically in the range of from about 0.0005 wt.% to about I wt.%, preferably, from about 0 0.001 wt.% to about 0.1 wt.%, more preferably, from about 0.001 to about 0.0025 wt.%, based on the total weight of polyol to be prepared.
Mo-6961 -10-The number average molecular weight of the polyol prepared by the process of the present invention is in the range of from about 500 to about 100,000 g/mol, preferably, from about 1,000 to about 12,000 g/mol, more preferably, from about 2,000 to about 8,000 g/mol. Polyols prepared by the process of the present invention have average hydroxyl functionalities of from about 1 to 8, preferably, from about 2 to 6, and more preferably, from about 2 to 3.
DMC catalysts of the present invention can be used to produce polyols which have reduced levels of high molecular weight tail (greater than 400 K). The amount of high molecular weight tail is quantified by any suitable method. A particularly convenient way to measure the amount of high molecular weight tail is by gel permeation chromatography (GPC). A
suitable technique for measuring high molecular weight tail is described below as well as in, for example, United States Patent No. 6,013,596.
Those skilled in the art will recognize many variations in the illustrative examples, that are within the invention.
Examples A DMC catalyst which was prepared according to any one of Examples 1-16 set forth below was used to prepare a 6000 MW
polyoxypropylene triol by adding propylene oxide over 4 hours to an activated mixture composed of the DMC and a propoxylated glycerin starter (hydroxyl number = 240 mg KOH/g). Catalyst levels of 30 ppm were used.
The hydroxyl number, viscosity and unsaturation of each product were measured by standard methods. A gel permeation chromatography (GPC) technique as described in United States Patent No. 6,013,596, was used to measure the amount of polyol component having a number average molecular weight (Mn) from 40,000 to > 400,000. The amount present (in ppm) is recorded and the percent of high molecular weight (HMW) tail reduction of the catalyst for each range of molecular DOCSMTL: 4436718\1 Mo-6961 weight is calculated using the following formula (hereinafter referred to as "Formula I"):
% Reduction*
(HMW tail of comparative example - HMW tail of polyol prepared with a DMC catalyst of the present invention) X 100%/
HMW tail of comparative control * no reduction of HMW tail is obtained if the % reduction is less than zero.
Example 1 Preparation of a DMC catalyst using sodium chloride and a polyoxypropylene diol:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnCI2) was diluted with deionized water (230 g.) and tert-butyl alcohol (38 g.) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and sodium chloride (4 g.) were dissolved in a 500-ml beaker with deionized water (100 g) and tert-butyl alcohol (15.5 g.) (Solution 2).
Solution 3 was prepared by dissolving a 1000 mol. wt. polyoxypropylene diol (8 g.) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 1,500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 1,500 rpm for 20 min. The mixing was stopped. Solution 3 was then added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 t nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g) and sodium chloride (2 g) and mixed at 1,500 rpm for 20 min. The mixing was stopped. 1000 mol. wt.
polyoxypropylene diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was filtered as described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and mixed as described above. 1000 mol. wt. polyoxypropylene diol (1 g.) was added and the product was Mo-6961 filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Cobalt = 9 wt.%; Zinc = 21.7 wt.%; Sodium = 0.75 wt.%;
Cl = 6.1 wt.%
Example 2 Preparation of a DMC catalyst using lithium chloride and a polyoxypropylene diol:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnCl2) was diluted with deionized water (230 g.) and tert-butyl-alcohol (38 g.) in a one-liter stirred reactor. Lithium chloride (0.3 g.) was added to this solution (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-m1 beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 3 was prepared by dissolving a 1000 mol. wt.
polyoxypropylene diol (8 g.) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 1,500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling.
Following the addition, mixing continued at 1,500 rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g..), deionized water (55 g.) and lithium chloride (2 g.) and mixed at 1,500 rpm for 20 min. The mixing was stopped. 1000 mol. wt.
polyoxypropylene diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was filtered as described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and lithium chloride (0.5 g.) and mixed as described above. 1000 mol. wt. polyoxypropylene diol (1 g.) was added and the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Cobalt = 9.1 wt.%; Zinc = 21.9 wt. / ;
Mo-6961 Lithium = 0.15 wt.%; Cl = 4.8 wt.%
Example 3 Preparation of a DMC catalyst using sodium bromide and a polyoxypropylene diol:
The procedure of Example 2 was followed, except that NaBr was used in lieu of LiCI.
Elemental analysis: Cobalt = 8.1 wt.%; Zinc = 21.9 wt.%;
Sodium = 0.48 wt.%; CI = 3.8 wt.%; Br = 3.8 wt.%
Example 4 Preparation of a DMC catalyst using lithium bromide and a polyoxypropylene diol:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnCl2) was diluted with deionized water (230 g.) and tent-butyl alcohol (38 g.) in a one-liter stirred reactor. Lithium bromide (4 g.) was added to this solution (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-ml beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 3 was prepared by dissolving a 1000 mol. wt.
polyoxypropylene diol (8 g.) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 1,500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling.
Following the addition, mixing continued at 1,500 rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 nylon membrane. The catalyst cake was re-slurried in a mixture of tent-butyl alcohol (100 g.) and deionized water (55 g) and mixed at 1,500 rpm for 20 min. The mixing was stopped. 1000 mol. wt. polyoxypropylene diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was filtered as described above. The cake was re-slurried in tent-butyl alcohol (144 g.) and mixed as described above. 1000 rnol. wt. polyoxypropylene Mo-6961 diol (1 g.) was added and the product was filtered as described above.
The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in.
(Hg) to constant weight.
Elemental Analysis Zn = 23.4 wt.% ; Co = 10.8 wt.%; Li = <0.02 wt.%;
Br: 0.4 wt.%; Cl = 3.6 wt.%
Example 5 Preparation of a DMC catalyst using sodium chloride and a diol of propylene oxide and ethylene oxide copolymer:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnC12) was diluted with deionized water (230 g.) and tert-butyl alcohol (38 g.) in a one-liter stirred reactor. Sodium chloride (0.3 g.) was added to this solution (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-m1 beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 3 was prepared by dissolving 8 g. of a 4000 mol. wt.
diol of propylene oxide and ethylene oxide copolymer (80:20 wt. ratio) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 900 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 900 rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 p nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g.) and sodium chloride (2 g.) and mixed at 900 rpm for 20 min. The mixing was stopped. 4000 mol. wt. diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was filtered as described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and sodium chloride (1 g.) and mixed as described above.
4000 mol. wt. diol (1 g.) was added and the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Cobalt = 8.8 wt.%; Zinc = 20.3 wt.%; Sodium = 2.4 wt.%
Mo-6961 Example 6 Preparation of a DMC catalyst using potassium chloride and a polyoxypropylene diol:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnCl2) was diluted with deionized water (230 g.) and tent-butyl alcohol (38 g.) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and potassium chloride (4.0 g) were dissolved in a 500-ml beaker with deionized water (100 g.) and tent-butyl alcohol (15.5 g.) (Solution 2).
Solution 3 was prepared by dissolving 8 g. of a 1000 mol. wt.
polyoxypropylene diol (8 g.) in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution 1 over 45 min. while mixing at 500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling.
Following the addition, mixing continued at 500 rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 [t nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g.) and mixed at 500 rpm for 20 min.
The mixing was stopped. 1000 mol. wt. diol (2 g.) and potassium chloride (2 g) were added and the mixture was stirred slowly for 3 min. The catalyst was isolated as described above. The cake was re-slurried in tent-butyl alcohol (125 g) and deionized water (30 g) and was mixed at 500 rpm for 20 min. The mixing was stopped. 1000 mol. wt. diol (2 g) and potassium chloride (2 g) were added and the mixture was stirred slowly for 3 min. The catalyst was filtered as-described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and mixed as described above.
1000 mol. wt. diol (1 g.) was added and the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Co = 9.4 wt. %; Zn = 20 wt. %; K = 6.1 wt. %.
Mo-6961 Example 7 Preparation of a DMC catalyst using potassium chloride, a polyoxypropylene diol and a polystyrene-alt-maleic acid, sodium salt) (30 wt % in water):
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnC12) was diluted with deionized water (230 g.) and tent-butyl alcohol (38 g.) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and potassium chloride (4.0 g.) were dissolved in a 500-ml beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2).
Solution 3 was prepared by dissolving 8 g. of a 1000 mol. wt.
polyoxypropylene diol in deionized water (50 g.) and tert-butyl alcohol (2 g.). Solution 2 was added to Solution I over 45 min. while mixing at 500 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 500 rpm for 20 min. The mixing was stopped.
Solution 3 was added, followed by slow stirring for 3 min.
The reaction mixture was filtered at 40 psig through a 0.45 , nylon membrane. The catalyst cake was re-slurried in a mixture of potassium chloride (2 g.), tert-butyl alcohol (100 g.), poly(styrene-alt-maleic acid, sodium salt) solution (7 g.) and deionized water (55 g.) and mixed at 800 rpm for 20 min. The mixing was stopped. 1000 mol. wt. diol (2 g.) was added and the mixture was stirred slowly for 3 min. The catalyst was isolated as described above. The cake was re-slurried in tert-butyl alcohol (144 g.) and mixed as described above. More 1000 mol. wt. diol (1 g.) was added and the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental analysis: Co = 10.1 wt. %; Zn = 22.4 wt. %; K = 1.86 wt. %.
Example 8 Preparation of a DMC catalyst using potassium chloride, a polyoxypropylene diol and a poly(methacrylic acid, sodium salt) (30 wt % solution in water):
Mo-6961 The procedure of Example 7 was followed, except that poly(methacrylic acid, sodium salt) (30 wt % solution in water) was used in lieu of poly(styrene-alt-maleic acid, sodium salt) (30 wt % solution in water).
Elemental analysis: Co = 8 wt. %; Zn = 21.6 wt. %; K = 4.3 wt. %.
Example 9 Preparation of a DMC catalyst using sodium chloride but no functionalized polymer:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnC12) was diluted with deionized water (230 g.) and tert-butyl alcohol (38 g.) in a one-liter stirred reactor. Sodium chloride (0.3 g.) was added to this solution (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-m1 beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 2 was added to Solution I over 45 min. while mixing at 800 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 800 rpm for 20 min. The mixing was stopped.
The reaction mixture was filtered at 40 psig through a 0.65 nylon membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g.) and sodium chloride (2 g.) and mixed at 800 rpm for 20 min. The mixing was stopped. The catalyst was isolated as described above. The cake was re-slurried in tent-butyl alcohol (144 g.) and sodium chloride and mixed as described above. The product was isolated as described above. The resulting catalyst residue was dried in a vacuum oven at 60 C, 30 in. (Hg) to constant weight.
Elemental Analysis: Zn = 25.9 wt. %; Co = 12 wt. %; Na = 1.29 wt. %.
Example 10 (Comparative) Preparation of a DMC catalyst using a functionalized polymer but no salt:
The procedure of Example 1 was followed, except that no NaCl was added.
Elemental analysis: Cobalt = 9 wt. %; Zinc = 21.6 wt. %; CI = 4.1 wt.%
Mo-6961 Examples 11, 12 and 13 (all Comparative) Preparation of a DMC catalyst using a functionalized polymer but no salt:
For Comparative Examples 11, 12 and 13, DMC catalysts were prepared according to the procedure of Example 1, except that no NaCl was added.
Elemental analysis: Cobalt = 10.3 wt. %; Zinc = 23.2 wt. %; Cl = 4.0 wt.%;
K= 0.21 wt. %
Example 14 (Comparative) Preparation of a DMC catalyst using no functionalized polymer and no salt:
An aqueous zinc chloride solution (120 g. of 62.5 wt. % ZnC12) was diluted with deionized water (230 g.) and tert-butyl alcohol (38 g.) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in a 500-m1 beaker with deionized water (100 g.) and tert-butyl alcohol (15.5 g.) (Solution 2). Solution 2 was added to Solution 1 over 45 min. while mixing at 800 rpm. The reaction temperature was kept at 50 C during the course of the reaction by using an internal coil for heating or cooling. Following the addition, mixing continued at 800 rpm for min. The mixing was stopped.
The reaction mixture was filtered at 40 psig through a 0.65 nylon 20 membrane. The catalyst cake was re-slurried in a mixture of tert-butyl alcohol (100 g.), deionized water (55 g.) and mixed at 800 rpm for 20 min.
The mixing was stopped. The catalyst was isolated as described above.
The cake was re-slurried in tert-butyl alcohol (144 g.) and mixed as described above. The product was isolated as described above.
The resulting catalyst residue was dried in a vacuum oven at 60 C, in. (Hg) to constant weight.
Elemental Analysis: Co = 12.4 wt. %; Zn = 26.8 wt. %.
Example 15 Preparation of a DMC catalyst using sodium chloride and a block copolymer 30 of NEODOL-(EO)m-IBO:
The procedure of Example 5 was followed except that a block copolymer of NEODOL-(EO)m-IBO was used in lieu of the 1000 mol. wt.
*trade-mark Mo-6961 - 19 -diol. The block copolymer was prepared using NEODOL* (which is available commercially from Shell Chemical Company) as a starter and a DMC catalyst prepared essentially by the method of United States Patent No. 5,482,908 to produce a polyoxyethylene having a molecular weight of about 1000. This di-blockcopolymer was end-capped by 1-2 units of isobutylene oxide.
Example 16 (Comparative) Preparation of a DMC catalyst using zinc hexacyanocobaltate/t-butyl alcohol and a polyoxypropylene diol:
The procedure of Example 1 was followed, except that no NaCl was added.
Elemental analysis: Cobalt = 9 wt. %; Zinc = 21.6 wt. %
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Claims (16)
- Claim 1. A process for preparing a double-metal cyanide catalyst comprising:
combining i) at least one metal salt selected from the group consisting of zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, zinc propionate, zinc formate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate and mixtures thereof;
ii) at least one metal cyanide salt selected from the group consisting of potassium hexacyanocobaltate (III), potassium hexacyanoferrate(II), lithium hexacyanoiridate(III), lithium hexacyanocobaltate(III), sodium hexacyanocobaltate(III) and cesium hexacyanocobaltate(III);
iii) at least one organic complexing ligand;
and iv) at least one alkaline metal salt;
under conditions sufficient to form a catalyst;
and adding the at least one alkali metal salt to the resultant catalyst in an amount such that the catalyst contains the at least one alkali metal salt in an amount of from 0.4 to 6 wt.%, based on the total weight of the catalyst. - Claim 2. The process of Claim 1 in which the organic complexing ligand is selected from the group consisting of tert-butyl alcohol, ethanol, isopropanol, n-butanol, iso-butanol and sec-butanol.
- Claim 3. The process of Claim 1 in which the alkaline metal salt is selected from the group consisting of potassium chloride, sodium chloride, sodium bromide, lithium chloride and lithium bromide.
- Claim 4. The process of Claim 1, additionally comprising at least functionalized polymer.
- Claim 5. The process of Claim 4 in which the functionalized polymer is selected from the group consisting of a polyether; polyester;
polycarbonate; polyalkylene glycol sorbitan ester; polyalkylene glycol glycidyl ether; polyacrylamide; poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylic acid-co-maleic acid), poly(N-vinylpyrrolidone-co-acrylic acid), poly(acrylic acid-co-styrene) or their salts; maleic acid, styrene or maleic anhydride copolymers or their salts; polyacrylonitriles; polyalkyl acrylate; polyalkyl methacrylate; polyvinyl methyl ether; polyvinyl ethyl ether; polyvinyl acetate; polyvinyl alcohol; poly-N-vinylpyrrolidone;
polyvinyl methyl ketone; poly(4-vinylphenol); oxazoline polymer;
polyalkyleneimine; hydroxyethylcellulose; polyacetal; glycidyl ether;
glycoside; carboxylic acid ester of polyhydric alcohol; bile acid or its salt, ester or amide; cyclodextrin; phosphorus compound; unsaturated carboxylic acid ester; an ionic surface-active compound and an interface-active compound. - Claim 6. The process of Claim 4, the functionalized polymer is present in an amount in the range of from 2 to 98 wt. %, based on the total weight of the double-metal cyanide catalyst.
- Claim 7. A double-metal cyanide catalyst prepared by combining i) at least one metal salt selected from the group consisting of zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, zinc propionate, zinc formate, iron(II) sulfate, iron(II) bromide, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel(II) nitrate and mixtures thereof;
ii) at least one metal cyanide salt selected from the group consisting of potassium hexacyanocobaitate (III) potassium hexacyanoferrate(II), lithium hexacyanoiridate(III), lithium hexacyanocobaltate(III), sodium hexacyanocobaltate(III) and cesium hexacyanocobaltate(III);
iii) at least one organic complexing ligand;
and iv) at least one alkaline metal salt;
to form a catalyst;
and adding at least one alkali metal salt to the resultant catalyst in an amount such that the catalyst contains the at least one alkali metal salt in an amount of from 0.4 to 6 wt.%, based on the total weight of the catalyst. - Claim 8. The double metal cyanide catalyst of Claim 7 in which the organic complexing ligand is selected from the group consisting of tert-butyl alcohol, ethanol, isopropanol, n-butanol, iso-butanol and sec-butanol.
- Claim 9. The double metal cyanide catalyst of Claim 7 in which the alkaline metal salt is selected from the group consisting of potassium chloride, sodium chloride, sodium bromide, lithium chloride and lithium bromide.
- Claim 10. The double metal cyanide catalyst of Claim 7 additionally comprising at least functionalized polymer.
- Claim 11. The double metal cyanide catalyst of Claim 10 in which the functionalized polymer is selected from the group consisting of a polyether;
polyester; polycarbonate; polyalkylene glycol sorbitan ester; polyalkylene glycol glycidyl ether; polyacrylamide; poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylic acid-co-maleic acid), poly(N-vinylpyrrolidone-co-acrylic acid), poly(acrylic acid-co-styrene) or their salts; maleic acid, styrene or maleic anhydride copolymers or their salts; polyacrylonitriles; polyalkyl acrylate;
polyalkyl methacrylate; polyvinyl methyl ether; polyvinyl ethyl ether;
polyvinyl acetate; polyvinyl alcohol; poly-N-vinylpyrrolidone; polyvinyl methyl ketone;
poly(4-vinylphenol); oxazoline polymer; polyalkyleneimine;
hydroxyethylcellulose;
polyacetal; glycidyl ether; glycoside; carboxylic acid ester of polyhydric alcohol;
bile acid or its salt, ester or amide; cyclodextrin; phosphorus compound;
unsaturated carboxylic acid ester; an ionic surface-active compound and an interface-active compound. - Claim 12. The double-metal cyanide catalyst prepared by the process of Claim 10, wherein the functionalized polymer is present in an amount in the range of from 2 to 98 wt. %, based on the total weight of the double-metal cyanide catalyst.
- Claim 13. A process for preparing a polyol comprising:
combining i) at least one starter compound which has active hydrogen atoms; with ii) at least one oxide;
in the presence of iii) at least one double-metal cyanide catalyst of Claim 9;
under conditions sufficient to form a polyol. - Claim 14. A polyether polyol prepared by the process of Claim 13.
- Claim 15. A polyester polyol prepared by the process of Claim 13.
- Claim 16. A polyetherester polyol prepared by the process of Claim 13.
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US10/251,155 US6696383B1 (en) | 2002-09-20 | 2002-09-20 | Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto |
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EP1400281A1 (en) | 2004-03-24 |
US20040102314A1 (en) | 2004-05-27 |
JP2004114037A (en) | 2004-04-15 |
ATE475479T1 (en) | 2010-08-15 |
US6867162B2 (en) | 2005-03-15 |
JP4949605B2 (en) | 2012-06-13 |
SG107154A1 (en) | 2004-11-29 |
CN1331600C (en) | 2007-08-15 |
BR0304147A (en) | 2004-09-08 |
PL362241A1 (en) | 2004-03-22 |
CA2441185A1 (en) | 2004-03-20 |
MXPA03008434A (en) | 2004-10-29 |
RU2003128081A (en) | 2005-03-27 |
RU2341328C2 (en) | 2008-12-20 |
CN101077480A (en) | 2007-11-28 |
US7223832B2 (en) | 2007-05-29 |
EP1400281B1 (en) | 2010-07-28 |
BR0304147B1 (en) | 2013-10-01 |
KR20040025838A (en) | 2004-03-26 |
KR101065163B1 (en) | 2011-09-15 |
DE60333524D1 (en) | 2010-09-09 |
HK1065739A1 (en) | 2005-03-04 |
US20040116281A1 (en) | 2004-06-17 |
US6696383B1 (en) | 2004-02-24 |
CN1494946A (en) | 2004-05-12 |
ES2347868T3 (en) | 2010-11-24 |
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