TH53983A - Thymethylxyanide catalyst Modified type with compound for complex composition - Google Patents

Abstract

DC60 (26/09/43) Metal complexes [hexacyanocobaltate, cobalt hexanitrite, nitroferosiside] are useful catalysts for alkylene oxide polymerization reactions. This metal is any metal that forms a precipitate with hexacyanocobaltate, cobalt hexanitrite, and nitroferosiside groups. These catalysts can be prepared from less expensive starting materials than ordinary zinc hexacyanocobaltate catalysts, and provide short induction times and, in many examples, are more controllable exothermic reactions. Furthermore, metal complexes [hexacyanocobaltate, cobalt hexanitrite, nitroferosiside] often yield polymers of poly(propylene oxide) that are very unsaturated, even when catalysts are applied. This reaction involves the formation of complexes with compounding agents, such as glyma. Metal complexes [hexacyanocobaltate, cobalt hexanitrite, nitroferosiside] are useful catalysts for the polymerization reactions of alkylene oxides. This metal is any metal that forms a precipitate with a hexacyanocobaltate, cobalt hexanitrite, or nitroferosiside group. These catalysts can be prepared from less expensive starting materials than ordinary zinc hexacyanocobaltate catalysts, and provide short induction times and, in many examples, are more controllable exothermic reactions. Furthermore, metal catalysts [hexacyanocobaltate, cobalt hexanitrite, nitroferricyclide] often yield poly(propylene oxide) polymers with very low unsaturation, even when these catalysts are complexed with complexing agents such as glymph.

Claims (17)

1. A metal catalyst, hexacyanocobaltate, cobalt hexanitrite, nitroferosisianide, which forms a complex with one or more organic complex compounds in which (a) this metal is any type that forms an insoluble precipitate with a hexacyanocobaltate, cobalt hexanitrite group. (b) the molar ratio of the hexacyanocobaltate group to the cobalt hexanitrite group is approximately 1:0.1-1.0, (c) the molar ratio of the hexacyanocobaltate group to the nitroferosisiide group is from approximately 1:0.1-1.0, and (d) the molar ratio of the hexacyanocobaltate group to the cobalt hexanitrite and nitroferosisiide group combined is approximately 1:0.5-1.5. 2. The catalyst for claim 1, which in this case is zinc. 3. The catalyst for claim 2, in which the molar ratio of hexacyanocobaltate ion to cobalt hexanitrite ion is approximately 1:0.15-0.6, the molar ratio of hexacyanocobaltate ion to nitroferosisianide ion is approximately 1:0.3-0.8, and the molar ratio of hexacyanocobaltate to the molar ratio of cobalt hexanitrite and nitroferosisianide groups combined is approximately 1:0.8-1.1. 4. The catalyst for claim 3, in this case the complex-forming compound is t-butanol, 1-t-butoxy-2-propanol, dimethyl sulfoxide, polyether polyol with an equivalent weight of approximately 75-350, or dialkyl ether of alkylene or polyalkylenol. 5. In the polymerization process of epoxide compounds containing a catalyst, the enhancement of which the catalyst is, in this case, the metal hexacyanocobaltate, cobalthexanitrite, or nitroferosisianide, which forms a complex with one or more organic complexing compounds, where such metal is any metal that forms an insoluble precipitate with the hexacyanocobaltate, cobalthexanitrite, and nitroferosisianide groups. 6. An improved methodology for claim 5, in which case this epoxide compound is propylene oxide or a mixture of propylene oxide and ethylene oxide up to approximately 15 percent by weight. 7. An improved process for claim 6, in which the product of this process is a polyether with an equivalent hydroxyl weight from approximately 800 to approximately 5000. 8. An improved methodology for claim 7, in which the polyether has no more than 0.02 millismum/gram of unsaturated fatty acids. 9. An improved methodology for claim 8, in which the polyether has no more than 0.01 millismum/gram of unsaturated fatty acids. 10. Improved processing of claim number 8, in which the metal is zinc. 11. An improved method for claim 10 in which the molar ratio of hexacyanocobaltate to cobalt hexanitrite is approximately 1:0.15-0.6, the molar ratio of hexacyanocobaltate to nitroferroxyanide ions is approximately 1:0.3-0.8, and the molar ratio of the hexacyanocobaltate group to the molar ratio of the cobalt hexanitrite and nitroferroxyanide groups combined is approximately 1:0.8-1.1. 12. The catalyst for claim 11, in this case the complexing agent is t-butanol, 1-t-butoxy-2-propanol, dimethyl sulfoxide, polyether polyol with an equivalent weight of approximately 75-350, or dialkyl ether of alkylene and polyalkylene glycol. 13. Methods for catalyzing the reactive polymerization reaction, which consist of (a) the preparation of a solution type 1 of aqueous hexacyanocobaltate, cobalthexanitrite, and nitroferrizzianide compounds, the said hexacyanocobaltate, cobalthexanitrite, and nitroferrizzianide compounds in proportions until the solution has a molar ratio of hexacyanocobaltate to cobalthexanitrite ions of approximately 1:0.1-1.0, a molar ratio of hexacyanocobaltate to nitroferrizzianide ions of approximately 1:0.1-1.0, and a molar ratio of hexacyanocobaltate to cobalthexanitrite and nitroferrizzianide groups of approximately 1:0.1-1.0. (b) mixing of the above solution type 1 and solution type 2 of the water-soluble metal salts, in which insoluble precipitates are formed with hexacyanocobaltate, cobalt hexanytrite, and nitroferrizianide groups until the precipitates of the hexacyanocobaltate, cobalt hexanytrite, and nitroferrizianide metals, and (c) either simultaneously or after step (b), contact of the above hexacyanocobaltate, cobalt hexanytrite, and nitroferrizianide metals with the organic compounds for complex formation and, if the stoichiometric use of the metal salts in step (b) is not sufficient, additional amounts of the metal salts are added. 14. Procedure of Claim 13, in which the aqueously soluble compounds hexacyanocobaltate, cobalt hexanitrite, and nitroferrizianides are represented by the structures B3[Co(CN)6], B3[Co(NO2)6], and B2[Fe(CN)5NO], respectively, where B is hydrogen or an alkali metal. 15. The procedure for claim number 14, in which the metal is zinc. 16. The procedure of claim 15, where the molar ratio of hexacyanocobaltate ion to cobalt hexanyrite ion is approximately 1:0.15-0.6, the molar ratio of hexacyanocobaltate to nitroferosisianide ion is approximately 1:0.3-0.8, and the molar ratio of the hexacyanocobaltate group to the molar ratio of the cobalt hexanyrite and nitroferosisianide groups combined is approximately 1:0.8-1.1. 17. The procedure for claim 16, in which case the compounds are t-butanol, 1-t-butoxy-2-propanol, dimethyl sulfoxide, polyether polyols with an equivalent weight of approximately 75-350, or dialkyl ethers of alkylene and polyalkylenes glycol.