Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto

• US 6,696,383 B1
• Filed: 09/20/2002
• Issued: 02/24/2004
• Est. Priority Date: 09/20/2002
• Status: Expired due to Term

• Current Assignee: Covestro LLC (Covestro AG)
• Original Assignee: Bayer Antwerpen NV (Bayer AG), Bayer Healthcare LLC (Bayer AG)
• Inventors: Le-Khac, Bi, Wang, Wei
• Primary Examiner(s): WOOD, ELIZABETH D
• Application Number:
  US10/251,155
• Time in Patent Office: 522 Days
• Field of Search: 502/175, 502/200
• US Class Current: 502/175
• CPC Class Codes: B01J 2231/10 Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
• CPC Class Codes: B01J 2531/0205 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
• CPC Class Codes: B01J 2531/26 Zinc
• CPC Class Codes: B01J 2531/827 Iridium
• CPC Class Codes: B01J 2531/84 Metals of the iron group
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 27/26 Cyanides
• CPC Class Codes: B01J 31/165 Polymer immobilised coordination complexes, e.g. organometallic complexes
• CPC Class Codes: B01J 31/1805 the ligands containing nitrogen
• CPC Class Codes: B01J 31/2208 Oxygen, e.g. acetylacetonates
• CPC Class Codes: B01J 31/2234 Beta-dicarbonyl ligands, e.g. acetylacetonates
• CPC Class Codes: B01J 31/26 containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• CPC Class Codes: B01J 31/28 of the platinum group metals, iron group metals or copper
• CPC Class Codes: C08G 65/2663 Metal cyanide catalysts, i.e. DMC's
• CPC Class Codes: Y02E 60/10 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 prepared according to the process of 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 weight tail.

Claims

1. A double-metal cyanide catalyst prepared by

combining

at least one metal salt,

at least one metal cyanide salt,

at least one organic complexing ligand,

at least one alkali metal salt, and

optionally, at least one functionalized polymer,

under conditions sufficient to form a catalyst;

and

adding the at least one alkali metal salt to the catalyst so formed in an amount such that the catalyst includes the at least one alkali metal salt in an amount of from about 0.4 to about 6 wt. % based on the total weight of the catalyst.

2. The double metal cyanide catalyst of claim 1, wherein the at least one metal salt is 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.

3. The double metal cyanide catalyst of claim 1, wherein the at least one metal cyanide salt is selected from the group consisting of potassium hexacyanocobaltate (III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), lithium hexacyanoiridate(III), lithium hexacyanocobaltate(III), sodium hexacyanocobaltate(III) and cesium hexacyanocobaltate(III).

4. The double metal cyanide catalyst of claim 1, wherein the at least one organic complexing ligand is selected from the group consisting of ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol and tert-butyl alcohol.

5. The double metal cyanide catalyst of claim 1, wherein the at least one alkali metal salt is selected from the group consisting of potassium chloride, sodium chloride, sodium bromide, lithium chloride and lithium bromide.

6. The double metal cyanide catalyst of claim 1, wherein the at least one functionalized polymer is present In an amount in the range of from about 2 to about 98 wt. %, based on the total weight of the double-metal cyanide catalyst.

7. The double metal cyanide catalyst of claim 1, wherein the at least one functionalized polymer is 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;

or an ionic surface or interface-active compound.

8. A process for preparing a double-metal cyanide catalyst comprising:

combining

at least one metal salt;

at least one metal cyanide salt;

at least one organic complexing ligand;

at least one alkali metal salt; and

optionally, at least one functionalized polymer;

under conditions sufficient to form a catalyst; and

adding at least one alkali metal salt to the catalyst so formed in an amount such that the catalyst includes the at least one alkali metal salt in an amount of from about 0.4 to about 6 wt. % based on the total weight of the catalyst.

9. The process of claim 8, wherein the at least one metal salt is 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.

10. The process of claim 8, wherein the at least one metal cyanide salt is selected from the group consisting of potassium hexacyanocobaltate (III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), lithium hexacyanoiridate(III), lithium hexacyanocobaltate(III), sodium hexacyanocobaltate(III) and cesium hexacyanocobaltate(III).

11. The process of claim 8, wherein the at least one organ complexing ligand is selected from the group consisting of ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol and tert-butyl alcohol.

12. The process of claim 8, wherein the at least one alkaline metal salt is selected from the group consisting of potassium chloride, sodium chloride, sodium bromide, lithium chloride and lithium bromide.

13. The process of claim 8, wherein the at least one functionalized polymer is present in an amount in the range of from about 2 to about 98 wt. %, based on the total weight of the double-metal cyanide catalyst.

14. The process of claim 8, wherein the at least one functionalized polymer is 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;

or an ionic surface- or interface-active compound.