Process for preparing highly active double metal cyanide catalysts and their use in the synthesis of polyether polyols

Patent metadata

Field	Value
Publication number	US-9605111-B2
Application number	US-201514944648-A
Country	US
Kind code	B2
Filing date	Nov 18, 2015
Priority date	May 17, 2011
Publication date	Mar 28, 2017
Grant date	Mar 28, 2017

Abstract

The present invention relates to a double metal cyanide (DMC) complex catalyst with an improved catalytic activity useful for epoxide polymerization. It also relates to polyether polyols prepared by a polymerization reaction using said DMC catalyst.

First claim

The invention claimed is:

1. A double metal cyanide complex catalyst produced by a process comprising:
a) synthesizing a solid double metal cyanide catalyst in the presence of an organic complexing agent and a polyether polyol ligand; and
b) first washing the catalyst obtained in step a) with an aqueous solution comprising:
90-100% by weight of water; and
0-10% by weight of a polyether polyol,
to form a slurry, wherein the aqueous solution does not contain any organic complexing agent.

2. The double metal cyanide complex catalyst according to claim 1 , wherein the process further comprises:
c) isolating the catalyst from the slurry obtained in step b); and
d) washing the solid catalyst obtained in step c) with a solution comprising:
90-100% by weight of an organic complexing agent; and
0-10% by weight of a polyether polyol,
to form a slurry.

3. The double metal cyanide complex catalyst according to claim 1 , wherein the synthesis of step a) comprises:
producing a catalyst slurry by reacting an aqueous solution of a metal salt with an aqueous solution of a metal cyanide salt in the presence of an organic complexing agent;
combining the catalyst slurry with a polyether polyol ligand; and
isolating a polyether-containing solid catalyst from the slurry.

4. The double metal cyanide complex catalyst according to claim 1 , wherein the polyether polyol ligand is synthesized by acidic catalysis.

5. The double metal cyanide complex catalyst according to claim 1 , wherein the polyether polyol is a diol or a triol, having number average molecular weight lower than 2000.

6. The double metal cyanide complex catalyst according to claim 1 , wherein the organic complexing agent is selected from monoalcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof.

7. The double metal cyanide complex catalyst according to claim 3 , wherein the metal salt is selected from zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt (II) thiocyanate, nickel (II) formate, nickel (II) nitrate and mixtures thereof.

8. The double metal cyanide complex catalyst according to claim 3 , wherein the metal cyanide salt is selected from potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III) and calcium hexacyanocobaltate (III).

9. The double metal cyanide complex catalyst according to claim 1 , wherein the synthesis of solid double metal cyanide catalyst is carried out at a temperature ranging from 30 to 70° C.

10. The double metal cyanide complex catalyst according to claim 1 , which comprises:
at least one double metal cyanide;
at least one organic complexing agent; and
at least one polyether polyol ligand having a number average molecular weight lower than 2000.

11. A process for polymerizing an epoxide, said process comprising reacting an epoxide and a hydroxyl group-containing initiator in the presence of a catalyst as defined in claim 1 .

12. The process according to claim 11 , wherein the hydroxyl group-containing initiator is a polyether polyol obtained by acidic catalysis.

13. The process according to claim 11 , wherein the polymerization is carried at a temperature higher than 110° C.

14. A polyether polyol produced by a process as defined in claim 11 .

15. The double metal cyanide complex catalyst according to claim 2 , wherein the organic complexing agent is selected from monoalcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides and mixtures thereof.

Assignees

• Repsol Sa

Inventors

• Blanco Gonzalez Maria Dolores
• Prieto Noguera Fernando

Classifications

• B01J31/0212

  Alkoxylates · CPC title

• B01J2231/14

  Other (co) polymerisation, e.g. of lactides or epoxides · CPC title

• B01J2531/845

  Cobalt · CPC title

• C08G65/2663 Primary

  Metal cyanide catalysts, i.e. DMC's · CPC title

• B01J2531/26

  Zinc · CPC title