Process for preparing double metal cyanide catalysts

Patent metadata

Field	Value
Publication number	US-12370535-B2
Application number	US-202117797161-A
Country	US
Kind code	B2
Filing date	Feb 17, 2021
Priority date	Feb 22, 2020
Publication date	Jul 29, 2025
Grant date	Jul 29, 2025

Abstract

The present invention relates to a process for preparing a double metal cyanide (DMC) catalyst, comprising the reaction of an aqueous solution of a cyanide-free metal salt, an aqueous solution of an alkaline metal cyanide salt, an organic complex ligand and optionally a complex-forming component, wherein the metal cyanide salt is one or more compound(s) and is selected from the group consisting of potassium hexacyanocobaltat(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III) and lithium hexacyanocobaltat(III), where the organic complex ligand is one or more compound(s) and is selected from the group consisting of dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether and 3-methyl-3-oxetanemethanol, and wherein the alkaline metal cyanide salt used has an alkalinity by the titration method disclosed in the Experimental of between 0.700% and 3.000% by weight of sodium hydroxide (NaOH) based on the total weight of the alkaline metal cyanide salt used. The invention further relates to double metal cyanide (DMC) catalysts obtainable by the process according to the invention and to the use of DMC catalysts for preparation of polyoxyalkylene polyols.

First claim

The invention claimed is:

1. A process for preparing a double metal cyanide catalyst (DMC) comprising reacting an aqueous solution of a cyanide-free metal salt, an aqueous solution of an alkaline metal cyanide salt, an organic complex ligand and optionally a complex-forming component, wherein the metal cyanide salt comprises potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III), lithium hexacyanocobaltate (III) or a mixture thereof,
wherein the organic complex ligand comprises dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether, 3-methyl-3-oxetanemethanol, or a mixture thereof, and
wherein the alkaline metal cyanide salt has an alkalinity, determined at 25° C. on a 24% by weight aqueous solution by titration with 0.1 mol/liter of hydrochloric acid, of between 0.700% and 3.000% by weight sodium hydroxide, based on the total weight of the alkaline metal cyanide salt used, and
wherein the alkaline metal cyanide salt contains a metal hydroxide, a metal carbonate, a metal oxide, or a mixture of any two or more thereof and is obtained by addition of the metal hydroxide, the metal carbonate, the metal oxide, or the mixture of any two or more thereof, during the preparation of the alkaline metal cyanide salt.

2. The process as claimed in claim 1 , wherein the alkalinity of the alkaline metal cyanide salt is between 0.700% and 2.000% by weight NaOH.

3. The process as claimed in claim 2 , wherein the alkalinity of the alkaline metal cyanide salt is between 0.800% and 1.500% by weight NaOH.

4. The process as claimed in claim 1 , wherein the alkaline metal cyanide salt is obtained by reaction of a metal cyanide salt with the metal hydroxide, the metal carbonate, the metal oxide, or the mixture of any two or more thereof.

5. The process as claimed in claim 4 , wherein the metal cyanide salt comprises potassium hexacyanocobaltate (III).

6. The process as claimed in claim 1 , wherein one or more metals of the first or second main group of the periodic table of the elements are present in the alkaline metal cyanide salt.

7. The process as claimed in claim 1 , wherein the metal hydroxide, metal oxide, metal carbonate, or mixture of any two or more thereof comprises sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, calcium oxide, calcium hydroxide, barium hydroxide, barium oxide, or a mixture of any two or more thereof.

8. The process as claimed in claim 7 , wherein the reaction is effected in the presence of the metal hydroxide, the metal carbonate, the metal oxide, or the mixture of any two or more thereof.

9. The process as claimed in claim 7 , wherein, for the reaction, 0.2 to 1.0 mol of base equivalents, based on 1 mol of the alkaline metal cyanide salt used for the catalyst synthesis, of metal hydroxide, metal carbonate, metal oxide, or mixture of any two or more thereof is used.

10. The process as claimed in claim 9 , wherein, for the reaction, 0.3 to 0.7 mol, of base equivalents, based on 1 mol of the alkaline metal cyanide salt used for the catalyst synthesis, of metal hydroxide, metal carbonate, metal oxide, or mixture of any two or more thereof is used.

11. The process as claimed in claim 1 wherein the aqueous solution comprises the complex-forming component, wherein the complex-forming component comprises a polyether.

12. The process as claimed in claim 11 , wherein the complex-forming component comprises a polyether polyol.

13. The process as claimed in claim 1 , wherein the organic complex ligand comprises tert-butanol.

14. The process as claimed in claim 1 , wherein the reaction is effected using a mixing nozzle.

15. The process as claimed in claim 14 , wherein the mixing nozzle comprises a jet disperser.

16. A double metal cyanide catalyst (DMC) obtained by the process of claim 1 .

17. A polyoxyalkylene polyol prepared using the double metal cyanide catalyst of claim 16 .

18. The polyoxyalkylene polyol of claim 17 , wherein the polyoxyalkylene polyol comprises a polyether polyol and/or polyethercarbonate polyol.

19. A process for preparing a double metal cyanide catalyst (DMC) comprising reacting an aqueous solution of a cyanide-free metal salt, an aqueous solution of an alkaline metal cyanide salt, an organic complex ligand and a complex-forming component comprising a polyether polyol, wherein the metal cyanide salt comprises potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III), lithium hexacyanocobaltate (III) or a mixture thereof,
wherein the organic complex ligand comprises dimethoxyethane, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether, 3-methyl-3-oxetanemethanol, or a mixture thereof, and
wherein the alkaline metal cyanide salt has an alkalinity, determined at 25° C. on a 24% by weight aqueous solution by titration with 0.1 mol/liter of hydrochloric acid, of between 0.700% and 3.000% by weight sodium hydroxide, based on the total weight of the alkaline metal cyanide salt used, and
wherein the alkaline metal cyanide salt contains a metal hydroxide, a metal carbonate, a metal oxide, or a mixture of any two or more thereof.

Assignees

• Covestro Deutschland Ag

Inventors

• Hofmann Joerg
• Gleixner Maria
• Asma Thomas

Classifications

• C08G65/2663

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

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• C08G65/2609

  containing aliphatic hydroxyl groups · CPC title

• B01J2531/845

  Cobalt · CPC title

• B01J2531/26

  Zinc · CPC title