Process for the preparation of polyether carbonate polyols

Patent metadata

Field	Value
Publication number	US-9045592-B2
Application number	US-201113821254-A
Country	US
Kind code	B2
Filing date	Sep 6, 2011
Priority date	Sep 9, 2010
Publication date	Jun 2, 2015
Grant date	Jun 2, 2015

Abstract

The present invention relates to a process for the preparation of polyether carbonate polyols from one or more alkylene oxides, carbon dioxide and optionally from one or more H-functional starter substances in the presence of at least one double metal cyanide catalyst, wherein the double metal cyanide catalyst comprises an unsaturated alcohol as a complexing ligand.

First claim

The invention claimed is:

1. A process for the preparation of polyether carbonate polyols comprising reacting one or more alkylene oxides and carbon dioxide in the presence of at least one double metal cyanide catalyst, wherein the double metal cyanide catalyst comprises an unsaturated alcohol as a complexing ligand.

2. The process according to claim 1 comprising reacting of one or more alkylene oxides, carbon dioxide and one or more H-functional starter substances in the presence of at least one double metal cyanide catalyst, wherein the double metal cyanide catalyst comprises an unsaturated alcohol as a complexing ligand.

3. The process according to claim 1 , wherein the double metal cyanide catalyst comprises an unsaturated alcohol of the formula (R 1 )(R 2 )(R 3 )C(OH), wherein R 1 is a hydrocarbon group of 2 to 20 carbon atoms having at least one C═C and/or at least one C≡C group and R 2 and R 3 independently of each other are hydrogen, C 1 to C 20 -alkyl, C 3 to C 12 -cycloalkyl, phenyl or a hydrocarbon group of 2 to 20 carbon atoms having at least one C═C and/or at least one C≡C group.

4. The process according to claim 1 , wherein the double metal cyanide catalyst comprises as the unsaturated alcohol 3-buten-1-ol, 3-butyn-1-ol, 2-propen-1-ol, 2-propyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, 3-buten-1-ol, 3-butyn-1-ol, 3-methyl-1-penten-3-ol or 3-methyl-1-pentyn-3-ol or derivative thereof, wherein one or more of the hydrogen atoms in the unsaturated alcohols is replaced by halogen atoms.

5. The process according to claim 1 , wherein the double metal cyanide catalyst comprises 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol or 3-methyl-1-pentyn-3-ol as the unsaturated alcohol.

6. The process according to claim 1 , wherein the double metal cyanide catalyst comprises 3-methyl-1-pentyn-3-ol as the unsaturated alcohol.

7. The process according to claim 1 , wherein the double metal cyanide catalyst is prepared by a procedure comprising:
(i) in a first step, reacting an aqueous solution of a cyanide-free metal salt with an aqueous solution of a metal cyanide salt in the presence of one or more organic complexing ligands, wherein one or more unsaturated alcohols is contained either in the aqueous solution of the cyanide-free metal salt, the aqueous solution of the metal cyanide salt or in both aqueous solutions,
(ii) in a second step, separating a solid from a suspension obtained from (i),
(iii) in a third step, washing the solid isolated from (ii) with an aqueous solution of an organic complexing ligand in the absence or presence of at least one unsaturated alcohol,
(iv) drying the solid obtained from (iii),
wherein in the first step or immediately after the second step, one or more organic complexing ligands are added.

8. The process according to claim 7 , wherein in the first step or immediately after the second step, one or more organic complexing ligands and one or more unsaturated alcohols are added.

9. The process according to claim 7 , wherein the cyanide-free metal salt is at least one metal salt selected from the group consisting of zinc chloride, zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron(II) sulfate, iron(II) bromide, iron(II) chloride, cobalt(II) chloride, cobalt(II) thiocyanate, nickel(II) chloride and nickel(II) nitrate.

10. The process according to claim 7 , wherein the cyanide-free metal salt is zinc chloride, zinc bromide or a mixture of zinc chloride and zinc bromide.

11. The process according to claim 7 , wherein the metal cyanide salt is at least one metal salt selected from the group consisting of potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), calcium hexacyanocobaltate(III) and lithium hexacyanocobaltate(III).

12. The process according to claim 2 , wherein
(a) the H-functional starter substance or a mixture of at least two H-functional starter substances is introduced into a reaction vessel and water and/or other readily volatile compounds are removed by drying, the double metal cyanide catalyst, the H-functional starter substance or the mixture of the at least two H-functional starter substances being added to the reaction vessel before or after the drying, and
(b) at least one alkylene oxide and carbon dioxide are added to the mixture resulting from step (a).

13. The process according to claim 2 , wherein
(a) the H-functional starter substance or a mixture of at least two H-functional starter substances is introduced into a reaction vessel and water and/or other readily volatile compounds are removed through drying by elevated temperature and/or reduced pressure, the double metal cyanide catalyst being added to the H-functional starter substance or the mixture of at least two H-functional starter substances before or after the drying,
(b) activation of the one or more alkylene oxides proceeds by the following first and second activation steps:
(b1) in a first activation step, adding to the mixture resulting from step (a) a first part amount of the one or more alkylene oxides based on the total amount of alkylene oxides employed in the activation and copolymerization of said one or more alkylene oxides in the process of reacting said alkylene oxides, wherein the addition of said part amount of the one or more alkylene oxides is optionally carried out in the presence of CO 2 ;
(b2) in a second activation step, after a temperature peak is reached in the first activation step, which temperature peak occurs due to an exothermic chemical reaction and/or a drop in pressure in the reaction vessel, adding to the mixture resulting from the first activation step a second part amount of the one or more alkylene oxides based on the total amount of the alkylene oxides employed in the activation and copolymerization of said one or more alkylene oxides in the process of reacting said alkylene oxides, wherein the addition of said part amount of the one or more alkylene oxides is optionally carried out in the presence of CO 2 ;

(c) adding one or more alkylene oxides and carbon dioxide to the mixture resulting from step (b).

14. The process according to claim 1 , wherein the double metal cyanide catalyst comprises no hexanitrometallate units [M 2 (NO 2 ) 6 ] 3− , wherein M 2 is a trivalent transition metal ion.

Assignees

• Gürtler Christoph
• Hofmann Jörg
• Wolf Aurel
• Grasser Stefan
• Bayer Ip Gmbh

Inventors

• Gürtler Christoph
• Hofmann Jörg
• Wolf Aurel
• Grasser Stefan

Classifications

• C08G64/183

  containing polyether sequences · CPC title

• C08G65/2663

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

• C08G65/2603

  the other compounds containing oxygen · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G65/26

  from cyclic ethers and other compounds · CPC title