Method for producing double metal cyanide catalysts

Patent metadata

Field	Value
Publication number	US-11976165-B2
Application number	US-202117791287-A
Country	US
Kind code	B2
Filing date	Jan 11, 2021
Priority date	Jan 21, 2020
Publication date	May 7, 2024
Grant date	May 7, 2024

Abstract

The present invention relates to a method for producing a double metal cyanide (DMC) catalyst, comprising the reaction of an aqueous solution of a cyanide-free metal salt, an aqueous solution of a metal cyanide salt, an organic complex ligand, optionally a complex-forming component to form a dispersion, the dispersion being produced using a mixing nozzle and a peroxide. The invention further relates to double metal cyanide (DMC) catalysts obtainable by means of the method according to the invention and to the use of DMC catalysts to produce polyoxyalkylene polyols.

First claim

The invention claimed is:

1. A process for preparing a double metal cyanide (DMC) catalyst comprising:
(i) reacting, in the presence of a peroxide, an aqueous solution of a cyanide-free metal salt, an aqueous solution of a metal cyanide salt, an organic complex ligand, and optionally a complex-forming component, to form a dispersion;
(ii) separating a solid from the dispersion obtained from (i) thereby providing an isolated solid;
(iii) washing the isolated solid by means of redispersion or filtercake washing to obtain a washed isolated solid, and
(iv) drying the washed isolated solid to obtain the DMC catalyst,
wherein the reaction in step i) is effected using a mixing nozzle,
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 double metal cyanide compounds of the formula (I) are present in the DMC catalyst
M x [M′ x ,(CN) y ] z   (I),

where
M comprises Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sr(II), Sn(II), Pb(II), Cu(II), or a mixture thereof
and
M′ comprises Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), V(V), or a mixture thereof
and

x, x′, y and z are integers and are selected such as to ensure the electronic neutrality of the double metal cyanide compound.

2. The process as claimed in claim 1 , wherein the peroxide and the organic complex ligand are used in a weight ratio of from 2:98 to 30:70.

3. The process as claimed in claim 1 , wherein the peroxide comprises an organic peroxide.

4. The process as claimed in claim 3 , wherein the organic peroxide comprises dibenzoyl peroxide, dilauroyl peroxide, acetylacetone peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide, di(2-tert-butylperoxyisopropyl)benzene, tert-butyl cumyl peroxide, di-tert-amyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,2-di(tert-butylperoxy)butane, tert-butyl peroxybenzoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, di(4-tert-butylcyclohexyl) peroxydicarbonate, tert-butyl peroxy-2-ethylhexylcarbonate, tert-butyl peroxyisopropylcarbonate, 1,3 1,4-bis(tert-butylperoxyisopropyl)benzene, tert-butyl cumyl peroxide, 2,5-di(tert-butylperoxy)-2,5-dimethylhexane, n-butyl 4,4′-di(tert-butylperoxy)valerate, di(2,4-dichlorobenzoyl) peroxide, tert-butyl peroxybenzoate, butyl 4,4-di(tert-butylperoxy)valerate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, di-tert-butyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyisobutyrate, tert-amyl peroxypivalate, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and dicumyl peroxide, or a mixture thereof.

5. The process as claimed in claim 4 , wherein the organic peroxide comprises tert-amyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, dibenzoyl peroxide, or a mixture thereof.

6. The process as claimed in claim 1 , wherein the peroxide comprises an inorganic peroxide.

7. The process as claimed in claim 6 , wherein the inorganic peroxide comprises hydrogen peroxide, a peroxoborate, a peroxocarbonate, a peroxochlorate, a peroxodiphosphate, peroxodiphosphoric acid, peroxodisulfuric acid, a peroxodisulfate, peroxodisulfuryl difluoride, a peroxohyponitrite, peroxocarbonic acid, a peroxonitrate, a peroxomolybdate, a peroxomonophosphate, peroxomonophosphoric acid, peroxonitric acid, peroxomonosulfuric acid, a peroxomonosulfate, a peroxotungstate, or a mixture thereof.

8. The process as claimed in claim 1 , wherein a complex-forming component is used.

9. The process as claimed in claim 8 , wherein the complex-forming component comprises a polyether.

10. The process as claimed in claim 1 , wherein the double metal cyanide compound comprises zinc hexacyanocobaltate(III), zinc hexacyanoiridate(III), zinc hexacyanoferrate(III), cobalt(II) hexacyanocobaltate(III), or a mixture thereof.

11. The process as claimed in claim 1 , wherein, in step (iii), the isolated solid is washed by means of filtercake washing with an aqueous solution of the organic complex ligand.

12. The process as claimed in claim 1 , wherein the mixing nozzle comprises a jet disperser.

13. The process as claimed in claim 1 , wherein the process temperature of the dispersion during the reaction in step i) is between 26° C. and 49° C.

14. A DMC catalyst obtained in accordance with claim 1 .

15. A process of preparing a polyoxyalkylene polyol by polyaddition of an alkylene oxide onto a starter compound having active hydrogen atoms, wherein the polyaddition takes place in the presence of the DMC catalyst as claimed in claim 14 .

16. The process of claim 1 , wherein x=3, x′=1, y=6 and z=2.

17. The process of claim 1 , wherein M comprises Zn(II), Fe(II), Co(II), Ni(II), or a mixture thereof, and M′ comprises Co(III), Fe(III), Cr(III), Ir(III), or a mixture thereof.

18. The process of claim 2 , wherein the peroxide and the organic complex ligand used in a weight ratio of from 5:95 to 20:80, based on the organic complex ligand.

19. The process as claimed in claim 9 , wherein the polyether comprises a polyether polyol.

20. The process as claimed in claim 10 , wherein the double metal cyanide compound comprises zinc hexacyanocobaltate(III).

Assignees

• Covestro Deutschland Ag

Inventors

• Hofmann Joerg
• Lorenz Klaus
• Vogelsang Elisabeth
• Gleixner Maria

Classifications

• C08G65/2663 Primary

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

• B01J27/26 Primary

  Cyanides · CPC title

• B01J37/0009

  Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst · CPC title

• C01C3/002

  Synthesis of metal cyanides or metal cyanamides from elementary nitrogen and carbides · CPC title

• B01J2208/00017

  Controlling the temperature · CPC title