Method for activating double metal cyanide catalysts for the production of polyether carbonate polyols

Patent metadata

Field	Value
Publication number	US-9309356-B2
Application number	US-201214232633-A
Country	US
Kind code	B2
Filing date	Jul 16, 2012
Priority date	Jul 18, 2011
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

The present invention relates to a process for the activation of double metal cyanide (DMC) catalysts with heterocumulenes for the preparation of polyether carbonate polyols by catalytic copolymerization of carbon dioxide (CO 2 ) with alkylene oxides in the presence of one or more H-functional starter substances, and to a process for the preparation of polyether carbonate polyols from one or more H-functional starter substances, one or more alkylene oxides and carbon dioxide in the presence of a double metal cyanide catalyst, characterized in that
(α) under an inert gas atmosphere, under an atmosphere of an inert gas/carbon dioxide mixture or under a pure carbon dioxide atmosphere, at temperatures of from 90 to 150° C., the DMC catalyst is mixed with a heterocumulene and H-functional starter substance, (β) alkylene oxide is added at temperatures of from 100 to 150° C. to the mixture from step (α) under an inert gas atmosphere, under an atmosphere of an inert gas/carbon dioxide mixture or under a pure carbon dioxide atmosphere, and (γ) one or more alkylene oxides and carbon dioxide are metered continuously into the mixture resulting from step (β).

First claim

The invention claimed is:

1. A process for the preparation of a polyether carbonate polyol from one or more H-functional starter substances, one or more alkylene oxides and carbon dioxide in the presence of a double metal cyanide (DMC) catalyst, comprising
(α) mixing, under an inert gas atmosphere, under an atmosphere of an inert gas/carbon dioxide mixture or under a pure carbon dioxide atmosphere, at temperatures of from 90 to 150° C., the DMC catalyst with a heterocumulene and one or more H-functional starter substance,
(β) adding alkylene oxide at temperatures of from 100 to 150° C. to the mixture from step (α) under an inert gas atmosphere, under an atmosphere of an inert gas/carbon dioxide mixture or under a pure carbon dioxide atmosphere, and
(γ) metering continuously one or more alkylene oxides and carbon dioxide into the mixture resulting from step (β).

2. The process according to claim 1 , wherein step (γ) is carried out at 90 to 130° C.

3. A process for activation of a DMC catalyst, comprising
(α) mixing, under an inert gas atmosphere, under an atmosphere of an inert gas/carbon dioxide mixture or under a pure carbon dioxide atmosphere, the DMC catalyst with a heterocumulene and an H-functional starter substance, and subsequently
(β) adding alkylene oxide at temperatures of from 90 to 150° C. to the mixture from step (α) under an inert gas atmosphere, under an atmosphere of an inert gas/carbon dioxide mixture or under a pure carbon dioxide atmosphere.

4. The process according to claim 1 , wherein in step (α)
(α1) the H-functional starter substance or a mixture of at least two H-functional starter substances is initially introduced into a reaction vessel and
(α2) the temperature of the starter substance or of the mixture of at least two H-functional starter substances is brought to 50 to 200° C. and/or the pressure in the reactor is adjusted to less than 500 mbar,

and wherein the DMC catalyst and heterocumulene are added to the H-functional starter substance or the mixture of at least two H-functional starter substances in step (α1) or subsequently during step (α2).

5. The process according to claim 1 , wherein the part amount of one or more alkylene oxides in step (β) is 0.1 to 25.0 wt. % based on the amount of H-functional starter substance in step (α).

6. The process according to claim 1 , wherein the heterocumulene comprises at least one functional group selected from the group consisting of isocyanate group, isothiocyanate group, carbodiimide group, ketene group, and thioketene group compounds containing at least one S═C═C< group).

7. The process according to claim 1 , wherein the heterocumulene comprises a compound of the formula (II)
R 1 —(−X—N═C═O) n   (II)

wherein
R 1 is an n-valent aliphatic, aromatic or araliphatic radical having 1 to 36 carbon atoms,
n is a natural number from 1 to 6 and
X is a single bond, an —SO 2 — or a —CO— group.

8. The process according to claim 1 , wherein the heterocumulene comprises a compound of the formulae (IIIa) and (IIIb)
R 2 —N═C═N—R 3   (IIIa)

OCN—R 4 —[−N═C═N—R 4 —] m —NCO  (IIIb)

wherein
R 2 and R 3 are a C 1 to C 22 alkyl, a C 6 -C 18 aryl or a C 7 -C 22 aralkyl radical,
R 4 is a divalent C 6 -C 36 aliphatic, aromatic or araliphatic radical and
m is a natural number from 3 to 300.

9. The process according to claim 1 , wherein the heterocumulene comprises at least one compound selected from the group consisting of tosyl isocyanate, benzoyl isocyanate, acetyl isocyanate, carbonyl-diisocyanate, sulfonyl-diisocyanate, benzenesulfonyl isocyanate, methansulfonyl-diisocyanate, o-, m- and p-phthaloyl-diisocyanate, 4,4′,4″-triisocyanatophenylmethane, 4,4′-methylene-diisocyanate, 2,4′-methylene-diisocyanate, 2,2′-methylene-diisocyanate, 2,4-toluylene-diisocyanate, 2,6-toluylene-diisocyanate, m- and p-phenylene-diisocyanate, diphenyl-diisocyanate, 3,3′-dimethyl-4,4′-diisocyanatodiphenyl, 3,4′-diisocyanatodiphenyl ether, 4,4′-diisocyanatodiphenyl ether, m- and p-bisisocyanatomethylbenzene, 1,3- and 1,4-bisisocyanatomethylcyclohexane, 1,3-bis-(1-isocyanato-1-methylethyl)benzene, 1,6-hexamethylene-diisocyanate (HDI), 2,2,4-trimethyl-1,6-hexamethylene-diisocyanate, isophorone-diisocyanate (IPDI), m-tetramethylxylene-diisocyanate (m-TMXDI), bisisocyanatomethylnorbornane, phenyl isocyanate, butyl isocyanate and methyl isocyanate, dicyclohexylcarbodiimide, di-p-toluylcarbodiimide, di-tert-butylcarbodiimide, diisopropylcarbodiimide, tert-butylethylcarbodiimide, and 3-dimethylaminopropylethylcarbodiimide.

10. The process according to claim 1 , wherein the one or more H-functional starter substance is selected from at least one of the group consisting of alcohols, amines, thiols, amino alcohols, thioalcohols, hydroxy esters, polyether polyols, polyester polyols, polyester ether polyols, polycarbonate polyols, polyether carbonate polyols, polyethyleneimines, polyether-amines, polytetrahydrofurans, polyether thiols, polyacrylate polyols, castor oil, the mono- or diglyceride of ricinoleic acid, monoglycerides of fatty acids, and chemically modified mono-, di- and/or triglycerides of fatty acids, and C 1 -C 24 -alkyl fatty acid esters which contain on average at least 2 OH groups per molecule.

11. The process according to claim 1 , wherein the one or more H-functional starter substance is selected from at least one of the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols, wherein the polyether polyol is built up from a di- or tri-H-functional starter substance and propylene oxide or a di- or tri-H-functional starter substance, propylene oxide and ethylene oxide and the polyether polyols have a molecular weight M n in the range of from 62 to 4,500 g/mol and a functionality of from 2 to 3.

12. The process according to claim 1 , wherein the DMC catalyst comprises at least one double cyanide compound selected from the group consisting of zinc hexacyanocobaltate(III), zinc hexacyanoiridate(III), zinc hexacyanoferrate(III), and cobalt(II) hexacyanocobaltate(III).

13. The process according to claim 1 , wherein the DMC catalyst comprises at least one organic complexing ligand selected from the group consisting of aliphatic ethers, ethanol, isopropanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-tert-butyl ether, tripropylene glycol monomethyl ether, and 3-methyl-3-oxetane-methanol.

14. The process according to claim 1 , wherein the process is carried out in a tube reactor, a stirred tank or a loop reactor.

15. The Process according to claim 1 , wherein the process is carried out in a stirred tank and wherein in step (γ) the one or more H-functional starter substances are metered continuously into a stirred tank during the reaction.

Assignees

• Müller Thomas Ernst
• Gürtler Christoph
• Dienes Yvonne
• Barruet Julien
• Köhler Burkhard
• Leitner Walter
• Bayer Ip Gmbh

Inventors

• Müller Thomas Ernst
• Gürtler Christoph
• Dienes Yvonne
• Barruet Julien
• Köhler Burkhard
• Leitner Walter

Classifications

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G65/2663

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

• C08G64/323 Primary

  and alcohols · CPC title

• C08G65/2603

  the other compounds containing oxygen · CPC title