Double metal cyanide catalysts for producing polyether polyols

• US 6,919,293 B1
• Filed: 10/26/2000
• Issued: 07/19/2005
• Est. Priority Date: 11/08/1999
• Status: Expired due to Fees

• Current Assignee: Bayer AG
• Original Assignee: Bayer AG
• Inventors: Ehlers, Stephan, Steinlein, Christian, Ooms, Pieter, Hofmann, Jörg
• Primary Examiner(s): Wood, Elizabeth D.
• Application Number:
  US10/129,579
• Time in Patent Office: 1,727 Days
• Field of Search: 502/175, 502/159, 502/150, 502/152, 502/153, 502/155, 502/156, 502/162, 502/167, 502/170, 502/172
• US Class Current: 502/175
• CPC Class Codes: B01J 2531/845 Cobalt
• CPC Class Codes: B01J 2531/96 Water
• CPC Class Codes: B01J 27/26 Cyanides
• CPC Class Codes: B01J 31/0202 Alcohols or phenols
• CPC Class Codes: B01J 31/0204 Ethers
• CPC Class Codes: B01J 31/0255 Phosphorus containing compounds
• CPC Class Codes: B01J 31/0259 comprising phosphorous acid (-ester) groups ((RO)P(OR')2) or the isomeric phosphonic acid (-ester) groups (R(R'O)2P=O), i.e. R= C, R'= C, H
• CPC Class Codes: B01J 31/06 containing polymers organometallic polymers B01J31/123; polymer-bound organometallic complexes B01J31/165; coordination polymers B01J31/1691
• CPC Class Codes: B01J 31/065 Cyclodextrins
• CPC Class Codes: B01J 31/185 Phosphites ((RO)3P) , their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
• CPC Class Codes: B01J 31/22 Organic complexes
• CPC Class Codes: B01J 31/2213 At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
• CPC Class Codes: B01J 31/2239 Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
• CPC Class Codes: C08G 65/2663 Metal cyanide catalysts, i.e. DMC's

Abstract

This invention relates to novel double metal cyanide (DMC) catalysts for the production of polyether polyols by polyaddition of alkylene oxides onto starter compound comprising active hydrogen atoms, wherein the catalyst contains a) double metal cyanide compounds, b) organic complex ligands other than c) and c) two or more complex-forming components from the classes of compounds comprising functionalised polymers, glycidyl ethers, glycosides, carboxylic acid esters of polyhydric alcohols, bile acids or the salts, esters or amides thereof, cyclodextrins, phosphorus compounds, α,β-unsaturated carboxylic acid esters or ionic surface- or interface-active compounds. The catalysts according to the invention exhibit greatly increased activity in polyether polyol production.

Claims

1. A double metal cyanide catalyst comprising:

a) at least one double metal cyanide compound;

b) at least one organic complexing ligand;

c) at least two complexing components chosen from polyether, polyester;

polycarbonate;

polyalkylene glycol sorbitan ester;

polyalkylene glycol glycidyl ether;

polyacrylamide;

poly(acrylamide-co-acrylic acid);

polyacrylic acid;

poly(acrylic acid-co-maleic acid);

polyacrylonitrile;

polyalkyl acrylate;

polyalkyl methacrylate;

polyvinyl methyl ether;

polyvinyl ethyl ether;

polyvinyl acetate;

polyvinyl alcohol;

poly-N-vinylpyrrolidone;

poly(N-vinylpyrrolidone-co-acrylic acid);

polyvinyl methyl ketone;

poly(4-vinylphenol);

poly(acrylic acid-co-styrene);

oxazoline polymer;

polyalkyleneimine;

maleic acid and maleic anhydride copolymers;

hydroxyethylcellulose;

polyacetal;

glycidyl ether;

glycoside;

carboxylic acid esters of polyhydric alcohol;

bile acid or its salt, ester or amide thereof;

cyclodextrins;

phosphorus compounds;

α

,β

-unsaturated carboxylic acid esters;

or ionic surface- or interface-active compounds,

wherein complexing components c) are not the same as organic complexing ligand b).

2. The double metal cyanide catalyst according to claim 1, further comprising water and/or one or more water-soluble metal salts.

3. The double metal cyanide catalyst according to claim 1, wherein the double metal cyanide compound is zinc hexacyanocobaltate (III).

4. The double metal cyanide catalyst according to claim 1, wherein the organic complexing ligand is tert.-butanol.

5. The double metal cyanide catalyst according to claim 1, wherein the double metal cyanide catalyst comprises up to about 80 wt. %, based on the total weight of the double metal cyanide catalyst, of a mixture of complexing components c).

6. A process for preparing a double metal cyanide catalyst comprising:

(1) reacting, in aqueous solution, (i) at least one metal salt, (ii) with at least one metal cyanide salt, in the presence of (iii) at least one organic complexing ligand to form a suspension;

(2) treating the suspension with at least two complexing components chosen from polyether;

polyester;

polycarbonate;

polyalkylene glycol sorbitan ester, polyalkylene glycol glycidyl ether;

polyacrylamide;

poly(acrylamide-co-acrylic acid);

polyacrylic acid;

poly(acrylic acid-co-maleic acid);

polyacrylonitrile;

polyalkyl acrylate;

polyalkyl methacrylate;

polyvinyl methyl ether;

polyvinyl ethyl ether;

polyvinyl acetate;

polyvinyl alcohol;

poly-N-vinylpyrrolidone;

poly(N-vinylpyrrolidone-co-acrylic acid);

polyvinyl methyl ketone;

poly(4-vinylphenol);

poly(acrylic acid-co-styrene);

oxazoline polymer;

polyalkyleneimine;

maleic acid and maleic anhydride copolymers;

hydroxyethylcellulose;

polyacetal;

glycidyl ether;

glycoside;

carboxylic acid esters of polyhydric alcohol;

bile acid or its salt, ester or amide thereof;

cyclodextrins;

phosphorus compounds;

α

,β

-unsaturated carboxylic acid esters;

or ionic surface- or interface-active compounds to form a double metal cyanide catalyst,

wherein the complexing components are not the same as the organic complexing ligand;

(3) isolating the double metal cyanide catalyst from the suspension;

(4) washing the double metal cyanide catalyst; and

(5) drying the double metal cyanide catalyst.