Alkylene oxide polymerization using a double metal cyanide catalyst complex and a magnesium, group 3-group 15 metal or lanthanide series metal compound

Patent metadata

Field	Value
Publication number	US-9556309-B2
Application number	US-201514694258-A
Country	US
Kind code	B2
Filing date	Apr 23, 2015
Priority date	Dec 27, 2010
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

Alkylene oxide polymerizations are performed in the presence of a double metal cyanide polymerization catalyst and certain magnesium, Group 3-Group 15 metal or lanthanide series metal compounds. The presence of the magnesium, Group 3-Group 15 metal or lanthanide series metal compound provides several benefits including more rapid catalyst activation, faster polymerization rates and the reduction in the amount of ultra high molecular weight polymers that are formed. The catalyst mixture is unexpectedly useful in making polyethers having low equivalent weights.

First claim

What is claimed is:

1. A method for producing a polyether monol or polyether polyol product, comprising polymerizing at least one alkylene oxide in the presence 2 to 100 parts per million of a double metal cyanide catalyst complex, based on the weight of the polyether monol or polyether polyol product, and at least one hafnium compound not present during the preparation of the double metal cyanide catalyst complex, which hafnium compound is selected from the group consisting of a hafnium alkyl; halnium tetramethoxide; hafnium tetraethoxide; hafnium tetraisopropoxide; hafnium tetra-t-butoxide; hafnium tatra-sec-butoxide; hafnium phenoxide; hafnium formate; hafnium acetate; hafnium propionate; hafnium 2-ethylhexanoate; hafnium benzoate; hafnium salicylate; hafnium 3.5-di-t-butyl salicylate; a hafnium phenoxide in which one or more of the phenoxide groups is ring-substituted with alkyl, CF 3 , cyano, COCH 3 , halogen, hydroxyl or alkoxyl; a hafnium amide; a hafnium alkoxide, wherein at least one alkoxide group of the hafnium alkoxide is a residue, after removal of at least one hydroxyl hydrogen, of a polyether monol or polyether polyol; and hafnium t-butylacetylacetonate, wherein the at least one hafnim compound is present in an amount sufficient to provide 0.005 to 0.25 moles of hafnium per gram of the double metal cyanide catalyst.

2. The method of claim 1 which includes the steps of:
combining (a) the double metal cyanide catalyst complex (b) the hafnium compound, (c) at least one initiator compound, and (d) at least one alkylene oxide to form a starting reaction mixture,
heating the starting reaction mixture to polymerization conditions until the double metal cyanide catalyst complex becomes activated, and then
feeding additional alkylene oxide to the reaction mixture under polymerization conditions.

3. The method of claim 1 which includes the steps of:
establishing steady-state concentrations of 1) the DMC catalyst, 2) the hafnium compound, 3) at least one initiator, 4) at least one alkylene oxide and 5) polymerizate in a continuous reactor under polymerization conditions,
continuously adding additional initiator, alkylene oxide, DMC catalyst complex, additional hafnium compound, or a catalyst mixture formed by combining the DMC catalyst complex and hafnium compound, to the continuous reactor under polymerization conditions and continuously withdrawing a product stream containing polyether monol or polyether polyol product from the continuous reactor.

4. A method for producing a polyether monol or polyether polyol product, comprising
(1) forming a catalyst mixture by combining (a) a double metal cyanide catalyst complex and (b) at least one hafnium compound not present during the preparation of the double metal cyanide catalyst complex, which hafnium compound is selected from the group consisting of a hafnium alkyl; hafnium tetramethoxide; hafnium tetraethoxide; hafnium tetraisopropoxide; hafnium tetra-t-butoxide; hafnium tetra-sec-butoxide; hafnium phenoxide; hafnium formate; hafnium acetate; hafnium propionate; hafnium 2-ethylhexanoate; hafnium benzoate; hafnium salicylate; hafnium 3,5-di-t-butyl salicylate; a hafnium phenoxide in which one or more of the phenoxide groups is ring-substituted with alkyl, CF 3 , cyano, COCH 3 , halogen, hydroxyl or alkoxyl; a hafnium amide; a hafnium alkoxide, wherein at least one alkoxide group of the hafnium alkoxide is a residue, after removal of at least one hydroxyl hydrogen, of a polyether monol or polyether polyol; and hafnium t-butylacetylacetonate, wherein the at least one hafnium compound is present in an amount sufficient to provide 0.005 to 0.25 moles of hafnium per gram of the double metal cyanide catalyst
(2) combining the catalyst mixture with at least one alkylene oxide and then
(3) polymerizing the alkylene oxide, wherein the amount of the double metal cyanide catalyst is 2 to 100 parts per million, based on the weight of the polyether monol or polyether polyol product.

5. The method of claim 4 wherein the catalyst mixture is formed by combining (a) the double metal cyanide catalyst complex, (b) the hafnium compound and (c) at least one compound having at least one hydroxyl group.

6. The method of claim 5 wherein the compound having at least one hydroxyl group includes an initiator compound.

7. The method of claim 6 wherein the compound having at least one hydroxyl group includes (i) a polyether monol or polyether polyol corresponding to the product of the polymerization, (ii) a polyether having a molecular weight intermediate to the molecular weights of the initiator and the product of the polymerization, or a mixture of (i) and (ii).

8. The method of claim 4 wherein step (2) includes combining the catalyst mixture with an alkylene oxide and, if the catalyst mixture does not include an initiator compound, at least one initiator compound to form a starting reaction mixture, and step (3) includes heating the starting reaction mixture to polymerization conditions until the double metal cyanide catalyst complex becomes activated and then feeding additional alkylene oxide to the reaction mixture under polymerization conditions.

9. The method of claim 4 wherein step (3) includes
establishing steady-state concentrations of the catalyst mixture, at least one alkylene oxide, polymerizate and, if the catalyst mixture does not contain an initiator compound, at least one initiator compound in a continuous reactor under polymerization conditions and
continuously adding additional DMC catalyst complex, additional hafnium compound, initiator and alkylene oxide to the continuous reactor under polymerization conditions and continuously withdrawing a product stream from the continuous reactor.

10. The method of claim 4 wherein a preliminary heating step is performed by heating the catalyst mixture to a temperature of from 80 to 220° C. at atmospheric or subatmospheric pressure for a period of 10 minutes or more prior to combining the catalyst mixture with the alkylene oxide.

11. The method of claim 6 wherein the initiator compound is one or more of diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, glycerin, trimethylolpropane, pentaerythritol, sucrose or sorbitol, or an alkoxylate of any thereof having a hydroxyl equivalent weight of up to 100.

12. The method of claim 11 , wherein polyether monol or polyether polyol product has a hydroxyl equivalent weight of up to about 400.

13. The method of claim 4 , wherein the alkylene oxide is propylene oxide or a mixture of propylene oxide and ethylene oxide that contains up to 20% by weight ethylene oxide.

14. A method for preparing an alkylene oxide polymerization catalyst mixture, comprising combining (a) a double metal cyanide catalyst complex and (b) at least one hafnium compound not present during the preparation of the double metal cyanide catalyst complex, which hafnium compound is selected from the group consisting of a hafnium alkyl; hafnium tetramethoxide; hafnium tetraethoxide; hafnium tetraisopropoxide; hafnium tetra-t-butoxide; hafnium tetra-sec-butoxide; hafnium phenoxide; hafnium formate; hafnium acetate; hafnium propionate; hafnium 2-ethylhexanoate; hafnium benzoate; hafnium salicylate; hafnium 3,5-di-t-butyl salicylate; a hafnium phenoxide in which one or more of the phenoxide groups is ring-substituted with alkyl, CF 3 , cyano, COCH 3 , halogen, hydroxyl or alkoxyl; a hafnium amide; a hafnium alkoxide, wherein at least one alkoxide group of the hafnium alkoxide is a residue, after removal of at least one hydroxyl hydrogen, of a polyether monol or polyether polyol to form a catalyst mixture in which the at least o

Assignees

• Laitar David S
• Babb David A
• Villa Carlos M
• Keaton Richard
• Masy Jean-Paul
• Dow Global Technologies Llc

Inventors

• Laitar David S
• Babb David A
• Villa Carlos M
• Keaton Richard
• Masy Jean-Paul

Classifications

• C08G65/34 Primary

  from hydroxy compounds or their metallic derivatives {(C08G65/26 takes precedence)} · CPC title

• C07C41/02

  from oxiranes · CPC title

• C08G65/2663 Primary

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

• C08G65/269

  Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ · CPC title

• C07C41/01

  Preparation of ethers · CPC title