Preparing polyether polyols with DMC catalysts

• US 6,359,101 B1
• Filed: 12/15/1999
• Issued: 03/19/2002
• Est. Priority Date: 12/15/1999
• Status: Expired due to Fees

• Current Assignee: Synuthane International Incorporated
• Original Assignee: Synuthane International Incorporated
• Inventors: Lickei, Donald L., OʼConnor, James M., Grieve, Robin L.
• Primary Examiner(s): Lovering, Richard D.
• Application Number:
  US09/464,281
• Time in Patent Office: 825 Days
• Field of Search: 528/412, 528/66, 525/403, 568/623
• US Class Current: 528/66
• CPC Class Codes: C08G 18/4866 having a low unsaturation value
• CPC Class Codes: C08G 65/2609 containing aliphatic hydroxyl groups
• CPC Class Codes: C08G 65/2663 Metal cyanide catalysts, i.e. DMC's

Abstract

A process for making polyether polyols employing a double metal cyanide (DMC) catalyst with specific low molecular weight polyether polyols as starters in combination with specific reaction conditions and impurity levels.

Claims

1. A process for making a polyether polyol, said process comprising:

(a) polymerizing an epoxide in the presence of a double metal cyanide (DMC) catalyst and a first starter wherein the epoxide and first starter are continuously added to the reactor during step (a) to produce a polyol intermediate; and

(b) reacting the polyol intermediate with additional epoxy to produce a polyether polyol;

wherein said first starter is selected from the group consisting of;

(i) at least one compound having the formula (I);

2. The process of claim 1 wherein said process is carried out in the absence of a solvent.

3. The process of claim 1 wherein a portion of the first starter is added to the reactor along with the double metal cyanide catalyst before the epoxide and the remainder of the first starter are continuously added to the reactor.

4. The process of claim 1 wherein a second starter is added during step (b), said second starter is also selected from the group consisting of compounds (i) to (viii).

5. The process of claim 1 wherein the epoxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxides, and mixtures thereof.

6. The process of claim 1 wherein additional double metal cyanide catalyst is added to the reactor during step (b).

7. The process of claim 1 wherein the double metal cyanide catalyst is zinc hexacyanocobaltate.

8. The process of claim 1 wherein a second starter is added during step (b), said second starter selected from the group consisting of water, at least one low molecular weight polyol having at least one hydroxyl group and a number average molecular weight of less than 300 and mixtures of water and at least one of these low molecular weight polyols.

9. The process of claim 8 wherein the second starter is selected from the group consisting of water, glycerin, propylene glycol, dipropylene glycol, ethylene glycol, trimethylol propane, sucrose, sorbitol, tripropylene glycol and mixtures thereof.

10. A polyether polyol prepared by the process of claim 1.

11. A polyurethane prepared by reacting at least one polyether polyol of claim 10 with a polyisocyanate.

12. A process for making a polyether polyol, said process comprising:

(a) polymerizing an epoxide in the presence of a double metal cyanide (DMC) catalyst and a first starter wherein the epoxide and first starter are continuously added to the reactor during step (a) to produce a polyol intermediate; and

(b) reacting the polyol intermediate with additional epoxy to produce a polyether polyol;

wherein step (a) is conducted with a mole ratio of total epoxide added to total first starter added of at least about 3;

1; and

wherein the total impurity level of water, propylene glycol and neutralized base residues in the added first starter is less than about 1000 parts per million by weight, and wherein the first starter is selected from the group consisting of;

(i) at least one compound having the formula (I);

13. The process of claim 12 wherein the mole ratio of total epoxide added to total first starter added is at least about 5:

1.

14. The process of claim 12 wherein the level of the total amount of water, propylene glycol and neutralized base residues is less than about 500 parts per million by weight.

15. The process of claim 12 wherein said process is carried out in the absence of a solvent.

16. The process of claim 12 wherein a portion of the first starter is added to the reactor along with the double metal cyanide catalyst before the epoxide and the remainder of first starter are continuously added to the reactor.

17. The process of claim 12 wherein the first starter is selected from the group consisting of dipropylene glycol, tripropylene glycol and mixtures thereof.

18. The process of claim 12 wherein the epoxide is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxides, and mixtures thereof.

19. The process of claim 12 wherein additional double metal cyanide catalyst is added to the reactor during step (b).

20. The process of claim 12 wherein the double metal cyanide catalyst is zinc hexacyanocobaltate.

21. A polyether polyol made by the process of claim 12.

22. A polyurethane prepared by reacting at least one polyether polyol of claim 21 with a polyisocyanate.

23. A two-stage batch process for making a polyether polyol in a reactor, said process comprising:

(a) polymerizing an epoxide in the presence of a double metal cyanide catalyst and a starter to produce a polyol intermediate; and

(b) adding additional epoxide and reacting the polyol intermediate with the additional epoxide in the reactor to produce a polyether polyol;

wherein said starter is selected from the group consisting of;

(i) at least one compound having the formula (I);

 

HO—

H₂C—

[CH₂]_n—

OH 

 

(I)

 

wherein n is an integer from 5 to 20;

(ii) cyclohexane dimethanol;

(iii) at least one compound having the formula (II);

 

wherein R₁ and R₂ are individually selected from the group consisting of an alkyl group having 1 to 6 carbon atoms;

(iv) at least one compound having the formulae (III) or (IIIA);

24. A polyether polyol made by the process of claim 23.

25. A polyurethane prepared by reacting at least one polyether polyol of claim 24 which a polyisocyanate.

26. A single batch process for making a polyether polyol, said batch process comprising:

polymerizing an epoxide in the presence of a double metal cyanide catalyst and a starter;

wherein the build ratio in the batch reactor is at least 20 and wherein the starter is selected from the group consisting of;

(i) at least one compound having the formula (I);

27. A polyether polyol made by the process of claim 26.

28. A polyurethane made by reacting at least one polyether polyol of claim 27 with a polyisocyanate.