Methods for polymer synthesis

• US 10,308,761 B2
• Filed: 12/02/2016
• Issued: 06/04/2019
• Est. Priority Date: 12/20/2011
• Status: Active Grant

• Current Assignee: Saudi Aramco Technologies Company (Government of Saudi Arabia)
• Original Assignee: Saudi Aramco Technologies Company (Government of Saudi Arabia)
• Inventors: Allen, Scott D., Simoneau, Christopher A., Keefe, William D., Conuel, Jeff R.
• Primary Examiner(s): Fang, Shane
• Application Number:
  US15/368,144
• Publication Number:
  US 20170183447A1
• Time in Patent Office: 914 Days
• CPC Class Codes: C08G 64/34 and cyclic ethers

Abstract

The present invention provides methods for reducing induction periods in epoxide-CO₂ copolymerizations. In certain embodiments, the methods include the step of contacting an epoxide with CO₂ in the presence of two catalysts: an epoxide hydrolysis catalyst and an epoxide CO₂ copolymerization catalyst. In another aspect, the invention provides catalyst compositions comprising a mixture of an epoxide hydrolysis catalyst and an epoxide CO₂ copolymerization catalyst.

Claims

1. A method for preparing aliphatic polycarbonate polymers comprising the step of contacting one or more epoxides with a first catalyst capable of catalyzing the hydrolysis of epoxides and a second catalyst capable of catalyzing the copolymerization of epoxides and CO₂;

wherein the first catalyst is an oligomeric metal complex; and

the second catalyst comprises a metal-ligand complex.

2. The method of claim 1, wherein the first catalyst comprises two or more

3. The method of claim 2, wherein the first catalyst is represented by the following structural formula:

4. The method of claim 3, wherein

5. The method of claim 4, wherein the metallosalenate complex is selected from the group consisting of:

6. The method of claim 5, wherein the metallosalenate complex is

7. The method of claim 3, wherein the first catalyst comprises:

8. The method of claim 3, wherein the first catalyst comprises:

9. The method of claim 2, wherein the first catalyst is represented by the following structural formula:

10. The method of claim 9, wherein

11. The method of claim 10, wherein the metallosalenate complex is selected from the group consisting of:

12. The method of claim 11, wherein the metallosalenate complex is

13. The method of claim 12, wherein the first catalyst is:

14. The method of claim 12, wherein the first catalyst is:

15. The method of claim 1, characterized in that the second catalyst, when used without the step of contacting the epoxide with the first catalyst exhibits an induction period and that when the second catalyst is used with the step of contacting the epoxide with the first catalyst, this induction period is lessened or eliminated.

16. The method of claim 1, wherein the one or more epoxides are contacted with both catalysts in the presence of CO₂.

17. The method of claim 1, wherein the step comprises a first substep comprising epoxide hydrolysis and a second substep comprising epoxide CO₂ copolymerization.

18. The method of claim 17, wherein the first and second substeps are performed at different times and the first substep comprises contacting one or more epoxides with the first catalyst prior to adding the second catalyst;

and the second substep comprises contacting the one or more epoxides with carbon dioxide in the presence of the second catalyst.

19. The method of claim 17, wherein the first and second substeps are performed at different times and the first substep comprises:

a) charging a reaction vessel with one or more epoxides,

b) contacting the one or more epoxides with the first catalyst,

c) allowing a period of time for epoxide hydrolysis, and

the second substep comprises adding the second catalyst to the vessel.

20. The method of claim 17, wherein the first and second substeps are performed sequentially and the method comprises:

a) simultaneously contacting one or more epoxides with the first catalyst and the second catalyst;

b) allowing the mixture to react for a period of time in the absence of CO₂, and

c) contacting the mixture of one or more epoxides, the first catalyst, and the second catalyst with carbon dioxide.

21. A method for the copolymerization of one or more epoxides and CO₂ to produce aliphatic polycarbonate polymers, the method comprising the steps of:

treating an epoxide feedstock comprising one or more epoxides by contacting it with a first catalyst capable of catalyzing epoxide hydrolysis and optionally a second catalyst capable of catalyzing epoxide CO₂ copolymerization; and

feeding the treated epoxide feedstock to an epoxide CO₂ copolymerization reaction where it is contacted with CO₂ in the presence of the second catalyst capable of catalyzing epoxide CO₂ copolymerization;

wherein

the first catalyst comprises an oligomeric metal complex; and

the second catalyst comprises a metal-ligand complex.

22. The method of claim 21, wherein only the first catalyst is present in the first step and the second catalyst is only present at the copolymerization step.

23. The method of claim 21, wherein the second catalyst is present during the step of treating the epoxide feedstock.

24. The method of claim 21, comprising the further step of removing the first catalyst from the treated epoxide feedstock prior to the feeding step.

25. The method of claim 21, wherein the first catalyst is a solid or solid-supported epoxide hydrolysis catalyst.