Polycarbonates made using high activity catalysts

• US 6,133,402 A
• Filed: 06/09/1999
• Issued: 10/17/2000
• Est. Priority Date: 08/04/1998
• Status: Expired due to Term

• Current Assignee: Cornell Research Foundation Incorporated (Cornell University)
• Original Assignee: Cornell Research Foundation Incorporated (Cornell University)
• Inventors: Cheng, Ming, Coates, Geoffrey W.
• Primary Examiner(s): Boykin, Terressa M.
• Application Number:
  US09/328,441
• Time in Patent Office: 496 Days
• Field of Search: 528/196, 528/296
• US Class Current: 528/196
• CPC Class Codes: C08G 64/34 and cyclic ethers

Abstract

Polycarbonates having M_n ranging from about 5,000 to about 40,000 and a molecular weight distribution ranging from 1.05 to 2.0 are prepared from epoxides and CO₂ using a catalyst which has a Zn center and two ligands where one of the ligands is a propagating group and the other of the ligands is not a propagating group and an activity of at least one turnover per hour, preferably at least 100 turnovers per hour. Preferred catalysts have a ##STR1## moiety with group on each nitrogen containing a phenyl moiety.

Claims

1. Compound having the formula ##STR15## where each R₁ is selected from the group consisting of C₁ -C₂₀ alkyl where one or more hydrogens is optionally replaced by halogen and C₆ -C₂₀ aryl where one or more hydrogens is optionally replaced by halogen and each R₁ is the same or different and each R₂ is selected from the group consisting of hydrogen, cyano, C₁ -C₂₀ alkyl where one or more hydrogens is optionally replaced by halogen and C₆ -C₂₀ aryl where one or more hydrogens is optionally replaced by halogen and each R₂ is the same or different, and R is selected from the group consisting of C₁ -C₂₀ alkyl, C₆ -C₂₀ aryl and polymer of weight average molecular weight up to 1,000,000 having at least one pendant carboxyl group, or dimer thereof, said compound or dimer thereof being effective to catalyze the reaction of epoxide and CO₂ to form polycarbonate.

2. Compound is claimed in claim 1 having the formula ##STR16## where R₄ is methyl, R₅ is hydrogen or cyano, R₆ and R₇ are the same or different and are C₁ -C₃ alkyl, R₈ is hydrogen or chloro, and R₉ is hydrogen, or dimer thereof.

3. The compound of claim 2 which is ##STR17##

4. The compound of claim 2 which is

15. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C4-C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 1.

16. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 2.

17. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 3.

18. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 4.

5. Compound having the formula where each R₁ is selected from the group consisting of C₁ -C₂₀ alkyl where one or more hydrogens is optionally replaced by halogen and C₆ -C₂₀ aryl where one or more hydrogens is optionally replaced by halogen and each R₁ is the same or different and each R₂ is selected from the group consisting of hydrogen, cyano, C₁ -C₂₀ alkyl where one or more hydrogens is optionally replaced by halogen and C₆ -C₂₀ aryl where one or more hydrogens is optionally replaced by halogen and each R₂ is the same or different, and R₃ is selected from the group consisting of hydrogen, C₁ -C₂₀ alkyl, C₆ -C₂₀ aryl and polymer of weight average molecular weight up to 1,000,000 having at least one pendant hydroxyl group, or dimer thereof, said compound or dimer thereof being effective do catalyze reaction of epoxide and CO₂ to for polycarbonate.

6. Compound as claimed claim 5 having the formula ##STR18## where R₄ is methyl, R₅ is hydrogen or cyano, R₆ and R₇ are the same or different and are C₁ -C₃ alkyl, R₈ is hydrogen or chloro, and R₉ is hydrogen, or dimer thereof.

7. The compound of claim 6 having the formula ##STR19##

8. The compound of claim 6 having the formula

9. The compound of claim 6 having the formula (VII) wherein R₄ is methyl, R₅ is hydrogen, R₆ is isopropyl, R₇ is methyl, R₈ is hydrogen, and R₉ is hydrogen.

10. The compound of claim 6 having the formula (VII) wherein R₄ is methyl, R₅ is hydrogen, R₆ is isopropyl, R₇ is ethyl, R₈ is hydrogen, and R₉ is hydrogen.

11. The compound of claim 6 having the formula (VII) wherein R₄ is methyl, R₅ is hydrogen, R₆ is ethyl, R₇ is ethyl, R₈ is chloro and R₉ is hydrogen.

12. The compound of claim 6 having the formula (VII) wherein R₄ is methyl, R₅ is cyano, R₆ is ethyl, R₇ is ethyl, R₈ is hydrogen, and R₉ is hydrogen.

19. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 5.

20. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 6.

21. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 7.

22. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 8.

23. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 9.

24. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 10.

25. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 11.

26. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a compound as claimed in claim 12.

13. A method for preparing polycarbonate, said method comprising copolymerizing monomers comprising CO₂ and epoxide selected from the group consisting of C₂ -C₂₀ alkylene oxides, C₄ -C₁₂ cycloalkene oxides and styrene oxide in the presence of a catalyst which has a Zn center and two ligands where one of the ligands is a propagating group and the other of the ligands is not a propagating group and an activity of at least one TO/hr.

14. The method of claim 13 wherein the catalyst has activity of at least 100 TO/hr.

27. Polycarbonate having a M_n ranging from about 5,000 to about 40,000 and a molecular weight distribution ranging from 1.05 to 2.0, the M_n and the molecular weight distribution being determined by gel permeation chromatography.

28. The polycarbonate of claim 27 which is selected from the group consisting of poly(C₂ -C₂₀ alkylene carbonates) and poly(C₄ -C₁₂ cycloalkenylene carbonates).

29. The polycarbonate of claim 28, wherein the molecular weight distribution ranges from 1.05 to 1.25.

30. The polycarbonate of claim 29 which contains at least 85% polycarbonate linkages.

31. The polycarbonate of claim 30 which is poly(cyclohexenylene carbonate).

32. The polycarbonate of claim 31 wherein the M_n ranges from 17,000 to 31,000.