Polycarbonate polyol compositions and methods

Patent metadata

Field	Value
Publication number	US-9376531-B2
Application number	US-201414573534-A
Country	US
Kind code	B2
Filing date	Dec 17, 2014
Priority date	Sep 8, 2008
Publication date	Jun 28, 2016
Grant date	Jun 28, 2016

Abstract

In one aspect, the present disclosure encompasses polymerization systems for the copolymerization of CO 2 and epoxides comprising 1) a catalyst including a metal coordination compound having a permanent ligand set and at least one ligand that is a polymerization initiator, and 2) a chain transfer agent having two or more sites that can initiate polymerization. In a second aspect, the present disclosure encompasses methods for the synthesis of polycarbonate polyols using the inventive polymerization systems. In a third aspect, the present disclosure encompasses polycarbonate polyol compositions characterized in that the polymer chains have a high percentage of —OH end groups and a high percentage of carbonate linkages. The compositions are further characterized in that they contain polymer chains having an embedded polyfunctional moiety linked to a plurality of individual polycarbonate chains.

First claim

What is claimed is:

1. A polycarbonate polyol composition comprising polymer chains denoted P 1 having the formula T-Y-A-(Y-T) n wherein:
each -T is a polycarbonate chain having a formula independently selected from the group consisting of:

wherein:
E is an optionally substituted C 2 unit derived from an epoxide, where E may represent a monomer unit derived from one type of epoxide, or a mixture of two or more types of epoxide, and
p ranges from about 5 to about 10,000,
each —Y-A-(Y—) n derives from a chain transfer agent where each —Y group is independently a functional group capable of initiating chain growth of epoxide CO 2 copolymers and each Y group may be the same or different,
-A- is a polyolefin chain or an optionally substituted C 3-20 aliphatic chain; and
n is an integer between 1 and 10 inclusive.

2. The polycarbonate polyol composition of claim 1 , further comprising polymer chains denoted P 2 having a formula selected from the group consisting of:

wherein
X is a bound form of an anion capable of initiating only one polymer chain.

3. The polycarbonate polyol composition of claim 2 , wherein the ratio of P 1 polymer chains to P 2 polymer chains is greater than 20:1.

4. The polycarbonate polyol composition of claim 2 , wherein ratio of P 1 polymer chains to P 2 polymer chains is greater than 40:1.

5. The polycarbonate polyol composition of claim 2 , wherein ratio of P 1 polymer chains to P 2 polymer chains is greater than 100:1.

6. The polycarbonate polyol composition of claim 1 , wherein n is 1.

7. The polycarbonate polyol composition of claim 1 , wherein chains of type P 1 have the formula:

8. The polycarbonate polyol composition of claim 7 , wherein -A- is an optionally substituted C 3-20 aliphatic chain.

9. The polycarbonate polyol composition of claim 1 , wherein chains of type P 1 have the formula:

where each z is 1.

10. The polycarbonate polyol composition of claim 9 , wherein -A- is an optionally substituted C 3-20 aliphatic chain.

11. The polycarbonate polyol composition of claim 1 , wherein the chain transfer agent is a diol, triol, or tetraol.

12. The polycarbonate polyol composition of claim 11 , wherein -A- is an optionally substituted C 3-20 aliphatic chain.

13. The polycarbonate polyol composition of claim 11 , wherein the chain transfer agent is an α-ω diol comprising an optionally substituted C 3-20 aliphatic chain.

14. The polycarbonate polyol composition of claim 13 , wherein the chain transfer agent is selected from 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol.

15. The polycarbonate polyol composition of claim 11 , wherein the chain transfer agent is a hydroxyl-terminated polyolefin.

16. The polycarbonate polyol composition of claim 15 , wherein the chain transfer agent is selected from a hydroxyl-terminated polybutadiene, a hydroxyl-terminated polyisobutylene, and a hydroxyl-terminated polybutadienestyrene.

17. The polycarbonate polyol composition of claim 16 , wherein the chain transfer agent is selected from Krasol®, Polytail® H, or Polytail® HA.

18. The polycarbonate polyol composition of claim 1 , wherein the chain transfer agent is a diacid, triacid, or tetracid or a salt thereof.

19. The polycarbonate polyol composition of claim 18 , wherein -A- is an optionally substituted C 3-20 aliphatic chain.

20. The polycarbonate polyol composition of claim 18 , wherein the chain transfer agent is selected from pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.

21. The polycarbonate polyol composition of claim 18 , wherein the chain transfer agent is a carboxy-terminated polyolefin.

22. The polycarbonate polyol composition of claim 21 , wherein the chain transfer agent is selected from a NISSO-PB C-series resin.

23. The polycarbonate polyol composition of claim 1 , wherein the chain transfer agent is a hydroxyacid or a salt thereof.

24. The polycarbonate polyol composition of claim 23 , wherein -A- is an optionally substituted C 3-20 aliphatic chain.

25. The polycarbonate polyol composition of claim 23 , wherein the chain transfer agent is an α-ω hydroxy acid comprising an optionally substituted C 3-20 aliphatic chain.

26. The polycarbonate polyol composition of claim 25 , wherein the chain transfer agent is 7-hydroxyheptanoic acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, or 12-hydroxydodecanoic acid.

27. The polycarbonate polyol composition of claim 1 , wherein the chain transfer agent is an amino alcohol.

28. The polycarbonate polyol composition of claim 27 , wherein -A- is an optionally substituted C 3-20 aliphatic chain.

29. The polycarbonate polyol composition of claim 1 , characterized in that the polycarbonate polyol has a Mn between 400 and 20,000 and greater than 95% of the polymer end groups are hydroxyl groups.

Assignees

• Novomer Inc

Inventors

• Allen Scott D
• Coates Geoffrey W
• Cherian Anna E
• Simoneau Chris A
• Gridnev Alexei A
• Farmer Jay J

Classifications

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G64/0208 Primary

  saturated · CPC title

• C08G18/44

  Polycarbonates · CPC title

• C08G64/0216

  containing a chain-terminating or -crosslinking agent · CPC title