Polycarbonate polyol compositions and methods

Patent metadata

Field	Value
Publication number	US-10301426-B2
Application number	US-201715719855-A
Country	US
Kind code	B2
Filing date	Sep 29, 2017
Priority date	Sep 8, 2008
Publication date	May 28, 2019
Grant date	May 28, 2019

Abstract

In one aspect, the present disclosure encompasses polymerization systems for the copolymerization of CO2 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 an epoxide CO 2 copolymer characterized in that the copolymer has:
an Mn between 400 and 20,000 g/mol,
greater than 90% carbonate linkages, and
wherein the composition comprises:
polymer chains denoted P 1 having the formula T-Y-A-(Y-T) n , derived from a chain transfer agent having a formula Y-A-(Y) n , wherein:
each -T is a polycarbonate chain having a formula independently selected from the group consisting of:

 wherein:
each E is independently an optionally substituted C 2 unit derived from an epoxide or a mixture of two or more epoxides;
p ranges from 5 to 10,000; and

each chain transfer agent of formula Y-A-(Y) n comprises two or more sites capable of initiating chain growth in the co-polymerization of an epoxide and carbon dioxide;
—Y group is independently a functional group capable of initiating chain growth of epoxide CO 2 copolymers and each Y group is the same or different,
-A- is a covalent bond or a multivalent moiety; and
n is an integer between 1 and 10 inclusive;

wherein the composition is characterized in that more than 97% of the epoxide CO 2 copolymer chains are of type P 1 .

2. The polycarbonate polyol composition of claim 1 , comprising greater than 95% carbonate linkages.

3. The polycarbonate polyol composition of claim 1 , comprising greater than 99% carbonate linkages.

4. The polycarbonate polyol composition of claim 1 , having an Mn between about 500 and about 5,000 g/mol.

5. The polycarbonate polyol composition of claim 1 , having an Mn between about 1,000 and about 3,000 g/mol.

6. 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;

wherein the ratio of P 1 polymer chains to P 2 polymer chains is greater than 40:1.

7. The polycarbonate polyol composition of claim 6 , wherein the ratio of P 1 polymer chains to P 2 polymer chains is greater than 100:1.

8. The polycarbonate polyol composition of claim 1 , further comprising polymer chains denoted P 1a having a formula:

9. The polycarbonate polyol composition of claim 1 , wherein each E is

where, R 21 , R 22 , R 23 , and R 24 , are each independently selected from the group consisting of: —H; and an optionally substituted group selected from C 1-30 aliphatic; C 6-14 aryl; 3- to 12-membered heterocycle, and 5- to 12-membered heteroaryl, where any two or more of R 21 , R 22 , R 23 , and R 24 can be taken together with intervening atoms to form one or more optionally substituted 3- to 12-membered rings, optionally containing one or more heteroatoms.

10. The polycarbonate polyol composition of claim 9 , wherein -E- is selected from the group consisting of:

and mixtures of any two or more of these,
wherein R x is selected from optionally substituted aliphatic, fluorinated aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl, fluorinated aryl, or optionally substituted heteroaryl.

11. The polycarbonate polyol composition of claim 9 , wherein -E- comprises predominantly —CH 2 CH 2 — units derived from ethylene oxide.

12. The polycarbonate polyol composition of claim 9 , wherein -E- comprises predominantly —CH 2 CH(CH 3 )— units derived from propylene oxide.

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

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

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

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

where each z is independently 0 or 1.

17. A polyurethane composition formed by reaction of one or more isocyanates with one or more aliphatic polycarbonate polyols of claim 1 .

18. An article of manufacture comprising the polycarbonate polyol composition of claim 1 .

19. An article of manufacture comprising the polycarbonate polyol composition of claim 1 .

20. The polycarbonate polyol composition of claim 1 , wherein the composition is characterized in that more than 99% of the epoxide CO 2 copolymer chains are of type P 1 .

Assignees

• Saudi Aramco Tech Co

Inventors

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

Classifications

• C08G64/0216

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

• C08G18/44

  Polycarbonates · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G64/0208

  saturated · CPC title