Aliphatic polycarbonate polyol compositions

Patent metadata

Field	Value
Publication number	US-10308759-B2
Application number	US-201515301095-A
Country	US
Kind code	B2
Filing date	Apr 3, 2015
Priority date	Apr 3, 2014
Publication date	Jun 4, 2019
Grant date	Jun 4, 2019

Abstract

The present invention encompasses CO2-based polycarbonate polyols that do not degrade from the chain ends to form cyclic carbonate. Importantly, the inventive polyol compositions retain —OH end group functionality desirable for thermoset applications.

First claim

What is claimed is:

1. A method comprising the steps of:
i) reacting a polycarbonate polyol of formula P1-OH,

with a cyclic acid anhydride having a formula

 to provide a polycarbonate polyol of formula P1-CO 2 H,

 and
ii) further treating this polyol with an epoxide of formula

 to yield a polymer composition of formula P1,

wherein:
is a multivalent moiety;
R 1 , R 2 , R 3 , and R 4 are at each occurrence, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-40 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R 1 , R 2 , R 3 , and R 4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;
R 1′ , R 2′ , R 3′ , and R 4′ are at each occurrence, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-40 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R 1′ , R 2′ , R 3′ and R 4′ may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;
each n is independently, on average in the composition, within a range from about 2 to about 200;
Q is an optionally substituted bivalent moiety; and
x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

2. The method of claim 1 , wherein the moiety

at each occurrence in the aliphatic polycarbonate chains is independently selected from the group consisting of:

wherein each R x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

3. The method of claim 1 , wherein the moiety

at each occurrence in the aliphatic polycarbonate chains is independently selected from the group consisting of:

wherein each R x is independently selected from the group consisting of: optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aryl and optionally substituted heteroaryl.

4. The method of claim 1 , wherein the moiety

at each occurrence in the aliphatic polycarbonate chains is

5. The method of claim 1 , wherein Q is an optionally substituted bivalent moiety selected from the group consisting of:

where R a and R b are each independently selected from the group consisting of: —H, halogen, optionally substituted C 1-8 aliphatic, and optionally substituted C 1-8 heteroaliphatic, where two or more R a and/or R b groups (whether on the same or different carbon atoms) may be taken together with intervening atoms to form one or more optionally substituted, optionally unsaturated rings, optionally containing one or more heteroatoms, and where two R a and R b groups on the same carbon atom or on adjacent carbon atoms may optionally be taken together to form an alkene or, if on the same carbon atom, an oxo group;
q is an integer from 1 to 10;
R d is optionally present, and if present are, independently at each occurrence selected from the group consisting of: halogen, —OR, —NR 2 , —SR, —CN, —NO 2 , —SO 2 R, —SOR, —SO 2 NR 2 , —CNO, —NRSO 2 R, —NCO, —N 3 , —SiR 3 ; or an optionally substituted group selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and
R is independently hydrogen, an optionally substituted C 1-20 aliphatic group, or an optionally substituted aryl group.

6. The method of claim 1 , wherein Q is an optionally substituted bivalent moiety selected from the group consisting of:

where R d is independently at each occurrence selected from the group consisting of: halogen, —OR, —NR 2 , —SR, —CN, —NO 2 , —SO 2 R, —SOR, —SO 2 NR 2 , —CNO, —NRSO 2 R, —NCO, —N 3 , —SiR 3 ; or
an optionally substituted group selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6-10-membered aryl; 5-10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4-7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; and
R is independently hydrogen, an optionally substituted C 1-20 aliphatic group, or an optionally substituted aryl group.

7. The method of claim 1 , wherein Q is:

8. The method of claim 1 , wherein Q is:

9. The method of claim 1 , wherein:
R 3′ is selected from the group consisting of an optionally substituted C 1-40 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted aryl group; and
R 1′ , R 2′ , and R 4′ are at each occurrence, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-40 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted aryl group, where any two or more of R 1′ , R 2′ , R 3′ and R 4′ may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

10. The method of claim 1 , wherein the moiety

is at each o

Assignees

• Saudi Aramco Tech Co

Inventors

• Simoneau Christopher A

Classifications

• C08G64/0216 Primary

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

• C08G18/72

  Polyisocyanates or polyisothiocyanates · CPC title

• C08G63/64 Primary

  Polyesters containing both carboxylic ester groups and carbonate groups · CPC title

• C08G18/44

  Polycarbonates · CPC title

• C08G64/42

  Chemical after-treatment · CPC title