Polycarbonate polyol compositions and methods

Patent metadata

Field	Value
Publication number	US-10836859-B2
Application number	US-201916379129-A
Country	US
Kind code	B2
Filing date	Apr 9, 2019
Priority date	Sep 8, 2008
Publication date	Nov 17, 2020
Grant date	Nov 17, 2020

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 method for the synthesis of aliphatic polycarbonate polyols, the method comprising the steps of:
a) providing a reaction mixture comprising:
(i) one or more epoxides;
(ii) carbon dioxide;
(iii) a metallosalenate metal complex; and
(iv) a chain transfer agent having a structure Y—A—(Y) n , 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 covalent bond or a multivalent moiety; and
n is an integer between 1 and 10, inclusive;
wherein the chain transfer agent and metal complex are present in a molar ratio ranging from 40:1 to 1000:1 or greater than 1000:1;

b) allowing the polymerization reaction to proceed; and
c) terminating the polymerization.

2. The method of claim 1 , wherein each Y group is independently selected from the group consisting of: —OH, —C(O)OH, —C(OR y )OH, —OC(R y )OH, —NHR y , —NHC(O)R y , —NHC═NR y , —NR y C═NH, —NR y C(NR y 2 )═NH; —NHC(NR y 2 )═NR y ; —NHC(O)OR y , —NHC(O)NR y 2 ; —C(O)NHR y , —C(S)NHR y , —OC(O)NHR y , —OC(S)NHR y , —SH, —C(O)SH, —B(OR y )OH, —P(O) a (R y ) b (OR y ) c (OH) d , —OP(O) a (R y ) b (OR y ) c (OH) d , —N(R y )OH, —ON(R y )H, ═NOH, and ═NN(R y )H, where each occurrence of R y is independently —H, or a radical which may be substituted selected from the group consisting of C 1-20 aliphatic, C 1-20 heteroaliphatic, 3- to 12-membered heterocyclic, and 6- to 12-membered aryl, a and b are each independently 0 or 1, c is 0, 1 or 2, d is 0 or 1, and the sum of a, b, and c is 1 or 2.

3. The method of claim 1 , wherein one or more Y groups are hydroxyl or a hydroxyl salt.

4. The method of claim 3 , wherein -A- is a C 3-20 aliphatic chain which may be substituted.

5. The method of claim 3 , wherein -A- is a polyether chain or a polyolefin chain.

6. The method of claim 1 , wherein at least one Y group is a carboxylic acid or a salt thereof.

7. The method of claim 1 , wherein an epoxide has a structure:

where, R 21 , R 22 , R 23 , and R 24 , are each independently selected from the group consisting of: —H, and a group which may be substituted 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 3- to 12-membered rings, which may be substituted and contain one or more heteroatoms.

8. The method of claim 1 , wherein an epoxide is selected from the group consisting of:

wherein each R x is, independently, selected from aliphatic which may be substituted, heteroaliphatic which may be substituted, aryl which may be substituted and heteroaryl which may be substituted.

9. The method of claim 1 , wherein an epoxide is ethylene oxide or propylene oxide.

10. The method of claim 1 , wherein the metallosalente metal complex is cobalt salen complex, chromium salen complex, or aluminum salen complex.

11. The method of claim 1 , wherein the metallosalenate metal complex is selected from the group consisting of:

wherein,
M is a metal atom;
Q, at each occurrence is independently O or S;
R 1 and R 1′ are independently selected from the group consisting of —H, C 1 to C 12 aliphatic which may be substituted, 3- to 14-membered carbocycle which may be substituted, 3- to 14-membered heterocycle which may be substituted, and R 21 ;
R 2 and R 2′ are independently selected from the group consisting of —H, C 1 to C 12 aliphatic which may be substituted, 3- to 14-membered carbocycle which may be substituted, 3- to 14-membered heterocycle which may be substituted, R 14 , R 20 , and R 21 ;
R 3 and R 3′ are independently selected from the group consisting of —H, C 1 to C 12 aliphatic which may be substituted, 3- to 14-membered carbocycle which may be substituted, 3- to 14-membered heterocycle which may be substituted, and R 21 ;
represents a moiety which may be substituted covalently linking two nitrogen atoms,
where any of [R 2′ and R 3′ ], [R 2 and R 3 ], [R 1 and R 2 ], and [R 1′ and R 2′ ] may be taken together with intervening atoms to form one or more rings which may in turn be substituted with one or more groups selected from R 14 , R 20 , and R 21 ;
R 14 at each occurrence is independently selected from the group consisting of halogen, C 1 to C 12 aliphatic which may be substituted, 3- to 14-membered carbocycle which may be substituted, 3- to 14-membered heterocycle which may be substituted, —OR 10 , —OC(O)R 13 , —OC(O)OR 13 , —OC(O)NR 11 R 12 , —CN, —CNO, —C(R 13 ) z H (3-z) , —C(O)R 13 , —C(O)OR 13 , —C(O)NR 11 R 12 , —NR 11 R 12 , —NR 11 C(O)R 13 , —NR 11 C(O)OR 13 , —NR 11 SO 2 R 13 , —N + R 11 R 12 R 13 X − , —P + (R 11 ) 3 X − , —P(R 11 ) 3 ═N + ═P(R 11 ) 3 X − , —As + R 11 R 12 R 13 X − , —NCO, —N 3 , —NO 2 , —S(O) x R 13 , and —SO 2 NR 11 R 12 ;
R 20 at each occurrence is independently selected from the group consisting of halogen, —OR 10 , —OC(O)R 13 , —OC(O)OR 13 , —N + (R 11 ) 3 X − , —P + (R 11 ) 3 X − , —P(R 11 ) 3 ═N + ═P(R 11 ) 3 X − , —As + R 11 R 12 R 13 X − , —OC(O)NR 11 R 12 , —CN, —CNO, —C(O)R 13 , —C(O)R 13 , —C(O)NR 11 R 12 , —C(R 13 ) z H (3-z) , —NR 11 R 12 , —NR 11 C(O)R 13 , —NR 11 C(O)OR 13 , —NCO, —NR 11 SO 2 R 13 , —S(O) x R 13 , —S(O) 2 NR 11 R 12 , —NO 2 , —N 3 , and —Si(R 13 ) (3-z) [(CH 2 ) k R 14 ] z ;
R 21 at each occurrence is independently selected from the group consisting of —(CH 2 ) k R 20 and —(CH 2 ) k —Z—(CH 2 ) k R 20 ;
X − is any anion;
Z is a divalent linker selected from the group consisting of —(CH═CH) a —, —(C≡C) a —, —C(O)—, —C(═NOR 11 )—, —C(═NNR 11 R 12 )—, —O—, —OC(O)—, —C(O)O—, —OC(O)O—, —N(R 11 )—, —N(C(O)R 13 )—, —C(O)NR 13 —, —N(C(O)R 13 )O—, —NR 13 C(O)R 13 N—, —S(O) x —, a polyether, and a polyamine;
R 10 at each occurrence is independently selected from the group consisting of —H, C 1-12 aliphatic which may be substituted, a 3- to 14-membered carbocycle which may be substituted, a 3- to 14-membered heterocycle which may be substituted, —S(O) 2 R 13 , —Si(R 15 ) 3 , —C(O)R 13 , and a hydroxyl protecting group;
R 11 and R 12 at each occurrence are independently selected from the group consisting of —H, C 1 to C 12 aliphatic which may be substituted, a 3- to 14-membered carbocycle which may be substituted, a 3- to 14-membered heterocycle which may be substituted, where two or more R 11 or R 12 groups can be taken together with intervening atoms to form a 3- to 10-membered ring which may be substituted;
R 13 at each occurrence is independently selected from the group consisting of —H, C 1 to C 12 aliphatic which may be substituted, a 3- to 14-membered carbocycle which may be substituted, and 3- to 14-membered heterocycle which may be substituted, where two or more R 13 groups on the same molecule may be taken together to form a ring;
R 15 at each occurrence is independently selected from the group consisting of C 1-12 aliphatic which may be substituted, a 3- to 14-membered carbocycle which may be substituted, and a 3- to 14-membered heterocycle which may be substituted;
a is 1, 2, 3, or 4;
k is independently at each occurrence an integer from 1 to 8 inclusive;
x is 0, 1, or 2; and
z is 1, 2, or 3.

12. The method of claim 11 , wherein M is selected from the gro

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

• C08G64/34 Primary

  and cyclic ethers · CPC title

• C08G18/44

  Polycarbonates · CPC title

• C08G64/0216

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

• C08G64/0208

  saturated · CPC title