# US 10,308,761 B2 · Methods for polymer synthesis

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- Number: US 10,308,761 B2
- Document ID: US10308761B2
- Status: Granted
- Kind: B2
- Application number: 15/368,144
- Filed: 2016-12-02
- Published: 2017-06-29
- Granted: 2019-06-04
- Earliest claimed: 2011-12-20
- Assignees: Saudi Aramco Technologies Company
- Applicants: Saudi Aramco Technologies Company
- Inventors: Scott D. Allen; Christopher A. Simoneau; William D. Keefe; Jeff R. Conuel
- Web page: https://patentgrep.com/patent/US10308761B2

## CPC

- C08G 64/34: and cyclic ethers
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS

## Abstract

The present invention provides methods for reducing induction periods in epoxide-CO2 copolymerizations. In certain embodiments, the methods include the step of contacting an epoxide with CO2 in the presence of two catalysts: an epoxide hydrolysis catalyst and an epoxide CO2 copolymerization catalyst. In another aspect, the invention provides catalyst compositions comprising a mixture of an epoxide hydrolysis catalyst and an epoxide CO2 copolymerization catalyst.

## Claims

### Claim 1

A method for preparing aliphatic polycarbonate polymers comprising the step of contacting one or more epoxides with a first catalyst capable of catalyzing the hydrolysis of epoxides and a second catalyst capable of catalyzing the copolymerization of epoxides and CO2;
wherein the first catalyst is an oligomeric metal complex; and
the second catalyst comprises a metal-ligand complex.

### Claim 2 (depends on 1)

The method of claim 1, wherein the first catalyst comprises two or more
groups covalently linked together, wherein
M is a metal atom; and
is a multidentate ligand.

### Claim 3 (depends on 2)

The method of claim 2, wherein the first catalyst is represented by the following structural formula:
wherein
s′ is an integer between 1 and 20;
M is a metal atom;
is a multidentate ligand; and
is alkyl, optionally comprising one or more sites of unsaturation, and optionally comprising one or more ether, ester, or amide linkages.

### Claim 4 (depends on 3)

The method of claim 3, wherein
is a metallosalenate complex represented by the following structural formula:
wherein:
M is a metal atom;
R1a and R1a′ are independently, hydrogen, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, and an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
R4b is selected from the group consisting of:
where
Rc at each occurrence is independently hydrogen, halogen, —OR, —NR2, —SR, —CN, —SO2R, —SOR, —SO2NR2, —CNO, —NRSO2R, —NCO, —N3, —SiR3, —C(O)NR2, —OC(O)NR2, —NR(CO)OR, —NRC(O)R, —CO2R, —OC(O)R, —OC(O)OR, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or
any two adjacent Rc groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more optionally substituted rings; or
any two Rc groups attached to the same carbon atom may optionally be taken together along with the carbon atom to which they are attached to form an optionally substituted moiety selected from the group consisting of: a 3- to 8-membered spirocyclic ring, a carbonyl, an oxime, a hydrazone, and an imine;
Rd at each occurrence is independently hydrogen, halogen, —OR, —NR2, —SR, —CN, —NO2, —SO2R, —SOR, —SO2NR2, —CNO, —NRSO2R, —NCO, —N3, —SiR3, —C(O)NR2, —OC(O)NR2, —NR(CO)OR, —NRC(O)R, —CO2R, —OC(O)R, —OC(O)OR, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or
any two adjacent Rd groups may be taken together with their intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms independently selected from nitrogen, oxygen, or sulfur;
R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl, C1-6 aliphatic, C1-6 heteroaliphatic, carbamoyl, arylalkyl, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, an oxygen protecting group, and a nitrogen protecting group; or
two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring,
X is an anion;
Y is a divalent linker selected from the group consisting of: —C(Rc)2—, —NR—, —N(R)C(O)—, —C(O)NR—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO2—, —SiR2—, —C(═S)—, —C(═NR)—, or —N═N—; —CR═CR—, a polyether; a C3 to C8 substituted or unsubstituted carbocycle; and a C1 to C8 substituted or unsubstituted heterocycle;
m is 0 or an integer from 1 to 6, inclusive;
m′ is 0 or an integer from 1 to 4, inclusive;
q is 0 or an integer from 1 to 4, inclusive; and
x is 1 or 2.

### Claim 5 (depends on 4)

The method of claim 4, wherein the metallosalenate complex is selected from the group consisting of:
wherein
R4a, R4a′, R5a, R5a′, R6a, R6a′, R7a, and R7a′ are each independently hydrogen, halogen, —OR, —NR2, —SR, —CN, —NO2, —SO2R, —SOR, —SO2NR2, —CNO, —NRSO2R, —NCO, —N3, —SiR3, —C(O)NR2, —OC(O)NR2, —NR(CO)OR, —NRC(O)R, —CO2R, —OC(O)R, —OC(O)OR, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, and an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or
any one or more of [R1a and R4a], [R1a′ and R4a′], [R4a and R5a], [R5a and R6a], [R6a and R7a], [R4a′ and R5a′], [R5a′ and R6′], [R6′ and R7a′] can optionally be taken together with their intervening atoms to form one or more optionally substituted rings;
w is 0 or an integer from 1 to 8, inclusive;
p is 0 or an integer from 1 to 4, inclusive; and
X is an anion.

### Claim 6 (depends on 5)

The method of claim 5, wherein the metallosalenate complex is

### Claim 7 (depends on 3)

The method of claim 3, wherein the first catalyst comprises:

### Claim 8 (depends on 3)

The method of claim 3, wherein the first catalyst comprises:

### Claim 9 (depends on 2)

The method of claim 2, wherein the first catalyst is represented by the following structural formula:
wherein
s′ is an integer between 1 and 20;
M is a metal atom;
is a multidentate ligand; and
is alkyl, optionally comprising with one or more sites of unsaturation, and optionally comprising one or more ether, ester, or amide linkages.

### Claim 10 (depends on 9)

The method of claim 9, wherein
is a metallosalenate complex represented by the following structural formula:
wherein:
M is a metal atom;
R1a and R1a′ are independently, hydrogen, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, and an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur;
R4b is selected from the group consisting of:
where
Rc at each occurrence is independently hydrogen, halogen, —OR, —NR2, —SR, —CN, —SO2R, —SOR, —SO2NR2, —CNO, —NRSO2R, —NCO, —N3, —SiR3, —C(O)NR2, —OC(O)NR2, —NR(CO)OR, —NRC(O)R, —CO2R, —OC(O)R, —OC(O)OR, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or
any two adjacent Rc groups may be taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more optionally substituted rings; or
any two Rc groups attached to the same carbon atom may optionally be taken together along with the carbon atom to which they are attached to form an optionally substituted moiety selected from the group consisting of: a 3- to 8-membered spirocyclic ring, a carbonyl, an oxime, a hydrazone, and an imine;
Rd at each occurrence is independently hydrogen, halogen, —OR, —NR2, —SR, —CN, —NO2, —SO2R, —SOR, —SO2NR2, —CNO, —NRSO2R, —NCO, —N3, —SiR3, —C(O)NR2, —OC(O)NR2, —NR(CO)OR, —NRC(O)R, —CO2R, —OC(O)R, —OC(O)OR, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or
any two adjacent Rd groups may be taken together with their intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms independently selected from nitrogen, oxygen, or sulfur;
R at each occurrence is independently hydrogen, an optionally substituted radical selected the group consisting of acyl, C1-6 aliphatic, C1-6 heteroaliphatic, carbamoyl, arylalkyl, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, an oxygen protecting group, and a nitrogen protecting group; or
two R groups on the same nitrogen atom can optionally be taken together to form an optionally substituted 3- to 7-membered ring,
X is an anion;
Y is a divalent linker selected from the group consisting of: —C(Rc)2—, —NR—, —N(R)C(O)—, —C(O)NR—, —O—, —C(O)—, —OC(O)—, —C(O)O—, —S—, —SO—, —SO2—, —SiR2—, —C(═S)—, —C(═NR)—, or —N═N—; —CR═CR—, a polyether; a C3 to C8 substituted or unsubstituted carbocycle; and a C1 to C8 substituted or unsubstituted heterocycle;
m is 0 or an integer from 1 to 6, inclusive;
m′ is 0 or an integer from 1 to 4, inclusive;
q is 0 or an integer from 1 to 4, inclusive; and
x is 1, or 2.

### Claim 11 (depends on 10)

The method of claim 10, wherein the metallosalenate complex is selected from the group consisting of:
wherein
R4a, R4a′, R5a, R5a′, R6a, R6a′, R7a, and R7a′ are each independently hydrogen, halogen, —OR, —NR2, —SR, —CN, —NO2, —SO2R, —SOR, —SO2NR2, —CNO, —NRSO2R, —NCO, —N3, —SiR3, —C(O)NR2, —OC(O)NR2, —NR(CO)OR, —NRC(O)R, —CO2R, —OC(O)R, —OC(O)OR, or an optionally substituted radical selected from the group consisting of C1-20 aliphatic, C1-20 heteroaliphatic, phenyl, a 3- to 8-membered saturated or partially unsaturated monocyclic carbocycle, a 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle, a 5- to 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 3- to 8-membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, a 6- to 12-membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur, and an 8- to 10-membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; or
any one or more of [R1a and R4a], [R1a′ and R4a′], [R4a and R5a], [R5a and R6a], [R6a and R7a], [R4a′ and R5a′], [R5a′ and R6′], [R6a′ and R7a′] can optionally be taken together with heir intervening atoms to form one or more optionally substituted rings;
w is 0 or an integer from 1 to 8, inclusive;
p is 0 or an integer from 1 to 4, inclusive; and
X is an anion.

### Claim 12 (depends on 11)

The method of claim 11, wherein the metallosalenate complex is

### Claim 13 (depends on 12)

The method of claim 12, wherein the first catalyst is:

### Claim 14 (depends on 12)

The method of claim 12, wherein the first catalyst is:

### Claim 15 (depends on 1)

The method of claim 1, characterized in that the second catalyst, when used without the step of contacting the epoxide with the first catalyst exhibits an induction period and that when the second catalyst is used with the step of contacting the epoxide with the first catalyst, this induction period is lessened or eliminated.

### Claim 16 (depends on 1)

The method of claim 1, wherein the one or more epoxides are contacted with both catalysts in the presence of CO2.

### Claim 17 (depends on 1)

The method of claim 1, wherein the step comprises a first substep comprising epoxide hydrolysis and a second substep comprising epoxide CO2 copolymerization.

### Claim 18 (depends on 17)

The method of claim 17, wherein the first and second substeps are performed at different times and the first substep comprises contacting one or more epoxides with the first catalyst prior to adding the second catalyst; and the second substep comprises contacting the one or more epoxides with carbon dioxide in the presence of the second catalyst.

### Claim 19 (depends on 17)

The method of claim 17, wherein the first and second substeps are performed at different times and the first substep comprises:
a) charging a reaction vessel with one or more epoxides,
b) contacting the one or more epoxides with the first catalyst,
c) allowing a period of time for epoxide hydrolysis, and
the second substep comprises adding the second catalyst to the vessel.

### Claim 20 (depends on 17)

The method of claim 17, wherein the first and second substeps are performed sequentially and the method comprises:
a) simultaneously contacting one or more epoxides with the first catalyst and the second catalyst;
b) allowing the mixture to react for a period of time in the absence of CO2, and
c) contacting the mixture of one or more epoxides, the first catalyst, and the second catalyst with carbon dioxide.

### Claim 21

A method for the copolymerization of one or more epoxides and CO2 to produce aliphatic polycarbonate polymers, the method comprising the steps of:
treating an epoxide feedstock comprising one or more epoxides by contacting it with a first catalyst capable of catalyzing epoxide hydrolysis and optionally a second catalyst capable of catalyzing epoxide CO2 copolymerization; and
feeding the treated epoxide feedstock to an epoxide CO2 copolymerization reaction where it is contacted with CO2 in the presence of the second catalyst capable of catalyzing epoxide CO2 copolymerization;
wherein
the first catalyst comprises an oligomeric metal complex; and
the second catalyst comprises a metal-ligand complex.

### Claim 22 (depends on 21)

The method of claim 21, wherein only the first catalyst is present in the first step and the second catalyst is only present at the copolymerization step.

### Claim 23 (depends on 21)

The method of claim 21, wherein the second catalyst is present during the step of treating the epoxide feedstock.

### Claim 24 (depends on 21)

The method of claim 21, comprising the further step of removing the first catalyst from the treated epoxide feedstock prior to the feeding step.

### Claim 25 (depends on 21)

The method of claim 21, wherein the first catalyst is a solid or solid-supported epoxide hydrolysis catalyst.