Polyesters and polyketoesters from carbonylative terpolymerization of enols, methods to produce, blends, and articles therefrom

Patent metadata

Field	Value
Publication number	US-12331159-B2
Application number	US-202117460558-A
Country	US
Kind code	B2
Filing date	Aug 30, 2021
Priority date	Sep 1, 2020
Publication date	Jun 17, 2025
Grant date	Jun 17, 2025

Abstract

This invention relates to a polymerization process for producing a polyketoester, or an olefin-polyketoester utilizing a hydroesterification catalyst and an olefin-CO copolymerization catalyst in a reaction medium. Polyketoester copolymers and olefin-polyketoester copolymers are also disclosed.

First claim

What is claimed is:

1. A polymerization process comprising:
contacting an alpha-omega enol having the general formula:

wherein R* is a divalent hydrocarbyl, a divalent hydrocarbyl substituted with one or more functional group comprising elements from Group 13-17 of the periodic table of the elements, or a combination thereof; and carbon monoxide (CO) in the presence of a hydroesterification catalyst and an olefin-CO copolymerization catalyst in a reaction medium within a reactor at a temperature, a CO pressure, and for a period of time sufficient to produce a polyketoester having an empirical formula:
( A ) a ( B ) b ( C ) c ( D ) d

wherein a>0, b≥0, c>0, and d≥0;
moieties A, B, C, and D may be arranged randomly, in blocks, or in any order;
moiety A having the general formula:

moiety B having the general formula:

moiety C having the general formula:

 and
moiety D having the general formula:

wherein R ++ is H, or a polyketoester chain having the empirical formula (A) a (B) b (C) c (D) d ; wherein a>0, b≥0, c>0, and d≥0.

2. The process of claim 1 , wherein the reaction medium further comprises an alpha olefin having the general formula:

wherein R 1 is H or a hydrocarbyl comprising 1 to 18 carbon atoms;
to produce an olefin-polyketoester or a branched olefin-polyketoester having an empirical formula:
( A ) a ( B ) b ( C ) c ( D ) d ( E ) e

wherein a>0, b≥0, c>0, d≥0; and e>0;
moieties A, B, C, D and E may be arranged randomly, in blocks, or in any order;
moiety E having the general formula:

and
wherein R ++ is H, or an olefin-polyketoester chain having the empirical formula (A) a (B) b (C) c (D) d (E) e ; wherein a>0, b≥0, c>0, d≥0; and e>0.

3. The process of claim 2 , wherein R*is a linear or branched divalent alkane radical having 1 to 19 carbon atoms.

4. The process of claim 2 , wherein the R* comprises at least one divalent aromatic ring system.

5. The process of claim 4 , wherein the alpha-omega enol is according to the formula:

or

wherein Ar represents a cyclic or aromatic ring system in which x≥1 and y+z≥1;
each R′, when present, is a divalent hydrocarbyl, a divalent hydrocarbyl substituted with one or more functional group comprising elements from Group 13-17 of the periodic table of the elements, or a combination thereof;
wherein each R″ is a divalent hydrocarbyl, a divalent hydrocarbyl substituted with one or more functional groups comprising elements from Group 13-17 of the periodic table of the elements, or a combination thereof.

6. The process of claim 5 , wherein the alpha-omega enol is according to the formula:

wherein each of R 2 , R 3 , R 4 , R 5 and R 6 is, independently, a hydrogen, a C 1 -C 20 hydrocarbyl radical, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or a combination thereof, or wherein two or more of R 2 , R 3 , R 4 , R 5 and R 6 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure subject to the proviso that at least one of R 2 , R 3 , R 4 , R 5 and R 6 comprise a moiety having a terminal carbon-carbon double bond.

7. The process of claim 5 , wherein the alpha-omega enol is according to the formula:

wherein x is from 1 to 20;
each of R 2 , R 3 , R 4 , R 5 and R 6 is, independently, a hydrogen, a C 1 -C 20 hydrocarbyl radical, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or a combination thereof, or wherein two or more of R 2 , R 3 , R 4 , R 5 and R 6 independently join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
R 7 is a divalent C 1 -C 20 hydrocarbyl radical, a divalent functional group comprising elements from Group 13-17 of the periodic table of the elements,
subject to the proviso that at least one of R 2 , R 3 , R 4 , R 5 and R 6 comprises a moiety having a terminal carbon-carbon double bond.

8. The process of claim 1 , wherein the olefin-CO copolymerization catalyst, the hydroesterification catalyst, or both comprise a metal from Groups 8, 9, or 10 of the periodic table of elements.

9. The process of claim 8 , wherein each of the olefin-CO copolymerization catalyst, the hydroesterification catalyst, or both independently comprise Ni or Pd.

10. The process of claim 1 , wherein the hydroesterification catalyst is produced in-situ via reaction of M (L) 2 +HA+P d X e Y f , to form the hydroesterification catalyst active to produce the copolymer;
wherein M is Ni or Pd;
each L is independently a ligand comprising a hydrocarbyl, a substituted hydrocarbyl, a functional group comprising elements from Group 13-17 of the periodic table of the elements, or a combination thereof, or each of the two ligands L join together to form a single divalent C 4 to C 62 cyclic or polycyclic ring structure;
A − is the conjugate base of an acid;
P d X e Y f is a phosphine ligand system comprising one or more phosphine moieties, each independently substituted with a combination of monovalent ligands X and divalent ligands Y;
each monovalent ligand X is independently a hydrocarbyl, a substituted hydrocarbyl, and/or a functional group comprising elements from Group 13-17 of the periodic table of the elements;
each divalent ligand Y is independently a hydrocarbyl, a substituted hydrocarbyl, and/or a functional group comprising elements from Group 13-17 of the periodic table of the elements;
d≥1; and
e+2*f=3*d.

11. The process of claim 10 , wherein the olefin-CO copolymerization catalyst and the hydroesterification catalyst are the same.

12. The process of claim 1 , wherein the olefin-CO copolymerization catalyst is a P—SO 3 bidentate Drent-type catalyst having the general formula:

wherein M is a Group 8, 9, or 10 metal;
each of R a 1 , R a 2 , R a 3 , R a 4 , R a 5 , and R a 6 , is, independently, a hydrogen, a C 1 -C 20 hydrocarbyl radical, a C 1 -C 20 substituted hydrocarbyl radical, and/or a functional group comprising elements from Group 13-17 of the periodic table of the elements; or two or more of R a 1 , R a 2 , R a 3 , and R a 4 , and/or both of R a 5 , and R a 6 join together to form a C 4 to C 62 cyclic or polycyclic ring structure;
wherein X is a monovalent functional group comprising e

Assignees

• Exxonmobil Chemical Patents Inc
• Univ Minnesota
• Exxon Mobil Chemical Patents Inc

Inventors

• Tonks Ian
• Carpenter Alex Edward

Classifications

• C08G67/02 Primary

  Copolymers of carbon monoxide and aliphatic unsaturated compounds · CPC title