Recyclable polymers based on ring-fused gamma-butyrolactones

Patent metadata

Field	Value
Publication number	US-10759899-B2
Application number	US-201816053225-A
Country	US
Kind code	B2
Filing date	Aug 2, 2018
Priority date	Aug 3, 2017
Publication date	Sep 1, 2020
Grant date	Sep 1, 2020

Abstract

The invention discloses a class of new polymers, trans-ring-fused poly(4-hydroxybutyrate)s (RF-P4HB) that exhibit a unique set of properties, including robust thermal stability and mechanical strength, quantitative recyclability to the building block monomers via thermolysis and/or chemical catalysis, and convenient production from the chemical ring-opening polymerization under ambient temperature and pressure. Another unique property is the formation of crystalline stereocomplexed polymers with high melting temperature upon mixing the two enantiomeric RF-P4HB chains via stereocomplexing co-crystallization. This invention also provides the corresponding ring-fused lactone monomer structures that enable the synthesis of the RF-P4HB polymers, through trans-fusing of rings to the parent γ-butyrolactone ring. Furthermore, a polymerization or copolymerization process for the synthesis of RF-P4HB polymers and copolymers is disclosed.

First claim

What is claimed is:

1. A polymer comprising Formula I, Formula II, or Formula III:

wherein
Q and R are the terminal ends of the polymer, or Q and R taken together form a cyclic polymer of Formula I, Formula II, or Formula III;
G is O, S, or NR z ;
R x , R y and R z are each independently H or —(C 1 -C 8 )alkyl;
m is about 20 to about 10 6 ; and
n is 1-20;

wherein the R y substituents have a trans-configuration relative to each other, each —(C 1 -C 8 )alkyl moiety is independently branched or unbranched, and each ring-embedded carbon independently has an optional —(C 1 -C 8 )alkyl substituent or phenyl substituent.

2. The polymer of claim 1 wherein G is O.

3. The polymer of claim 1 wherein R x is H, or R y is H.

4. The polymer of claim 1 wherein Q is —(C 1 -C 8 )alkyl, N(R A ) 2 , OR A , or SR A , and R is H, wherein each R A is independently H, —(C 1 -C 8 )alkyl, Ph 2 CHCH 2 —, or —Si[(C 1 -C 8 )alkyl] 3 .

5. The polymer of claim 1 wherein the polymer has a number average molecular weight (M n ) of about 0.1 kg mol −1 to about 5×10 6 kg mol −1 , and/or the polymer has a polydispersity index of about 1 to about 3.

6. The polymer of claim 1 wherein the polymer is thermally depolymerizable or chemically depolymerizable to a monomer.

7. The polymer of claim 6 wherein thermal or chemical depolymerization of the polymer provides about 95% or greater conversion of the polymer to the monomer.

8. A method for polymerization comprising contacting a monomer with a catalyst and an optional protic initiator to form a polymer via a ring opening polymerization reaction of the monomer, wherein the monomer is a monomer of Formula IV or Formula V:

or an enantiomer or mixture thereof, wherein:
G 1 is —C(═O)— and G 2 is O, S, or NR z ; or
G 1 is O, S, or NR z and G 2 is —C(═O)—;
G 3 is O, S, or NR z ;
R x , R y and R z are each independently H or —(C 1 -C 8 )alkyl; and
n is 0-20;
wherein each —(C 1 -C 8 )alkyl moiety is independently branched or unbranched, and each ring-embedded carbon independently has an optional —(C 1 -C 8 )alkyl substituent or phenyl substituent.

9. The method of claim 8 comprising forming the polymer at a pressure of about 1 atm to about 10 atm and at a temperature of about 0° C. to about 100° C.

10. The method of claim 8 wherein the catalyst is a metal-based catalyst or an organic catalyst.

11. The method of claim 10 wherein the metal-based catalyst is tris[N,N-bis(trimethylsilyl)amide]lanthanum(III),

wherein X is a donor solvent molecule.

12. The method of claim 8 wherein the protic initiator is an alcohol, a thiol, or an amine.

13. The method of claim 8 wherein the monomer is a monomer of Formula IVA or Formula IVB:

or an enantiomer or mixture thereof, wherein n is 1-20.

14. The method of claim 8 wherein the monomer is a monomer of Formula IVC or Formula IVD:

or an enantiomer or mixture thereof, wherein n is 1-20.

15. The method of claim 8 further comprising quenching the polymerization reaction to form a polymer.

16. The method of claim 15 wherein the monomer is a monomer of Formula IVA:

or an enantiomer or mixture thereof, wherein n is 1-20;
the catalyst comprises a nucleophile (Q); and
the polyester is a polyester of Formula VI:

wherein:
Q is the nucleophile and R is H, or Q and R taken together form a cyclic polymer of Formula VI; and m is about 20 to about 10 6 .

17. The method of claim 15 wherein the monomer is a monomer of Formula IVB:

or an enantiomer or mixture thereof, wherein n is 1-20;
the catalyst comprises a nucleophile (Q); and
the polyester is a polyester of Formula VII:

wherein
Q is the nucleophile and R is H, or Q and R taken together form a cyclic polymer of Formula VII; and
m is about 20 to about 10 6 .

18. The method of claim 8 wherein the method further comprises contacting the polymerization reaction with a second monomer.

19. The method of claim 18 wherein the second monomer is a lactone or lactide.

20. The method of claim 18 wherein a block or random copolymer is formed by contacting the polymerization reaction with a second monomer.

21. The method of claim 16 wherein the polymer is recycled to the monomer by thermal depolymerization or chemical depolymerization.

22. The method of claim 16 wherein stoichiometric amounts of a polyester having a stereo-configuration formed from one enantiomer of the monomer, and a second polyester having the opposite stereo-configuration formed from the other enantiomer of the monomer are co-crystallized to form a crystalline stereocomplex, wherein the crystalline stereocomplex has a higher melting temperature than said polyester having the stereo-configuration or opposite stereo-configuration.

Assignees

• Univ Colorado State Res Found

Inventors

• Chen Eugene Y
• Zhu jian-bo

Classifications

• C08G63/826

  Metals not provided for in groups C08G63/83 - C08G63/86 (C08G63/823 takes precedence) · CPC title

• C08G63/08 Primary

  Lactones or lactides · CPC title

• C08J11/12

  by dry-heat treatment only · CPC title

• C08J2367/04

  Polyesters derived from hydroxy carboxylic acids, e.g. lactones (C08J2367/06 takes precedence) · CPC title

• C08G63/823

  for the preparation of polylactones or polylactides · CPC title