Method of copolymerizing ethylene carbonate with one or more cyclic esters

Patent metadata

Field	Value
Publication number	US-9371418-B2
Application number	US-201314407834-A
Country	US
Kind code	B2
Filing date	Jun 13, 2013
Priority date	Jun 15, 2012
Publication date	Jun 21, 2016
Grant date	Jun 21, 2016

Abstract

A process for copolymerizing selectively i) ethylene carbonate with ii) one or more cyclic esters can include contacting the ethylene carbonate with the one or more cyclic esters in the presence of a catalyst. The catalyst can be a Zn-complex with a diaminophenolate ligand (NNO) or a β-diiminate ligand (BDI).

First claim

The invention claimed is:

1. A process for copolymerizing i) ethylene carbonate with ii) one or more cyclic esters, comprising contacting the ethylene carbonate with the one or more cyclic esters in the presence of one or more catalysts of formula (I) or (II),

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are each independently selected from the group consisting of hydrogen, optionally substituted C 1-12 alkyl, and an inert functional group, and wherein two or more of said groups are optionally linked together to form one or more rings;
wherein X is —N(SiR 27 3 ) 2 , C 1-12 alkyl, C 1-12 alkoxy, —NR 9 R 10 or —BH 4 , and each R 27 is independently selected from hydrogen and C 1-6 alkyl;
wherein each R 9 and R 10 is independently selected from hydrogen and C 1-6 alkyl;
wherein R 11 and R 12 are each independently C 1-10 alkyl;
wherein R 13 , R 14 , and R 15 are each independently C 1-10 alkyl, or wherein R 13 and R 14 are covalently bound to each other and are each a methylene and R 15 is C 1-10 alkyl,
wherein X 11 is selected from C 1-10 alkyl, —OR 16 , and —N(SiR 17 3 ) 2 ;
wherein R 16 is C 1-10 alkyl; and
wherein each R 17 is independently selected from hydrogen and C 1-6 alkyl.

2. The process according to claim 1 , wherein R 11 and R 12 are each independently C 1-6 alkyl.

3. The process according to claim 1 , wherein R 13 , R 14 and R 15 are each independently C 1-6 alkyl.

4. The process according to claim 1 , wherein X 11 is selected from C 1-6 alkyl, —OR 16 , or —N(SiR 17 3 ) 2 , R 16 is C 1-6 alkyl, and each R 17 is independently selected from hydrogen and C 1-4 alkyl.

5. The process according to claim 1 , wherein the one or more catalysts are selected from [(NNO)ZnEt], [BDI]Zn(N(SiMe 3 ) 2 ), [BDI]Zn(Et) and {[BDI]Zn(OR 30 )} 2 wherein R 30 is C 1-6 alkyl.

6. The process according to claim 1 , wherein the process is performed in the presence of a compound of formula (III), acting as a co-initiator and transfer agent of the polymerization,
R 8 —OH  (III)

wherein R 8 is selected from the group consisting of C 1-20 alkyl, C 6-30 aryl, and C 6-30 aryl C 1-20 alkyl optionally substituted by one or more substituents selected from the group consisting of halogen, hydroxyl, and C 1-6 alkyl.

7. The process according to claim 6 , wherein the compound of formula (III) is 1-octanol, isopropanol, propanediol, trimethylolpropane, 2-butanol, 3-buten-2-ol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol, benzyl alcohol, 4-bromophenol,1,4-benzenedimethanol, and (4-trifluoromethyl)benzyl alcohol.

8. The process according to claim 1 , wherein the one or more cyclic esters are selected from the group consisting of glycolide, lactide, β-butyrolactone, δ-valerolactone, and ε-caprolactone.

9. The process according to claim 1 , wherein the process is performed with or without solvent.

10. The process according to claim 9 , wherein the process is performed with solvent, and wherein the solvent is selected from an aliphatic or aromatic hydrocarbon, an ether or an halogenated solvent.

11. The process according to claim 1 , wherein the process is performed in bulk.

12. The process according to claim 1 , wherein the process is performed with a lactone selected from the group consisting of β-butyrolactone, δ-valerolactone, and ε-caprolactone, in the presence of a solvent and at a temperature of at least 60° C. and at most 110° C.

13. The process according to claim 1 , wherein the process is performed with a lactone selected from the group consisting of β-butyrolactone, δ-valerolactone, and ε-caprolactone, in bulk and at a temperature of at least 60° C. and at most 80° C.

14. The process according to claim 1 , wherein the process is performed with glycolide or a lactide and at a temperature of at least 60° C. and at most 120° C.

15. The process according to claim 1 , wherein the copolymer prepared is an ether-free polyethylenecarbonate/polyester copolymer.

16. The process according to claim 1 , wherein the one or more catalysts comprise [(NNO)ZnEt], having the structure:

17. The process according to claim 1 , wherein the one or more catalysts comprise:

Assignees

• Total Res & Technology Feluy
• Centre Nat Rech Scient
• Centre Nat Recherche

Inventors

• Carpentier Jean-François
• Guillaume Sophie
• Guerin William

Classifications

• C08G64/18

  Block or graft polymers · CPC title

• C08G63/823

  for the preparation of polylactones or polylactides · CPC title

• C08G63/08

  Lactones or lactides · CPC title

• C08G63/83

  Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof {(C08G63/823 takes precedence)} · CPC title

• C08G63/64 Primary

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