Method for preparing a polymer from at least one cyclic monomer

Patent metadata

Field	Value
Publication number	US-9738751-B2
Application number	US-201014421069-A
Country	US
Kind code	B2
Filing date	Dec 7, 2010
Priority date	Dec 8, 2009
Publication date	Aug 22, 2017
Grant date	Aug 22, 2017

Abstract

The present invention relates to a method for preparing a copolymer from at least one cyclic monomer selected from: a lactone, a lactam, a carbonate, a lactide and a glycolide, an oxazoline, an epoxide, a cyclosiloxane, comprising the step consisting of reacting said cyclic monomer in the presence of a substituted phosphorus-containing compound.
It also relates to the polymer composition obtained according to this method, as well as the uses thereof, notably as antistatic additives, biocompatible materials, as membranes for treatment of effluents or in electrochemical systems for energy storage.

First claim

The invention claimed is:

1. A method for preparing a (co)polymer from at least one cyclic monomer selected from the group consisting of a lactone, a lactam, a carbonate, a lactide, a glycolide, an oxazoline, an epoxide, and a cyclosiloxane, wherein the method comprises a step of polymerizing, without using as a catalyst any metal compounds or species, the cyclic monomer or monomers, wherein a substituted phosphorus-containing compound selected from the following compounds is used as a catalyst for the polymerizing:

2. The method as claimed in claim 1 , wherein an initiator is used.

3. The method as claimed in claim 1 , wherein the cyclic monomer is selected from saturated or unsaturated, substituted or unsubstituted β-, γ-, δ- and ε-lactones, having from 4 to 11 carbon atoms.

4. The method as claimed in claim 3 , wherein the cyclic monomer is ε-caprolactone.

5. The method as claimed in claim 1 , wherein the cyclic monomer is a lactam selected from the group consisting of caprolactam, enantholactam, lauryllactam, pyrrolidinone and piperidone.

6. The method as claimed in claim 1 , wherein the cyclic monomer is a cyclic carbonate of the following formula I:

where R denotes a linear alkyl group containing from 2 to 20 carbon atoms or a branched alkyl or alkaryl group containing from 2 to 20 carbon atoms, optionally substituted with one or more substituents selected independently from oxo and halo groups.

7. The method as claimed in claim 1 , wherein the cyclic monomer is selected from the group consisting of lactides in racemic, enantiomerically pure or meso form.

8. The method as claimed in claim 1 , wherein the cyclic monomer is glycolide.

9. The method as claimed in claim 2 , wherein the initiator is water, pentanol or a polymer bearing at least one hydroxyl function.

10. The method as claimed in claim 2 , wherein the initiator is selected from the group consisting of (alkoxy)polyalkylene glycols; poly(alkyl)alkylene adipate diols; optionally hydrogenated, α-hydroxylated or α,ω-dihydroxylated polydienes; mono- and polyhydroxylated polyalkylenes; polylactides containing terminal hydroxyl functions; polyhydroxyalkanoates; polysaccharides and mono- and oligo-saccharides, modified or unmodified; and mixtures thereof.

11. The method as claimed in claim 2 , wherein the inititiator is a polymer bearing at least one hydroxyl function selected from the group consisting of (methoxy)polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly(2-methyl-1,3-propylene adipate)diol, poly(1,4-butylene adipate)diol, polybutadiene α,ω-dihydroxylated, polyisoprene α,ω-dihydroxylated, mono- and polyhydroxylated polyisobutylene, poly(3-hydroxybutyrate), poly(3-hydroxyvalerate), starch, chitin, chitosan, dextran, cellulose, sucrose, and isomaltulose and mixtures thereof.

12. The method as claimed in claim 2 , wherein the initiator is a polymer bearing at least one thiol function.

13. The method as claimed in claim 12 , wherein the initiator is selected from the group consisting of α-thiolated and α,ω-thiolated polystyrenes, α-thiolated and α,ω-thiolated poly(meth)acrylates, α-thiolated and α,ω-thiolated polybutadienes, and mixtures thereof.

14. The method as claimed in claim 2 , wherein the initiator is a vinyl co-oligomer or copolymer from the family of acrylic, methacrylic, styrene or diene polymers, resulting from copolymerization between acrylic, methacrylic, styrene or diene monomers and functional monomers having either a hydroxyl group, or a thiol group.

15. The method as claimed in claim 1 , wherein the substituted phosphorus-containing compound is diphenylphosphate.

16. The method as claimed in claim 1 , wherein the substituted phosphorus-containing compound is (R)-3,3′-bis[3,5-bis(trifluoromethyl)phenyl]-1,1′-binaphthyl-2,2′-diyl hydrogen phosphate.

17. The method as claimed in claim 1 , wherein the substituted phosphorus-containing compound is N-[(trifluoromethyl)sulfonyl]-,diphenyl ester of phosphoramidic acid.

18. The method as claimed in claim 1 , wherein the molar ratio of the cyclic monomer to the polymeric initiator is in the range from 5 to 500.

19. The method as claimed in claim 2 , wherein the molar ratio of the substituted phosphorus-containing compound to each hydroxyl or thiol function of the initiator is from 1 to 3.

20. The method as claimed in claim 1 , the reaction is carried out at a temperature in the range from 0° C. at 230° C.

21. A method for improving the antistatic properties of a polymeric resin, improving the impact toughness of a resin, or plasticizing PVC, comprising using a copolymer prepared in accordance with the method of claim 1 as an additive.

Assignees

• Navarro Christophe
• Delcroix Damien
• Martin-Vaca Blanca
• Bourissou Didier
• Arkema France
• Centre Nat Rech Scient

Inventors

• Navarro Christophe
• Delcroix Damien
• Martin-Vaca Blanca
• Bourissou Didier

Classifications

• C08G63/912

  derived from hydroxycarboxylic acids · CPC title

• C08G64/38

  using other monomers · CPC title

• C08G63/823 Primary

  for the preparation of polylactones or polylactides · CPC title

• C08G63/08 Primary

  Lactones or lactides · CPC title

• C08G65/10

  characterised by the catalysts used · CPC title