PROCEDE DE POLYMERISATION PAR VOIE CATALYTIQUE DE 1,4-DIOXANES-2,5-DIONES ET LES POLYMERES CORRESPONDANTS

• US 20120035341A1
• Filed: 03/08/2010
• Published: 02/09/2012
• Est. Priority Date: 03/06/2009
• Status: Abandoned Application

• Current Assignee: Centre National De La Recherche Scientifique, Minasolve Germany GmbH, Universite Paul Sabatier Toulouse Iii
• Original Assignee: Centre National De La Recherche Scientifique, Minasolve Germany GmbH, Universite Paul Sabatier Toulouse Iii
• Inventors: Thillaye Du Boullay, Olivier, Bourissou, Didier, Martin-Vaca, Blanca, Diehl, Jean-Pierre
• Application Number:
  US13/254,870
• Publication Number:
  US 20120035341A1
• Time in Patent Office: Days
• US Class Current: 528/223
• CPC Class Codes: C07D 319/12 not condensed with other rings
• CPC Class Codes: C08G 63/06 derived from hydroxycarboxylic acids
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 63/823 for the preparation of polylactones or polylactides
• CPC Class Codes: C08L 2203/02 for biomedical use

Abstract

A method for polymerizing 1,4-dioxane-2,5-diones in the presence of a generally protic initiator and at least one catalyst including at least one metal-free organic compound. The latter is a non-metal organic catalyst most often selected from among pyridines of which DMAP is a derivative, sulfonic acids, polycyclic tertiary amines, phosphazenes, thioureas, thioureas/amines, and guanidines. The invention also relates to polymers obtained by the method.

Claims

1. Polymerization method for 1,4-dioxane-2,5-diones in the presence of at least one generally protic initiator and at least one catalyst, said method being characterized in that the catalyst comprises at least one organic compound devoid of metal.

2. Polymerization method according to claim 1 in which said one catalyst is chosen from:

the pyridines, substituted or not;

the sulphonic acids of formula R′

SO₃H, where R′

is an aryl or alkyl group;

the cyclic or acyclic guanidines;

the polycyclic tertiary amines;

the mono or poly-phosphazenes;

the combinations;

of at least one thiourea of general formula R₁NH—

C(═

S)—

NHR₂ in which the R₁ and R₂ groups, distinct or not, are aryl or alkyl groups, optionally substituted, and

of at least one tertiary amine, aliphatic or aromatic, mono or polyamine,

with a thiourea/tertiary amine ratio preferably of 0.1 to 10;

the thioureas of general formula R₃NH—

C(═

S)—

NHR₄ in which the R₃ and R₄ groups, distinct or not, are aryl or alkyl groups, optionally substituted, comprising at least one tertiary amine function;

the combinations;

of at least one thiourea of general formula R₅NH—

C(═

S)—

NHR₆ in which the R₅ and R₆ groups, distinct or not, are aryl or alkyl groups, optionally substituted, comprising at least one tertiary amine function, and

of at least one tertiary amine, aliphatic or aromatic, mono or polyamine.

3. Method according to claim 1 in which said generally protic initiator is a protic reagent such as water, an alcohol, a thiol, a primary amine, and preferably said generally protic initiator is n-pentanol.

4. Method according to claim 1 in which said 1,4-dioxane-2,5-diones are chosen from the compounds of formulae (I) to (VI) in the form of a pure enantiomer or a mixture of enantiomers:

5. Polymerization method according to claim 4 such that the Gp group is benzyl for the compounds of formula (I), (II), (III), (IV) and (VI) and such that the Gp group is benzyloxycarbonyl for the compound of formula (V).

6. Method according to claim 1 characterized in that said 1,4-dioxane-2,5-dione is 3-(2-benzyloxycarbonyl)ethyl 1,4-dioxane-2,5-dione, preferably 3(S)-(2-benzyloxycarbonyl)ethyl 1,4-dioxane-2,5-dione, and the organic catalyst is a 4-aminopyridine, preferably DMAP.

7. Method according to claim 1 characterized in that said 1,4-dioxane-2,5-dione is 3-(2-benzyloxycarbonyl)ethyl 1,4-dioxane-2,5-dione, preferably 3(S)-(2-benzyloxycarbonyl)ethyl 1,4-dioxane-2,5-dione, and the organic catalyst is a thiourea comprising a tertiary amine, or a combination of at least one thiourea, optionally comprising a tertiary amine, and at least one tertiary amine.

8. Method according to claim 1, characterized in that a homopolymer is obtained.

9. Polymer obtained by the implementation of the method according to claim 8, characterized in that said polymer is a homopolymer.

10. Method according to claim 1, in which two monomers distinct from each other are copolymerized,

at least one of said monomers being chosen from the compounds of formulae (I) to (VI) in the form of a pure enantiomer or of a mixture of enantiomers, and

at least the other of said monomers being chosen from the compounds of formulae (I) to (VI) in the form of a pure enantiomer or of a mixture of enantiomers, and glycolide, optionally substituted.

11. Polymer obtained by the implementation of the method according to claim 10, characterized in that said polymer is a copolymer.

12. Polymer of a formula chosen from:

13. Polymer comprising the repetition of two monomer units distinct from each other, at least one of said monomer units being chosen from the monomer units of formulae: