Phenol polymer with 5,5′-biaryl bonds, method for preparing same, and uses thereof

Patent metadata

Field	Value
Publication number	US-10167412-B2
Application number	US-201415028812-A
Country	US
Kind code	B2
Filing date	Oct 13, 2014
Priority date	Oct 14, 2013
Publication date	Jan 1, 2019
Grant date	Jan 1, 2019

Abstract

A phenol polymer is obtainable by oligomerization of one or more macropolyphenols serving as monomers, wherein the oligomerization step is catalyzed by an oxidase enzyme. The bonds between the macropolyphenol fragments in the polymer are exclusively 5,5-biaryl bonds. This polymer is useful as an antioxidant, chelating agent, plasticizing agent, or antimicrobial agent.

First claim

The invention claimed is:

1. A phenol polymer obtained by oligomerization catalyzed by an enzyme of oxidase type, said phenol polymer comprising a plurality of monomers, said monomers being of one or more macropolyphenol(s), each macropolyphenol having a structure with at least two phenol rings corresponding to general formula (I):

wherein:
p represents an integer between 1 and 30,
R 1 , R′ 1 , R 2 , R′ 2 , R 3 and R′ 3 , which may be identical or different, each represent a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, or an alkyl, benzyl, Xalkyl, where appropriate substituted, Xbenzyl, where appropriate substituted, Xacyl, B(OR′) 2 , NHR′, NO 2 , SR′O or SO 2 R′ group,
where X represents N, O, S or P
and R′ represents an alkyl group or an aryl group,

R 1 and R′ 1 do not represent a hydrogen atom,
Y and Y′, which may be identical or different, each represent:
either an oxygen atom, a sulfur atom or a deconjugating group, said deconjugating group comprising neither an epoxide ring, nor an aziridine ring, nor a phenol group which is not substituted on all its carbon atoms, said deconjugating group not comprising a bond conjugated with the phenol ring to which said deconjugating group is bonded,
or a group corresponding to formula (II):

wherein:
q represents an integer between 1 and 8,

Y 1 represents an oxygen atom, a sulfur atom or a deconjugating group, said deconjugating group comprising neither an epoxide ring, nor an aziridine ring, nor a phenol group which is not substituted on all its carbon atoms, said deconjugating group not comprising a bond conjugated with the phenol ring of the group of formula (II),
Z 1 represents a heteroatom or a spacer group comprising neither an epoxide ring, nor an aziridine ring, nor a phenol group which is not substituted on all its carbon atoms, nor an alkenyl group, nor an alkynyl group,
and Z represents:
either a heteroatom or a spacer group comprising neither an epoxide ring, nor an aziridine ring, nor a phenol group which is not substituted on all its carbon atoms, nor an alkenyl group, nor an alkynyl group,
or a group corresponding to formula (III):

wherein q represents an integer between 1 and 8,

the bonds between the monomers of the one or more macropolyphenol(s) of general formula (I), within said polymer, being exclusively 5,5-biaryl bonds.

2. The polymer as claimed in claim 1 , wherein R 1 and/or R′ 1 represent(s) a linear or branched, saturated hydrocarbon-based radical comprising from 1 to 5 carbon atoms, or an OR 4 group, where R 4 represents a linear or branched, saturated hydrocarbon-based radical comprising from 1 to 5 carbon atoms.

3. The polymer as claimed in claim 1 , wherein R 2 , R 3 , R′ 2 and/or R′ 3 represent(s) a hydrogen atom.

4. The polymer as claimed in claim 1 , wherein Y and/or Y′ represent(s) a group of general formula (V):
—(CH 2 ) m —X′—  (V)

wherein:
m is between 1 and 5,
and X′ represents an oxygen atom or a sulfur atom or a group selected from the group consisting of:

NR″, NH and SO 2 , where R″ represents an alkyl group or an aryl group.

5. The polymer as claimed in claim 1 , wherein Y and Y′, and where appropriate Y 1 , each represent a group of general formula (VI):

6. The polymer as claimed in claim 1 , wherein Z represents a linear or branched, saturated hydrocarbon group, where appropriate substituted, comprising from 1 to 6 carbon atoms, which can comprise one or more heteroatoms, or a saturated cyclic hydrocarbon group, where appropriate substituted, comprising from 1 to 6 carbon atoms, which can comprise a single ring or several condensed rings, and which can comprise one or more heteroatoms.

7. The polymer as claimed in claim 1 , corresponding to general formula (IV):

wherein n represents an integer between 2 and 100.

8. The polymer as claimed in claim 1 , corresponding to one of formulae (IVa), (IVb), (IVc) and (IVd)

wherein n represents an integer between 2 and 100.

9. The polymer as claimed in claim 1 , corresponding to general formula (VII):

wherein n represents an integer between 2 and 100.

10. A process for synthesizing a phenol polymer as claimed in claim 1 , comprising a step of oligomerization of one or more macropolyphenol(s) each corresponding to general formula (I), catalyzed by an enzyme of oxidase type.

11. The process as claimed in claim 10 , wherein said enzyme is a laccase.

12. The process as claimed in claim 10 , wherein said oligomerization step is carried out in an aqueous solution at a temperature of between 0 and 75° C.

13. The process as claimed in claim 10 , wherein said oligomerization step is carried out in an aqueous solution at a pH of between 3 and 8.

14. The process as claimed in claim 10 , wherein said oligomerization step is carried out in an aqueous solution comprising from 0 to 80% (v/v) of an organic solvent.

15. The process as claimed in claim 10 , wherein said oligomerization step is carried out in an ionic liquid.

16. A composition comprising a phenol polymer as claimed in claim 1 .

17. A part having a surface which is coated with a layer made up of a polymer as claimed in claim 1 .

Assignees

• Agronomique Inst Nat Rech
• Inst Sciences Ind Vivant Environnement
• Inst Sciences Ind Vivant Environnment

Inventors

• Allais Florent
• Pion Florian
• Reano Armando
• Ducrot Paul-Henri
• Spinnler Henry Eric

Classifications

• C09D167/04 Primary

  Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C09D167/06 takes precedence) · CPC title

• C12P7/22 Primary

  aromatic · CPC title

• C12P7/62

  Carboxylic acid esters · CPC title

• C12P17/181

  Heterocyclic compounds containing oxygen atoms as the only ring heteroatoms in the condensed system, e.g. Salinomycin, Septamycin · CPC title