Aromatic monomers deriving from glycerol units, process for their preparation and use thereof for the preparation of water-soluble conjugated polymers

Patent metadata

Field	Value
Publication number	US-9567321-B2
Application number	US-201514880645-A
Country	US
Kind code	B2
Filing date	Oct 12, 2015
Priority date	May 3, 2010
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

Monomers having formula (I) and process for their synthesis which comprises the etherification reaction of a halogen-derivative (Z═Cl, Br, I) having formula (III) with the hydroxyl group of the glycerol derivative (IV), according to the following scheme:

First claim

The invention claimed is:

1. A monomer of formula (II):

wherein:
Ar represents a C 6 -C 12 aromatic radical, a C 12 -C 18 polycyclic aromatic radical, or a heteroaromatic radical comprising a heteroatom, optionally polycondensed;
X represents a functional group which can be polymerized by Suzuki, Stille, Heck or Yamamoto reaction, said functional group selected from the group consisting of —Br, —Cl, —I, —O—(SO 2 )—CF 3 , —B(OH) 2 , —B(OR′) 2 , —SnR′ 3 , —B(OR″O) and vinyl, such that R′ represents a C 1 -C 6 alkyl radical and R″ represents an ethylene radical, optionally substituted with C 1 -C 1 alkyl groups;
R 1 and R 2 independently represent a hydrogen atom or a C 1 -C 6 alkyl radical;
R represents a divalent C 1 -C 12 alkylene radical;
n ranges from 1 to 4;
Ar′ represents a heteroaromatic radical comprising a heteroatom; and
m=1 or 2.

2. The monomers according to claim 1 , wherein Ar is a radical deriving from benzene, fluorene, thiophene, carbazole, dithienocyclopentadiene or from phenothiazine.

3. The monomers according to claim 1 , wherein Ar′ is a radical deriving from thiophene, thieno-thiophene, thiazole, carbazole, dithienocyclopentadiene or from phenothiazine.

4. A process for synthesizing the monomer of claim 1 , the process comprising condensing a monomer of formula (I) with a compound of formula (IX) to form an intermediate of formula (X)

followed by halogenation of the intermediate of formula (X) to form the monomer of formula (II),
wherein W represents SnR′ 3 , —B(OH) 2 , or —B(OR) 2 .

5. The process according to claim 4 , wherein a molar ratio of the monomer of formula (I): to the compound of formula (IX) is between 1:2 and 1:4.

6. The process according to claim 4 , wherein the condensing occurs at temperatures ranging from 10 to 200° C.

7. A process for preparing a conjugated polymer or copolymer, the process comprising reacting at least one monomer of claim 2 with at least one co-monomer selected from the group consisting of:

followed by acid hydrolysis of an initially-obtained polymer or copolymer, to yield a conjugated polymer or copolymer,
wherein:
R 3 -R 10 independently represents a hydrogen atom, an optionally branched C 1 -C 37 alkyl group, and an —OC 1 -OC 16 alkoxyl group; and
Y is a group which can be polymerized by Suzuki, Stille, Heck or Yamamoto reaction.

8. The process according to claim 7 , wherein the reacting occurs by a condensation reaction, which is catalyzed by a derivative of:
palladium, in the case of a Suzuki, Stille or Heck reaction; or nickel, in the case of a Yamamoto reaction.

9. The process according to claim 6 , wherein the reaction is carried out at temperatures ranging from 30 to 150° C.

10. The process of claim 7 , wherein the polymer or copolymer is soluble in water.

11. The process according to claim 1 , wherein Ar′ is a heteroatom selected from the group consisting of S, N and Se.

Assignees

• Eni Spa

Inventors

• Schimperna Giuliana
• Po′ Riccardo
• Pellegrino Andrea
• Caldararo Maria

Classifications

• H10K30/53

  in the form of fibres or tubes, e.g. photovoltaic fibres · CPC title

• C08G2261/91

  Photovoltaic applications · CPC title

• C08G61/124

  with a five-membered ring containing one nitrogen atom in the ring · CPC title

• H01L51/0072

  Electricity · mapped topic

• C07D409/12

  linked by a chain containing hetero atoms as chain links · CPC title