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-9290483-B2
Application number	US-201113643438-A
Country	US
Kind code	B2
Filing date	Apr 29, 2011
Priority date	May 3, 2010
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

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:(Formula III, IV & I) (III) (IV) (I)

First claim

The invention claim is:

1. A monomer of formula (I):

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 2 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 or C 3 alkylene radical; and
n ranges from 1 to 4.

2. The monomer of claim 1 , wherein Ar is a radical obtained from benzene, fluorene, thiophene, carbazole, dithienocyclopentadiene or from phenothiazine.

3. A process for synthesizing the monomer of claim 1 , the process comprising reacting by etherification a halogen-derivative of formula (III) with the hydroxyl group of a glycerol of formula (IV):

to form the monomer of formula (I), wherein Z═Cl, Br or I.

4. The process according to claim 3 , wherein a molar ratio of an amount of the halogen-derivative of formula (III) : to an amount of the glycerol of formula (IV) : to an amount of a base present in the etherification ranges from 1:1.1:1.15 to 1:3:3.3.

5. The process according to claim 3 , wherein the etherification occurs at temperatures ranging from 15° C. to 150° C.

6. A process for preparing a conjugated polymer or copolymer, the process comprising reacting at least one monomer of claim 1 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.

7. The process according to claim 6 , 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.

8. The process according to claim 4 , wherein the etherification occurs at temperatures ranging from 15° C. to 150° C.

9. The process of claim 6 , wherein the polymer or copolymer is soluble in water.

10. A monomer of formula (I):

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 2 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 3 -C 12 alkylene radical; and
n ranges from 1 to 4.

11. The monomer of claim 1 , wherein Ar represents a C 12 -C 18 polycyclic aromatic radical, or a heteroaromatic radical comprising a heteroatom, optionally polycondensed.

Assignees

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

• C08G2261/3223

  containing one or more sulfur atoms as the only heteroatom, e.g. thiophene · CPC title

• H01L51/0072

  Electricity · mapped topic

• C08G61/123

  derived from five-membered heterocyclic compounds · CPC title

• C08G61/124

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