# US 9,006,568 B2 · Synthesis of photovoltaic conjugated polymers

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- Number: US 9,006,568 B2
- Document ID: US9006568B2
- Status: Granted
- Kind: B2
- Application number: 13/764,919
- Filed: 2013-02-12
- Published: 2013-08-22
- Granted: 2015-04-14
- Earliest claimed: 2012-02-15
- Assignees: Phillips 66 Company; Solarmer Energy, Inc.
- Applicants: Phillips 66 Company; Solarmer Energy, Inc.
- Inventors: Shuangxi Wang; Chenjun Shi; Ruby Chen; Junlian Zhang; Hui Huang; Yue Wu; Wei Wang; Amit Palkar; Ting He
- Web page: https://patentgrep.com/patent/US9006568B2

## CPC

- C08G 61/126: {with a five-membered ring containing one sulfur atom in the ring}
- C07D 409/02: containing two hetero rings
- C07D 495/04: Ortho-condensed systems
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- H10K 85/151: {Copolymers}
- C08G 2261/12: Copolymers
- C08G 2261/124: alternating
- C08G 2261/1412: Saturated aliphatic units
- C08G 2261/1426: containing carboxy groups (COOH) and/or -C(=O)O-moieties
- C08G 2261/1428: containing acyl groups
- C08G 2261/146: Side-chains containing halogens
- C08G 2261/149: Side-chains having heteroaromatic units
- C08G 2261/18: conjugated
- C08G 2261/3223: containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
- C08G 2261/3243: containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
- C08G 2261/91: Photovoltaic applications
- H10K 30/30: comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
- H10K 30/50: Photovoltaic [PV] devices
- H10K 85/1135: {Polyethylene dioxythiophene [PEDOT]; Derivatives thereof}
- H10K 2102/103: {comprising indium oxides, e.g. ITO}
- Y02E 10/50: Photovoltaic [PV] energy
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A method of making a fluorothieno[3,4-b]thiophene derivatives and photovoltaic polymers containing same using 3-bromothiophene-2-carboxylic acid as a starting material. This synthetic route provides an easier synthesis as well as greater yield and a purer product, which produces superior results over the prior art less pure products. The resulting materials can be used in a variety of photovoltaic applications and devices, especially solar cells.

## Claims

### Claim 1

A method of making a fused heterocycle, comprising using a compound according to formula (I) or a protected derivative thereof as a starting material:
to form a fused heterocycle of formulae (II) or (III):
wherein R is hydrogen, C1-C20 alkyl, C1-C20 haloalkyl, aryl, heteroaryl, C1-C20 alkoxy, C1-C20 haloalkoxy, aryloxy, —C1-C20 alkyl-O—C1-C10 alkyl, —C1-C10 alkyl-O-aryl, nitro, halo, amino, or mono- or di alkyl amino.

### Claim 2 (depends on 1)

The method of claim 1, wherein the method comprises the following reactions: i) protection of carboxylic acid with a protection group, ii) chloromethylation with two chloromethyl groups, iii) a cyclization reaction at the two chloromethyl groups, iv) hydrolysis of the carboxylate protection group, v) exchange fluorine for bromine, and vi) optional esterification of the carboxylate.

### Claim 3 (depends on 1)

The method of claim 1, wherein the method comprises the following steps or their equivalents:

### Claim 4 (depends on 3)

The method of claim 3, wherein the method comprises the following steps or their equivalents: