Polymers of benzodithiophene and their use as organic semiconductors

Patent metadata

Field	Value
Publication number	US-10050201-B2
Application number	US-201113642180-A
Country	US
Kind code	B2
Filing date	Mar 23, 2011
Priority date	Apr 19, 2010
Publication date	Aug 14, 2018
Grant date	Aug 14, 2018

Abstract

The invention relates to novel polymers of benzodithiophene, methods and materials for their preparation, their use as semiconductors in organic electronic (OE) devices, and to OE devices comprising these polymers.

First claim

The invention claimed is:

1. A random copolymer of random repeating units of formula I

which random copolymer consists of identical units of formula I wherein i=m=1 and k=o=0 and identical units of formula I wherein k=o=1 and i=m=0
wherein
A is on each occurrence identically or differently a group selected from the group consisting of the following formulae

B is on each occurrence identically or differently a group selected from the group consisting of the following formulae

X 1 and X 2 are on each occurrence identically or differently, and independently of each other, O, S or Se,
R 1 and R 2 are on each occurrence identically or differently, and independently of each other, halogen, a straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or an aryl, heteroaryl, aryloxy or heteroaryloxy group having 2 to 40 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 5 ,
R 3 and R 4 on each occurrence identically or differently, and independently of each other, denote H or have one of the meanings given for R 1 ,
R 0 and R 00 are independently of each other H or an optionally substituted carbyl or hydrocarbyl group optionally comprising one or more hetero atoms,
Ar is on each occurrence identically or differently an aryl or heteroaryl group that is optionally substituted by one or more groups R 1 ,
R 5 is on each occurrence identically or differently H, halogen, —CN, —NC, —NCO, —NCS, —OCN, —SCN, —C(═O)NR 0 R 00 , —C(═O)X 0 , —C(═O)R 0 , —NH 2 , —NR 0 R 00 , —SH, —SR 0 , —SO 3 H, —SO 2 R 0 , —OH, —NO 2 , —CF 3 , —SF 5 , or optionally substituted silyl, carbyl or hydrocarbyl with 1 to 40 C atoms that is optionally substituted and optionally comprises one or more hetero atoms, or P-Sp-,
P is a polymerisable group,
Sp is a spacer group or a single bond,
X 0 is halogen, and
n is an integer >1,
wherein the resultant polymer is a random copolymer.

2. The copolymer according to claim 1 , which is of the following formula

wherein R 1-4 , A, B, Ar, i, k, m, n and o on each occurrence identically or differently have the meanings given for the polymer of formula I, and R 6 and R 7 are, on each occurrence identically or differently, and independently of each other, H, halogen, a straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or an aryl, heteroaryl, aryloxy or heteroaryloxy group having 2 to 40 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 5 , or are —CH 2 Cl, —CHO, —CH═CH 2 , —SiR′R″R′″, —SnR′R″R′″, —BR′R″, —B(OR′)(OR″), —B(OH) 2 , or P-Sp, wherein P and Sp are as defined for the polymer of formula I, R′, R″ and R′″ have independently of each other one of the meanings of H or an optionally substituted carbyl or hydrocarbyl group optionally comprising one or more hetero atoms, and R′ and R″ may also form a ring together with the hetero atom to which they are attached, and R 0 , R 00 and R 5 are as defined for the polymer of formula I.

3. The copolymer according to claim 1 , wherein Ar is selected from the group consisting of benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkyl-benzo[2,1,3]thiadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]thiadiazole-4,7-diyl, benzo[2,1,3]selenadiazole-4,7-diyl, 5,6-dialkoxy-benzo[2,1,3]selenadiazole-4,7-diyl, benzo[1,2,5]thiadiazole-4,7,diyl, benzo[1,2,5]selenadiazole-4,7,diyl, benzo[2,1,3]oxadiazole-4,7-diyl, 5,6-dialkoxybenzo[2,1,3]oxadiazole-4,7-diyl, 2H-benzotriazole-4,7-diyl, 2,3-dicyano-1,4-phenylene, 2,5-dicyano, 1,4-phenylene, 2,3-difluro-1,4-phenylene, 2,5-difluoro, 1,4-phenylene, 2,3,5,6-tetrafluoro, 1,4-phenylene, 3,4-difluorothiophene-2,5-diyl, thieno[3,4-b]pyrazine-2,5-diyl, quinoxaline-5,8-diyl, thieno[3,4-b]thiophene-4,6-diyl, thieno[3,4-b]thiophene-6,4-diyl, and 3,6- pyrrolo[3,4-c]pyrrole-1,4-dione, all of which are unsubstituted, mono- or polysubstituted on each occurrence identically or differently, and independently of each other, with halogen, a straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or an aryl, heteroaryl, aryloxy or heteroaryloxy group having 2 to 40 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 5 , and wherein “alkyl” means a straight-chain or branched alkyl group with 1 to 30 C atoms and “alkoxy” means a straight-chain or branched alkoxy group with 1 to 30 C atoms, and R 0 , R 00 and R 5 are as defined for the polymer of formula I.

4. The copolymer according to claim 1 , which contains repeating units selected from the following formulae

wherein R 1 , R 2 , R 3 , R 4 and n have the meanings given for the copolymer of formula I, with R 4 being different from H, R 10 and R 11 are, on each occurrence identically or differently, and independently of each other, halogen, a straight-chain, branched or cyclic alkyl with 1 to 35 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—O—, —CR 0 ═CR 00 — or —C≡C— and in which one or more H atoms are optionally replaced by F, Cl, Br, I or CN, or an aryl, heteroaryl, aryloxy or heteroaryloxy group having 2 to 40 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 5 , wherein R 0 , R 00 and R 5 are as defined for the polymer of formula I, and wherein formula I2, I4, I6, I8, I10, I12, I14, I16, I18 and I20 denote random copolymers formed by units wherein a=1 and b=0 and units wherein a=0 and b=1.

5. The copolymer according to claim 4 , wherein n is 50 to 1000.

6. The copolymer according to claim 1 , wherein n is 10 to 2000.

7. The copolymer according to claim 1 , wherein n is 50 to 1000.

8. The copolymer according to claim 1 , wherein n is 50 to 500.

9. The copolymer according to claim 1 , wherein R 1 and R 2 denote straight-chain or branched alkyl, alkoxy, thioalkyl with 1 to 30 C atoms, or ketone (—CO—R y ) or carboxylic acid ester (—CO—O—R y ), wherein R y is straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, and wherein in all aforementioned groups one or more H atoms are optionally replaced by F.

10. The copolymer according to claim 1 , wherein R 3 and R 4 denote straight-chain or branched alkyl, alkoxy or thioalkyl with 1 to 15 C atoms, wherein one or more H atoms are optionally replaced by F.

11. A polymer blend comprising one

Assignees

• Tierney Steven
• Blouin Nicolas
• Mitchell William
• Wang Changsheng
• Carrasco Orozco Miguel
• Meyer Frank Egon
• Merck Patent Gmbh

Inventors

• Tierney Steven
• Blouin Nicolas
• Mitchell William
• Wang Changsheng
• Carrasco-Orozco Miguel
• Meyer Frank Egon

Classifications

• C07D498/04

  Ortho-condensed systems · CPC title

• H01B1/127

  comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes · CPC title

• C07D519/00

  Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00 · CPC title

• C08G2261/141

  Side-chains having aliphatic units · CPC title

• C07D513/04

  Ortho-condensed systems · CPC title