Conjugated polymers

Patent metadata

Field	Value
Publication number	US-9559303-B2
Application number	US-201113879249-A
Country	US
Kind code	B2
Filing date	Sep 21, 2011
Priority date	Oct 20, 2010
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

The invention relates to novel polymers containing repeating units based on benzo[1,2-d;4,3-d′]bisthiazole, monomers and methods for their preparation, their use as semiconductors in organic electronic (OE) devices, especially in organic photovoltaic (OPV) devices, and to OE and OPV devices comprising these polymers.

First claim

The invention claimed is:

1. Polymer of formula II
—[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ] n —  II

wherein
U is on each occurrence identically or differently a moiety of formula I,

wherein an asterisk indicates a link to a neighboured group, and R 1 and R 2 are each independently of one another, H, halogen, or an optionally substituted carbyl or hydrocarbyl group,
Ar 1 and Ar 2 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is optionally substituted, and one or both of Ar 1 and Ar 2 may also denote a single bond,
x is on each occurrence identically or differently 0, 1 or 2, wherein in at least one repeating unit, i.e. in at least one unit —[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ]—, x is 1,
y is on each occurrence identically or differently 1 or 2,
n is an integer >1,
Ar 3 is, on each occurrence identically or differently, selected from the group consisting of selenophene-2,5-diyl, selenopheno[3,2-b]selenophene-2,5-diyl, selenopheno[2,3-b]seleno-phene-2,5-diyl, selenopheno[3,2-b]thiophene-2,5-diyl, seleno-pheno[2,3-b]thiophene-2,5-diyl, benzo[1,2-b:4,5-b′]di-thiophene-2,6-diyl, 2,2-dithiophene, 2,2-diselenophene, indaceno[1,2-b:5,6-b′]di-thiophene-2,7-diyl, benzo[1″,2″:4,5;4″,5″:4′,5′]bis(silolo[3,2-b:3′,2′-b′]thiophene)-2,7-diyl, phenanthro[1,10,9,8-c,d,e,f,g]carbazole-2,7-diyl,-benzo[2,1,3]selenadiazole-4,7-diyl, quinoxaline-5,8-diyl, thieno[3,4-c]pyrrole-4,6-dione-1,3-diyl, all of which are unsubstituted, or mono- or polysubstituted with R 1 , R 2 or R 3
R 3 is on each occurrence identically or differently F, Br, Cl, —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 , 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-,
R 0 and R 00 are independently of each other H or optionally substituted C 1-40 carbyl or hydrocarbyl,
P is a polymerisable or crosslinkable group,
Sp is a single bond or is alkylene with up to 30 C atoms which is unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN, it being also possible for one or more non-adjacent CH 2 groups to be replaced, in each case independently from one another, by —O—, —S—, —NH—, —NR 0 —, —SiR 0 R 00 —, —C(O)—, —C(O)O—, —OC(O)—, —OC(O)—O—, —S—C(O)—, —C(O)—S—, —CH═CH— or —C≡C— in such a manner that O and/or S atoms are not linked directly to one another, and
X 0 is halogen.

2. Polymer according to claim 1 , wherein R 1 and R 2 in formula I are selected from H, 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—, —C(O)—, —C(O)—O—, —O—C(O)—, —O—C(O)—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 denote aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl or heteroaryloxycarbonyl having 4 to 30 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 3 .

3. Polymer according to claim 1 , which is of formula IIa
R 4 —[(Ar 1 —U—Ar 2 ) x —(Ar 3 ) y ] n —R 5   IIa

wherein U, Ar 1-3 , n, x and y have the meanings of claim 1 , and
R 4 and R 5 have independently of each other one of the meanings of R 3 in claim 1 , or denote —CH 2 Cl, —CHO, —CH═CH 2 , —SiR′R″R′″, —SiX′X″R′, —SiR′R″X′, —SnR′R″R′″, —BR′R″, —B(OR′)(OR″), —B(OH) 2 , O—SO 2 —R′, —ZnX′, —C≡CH, —C≡C—SiR′R″R″ or P-Sp-, wherein P and Sp are as defined above, and R′, R″ and R″ have independently of each other one of the meanings of R 0 , as defined in claim 1 and two of R′, R″ and W′ may also form a ring together with the hetero atom to which they are attached, and X′ and X″ are halogen atoms.

4. Polymer according to claim 1 , wherein Ar 1 and Ar 2 are independently of each other selected from the group consisting of, thiophene-2,5-diyl, thiazole-2,5-diyl, selenophene-2,5-diyl, furan-2,5-diyl, thieno[3,2-b]thiophene-2,5-diyl, thieno[2,3-b]thiophene-2,5-diyl, selenopheno[3,2-b]selenophene-2,5-diyl, selenopheno[2,3-b]selenophene-2,5-diyl, selenopheno[3,2-b]thiophene-2,5-diyl, and selenopheno[2,3-b]thiophene-2,5-diyl, all of which are unsubstituted, or mono- or polysubstituted with R 3 as defined in claim 1 , and one of Ar 1 and Ar 2 may also denote a single bond.

5. Polymer according to claim 1 , wherein R 1 and/or R 2 are selected from the following groups:
a) the group consisting of primary alkyl or alkoxy with 1 to 30 C atoms, secondary alkyl or alkoxy with 3 to 30 C atoms, and tertiary alkyl or alkoxy with 4 to 30 C atoms, wherein in all these groups one or more H atoms are optionally replaced by F,
b) the group consisting of —C(O)—R 6 , —C(O)—O—R 6 , —O—C(O)—R 6 , wherein R 6 is straight-chain, branched or cyclic alkyl with 1 to 30 C atoms, in which one or more non-adjacent C atoms are optionally replaced by —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)—, —O—C(O)—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,
c) the group consisting of aryl, aryloxy, heteroaryl and heteroaryloxy that is optionally alkylated or alkoxylated and has 4 to 30 ring atoms.

6. Polymer according to claim 1 , which is selected from the group consisting of the following subformulae:

wherein R1, R 2 , Ar 1 , Ar 2 , Ar 3 and n have meanings given in claim 1 and wherein Ar 1 , Ar 2 and Ar 3 do not denote a single bond.

7. Polymer according to claim 1 , which is selected from the group consisting of the following subformulae:

wherein R 1 , R 2 , R 3 and n have meanings given in claim 1 .

8. A polymer of the formula
R 4 -chain-R 5
wherein “chain” is a polymer chain selected from formulae IIA-IID and II9,

wherein
R 1 and R 2 are selected from H, 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—, —C(O)—, —C(O)—O—, —O—C(O)—, —O—C(O)—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 denote aryl, heteroaryl, aryloxy, heteroaryloxy, arylcarbonyl, heteroarylcarbonyl, arylcarbonyloxy, heteroarylcarbonyloxy, aryloxycarbonyl or heteroaryloxycarbonyl having 4 to 30 ring atoms that is unsubstituted or substituted by one or more non-aromatic groups R 3 ,
n is an integer >1,
Ar 1 and Ar 2 are, on each occurrence identically or differently, and independently of each other, aryl or heteroaryl that is optionally substituted by one or more groups R 3
Ar 3 is, on each occurrence identically or differently, selected from the group consisting of selenophene-2,5-diyl, selenopheno[3,2-b]selenophene-2,5-diyl, selenopheno[2,3-b]seleno-phene-2,5-diyl, selenopheno[3,2-b]thiophene-2,5-diyl, seleno-pheno[2,3-b]thiophene-2,5-diyl, benzo[1,2-b:4,5-b′]di-thiophene-2,6-diyl, 2,2-dithiophene, 2,2-diselenophene, indaceno[1,2-b:5,6-b′]di-thiophene-2,7-diyl, benzo[1″,2″:4,5;4″,5″:4′,5′]bis(silolo[3,2-b:3′,2′-b′]thiophene)-2,7-diyl, phenanthro[1,10,9,8-c,d,e,f,g]carbazole-2,7-diyl,

Assignees

• Mitchell William
• D'Lavari Mansoor
• Tierney Steven
• Blouin Nicolas
• Schwalm Thorsten
• Merck Patent Gmbh

Inventors

• Mitchell William
• D'Lavari Mansoor
• Tierney Steven
• Blouin Nicolas
• Schwalm Thorsten

Classifications

• C08G2261/91

  Photovoltaic applications · CPC title

• C08G2261/12

  Copolymers · CPC title

• C08G2261/3223

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

• C08G2261/3246

  containing nitrogen and sulfur as heteroatoms · CPC title

• H10K85/151

  Copolymers · CPC title