# US 9,175,132 B2 · Polymers comprising structural units which contain alkylalkoxy groups, blends comprising these polymers, and opto-electronic devices comprising these polymers and blends

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,175,132 B2
- Document ID: US9175132B2
- Status: Granted
- Kind: B2
- Application number: 13/379,394
- Filed: 2010-06-01
- Published: 2012-04-26
- Granted: 2015-11-03
- Earliest claimed: 2009-06-26
- Assignees: Merck Patent GmbH
- Applicants: Frank Egon Meyer; Niels Schulte; Anna Hayer; Aurélie Ludemann; Rémi Manouk Anémian
- Inventors: Frank Egon Meyer; Niels Schulte; Anna Hayer; Aurélie Ludemann; Rémi Manouk Anémian
- Web page: https://patentgrep.com/patent/US9175132B2

## CPC

- C08G 61/12: Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G 61/02: Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08L 65/00: Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers
- C09K 11/06: containing organic luminescent materials
- H05B 33/14: characterised by the chemical or physical composition or the arrangement of the electroluminescent material {, or by the simultaneous addition of the electroluminescent material in or onto the light source}
- H10K 85/151: {Copolymers}
- C08G 2261/1424: containing ether groups, including alkoxy
- C08G 2261/18: conjugated
- C08G 2261/3142: fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
- C08G 2261/411: Suzuki reactions
- C08G 2261/5222: electrofluorescent
- C08L 2205/02: containing two or more polymers of the same C08L -group
- C09K 2211/1007: Non-condensed systems
- C09K 2211/1011: Condensed systems
- C09K 2211/1416: Condensed systems
- C09K 2211/1425: Non-condensed systems
- C09K 2211/1433: bridged by heteroatoms, e.g. N, P, Si or B
- H10K 85/115: {Polyfluorene; Derivatives thereof}
- Y02E 10/549: Organic PV cells
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- H05B: ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention relates to polymers comprising structural units which contain alkylalkoxy groups, and blends which comprise the polymers according to the invention. The invention is also directed to the use of the polymers and blends according to the invention in opto-electronic devices and to these devices themselves.

## Claims

### Claim 1

A polymer comprising, as structural unit Z, an aromatic or heteroaromatic ring system, where at least one H atom of said aromatic or heteroaromatic ring system is substituted by an alkylalkoxy group A which is bonded to said aromatic or heteroaromatic ring system via a C atom of the alkylalkoxy group and where said aromatic or heteroaromatic ring system is substituted by one or more substituents R1 wherein
R1 is in each case, independently of one another, a bond to a further structural unit or denotes H, D, F, Cl, Br, I, N(R2)2, N(Ar)2, C(═O)Ar, P(═O)Ar2, S(═O)Ar, S(═O)2Ar, CR2═CR2Ar, CN, NO2, Si(R2)3, B(OR2)2, OSO2R2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C═CR2, Si(R2)2, Ge(R2)2, Sn(R2)2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; where, in addition, two or more substituents R optionally forms a mono- or polycyclic, aliphatic or aromatic ring system with one another, and
R2 is in each case, independently of one another, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms and wherein the alkylalkoxy group A is bonded to the aromatic or heteroaromatic ring system via an aromatic or heteroaromatic group Ar,
and wherein the structural unit Z is selected from the group consisting of substituted or unsubstituted trans-indenofluorene, benzo-trans-indenofluorene, dibenzo-trans-indenofluorene, cis-indenofluorene, benzo-cis-indenofluorene, dibenzo-cis-indenofluorene, spirobifluorene, dihydrophenanthrene, phenanthrene, dibenzofuran, benzofluorene, benzochromene, dibenzooxepine and anthracene and wherein, the alkylalkoxy group A conforms to the formula —Arn—(CR2)m—O—(CR2)0—Ox—(CR2)p—CR3, in which R can adopt, independently of one another, identically or differently, one of the meanings indicated for R1 and in which individual CR2 groups is optionally replaced by alkenyl, alkynyl, aryl or heteroaryl groups, n≧0, m>0, o≧0, x is 0 and p≧0.

### Claim 2 (depends on 1)

The polymer according to claim 1, wherein the structural unit Z conforms to the general formula I
where at least one of the radicals R3 to R16 denotes a bond to a further structural unit, at least one of the radicals R3 to R16 denotes a linear or branched alkylalkoxy group A, which is bonded to the compound of the general formula I via a C atom, and where the remaining radicals R3 to R16 in each case, independently of one another, a bond to a further structural unit or denotes H, D, F, Cl, Br, I, N(R2)2, N(Ar)2, C(═O)Ar, P(═O)Ar2, S(═O)Ar, S(═O)2Ar, CR2═CR2Ar, CN, NO2, Si(R2)3, B(OR2)2, OSO2R2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C═CR2, Si(R2)2, Ge(R2)2, Sn(R2)2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; where, in addition, two or more substituents R optionally forms a mono- or polycyclic, aliphatic or aromatic ring system with one another, and
R2 is in each case, independently of one another, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms.

### Claim 3 (depends on 2)

The polymer according to claim 2, wherein the structural unit Z conforms to the formula Ia, Ib or Ic:
where n≧1, and the dashed lines represent the bonds to the adjacent structural units in the polymer.

### Claim 4 (depends on 1)

The polymer according to claim 1, wherein the structural unit Z conforms to the general formula II
where at least one of the radicals R17 to R30 denotes a bond to a further structural unit, at least one of the radicals R17 to R30 denotes a linear or branched alkylalkoxy group A which is bonded to the compound of the general formula II via a C atom and
where the remaining radicals R17 to R30 in each case, independently of one another, a bond to a further structural unit or denotes H, D, F, Cl, Br, I, N(R2)2, N(Ar)2, C(═O)Ar, P(═O)Ar2, S(═O)Ar, S(═O)2Ar, CR2═CR2Ar, CN, NO2, Si(R2)3, B(OR2)2, OSO2R2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C═CR2, CEC, Si(R2)2, Ge(R2)2, Sn(R2)2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; where, in addition, two or more substituents R optionally forms a mono- or polycyclic, aliphatic or aromatic ring system with one another, and
R2 is in each case, independently of one another, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms.

### Claim 5 (depends on 4)

The polymer according to claim 4, wherein the structural unit Z conforms to the formula IIa, IIb or IIc:
where n≧1, and the dashed lines represent the bonds to the adjacent structural units in the polymer.

### Claim 6 (depends on 1)

The polymer according to claim 1, wherein the structural unit Z conforms to the formula IIIc, IIId, or IIIg:
where n≧1, and the dashed lines represent the bonds to the adjacent structural units in the polymer.

### Claim 7 (depends on 1)

The polymer according to claim 1, wherein the structural unit Z conforms to the general formula IV
where at least one of the radicals R39 to R60 denotes a bond to a further structural unit, at least one of the radicals R39 to R60 denotes a linear or branched alkylalkoxy group A which is bonded to the compound of the general formula IV via a C atom, and
the remaining radicals R39 to R60 in each case, independently of one another, a bond to a further structural unit or denotes H, D, F, Cl, Br, I, N(R2)2, N(Ar)2, C(═O)Ar, P(═O)Ar2, S(═O)Ar, S(═O)2Ar, CR2═CR2Ar, CN, NO2, Si(R2)3, B(OR2)2, OSO2R2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C═CR2, C≡C, Si(R2)2, Ge(R2)2, Sn(R2)2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; where, in addition, two or more substituents R optionally forms a mono- or polycyclic, aliphatic or aromatic ring system with one another, and
R2 is in each case, independently of one another, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms.

### Claim 8 (depends on 7)

The polymer according to claim 7, wherein the structural unit Z conforms to the general formula IVa or IVb:
where n≧1, and the dashed lines represent the bonds to the adjacent structural units in the polymer.

### Claim 9 (depends on 1)

The polymer according to claim 1, wherein the polymer comprises combinations of the structural units Z and/or one or more further structural units which are different from the structural unit Z.

### Claim 10 (depends on 9)

The polymer according to claim 9, wherein the further structural units are a hole-injection, hole-transport, hole-blocking, electron-injection, electron-transport, electron-blocking, emitter, exciton-generating unit or a backbone unit.

### Claim 11 (depends on 9)

The polymer according to claim 9, wherein a further structural unit is selected from the following structural units Va, Vb, Vc, Vd, Ve, Vf, Vg and Vh:
where R, independently of one another, identically or differently, can have the meanings indicated for R1 or Ar1 and Ar2,
R1 is in each case, independently of one another, a bond to a further structural unit or denotes H, D, F, Cl, Br, I, N(R2)2, N(Ar)2, C(═O)Ar, P(═O)Ar2, S(═O)Ar, S(═O)2Ar, CR2═CR2Ar, CN, NO2, Si(R2)3, B(OR2)2, OSO2R2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C═CR2, C≡C, Si(R2)2, Ge(R2)2, Sn(R2)2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; where, in addition, two or more substituents R optionally forms a mono- or polycyclic, aliphatic or aromatic ring system with one another,
R2 is in each case, independently of one another, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms,
X1, X2, X3 and X4 each, independently of one another, have the meanings indicated for R1, X5 is o, S or NR1, X6 is an alkylene group which is substituted by R1 or unsubstituted, where one or more C atoms is optionally replaced by O, or is an aromatic ring system,
Ar1 and Are are each, independently of one another, an aromatic or heteroaromatic group,
n≧1, and
the dashed lines represent the bonds to the adjacent structural units in the polymer.

### Claim 12 (depends on 1)

The polymer according to claim 1, wherein the polymer is a conjugated or partially conjugated polymer and/or a block copolymer.

### Claim 13 (depends on 1)

A blend comprising a polymer according to claim 1 and at least one further organic, organometallic or polymeric compound.

### Claim 14 (depends on 13)

The blend according to claim 13, wherein the further polymeric compound comprises structural units selected from a hole-injection, hole-transport, hole-blocking, electron-injection, electron-transport, electron-blocking, emitter, exciton-generating unit or a backbone unit, or combinations of the said structural units.

### Claim 15 (depends on 13)

The blend according to claim 13, wherein the further polymeric compound comprises the structural units Va, Vb, Vc, Vd, Ve, Vf, Vg and Vh:
where R, independently of one another, identically or differently, can have the meanings indicated for R1 or Ar1 and Ar2,
R1 is in each case, independently of one another, a bond to a further structural unit or denotes H, D, F, Cl, Br, I, N(R2)2, N(Ar)2, C(═O)Ar, P(═O)Ar2, S(═O)Ar, S(═O)2Ar, CR2═CR2Ar, CN, NO2, Si(R2)3, B(OR2)2, OSO2R2, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 C atoms, each of which is optionally substituted by one or more radicals R2, where one or more non-adjacent CH2 groups is optionally replaced by R2C═CR2, C≡C, Si(R2)2, Ge(R2)2, Sn(R2)2, C═O, C═S, C═Se, C═NR2, P(═O)(R2), SO, SO2, NR2, O, S or CONR2 and where one or more H atoms is optionally replaced by F, Cl, Br, I, CN or NO2, or an aromatic or heteroaromatic ring system having 5 to 40 aromatic ring atoms, which optionally in each case is substituted by one or more radicals R2, or an aryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms, which is optionally substituted by one or more radicals R2, or a combination of these systems; where, in addition, two or more substituents R optionally forms a mono- or polycyclic, aliphatic or aromatic ring system with one another,
R2 is in each case, independently of one another, H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms.
X1, X2, X3 and X4 each, independently of one another, have the meanings indicated for R1, X5 is O, S or NR1, X5 is an alkylene group which is substituted by R1 or unsubstituted, where one or more C atoms is optionally replaced by O, or is an aromatic ring system,
Ar1 and Are are each, independently of one another, an aromatic or heteroaromatic group,
n≧1, and
the dashed lines represent the bonds to the adjacent structural units in the polymer.

### Claim 16 (depends on 1)

A blend comprising the polymer according to claim 1, a polymeric compound comprising an emitter unit and a polymeric compound comprising a hole-blocking unit.

### Claim 17 (depends on 13)

The blend according to claim 13, wherein the blend comprises further polymers, each of which comprise, independently of one another, a hole-injection, hole-transport, hole-blocking, electron-injection, electron-transport, electron-blocking, emitter or exciton-generating unit.

### Claim 18 (depends on 1)

A formulation comprising the polymer according to claim 1 and one or more solvents.

### Claim 19 (depends on 13)

A formulation comprising the blend according to claim 13 and one or more solvents.

### Claim 20 (depends on 1)

An organic electronic device comprising one or more layers, where at least one layer comprises the polymer according to claim 1.

### Claim 21 (depends on 13)

An organic electronic device comprising one or more layers, where at least one layer comprises the blend according to claim 13.

### Claim 22 (depends on 21)

Organic electronic device according to claim 21, wherein the electronic device is an organic electroluminescent device (OLED), a polymeric electroluminescent device (PLED), an organic integrated circuit (o-IC), an organic field-effect transistor (o-FET), an organic thin-film transistor (o-TFT), an organic light-emitting transistor (o-LET), an organic solar cell (o-SC), an organic optical detector, an organic photoreceptor, an organic field-quench device (o-FQD), a light-emitting electrochemical cell (LEC) or an organic laser diode (o-laser).