WO2007090773A1

WO2007090773A1 - Novel polymers

Info

Publication number: WO2007090773A1
Application number: PCT/EP2007/050934
Authority: WO
Inventors: Natalia Chebotareva; Roger PRÉTÔT; Paul Adriaan Van Der Schaaf; Thomas Schäfer; Beat Schmidhalter; Peter Murer
Original assignee: Ciba Holding Inc.
Priority date: 2006-02-10
Filing date: 2007-01-31
Publication date: 2007-08-16
Also published as: JP5553993B2; EP1981929B1; ATE492581T1; KR101368183B1; EP1981929A1; JP2009526111A; US20100249349A1; CA2638046A1; US8138303B2; TW200736295A; KR20080093158A; DE602007011396D1

Abstract

The present invention relates to novel polymers comprising a repeating unit of the formula (I) and their use in electronic devices. The polymers according to the invention have excellent solubility in organic solvents and excellent film-forming properties. In addition, high charge carrier mobilities and high stability of the emission color can be observed, if the polymers according to the invention are used in organic light emitting diodes (OLEDs).

Description

Novel Polymers

The present invention relates to novel polymers comprising a repeating unit of the formula (I) and their use in electronic devices. The polymers according to the invention may have excellent solubility in organic solvents and excellent film-forming properties. In addition, high charge carrier mobilities and high stability of the emission color can be observed, if the polymers according to the invention are used in organic light emitting diodes (OLEDs).

JP05273618 discloses phenanthroimidazole compounds which where used as antiinflammants. WO04016086 relates to the preparation of 2,4,5-trisubstituted imidazoles and their use as antibacterial and/or antifungal agents. Among others the following

compound is explicitly mentioned in WO04016086:

US-B-4,215,135 relates to 2-substituted-1 H-phenanthro[9,10-d]-imidazoles, which are useful as antiinflammatory agents. Among others the following compound is explicitly mentioned in

US-B-4,215,135: . US 3 635 544 relates to a photochromic polymer

matrix, comprising the following compound as light absorbing compound.

JP09188874, JP09013025, JP07026255, JP06207169, US2004076853, WO2004043937, US6713781 , WO2004006352, WO2003058667 and WO2004006355 disclose phenanthrene- fused or phenathroline-fused phenazines and their use in EL devices. US20042091 17 relates to an EL device, comprising an azole compound of the formula

of O, S, and -N(R)-, wherein R is a hydrocarbyl group of from 1 to about 30 carbons; Z¹ and Z² are each a substituent selected from the group consisting of hydrogen, an alkyl group of from 1 to about 25 carbon atoms, an aryl group of about 6 to about 30 carbon atoms, an alkoxy group of from 1 to about 25 carbon atoms, a halogen, and a cyano group; and Ar is an aromatic component. JP2004161892, JP2002050473 and JP2001023777 disclose phenanthroimidazol compounds and their use in EL devices.

WO04/030029 relates to a photovoltaic EL cell, comprising polymers containing groups:

. WO03/020790 relates to conjugated polymers comprising spirobifluorene units. The polymers can comprise repeating units derived from the following

compound

EP0757035A1 relates to phenanthrylenediamine derivatives represented by the general

formula , which are excellent in the electric charge transferring capability, the compatibility with a binding resin and the stability, thereby providing a photosensitive material which is highly sensitive and excellent in the durability.

US200100871 1 relates to an organic light-emitting device comprising a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer formed between a pair of electrodes, wherein at least one layer comprises at least one kind of compound represented by the following formula NR₁₁R-₁₂R-₁₃: wherein R₁₁ , R₁₂ and R₁₃ each represents a group having a cyclocondensed polycyclic hydrocarbon structure in which three or more rings are cyclocondensed; and a novel cyclocondensed polycyclic hydrocarbon compound.

US2004/0028944 relates to organic electroluminescent devices comprising a triarylamine derivative represented by the general formula N(Ar₁)(Ar₂)(Ar₃), wherein Ar₁ to Ar₃ are substituted or unsubstituted aryl groups and at least one Of Ar₁ to Ar₃ is a 9-phenanthryl group.

EP1440959A1 relates to a novel soluble compound of formula

, wherein Ar₃ represents a substituted or unsubstituted anthracendiyl group, or a substituted or unsubstituted fluorendiyl group and to its use in an electroluminescent device.

WO03/064373 relates to triarylamine derivatives and the use thereof as hole transport material in organic electroluminescent and electrophotographic devices.

WO04/005288 relates to charge transport compositions comprising a phenanthroline

derivative having formula

, wherein: R₁ and R₂ are the same or different at each occurrence and are selected from H, F, Cl, Br, alkyl, heteroalkyl, alkenyl, alkynyl, aryl, heteroaryl, C_nH_aF_b, OC_nH_aF_b,C₆H_cF_d, and OC₆H_cF_d; a, b, c, and d are 0 or an integer such that a + b = 2n + 1 , and c + d = 5, n is an integer; x is 0 or an integer from 1 through 3; y is 0, 1 or 2; with the proviso that there is at least one substituent on an aromatic group selected from F, C_nH_aF_b, OC_nH_aF_b,C_gH_cF_d, and OC₆H_cF_d.

WO05/014689 relates to conjugated polymers containing dihydrophenanthrene units of

formula

and their use in polymer organic light emitting diodes.

US2005/0156516 relates to soluble poly(aryl-oxadiazole) conjugated polymers comprising at least about 20 repeat units, which may independently be the same or different, the repeat

N-N .

H^~Α _xrn_om_4 y^ units represented by formula: .wherein Arom is a moiety selected from

Formulae (1 ) and (2):

— ^₂)

wherein each ARY, which may independently be the same or different, is selected from an aromatic hydrocarbon ring and a C₂₊ aromatic heterocyclic ring, wherein the aromatic hydrocarbon ring is selected from fluorenyl, terphenyl, tetraphenyl, pyrenyl, and phenanthryl, and the C₂₊ heterocyclic ring is selected from pyrrolyl, furanyl, imidazolyl, triazolyl, isoxazolyl, oxadiazolyl, furazanyl, pyridazinyl, pyrimidyl, pyrazinyl, triazinyl, tetrazinyl, benzofuranyl, benzothiophenyl, indolyl, isoindazolyl, benzimidazolyl, benzotriazolyl, benzoxazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, naphthyridyl, phthalazyl, phentriazyl, benzotetrazyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, acridyl, and phenazyl; wherein L is selected from an ethynyl group and a substituted or unsubstituted ethenyl group; wherein each R, which may independently be the same or different and which may be unsubstituted or substituted by a substituent selected from cyano, nitro, and halogen, is selected from the group consisting of hydrogen, aryl, alkylaryl, arylalkyl, and alkyl, wherein none or one or more -CH₂- units of the alkyl are replaced by a moiety selected from -O- , -S-, C₂.₁₄aryl, and - NR'- wherein each R', which may independently be the same or different, comprises a C₁-₁₀₀ saturated acyclic hydrocarbyl group; and wherein each x is the number of hydrogen atoms of Ary capable of substitution by R. WO2005030828 relates to conjugated polymers containing structural units according to formula

(1 ) and formula

(2) and their use in a polymer organic light-emitting diode

US20050106418 relates to cyclopentaphenanthrene-based compounds and their use in organoelectroluminescent devices.

WO05/104264 relates to polymers comprising structural units of formula

, wherein both groups R among others can form together a mono- or polycyclic, aliphatic ring system.

WO2006/097419, which enjoys an earlier priority date than the present invention, but has been published after the priority date of the present invention, relates to polymers comprising a repeating unit(s) of the formula

and their use in EL devices.

There are a number of challenges faced with the introduction of organic EL displays when their performance is compared with existing technologies. Obtaining the exact color coordinates required by specific guidelines (i.e. NTSC) has been problematic. The operational lifetime of the EL device is still lower when contrasted to the existing inorganic technology for cathode ray tubes (CRTs) and liquid crystal displays (LCDs). In addition, producing a device with a pure blue, green, red color and a long lifetime is one of the greatest problems for this industry.

Accordingly, it is the object of the present invention to provide novel materials, which, when incorporated in electro-optical devices, cause significant advantages in color purity, device efficiency and/or operational lifetime.

Said object is solved by the polymers of the present invention comprising repeating units of formula I. Organic light emitting devices (OLEDs) based on the polymers of the present invention, can show significant advantages in color purity, device efficiency and/or operational lifetime. In addition, the polymers can have good solubility characteristics and relatively high glass transition temperatures, which facilitates their fabrication into coatings and thin films, that are thermally and mechnically stable and relatively free of defects.

Hence, the present invention relates to polymers comprising repeating unit(s) of the formula

wherein A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur, especially one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur, R^a, R¹, R², R³, R⁴, R¹ , R² , R³ and R⁴ are independently of each other hydrogen, halogen, especially fluorine, or an organic substituent, or

R^a, R¹, R², R³, R⁴, R¹ , R² , R³ and R⁴ , if possible, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted, R⁷ is halogen, especially fluorine, or an organic substituent, wherein two or more substituents R⁷ in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system, wherein at least one of R^a, R¹, R², R³, R⁴, R¹ , R² , R³ and R⁴ is a group R¹⁰, wherein R¹⁰ is a group -(Sp)_xr[PG']<, wherein Sp is a spacer unit, PG' is a group derived from a polymerisable group, x1 is 0, or 1 , and x is 0, or an integer of 1 to 4.

A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulphur, which can be substituted and/or can be part of a fused aromatic or heteroaromatic ring system. Non-limiting examples of A are:

, wherein R⁷ has the meaning of

R⁸, R⁸ has the meaning of R⁸, X is O, S, N-R¹⁷, wherein R²⁰⁵, R²⁰⁶, R²⁰⁷, R²⁰⁸, R²⁰⁹, R²¹⁰, R⁸, R⁹, R⁹ , R⁹ , R", R" , R¹⁰ and R¹⁷ are as defined below, p' is 0, 1 , or 2 and the dotted line indicates the bonding to the benzene ring.

Preferably, A is one of the above 5-, 6-, or 7-membered heteroaromatic rings, containing one nitrogen atom and at least one further heteroatom selected from nitrogen, oxygen and sulphur. If the heteroatom is nitrogen, it can be a group =N-, or -NR-, especially -N-R¹⁷, or - NR¹⁰-, wherein R is an organic substituent, R¹⁷ and R¹⁰ are as defined below.

The polymers of the present invention should have a glass transition temperature above 100⁰C.

Preferably, the polymers of the present invention comprise a repeating unit(s) of the formula

R¹ and R¹ are independently of each other hydrogen, halogen, CrCi₈alkyl, CrCi₈alkyl which is substituted by E and/or interrupted by D, d-C^perfluoroalkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C_1SaIkOXy, d-C^alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R²⁸, R², R³ R⁴, R², R³ and R⁴ _, are independently of each other H, halogen, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, d-C^perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂- C₁₈alkenyl, C₂-C₁₈alkynyl, d-C^alkoxy, d-C^alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, CN, or -CO-R²⁸, R⁸ is H, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₁- C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂- C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-C^alkoxy, C₁- C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, CN, or -CO-R²⁸, R⁹ , R⁹ , R" and R⁹⁹ is H, Ci-Ci₈alkyl, CrC₁₈alkyl which is substituted by E and/or interrupted by D, d-C^perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-dsalkoxy, C₁- C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or -CO-R²⁸, R¹⁰ is a group -(Sp)_x1-[PG']<, wherein Sp is a spacer unit, PG' is a group derived from a polymerisable group, and x1 is O, or 1 , or

R^B and R¹⁰ together form a group

, wherein one of the substituents R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸, and one of the substituents R²⁰⁸ and R²¹⁰ is a group R¹⁰ and the other substituents are independently of each other H, CrC₁₈alkyl, CrC₁₈alkyl which is substituted by E and/or interrupted by D, d-C^alkoxy, or d-C^alkoxy which is substituted by E and/or interrupted by D,

R¹¹ and R¹¹ are independently of each other hydrogen, halogen, especially fluorine, C₁- C₁₈alkyl, CrC₁₈alkyl which is substituted by E and/or interrupted by D, Crdsperfluoroalkyl,

C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-C^alkoxy, d-C^alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R²⁸,

R¹², R¹³ _, R¹⁴, R¹² , R¹³ and R¹⁴ are independently of each other H, halogen, especially fluorine, C-ι-C₁₈alkyl, C-ι-C₁₈alkyl which is substituted by E and/or interrupted by D, C₁- C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-

C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-C^alkoxy, C₁-

C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, CN or -CO-R²⁸, X is O, S, or NR¹⁷, wherein R¹⁷ is Ci-Ci₈alkyl, CrCi₈alkyl which is substituted by E and/or interrupted by D, d-C^perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂- C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₇- C₂₅aralkyl, or -CO-R²⁸; or two substituents R¹, R², R³ and R⁴; R¹ , R² , R³ and R⁴ ; R¹¹, R¹², R¹³ and R¹⁴; R¹¹ , R¹² , R¹³

and R¹⁴ , which are adjacent to each other, together form a group

or

or two substituents R and R , which are adjacent to each other, together

form a group

or two substituents R and R , and/or R and R , which are adjacent to each other, together

form a group

or NR¹', wherein R¹' is as defined above, R¹⁰⁵, R¹⁰⁶, R¹⁰⁷, R¹⁰⁸, R¹⁰⁵ , R¹⁰⁶ , R¹⁰⁷ and R¹⁰⁸ are independently of each other H, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₁-C_1SaIkOXy, or d-C^alkoxy which is substituted by E and/or interrupted by D, R¹¹⁹ and R¹²⁰ are independently of each other H, CrC₁₈alkyl, CrC₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-

C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁- C₁₈alkoxy, d-C^alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or R¹¹⁹ and R¹²⁰ together form a five or six membered ring, which optionally can be substituted by CrC₁₈alkyl, CrC₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆- C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, CrC₁₈alkoxy, CrC₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or -C(=O)-R¹²⁷, or R¹¹⁹ and R¹²⁰ together form a group of formula =CR¹²¹R¹²², wherein

R¹²¹ and R¹²² are independently of each other H, C-ι-C₁₈alkyl, C-ι-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂- C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, R¹²⁷ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C-ι-C₁₈alkyl, or C-ι-C₁₈alkoxy; C₁- Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-,

D is -CO-; -COO-; -S-; -SO-; -SO₂-; -O-; -NR²⁵-; -SiR³⁰R³¹-; -POR³²-; -CR²³=CR²⁴-; or -C≡C-; and

E is -OR²⁹; -SR²⁹; -NR²⁵R²⁶; -COR²⁸; -COOR²⁷; -CONR²⁵R²⁶; -CN; or halogen; G is E, C₁- C₁₈alkyl, C-ι-C₁₈alkyl which is interrupted by D, d-C^perfluoroalkyl, or d-C^alkoxy which is substituted by E and/or interrupted by D, wherein

R²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C-ι-C₁₈alkyl, or d-C^alkoxy; C-ι-C₁₈alkyl; or C-ι-C₁₈alkyl which is interrupted by -0-; or

R²⁵ and R²⁶ together form a five or six membered ring, in particular

R²⁷ and R²⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by

CrC₁₈alkyl, or CrC₁₈alkoxy; CrC₁₈alkyl; or CrC₁₈alkyl which is interrupted by -0-,

R²⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by C-ι-C₁₈alkyl, or d-C^alkoxy; C₁- C₁₈alkyl; or C-ι-C₁₈alkyl which is interrupted by -0-,

R³⁰ and R³¹ are independently of each other C-ι-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by C-ι-C₁₈alkyl, and

R³² is C-ι-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by CrC₁₈alkyl, or

R⁹ , R¹², R¹³ R¹⁴, R¹² , R¹³ and R¹⁴ are a group -(Sp)_x1-HEI, wherein Sp is a spacer unit,

HEI is a group (HEl'), which increases the hole-injection or hole-transport properties of the polymers; or a group (HEl"), which increases the electron-injection or electron-transport properties of the polymers, x1 is 0, or 1 , with the proviso that in case of the compound of the formula XIV at least one of the substituents R¹², R¹³, R¹² and R¹³ is a group R¹⁰.

R^y , RΛ R^πj R¹⁴, FT= , R^πj and R¹⁴ can be a group -(Sp)_x1-HEI, wherein Sp, HEI and x1 are as defined above.

Preferred HEI , which increase the hole-injection or hole-transport properties of the polymers, are:

R⁴¹ can be the same or different at each occurence and is Cl, F, CN, N(R⁴⁵)₂, a Ci-C_∑salkyI group, a C₄-C₁₈cycloalkyl group, a C₁-C_2SaIkOXy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR⁴⁵-, -O-, -S-, -C(=O)- O-, or -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C₆- C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R⁴¹, or two or more groups R⁴¹ form a ring system;

R⁴² can be the same or different at each occurence and is CN, a d-C₂₅alkyl group, a C₄- C₁₈cycloalkyl group, a C₁-C_2SaIkOXy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR⁴⁵-, -O-, -S-, -C(=O)-O-, or -O- C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R⁴¹ , or two or more groups R⁴¹ form a ring system;

R⁴⁴ can be the same or different at each occurence and are a hydrogen atom, a d-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, a d-C₂₅alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR⁴⁵-, -O-, -S-, -C(=O)- O-, or, -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups

R⁴¹, or CN, or two or more groups R⁴⁴, which are in neighbourhood to each other, form a ring;

R⁴⁵ is H, a d-C₂₅alkyl group, a C₄-C₁₈cycloalkyl group, a d-C₂₅alkoxy group, in which one or more carbon atoms which are not in neighbourhood to each other could be replaced by -NR⁴⁵-, -O-, -S-, -C(=O)-O-, or, -O-C(=O)-O-, and/or wherein one or more hydrogen atoms can be replaced by F, a C₆-C₂₄aryl group, or a C₆-C₂₄aryloxy group, wherein one or more carbon atoms can be replaced by O, S, or N, and/or which can be substituted by one or more non-aromatic groups R⁴¹; m can be the same or different at each occurence and is 0, 1 , 2, or 3, especially 0, 1 , or 2, very especially 0 or 1 ; n can be the same or different at each occurence and is 0, 1 , 2, or 3, especially 0, 1 , or 2, very especially 0 or 1 ; A¹ and A¹ are independently of each other a C₆-C₂₄aryl group, a C₂-C₃₀heteroaryl group, which can be substituted by one or more non-aromatic groups R⁴¹, or NO₂, especially phenyl, naphthyl, anthryl, biphenylyl, 2-fluorenyl, phenanthryl, or perylenyl, which can be substituted

by one or more non-aromatic groups R⁴¹, such as

^κ

A is a C₆-C₃oarylene group, or a C₂-C₂₄heteroarylene group, which can optionally be

substituted, especially

, wherein R¹¹⁶ and R¹¹⁷ are independently of each other H, halogen, -CN, CrCi₈alkyl, CrCi₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂oheteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁-C_1SaIkOXy, d-C^alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, - C(=O)-R¹²⁷, -C(=O)OR¹²⁷, or -C(=O)NR¹²⁷R¹²⁶,

R¹¹⁹ and R¹²⁰ are independently of each other H, CrC₁₈alkyl, CrC₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂- C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, C₁- C₁₈alkoxy, d-C^alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or R¹¹⁹ and R¹²⁰ together form a group of formula =CR¹²¹R¹²², wherein

R¹²¹ and R¹²² are independently of each other H, C-ι-C₁₈alkyl, C-ι-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂- C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or R¹¹⁹ and R¹²⁰ together form a five or six membered ring, which optionally can be substituted by CrC₁₈alkyl, CrC₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆- C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, CrC₁₈alkoxy, CrC₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or -C(=O)-R¹²⁷, and R¹²⁶ and R¹²⁷ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by CrC₁₈alkyl, or CrC₁₈alkoxy; CrC₁₈alkyl; or CrC₁₈alkyl which is interrupted by -O-,

D is -CO-, -COO-, -S-, -SO-, -SO₂-, -O-, -NR⁶⁵-, -SiR⁷⁰R⁷¹-, -POR⁷²-, -CR⁶³=CR⁶⁴-, or -C≡C-, and

E is -OR⁶⁹, -SR⁶⁹, -NR⁶⁵R⁶⁶, -COR⁶⁸, -COOR⁶⁷, -CONR⁶⁵R⁶⁶, -CN, or halogen,

G is E, or Crdsalkyl, R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by C-ι-C₁₈alkyl, d-C^alkoxy; C-ι-C₁₈alkyl; or C-ι-C₁₈alkyl which is interrupted by - 0-; or

R⁶⁵ and R⁶⁶ together form a five or six membered ring, in particular

R⁶⁷ and R⁶⁸ are independently of each other H, C₆-Ci₈aryl, C₆-Ci₈aryl which is substituted by

Ci-Ci₈alkyl, or d-C₁₈alkoxy, d-C₁₈alkyl, or d-C₁₈alkyl which is interrupted by -O-,

R⁶⁹ is H, C₆-C₁₈aryl, C₆-C₁₈aryl, which is substituted by C-ι-C₁₈alkyl, C-ι-C₁₈alkoxy, C-ι-C₁₈alkyl, or d-C₁₈alkyl which is interrupted by -O-,

R⁷⁰ and R⁷¹ are independently of each other d-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by d-d₈alkyl, and

R⁷² is d-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by d-d₈alkyl

A¹ is preferably a phenyl group, which is substituted by Ci-C₄alkyl, or NO₂, in particular

, , or an anthryl group, in particular an anthr-2-yl group

Preferably, R¹¹⁶ and R¹¹⁷ are independently of each other H, d-d₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, or n-heptyl, d-d₂alkyl which is substituted by E and/or interrupted by D, such as -CH₂OCH₃, -CH₂OCH₂CH₃, -CH₂OCH₂CH₂OCH₃, or -CH₂OCH₂CH₂OCH₂CH₃ , C₆-Ci₄aryl, such as phenyl, naphthyl, or biphenylyl, C₅- Ci₂cycloalkyl, such as cyclohexyl, C₆-d₄aryl which is substituted by G, such as -C₆H₄OCH₃, -C₆H₄OCH₂CH₃, -C₆H₃(OCH₃)₂, or -C₆H₃(OCH₂CH₃)₂, -C₆H₄CH₃, -C₆H₃(CH₃),, -C₆H₂(CH₃),, or -C₆H₄tBu

R⁶⁵ is preferably H, Ci-d,₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, or C₆- C₁₄aryl, such as phenyl, naphthyl, or biphenylyl, which can optionally be substituted

Preferably, R¹¹⁹ and R¹²⁰ are independently of each other H, d-C₁₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, hexyl, o- tyl, or 2-ethyl-hexyl, Ci-d,₂alkyl which is substituted by E and/or interrupted by D, such as -CH₂(OCH₂CH₂)_WOCH₃, w = 1 , 2, 3, or 4, C₆-Ci₄aryl, such as phenyl, naphthyl, or biphenylyl, C₆-Ci₄aryl which is substituted by G, such as -C₆H₄OCH₃, -C₆H₄OCH₂CH₃, -C₆H₃(OCH₃)₂, -C₆H₃(OCH₂CH₃)₂, -C₆H₄CH₃, -C₆H₃(CH₃),, -C₆H₂(CH₃)₃, or -C₆H₄tBu, or R⁹ and R¹⁰ together form a 4 to 8 membered ring, especially a 5 or 6 membered ring, such as cyclohexyl, or cyclopentyl, which can optionally be substituted by Ci-C₈alkyl D is preferably -CO-, -COO-, -S-, -SO-, -SO₂-, -O-, -NR⁶⁵-, wherein R⁶⁵ is CrCi₂alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C₆-C₁₄aryl, such as phenyl, naphthyl, or biphenylyl.

E is preferably -OR⁶⁹; -SR⁶⁹; -NR⁶⁵R⁶⁵; -COR⁶⁸; -COOR⁶⁷; -CONR⁶⁵R⁶⁵; or -CN; wherein R⁶⁵, R⁶⁷, R⁶⁸ and R⁶⁹ are independently of each other Ci-Ci_∑alkyI, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl, or C₆-C₁₄ aryl, such as phenyl, naphthyl, or biphenylyl.

G has the same preferences as E, or is CrCi₈alkyl, especially Ci-Ci_∑alkyI, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl, or 2-ethyl-hexyl.

Preferred units of group HEl", which increase the electron-injection or electron-transport properties of the polymers, are:

wherein R⁴¹ and m and n are as defined above and p is 0,1 , or 2, especially 0 or 1 , R⁴²' is H, or R⁴². Among the above units of group III the units of formula MIa, IMi, IMj, and MIk are more preferred. Examples of the compound of formula XIV are:

wherein R , R and R are as defined

above, such as and wherein R and R are C₁- C-isalkyl.

In one embodiment of the present invention polymers are preferred, comprising a repeating unit of the formula X, or Xl, wherein R¹ and R¹ are hydrogen,

R², R³ R⁴, R² , R³ and R⁴ are independently of each other H, d-C₁₈alkyl, d-C₁₈alkyl which is interrupted by D, d-C₁₈perfluoroalkyl, d-C₁₈alkoxy, d-d₈alkoxy which is interrupted by D, or d-dβaralkyl,

R⁸ is H, d-d₈alkyl, d-d₈alkyl which is interrupted by D, d-dsperfluoroalkyl, d-d₈alkoxy, or d-d₈alkoxy which is interrupted by D, or two substituents R¹, R², R³ R⁴, R¹ , R² , R³ and R⁴ , which are adjacent to each other, together

form a group

, or two substituents R⁴ and R⁴ , which are adjacent to each other,

together form a group

other H, or Ci-C₈alkyl,

R¹⁰ is a group -(Sp)_x1-[PG']<, wherein Sp is a spacer unit, PG' is a group derived from a polymerisable group, and x1 is 0, or 1 , D is -CO-; -COO-; -S-; -SO-; -SO₂-; -O-; -NR²⁵-; -CR²³=CR²⁴-; or -C≡d; wherein R²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by d-C₈alkyl, or d-C₈alkoxy; Ci-C₈alkyl; or d-C₈alkyl which is interrupted by -

O-, or R²⁵ and R²⁶ together form a five or six membered ring, in particular

; or polymers are preferred, comprising a repeating unit of the formula

(XIII), wherein

R⁹ is H, C₆-C₁₈aryl, which can be substituted by G, C₂-C₁₈heteroaryl, which can be substituted by G, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is interrupted by D, Ci-Ci₈perfluoroalkyl, d- C₁₈alkoxy, or d-d₈alkoxy which is substituted by E and/or interrupted by D,

R¹¹ and R¹¹ are hydrogen,

R¹², R¹³ _, R¹⁴, R¹² , R¹³ and R¹⁴ are hydrogen,

R¹⁷ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by d-C₁₈alkyl, or d-d₈alkoxy; d-d₈alkyl; or d-d₈alkyl which is interrupted by -O-; or two substituents R¹¹ , R¹², R¹³ _, R¹⁴, R¹¹ , R¹² , R¹³ and R¹⁴ , which are adjacent to each other,

together form a group

, or two substituents R¹⁴ and R¹⁴ , which are adjacent to each other, together form a group

, wherein R¹⁰⁵, R¹⁰⁶, R¹⁰⁷, R¹⁰⁸, D, E and R¹⁰ are as defined above.

In addition, R¹², R¹³ R¹⁴, R¹² , R¹³ and R¹⁴ can be selected from groups HEl' and HEl".

Sp is selected from -Ar-, -ArY-, -YAr-, -YAr(CR⁴⁷R⁴⁸)_n-, -(CR⁴⁷R⁴⁸)_n-, -(YCR⁴⁷R⁴⁸)_n-, or -

(CR⁴⁷R⁴⁸Y)_n-, wherein

Y is NR⁵, O, S, C=O, C(=O)O, wherein R⁵ is H; C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by

C₁-C_1SaIkVl, or d-C^alkoxy; C-ι-C₁₈alkyl; or C-ι-C₁₈alkyl which is interrupted by -O-; R⁴⁷ and R⁴⁸ are independently of each other hydrogen, fluorine, or C-rC₂₀alkyl, n is an integer of 1 to 20,

Ar is alkylen, cycloalkylen, arylen, aralkylene, or heteroarylen, which can optionally be substituted.

PG' is a group derived from a polymerisable group and is preferably selected from -C(R⁴⁴)=CH₂, -NHC(O)-C(R⁴⁵)=CH₂, -OCH₂CH₂OC(O)-C(R⁴⁵)=CH₂, -OC(O)-C(R⁴⁵)=CH₂,

-C(O)-C(R⁴⁶)=CH₂, -C≡C-, -N≡C, -O-CH(CH₂CH₂CH=CH₂)₂; C₅-C₈cycloalkenyl, bicycloalkenyl

(a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms),

(1 ,2-epoxyether),

-N CO

¹ (CH₂)_S^ , wherein s is an integer from 1 to 6, ml is an integer from 1 to 6, R⁶ is hydrogen, or CrC₂₀alkyl, R⁴⁴ is hydrogen, or Ci-C₄alkyl, or halogen, R⁴⁵ is hydrogen, Ci-C₄alkyl, or halogen, and R⁴⁶ is hydrogen, C-rC₄alkyl, or C₆-C₁₂aryl, or

PG' is a group derived from a polymerisable group | , wherein

R²¹²-AHG AHG is an aromatic, or heteroaromatic residue, which can optionally be substituted, such as

, or

R²¹¹ and R²¹² are independently of each other halogen, -C≡CH, boronic acid, or boronic esters, -Mg-HaI, -Zn-HaI, -Sn (R²¹³)₃, wherein Hal is halogen, and R²¹³ is d-C₁₈alkyl, R²¹⁴ and R²¹⁴ are independently of each other H, d-C₁₈alkyl, d-C₁₈alkyl which is interrupted by D, CrC-isperfluoroalkyl, d-C₁₈alkoxy, d-d₈alkoxy which is interrupted by D, or C₇- C₂₅aralkyl.

R" ¹ R²¹²-AHG

If PG' is a group derived from a polymerisable group , the following processes can be used for the production of polymers:

Polymerization processes involving only dihalo-functional reactants may be carried out using nickel coupling reactions. One such coupling reaction was described by Colon et al. in J. Pol. Sci., Part A, Polymer Chemistry Edition 28 (1990) 367, and by Colon et al. in J. Org. Chem. 51 (1986) 2627. The reaction is typically conducted in a polar aprotic solvent (e.g., dimethylacetamide) with a catalytic amount of nickel salt, a substantial amount of triphenylphosphine and a large excess of zinc dust. A variant of this process is described by loyda et al. in Bull. Chem. Soc. Jpn, 63 (1990) 80 wherein an organo-soluble iodide was used as an accelerator.

Another nickel-coupling reaction was disclosed by Yamamoto in Progress in Polymer Science 17 (1992) 1 153 wherein a mixture of dihaloaromatic compounds was treated with an excess amount of nickel (1 ,5-cyclooctadiene) complex in an inert solvent. All nickel-coupling reactions when applied to reactant mixtures of two or more aromatic dihalides yield essentially random copolymers. Such polymerization reactions may be terminated by the addition of small amounts of water to the polymerization reaction mixture, which will replace the terminal halogen groups with hydrogen groups. Alternatively, a monofunctional aryl halide may be used as a chain-terminator in such reactions, which will result in the formation of a terminal aryl group.

Nickel-coupling polymerizations yield essentially homopolymers or random copolymers comprising units of formula I and units derived from other co-monomers.

X¹-^ Ar³-

Homopolymers of formula (VII) can be obtained, for example, by the

Suzuki reaction, wherein X¹⁰ is a repeating unit of formula I, especially X, Xl, XIII and XIV; Ar³ is selected from the following groups: group II: units, which increase the hole-injection or hole-transport properties of the polymers; group III: units, which increase the electron-injection or electron-transport properties of the polymers; group IV: units, which are combinations of units of group Il and III; group V:

(Vm), or (Vn), wherein r is an integer from 1 to 10, especially 1 , 2 or 3, q is an integer from 1 to 10, especially 1 , 2 or 3, s is an integer from 1 to 10, especially 1 , 2 or 3,

R¹¹⁶ and R¹¹⁷ are independently of each other H, halogen, -CN, CrCi₈alkyl, CrCi₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂oheteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl,

Ci-Ci₈alkoxy, Ci-Ci₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, -

C(=O)-R¹²⁷, -C(=O)OR¹²⁷, or -C(=O)NR¹²⁷R¹²⁶,

R¹¹⁹ and R¹²⁰ are independently of each other H, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂- C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, d-

C₁₈alkoxy, d-C₁₈alkoxy which is substituted by E and/or interrupted by D, or C₇-C₂₅aralkyl, or

R¹¹⁹ and R¹²⁰ together form a group of formula =CR¹²¹R¹²², wherein

R¹²¹ and R¹²² are independently of each other H, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, or C₂- C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or R¹¹⁹ and R¹²⁰ together form a five or six membered ring, which optionally can be substituted by d-C₁₈alkyl, d-C₁₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆- C₂₄aryl which is substituted by G, C₂-C₂oheteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-C₁₈alkoxy, d-C₁₈alkoxy which is substituted by E and/or interrupted by D, d-C₂₅aralkyl, or -C(=O)-R¹²⁷, and

R¹²⁶ and R¹²⁷ are independently of each other H; C₆-d₈aryl; C₆-d₈aryl which is substituted by d-d₈alkyl, or d-d₈alkoxy; d-d₈alkyl; or d-d₈alkyl which is interrupted by -O-, D is -CO-, -COO-, -S-, -SO-, -SO₂-, -0-, -NR⁶⁵-, -SiR⁷⁰R⁷¹-, -POR⁷²-, -CR⁶³=CR⁶⁴-, or -C≡d, and E is -OR⁶⁹, -SR⁶⁹, -NR⁶⁵R⁶⁶, -COR⁶⁸, -COOR⁶⁷, -CONR⁶⁵R⁶⁶, -CN, or halogen, G is E, or Ci-Ci₈alkyl,

R⁶³, R⁶⁴, R⁶⁵ and R⁶⁶ are independently of each other H; C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by d-C₁₈alkyl, d-C₁₈alkoxy; d-C₁₈alkyl; or d-C₁₈alkyl which is interrupted by - 0-; or

R⁶⁵ and R⁶⁶ together form a five or six membered ring, in particular

R⁶⁷ and R⁶⁸ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by Ci-d|₈alkyl, or Ci-d,₈alkoxy; Ci-d,₈alkyl; or Ci-d,₈alkyl which is interrupted by -0-, R⁶⁹ is H; C₆-C₁₈aryl; C₆-C₁₈aryl, which is substituted by d-C₁₈alkyl, d-C₁₈alkoxy; d-C₁₈alkyl; or Ci-d|₈alkyl which is interrupted by -O-,

R⁷⁰ and R⁷¹ are independently of each other d-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by Ci-d,₈alkyl, and

R⁷² is d-C₁₈alkyl, C₆-C₁₈aryl, or C₆-C₁₈aryl, which is substituted by d-C₁₈alkyl.

Examples of units of groups II, III and IV are contained in WO2005/049695, page 1 1 , line 13 to page 22, line 9.

In a preferred embodiment of the present invention the polymer comprises repeating units of formula

The condensation reaction of an aromatic boronate and a halogenide, especially a bromide, commonly referred to as the "Suzuki reaction", is tolerant of the presence of a variety of organic functional groups as reported by N. Miyaua and A. Suzuki in Chemical Reviews, Vol. 95, pp. 457-2483 (1995). This reaction can be applied to preparing high molecular weight polymers and copolymers.

To prepare polymers corresponding to formula VII, a dihalogenide, such as a dibromide or dichloride, especially a dibromide corresponding to formula

is reacted with an

X¹¹-^Ar³-}x¹ equimolar amount of a diboronic acid or diboronate corresponding to formula

-B X wherein X¹¹ is independently in each occurrence -B(OH)₂, -B(OY¹)₂ or , wherein

Y¹ is independently in each occurrence a d-C^alkyl group and Y² is independently in each occurrence a C₂-C₁₀alkylene group, such as -CYV-CY⁵Y⁶-, or -CY⁷Y⁸-CY⁹Y¹⁰- CY¹¹Y¹²-, wherein Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ and Y¹² are independently of each other hydrogen, or a Ci-Ci_Oalkyl group, especially -C(CH₃)₂C(CH₃)₂-, or -C(CH₃)₂CH₂C(CH₃)₂-, under the catalytic action of Pd and triphenylphosphine. The reaction is typically conducted at about 70 °C to 180 °C in an aromatic hydrocarbon solvent such as toluene. Other solvents such as dimethylformamide and tetrahydrofuran can also be used alone, or in mixtures with an aromatic hydrocarbon. An aqueous base, preferably sodium carbonate or bicarbonate, is used as the HBr scavenger. Depending on the reactivities of the reactants, a polymerization reaction may take 2 to 100 hours. Organic bases, such as, for example, tetraalkylammonium hydroxide, and phase transfer catalysts, such as, for example TBAB, can promote the activity of the boron (see, for example, Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are given by T. I. Wallow and B. M. Novak in J. Org. Chem. 59 (1994) 5034-5037; and M. Remmers, M. Schulze, and G. Wegner in Macromol. Rapid Commun. 17 (1996) 239-252.

If desired, a monofunctional aryl halide or aryl boronate may be used as a chain-terminator in such reactions, which will result in the formation of a terminal aryl group.

It is possible to control the sequencing of the monomeric units in the resulting copolymer by controlling the order and composition of monomer feeds in the Suzuki reaction.

R²¹²-AHG

If PG' is different from a polymerisable group , the polymers can contain in addition to the repeating units of formula X - XXI one or more repeating units RG¹ and/or RG":

RG¹: units, which increase the hole-injection or hole-transport properties of the polymers;

RG": units, which increase the electron-injection or electron-transport properties of the polymers.

Preferred units of RG¹, which increase the hole-injection or hole-transport properties of the polymers, are:

R⁴¹, R⁴², R⁴⁴, R⁴⁵, A¹, A¹ , A², m, n, PG, and Sp are as defined above. Preferred units of RG", which increase the electron-injection or electron-transport properties of the polymers, are:

above and p is

0,1 , or 2, especially 0 or 1.

According to the present invention homopolymers A-1 , A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-1 1 , A-12, A-13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21 , A-22, A-23, A-24, A- 25, A-26, A-27, A-28, A-29, A-30, A-31 , A-32, A-33, A-34, A-35, A-36, A-37, A-38, A-39, A- 40, A-41 , A-42, A-43, A-44, A-45, A-46, A-47, A-48, A-49, A-50, A-51 , A-52, A-53, A-54, A- 55, A-56, A-57, A-58, A-59, A-60, A-61 , A-62, A-63, A-64, A-65, A-66, A-67, A-68, A-69, A- 70, A-71 , A-72, A-73, A-74, A-75, A-76, A-77, A-78, A-79, B-1 , B-2, B-3, B-4, B-5, B-6, B-7, B-8, B-9, B-10, B-1 1 , B-12, B-13, B-14, B-15, B-16, B-17, B-18, B-19, B-20, B-21 , B-22, B- 23, B-24, B-25, B-26, B-27, B-28, B-29, B-30, B-31 , B-32, B-33, B-34, B-35, B-36, B-37, B- 38, B-39, C-1 , C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-9, C-10, C-1 1 , C-12, C-13, C-14, C-15, C- 16, C-17, C-18, C-19, C-20, C-21 , C-22, C-23, C-24, C-25, C-26, C-27, C-28, C-29, C-30, C- 31 , C-32, C-33, C-34, C-35, C-36, C-37, C-38, C-39, C-40, C-41 , C-42, C-43, C-44, C-45, C- 46, C-47, C-48, C-49, C-50, C-51 , C-52, C-53, C-54, C-55, C-56, C-57, C-58, C-59, C-60, C- 61 , C-62, C-63, C-64, C-65, C-66, C-67, C-68, C-69, C-70, C-71 , C-72, C-73, C-74, C-75, C- 76, C-77, C-78, D-1 , D-2, D-3, D-4, D-5, D-6, D-7, D-8, D-9, D-10, D-1 1 , D-12, D-13, D-14, D-15, D-16, D-17, D-18, D-19, D-20, D-21 , D-22, D-23, D-24, D-25, D-26, D-27, D-28, D-29, D-30, D-31 , D-32, D-33, D-34, D-35, D-36, D-37, D-38, D-39, D-40, D-41 , D-42, D-43, D-44, D-45, D-46, D-47, D-48, D-49, D-50, D-51 , D-52, E-1 , E-2, E-3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-1 1 , E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21 , E-22, E-23, E-24, E- 25, E-26, E-27, E-28, E-29, E-30, E-31 , E-32, E-33, E-34, E-35, E-36, E-37, E-38, E-39, E- 40, E-41 , E-42, E-43, E-44, E-45, E-46, E-47, E-48, E-49, E-50, E-51 , and E-52, F-1 to F-36, G-1 to G-37, H-1 to H-42, 1-1 to I-8, J-1 to J-31 , and K-1 to K-34 are especially preferred. Reference is made to claim 5.

In one embodiment, the polymer comprise repeating units of formula

, wherein

R²¹⁶ and R²¹⁷ are independently of each other d-C^alkyl, or C₆-C₈aryl, which can optionally be substituted by one, or more d-C^alkyl groups, and R¹⁷ is C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by d-C^alkyl, or d-C^alkoxy; d-C₁₈alkyl; or d-d₈alkyl which is interrupted by -O-.

In one embodiment, the polymers according to the invention consist only of one or more type of repeating units of formula I. In a preferred embodiment, the polymers according to the invention consist of precisely one type of repeating unit of formula I (homopolymers).

According to the present invention the term "polymer" comprises polymers as well as oligomers, wherein a polymer is a molecule of high relative molecular mass, the structure of which essentially comprises the repetition of units derived, actually or conceptually, from molecules of low relative molecular mass and an oligomer is a molecule of intermediate molecular mass, the structure of which essentially comprises a small plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass. A molecule is regarded as having a high relative molecular mass if it has properties which do not vary significantly with the removal of one or a few of the units. A molecule is regarded as having an intermediate molecular mass if it has properties which do vary significantly with the removal of one or a few of the units.

According to the present invention a homopolymer is a polymer derived from one species of (real, implicit, or hypothetical) monomer. Many polymers are made by the mutual reaction of complementary monomers. These monomers can readily be visualized as reacting to give an "implicit monomer", the homopolymerisation of which would give the actual product, which can be regarded as a homopolymer. Some polymers are obtained by chemical modification of other polymers, such that the structure of the macromolecules that constitute the resulting polymer can be thought of having been formed by the homopolymerisation of a hypothetical monomer.

Accordingly a copolymer is a polymer derived from more than one species of monomer, e.g. bipolymer, terpolymer, quaterpolymer, etc.

The oligomers of this invention have a weight average molecular weight of < 2,000 Daltons. The polymers of this invention preferably have a weight average molecular weight of 2,000 Daltons or greater, especially 2,000 to 250,000 Daltons, more preferably 10,000 to 250,000 and most preferably 20,000 to 200,000 Daltons. Molecular weights are determined according to gel permeation chromatography using polystyrene standards and/or light scattering detectors.

A further embodiment of the present invention is represented by the compounds (monomers) of the formula

wherein x, A, R^a, R¹, R², R³, R⁴, R¹ , R² , R³ , R⁴ and R⁷ are as defined above, at least one of R^a, R¹, R², R³, R⁴, R¹ , R² , R³ and R⁴ is a group R¹⁰ , wherein

R¹⁰ is a group -(Sp)_xr[PG]<, wherein

Sp is a spacer unit,

PG is a polymerisable group, x1 is 0, or 1 , and x is 0, or an integer of 1 to 5, with the proviso that the following compounds are excluded:

Compounds of the formula

(XIII'),

(XX') and/or (XXI'), wherein X, R¹, R¹ , R², R³ R⁴, R² , R³ , R⁴ _, R⁸, R⁹ , R⁹ , R", R" , R¹⁷, R¹¹ , R¹¹ , R¹², R¹³ _, R¹⁴, R¹² , R¹³ and R¹⁴ are as defined above, R¹⁰ is a group -(Sp)_x1-[PG], wherein Sp is a spacer unit, PG is a

polymerisable group, and x1 is 0, or 1 , or R and R together form a group

, or

,209

R'

N ,210

, wherein one of the substituents R , R , R^^υ' and R , and one of the substituents R²⁰⁸ and R²¹⁰ is a group R¹⁰ and the other substituents are independently of each other H, C-rC₁₈alkyl, C-rC₁₈alkyl which is substituted by E and/or interrupted by D, C₁-C_1SaIkOXy, or d-C^alkoxy which is substituted by E and/or interrupted by D, with the proviso that in case of the compound of the formula XIV at least one of the substituents R¹², R¹³, R¹² and R¹³ is a group R¹⁰.

Sp is preferably selected from -Ar-, -ArY-, -YAr-, -YAr(CR⁴⁷R⁴⁸)_n-, -ArY(CR⁴⁷R⁴⁸)_nAr-,

-ArY(CR⁴⁷R⁴⁸)_n-, -(CR⁴⁷R⁴⁸)_n-, -(YCR⁴⁷R⁴⁸)_n-, or -(CR⁴⁷R⁴⁸Y)_n-, wherein

Y is NR⁵, O, S, C=O, C(=O)O, wherein R⁵ is H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by

Ci-Ci₈alkyl, or d-C^alkoxy; C-ι-C₁₈alkyl; or C-ι-C₁₈alkyl which is interrupted by -O-;

R⁴⁷ and R⁴⁸ are independently of each other hydrogen, fluorine, or C-ι-C₂oalkyl, n is an integer of 1 to 20,

PG is a polymerisable group and is preferably selected from -C(R⁴⁴)=CH₂, -NHC(O)-

C(R⁴⁵)=CH₂, -OCH₂CH₂OC(O)-C(R⁴⁵)=CH₂, -OC(O)-C(R⁴⁵)=CH₂, -C(O)-C(R⁴⁶)=CH₂, -C≡C-, - N≡C, -O-CH(CH₂CH₂CH=CH2)2; C₅-C₈cycloalkenyl, bicycloalkenyl (a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms),

\

( C H 2 / m 1 CH - C- R⁶ \ H (CH₂)m 1 -CH — C — R

(1 ,2-epoxyether),

-N- CO

-(CH '₂2)>,s

, wherein s is an integer from 1 to 6, ml is an integer from 1 to 6, R⁶ is hydrogen, or Ci-C₂oalkyl, R⁴⁴ is hydrogen, or d-C₄alkyl, or halogen, R⁴⁵ is hydrogen, Ci-C₄alkyl, or halogen, and R⁴⁶ is hydrogen, Ci-C₄alkyl, or C₆-Ci₂aryl, or

PG is a polymerisable group , wherein

R²¹²-AHG

AHG is an aromatic, or heteroaromatic residue, which can optionally be substituted, such as

, or R²¹¹ and R²¹² are independently of each other halogen, -C≡CH, boronic acid, or boronic esters, -Mg-HaI, -Zn-HaI, -Sn (R²¹³)₃, wherein Hal is halogen, and R²¹³ is d-C^alkyl, R²¹⁴ and R²¹⁴ are independently of each other H, d-C^alkyl, d-C^alkyl which is interrupted by D, d-dsperfluoroalkyl, d-d₈alkoxy, d-d₈alkoxy which is interrupted by D, or C₁- dsaralkyl. Monomers are preferred, wherein at least one of the substituents R³, R³ , R¹³, R¹³ , R⁸ and/or R⁹ and R¹⁰ are different from a hydrogen atom and are in particular a solubilizing substituent which is especially selected from C₆-C₁₈aryl, which can be substituted by G, C₂- C₁₈heteroaryl, which can be substituted by G, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is interrupted by D, CrC-isperfluoroalkyl, d-C^alkoxy, or d-C^alkoxy which is substituted by E and/or interrupted by D.

R¹⁷ is preferably different from a hydrogen atom and is very especially CrCi₈alkyl, or C₁- C₁₈alkyl which is interrupted by D.

In particular R⁸, R⁹ and/or R¹⁷ are a solubilizing substituent and are in particular selected from C₆-C₁₈aryl, which can be substituted by G, C₂-C₁₈heteroaryl, which can be substituted by G, Ci-C|₈alkyl, Ci-Ci₈alkyl which is interrupted by D, Ci-Ci₈perfluoroalkyl, Ci-Ci₈alkoxy, or C₁-C_1SaIkOXy which is substituted by E and/or interrupted by D.

Halogen is fluorine, chlorine, bromine and iodine.

Conjugated polymers can be obtained by using monomers having groups, such as

The actual preparation of polymers is known from the state of the art (described, inter alia, in Houben-Weyl "Methoden der Organischen Chemie", "Makromolekulare Stoffe", Vol. E20, parts 1-3 (1986,1987).

Possible polymerisation methods and suitable compounds therefore are listed below: a) Radical polymerisation:

If the monomers of formula I' contain -CH=CH₂-, acrylate or methacrylate groups, the polymerisation can be carried out e.g. photochemically, one of the customary photoinitiators (see e.g. "Chemistry & Technology of UV & EB Formulations for Coatings, Inks and Paints, Vol. 3: Photoinitiators for Free Radical and Cationic Polymerization" 1991 , p. 1 1 15-325) usually being added to the reaction mixture in an amount in the range from typically 0.5 to 5 % by weight, based on the sum of all monomers used.

Examples of additional particularly suitable monomers are shown below:

Examples of additional particularly suitable monomers are shown below:

c) Various metathesis reactions are described in Ivin, K. J. and MoI, J. C, Olefin Metathesis and Metathesis Polymerization (Academic Press 1997). - ROMP (Ring Opening Metathesis Polymerisation):

Examples of additional particularly suitable monomers are shown below:

- ADMET (Acyclic Diene Olefin Metathesis):

Examples of additional particularly suitable monomers are shown below:

d) Hydrosilylation:

The hydrosilylation can be initiated by UV radiation and can be catalysed by radical formers, transition metal complexes, or Lewis bases. Examples of hydrosilylation catalysts are H₂PtCI₆, RhCI(PPh₃)₃ or trans-lrCI(CO)(PPh₃)₂.

; wherein R²¹⁶ and

R²¹⁷ are independently of each other a d-C₈alkyl group, a C₆-C₂₄aryl group or a C₇- C₁₂aralkylgroup. - Progress in Polymer Science 28 (2003) 1297-1353:

- Journal of Polymer Science: Part A, vol. 41 (2003) 1 167-1 187:

.

Examples of additional particularly suitable monomers are shown below:

d-C^alkyl is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2- dimethylpropyl, 1 ,1 ,3,3-tetramethylpentyl, n-hexyl, 1 -methylhexyl, 1 ,1 ,3,3,5,5- hexamethylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylhep- tyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, heneicosyl, docosyl, tetracosyl or pentacosyl. CrC₈alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n- hexyl, n-heptyl, n-octyl, 1 ,1 ,3,3-tetramethylbutyl and 2-ethylhexyl. CrC₄alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl.

C₁-C_2SaIkOXy groups are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of d-Csalkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n- octyloxy, 1 ,1 ,3,3-tetramethylbutoxy and 2-ethylhexyloxy, preferably C₁-C₄BIkOXy such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy. The term "alkylthio group" means the same groups as the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulfur atom.

C₂-C₂₅alkenyl groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2- enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

C₂.₂₄alkynyl is straight-chain or branched and preferably C₂.₈alkynyl, which may be unsubstituted or substituted, such as, for example, ethynyl, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1 ,4-pentadiyn-3-yl, 1 ,3-pentadiyn-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-penten-4-yn-1 -yl, trans-3-methyl-2-penten-4-yn-1 -yl, 1 ,3-hexadiyn-5-yl, 1-octyn-8-yl, 1-nonyn-9-yl, 1 -decyn-10-yl, or 1-tetracosyn-24-yl.

d-C^perfluoroalkyl, especially d-dperfluoroalkyl, is a branched or unbranched radical such as for example -CF₃, -CF₂CF₃, -CF₂CF₂CF_3, -CF(CF₃)_2, -(CF₂)₃CF₃, and -C(CF₃)₃.

The terms "haloalkyl, haloalkenyl and haloalkynyl" mean groups given by partially or wholly substituting the above-mentioned alkyl group, alkenyl group and alkynyl group with halogen, such as trifluoromethyl etc. The "aldehyde group, ketone group, ester group, carbamoyl group and amino group" include those substituted by an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group, wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group and the heterocyclic group may be unsubstituted or substituted. The term "silyl group" means a group of formula -SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are independently of each other a CrC₈alkyl group, in particular a CrC₄ alkyl group, a C₆-C₂₄aryl group or a C₇-C₁₂aralkylgroup, such as a trimethylsilyl group. The term "siloxanyl group" means a group of formula -0-SiR⁶²R⁶³R⁶⁴, wherein R⁶², R⁶³ and R⁶⁴ are as defined above, such as a trimethylsiloxanyl group.

The term "cycloalkyl group" is typically C₅-Ci₂cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted. The term "cycloalkenyl group" means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as cyclopentenyl, cyclopentadienyl, cyclohexenyl and the like, which may be unsubstituted or substituted. The cycloalkyl group, in particular a cyclohexyl group, can be condensed one or two times by phenyl which can be substituted one to three times with d-C₄-alkyl, halogen and cyano. Examples of such condensed

in particular

or . wherein R⁵¹, R⁵², R⁵³, R⁵⁴, R⁵⁵ and

R⁵⁶ are independently of each other d-C₈-alkyl, d-Cs-alkoxy, halogen and cyano, in particular hydrogen.

Aryl is usually C₆-C₃₀aryl, preferably C₆-C₂₄aryl, which optionally can be substituted, such as, for example, phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1 -naphthyl, or 2- naphthyl, biphenylyl, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl, anthryl, tetracyl, pentacyl, hexacyl, or quaderphenylyl, which may be unsubstituted or substituted.

The term "aralkyl group" is typically C₇-C₂₄aralkyl, such as benzyl, 2-benzyl-2-propyl, β- phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl- dodecyl, ω-phenyl-octadecyl, ω-phenyl-eicosyl or ω-phenyl-docosyl, preferably C₇-Ci₈aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, ω,ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl, and particularly preferred C₇-C₁₂aralkyl such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenyl-butyl, or ω,ω-dimethyl-ω-phenyl-butyl, in which both the aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted.

The term "aryl ether group" is typically a C₆-₂₄aryloxy group, that is to say O-C₆-₂₄aryl, such as, for example, phenoxy or 4-methoxyphenyl. The term "aryl thioether group" is typically a C₆-₂₄arylthio group, that is to say S-C₆-₂₄aryl, such as, for example, phenylthio or 4-methoxyphenylthio. The term "carbamoyl group" is typically a C-_Mscarbamoyl radical, preferably Ci-₈carbamoyl radical, which may be unsubstituted or substituted, such as, for example, carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, tert- butylcarbamoyl, dimethylcarbamoyloxy, morpholinocarbamoyl or pyrrolidinocarbamoyl.

The terms "aryl" and "alkyl" in alkylamino groups, dialkylamino groups, alkylarylamino groups, arylamino groups and diarylgroups are typically Ci-C_∑salkyI and C₆-C₂₄aryl, respectively. Alkylaryl refers to alkyl-substituted aryl radicals, especially C₇-Ci₂alkylaryl. Examples are tolyl, such as 3-methyl-, or 4-methylphenyl, or xylyl, such as 3,4-dimethylphenyl, or 3,5- dimethylphenyl.

Heteroaryl is typically C₂-C₂₆heteroaryl, i.e. a ring with five to seven ring atoms or a condensed ring system, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic group with five to 30 atoms having at least six conjugated π-electrons such as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, chinolyl, isochinolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, chinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, which can be unsubstituted or substituted.

Examples of a five or six membered ring formed by, for example, R¹⁶ and R¹⁷, or R⁶⁵ and R⁶⁶, respectively are heterocycloalkanes or heterocycloalkenes having from 3 to 5 carbon atoms which can have one additional hetero atom selected from nitrogen, oxygen and sulfur, for

example , which can be part of a bicyclic system,

for examp

le or

Possible substituents of the above-mentioned groups are d-C₈alkyl, a hydroxyl group, a mercapto group, CrC₈alkoxy, CrC₈alkylthio, halogen, halo-CrC₈alkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group or a silyl group.

If a substituent, such as, for example R⁷ occurs more than one time in a group, it can be different in each occurrence. The wording "substituted by G" means that one, or more, especially one to three substituents G might be present.

As described above, the aforementioned groups may be substituted by E and/or, if desired, interrupted by D. Interruptions are of course possible only in the case of groups containing at least 2 carbon atoms connected to one another by single bonds; C₆-C₁₈aryl is not interrupted; interrupted arylalkyl or alkylaryl contains the unit D in the alkyl moiety. CrCi₈alkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (CH₂CH₂O)₁.₉-R^X, where R^x is H or C_rCi_Oalkyl or C₂-C₁₀alkanoyl (e.g. CO-CH(C₂H₅)C₄H₉), CH₂-CH(OR^y')-CH₂- O-R^y, where R^y is d-C₁₈alkyl, C₅-C₁₂cycloalkyl, phenyl, C₇-C₁₅phenylalkyl, and R^y' embraces the same definitions as R^y or is H;

CrC₈alkylene-COO-R^z, e.g. CH₂COOR_Z, CH(CH₃)COOR^Z, C(CH₃)₂COOR^Z, where R^z is H, Ci-Ci₈alkyl, (CH₂CH₂O)₁.₉-R^X, and R^x embraces the definitions indicated above; CH₂CH₂-O-CO-CH=CH₂; CH₂CH(OH)CH₂-O-CO-C(CH₃)=CH₂.

Preferred arylene radicals are 1 ,4-phenylene, 2,5-tolylene, 1 ,4-naphthylene, 1 ,9 antracylene, 2,7-phenantrylene and 2,7-dihydrophenantrylene.

Preferred heteroarylene radicals are 2,5-pyrazinylene, 3,6-pyridazinylene, 2,5-pyridinylene, 2,5-pyrimidinylene, 1 ,3,4-thiadiazol-2,5-ylene, 1 ,3-thiazol-2,4-ylene, 1 ,3-thiazol-2,5-ylene, 2,4-thiophenylene, 2,5-thiophenylene, 1 ,3-oxazol-2,4-ylene, 1 ,3-oxazol-2,5-ylene and 1 ,3,4- oxadiazol-2,5-ylene, 2,5-indenylene and 2,6-indenylene.

The term "alkylene (spacer)" is typically d-C₃₀alkylene, preferably d-C₁₈alkylene, and embraces the linear as well as the branched representatives and can be, for example, -CH₂- and C₂-C₃₀alkylene, such as -(CHz)₂-, -CH(Me)-, -(CHz)₃-, -CH₂-CH(Me)-, -C(Me)₂-, -(CHz)₄-, -(CH₂)₅-, -(CH₂)₆-, -(CH₂)_/-, -(CH₂)₈-, -(CH₂)₉-, -(CH₂)₁₀-, -(CH₂)n-, -(CH₂)₁₂-, -(CH₂)₁₃-, -(CHz)i4-, -(CH₂)I₅-, -(CH₂)I₆-, -(CH₂)₁₇-, -(CH₂)iβ-, -(CHz)₁₉-, -(CH₂)₂₀ , -(CH₂)zi-, -(CHz)₂₂-, -(CHz)₂₃-, -(CHz)₂₄-, -(CH₂)₂₅-,-(CH₂)₂₆-, -(CHz)₂₇-, -(CH₂)₂₈-, -(CHz)₂₉-. -(CHz)₃₀-, preferably -CH₂-, -(CHz)₂-, -(CH₂)₃-, -(CHz)₄-, -(CHz)₅-, -(CHz)₆-, -(CHz)₇-, -(CHz)₈-, -(CHz)₉-, -(CH₂)io-, -(CHz)₁₁-, -(CHz)₁₂-, -(CHz)₁₃-, -(CHz)₁₄-, -(CHz)₁₅-, -(CHz)₁₆-, -(CHz)₁₇-, -(CHz)₁₈-, and also -CH(C₂-C₃₀alkylene)-. The "alkylene spacer" can optionally comprise one or more, in particular one or two groups selected from -O-, -S-, -NR⁴³-, -CO-, -CONH-, -CON⁴³-, or - COO- as linking group. d-C₃₀alkylene can, for example, be interrupted several times by -O-, -S-, -NH- Or -C(O)NH-, such as -(CH₂)₂-O-(CH₂)-, -(CH₂)₂-O-(CH₂)₂-, -(CH₂)₂-S-(CH₂)₂-, - CH₂-CH-CH₂-O-(CH₂)_PI-CH₃, wherein p1 is an integer from 1 to 10; or -CHX₁₃CH₂-(X₁₄)n3- OH, wherein X₁₃ is d-C₈alkyl, X₁₄ is an alkylene oxide monomer, preferably ethylene oxide or propylene oxide, or alkylene amino monomer, preferably amino ethylene or amino propylene, and n3 is an integer from 1 to 10, preferably 1 to 5; or -(CH₂)₂-NH-(CH₂)₂- or -(CH₂)₂-C(O)NH-(CH₂)₂-.

"Arylene (spacer)" is an unsubstituted or substituted carbocylic or heterocyclic arylene group, preferably containing 6 to 14 carbon atoms, typically phenylene, naphthylene, anthracenylene, anthraquinonylene, pyridinylene, quinolinylene, preferably a group

wherein X₁₁ is a single bond in ortho-, meta- or para-position, or -O-, -S-, -NR⁴³-, -CO-, - CONH-, -CONR⁴³-, or -COO- in ortho-, meta- or para-position; para-phenylene and para- phenylenoxy are preferred, wherein R⁴³ has the meaning of R⁶⁵.

"Aralkylene (spacer)" is an unsubstituted or substituted carbocylic or heterocyclic aralkylene

group, preferably containing 6 to 14 carbon atoms, preferably a group

wherein X₁₁ is a single bond in ortho-, meta- or para-position, or -O-, -S-, -NR⁴³-, -CO-, -CONH-, -CONR⁴³-, or -COO- in ortho-, meta- or para-position, and X₁₂ is alkylene, or a

group , wherein X₁₂ is alkylene in ortho-, meta- or para-position and

X₁₁ is a single bond, -O-, -S-, -NR⁴³-, -CO-, -CONH-, -CONR⁴³-, or -COO-, wherein R⁴³ has the meaning of R⁶⁵.

"Cycloalkylene (spacer)" is an unsubstituted or substituted carbocylic or heterocyclic cycloalkylene group, preferably containing 6 to 14 carbon atoms, typically cyclohexylene,

preferably a group

1

wherein X₁₁ is a single bond in 2-, 3- or 4-position, or -0-, -S-, -NR⁴³-, -CO-, -CONH-, -CONR⁴³-, or -COO- in 2-, 3- or 4-position; 4-cyclohexylene and 4-cyclohexylenoxy are preferred, wherein R⁴³ has the meaning of R⁶⁵.

A further embodiment of the present invention is directed to an electronic device or a component therefore, comprising a substrate and a polymer according to the present invention.

In such a device the polymers according to the present invention are used as electroluminescent material. For the purposes of the present invention, the term "electroluminescent material" is taken to mean materials which can be used as or in an active layer in an electroluminescent device. The term "active layer" means that the layer is capable of emitting light (light-emitting layer) on application of an electric field and/or that it improves the injection and/or transport of the positive and/or negative charges (charge injection or charge transport layer). The invention therefore also relates to the use of the polymers according to the invention as electroluminescent material. The invention furthermore relates to an electroluminescent material which comprises the polymers according to the invention. Electroluminescent devices are used, for example, as self-illuminating display elements, such as control lamps, alphanumeric displays, signs and in opto-electronic couplers.

A device according to the present invention may be prepared in accordance with the disclosure of WO99/48160, the contents of which are incorporated by reference.

The EL device emits light in the visible electro-magnetic spectrum between 400 nm and 780 nm, preferably between 430 nm and 470 nm for a blue color, preferably between 520 nm and 560 nm for a green color, preferably between 600 nm and 650 nm for a red color.

It will be appreciated that the light emissive layer may be formed from a blend or mixture of materials including one or more polymers according to the present invention, and optionally further compounds. The non-conjugated polymers of the present invention are especially used as host material for phosphorescent compounds (triplett emitter) in organic light emitting diodes (OLEDs).

An organic EL device typically consists of an organic film sandwiched between an anode and a cathode such that when a positive bias is applied to the device, holes are injected into the organic film from the anode, and electrons are injected into the organic film from the cathode. The combination of a hole and an electron may give rise to an exciton, which may undergo radiative decay to the ground state by liberating a photon. In practice the anode is commonly an mixed oxide of tin and indium for its conductivity and transparency. The mixed oxide (ITO) is deposited on a transparent substrate such as glass or plastic so that the light emitted by the organic film may be observed. The organic film may be the composite of several individual layers each designed for a distinct function. Since holes are injected from the anode, the layer next to the anode needs to have the functionality of transporting holes. Similarly, the layer next to the cathode needs to have the functionality of transporting electrons. In many instances, the hole-(electron) transporting layer also acts as the emitting layer. In some instances one layer can perform the combined functions of hole and electron transport and light emission. The individual layers of the organic film may be all polymeric in nature or combinations of films of polymers and films of small molecules deposited by thermal evaporation. It is preferred that the total thickness of the organic film be less than 1000 nanometers (nm). It is more preferred that the total thickness be less than 500 nm. It is most preferred that the total thickness be less than 300 nm. It is preferred that the thickness of the active (light emitting) layer be less than 400 nanometers (nm). It is more preferred that the thickness is in the range of from 40 to 160 nm.

The ITO-glass, which serves as the substrate and the anode, may be used for coating after the usual cleaning with detergent, organic solvents and UV-ozone treatment. It may also be first coated with a thin layer of a conducting substance to facilitate hole injection. Such substances include copper phthalocyanine, polyaniline (PANI) and poly(3,4-ethylenedioxy- thiophene) (PEDOT); the last two in their (doped) conductive forms, doped, for example, with FeCI₃ or Na₂S₂O₈. They contain poly(styrenesulfonic acid) (PSS) as counter-ion to ensure water solubility. It is preferred that the thickness of this layer be 200 nm or less; it is more preferred that the thickness be 100 nm or less.

In the cases where a hole-transporting layer is used, the polymeric arylamines described in U.S. Pat. No. 5,728,801 , may be used. Other known hole-conducting polymers, such as polyvinylcarbazole, may also be used. The resistance of this layer to erosion by the solution of the copolymer film which is to be applied next is obviously critical to the successful fabrication of multi-layer devices. The thickness of this layer may be 500 nm or less, preferably 300 nm or less, most preferably 150 nm or less.

In the case where an electron-transporting layer is used, it may be applied either by thermal evaporation of low molecular weight materials or by solution coating of a polymer with a solvent that would not cause significant damage to the underlying film. Examples of low molecular weight materials include the metal complexes of 8- hydroxyquinoline (as described by Burrows et al. in Appl. Phys. Lett. 64 (1994) 2718-2720), metallic complexes of 10-hydroxybenzoquinoline (as described by Hamada et al. in Chem. Lett. (1993) 906-906), 1 ,3,4-oxadiazoles (as described by Hamada et al. in Optoelectronics- Devices and Technologies 7 (1992) 83-93), 1 ,3,4-triazoles (as described by Kido et al. in Chem. Lett. (1996) 47-48), and dicarboximides of perylene (as described by Yoshida et al. in Appl. Phys. Lett. 69 (1996) 734-736).

Polymeric electron-transporting materials are exemplified by 1 ,3,4-oxadiazole-containing polymers (as described by Li et al. in J. Chem. Soc. (1995) 221 1-2212, by Yang and Pei in J. Appl. Phys. 77 (1995) 4807-4809), 1 ,3,4-triazole-containing polymers (as described by Strukelj et al. in Science 267 (1995) 1969-1972), quinoxaline-containing polymers (as described by Yamamoto et al. in Jpn. J. Appl. Phys. 33 (1994) L250-L253, O'Brien et al. in Synth. Met. 76 (1996) 105-108), and cyano-PPV (as described by Weaver et al. in Thin Solid Films 273 (1996) 39-47). The thickness of this layer may be 500 nm or less, preferably 300 nm or less, most preferably 150 nm or less.

The cathode material may be deposited either by thermal evaporation or by sputtering. The thickness of the cathode may be from 1 nm to 10,000 nm, preferably 5 nm to 500 nm.

OLEDs made according to the present invention may include phosphorescent dopants dispersed in the device's emissive layer, capable of achieving internal quantum efficiencies approaching 100%. As used herein, the term "phosphorescence refers to emission from a triplet excited state of an organic or metal-organic molecule. High efficiency organic light emitting devices using phosphorescent dopants have been demonstrated using several different conducting host materials (M. A. Baldo et al., Nature, VoI 395, 151 (1998), C. Adachi et al., Appl. Phys. Lett., Vol. 77, 904 (2000)). The non-conjugated polymers of the present invention are especially suitable as host material for such phosphorescent dopants (triplett emitters).

The term "hole-transporting polymer film" as used herein refers to a layer of a film of a polymer which when disposed between two electrodes to which a field is applied and holes are injected from the anode, permits adequate transport of holes into the emitting polymer. Hole-transporting polymers typically are comprised of triarylamine moieties. The term "anode material" as used herein refers to a semi-transparent, or transparent, conducting film with a work function between 4.5 electron volts (eV) and 5.5 eV. Examples are gold, silver, copper, aluminum, indium, iron, zinc, tin, chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungsten and the like, metallic alloys such as magnesium/copper, magnesium/silver, magnesium/aluminum, aluminum/indium and the like, semiconductors such as Si, Ge, GaAs and the like, metallic oxides such as indium-tin-oxide ("ITO"), ZnO and the like, metallic compounds such as CuI and the like, and furthermore, electroconducting polymers such polyacetylene, polyaniline, polythiophene, polypyrrole, polyparaphenylene and the like. Oxides and mixed oxides of indium and tin, and gold are preferred. Most preferred is ITO, especially ITO on glass, or on a plastics material, such as polyester, for example polyethylene terephthalate (PET), as substrate.

The term "cathode material" as used herein refers to a conducting film with a work function between 2.0 eV and 4.5 eV. Examples are alkali metals, earth alkaline metals, group 13 elements, silver, and copper as well as alloys or mixtures thereof such as sodium, lithium, potassium, calcium, lithium fluoride (LiF), sodium-potassium alloy, magnesium, magnesium- silver alloy, magnesium-copper alloy, magnesium-aluminum alloy, magnesium-indium alloy, aluminum, aluminum-aluminum oxide alloy, aluminum-lithium alloy, indium, calcium, and materials exemplified in EP-A 499,01 1 , such as electroconducting polymers e.g. polypyrrole, polythiophene, polyaniline, polyacetylene etc. Preferably lithium, calcium, barium, magnesium, indium, silver, aluminum, or blends and alloys of the above are used. In the case of using a metal or a metallic alloy as a material for an electrode, the electrode can be formed also by the vacuum deposition method. In the case of using a metal or a metallic alloy as a material forming an electrode, the electrode can be formed, furthermore, by the chemical plating method (see for example, Handbook of Electrochemistry, pp 383-387, Mazuren, 1985). In the case of using an electroconducting polymer, an electrode can be made by forming it into a film by means of anodic oxidation polymerization method onto a substrate, which is previously provided with an electroconducting coating.

As methods for forming said thin films, there are, for example, the vacuum deposition method, the spin-coating method, the casting method, the Langmuir-Blodgett ("LB") method, the ink jet printing method and the like. Among these methods, the vacuum deposition method, the spin-coating method, the ink jet printing method and the casting method are particularly preferred in view of ease of operation and cost.

In the case of forming the layers by using the spin-coating method, the casting method and ink jet printing method, the coating can be carried out using a solution prepared by dissolving the composition in a concentration of from 0.0001 to 90% by weight in an appropriate organic solvent such as benzene, toluene, xylene, tetrahydrofurane, methyltetrahydrofurane, N, N- dimethylformamide, acetone, acetonitrile, anisole, dichloromethane, dimethylsulfoxide and mixtures thereof.

The organic EL device of the present invention is seen as a future replacement technology for a flat panel display of an on-wall television set, a flat light-emitting device, such as a wall paper, a light source for a copying machine or a printer, a light source for a liquid crystal display or counter, a display signboard and a signal light and perhaps even to replace incandescent and fluorescent lamps. The polymers and compositions of the present invention can be used in the fields of an organic EL device, a photovoltaic device, an electrophotographic photoreceptor, a photoelectric converter, a solar cell, an image sensor, and the like.

Accordingly, the present invention relates also to OLEDs, organic integrated circuits (O-ICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic solar cells (0-SCs), thermoelectric devices, or organic laser diodes comprising one or more of the polymers according to the present invention.

The following examples are included for illustrative purposes only and do not limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight. (PD) = 3.095 Molecular weights and polydispersities are determined according to gel permeation chromatography using polystyrene standards and/or light scattering detectors.

Examples

Example 1

a) To 5.00 g (24.0 mmol) of phenanthrene-9,10-dione in 125 ml ethanol (abs) 6.66 g (36.0 mmol) 4-bromobenzaldehyde and 12.96 g (0.168 mol) ammonium acetate are added. The reaction mixture is heated at reflux under nitrogen overnight, cooled to 25 °C, the product is filtered off and washed with ethanol (yield: 7.70 g (85.8%)).

b) To 8 g (21.4 mmol) of the product of example 1a, 8.28 g (42.8 mmol) n-octylbromide (Oct), 8.89 g (64.30 mmol) of potassium carbonate and 100 ml dimethylformamide (DMF) are added. The reaction mixture is stirred under nitrogen at 120 °C overnight, filtered, the DMF is evaporated and the product is purified by column chromatography on silica gel with dichloromethane as an eluent (yield: 7.3 g (70%)).

c) 3.07 ml of 2.5M BuLi in hexane are added to 4g (8.24 mmol) of the product of example 1 b dissolved in 50 ml dry THF at -78 ⁰C. The reaction mixture is stirred for 1 h and 3g (41.2 mmol) of dry DMF are added and allowed to warm to room temperature. The reaction is quenched with 0.5M HCI and the product is purified with column chromatography on silica gel with chloroform/MeOH (9.9:0.1 ) as an eluent (yield: 2.2g (61.5 %)).

d) 6.58 g (18.41 mmol) of methyltriphenylphosphine bromide, 2.8 g (18.41 mmol) 1 ,8- diazabicyclo[5.4.0]undec-7-ene (DBU) are refluxed in 60 ml dichloromethane for 45 minutes, 2 g (4.6 mmol) of the product of example 1c in 20 ml dichloromethane are added and reflux is continued overnight. The dichloromethane solution is washed with water and purified by column chromatography with dichloromethane as an eluent (yield: 1.6g (80%)).

Example 2

a) To 10.00 g (48.0 mmol) of phenanthrene-9,10-dione in 250 ml ethanol (abs) 13.33 g (72.0 mmol) 4-bromobenzaldehyde and 18.98 g (0.24 mol) ammonium hydrogencarbonate are added. The reaction mixture is heated at reflux under nitrogen overnight, cooled to 25 °C, the product is filtered off and washed with ethanol (yield: 12.70 g (70.7%)).

b) The product is prepared according example 1c (yield: 77.0 %).

c) The product is prepared according example 1d (yield: 80.0 %).

Example 3

a) 1g of the product of example 1d and 0.05g of 2,2'-azobisisobutyronitrile (AIBN) are dissolved in 7ml THF, degassed and stirred at 60 ⁰C for 2 days. The polymer is purified by precipitation in methanol (yield: 0.9 g (90%); M_w = 40 000, PDI = 2.35). b) 0.6 g of example 1d and 3.8 mg of alkoxyamine initiator

] are dissolved in 0.5 ml chlorobenzene, degassed and stirred at 120 ⁰C for 2Oh. The obtained polymer is purified by precipitation in MeOH (yield: 0.4 g (66.6%)). Mw = 120 000, PDI = 1.43. Example 4

The product is prepared according to example 3, except that instead of the product of example 1d the product of example 2c is used (yield: 75.0 %; M_w = 8 000, PDI = 1.33).

Example 5

a) To 1.1 g (3.0 mmol) of 3,6-dibromo-phenanthrene-9,10-dione in 30 ml acetic acid (>98 %) 0.35 g (3.3 mmol) benzaldehyde, 0.36 g (3.3 mmol) 4-hydroxyaniline and 0.92 g (12.0 mmol) ammonium acetate are added. The reaction mixture is heated at reflux under nitrogen overnight and is cooled to 25 °C. The product is filtered off, washed with acetic acid, water, sodiumhydrogencarbonate solution and water (yield: 1.06 g (64.9 %)).

b) 20 ml of 1 M octyl magnesium bromide in THF are added to 2g (3.67 mmol) of the product of example 5a and 100 mg of Pd(dppf)CI₂ in 10 ml THF. The reaction mixture is refluxed for 48h and quenched with 4M HCI. The product is extracted with chloroform and purified by column chromatography with chloroform as an eluent (yield: 1.23 g (54.8%)).

c) 1.23 g (2 mmol) of the product of example 5b, 0.61 g (4 mmol) of 4-vinylbenzylchloride and 0.23 g (4 mmol) of KOH are stirred in 20 ml DMF overnight and quenched with water. The product is filtered and purified by column chromatography with dichloromethane as an eluent (yield: 1.26g (86.3%)).

Example 6

0.5 g of the product of example 5c and 15 mg of AIBN are dissolved in 1 ml THF, degassed and stirred at 60 ⁰C for 24h. The obtained polymer is purified by precipitation in MeOH (yield: 0.4 g (80%)). Mw = 47 000, PDI = 1.91 ; Oct = n-octyl

Example 7

a) 5 g (18 mmol) of 4-cyano-4'-heptylbiphenyl, 1.76 g (27 mmol) of NaN₃, 1.45 g (27 mmol) of NH₄CI are dissolved in 35 ml dry DMF and stirred overnight at 100 ⁰C. The reaction mixture is poured in 300 ml H₂O, acidified with 4M HCI, filtered and dried in vacuum at 60 ⁰C (yield: 5.7 (100%)).

b) 4.76 g (27 mmol) of the product of example 7a, 5.62 g (33.75 mmol) of p-vinylbenzoyl chloride and a little amount of hydroquinone are dissolved in 40 ml pyridine and reflux for 2 h. The obtained product is poured on 300 ml of water, filtered and purified by column chromatography on silica gel with chloroform as an eluent (yield: 1.2 g (20 %)).

c) 0.7 g of the product of example 1d, 0.3 g of the oxadiazole of example 7b and 6.3 mg of

alkoxyamine initiator

) are dissolved in 1 ml chlorobenzene with 0.1 ml acetanhydride , degassed and stirred at 120 ⁰C for 48h. The obtained polymer iss purified by precipitation in MeOH (yield: 0.93 g (93%)). Mw = 50 000, PDI = 1.75, n = 0.66, m = 0.34. Oct = n-octyl; Hept = n-heptyl.

Example 8

a) To 1.0 g (4.8 mmol) of phenanthrene-9,10-dione in 50 ml acetic acid (>98 %) 1.44 g (5.3 mmol) 4-(N,N-diphenylamino)benzaldehyde, 0.6 g (5.5 mmol) 4-hydroxyaniline and 1.48 g (19.2 mmol) ammonium acetate are added. The reaction mixture is heated at reflux under nitrogen overnight and cooled to 25 °C. The product is filtered off, washed with acetic acid, water, sodiumhydrogencarbonate solution and water and is further purified by column chromatography on silica gel with CHCI₃ as an eluent (yield: 0.74 g (30.0 %)).

b) 1.0 g (1.8 mmol) of the product of example 8a, 0.55 g (3.6 mmol) of 4-vinylbenzylchloride and 0.2 g (3.6 mmol) of KOH are stirred in 20 ml DMF overnight and quenched with water. The product is filtered, washed with hexane and purified by column chromatography with dichloromethane as an eluent (yield: 0.6 g (50%)).

Example 9

0.5 g of the product of example 8b and 15 mg of AIBN are dissolved in 1 ml THF, degassed and stirred at 60 ⁰C for 24h. The obtained polymer is purified by precipitation in MeOH (yield: 0.4 g (80%)). Mw = 58 000, PDI = 2.0.

Example 10

a) To 5.0 g (13.6 mmol) of 3,6-dibromo-phenanthrene-9,10-dione in 200 ml o-xylene 10.8 g (54.6 mmol) diphenylamine and 5.25 g (54.6 mmol) sodium tert-butoxide are added. Nitrogen is bubbled through the reaction mixture for 10 min. and 80 mg Pd(dba)₃ and tri-tert- butylphosphine are added. The reaction mixture is heated at 130 °C under nitrogen overnight and cooled to 25 °C. The solvent is evaporated and the product is purified by column chromatography on silica gel with CHCI₃ as an eluent followed by precipitation in hexane (yield: 4. 85 g (65.4 %)).

b) To 4.85 g (8.9 mmol) of the product of example 10a in 120 ml ethanol (abs) 2.5 g (13.4 mmol) 4-bromobenzaldehyde and 3.4 g (44.7 mol) ammonium acetate are added. The reaction mixture is heated at reflux under nitrogen overnight and cooled to 25 °C. The ethanol is evaporated and product is purified by column chromatography on silica gel with CHCI₃: MeOH (9.7:0.3) as an eluent followed by precipitation in hexane (yield: 4.0 g (63.5

c) The product is prepared according example 1 b (yield: 75.0 %). Oct = n-octyl

d) The product is prepared according example 1c (yield: 55.0 %). Oct = n-octyl

e) The product is prepared according example 1d (yield: 60.0 %). Oct = n-octyl

Example 11

The product is prepared according example 9. Yield: 0.3 g (60%)). Mw = 134 000, PDI = 2.38. Oct = n-octyl.

Example 12

a) To 10.0 g (48.0 mmol) of phenanthrene-9,10-dione in 40 ml trifluoromethanesulfonic acid 10.8 g (48.0 mmol) N-iodosuccinimide is added at 0 °C. The reaction mixture is stirred overnight at room temperature and poured into ice, filtered and recrystallized from acetic acid. Yield 4.6 g (30%).

b) To 4.6 g (13.7 mmol) of 2-iodo-phenanthrene-9,10-dione in 120 ml ethanol (abs) 2.19 g (20.6 mmol) benzaldehyde and 5.3 g (68.6 mmol) ammonium acetate are added. The reaction mixture is heated at reflux under nitrogen overnight and cooled to 25 °C. The product is filtered off and washed with ethanol (yield: 3.9 g (67.9%)).

c) The product is prepared according example 1 b (yield: 4.25 g ( 83.0 %)). Oct = n-octyl

d) The product is prepared according to example 1c (yield: 0.9g (41.6 %)). Oct = n-octyl.

e) The product is prepared according example 1d (yield: 0.85 g ( 95.5 %). Oct = n-octyl

Example 13

0.5 g of the product of example 12e and 3.1 mg of alkoxyamine initiator CG-39-0401

) are dissolved in 1 ml chlorobenzene with 0.1 ml acetanhydride, degassed and stirred at 120 ⁰C for 48h. The obtained polymer is purified by precipitation in MeOH (yield: 0.3g (60%)). Mw = 215 000, PDI = 3.26. Oct = n-octyl.

Example 14

To 1.2 g (2.25 mmol) of the product of example 12c in 100 ml toluene are added 50 ml of 1 M K₂CO₃ aqueous solution. Nitrogen is bubbled through the reaction mixture for 10 min and 0.67 g (4.5 mmol) of 4-vinylphenylboronic acid and 0.52 g (0.45 mmol) Pd[Ph₃P]₄ are added. The reaction mixture is stirred at 80 ⁰C for 2h and overnight at room temperature. The reaction mixture is washed with Na₂S₂O₃ aq., extracted with chloroform and precipitated in methanol. Yield 0.78 g (68.4 %). Oct = n-octyl.

Example 15

0.6 g of the product of example 14 and 15 mg of AIBN are dissolved in 2 ml THF, degassed and stirred at 60 ⁰C for 24h. The obtained polymer is purified by precipitation in MeOH (yield: 0.5 g (83.3%)). Mw = 286 000, PDI = 1.8. Oct = n-octyl.

Example 16

a) 5 g (29 mmol) of 4-n-pentylphenylacetylene, 1 1.2 g (37.7 mmol) of 5-bromo-2-iodotoluene, 0.55 g (2.9 mmol) CuI and 0.76 g (2.9 mmol) triphenylphosphine is dissolved in 100 mol dry THF under inert atmosphere. 29.3g (0.29 mol) triethylamine and 1.02 g (1.5 mmol) Pd[Ph₃P]₂CI₂ are added and reaction mixture is stirred overnight at room temperature. 2M HCI is added to quench the reaction. The product is extracted with dichloromethane and purified by column chromatography on silica gel with petrol benzene as an eluent. Yield 6.7 g (68%). Pent = n-pentyl.

I₂, DMSO

b) 6.7 g (19.6 mmol) of the product of example 16a and 2.5 g (9.8 mmol) iodine is dissolved in 80 ml DMSO and heated at 155 ⁰C overnight. Water is added to quench the reaction and the product is extracted with petrol benzene and purified by column chromatography on silica gel with petrol benzene : ethyl acetate (10:0.5) as an eluent. Yield 5.12 g (76.4 %). Pent = n- pentyl.

c) 1 g (4.8 mmol) 9,10-diaminophenanthrene and 1.7 g (4.56 mmol) of the product of example 16b are dissolved in ethanol and refluxed for 48h. The reaction mixture is cooled down, filtered and reprecipitated from ethyl acetate to methanol. Yield 2 g (80.6 %). Pent = n-pentyl.

d) To 1.0 g (1.83 mmol) of the product of example 16c in 50 ml toluene are added 25 ml of 1 M K₂CO₃ aqueous solution. Nitrogen is bubbled through the reaction mixture for 10 min and 0.54 g (3.67 mmol) of 4-vinylphenylboronic acid and 0.42 g (0.37 mmol) Pd[Ph₃P]₄ are added. The reaction mixture is stirred at 80 ⁰C for 2h and overnight at room temperature. The reaction mixture is washed with Na₂S₂O₃ aq., extracted with chloroform and purified by column chromatography on silica gel with hexane:ethyl acetate (9:1 ) as an eluent and further precipitated in methanol. Yield 0.84 g (80.7 %). Pent = n-pentyl.

Example 17

0.5 g of example 16d and 2.9 mg of alkoxyamine initiator CG-39-0401

] are dissolved in 0.5 ml chlorobenzene, degassed and stirred at 120 ⁰C for 2Oh. The obtained polymer is purified by precipitation in MeOH (yield: 0.35 g (70%)). Mw = 29 000, PDI = 1.46.

Example 18

a) 3 g (15.44 mmol) 9-phenanthrol and 0.48 ml hydrazine monohydrate are sealed in autoclave and heated to 180 ⁰C overnight. The product is washed with hexane. Yield 2.5 g (80 %).

salt

b) 1.8 g (4.9 mmol) of the product of example 18a is dissolved in 27 ml dry DMF and a suspension of 0.18 g (7.5 mmol) NaH in 1 1 ml DMF is added and the reaction mixture is stirred 20 min at room temperature. 1.64 g (7.3 mmol) 2-(3-bromopropoxy)tetrahydro-2h- pyran is added and the reaction mixture is stirred overnight at 120 ⁰C. DMF is evaporated and the residue is redissolved in ethanol. 3 g (1 1.9 mmol) p-toluenesulfonic acid pyridine salt is added and stirred 3h at 70 ⁰C. Water is added to quench the reaction and the product is extracted with chloroform and further purified by column chromatography on silica gel with heptane : ethyl acetate (8 : 2) as an eluent. Yield 1.3 g (46.3 %).

c) 1.2 g (2.8 mmol) of the product of example 18b are dissolved in 15 ml dichloromethane with 1 ml diisopropylethylamine and cooled down to 0 ⁰C. 0.4 g (4.32 mmol) acrylic acid chloride are added and the reaction mixture is stirred for 30 min at 0 ⁰C. The product is purified by column chromatography on silica gel with heptane : ethyl acetate (1 : 1 ) as an eluent. Yield 1.05 g (77.7 %).

Example 19

0.5 g of the product of example 18c and 15 mg of AIBN are dissolved in 3 ml THF, degassed and stirred at 60 ⁰C for 24h. The obtained polymer is purified by precipitation in MeOH (yield: 0.41 g (82.0%)). Mw = 12 000, PDI = 1.82.

Example 20 DMF

To 1.3 g (3.54 mmol) of the product of example 18a and 4 g NaOH in 5 ml DMF 6.65 g (35.3 mmol) dibromoethane is added and stirred overnight at 120 ⁰C. The solvent is changed to ethanol and an excess of KOH is added and the reaction mixture is refluxed for 3h. The product is purified by column chromatography on silica gel with heptane : toluene (8 : 2) as an eluent. Yield 1.0 g (71.9 %). Example 21

a) 3 g (14.4 mmol) phenanthrene-9,10-dione and 2.15 g (17.36 mmol) 2,3-diaminophenol are dissolved in 120 ml ethanol and refluxed for 24h. The reaction mixture is cooled down, filtered and washed with ethanol. Yield 3.94 g (92.3 %).

b) To 2g (6.75 mmol) of the product of example 21a and 2.33 g (16.87 mmol) K₂CO₃ in 20 ml dry dimethylformamide (DMF) 2.82 g (13.5 mmol) 8-bromo-1 -octanol are added and stirred overnight at 120 ⁰C. The DMF is evaporated. The residue is redissolved in ethyl acetate and reprecipitated in heptane. Yield 0.89 g (31 %).

c) The product is prepared according to example 18c (yield: 0.5g (29.7 %)).

Example 22

0.5 g of the product of example 21c and 15 mg of AIBN are dissolved in 5 ml chlorobenzene, degassed and stirred at 60 ⁰C for 24h. The obtained polymer is purified by precipitation in MeOH (yield: 0.41 g (82.0%)).

Claims

1. A polymer comprising a repeating unit(s) of the formula

wherein A is a 5-, 6-, or 7-membered heteroaromatic ring, containing at least one heteroatom selected from nitrogen, oxygen and sulfur, especially one nitrogen atom and at least one further heteroatom selected from nitrogen, substituted nitrogen, oxygen and sulfur,

R^a, R¹, R², R³, R⁴, R¹ , R² , R³ and R⁴ are independently of each other hydrogen, halogen, especially fluorine, or an organic substituent, or

R^a, R¹, R², R³, R⁴, R¹ , R² , R³ and R⁴ , if possible, together form an aromatic, or heteroaromatic ring, or ring system, which can optionally be substituted,

R⁷ is halogen, especially fluorine, or an organic substituent, wherein two or more substituents R⁷ in the same molecule may have different meanings, or can form together an aromatic, or heteroaromatic ring, or ring system, wherein at least one of R^a, R¹, R², R³, R⁴, R¹ , R² , R³ and R⁴ is a group R¹⁰, wherein

R¹⁰ is a group -(Sp)_xr[PG']<, wherein

Sp is a spacer unit,

PG' is a group derived from a polymerisable group, x1 is 0, or 1 , and x is 0, or an integer of 1 to 4.

2. A polymer according to claim 1 , comprising a repeating unit(s) of the formula

(XX) and/or (XXI), wherein

R¹ and R¹ are independently of each other hydrogen, halogen, d-Ci₈alkyl, CrCi₈alkyl which is substituted by E and/or interrupted by D, d-C₁₈perfluoroalkyl, C₂-C₁₈alkenyl, C₂-Ci₈alkynyl, Ci-Ci₈alkoxy, Ci-Ci₈alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R²⁸,

R², R³ R⁴, R², R³ and R⁴ _, are independently of each other H, halogen, Ci-Ci₈alkyl, d- C₁₈alkyl which is substituted by E and/or interrupted by D, d-C₁₈perfluoroalkyl, C₆- C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-Ci₈alkenyl, C₂-Ci₈alkynyl, d-Ci₈alkoxy, CrCi₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, CN, or -CO-R²⁸,

R⁸ is H, d-C₁₈alkyl, d-C₁₈alkyl which is substituted by E and/or interrupted by D, C₁-

C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-

C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-C₁₈alkoxy, C₁-

C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, CN, or -CO-

R²⁸,

R⁹ , R⁹ , R" and R⁹⁹ is H, d-C₁₈alkyl, d-C₁₈alkyl which is substituted by E and/or interrupted by D, d-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G,

C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-

C₁₈alkynyl, d-C₁₈alkoxy, d-C₁₈alkoxy which is substituted by E and/or interrupted by

D, C₇-C₂₅aralkyl, or -CO-R²⁸,

R¹⁰ is a group -(Sp)_x1-[PG']<, wherein Sp is a spacer unit, PG' is a group derived from a polymerisable group, and x1 is O, or 1 , or

R^B and R^πυ together form a group

wherein one of the substituents F -r>₂0"5⁰, R**, R ' „ a„nd j R^^υB, _n an_nd_ri o „„n„e o „{f u th,_Λe s „.u.!b,s„+t:i+.

^^υ tu .„e„n+ts„ _n a_nnd_ri

;is a group R¹⁰ and the other substituents are independently of each other H, d-C₁₈alkyl, C₁-

C₁₈alkyl which is substituted by E and/or interrupted by D, d-C₁₈alkoxy, or C₁-

C₁₈alkoxy which is substituted by E and/or interrupted by D,

R¹¹ and R¹¹ are independently of each other hydrogen, halogen, especially fluorine, C₁-

C₁₈alkyl, d-C₁₈alkyl which is substituted by E and/or interrupted by D, C₁-

C₁₈perfluoroalkyl, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-C₁₈alkoxy, d-C₁₈alkoxy which is substituted by E and/or interrupted by D, CN, or -CO-R²⁸,

R¹², R¹³ R¹⁴, R¹² , R¹³ and R¹⁴ are independently of each other H, halogen, especially fluorine, d-C₁₈alkyl, d-C₁₈alkyl which is substituted by E and/or interrupted by D, C₁-

C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂- doheteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-C₁₈alkoxy, C₁-

C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, CN or -CO-

R²⁸,

X is O, S, or NR¹⁷, wherein R¹⁷ is d-C₁₈alkyl, d-C₁₈alkyl which is substituted by E and/or interrupted by D, d-C₁₈perfluoroalkyl, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂₀heteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-

C₁₈alkynyl, C₇-C₂₅aralkyl, or -CO-R²⁸; or two substituents R¹ , R², R³ and R⁴; R¹ , R² , R³ and R⁴ ; R¹¹ , R¹², R¹³ and R¹⁴; R¹¹ ,

R¹² , R¹³ and R¹⁴ , which are adjacent to each other, together form a group

or

or two substituents R and R , which are adjacent to each other,

together form a group

, or

or two substituents R and R , and/or R and R , which are

;x³ adjacent to each other, together form a group , or , wherein X³ is O, S,

C(R¹¹⁹KR¹²⁰), or NR¹⁷, wherein R¹⁷ is as defined above, R¹⁰⁵, R¹⁰⁶, R¹⁰⁷, R¹⁰⁸, R¹⁰⁵ , R¹⁰⁶ ,

R¹⁰⁷ and R¹⁰⁸ are independently of each other H, CrCi₈alkyl, CrCi₈alkyl which is substituted by E and/or interrupted by D, d-C₁₈alkoxy, or d-C₁₈alkoxy which is substituted by E and/or interrupted by D,

R¹¹⁹ and R¹²⁰ are independently of each other H, Ci-Ci₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by

G, C₂-C₂oheteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-

D, or C₇-C₂₅aralkyl, or

R¹²¹ and R¹²² are independently of each other H, Ci-d,₈alkyl, Ci-Ci₈alkyl which is substituted by E and/or interrupted by D, C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by

G, or C₂-C₂₀heteroaryl, or C₂-C₂₀heteroaryl which is substituted by G, or R¹¹⁹ and R¹²⁰ together form a five or six membered ring, which optionally can be substituted by d-C₁₈alkyl, d-C₁₈alkyl which is substituted by E and/or interrupted by D,

C₆-C₂₄aryl, C₆-C₂₄aryl which is substituted by G, C₂-C₂oheteroaryl, C₂-C₂₀heteroaryl which is substituted by G, C₂-C₁₈alkenyl, C₂-C₁₈alkynyl, d-C₁₈alkoxy, d-C₁₈alkoxy which is substituted by E and/or interrupted by D, C₇-C₂₅aralkyl, or -C(=O)-R¹²⁷, and

R¹²⁷ is H; C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by d-d₈alkyl, or d-d₈alkoxy; d-

C₁₈alkyl; or d-C₁₈alkyl which is interrupted by -O-,

D is -CO-; -COO-; -S-; -SO-; -SO₂-; -0-; -NR²⁵-; -SiR³⁰R³¹-; -POR³²-; -CR²³=CR²⁴-; or -

C≡d; and

E is -OR²⁹; -SR²⁹; -NR²⁵R²⁶; -COR²⁸; -COOR²⁷; -CONR²⁵R²⁶; -CN; or halogen; G is E,

Ci-d|₈alkyl, Ci-d,₈alkyl which is interrupted by D, Ci-Ci₈perfluoroalkyl, or Ci-d,₈alkoxy which is substituted by E and/or interrupted by D, wherein

R²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-C₁₈aryl; C₆-C₁₈aryl which is substituted by d-C₁₈alkyl, or d-C₁₈alkoxy; d-C₁₈alkyl; or d-C₁₈alkyl which is interrupted by -0-; or

R²⁵ and R²⁶ together form a five or six membered ring, in particular

R²⁷ and R²⁸ are independently of each other H; C₆-d₈aryl; C₆-d₈aryl which is substituted by d-C₁₈alkyl, or d-C₁₈alkoxy; d-C₁₈alkyl; or d-C₁₈alkyl which is interrupted by -0-,

R²⁹ is H; C₆-Ci₈aryl; C₆-d₈aryl, which is substituted by Ci-d,₈alkyl, or Ci-Ci₈alkoxy; Ci C₁₈alkyl; or d-C₁₈alkyl which is interrupted by -0-,

R³⁰ and R³¹ are independently of each other Ci-d,₈alkyl, C₆-d₈aryl, or C₆-d₈aryl, which is substituted by d-C₁₈alkyl, and

R³² is Ci-d|₈alkyl, C₆-d₈aryl, or C₆-d₈aryl, which is substituted by Ci-d,₈alkyl, or R⁹ , R¹², R¹³ R¹⁴, R¹² , R¹³ and R¹⁴ are a group -(Sp)_x1-HEI, wherein Sp is a spacer unit, HEI is a group (HEI¹), which increases the hole-injection or hole-transport properties of the polymers; or a group (HEl"), which increases the electron-injection or electron- transport properties of the polymers, x1 is 0, or 1 , with the proviso that in case of the compound of the formula XIV at least one of the substituents R¹², R¹³, R¹² and R¹³ is a group R¹⁰.

3. A polymer according to claim 2, comprising a repeating unit of the formula X, or Xl, wherein R¹ and R¹ are hydrogen,

R², R³ R⁴, R² , R³ and R⁴ are independently of each other H, d-C₁₈alkyl, d-C₁₈alkyl which is interrupted by D, CrCi₈perfluoroalkyl, CrCi₈alkoxy, CrCi₈alkoxy which is interrupted by D, or C₇-C₂₅aralkyl,

R⁸ is H, d-dsalkyl, d-d₈alkyl which is interrupted by D, d-C₁₈perfluoroalkyl, C₁- d₈alkoxy, or d-d₈alkoxy which is interrupted by D, two substituents R¹, R², R³ R⁴, R¹ , R² , R³ and R⁴ , which are adjacent to each other,

together form a group

, or two substituents R⁴ and R⁴ , which are adjacent

to each other, together form a group

, wherein R¹⁰⁵, R¹⁰⁶, R¹⁰⁷ and -R¹⁰⁸ are independently of each other H, or d-C₈alkyl,

R¹⁰ is a group -(Sp)_xr[PG']<, wherein Sp is a spacer unit, PG' is a group derived from a polymerisable group, and x1 is 0, or 1 ,

D is -CO-; -COO-; -S-; -SO-; -SO₂-; -O-; -NR²⁵-; -CR²³=CR²⁴-; or -C≡C-; wherein R²³, R²⁴, R²⁵ and R²⁶ are independently of each other H; C₆-d₈aryl; C₆-Ci₈aryl which is substituted by d-C₈alkyl, or d-C₈alkoxy; d-C₈alkyl; or d-C₈alkyl which is interrupted by -O-, or R²⁵ and R²⁶ together form a five or six membered ring, in particular

a polymer according to claim 2, comprising a repeating unit of the formula

(XIII), wherein

R⁹ is H, C₆-C₁₈aryl, which can be substituted by G, C₂-C₁₈heteroaryl, which can be substituted by G, Ci-Ci₈alkyl, CrCi₈alkyl which is interrupted by D, d-

C₁₈perfluoroalkyl, d-C₁₈alkoxy, or d-C₁₈alkoxy which is substituted by E and/or interrupted by D,

R¹¹ and R¹¹ are hydrogen,

R¹², R¹³ R¹⁴, R¹² , R¹³ and R¹⁴ are hydrogen,

R¹⁷ is C₆-Ci₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; d-

C₁₈alkyl; or d-C₁₈alkyl which is interrupted by -O-; or two substituents R¹¹ , R¹², R¹³ R¹⁴, R¹¹ , R¹² , R¹³ and R¹⁴ , which are adjacent to each

other, together form a group

, or two substituents R¹⁴ and R¹⁴ , which are

adjacent to each other, together form a group

, wherein R¹⁰⁵, R¹⁰⁶, R¹⁰⁷, R¹⁰⁸, D, E, and R¹⁰ are as defined above.

4. A polymer according to any of claims 1 to 3, wherein Sp is selected from -Ar-, -ArY-, - YAr-, -YAr(CR⁴⁷R⁴⁸V, -ArY(CR⁴⁷R⁴⁸)_nAr-, -ArY(CR⁴⁷R⁴⁸)_n-, -(CR⁴⁷R⁴⁸)_n-, -(YCR⁴⁷R⁴⁸)_n- or -(CR⁴⁷R⁴⁸Y)_n-, wherein

Y is NR⁵, O, S, C=O, C(=O)O, wherein R⁵ is H; C₆-d₈aryl; C₆-d₈aryl which is substituted by d-C₁₈alkyl, or d-C₁₈alkoxy; d-C₁₈alkyl; or d-C₁₈alkyl which is interrupted by -O-; R⁴⁷ and R⁴⁸ are independently of each other hydrogen, fluorine, or Ci-C₂oalkyl, n is an integer of 1 to 20,

Ar is alkylen, cycloalkylen, arylen, aralkylene, or heteroarylen, which can optionally be substituted,

PG' is a group derived from a polymerisable group selected from -C(R⁴⁴)=CH₂,

-NHC(O)-C(R⁴⁵)=CH₂, -OCH₂CH₂OC(O)-C(R⁴⁵)=CH₂, -OC(O)-C(R⁴⁵)=CH₂, -C(O)-

C(R⁴⁶)=CH₂, -C≡C-, -N≡C, -O-CH(CH₂CH₂CH=CH₂)₂; C₅-C₈cycloalkenyl, bicycloalkenyl

'(C H₂)- C H -C-R \ H (CH₂)m 1 -CH — C — R

(1 ,2-epoxyether),

-N CO

¹ (CH₂)_S^

, wherein s is an integer from 1 to 6, ml is an integer from 1 to 6,

R⁶ is hydrogen, or CrC₂₀alkyl,

R⁴⁴ is hydrogen, or d-C₄alkyl, or halogen,

R⁴⁵ is hydrogen, Ci-C₄alkyl, or halogen, and

R⁴⁶ is hydrogen, Ci-C₄alkyl, or C₆-C₁₂aryl, or

PG' is a group derived from a polymerisable group ? , wherein

R²¹²-AHG

AHG is an aromatic, or heteroaromatic residue, which can optionally be substituted,

, or

R²¹¹ and R²¹² are independently of each other halogen, -C=CH, boronic acid, or boronic esters, -Mg-HaI, -Zn-HaI, -Sn (R²¹³)₃, wherein Hal is halogen, and R²¹³ is CrCi₈alkyl, R²¹⁴ and R²¹⁴ are independently of each other H, C-ι-C₁₈alkyl, C-ι-C₁₈alkyl which is interrupted by D, Ci-Ci₈perfluoroalkyl, CrCi₈alkoxy, CrCi₈alkoxy which is interrupted by D, or C₇-C₂₅aralkyl.

5. The polymer according to any of claims 1 to 4, wherein the polymer is a

a homopolymer of formula

, or

a homopolymer of formula

or

a homopolymer of formula or

a homopolymer of formula or

a homopolymer of formula

F-8 ditto H H

F-9 ditto H H

F-10 ditto H H

O O

F-11 ditto H H

F-12 ditto H H

a homopolymer of formula

, or

G-16 ditto H H

G-17 ditto H H

G-18 ditto H H tBu

G-19 ditto H H r^"V^CF3

G-20 ditto H H tBu

G-21 ditto H H

N - 0-

G-22 ditto H H

O^" O-

G-23 ditto H H ύ- ύ-

G-24 ditto H H

& ύ-

G-25 ditto N(Ph)₂ N(Ph)₂ ditto ditto

G-26 ditto C₈H 17 C ^■ ₈8Hπ i7 ditto ditto

G-27 ditto ditto ditto ditto

G-28 CH, ditto ditto ditto ditto

O-

a homopolymer of formula

H-8 ditto H

H-9 ditto H

H-10 ditto H

O O

H-11 ditto H

H-12 ditto H

H-13 ditto H

O O

H-14 ditto H

/ C

H-15 ditto H

H-16 ditto H

H-17 ditto H CH₃OJ^

H-18 ditto H tBu

H-19 ditto H ^\^^CF3

H-20 ditto H N tBu

H-21 ditto H

O N . O N .

H-22 ditto H

O^" O^"

H-23 ditto H

H-24 ditto -CH₃ ditto ditto

H-25 ditto -n-C₈H 17 ditto ditto

a homopolymer of formula

a homopolymer of formula

J -5 ditto ditto H H CN

J -6 ditto ditto H H O-πC₁₆H₃₃

J -7 ditto ditto H H

J -8 ditto ditto H H

J -9 ditto ditto H H

O

J-10 ditto ditto H H

J-11 ditto ditto H H

J-12 ditto ditto H H

O

J-13 ditto ditto H H

/ C

J-14 ditto ditto H H

J-15 ditto ditto H H

J-16 ditto ditto H H

J-17 ditto ditto H H

J-18 ditto ditto H H r^"V^CF3

J-19 ditto ditto H H tBu

J -20 ditto ditto TT TT

J-21 ditto ditto H H

O^""

J -22 ditto ditto H H

J -23 ditto ditto H H

J -24 ditto ditto N(Ph)₂ N(Ph)₂ ditto

J -25 ditto ditto CβHi₇ C₈H 17 ditto

or a homopolymer of formula

6. The polymer according to claim 1 , wherein the polymer comprises repeating units of formula

, or , wherein

R²¹⁶ and R²¹⁷ are independently of each other d-C^alkyl, or C₆-C₈aryl, which can optionally be substituted by one, or more d-C^alkyl groups, and R¹⁷ is C₆-C₁₈aryl; C₆- C₁₈aryl which is substituted by d-C^alkyl, or d-C^alkoxy; d-d₈alkyl; or d-d₈alkyl which is interrupted by -O-; or the polymer comprises

'17

7. An electronic device or a component therefore, comprising the polymer according to any of claims 1 to 6.

8. Use of the polymers according to any of claims 1 to 6, in organic light emitting diodes (OLEDs), especially as host material for phosphorescent compounds.

9. OLEDs, organic integrated circuits (0-ICs), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic solar cells (0-SCs), thermoelectric decices, or organic laser diodes comprising one or more of the polymers according to any of claims 1 to 6.

10. A compound of the formula

wherein x, A, R^a, R¹, R², R³, R⁴, R¹ , R² , R³ , R⁴ and R⁷ are as defined in claim 1 , at least one of R^a, R¹, R², R³, R⁴, R¹ , R² , R³ and R⁴ is a group R¹⁰ , wherein

R¹⁰ is a group -(Sp)_x1-[PG]<, wherein

Sp is a spacer unit,

1 1 . A compound according to claim 10 of the formula

X, R¹, R¹, R², R³ _, R⁴, R², R³, R⁴ _, R⁸, R⁹, R⁹ , R⁹⁹, R⁹⁹, R¹⁷, R¹¹, R¹¹, R¹², R¹³ _, R¹⁴, R¹², R¹³ and R¹⁴ are as defined in claim 2, R¹⁰ is a group -(Sp)_x1-[PG], wherein Sp is a spacer unit, PG is a polymerisable group, and x1 is 0, or 1, or R⁸ and R¹⁰ together form

a group

, wherein one of the substituents R²⁰⁵, R²⁰⁶, R²⁰⁷ and R²⁰⁸, and one of the substituents R²⁰⁸ and R²¹⁰ is a group R¹⁰ and the other substituents are independently of each other H, CrCi₈alkyl, d-Ci₈alkyl which is substituted by E and/or interrupted by D, d-C^alkoxy, or d-C^alkoxy which is substituted by E and/or interrupted by D, with the proviso that in case of the compound of the formula XIV at least one of the substituents R¹², R¹³, R¹² and R¹³ is a group R¹⁰.

12. A compound according to claim 10, or 1 1 , wherein Sp is selected from -Ar-, -ArY-, - YAr-, -YAr(CR⁴⁷R⁴⁸V, -(CR⁴⁷R⁴⁸)_n-, -(YCR⁴⁷R⁴⁸)_n-, or -(CR⁴⁷R⁴⁸Y)_n-, wherein Y is NR⁵, O, S, C=O, C(=O)O, wherein R⁵ is H; C₆-Ci ₈aryl; C₆-Ci₈aryl which is substituted by Ci-Ci₈alkyl, or Ci-Ci₈alkoxy; Ci-Ci₈alkyl; or Ci-Ci₈alkyl which is interrupted by -O-;

R⁴⁷ and R⁴⁸ are independently of each other hydrogen, fluorine, or Ci-C₂₀alkyl, n is an integer of 1 to 20,

PG is a polymerisable group selected from -C(R⁴⁴)=CH₂, -NHC(O)-C(R⁴⁵)=CH₂, - OCH₂CH₂OC(O)-C(R⁴⁵)=CH₂, -OC(O)-C(R⁴⁵)=CH₂, -C(O)-C(R⁴⁶)=CH₂, -C≡C-, -N≡C, - O-CH(CH₂CH₂CH=CH₂)₂; C₅-C₈cycloalkenyl, bicycloalkenyl (a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms),

(1 ,2-epoxyether),

-N CO

¹ (CH₂)_S^

, wherein s is an integer from 1 to 6, ml is an integer from 1 to 6,

R⁶ is hydrogen, or Ci-C₂₀alkyl,

R⁴⁴ is hydrogen, or CrC₄alkyl, or halogen,

R⁴⁵ is hydrogen, Ci-C₄alkyl, or halogen, and

R⁴⁶ is hydrogen, Ci-C₄alkyl, or C₆-Ci₂aryl, or PG is a polymerisable group _| , wherein AHG is an aromatic, or heteroaromatic

R²¹²-AHG

residue, which can optionally be substituted, such as

, or

R²¹¹ and R²¹² are independently of each other halogen, -C≡CH, boronic acid, or boronic esters, -Mg-HaI, -Zn-HaI, -Sn (R²¹³)₃, wherein Hal is halogen, and R²¹³ is d-dsalkyl, R²¹⁴ and R²¹⁴ are independently of each other H, CrCi₈alkyl, CrCi₈alkyl which is interrupted by D, d-dsperfluoroalkyl, d-dsalkoxy, d-dsalkoxy which is interrupted by D, or C₇-C₂₅aralkyl.