DE19643097A1 - Novel thermally-crosslinkable tri:aryl:amine(s) - Google Patents

Abstract

Novel triarylamines of formula (I)a re claimed. Also claimed are: (1) mixtures of (I) with triarylamines of formula (II); (2) compositions comprising (I) (and optionally also (II)) together with comonomers; and (3) polymers obtained by thermally crosslinking any of the above. Ar<1> and Ar<2> = benzo-annelated homo- or hetero-aromatic groups optionally with one to four 1-6C alkyl, alkoxy or acyl, -COO(1-6C alkyl), oxy(1-6C acyl), halogen, COOH, CHO, OH, SO2H, SO3H, CN, SCN, OCN or NO2 substituents but with the proviso that Ar<1> and/or Ar<2> is substituted by an ethinyl group -C?=CH; X = m-valent group with one or more -C?=CH substituents; m = 1 is as for Ar<1> and Ar<2>; m and n = 1-6; Ar<3> and Ar<4> = as for Ar<1> and Ar<2> but with the proviso that at least one of them is substituted with at least one -C?=C-Z-R<1> group; Z = a single bond, -O-, -CO-, -COO-, -OOC-, -N(1-6C alkyl)-CO-, -OC-N(1-6C alkyl)- or -(CH2)1-6-; R<1> = H, 1-6C alkyl or benzo-annelated homo- or hetero -aromatic group with 1-4 substituents as per Ar<1> and Ar<2> above with the proviso that at least one R<1> is not H when Z is a single bond and (II) contains more than one -C?=C-Z-R<1> group; Y = an n-valent group which is optionally substituted by one or more -C?=C-Z-R<1> groups; and which is as per Ar<3> and Ar<4> when n = 1.

Description

Triphenylamine derivatives are among the best known organic Ladders with charge transport through perforated cable. Technical They are therefore used e.g. B. in electrophotography (Photocopier, laser printer) in electroluminescent elements as in photorefractive materials (holographic data memory, optical modulation).

The use of triphenylamine derivatives in electrophotographic Photoconductors are described in DE-A 38 10 522 and in one Article by Bässler (Adv. Mater. 5, pp. 662-665 (1993)) ben.

Electrophotographic applications based on triarylaminderi Data containing ethynyl groups -C∼C- are in Japanese script Hei 3-163 459 and script EP-A 399 403 listed. The first script deals with symme trisch p-substituted triphenylamines, the p-substituents ten of the phenyl groups with various u. a. aromatic or heteroaromatic, mononuclear or polynuclear residues substi tuuted ethynyl groups exist. The latter describes Triaryl derivatives which are obtained by azo coupling starting from amines, such as tris- [4- (4'-aminophenylethynyl) phenyl)] amine with under different coupling components are manufactured.

Organic electroluminescent elements, the triphenylamine derivatives contain as a hole-conducting layer, z. B. at Tang et al. (Appl. Phys. Lett. 51, pp. 913-915 (1987)). The Use of triphenylamine derivatives in photorefractive mate rialien is developed by W.E. Moerner and S.M. Silence (Chem. Rev. 94, 127-155 (1994)).

For the generation of layers which transport such charges contain the triphenylamine derivatives in the amorphous state or from such connections exist, it is advantageous to settle down to use molecular substances. These usually have good solves in common solvents and / or have relative low melting points without decomposing during melting Zen.  

These layers are therefore usually covered by, for example Evaporation or knife coating or spin coating of the in organic solvents or compounds Pour obtained from the melt.

On the other hand, these low molecular weight triphenylamine derivatives often not due to their undesirable tendency to crystallize as pure substances, but dissolved in a polymer such as. B. Poly carbonate, polyvinyl butyrate, polystyrene or polyester used. However, the concentration of the triphenylamine derivative must be sufficient be high enough to ensure proper charge transport to ensure the layer. So z. B. the charge carrier mobility of 1,1-bis (di-4-tolylaminophenyl) cyclohexane according to Un research by P.M. Borsenberger et al. (J. Chem. Phys. 94, S. 8276-8281 (1991)) for the amorphous material by about two sizes orders if you replace the pure substance with the same sub punch used to 75 wt .-% in a polycarbonate matrix. For practical applications will be the share of that for the cargo oil connection responsible for sport usually even reduced to about 50% adorns, because only in this way a perfect condition of the coating can be guaranteed and phase separation processes from can be prevented sufficiently.

Therefore, when using low molecular weight triphenyl amines, you are repeatedly faced with the following problems:

• - The tendency of low molecular weight triarylamine compounds to Crystallization can lead to the formation of cracks and domain sizes lead zen by which the function of the components is pregnant.
• - The use of solutions to apply additional layers on the layer of the triphenylamine derivative by means of doctor blades or spin-coat, depending on the solvents used, a dissolving or at least swelling of the first layer Act. This then leads to a mixture of the two Layers at the interface, what the function of the Bauele ment impaired. These problems are discussed in the Document US 45 39 507 described.
• - Unwanted Ver mixtures by (inter-) diffusion of the low molecular weight Connections take place at the interface.  
• - When embedding a triphenylamine derivative in a poly meren matrix is particularly at high concentration of la manure transport material the danger of a phase separation given.
• - Through sublimation processes but also diffusion processes the use of low molecular charge transport compounds in applications such as organic light emitting diodes (operating temperature temperatures <100 ° C) severely restricted or even prevented. A quick decrease in performance is often observed here or a complete loss of function.

In the document EP-A 637 899 is used as a solution to these problems the use of thermally or photochemically crosslinkable monomers described the manufacture of electroluminescent elements. The functional molecules are first in a conventional manner applied and then crosslinked to form insoluble materials. Acrylates, epoxides and cinnamic acid are used as crosslinkable groups derivatives listed.

The object of the present invention was therefore crosslinking capable triarylamine derivatives and mixtures of such derivatives for To make available both in the manufacturing process of layers are easy to handle and also according to their polymer sation homogeneous, chemically and physically resistant Form layers that are also good charge-transporting eggs have properties.

It has been found that this property profile is met in a comprehensive manner by compounds of the formula I.

in what mean
Ar ¹ and Ar ^2, independently of one another, are each homo- or heteroaromatic groups which are benzo-fused and, independently of one another, one to four substituents from the group C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -acyl, COO (C ₁ -C ₆ -alkyl), oxy (C ₁ -C ₆ -acyl), halo gen, COOH, CHO, OH, SO ₂ H, SO ₃ H, CN, SCN, OCN, NO _{2 can} wear, with the proviso that at least one of the groups Ar ¹ or Ar ^{2 is} additionally substituted with at least one ethynyl radical of the formula

-C∼CH, X is an m-valent group which can be substituted by one or more ethynyl radicals of the formula -C∼CH and, in the case of m = 1, has the same meaning as the groups Ar ¹ and Ar ² ,
m is an integer from 1 to 6.

Mixtures containing components can also be used

• a) at least one compound of formula I, and
• b) at least one compound of the formula II
  

in what mean
Ar ³

and Ar ⁴

independently of one another in each case homo- or heteroaromatic groups which are benzo-fused and, independently of one another, one to four substituents from group C ₁

-C ₆

-Alkyl, C ₁

-C ₆

Alkoxy, C ₁

-C ₆

-Acyl, COO (C ₁

-C ₆

-Alkyl), oxy (C ₁

-C ₆

-Acyl), halo gene, COOH, CHO, OH ₁

SO ₂

H, SO ₃

H, CN, SCN, OCN, NO ₂

can wear, with the proviso that at least one of the groups Ar ³

or Ar ⁴

is additionally substituted with at least one radical of formula III

-C∼CZR ¹ (III),

in what mean
Z is a single chemical bond, -O-, -CO-, -COO-, -OOC-, -N (C ₁ -C ₆ alkyl) -CO-, -OC-N (C ₁ -C ₆ alkyl) - or - (CH ₂ ) _r -,
r is an integer from 1 to 6,
R ^{1 is} hydrogen, C ₁ -C ₆ -alkyl, a homo- or heteroaromatic table which is benzo-fused and one to four substituents from the group C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -acyl, oxy (C ₁ -C ₆ -acyl), COO (C ₁ -C ₆ -alkyl), halogen, COOH, CHO, OH, SO ₂ H, SO ₃ H, CN, SCN, OCN, Can carry NO ₂ , in the event that Z is a chemical single bond and the compound of formula II carries more than one radical of the formula III, at least one of the radicals R ^{1 is} different from hydrogen,
Y is an n-valent group which can be substituted with one or more radicals of the formula III and, if n is 1, has the same meaning as the groups Ar ³ and Ar ⁴ ,
n is an integer from 1 to 6.

Aromatic groups Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include isocyclic radicals such as phenyl but also heterocyclic five-membered radicals such as pyrryl, furanyl, thienyl, pyrazolyl, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1, 2,3-, 1,2,4-, 1,3,4- or 1,2,5-oxadiazolyl and the corresponding thiadiazolyl radicals as well as six-membered radicals such as pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,2,3- , 1,2,4- and 1,3,5-triazinyl in question. Benzo-fused radicals Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include groups such as naphthyl, indolyl (benzo [b] pyrryl), carbazolyl, benzo [b] furanyl, dibenzofuranyl, benzo [b] thienyl, dibenzothienyl, 1H- and 2H-indazolyl, 1H- and 3H-benzimidazolyl, indoxazolyl (benzo [b] isoxazolyl), benzoxazolyl, benzo [d] isothiazolyl, benzothiazolyl, 1,2,3-benzo [d] oxadiazolyl, 1,2,5-benzo [c] oxadiazolyl, 1,2,3-benzo [d] thiadiazolyl, 1,2,5-benzo [c] thiadiazolyl, quinolinyl, isoquinolinyl, acridinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, phenazinyl, benzo [g] cinnolinyl , Benzo [g] quinazolinyl, benzo [g] quinoxalinyl, benzo [g] quinolinyl, benzo [g] isoquinolinyl, phenantridinyl, 1,2,3-benzo [e] triazinyl and 1,2,4-benzo [e] triazinyl . If Ar ¹ , Ar ² , Ar ³ and Ar ⁴ mean heteroaromatic groupings, the connection to the amine N atom should not be via the hetero atom but via carbon. Furthermore, all groups Ar ¹ , Ar ² , Ar ³ and Ar ^{4 can} independently of one another one to four substituents from the group C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ acyl, COO ( C ₁ -C ₆ alkyl), oxy (C ₁ -C ₆ acyl), halogen, COOH, CHO, OH, SO ₂ H, SO ₃ H, CN, SCN, OCN and NO ₂ . C ₁ -C ₆ alkyl includes not only the straight-chain radicals methyl, ethyl, propyl, butyl, pentyl and hexyl but also branched radicals such as isopropyl, 1-, 2-methylpropyl (isobutyl), tert-butyl, 1- , 2-, 3-methylbutyl (isoamyl), 1-ethylpropyl, neopentyl, 1-, 2-, 3-, 4-methylpentyl and 1-, 2-ethylbutyl.

Analog come designated in this listing C ₁ -C ₅ radicals as fragments of the oxy (C ₁ -C ₆ acyl) -, and the C ₁ -C ₆ acyl, the benann th C ₁ -C ₆ radicals as Fragments of the C ₁ -C ₆ alkoxy and COO (C ₁ -C ₆ alkyl) substituents in question.

The substituents are attached via carbon atoms of the homo- or heteroaromatic groups. However, if one of the radicals Ar ¹ , Ar ² , Ar ³ and / or Ar ⁴ has the meaning of an N-heteroaromatic group which has a hydrogen atom on the N atom (for example pyrrole or indole), this can be substituted by the substituents C ₁ -C ₆ alkyl, C ₁ -C ₆ acyl, COO (C ₁ -C ₆ alkyl), COOH, CHO and CN it sets.

Halogen substituents are preferably Cl, Br and I. In the event that m or n in the formulas I or II is 1, the selection of the possible groups X or Y covers the same range as for the groups Ar ¹ , Ar ² or Ar ³ , Ar ⁴ . Be preferred groups X and Y, which are still C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy ,. C ₁ -C ₆ acyl, oxy (C ₁ -C ₆ acyl), COO (C ₁ -C ₆ alkyl) - as described -, Cl, Br, I, CN, NO ₂ and OH can be substituted , are equal to 2 for m or n, for example:

Preferred as divalent groups X and Y are also:

Particularly preferred divalent radicals X and Y are

where R ² and R ^{3 are} independently I, Cl, Br, OH or C ₁ -C ₆ alkyl, which may contain O in ether function or N (R ⁴ ) in imino function and terminating OH or NHR ⁴ , and where R ⁴ as a C ₁ -C ₆ alkyl group. Examples of such aliphatic C ₁ -C ₆ radicals have already been listed as examples above.

Furthermore, both radicals R ² and R ³ together with the carbon atom to which they are attached can form a saturated, he tero- or isocyclic five-, six- or seven-membered ring. If necessary, this ring can also be substituted with one or more alkyl radicals, the number of carbon atoms (without the carbon atom bearing the radicals R ² and R ³ ), which is present in the ring system and in the substituents, no longer than 12. Examples of such (substituted) diphenyl methane groups as divalent radicals X and Y are

Trivalent radicals X and Y can e.g. B. be:

Preferred radicals X and Y are:

Examples of suitable tetravalent radicals X and Y are perylene groups, such as

where T is H, Cl, phenoxy, and where these substituents T can either be all the same or partially different from one another,
or groups like

Pentavalent groups X and Y can be, for example

As hexavalent groups X and Y z. B. act

or also triphenylene residues, such as

The linking single time Z in the ethynyl group of the formula III includes, inter alia, groups such as -N (C ₁ -C ₆ -alkyl) CO-, -OC-N (C ₁ -C ₆ -alkyl) - and - (CH ₂ ) _r - . C ₁ -C ₆ -alkyl should again be understood to mean the linear and branched groups already exemplified above. - (CH ₂ ) _r - includes the groups methylene, ethylene, propylene, butylene, pentylene and hexamethylene.

In formula III, the radicals R ¹ which are bonded to the ethynyl group via the linking unit Z are all (sub-substituted) homo- or heteroaromatic groups already mentioned under the definition of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ . The groups C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -acyl, oxy (C ₁ -C ₆ -acyl), COO (C ₁ -C ₆ - Alkyl) and halogen can also serve as substituents of the homo- or heteroaromatic group. In addition, R ^{1 can} also be C ₁ -C ₆ -alkyl, as listed above, or hydrogen. In the event that Z corresponds to a single chemical bond and the compound of formula II carries more than one radical of formula III, hydrogen should be excluded as a possible meaning of all groups R ¹ , since such compounds are already included in the definition of compounds I. .

The groups Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are preferably, independently of one another, homoaromatic radicals which, independently of one another - apart from one or more possible ethynyl group (s) —C-CH— - at most one further C C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy group.

Examples of preferred radicals Ar ¹ and Ar ² in the group Ar ¹ Ar ² N- of compound I are:

In the case where m is 1, X includes the same preferred selection as Ar ¹ and Ar ² .

The groups Ar ¹ , Ar ² and X can in this case be the same or different from one another. However, it must be ensured that at least one of the groups Ar ¹ , Ar ² or X carries at least one ethynyl radical -C∼CH. Preferred triarylamine compounds for m equal to 1 are those in which at least two groups of Ar ¹ , Ar ² and X are identical. Examples for this are:

For m = 2, particularly preferred groups are X

the meaning of R ² and R ^{3 was} already discussed above.

The groups X, which are divalent to hexavalent, can carry different groups Ar ¹ Ar ² N-. However, identical groupings are preferred.

If the radicals Ar ¹ and Ar ^{2 are} also the same, they must, according to the definition of the compounds I, have at least one ethynyl radical —CH∼ as additional substituent. Preferred groups are:

Examples of compounds in which the groupings Ar ¹ Ar ² N- are identical are
with bivalent group X:

with trivalent group X:

with tetravalent group X:

with pentavalent group X

as well as with hexavalent group X:

The m-valent group X can also have one or more ethynyl groups -C∼CH, so that, for example, the following compounds can also be used:

The compounds of the formula II to be used in a mixture with the compounds of the formula I according to the invention can be formally derived from the former by replacing at least one ethynyl radical -C∼CH by a radical of the formula III, which of course then does not mean a group -C∼ CH may have. Compounds II are preferably used in which the substituted ethynyl radicals are the same, but compounds with different ethynyl radicals and additionally present -C∼CH groups should not be excluded. Preferred radicals of the formula III are those in which the variables Z, r and R ^{1 have} the meaning:
Z is a chemical single bond or - (CH ₂ ) _r -,
r is an integer from 1 to 6,
R ^{1 is} hydrogen, C ₁ -C ₆ -alkyl, a homo- or heteroaromatic group which is benzo-fused and one to four substituents from the group C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ - C ₆ -acyl, COO (C ₁ -C ₆ -alkyl), oxy (C ₁ -C ₆ -acyl), halogen, OCN.

The residues are particularly preferred:

-C∼CR ¹ and -C∼C- (CH ₂ ) _r -R ¹

where r assumes the values 1 and 2, ie represents the groups -CH ₂ - and -CH ₂ -CH ₂ - and R ¹ denotes

where these radicals R ^{1 are} also one to four substituents from the group C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ acyl, oxy (C ₁ -C ₆ acyl), COO ( C ₁ -C ₆ alkyl), halogen, COOH, CHO, OH, SO ₂ H, SO ₃ H, CN, SCN, OCN, NO _{2 can} carry. The substituents methyl, ethyl, methoxy, ethoxy, Cl, Br and I are preferred here.

Mixtures of compounds of the formulas I and II in which the groups Ar ¹ , Ar ² or Ar ³ , Ar ⁴ are independently homoaromatic groups and, independently of one another, a maximum of one to four substituents from the group C ₁ -C ₆ are further preferred -Alkyl and C ₁ -C ₆ alkoxy and in which the variables Z, r, R ¹ in formula III have the meaning
Z is a chemical single bond or - (CH ₂ ) _r -,
r is an integer from 1 to 6,
R ^{1 is} hydrogen, C ₁ -C ₆ alkyl, a homo- or heteroaromatic group which can be benzo-fused and which has one to four substituents from the group C ₁ -C ₆ alkyl, C ₁ alkoxy, C ₁ -C ₆ -Acyl, COO (C ₁ -C ₆ alkyl), oxy (C ₁ -C ₆ acyl), halogen, OCN can wear.

Mixtures in which the Compounds II the particularly preferred already mentioned above Leftovers

-C∼CR ¹ or -C∼C- (CH ₂ ) _r -R ¹

exhibit.

Ar ³ and Ar ⁴ in the grouping Ar ³ Ar ⁴ N- of the compounds II are preferably those groups which are formally replaced by the replacement of existing ethynyl residues -C∼CH in the residues Ar ¹ and Ar ² already mentioned and which are preferably used of the compounds I by radicals of the formula III or the particularly preferred radicals mentioned above

-C∼CR ¹ and -C∼C- (CH ₂ ) _r -R ¹

let derive. For n equal to 1, as also already mentioned, the monovalent group Y comprises the same selection as that of Ar ³ and Ar ⁴ . Examples of such connections are:

Furthermore, identical groups Ar ³ Ar ⁴ N- are preferably linked to groups Y, which are divalent to hexavalent, examples of preferred groupings being:

Examples of compounds II with identical, substituted ethynyl groups can easily be obtained from the examples for compounds I already mentioned above by formal replacement of the ethynyl groups -C∼CH by identical groups of the formula III or particularly preferred groups -C∼CR ¹ or - Derive C∼C- (CH ₂ ) _r -R ¹ . Further compounds II result by linking the multi-bonded group Y with (preferably identical) groupings Ar ³ Ar ⁴ N-, which are listed above by way of example, and are readily apparent to the person skilled in the art.

The compounds I according to the invention are preferably prepared from the optionally substituted triarylamines by bromination by the action of bromine or N-bromo-succinimide (NBS), subsequent substitution of the bromine in an advantageous manner by an acetylene compound protected on one side, for. B. HC∼C-Si (CH ₃ ) ₃ and exchange of the protective group against hydrogen. In the case of the protective group -Si (CH ₃ ) ₃ , this is preferably accomplished with KF in methanol. The nucleophilic exchange of the bromine is preferably carried out with palladium, copper, palladium / copper or nickel catalysis in the presence of a reducing agent such as P (C ₅ H ₆ ) ₃ . In this way, the disubstitution of acetylene can be prevented.

The following scheme 1 illustrates this reaction sequence exem Plural for the triphenylamine:  

Scheme 1

If, in addition or even finally substituted -C∼CZR ¹ radicals are used instead of the -C∼CH unit, one opens up the way to the compounds II to be used in a mixture with the compounds I. B. from the monobrominated or triple brominated triphenylamine (A) or (B) of scheme 1 with phenylacetylene, the single or triple substituted compound

A dimeric product of compound (B) can also be obtained Prepare Scheme 1 (Scheme 2a).  

Scheme 2a

The reaction of the brominated compound with the -C∼CH building block b mentioned or a monosubstituted acetylene HC∼CZR ¹ provides the corresponding representatives of the compounds I or II.

Other synthetic routes for compounds with a phenylene bridge, here the divalent radicals X or Y consist of the group

shows scheme 2b.  

Scheme 2b

The reaction of the brominated compound with the -C∼CH building block mentioned or a monosubstituted acetylene HC∼CZR ¹ in turn provides the desired representatives of the compounds I or II.

For the synthesis of the compounds I and II, in addition to the reactions already mentioned, synthetic reactions which are familiar to the person skilled in the art can also be used to give carbon or sulfonamides. For example, (multiple) carboxylic or sulfonic acids of the polyvalent groups X or Y, in the following scheme 3 as X '(COOH) _n , X' (SO ₃ H) _n , Y '(COOH) _m and Y' (SO ₃ H) _m denotes, with the brominated diphenylamines under azeotropic distillation using an entrainer such. B. toluene or xylene, and optionally in the presence of catalytic traces of a strong acid to the acid amides:

Scheme 3

The further implementation of the bromine compounds with the (substituted ten) acetylene units takes place in the already described Wise.

As a water-binding agent in acid amide formation can be advantageous dicyclohexylcarbodiimide can also be used.

In the case of inert acids and / or diphenylamines emp is the use of more reactive acid derivatives such. B. the Acid halides, preferably the acid chlorides, and the one set of auxiliary bases, such as the tertiary amines trimethyl, Triethylamine and dimethylcyclohexylamine. The reactions will be then preferably in inert suspension or solvents,  such as toluene, N-methylpyrrolidone, dimethylformamide, methylene chloride or carried out the pure auxiliary bases. The in particular If appropriate conditions and the auxiliary base to be used or Suspension or solvent to be used can be from Determine a specialist with a few preliminary tests or be him knows.

Of course, besides the brominated ones mentioned Triarylamine educts also use those which have more Have substituents in the following reactions to the ethinylated products remain unchanged and thus provide correspondingly substituted target compounds.

According to the invention, compositions can be used which contain components

• a) at least one compound of formula I or a mixture from at least one compound of the formula I and the form mel II,
• b) further monomers which are thermally linked to the compounds or Mixtures of a) can be copolymerized and, if appropriate, other additives.

Preferred and particularly preferred compositions are obtained by using the preferred or particularly preferred compounds I and II. Monoethylenically unsaturated compounds which can be used as monomers are, for example:
vinyl aromatic monomers, such as styrene or styrene derivatives of the general formula

in which S ¹ and S ^{2 represent} hydrogen or C ₁ - to C ₆ -alkyl;
Acrylonitrile, methacrylonitrile, cyanoacrylonitrile;
C ₁ - to C ₄ -alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl, i-propyl, n-butyl acrylate, iso butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylate ethylhexyl and the corresponding esters of methacrylic acid and cyanoacrylic ; also the glycidyl esters, glycidyl acrylate and methacrylate.

Crosslinking monomers which can be used are bi- or polyfunctional compounds having at least 2 olefinic double bonds, for example butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl and divinyl ethers of bifunctional alcohols such as ethylene glycol and butane-1,4- diols, diesters of acrylic acid and methacrylic acid with the bifunctional alcohols mentioned, 1,4-divinylbenzene, triallyl cyanurate, acrylic acid esters of tricyclodecenyl alcohol of the formula below

known under the name dihydrodicyclopentadienyl acrylate, as well the allyl esters of acrylic acid, methacrylic acid and cyana crylic acid.

Dyes (which should also be understood to include fluorescent dyes) can be added to the compositions as further additives. Suitable substances are mentioned that can also be used according to the invention, for. As in document EP-A 0 637 899. Furthermore, can be used Pery lenderivate, styryl compounds, metal complexes, dyes, indanthrene the brand ^® (BASF Aktiengesellschaft), Triarylmethanfarb materials, azo, bisazo and trisazo dyes, cyanine dyes, merocyanine dyes, phthalocyanine dyes and Quinacridone dyes.

Examples of perylene dyes are:

where mean
R ^{5 is} hydrogen, alkyl, aryl and substituted aryl; for example linear or branched C ₁ -C ₆ -alkyl radicals (examples of which have already been listed above), phenyl or naphthyl, 2,6-di-sec.-butylphenyl, 2,6-di-tert.-butylphenyl, 2, 6-di-isopropylphenyl,
R ⁶ H, CN, Cl, F, Br, -COOR ⁵ , -SO ₃ H, -SO ₂ R ⁵ , -NR ⁵ -CO (C ₁ -C ₆ alkyl), -OR ⁵ , -SR ⁵ ,
TH, Cl, phenoxy, preference being given to using either the quadruple Cl- or phenoxy-substituted compounds or also the compounds substituted with Cl and phenoxy.

Examples of styryl compounds are:

wherein the radicals R ⁵ and R ^{6 have} the above meaning and are preferably the same.

Examples of metal complexes, especially those of 8-hydroxy quinoline, are:

Examples of naphthalimides are compounds with the structures

where R ⁵ and R ^{6 have} the meaning as before.

Examples of coumarin derivatives are compounds with the structures

where R ^{5 has} the same meaning as before and R ⁷

can be.

Examples of Indanethrene ^® dyes (BASF Aktiengesellschaft) are known to the expert from the literature (eg. As Römpp Chemie-Lexikon, Volume 3 (HL), 9th ed. 1990, pp 1,960 to 1,962).

Examples of triarylmethane dyes (1),
Azo, bisazo and trisazo dyes (2),
Cyanine dyes (3),
Merocyanine dyes (4),
Phthalocyanine dyes (5),
Quinacridone Dyes (6)
are also known to the person skilled in the art from the literature (for example 1: Römpp Chemie-Lexikon, Volume 6 (TZ), 9th edition, 1992, pp. 4696-4697; 2: Kirk-Othmer, Enc. Chem. Technol. , Third Ed., Vol. 3, pp. 387-433; 3: dto, Vol. 7, pp. 335-358; 4: dto, Vol. 18, pp. 848-874; 5: dto, Vol. 17 , Pp. 777-787; 6: dto, vol. 17, pp. 857-859).

The dyes mentioned can be provided with one or more groups which ensure better fixation when the compositions of the invention are polymerized. As such groups z. B. act maleate

Vinyl, allyl, glycidyl

Iso cyanate, ethynyl (e.g. also the groups of the formula III, which be have already been listed as examples above), acrylate, meth acrylate or cyanoacrylate.

Of course, the dyes mentioned can also be used the compounds I alone or in a mixture thereof Insert connections II.

The compositions according to the invention can be used as further additives gene as well as the mixtures of the compounds I alone their mixtures with compounds II metal salts and metal contain organic compounds, which are typical for the Cyclization of (substituted) acetylenes find use and the person skilled in the literature (e.g. Cotton-Wilkinson, Anorg. Chemistry, 4th ed., 1982, pp. 1173-1179) are known. Examples such metal compounds include:

η ⁵ -C ₅ H ₅ (Co (CO) ₂ , Co ₂ (CO) ₈ , [Co (C ₅ H ₅ ) (C ₈ H ₁₂ )], NiCl ₂ , NiBr ₂ , [η ⁵ -C ₅ H ₅ Fe (CO) ₂ ] ₂ .

These metal compounds are only used in small quantities added, preferably less than 1 wt .-% based on the total amount of composition or mixture, and can on the one hand for lowering or specifically setting the networking temperature serve and on the other hand by favoring the Aus formation of unsaturated, cyclic structural elements within the Polymer influence on the conductivity of the films produced or take layers.

The compositions according to the invention preferably contain the 5 component a) (the compounds I or the mixtures thereof Compounds with compounds II) in a proportion of 30 to 95% by weight and component b) in a proportion of 5 to 70% by weight of the total composition.

Particularly preferred proportions for component a) or b) are 70 to 95% by weight or 5 to 30% by weight.

If component a) is a mixture of compounds I and II before, the former are preferred in a proportion of more than 50 wt .-%, particularly preferably more than 70 wt .-%, the latter in a proportion of less than 50% by weight, particularly preferably less  less than 30% by weight, based on the total amount of component a), used.

The proportion of other additives that may have to be added depends on on the use of the compositions. For production of nonlinear optical (NLO) or photorefractive materials The compositions according to the invention can range from 1 ppm to 50% by weight of other additives - based on the total settlement - included. These additives are preferably the ones already dyes or mixtures thereof mentioned above. For applications in the field of copying (laser printers, copiers), in the field of Pho tovoltaik or the display technology are the amounts of additives, preferably again the dyes or Mixtures thereof, at 1 ppm to 5% by weight, are particularly preferred at 10 ppm to 1 wt .-% again based on the total together settlement.

The compositions according to the invention but also those according to the invention compounds I and mixtures thereof with compounds II can, if appropriate in a suitable solvent solves on the substrate defined by the problem (e.g. Glass when used in display technology or photovol taik, metal in case of application in copiers, thermosta bile plastics in case of use for electrostatic Shielding) in a conventional manner (vapor deposition, casting, spin Apply coating, knife coating etc.) and polymerize by heating Networking films. Because depending on the components included this compositions or mixtures different temperatures necessary may be, you will first make preliminary examinations. Very Thermal analysis methods such as that are also suitable for this Differential scanning calorimetry (DSC). This is the subject quick determination of the optimal networking or bottom Lymerisation conditions possible without much expenditure of time Lich.

Induction of crosslinking is not only purely thermal, but also z. B. laser-induced possible if appropriate Chromophores are present in the compositions or mixtures are which can convert the laser light into thermal energy. The latter procedure in particular also makes it possible to "draw" fine structures using laser light and not to remove exposed, uncrosslinked areas. This ge equips the manufacture of the smallest, cargo-transporting Structures. The from the compositions according to the invention or Draw mixtures of polymer films or layers high scratch resistance and excellent resistance against various solvents, so that even one  Overlay without disruptive dissolving processes or (In ter-) diffusion processes is easily possible.

The composition mixed with the above-mentioned dyes gene or mixtures, optionally with the addition of other Additives, such as the metal compounds also mentioned, in the Manufacture of photorefractive materials are used. Here, a polarity of the NLO chromophores performed and their asymmetrical orientation then by thermal crosslinking of the assemblies according to the invention Settlements or mixtures can be fixed in the polymer network.

These compositions or mixtures can also be preferred wise without the addition of dyes, in electro-optical displays elements for the production of charge-transporting layers deploy. After thermal crosslinking, these films can be or occupy shifts with subsequent shifts. Because the former films or layers are chemically and physically extremely resistant are not annoying with these other coatings Processes such as (inter) diffusion, swelling or dissolution take place. The Subsequent layers can in turn by networking the invention according composition or mixtures are formed, wherein then additives such as the dyes mentioned and / or metal salts can be present.

Furthermore, the pure dyes, such as the already mentioned 8-hydroxyquinoline complexes of Al or Mg, or other photoluminescent materials can also be used as a subsequent layer. Oligomers or polymers of the structures are suitable here:

where mean
R ⁸ , R ⁹ independently of one another H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy as stated above
n is an integer from 5 to 100.

Other conductive oligomers or polymers based on condensation aromatic systems, which are also used here can, are described in the literature (Scherf, Müllen, Macromol. Chem., Rapid Comm. 12, p. 489, (1991)).

The subsequent layers of these oligomeric or polymeric Ma materials can, depending on u. a. degree of polymerization, either by vapor deposition or in the form of a solution subsequent removal of the solvent on the base layer apply. It is also possible to use the oligomers or polymers starting from suitable monomers on the base layer lymerize.

It is also possible to use more complex layer sequences realize. In this case, layers made of the same or different compositions according to the invention or Mixture were made with the above layers oligomeric or polymeric materials, other conductive Layers of, for example, aluminum, antimony-tin, or indi um tin oxide (ITO), as well as from the dyes mentioned above  switch, the basic as well as for electro-optical application The top layer is usually made of a conductive material is.

Since after the thermal crosslinking of the composite according to the invention Resolutions or mixtures, as already mentioned, are very much in conflict stable layers can be obtained with this gene rell surfaces that are stable under the crosslinking conditions protect against mechanical (scratching) and chemical influences Zen. These coatings can also be used with the aforementioned Dyes - possibly also with a view to decorative uses - color or due to their charge-transporting properties which vary within wide limits due to doping can be used in drums for photocopiers or laser printers deploy. Applications in the field of photovoltaics are also possible. Here can, in reverse of the application in elektrolu minescent arrangements, win electrical energy from light nen.

Examples

The FTIR, ¹ H and ¹³ C NMR spectra of the synthesized products and intermediates were recorded using devices from the companies
FTIR spectroscopy: BIO-RAD Digilab FTS-40 (FTIR); the data were obtained as transmission spectra
¹ H-NMR spectroscopy: BRUKER AC 250 (250 MHZ)
¹³ C-NMR spectroscopy: BRUKER AC 250 (62.5 MHz).

The thermal behavior was determined by means of DSC with a Ge advises of type NETZSCH DSC 200.

example 1 a) Synthesis of tris- [4- (trimethylsilyl) ethynylphenyl] amine

4.82 g (10 mmol) tris (4-bromophenyl) amine, 0.4 g triphenyl phosphine and 55 ml of diisopropylamine were under stick for 20 min boiled under reflux. After adding 60 mg Palladium (II) chloride and 30 mg copper (II) acetate hydrate were added dropwise 11.3 ml (80 mmol) of trimethylsilylacetylene dropped a septum. The reaction solution was then Boiled under reflux for 5 h with a gentle stream of nitrogen. After After cooling, the solution was filtered, the residue was formed Lich washed with toluene and the solvent removed in vacuo drawn. After purification via column chromatography (sili  cagel; Eluent: hexane / toluene 6: 1) became 4.83 g (90.4% yield) yellow-brown powder obtained.

characterization

Schm .: 170-173 ° C
IR (film): 2957; 2897; 2157; 1596; 1505; 1495; 1409; 1320; 1271; 1249; 1228; 1178; 1115; 1012; 867; 844; 837; 759; 726; 698; 650; 636 cm ^-1
1 H NMR (CDCl ₃ ): 0.2 (s; 27H, SiMe ₃ ); 6.95 (D; 6H, aromatics); 7.35 (d; 6H, aromatics) ppm
¹³ C NMR (CDCl ₃ ): 0; 93; 9; 104.9; 117.8; 123.8; 133.2; 146.8 ppm

b) Synthesis of tris- (4-ethynylphenyl) amine [TEPA]

4 g (7.48 mm) tris [4- (trimethylsilyl) ethynylphenyl] amine and 2.6 g of potassium fluoride was added to a mixture of 50 ml of metha added and 25 ml of THF and stirred at 50 ° C for 2 h. The Solvent mixture was removed in vacuo and the back was recorded in ether. The solution was filtered and washed with water. The ether was removed and the crude product recrystallized from hexane. 1.4 g (59%) Tris (4-ethynylphenyl) amine obtained as a yellow powder.  

characterization

Mp: 110-112 ° C
IR (film): 3277; 3267; 3036; 2102; 1598; 1498; 1319; 1288; 1272; 1176; 1111; 837; 761; 724; 675; 663; 640; 559; 540; 517; 429 cm ^-1
1 H NMR (CDCl ₃ ): 3.0 (s; 1H, acetylene proton); 6.95 (d; 2H, aromatics); 7.35 (d; 2H, aromatics) ppm
¹³ C NMR (CDCl ₃ ): 77.0; 83.3; 116.7; 123.8; 133.2; 146.9 ppm

Example 2 Synthesis of N, N, N-tris (4- (2-phenylethynyl) phenyl) amine [TPPA]

4.82 g (10 mmol) of tris (4-bromophenyl) amine were boiled under reflux with 0.4 g of tri phenylphosphine in 60 ml of diisopropylamine for 30 minutes under a nitrogen atmosphere. After the addition of 60 mg of PdCl ₂ and 30 mg of copper (II) acetate hydrate, 8.16 g (80 mmol) of phenylacetylene were added dropwise via a septum. After 5 h of boiling under a weak stream of nitrogen, the solution was filtered after cooling, the residue was washed thoroughly with toluene and the solvent was then evaporated. After purification by column chromatography (silica gel; eluent: hexane / toluene 6: 1), 1.3 g (24% yield) of the pure product were obtained as a yellow powder.

characterization

Mp: 145-148 ° C
IR (KBr): 3038, 2214; 1591; 1506; 1486; 1319; 1286; 1271; 1173; 1070; 1007; 913; 831; 759; 723; 710; 688; 565; 538; 520; 500 cm ^-1
1 H NMR (CDCl ₃ ): 6.8-7.7 ppm
¹³ C NMR (CDCl ₃ ): 89; 117; 118; 123; 128; 132; 133; 146; 147 ppm

Example 3 a) Synthesis of N, N-diphenyl-N- (4-trimethylsilylethynylphenyl) amine

2.73 g (8.4 mmol) of monobromotriphenylamine were refluxed with 0.11 g of triphenylphosphine in 21 ml of diisopropylamine under a nitrogen atmosphere for 30 minutes. After adding 17 mg of PdCl ₂ and 8.5 mg of copper (II) acetate hydrate, 1.55 ml (11 mmol) of triphenylsilylacetylene were added dropwise via a septum. After boiling for 5 hours under a gentle stream of nitrogen, the solution was filtered cold and the residue was washed with toluene. After the solvent had been stripped off and purified by column chromatography (silica gel; mobile phase: hexane / toluene 6: 1), 2.2 g (yield: 77%) of the white, difficult-to-crystallize product were obtained.

characterization

Mp: 95 ° C
IR (KBr): 3037; 2960; 2154; 1589; 1489; 1314; 1280; 1176; 1074; 1029; 1007; 863; 843; 821; 755; 698; 642; 543; 514 cm ^-1
1 H NMR (CDCl ₃ ): 0.25; 6.8-7.4 ppm
¹³ C NMR (CDCl ₃ ): 0; 115; 122; 123; 123.5; 124; 125; 129; 132; 133; 147 ppm

c) Synthesis of N- (4-ethynylphenyl) -N, N-diphenylamine [EPDA]

2 g (5.86 mmol) of N, N-diphenyl-N- (4-trimethylsilylethynylphenyl) amine were mixed with 0.68 g (11.72 mmol) of potassium fluoride in a mixture of 25 ml of THF and 25 ml of methanol for 2 h heated to 50 ° C. The solution was then evaporated, the residue was dissolved in ether and the solution washed with water. After the ether solution had been dried over Na ₂ SO ₄ , the solvent was stripped off and the crude product was recrystallized from hexane. There were obtained 0.83 g (yield: 53%) of the yellow product.

characterization

Mp: 107-109 ° C
IR (KBr): 3303; 3061; 3033; 2106; 1580; 1486; 1332; 1319; 1284; 1267; 1176; 1027; 1001; 903; 823; 759; 699; 515; 498 cm ^-1
1 H NMR (CDCl ₃ ): 6.8-7.4; 3 ppm
¹³ C NMR (CDCl ₃ ): 115; 122; 124; 124.4; 124.5; 125; 129; 132; 133; 147 ppm

Example 4 Thermal crosslinking from TEPA

The thermal crosslinking of TEPA was monitored by means of DSC (heating rate: 10 ° C./min) and IR spectroscopy. A sharp endothermic (melting point 113 ° C) and a broad exothermic peak (crosslinking: 180 ° C) could be detected in the DSC curve. For IR-spectroscopic reaction monitoring, thin films were formed on KBr compacts using a solution of TEPA in THF, which were then treated under a nitrogen atmosphere according to a temperature program that was changed compared to the DSC measurement. Here, heating was carried out from room temperature to 120 ° C. at a heating rate of 10 ° C./min, left at this temperature for 30 minutes and then further heated to a final temperature of 180 ° C. at a changed heating rate of 5 ° C./min. The course of the crosslinking can be followed from the decrease in the CC stretching vibration at 2100 cm ^-1 or the CH stretching vibration at 3300 cm ^-1 . After annealing for 60 minutes at 180 ° C., the maximum degree of crosslinking is reached (approx. 70% conversion of the acetylene groups). The films obtained are insoluble in all common solvents.

Examples 5 to 7 Thermally cross-linked films

Films with a thickness of 50-1200 nm were produced from 5% solutions of acetylene-functionalized triphenylamines in cyclohexanone by spin coating (spin coating, speed of rotation: 1000 min ^-1 ). The films were dried in vacuo at 60 ° C. for 24 h and then thermally crosslinked on a hot bench under a nitrogen atmosphere (30 min at 200 ° C.).

The layers turned out to be very scratch-resistant and pronounced temperature stable.

The thermogravimetric analysis of a TEPA layer (N ₂ atmosphere, heating rate: 10 ° C / min) showed no change in weight from 110 ° C up to 500 ° C. An initial weight decrease of approximately 2% by weight is due to the evaporation of solvent residues.

Example 8

By spin coating at 1000 revolutions / min a 5% solution of TEPA / TPPA (weight ratio: 9: 1) in Cyclohexanone on a glass sputtered with ITO (indium tin oxide) plate applied. After drying in vacuo at 60 ° C Crosslinked under a nitrogen atmosphere at 200 ° C. The layer thickness was 70 nm.

On the homogeneous film obtained, a 40 nm thick tris (8-hydroxyquinolinato) aluminum (Alq ₃ ) layer, then an aluminum layer was first evaporated in a high vacuum at 10 ^-6 mbar using a Balzers evaporation system.

The ITO and aluminum electrodes were connected to a voltage source connected.

To determine the current-voltage characteristic (through current I ₁ in amperes against voltage U in volts) and the electroluminescent voltage characteristic (photocurrent I ₂ in amperes against voltage U in volts), the applied voltage was in the interval from -10 volts to +10 volts after a period of 3 seconds for 5 seconds, switched off, increased by 0.5 volts during this time and then switched on again until the voltage interval was measured. The electroluminescence was quantified on the basis of the photocurrent I ₂ , which was provided by a photomultiplier set to a voltage of 300 volts. In the drawing, the dependence of I ₁ against U is shown by filled squares, of I ₂ against U by open, lying triangles.

With negative voltage, the polarity of the generated element corresponds to:
negative pole on ITO electrode,
positive pole on aluminum electrode,
reverse with positive voltage.

The current-voltage and the electroluminescence-voltage characteristics (see drawing) show a clear rectifier behavior and a threshold voltage for the electroluminescence of approx. 5.5 V. The electroluminescence spectrum corresponds to the fluorescence spectrum of Alq ₃ .

Claims (12)

1. Compounds of formula I.
in what mean
Ar ¹ and Ar ² independently of one another are in each case homo- or heteroaromatic groups which are fused to benzo and, independently of one another, from one to four substituents from the group C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -Acyl, COO (C ₁ -C ₆ alkyl), oxy (C ₁ -C ₆ acyl), halogen, COOH, CHO, OH, SO ₂ H, SO ₃ H, CN, SCN, OCN, NO ₂ can, with the proviso that at least one of the groups Ar ¹ or Ar ^{2 is} additionally sub-substituted with at least one ethynyl radical of the formula-C∼CH, X an m-valent group which with one or more ethynyl radicals of the formula -C∼CH can be substituted and in the case
m has the same meaning as the groups Ar ¹ and Ar ² ,
m is an integer from 1 to 6. 2. Mixtures containing as components

• a) at least one compound of formula I according to claim 1, and
• b) at least one compound of the formula II
  

in what mean
Ar ³ and Ar ⁴ independently of one another in each case homo- or heteroaromatic groups which are fused to benzo and, independently of one another, one to four substituents from the group C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ -Acyl, COO (C ₁ -C ₆ alkyl), oxy (C ₁ -C ₆ acyl), halogen, COOH, CHO, OH, SO ₂ H, SO ₃ H, CN, SCN, OCN, NO ₂ can, with the proviso that at least one of the groups Ar ³ or Ar ^{4 is} additionally substituted with at least one radical of the formula III-C∼-CZ-R ¹ (III) in which
Z is a single chemical bond, -O-, -CO-, -COO-, -OOC-, -N (C ₁ -C ₆ alkyl) -CO-, -OC-N (C ₁ -C ₆ alkyl) - or (CH ₂ ) _r -,
r is an integer from 1 to 6,
R ^{1 is} hydrogen, C ₁ -C ₆ -alkyl, a homo- or heteroaromatic group which is benzo-fused and one to four substituents from the group C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -acyl, oxy (C ₁ -C ₆ -acyl), COO (C ₁ -C ₆ -alkyl), halogen, COOH, CHO, OH, SO ₂ H, SO ₃ H, CN, SCN, OCN, Can carry NO ₂ , in the event that Z is a chemical single bond and the compound of the formula II carries more than one radical of the formula III, at least one of the radicals R ^{1 is} different from hydrogen,
Y is an n-valent group which can be substituted by one or more radicals of the formula III and, if n is 1, has the same meaning as the groups Ar ³ and Ar ⁴ ,
n is an integer from 1 to 6. 3. Compounds according to claim 1, in which the groups Ar ¹ and Ar ^{2 are} independently homoaromatic groups and independently of one another carry at most one substituent from the group C ₁ -C ₆ alkyl and C ₁ -C ₆ alkoxy. 4. Mixtures according to claim 2, in which the groups Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are} independently homoaromatic groups and independently of one another at most one substituent from the group C ₁ -C ₆ alkyl and C ₁ -C ₆ - Wear alkoxy. 5. Mixtures according to claims 2 or 4, in which the Va riablen Z, r, R ¹ in formula III have the meaning
Z is a chemical single bond or - (CH ₂ ) _r -,
r is an integer from 1 to 6,
R ^{1 is} hydrogen, C ₁ -C ₆ -alkyl, a homo- or heteroaromatic table which is benzo-fused and one to four substituents from the group C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₁ - C ₆ -acyl, COO (C ₁ -C ₆ -alkyl), oxy (C ₁ -C ₆ -acyl), halogen, OCN. 6. Mixtures according to claims 2, 4 or 5, in which the groups Ar ¹ , Ar ² , Ar ³ and Ar ^{4 are} independently homoaromatic groups and independently of one another a maximum of one to four substituents from the group C ₁ -C ₆ - Alkyl and C ₁ -C ₆ alkoxy and in which the variables Z, r, R ¹ in formula III have the meaning
Z is a chemical single bond or - (CH ₂ ) _r -,
r is an integer from 1 to 6,
R ^{1 is} hydrogen, C ₁ -C ₆ alkyl, a homo- or heteroaromatic table which can be benzo-fused and which has one to four substituents from the group C ₁ -C ₆ alkyl, C ₁ alkoxy, C ₁ -C ₆ -acyl, COO (C ₁ -C ₆ -alkyl), oxy (C ₁ -C ₆ -acyl), halogen, OCN. 7. Compositions containing as ingredients

• a) at least one compound according to claims 1 or 3 or a mixture according to claims 2, 4, 5 or 6,
• b) further monomers which can be thermally copolymerized with the compounds or mixtures from a), such as, if appropriate, further additives.

8. Compositions according to claim 7, containing
Component a) in 30 to 95% by weight,
Component b) in 5 to 70% by weight,
each based on the total composition. 9. Polymers obtainable by thermal crosslinking of the Compounds, mixtures or compositions according to the An sayings 1 to 8. 10. Use of the polymers according to claim 9 as a charge transport materials. 11. Process for coating substrates, characterized records that compounds, mixtures or compositions according to claims 1 to 8 on the sub to be coated strat applied and then thermally crosslinked. 12. Articles which according to the method of claim 11 are coated.