DE19532574A1 - New electroluminescent material, esp for hole conduction layer - Google Patents

Abstract

Electroluminescent material (ELM), contg. polymer(s) with repeating units of formula (I), in which Ar<1>-Ar<6> = opt. substd. mono- or poly-nuclear, opt. bridged and/or condensed aryl(ene) and/or heteroaryl(ene) gps.; R<1> = H, 1-22C hydrocarbyl or Ar<7>, with Ar<7> = as for Ar<1>-Ar<6>; n = 0, 1 or 2. Also claimed is (i) a process for the prodn. of ELM, (ii) an electroluminescent device with one or more active layers, at least one of which comprises the ELM, and (iii) a polymer contg. units (I) as above.

Description

There is a high industrial need for large-area solid-state Light sources for a number of applications, mainly in the area of Display elements, screen technology and lighting technology. The none of the requirements currently imposed on these light sources existing technologies can be solved completely satisfactorily.

As an alternative to conventional display and lighting elements such as Incandescent, gas discharge and non-self-illuminating Liquid crystal display elements have been around for some time Electroluminescence (EL) materials and devices, such as light emitting Diodes (LED), in use.

DE-A 25 45 784 (corresponds to US-A 3,995,299) is one Electroluminescent device with a radiation source described, consisting of a layer of an amorphous or predominantly amorphous polymer material noticeable electric charge mobility and low ionization potential, a strong electron donor, a strong electron acceptor and preferably at least one luminescent additive, wherein electrical connections are provided through which an electrical current passes the thickness of the layer for excitation of radiation can be guided therefrom.

Conjugated polymers such as poly (p-phenylene vinylene) are suitable as polymer materials. (see, for example, WO-A 90/13148), as well as non-conjugated polymers (see, e.g., I. Sokolik et al., J. Appl. Phys. 1993, 74, 3584), where conjugated materials generally have the advantage of a higher  Carrier mobility and thus better efficiencies and lower Have threshold voltages.

In addition to devices based on polymers have also been around for a long time known low molecular weight organic electroluminescent devices. Saito et al. (Appl. Phys. Lett. 1990, 56, 799) also describe such devices Triarylaminstilbenen as light-emitting layers.

Although good results have been achieved with these materials, it is Property profile of these compounds can still be improved.

Since also the development of electroluminescent materials, especially on Basis of polymers, in no way considered complete are the manufacturers of lighting and display devices on the most diverse electroluminescent materials for such Devices interested.

This is partly due to the fact that only the cooperation of the Electroluminescent materials with the other components of the devices Allows conclusions to be drawn about the quality of the electroluminescent material.

The object of the present invention was therefore to create new ones To provide electroluminescent materials which, when used in Lighting or display devices are suitable, the property profile to improve these devices.

It has now surprisingly been found that certain polymers are associated with Triarylamine units in a special way as electroluminescent materials own.

Such compounds are sometimes used as photosensitive components for electrophotographic processes and as sensitizers for electrical  photosensitive dyes (US-A 4,323,203) known to be suitable However, electroluminescent material cannot be derived from this.

The invention therefore relates to an electroluminescent material containing one or more polymers containing repeating units of the formula (I),

where the symbols and indices have the following meanings:
Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ are identical or different mono- and / or polynuclear, optionally linked by a bridge, and / or fused aryl and / or heteroaryl groups, preferably with 4 to 20 carbon atoms, which are optionally substituted can, where Ar¹, Ar³, Ar⁵ and Ar⁶ each have two bonds and Ar² and Ar⁴ each have a bond;
R¹ is H, a hydrocarbon radical having 1 to 22 carbon atoms or Ar⁷, where Ar⁷ can have the same meanings as Ar¹ to Ar⁶;
n is 0, 1 or 2, preferably 0 or 1, particularly preferably 0.

Polymers consisting of repeating units of the formula (I) are preferred. The electroluminescent material according to the invention is distinguished, inter alia due to a low threshold voltage of electroluminescence and a high one Efficiency, even though they are non-conjugated polymers. It is also in multi-layer structures, especially as one of the components of the Hole conductor layer suitable.

For the purposes of the invention, electroluminescent materials are materials which find use as an active layer in an electroluminescent device can. Active shift means that the shift is capable of creating one electric field to emit light (light emitting layer) and / or that  they inject and / or transport the positive and / or negative Charges improved (charge injection or charge transport layer).

The invention therefore also relates to the use of a polymer containing repeating units of the formula (I) as electroluminescent material, especially as a hole conductor layer.

The polymers according to the invention generally have 2 to 1000, preferably 3 to 500, particularly preferably 4 to 300, repeating units on.

Polymers containing repeating units of the formula (I) in which the symbols and indices have the following meanings are preferred:
Ar¹, Ar³, Ar⁵, Ar⁶ are the same or different

Ar², Ar⁴, identical or different from Ar¹, Ar³, Ar⁵ and Ar⁶, have the same meanings as Ar¹, Ar³, Ar⁵ and Ar⁶, only one of the two possible binding sites to the polymer being realized;
Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ can be substituted identically or differently with one or more radicals R²-R⁷;
X is a single bond -O-, -S-, -SO-, -SO₂-, -CR²R³, CR⁴-CR⁵- or CHR⁶-CHR⁷-;
Y: -O-, -S-, -C (O) - or -NR⁸-;
R¹ is H, a hydrocarbon radical having 1 to 22 carbon atoms or Ar⁷, where Ar⁷ can have the same meanings as Ar¹ to Ar⁶;
R²-R⁷ are the same or different H, an alkyl group having 1 to 22, preferably 1 to 12, carbon atoms, and also one or two non-adjacent CH₂ groups by -O-, -S-, -CO-, -CO-O -, -O-OC- or -Si (CH₃) ₂- can be replaced, -CF₃₁ -Ph, -O-Ph, -S-Ph, -SO-Ph, -SO₂-Ph, F, Cl, Br, I or -CN;
R⁸, identical or different from R¹, has the same meanings as R¹;
n 0, 1 or 2, preferably 0 or 1, particularly preferably 0.

Polymers of the formula (I) in which the symbols and Indices have the following meanings:

Ar¹, Ar³, Ar⁵, Ar⁶ are the same or different

Ar², Ar⁴, the same or different, have the same meanings as Ar¹, Ar³, Ar⁵, Ar⁶ have, but only one of the two possible Binding sites to the polymer is realized or are

R⁹-R¹¹ are the same or different F, Cl, a straight chain or branched alkyl or alkoxy group with 1 to 22, preferably 1 to 12, carbon atoms.

Polymers of the formula (I) in which Ar¹ and Ar³ and optionally Ar² and Ar⁴ each have the same meaning to have.

The following groups of polymers of the general are particularly preferred Formula (I):

Some of the polymers of formula (I) are known and some are new.  

The invention therefore also relates to polymers containing Repeating units of the formula (I),

where the symbols and indices have the following meanings:

Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ are identical or different mono- and / or polynuclear, optionally linked by a bridge, and / or fused aryl and / or heteroaryl groups, which may optionally be substituted, and where Ar¹, Ar³, Ar⁵ and Ar⁶ each have two bonds and Ar² and Ar⁴ each have one bond;
R¹ is a hydrocarbon radical having 1 to 22, preferably 1 to 12, carbon atoms or Ar⁷, where Ar⁷ can have the same meanings as Ar¹ to Ar⁶;
n is 0, 1 or 2, preferably 0 or 1, particularly preferably 0.

Preferred areas of new polymers containing repeat units of Formula (I) are analogous to those given above Electroluminescent materials.

Polymers consisting of repeating units of the formula (I) are preferred.

The preparation of the inventive or used according to the invention Polymers are advantageously carried out by condensation of bis-aldehydes or bisketones of the formula (II),

wherein Ar¹, Ar², Ar³, Ar⁴, Ar⁵ and R¹ are those given in formula (I)  Have meanings with organophosphorus compounds of the formula (III)

wherein Ar⁶ has the meanings given in formula (I) and Z for C₁-C₂₂ alkoxy, preferably ethoxy, or aryl radicals, preferably phenyl, stands.

The condensation takes place through the action of a basic Condensing agent, preferably of potassium tert-butoxide or Sodium hydride.

The polycondensation is advantageously carried out in such a way that equimolar mixture of the starting components (II) and (III) in one Solvent submitted and preferably under an inert gas atmosphere and stirring at least molar amounts of condensing agent in solution or suspension registers.

According to another working variant, the condensing agent can also be used alone or presented with the biscetone in a solvent and the Bisphosphorus component are added. As a solvent preferably benzene, toluene, xylene or dimethylformamide used Reaction temperature is preferably 60 to 120 ° C and the reaction time 0.1 to 20, preferably 0.1 to 5, particularly preferably 0.1 to 1 hours. The Implementations are almost quantitative.

By adding water, optionally an acid such as acetic acid, and The organic reaction phases can be separated off and worked up. The condensation products obtained can be extracted for purification, e.g. B. with Alcohols or acetic acid, or from solution in a solvent of a non-solvent.  

This manufacturing process is generally described, for example, in DD 84 272, Hörhold, H.-H .: Z. Chem. 12, 41-52 (1972); Hörhold, H.-H .; Bergmann, R .; Gottschaldt, J .; Drefahl, G .: Acta Chim. Acad. Sci. Hung. 81, 239-251; Hörhold, H.-H .; Bergmann, R .: Advances in the Chemistry of Thermally Stable Polymers, Warszawa, Polish Scientific Publishers, 29-48 (1977); Hörhold, H.-H .; Helbig, M .: Makromol. Chem., Macromol. Symp. 12, 229-258 (1987) and Hörhold, H.-H .; Helbig, M .; Raabe, D .; Sacrifice man, J .; Scherf, U., Stockmann, R .; Weiß, D .: Z. Chem. 27, 126 (1987).

Bisketones (R¹ ≠ H) are used in the Horner reaction to form E / Z isomers. Isomers also result from the possible position of the two Double bonds to each other (trans-trans-anti, trans-trans-syn, cis-trans-anti, cis-trans-syn, cis-cis-anti, cis-cis-syn); they are all encompassed by the invention.

By using different bisaldehydes or bisketones and / or Bisphosphonates are easily obtained copolymers that have different repeating units of the formula (I). In such Copolymers may optionally also be the radicals R 1 in formula (I) have different meanings. Furthermore, by delayed addition of given at least one of the comonomers the possibility of block copolymers to manufacture.

Smaller groups of polymers of formula (I), in which Ar¹ is the meaning Ar⁸-Ar⁸ has, where Ar⁸ for an electron-rich aromatic, preferably Thiophene-2,5-ylene, which may optionally also be substituted, can alternatively also be oxidative, e.g. B. with FeCl₃ (see inter alia P. Kovacic, N. B. Jones, Chem. Ber. 1987, 87, 357 to 379; M. Weda, T. Abe, H. Awano, Macromolecules 1992, 25, 5125), or electrochemical (see e.g. N. Saito, T. Kanbara, T. Sato, T. Yamamoto, Polym. Bull. 1993, 30, 285) polymerized will:  

Polymerization through oxidation

It is also possible to use aromatic compounds under the conditions of To couple the Scholl reaction oxidatively:

(see e.g. J. March, Advanced Organic Chemistry, 3rd ed. pp. 484 f., McGraw Hill and the literature cited there).  

It can be expedient to regulate the molar mass during the polymerization monofunctional aldehydes or ketones to form defined end groups to add, for example the commercially available (H.W. Sands, Jupiter FI., USA) 4- (N, N-Diphenylamino) benzaldehyde:

Are two moles of a monofunctional aldehyde or ketone, such as 4- (N, N-Diphenylamino) benzaldehyde with one mole of an organophosphorus If compound of formula (III) is used, sesquimers of formula (Ia) are obtained,

the symbols and indices having the same meanings and preferences as in formula (I).

Such compounds are suitable, especially in a mixture with the Polymers according to the invention, also as electroluminescent materials.

In the polymerization of starting compounds with meta-substituted Structural elements can form macrocyclic compounds.

The polymers according to the invention or used according to the invention can therefore also in a mixture with these macrocyclic compounds, which does not interfere with the use as an electroluminescent material.

The starting compounds (II) and (III) are prepared per se methods known from the literature, as used in standard works on organic matter  Synthesis, e.g. B. Houben-Weyl, Methods of Organic Chemistry, Georg- Thieme-Verlag, Stuttgart.

The production takes place under reaction conditions for the above Implementations are known and suitable. It can also by itself known variants not mentioned here can be used.

The bis (diphenylphosphine oxides) or Bis (phosphonic acid esters) are, for example, using the Michaelis Arbusov reaction from the corresponding bis (halogenomethyl) compounds with Diphenylphosphinigsäureethylester (C₆H₅) ₂P-O-C₂H₅ or with triethyl phosphite easily accessible.

The synthesis of bisaldehydes of the formula (II) can be carried out according to various Reaction types familiar to those skilled in the art are carried out.

For example, aldehydes can be derived from bis-carboxylic acid derivatives controlled reduction with reducing agents such as lithium tris alkoxyalanates or H₂ / Pd ("Rosenmund reduction") can be obtained:

(See, e.g., Fuson in Patai, "The Chemistry of the Carbonyl Group", Vol. 1, Pp. 211-232, Interscience, New York 1966)

(see e.g. Tylander, "Catalytic Hydrogenation over Platinum Metals, p. 398-404, Academic Press, New York 1967).

From bischloromethyl precursors, for example, Bisaldehyde reaction obtained

(see e.g. Angyal, Organic Reactions 1954, 8, 197).

However, the underlying amines (IV) and (V) are preferred

subjected to electrophilic aromatic substitution. Numerous methods are known for this, for example the Gattermann Koch Reaction:

(see e.g. Crounse, Organic Reactions 1949, 5, 290-300); The Gattermann reaction:

(see, e.g., Truce, Organ. Reactions 1957, 9, 37-72); or the reaction of aromatics with dichloromethyl methyl ether:

(see e.g. Rieche et al., Chem. Ber. 1960, 93, 88 or Lewin et al., Org. Prep. Proced. Int. 1978, 10, 201).  

However, the Vilsmeier reaction (also with DMF) is preferred:

(see e.g. Jutz in Advances in Organic Chemistry, Vol. 9, Part 1 pp. 225-342, Böhme, Viche Eds. Interscience, New York 1976, or Jackson, J. Am. Chem. Soc. 1981, 103, 533).

If R1 in formula (I) is not hydrogen, bisketones are considered as Starting materials used.

These can be caused, for example, by the Vilsmeier reaction described above be produced if the amide used is not formamide.

Bisketones can also be produced by Friedel-Crafts acylation will:

(see for example Olah, Friedel-Crafts and Related Reactions, vol. 2, 979-1047, Interscience, New York 1963-65); or by a Grignard reaction with cyanoarylene:

(see e.g. Kharasch and Rainmuth, Grignard Reactions of Nonmetallic Substances, pp. 767-845, Prentice Hall, Eaglewood Cliffs N.J. 1954).  

The starting compounds for bisaldehydes and bisketones are the tertiary, aromatic amines (IV) and (V). They can be classified according to the known Establish reactions familiar to a specialist.

An overview of technical manufacturing processes of tertiary and secondary aromatic amines are found, for example, in Mc Ketta, Encyclopedia of Chemical Processing and Design, Vol. 3, pp. 134-196, Decker, New York.

Starting from secondary, aromatic amines, tertiary aromatic Amines, for example, also according to the method given in Scheme 1 getting produced.  

Formula scheme 1

Are alkyl-substituted amino aromatics with iodo aromatics under copper catalysis implemented, for example N- (alkylaryl) diarylamines can be obtained:

R: alkyl, preferably C₁-C₂₂, particularly preferably t-butyl or neopentyl.

As a starting material for compounds in which Ar³ is a biphenyl group, For example, the commercially available (H. W. Sands, Jupiter, FI., USA) N, N'-diphenyl-N, N'-di-m-tolylbenzidine serve.

Starting compounds for polymers of the formula (I) in which n is 1, can be produced, for example, according to the following scheme 2:

Scheme 2

In order to find use as electroluminescent materials, the Polymers of the formula (I) are generally known to those skilled in the art common methods, such as dipping or spin coating, in the form of a Film applied to a substrate.

The invention therefore also relates to a method for producing a Electroluminescent material, characterized in that one

• a) an organophosphorus compound of the formula (III) with a bisaldehyde or bisketone of the formula (II) condensed to a polymer containing repeating units of the formula (I) under the action of a basic condensing agent, where the symbols and indices have the following meanings:
  Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ identical or different mono- and / or polynuclear, optionally linked by a bridge, and / or fused aryl and / or heteroaryl groups, preferably with 4 to 20 carbon atoms, which can optionally be substituted , whereby Ar¹, Ar³, Ar⁵ and Ar⁶ each have two bonds and Ar² and Ar⁴ each have a bond;
  R¹ is H, a hydrocarbon radical having 1 to 22 carbon atoms or Ar⁷, where Ar⁷ can have the same meanings as Ar¹ to Ar⁶;
  n is 0, 1 or 2, preferably 0 or 1, particularly preferably 0,
  and
• b) the polymer thus obtained, containing repeat units of the formula (I), in Form a film on a substrate that may already be different Contains layers.

The invention further relates to an electroluminescent device one or more active layers, at least one of these active Layers contains one or more polymers according to the invention. The active one Layer can for example be a light emitting layer and / or Transport layer and / or a charge injection layer.

The general structure of such electroluminescent devices is described for example in US 4,539,507 and US 5,151,629. Polymers containing electroluminescent devices are for example in WO-A 90/13148 or EP-A 0 443 861.

They usually contain an electroluminescent layer between one Cathode and an anode, wherein at least one of the electrodes is transparent. In addition, there can be between the electroluminescent layer and the cathode an electron injection and / or electron transport layer can be introduced and / or between the electroluminescent layer and the anode Hole injection and / or hole transport layer can be introduced. As a cathode can metals, e.g. B. Ca, Mg, Al, In, Mg / Ag serve. Metals, e.g. B. Au or other metallically conductive substances, for. B. ITO (indium oxide / tin oxide)  on a transparent substrate, e.g. B. made of glass or a transparent Polymer.

In operation, the cathode is at a negative potential with respect to the anode set. Electrons are transferred from the cathode to the Electron injection layer / electron transport layer or directly into the light emitting layer injected. At the same time, holes from the anode are in the hole injection layer / hole transport layer or directly into the light emitting layer injected.

The injected charge carriers move under the influence of the applied ones Tension towards each other through the active layers. This leads to the Interface between charge transport layer and light emitting layer or within the light-emitting layer to form electron / hole pairs recombine emitting light.

The color of the emitted light can by the light-emitting layer used materials can be varied.

Electroluminescent devices are used for. B. as self-luminous Display elements such as indicator lights, alphanumeric displays, Information signs, and in optoelectronic couplers.

The invention is illustrated by the examples, without thereby want to restrict.

Mean it
Tg: glass transition temperature, measured by means of differential scanning calorimetry (DSC)
M _n : number average molecular weight
VPO: Vapor Pressure Osmometry (see e.g. Cherdron, Kern, Braun, Internship in Macromolecular Chemistry)
GPC: gel permeation chromatography, standard polystyrene

Examples Synthesis route example 1 4,4'-diformyl-triphenylamine

Triphenylamine [245.35] = 5 g (0.020 mol)
Phosphoryl chloride [153.33] = 13.74 g (0.089 mol)
Dimethylformamide [73.10] = 6.54 g (0.089 mol).

Phosphoryl chloride and DMF are protected from moisture and Ice cooling mixed and after 20 minutes in portions with the Triphenylamine added. The mixture is then stirred at 80 ° C. for eight hours and poured onto 300 g crushed ice, bring to room temperature and extract with Chloroform. After removing the solvent, you take that dark green oil in toluene and filtered over with a neutral alumina loaded glass filter frit. The clear, yellow solution is evaporated to dryness and recrystallized from petroleum ether / toluene. Yellow crystals in 71% strength are obtained Yield. Melting point 142 ° C.

C₂₀H₁₅NO₂ (301.31):
calcd. C: 79.71; H: 5.01; N: 4.64;
found C: 80.12; H: 5.16; N: 4.58.

1 H-NMR (CD₂Cl₂) δ = 7.1-7.8 (m, 13 aromatics), 9.8 (s, 2 CHO).

Example 2 2,5-dioctyloxy-1,4-bis (bromomethyl) benzene

22 g of hydroquinone dioctyl ether (0.066 mol), 27.8 g of paraformaldehyde (0.927 mol), 34.7 g of sodium bromide (0.337 mol) and 400 ml of glacial acetic acid are heated to 80 ° C. in a 1 l three-necked flask with a stirrer, reflux condenser and dropping funnel and added dropwise within a hour with a mixture of 35 ml of concentrated sulfuric acid and 45 ml of glacial acetic acid. The mixture is stirred at 80 ° C. for 5 hours and then cooled to room temperature. The separated solid is filtered off and washed several times with water. The organic filtrate is carefully poured into 500 ml of distilled water and extracted several times with methylene chloride. After combining the extract with the solid, it is dried over CaCl₂ and then the solvent is distilled off. After recrystallization of the residue from hexane, white, matted crystals are obtained, melting point 83 ° C.
Yield: 26.6 g = 77% of theory. theory

C₂₄H₄₀Br₂O₂ (520.366)
calc. C 55.40; H 7.60; Br 30.72;
found C 55.56; H 7.69; Br 30.08.

Example 3 2,5-dioctyloxy-1,4-xylylene-bis (diethylphosphonate)

20.81 g 2,5-dioctoxy-1,4-bis (bromomethyl) benzene (0.04 mol) and 13.29 g Triethyl phosphite (0.08 mol) are in a 250 ml two-necked flask Magnetic stirrer and distillation bridge heated to 130 ° C, resulting Distilled ethyl bromide. It is heated to 190 ° C. within 1 hour and still Stirred at this temperature for 3 hours. Remaining for removal Triethyl phosphite is vacuum at this temperature for 30 minutes created. After cooling, the residue solidifies into a waxy mass, which is recrystallized from petroleum ether. You get fine white crystals, Melting point 41 ° C (Lit. melting point 41 ° C [8]).

Yield: 20.8 g = 82% of theory. Theory.

Example 4 Poly (phenylimino-1,4-phenylene-1,2-ethenylene-2,5-dioctoxy-1,4-phenyle-n-1,2-ethenylene-1,4-phenylene)

2,5-dioctoxy-p-xylylene-bis (diethylphosphonate) [634.18] = 4.20 g (0.006 mol)
4,4′-diformyl-triphenylamine [301.31] = 2.00 g (0.006 mol)
Potassium tert-butoxide [112.21] = 2.00 g (0.017 mol)
Solvent: toluene.

4.2 g diphosphonate and 2.0 g bisaldehyde are under protective gas in so little as possible toluene (approx. 20 ml) dissolved at the boiling point and with 2.0 g of potassium Tert-butoxide in solid form with stirring. The reaction mixture foams vehemently and suddenly becomes viscous. After a few minutes carefully metered in toluene (about 10 ml) so that the mixture can be stirred remains. After two hours, the solvent is drawn off under reduced pressure decreases, takes up in chloroform with heating and falls in isopropanol. After the suction is extracted for five hours with methanol. The polymer falls into yellow, shiny fibers in 86% yield.

UV / VIS spectroscopy:
λ _max 443 nm (Ig ε = 4.7)
second maximum at 475 nm
0.1 λ _max = 494 nm
DSC:
Glass point at 79 ° C
Fluorescence spectroscopy:
λ _max = 445 nm
λ _max = 494 nm
0-0 transition at 480 nm
Electrochemistry:
DPP: E ^OX1 = 0.67 VE ^OX2 = 0.74 V
According to the CV, both levels are reversible
Molecular weight:
Mn = 22 600 (VPO)
Mw = 55,400 (GPC)
Band gap:
E = 2.51 eV (0.1 λ _max UV)
E = 2.58 eV (0-0 transition).

Example 5 Electroluminescent device

A solution of the polymer from Example 4 in chlorobenzene (20 mg / ml) is added Nitrogen by spin coating at 1000 rpm on one with ITO (indium tin Oxide) coated glass carrier (structured, strips 2 mm wide) applied.  

The glass carrier is transferred to a high-vacuum evaporation system via a lock while maintaining the protective gas atmosphere. At 2 × 10⁵ mbar, Ca strips (2 mm wide, 230 nm thick) are evaporated onto the polymer layer transversely to the ITO strips using a mask. The device obtained in this way, ITO / polymer / Ca, is placed in a sample holder and the electrodes are connected to a current source via spring contacts, an ITO strip being positive and a Ca strip being negative. When a sufficiently high voltage is applied, green electroluminescence is observed on the corresponding matrix element.
Threshold voltage: 6.7 V.
Max. Efficiency: 0.047% at 10.0 V and 0.003 A / cm²
Max. Luminance: 60 Cd / m².

Example 6 2,5-dioctoxy-1,4-bis (4-diphenylaminostyryl) benzene Synthesis route

4-diphenylaminobenzaldehyde [273.31] = 1.3 g (0.0047 mol)
2,5-dioctoxy-p-xylylene-diethylphosphonate [634.18] = 1.5 g (0.0023 mol)
Potassium tert-butoxide [112.21] = 0.5 g (0.0047 mol)
Solvent: toluene.

The diphenylaminobenzaldehyde and the bisphosphonate are placed under protective gas in 150 ml of toluene. While stirring, the potassium tert-butoxide is added in one portion at the boiling point, the mixture foaming strongly. The mixture is stirred for a further two hours at 80 ° C. and then hydrolyzed with 200 ml of a 10% acetic acid solution. The mixture is stirred vigorously and then transferred to a separatory funnel. The organic phase is shaken out several times with water and then dried over anhydrous sodium sulfate. It is strongly concentrated and the crude product is purified by column chromatography (neutral aluminum oxide, eluent toluene). After stripping off the solvent and drying, bright orange crystals are obtained in 82% yield.
analytical data:
- UV / VIS: λ _max = 423 nm lg ε = 4.8 Eg ^OPT = 2.60 eV
- Fp (DSC) =
- Molar mass (MS) = 873 (Molpeak)
- Oxidation potential E ^OXI = 0.71 V against Ag / AgCl.

Example 7 Poly [phenylimino-1,4-phenylene-1-phenyl-1,2-ethenylene-2,5-dioctoxy-1,4-phenylene-2-phenyl-1,2-ethenylene-1,4-phenylene] Synthesis route

4,4'-dibenzoyl-triphenylamine = 0.0047 mol
2,5-dioctoxy-p-xylylene-bis- (diethylphosphonate) = 0.0047 mol
Potassium tert-butoxide = 0.0178 mol)
Solvent: toluene

4,4'-dibenzoyl-triphenylamine [mp. 143 ° C, S. Staskun, J. Org. Chem. 1968, 33 (1968) 3031], which was obtained by direct Friedel-Crafts benzoylation of triphenylamine, is mixed with the bisphosphonate with stirring and protective gas in as little as possible toluene (approx. 30 ml) dissolved in boiling heat and mixed with potassium tert-butoxide in solid form. The mixture becomes viscous after a short time, is diluted with further toluene, heated for a further 3 hours and worked up as in the examples described above. Yellow polymer M _n <4000 (VPO).

Example 8 Poly (phenylimino-1,4-phenylene-1,2-vinylene-1,3-phenylene-1,2-vinylene)

4,4'-diformyl-triphenylamine [300.1]
1,3-phenylene-bis (methylylenephosphonate diethyl ester) [378]
Potassium tert-butoxide [112].

1,500 g (5 mmol) of the bisaldehyde according to Example 1 are mixed with 1.89 g (5 mmol) of the bisphosphonate in 50 ml of toluene under inert gas and heating solved. At 100 ° C, 1.232 g (11 mmol) of the base are suspended in 10 ml Toluene added all at once. The reaction mixture foams and becomes viscous. After one hour under reflux conditions, the mixture is agitated Precipitates in methanol worked up as described in Example 4.

Claims (14)

1. An electroluminescent material containing one or more polymers which contain repeating units of the formula (I) where the symbols and indices have the following meanings:
Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ are identical or different mono- and / or polynuclear, optionally linked by a bridge, and / or fused aryl and / or heteroaryl groups, which may be substituted, whereby Ar¹, Ar³ , Ar⁵ and Ar⁶ each have two bonds and Ar² and Ar⁴ each have one bond;
R¹ is H, a hydrocarbon radical having 1 to 22 carbon atoms or Ar⁷, where Ar⁷ can have the same meanings as Ar¹ to Ar⁶;
n is 0, 1 or 2. 2. Electroluminescent material according to claim 1, characterized in that that the polymer or polymers consist of repeating units of the formula (4). 3. Electroluminescent material according to claim 1 and / or 2, characterized characterized in that the polymer or polymers containing repeat units of Formula (I), have 2 to 1000 repeating units. 4. Electroluminescent material according to one or more of the preceding claims, characterized in that a polymer contains different repeating units of the formula (I). 5. Electroluminescent material according to one or more of the preceding claims, characterized in that the symbols and indices in the formula (I) have the following meanings,
Ar¹, Ar³, Ar⁵, Ar⁶ are the same or different Ar², Ar⁴, identical or different from Ar¹, Ar³, Ar⁵ and Ar⁶, have the same meanings as Ar¹, Ar³, Ar⁵ and Ar⁶, only one of the two possible binding sites to the polymer being realized;
Ar¹, Ar², Ar³, Ar⁴₁ Ar⁵, Ar⁶ can be substituted identically or differently with one or more radicals R²-R⁷;
X is a single bond -O-, -S-, -SO-, -SO₂-, -CR²R³-, -CR⁴ = -CR⁵- or CHR⁶-CHR⁷-;
Y: -O-, -S-, -C (O) - or -NR⁸-;
R¹ is H, a hydrocarbon radical having 1 to 22 carbon atoms or Ar⁷, where Ar⁷ can have the same meanings as Ar¹ to Ar⁶;
R²-R⁷ are the same or different H, an alkyl group with 1 to 22 carbon atoms, with one or two non-adjacent CH₂ groups by -O-, -S-, -CO-, -CO-O-, -O-OC - or -Si (CH₃) ₂- can be replaced, -CF₃, -Ph, -O-Ph, -S-Ph, -SO-Ph, -SO₂-Ph, F, Cl, Br, I or -CN;
R⁸, identical or different from R¹, has the same meanings as R¹;
n 0, 1 or 2. 6. Electroluminescent material according to one or more of the preceding claims, characterized in that the symbols and indices in the formula (I) have the following meanings:
Ar¹, Ar³, Ar⁵, Ar⁶ are the same or different Ar², Ar⁴ may have the same meanings as Ar¹, Ar³, Ar⁵, Ar⁶, the same or different, but only one of the two possible binding sites to the polymer is or are realized R⁹-R¹¹ are the same or different F, Cl, a straight-chain or branched alkyl or alkoxy group with 1 to 22 carbon atoms. 7. Electroluminescent material according to one or more of the preceding claims, characterized in that in formula (I) Ar¹ and Ar³ and optionally Ar² and Ar⁴ each have the same meanings to have. 8. Electroluminescent material according to one or more of the preceding claims, comprising one or more compounds of the formula (Ia) in addition to one or more polymers of the formula (I), where the symbols and indices, identical or different from the polymer of the formula (I), have the same meanings as in the formula (I). 9. Use of a polymer according to one or more of claims 1 to 7 as electroluminescent material. 10. Use of a polymer according to one or more of claims 1 up to 7 as hole conductor. 11. A method for producing an electroluminescent material according to one or more of claims 1 to 7, characterized in that

• a) an organophosphorus compound of the formula (III) with a bisaldehyde or bisketone of the formula (II) condensed to a polymer containing repeating units of the formula (I) under the action of a basic condensing agent, where the symbols and indices have the following meanings:
  Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ the same or different mono- and / or polynuclear, optionally linked by a bridge, and / or fused aryl and / or heteroaryl groups, preferably with 4 to 20 carbon atoms, which can optionally be substituted , whereby Ar¹, Ar³, Ar⁵ and Ar⁶ each have two bonds and Ar² and Ar⁴ each have a bond;
  R¹ is H, a hydrocarbon radical having 1 to 22 carbon atoms or Ar⁷, where Ar⁷ can have the same meanings as Ar¹ to Ar⁶;
  n is 0, 1 or 2 and
• b) the polymer thus obtained, containing repeating units of the formula (I), is applied in the form of a film to a substrate which may already contain other layers.

12. An electroluminescent device with one or more active Layers, wherein at least one of these active layers Electroluminescent material according to one or more of claims 1 to 7 is.   13. A polymer containing repeating units of the formula (I) where the symbols and indices have the following meanings:
Ar¹, Ar², Ar³, Ar⁴, Ar⁵, Ar⁶ are identical or different mono- and / or polynuclear, optionally linked by a bridge, and / or fused aryl and / or heteroaryl groups, which may optionally be substituted, and where Ar¹, Ar³, Ar⁵ and Ar⁶ each have two bonds and Ar² and Ar⁴ each have one bond;
R¹ is a hydrocarbon radical having 1 to 22 carbon atoms or Ar⁷, where Ar⁷ can have the same meanings as Ar¹ to Ar⁶;
n is 0, 1 or 2. 14. The polymer of claim 13, consisting of repeat units of Formula (I).