DE19832943A1 - Electroactive, light-emitting film-forming polymer materials used in electrophotography, electroluminescent material and electrochromic display are derived from bis(aryl-hydroxymethyl)-(hetero)arene and N,N'-diaryl-arylene diamine - Google Patents

Abstract

Electroactive and light-emitting polymer materials, forming films from solution, contain polymer(s) (I), comprising polycondensates of bis(aryl-hydroxymethyl)-(hetero)aromatic compounds and N,N'-diaryl-arylene diamines. Electroactive and light-emitting polymer materials, forming films from solution, contain polymer(s) of formula (I), comprising polycondensates of bis(aryl-hydroxymethyl)-(hetero)aromatic compounds and N,N'-diaryl-arylene diamines. Y = a divalent aryl-substituted arylene diamine derivative of formula (II); m = 1, 2 or 3; R = alkyl or aryl; R' = alkyl, alkoxy or halogen; Z = divalent (hetero)aromatic groups; Ar, Ar' = aryl; n = 5-5000 The full definitions are given in the DEFINITIONS (Full Definitions) Field. An Independent claim is also included for the preparation of a (I) solution.

Description

The invention relates to new solution-forming, electroactive and light-emitting Polymer materials and processes for their manufacture.

Substituted benzidines and arylenediamines are considered to be electroactive and electroluminescent known photoconductive materials. Because of their low molecular weight, they are not film-forming and can only by vapor deposition or in a mixture with compatible polymers processed into films and coatings.

Also higher molecular weight benzidine derivatives and polymers containing benzidine and arylenediamine with better film formation have been made accessible. Poly (2-vinyl-N, N, N ', N'-tetramethyl benzidine) JP 63 125 945 (30.05.88), polycarbonate EP 295 127 (14.12.88), polyurethane EP 452 683 (10/23/91), polycarbonate JP 03 221 522 (9/30/91), styrene type, methacrylate type and phosphazene-type polymers, Kobunshi Robunshu (1995), 52 (4), 211-15, polyester EP 687 958 (20.12.95), PMMA copolymers with benzidine in the side chain JP O8 101 523 (16.04. 96), polysilanes DE 196 14 249 (10/17/96), polymethacrylamides JP 08 269 133 (10/15/96), Polyetheresteramine JP 09 110 974 (28.04.97), Polyarylenvinylene WO 9709394 A1 (13.03. 97)

The object of the present invention is to develop new, electroactive and film-forming from solution to develop light-emitting polymer materials.

The objects are achieved according to the invention in that new, film-forming, electroactive and light-emitting polymer materials have been found which are characterized in that they contain aromatic and heteroaromatic polymers and oligomers having units of the formula 1,

wherein Y is double-bonded aryl-substituted arylenediamine derivatives of the formula 2

embodies and
m integers 1,2,3
R alkyl radicals, preferably methyl, ethyl, propyl, isopropyl, cyclohexyl, aralkyl, benzyl and the like and aryl radicals, such as phenyl, substituted phenyl, naphthyl, etc. and
R 'alkyl, alkoxy, halogen
and Z
mean different aromatic and / or heteroaromatic radicals, each of which has two bonds, and in which Z is derived from aromatic and heteroaromatic compounds, preferably from benzene, hydroquinone dialkyl ethers, diphenyl ether, diphenyl sulfide, biphenyl, naphthalene and all aromatics and their compounds and heteroaromatics and their compounds, which can be substituted electrophilically twice
and Ar and Ar 'identical or different aryl residues, preferably phenyl residues and substituted phenyl residues such as fluorophenyl, chlorophenyl
and n are integers 5 to 5000.

Without restricting the scope of the present invention, the following new solution-forming, electroactive and light-emitting polymer materials of the formulas 3 to 13 are to be listed in more detail as representatives of the general formula 1.

The preparation of the polymers, the units of general formula 1

contained, is carried out according to the invention by polycondensation of arylene diamine derivatives of the structure HYH with dialcohols of the structure Ar-CHOH-Z-CHOH-Ar ', according to the reaction equation

wherein Y arylenediamine derivatives of formula 2

embodies what
m integers 1,2,3
R alkyl radicals, preferably methyl, ethyl, propyl, isopropyl, cyclohexyl, aralkyl, benzyl and the like and aryl radicals, such as phenyl, substituted phenyl, naphthyl, etc. and R 'alkyl, alkoxy, halogen and
Z means different aromatic and / or heteroaromatic radicals, each of which has two bonds, and in which Z is derived from aromatic and heteroaromatic compounds, preferably from benzene, hydroquinone dialkyl ethers, diphenyl ether, diphenyl sulfide, biphenyl, naphthalene and all aromatics and their compounds and heteroaromatics and their compounds which can be substituted electrophilically twice, and
Ar and Ar 'are identical or different aryl radicals, preferably phenyl radicals and substituted phenyl radicals such as fluorophenyl, chlorophenyl and n integers 5 to 5000.

Substituted benzidines and / or are used as arylene diamine derivatives of the structure H-Y-H p-phenylenediamines and / or terphenyldiamines, preferably N, N'-bis (3-methylphenyl) - N, N'-diphenyl-benzidine, N, N, N ', N'-tetraphenylbenzidine, N, N'-diethyl-N, N'-diphenyl-benzi din, N, N'-dicyclohexyl-N, N'-diphenyl-benzidine, N, N, N ', N'-tetraphenyl-p-phenylenediamine, N, N'-dimethyl-N, N'-diphenyl-p-phenylene-diamine, N, N'-diethyl-N, N'-diphenyl-p-phenylene diamine, N, N'-dicyclohexyl-N, N'-diphenyl-p-phenylenediamine used.

Bis (aryl-hydroxymethyl) aromatics and bis- (aryl-hydroxymethyl) heteroaromatics are used as dialcohols Ar-CHOH-Z-CHOH-Ar '. A selection may be mentioned:
1,4-bis (phenylhydroxymethyl) benzene, 1,3-bis (phenylhydroxymethyl) benzene, 4,4'-bis (phenyl hydroxymethyl) biphenyl, bis (4-phenylhydroxymethylphenyl) ether, bis (4-phenylhydroxymethylphenyl) ) sulfide, 2,6-bis (phenylhydroxymethyl) naphthalene, 1,4-bis (4-fluorophenyl-hydroxy methyl) benzene, 1,3-bis (4-fluorophenyl-hydroxymethyl) benzene.

The present invention particularly relates to polymers which are obtained by reaction of N, N'-bis (3-methylphenyl) -N, N'-diphenyl-benzidine with 1,4-bis (phenylhydroxymethyl) benzene and / or 1,3-bis (phenylhydroxymethyl) benzene, and which have a high photo have conductivity that can be spectrally sensitized, an intense photolumines zenz with a reversible low redox potential, determined by cyclic voltammetry of 0.77 V vs. Connect Ag / AgCl, in addition, a high glass transition temperature Tg <200 ° C and form homogeneous layers on glass, metal and other substrates.

The polycondensation is carried out by dialcohol Ar-CHOH-Z-CHOH-Ar 'and arylene diamond derivative H-Y-H in the presence of acidic condensing agents, protonic acids and / or Lewis acids are reacted. High molecular weight film-forming from solution electroactive and light-emitting polymer materials are obtained according to the invention, if a molar ratio between the components used of 0.7 to 1.3 mol of arylene Diamond derivative H-Y-H per 1 mol of dialcohol Ar-CHOH-Z-CHOH-Ar 'is selected.

The polycondensation can be carried out in organic solvents. As examples for such solvents are methylene chloride, 1,2-dichloroethane, carbon tetrachloride, nitro called benzene, chlorinated aromatics such as chlorobenzene and 1,2-dichlorobenzene. Has proven itself phosphorus oxychloride in which most of the polymers according to the invention are soluble,  and therefore in excess at the same time as solvent and acidic condensation tel can be applied. The polycondensation batches are worked up by Hydrolysis, polymer precipitation and reprecipitation. For certain uses polycondensates without reprecipitation are also suitable.

DE 44 45 619 (06/27/96) describes the reaction of various bis (aryl-hydroxymethyl) aro mate and bis (aryl-hydroxymethyl) heteroaromatics with various aromatics and hetero aromatics and their compounds in the presence of acidic condensation reagents described. In example 6 in DE 44 45 619 (06/27/96) the polycondensation is also one aromatic monoamines, namely the reaction of triphenylamine with 1,4-bis (phenyl hydroxy) benzene. The polymer obtained in this way has a 0.98 V. significantly higher oxidation potential than that according to the invention from aromatic diamines and dialcohols Ar-CHOH-Z-CHOH-Ar polymers and is for fiction appropriate uses that require an oxidation potential below 0.9 V are not suitable. In contrast, it was found that the arylene diamine derivatives and Polymers made from Ar-CHOH-Z-CHOH-Ar alcohols Oxidation potentials <0.9 V own and for the use claimed in the invention as a highly effective hole-trans port material, electrochromic material and material with high photoluminescence are suitable. The polycondensate from 1,4-bis (phenyl-hydroxymethyl) benzene and N, N'-bis (3-methylphenyl) -N, N'-diphenyl-benzidine according to Example 1 has an oxidation po potential of 0.77 V determined by differential pulse polarography and cyclic voltammetry vs. Ag / AgCl.

For the applications according to the invention, reaching high molecular weights is not inevitable necessary because oligomers consisting of more than 5 units according to the invention Suitable as film-forming, electroactive and light-emitting polymer materials from solution and, moreover, better film formation and improved miscibility with others film-forming polymers is achieved.

The preferred method of preparation for polymers and oligomers is the reaction of Dialcohols Ar-CHOH-Z-CHOH-Ar with arylenediamine derivatives of formula 2. However polymers and oligomers obtained according to the invention also on other synthetic routes, which have structural features according to the invention, as film-forming, electroactive from solution and light-emitting polymer materials.

Resulting from the incorporation of the arylenediamine units into the polymers according to the invention new valuable properties, from which new applications emerge as film-forming from solution photoconductive materials, as from film-forming photoluminescent substances and from Solution film-forming electrochromic polymer materials result.

The polymers according to the invention are soluble in organic solvents and the moles masses are so high that film formation is achieved from solution. As example 1 shows, who receive the amorphous polymer materials according to the invention with a high glass transition temperature of 243 ° C. The glass transition temperatures of the polymers obtained are compared to the low molecular weight ones Tetraarylbenzidine materials are surprisingly high and particularly valuable for the various Applications of these polymer materials. The well-known hole-transport materials from Aromatic diamines of the tetraarylbenzidine type generally have a glass temperature ren below 100 ° C z. B. TPD 60 ° C.  

The polymers according to the invention form films from solution for semiconductor applications e.g. B. as a photoconductor in electrophotographic recording processes or as a photoconductive Sensors, as photoconductive materials for photorefractive or photovoltaic devices or as light-emitting materials in electroluminescent devices and photolumines zenzanlagen or as electrochromic materials are used according to the invention.

The invention therefore also relates to the use of the invention Polymers as film-forming photoconductor material.

The invention therefore also relates to the use of the invention Polymers as film-forming electroluminescent material.

The invention therefore also relates to the use of the invention Polymers as a film-forming electrochromic material.

The electroactive and light-emitting polymer materials according to the invention have due to their structure, sensitivity in the blue and ultraviolet spectral range. For an increase in sensitivity and an expansion in the long-wave spectral range this includes sensitization with suitable dye sensitizers and / or electrons acceptable expedient.

The good compatibility of the polymers and oligomers obtained is also remarkable with low molecular weight electroactive and electroluminescent, photoconductive materials of the arylenediamine and benzidine type, such as N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine, Tetraphenylbenzidine and / or tetraphenyl-p-phenylenediamine, which is also the preparation of homogeneous mixed layers allowed.

In addition to the polymers and oligomers according to the invention, copolymers are also produced by reaction of mixtures of different dialcohols Ar-CHOH-Z-CHOH-Ar 'with Mi of various arylene diamine derivatives H-Y-H where Y is double-bonded aryl Substituted arylenediamine derivatives of formula 2 means and / or other aromatics than from Solution film-forming, electroactive and light emitting polymer materials suitable if at least one of the aromatic components in the copolymers is an arylenediamine di vat Y of Formula 2.

To improve the mechanical properties of polymer layers from these and the other polymers according to the invention can include plasticizers, stabilizers and binders be added. By alloying / blending with other polymers, both Processing properties of the casting solution as well as the mechanical properties of the Solution film-forming, electroactive and light-emitting polymer materials improved become.  

Embodiments example 1

Synthesis instructions of an electroactive and light emitting film forming from solution Polymer material by polycondensation of 1,4-bis (phenylhydroxymethyl) benzene and N, N'-bis (3-methylphenyl) -N, N'-diphenyl-benzidine

2.61 g of 1,4-bis (phenylhydroxymethyl) benzene (0.009 mol) and 5.16 g of N, N'-bis (3-methylphenyl) -N, N'-diphenyl-benzidine (0.010 mol) are added in 80 ml of phosphorus oxychloride (POCl ₃ ) dissolved. The mixture is stirred for 30 min and then warmed to 45 ° C. within 90 min. After cooling, it is decomposed by careful pouring into plenty of water and methylene chloride, the organic phase is separated off and washed with water. The solution is concentrated and precipitated in ethanol. After washing with ethanol and drying, the mixture is taken up in toluene and precipitated in ethanol. After reprecipitation from toluene / acetone and drying, 5.4 g (70% of theory) of colorless powder, M _n 7900 (VPO in CHCl ₃ ), GPC: M _n 7000, M _W 47700, T _g 243 ° C.
(C ₅₈ H ₄₆ N ₂ ) _n 771.03
calculated: C 90.35; H 6.01; N 3.63
found: C 90.31; H 6.24; N 3.68

The UV-VIS absorption spectrum of the polycondensate, produced according to an example, is shown in Fig. 1.

Fig. 1 UV / VIS spectrum in dioxane

The strong electron donor character of the polymer according to the invention, produced according to Example 1, is demonstrated using the differential pulse polarogram DPP and the cyclic voltammo CV, Fig. 2. E ^Ox1 = 0.77 V vs. Ag / AgCl, E ^Ox2 = 1.00 V vs. Ag / AgCl.

Fig. 2 Electrochemical oxidation (TBAPF ₆ / CH ₂ Cl ₂ , Pt electrode against Ag / AgCl)

Example 2

Synthesis instructions of an electroactive and light emitting film forming from solution Polymer material by polycondensation of 1,4-bis (phenylhydroxymethyl) benzene and N, N'-bis (3-methylphenyl) -N, N'-diphenyl-benzidine without reprecipitation.

13.07 g of 1,4-bis (phenylhydroxymethyl) benzene (0.045 mol) and 25.83 g of N, N'-bis (3-methylphenyl) -N, N'-diphenyl-benzidine (0.050 mol) are introduced and 400 ml of phosphorus oxide chloride (POCl ₃ ) was added through the reflux condenser. The mixture is stirred and then heated to 48-50 ° C. within 90 minutes. After cooling, the mixture is decomposed by careful pouring into ice water and methylene chloride with stirring, the temperature being kept below 30 ° C. by adding ice. After separating the organic phase and complete neutralization, the organic phase is dried, concentrated and precipitated in methanol. After washing several times with methanol and drying, 36.0 g (93% of theory) of colorless powder, GPC: M _n 2600, M _W 56500.
(C ₅₈ H ₄₆ N ₂ ) 771.03
calculated: C 90.35 H 6.01 N 3.63
found: C 89.81 H 6.17 N 3.73

Example 3

Photoconductor layer, made of polymer according to Example 2. The photoconductivity spectrum is shown in Fig. 3.

Fig. 3 Photoconductivity spectrum of the polymer layer according to Example 3

Example 4 Photoconductor layer, made of polymer according to Example 1. The photoconductivity spectrum is shown in Fig. 4

Fig. 4 Photoconductivity spectrum of the polymer layer according to Example 4

Example 5

Photoconductor layer containing 100 parts of photoconductor polymer, produced according to Example 1, and 3 parts of 1,4-bis (2-cyanstyryl-2,5-dimethoxy-benzene)
The photoconductivity spectrum is shown in Fig. 4 I _ph 24,000 cm ^-1 = 5.9 × 10 ^-11 A (dashed line)

Example 6

Photoconductor layer containing 100 parts of photoconductor polymer, produced according to Example 1, and 2 parts of malachite green picrate
The photoconductivity spectrum is shown in Fig. 4 I _ph 16.200 ^-1 cm = 1.9 × 10 ^-11 A (dotted line)

Example 7

Photoconductor layer containing 100 parts of photoconductor polymer, produced according to Example 1, and 10 parts of trinitrofluorenone TNF
The photoconductivity spectrum is shown in Fig. 4 I _ph 17,500 cm ^-1 = 3.8 × 10 ^-12 A
(dotted and dashed line)
compared to the non-sensitized material (solid line)

Fig. 5 Photoconductivity spectra of the polymer layers according to Example 5, Example 6, and Example 7

Example 8

Fluorescent polymer layer with material, produced according to Example 2. The fluorescence excitation and emission spectrum and the absorption spectrum (dotted line) is shown in Fig. 6. Fig. 7 shows the spectrum in solution for comparison.

Fig. 6 Fluorescence excitation and emission spectrum of the polymer layer

Fig. 7 Fluorescence excitation and emission spectrum in dioxane

Example 9

By electrooxidation of the material according to the invention, produced according to Example 2, arises reversibly a blue color.

Claims (23)

1. From solution, film-forming, electroactive and light-emitting polymer materials containing one or more polymers which contain units of the formula 1
where the symbols and indices have the following meaning:
Y double-bonded aryl-substituted arylenediamine derivatives of the formula 2,
m integers 1, 2, 3
R alkyl radicals, preferably methyl, ethyl, propyl, isopropyl, cyclohexyl, aralkyl, benzyl and the like and aryl radicals, such as phenyl, substituted phenyl, naphthyl, etc. and
R 'alkyl, alkoxy, halogen
Z various aromatic and / or heteroaromatic radicals, each of which starts from two bonds, and in which Z is derived from aromatic and heteroaromatic compounds, preferably from benzene, hydroquinone dialkyl ethers, diphenyl ether, diphenyl sulfide, biphenyl, naphthalene and all aromatics and their compounds and heteroaromatics and their compounds, which can be substituted electrophilically twice,
Ar and Ar 'identical or different aryl residues, preferably phenyl residues and substituted phenyl residues such as fluorophenyl, chlorophenyl
and n integers 5 to 5000. 2. A process for the preparation of electro-active and light-emitting polymer materials which form films from solution and which contain units of the formula 1
where the symbols and indices have the following meaning:
Y double-bonded aryl-substituted arylenediamine derivatives of the formula 2,
m integers 1, 2, 3
R alkyl radicals, preferably methyl, ethyl, propyl, isopropyl, cyclohexyl, aralkyl, benzyl and the like and aryl radicals, such as phenyl, substituted phenyl, naphthyl, etc. and
R 'alkyl, alkoxy, halogen
Z various aromatic and / or heteroaromatic radicals, each of which starts from two bonds, and in which Z is derived from aromatic and heteroaromatic compounds, preferably from benzene, hydroquinone dialkyl ethers, diphenyl ether, diphenyl sulfide, biphenyl, naphthalene and all aromatics and their compounds and heteroaromatics and their compounds, which can be substituted electrophilically twice,
and Ar and Ar 'identical or different aryl residues, preferably phenyl residues and substituted phenyl residues such as fluorophenyl, chlorophenyl
and n integers 5 to 5000,
characterized in that arylenediamine derivatives of the structure HYH with dialcohols of the structure Ar-CHOH-Z-CHOH-Ar ', according to the reaction equation Eq. 1
be implemented
and the symbols and indices have the meaning given above. 3. Process for the production of electroactive and light emitting film-forming from solution the polymer materials according to claim 2, characterized in that the polycondensation  of dialcohol Ar-CHOH-Z-CHOH-Ar 'and arylenediamine derivative H-Y-H in the presence of acidic condensing agents, protonic acids and / or Lewis acids, preferably in the presence of phosphorus oxychloride is carried out, and between the components used Molar ratio of 0.7 to 1.3 moles arylene diamine derivative H-Y-H per 1 mole of dialcohol Ar-CHOH-Z-CHOH-Ar 'is selected. 4. A process for the preparation of film-forming, electroactive and light-emitting polymer materials according to claim 2 and 3, characterized in that as dialcohols Ar-CHOH-Z-CHOH-Ar 'bis (aryl-hydroxymethyl) aromatics and bis- (aryl- hydroxymethyl) heteroaromatics, preferably
1,4-bis (phenylhydroxymethyl) benzene, 1,3-bis (phenylhydroxymethyl) benzene, 4,4'-bis (phenyl hydroxymethyl) biphenyl, bis (4-phenylhydroxymethylphenyl) ether, bis (4-phenylhydroxymethylphenyl) ) sulfide, 2,6-bis (phenylhydroxymethyl) naphthalene, 1,4-bis (4-fluorophenyl-hydroxymethyl) benzene, 1,3-bis (4-fluorophenyl-hydroxymethyl) benzene. 5. Process for the production of electroactive and light emitting film-forming from solution the polymer materials according to claim 2 and 3, characterized in that as arylenediamine derivatives of the structure H-Y-H substituted benzidines and / or p-phenylenediamines, preferably N, N'-bis (3-methylphenyl) -N, N'-diphenyl-benzidine, N, N, N'N'-tetraphenyl benzidine, N, N'-diethyl-N, N'-diphenyl-benzidine, N, N'-dicyclohexyl-N, N'-diphenyl-benzidine, N, N, N'N'-tetraphenyl-p-phenylenediamine, N, N'-dimethyl-N, N'-diphenyl-p-phenylene-diamine, N, N'-diethyl-N, N'-diphenyl-p-phenylenediamine, N, N'-dicyclohexyl-N, N'-diphenyl-p-phenylene diamine can be used. 6. Process for the production of electroactive and light emitting film-forming from solution the polymer materials according to claim 2, 3 and 4, characterized in that the polycon densation in organic solvents, preferably in methylene chloride, 1,2-dichloroethane, Carbon tetrachloride, nitrobenzene, chlorinated aromatics such as chlorobenzene and 1,2-dichlorobenzene is performed. 7. Film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 3 as oligomers and polymers of formula 1
8. From solution, film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 4 as oligomers and polymers of formula 1.
9. From solution film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 5 as oligomers and polymers of formula 1.
10. From solution film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 6 as oligomers and polymers of formula 1.
11. Film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 7 as oligomers and polymers of formula 1.
12. From solution, film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 8 as oligomers and polymers of formula 1.
13. From solution, film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 9 as oligomers and polymers of formula 1.
14. Film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 10 as oligomers and polymers of formula 1.
15. Film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 11 as oligomers and polymers of formula 1.
16. Film-forming, electroactive and light-emitting polymer materials according to Claim 1, characterized in that they contain units of the formula 12 as oligomers and polymers of the formula 1.
17. Film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 13 as oligomers and polymers of formula 1.
18. Film-forming, electroactive and light-emitting polymer materials according to claim 1, characterized in that they contain units of formula 14 as oligomers and polymers of formula 1.
19. Use of one or more polymer materials according to claims 1 and 7 to 18 as film-forming photoconductive components in electrophotographic recording processes ren. 20. Film-forming, electroactive and light-emitting polymer materials from solution Claims 1 and 7 to 19, characterized in that they improve the electrophoto graphic sensitivity sensitizers included. 21. Use of one or more polymer materials according to claims 1 and 7 to 18 as film-forming light-emitting components in electroluminescent materials. 22. Use of one or more polymer materials according to claims 1 and 7 to 18 as film-forming components in electrochromic displays. 23. Film-forming, electroactive and light-emitting polymer materials from solution Claims 1 and 7 to 22, characterized in that they improve the mechanical Properties contain plasticizers, stabilizers and binders.