DE4301800A1 - Substd. zircon-aza-alkene(s) obtd. from butadiene-zirconocene and nitrile(s) - Google Patents

Abstract

Substd. zircon-aza-alkenes (ZAA) are claimed; (I) are obtd. by reaction of butadiene-zirconocene (BZC) with nitriles of formula (I-III) (where R1 = 2-10C alkenyl or alkynyl or a 4-20C heterocyclic system; R2 = 2-20C alkenyl or cycloalkenyl; both R gps. can be substd. with 1-10C alkyl or alkoxy, Ph, nitro, F, Cl, Br or CF3).Also claimed are polymers (IV), obtd. by hydrolysis of ZAA, and polymers (V) obtd. by polymerisation of ZAA followed by hydrolysis, or by electrochemical polymerisation of ZAA. The invention enables the prodn. of low-mol. wt. and high-mol. wt. polymers contg. amino gps. and perconjugated double bonds. These polymers are therefore soluble and easy to handle and process, e.g. by doping in soln. and further processing to form optoelectronic devices.

Description

The present invention relates to substituted zirconia-aza-al kene by reacting butadiene zirconocene with nitriles of the general formula

wherein R ^{1 is} a C ₄ to C ₂₀ heterocyclic system or a C ₂ to C ₁₀ alkenyl or a C ₂ to C ₁₀ alkynyl group and R ^{2 is} a C ₂ to C ₂₀ alkenyl or cycloalkenyl radical , where these systems, groups or radicals can each be substituted with C ₁ - to C ₁₀ -alkyl groups, C ₁ - to C ₁₀ -alkoxy groups, phenyl, NO ₂ , Cl, Br, F or CF ₃ .

The invention further relates to processes for producing the like substituted zirkona aza alkenes and their use for the preparation of polymers containing amino groups.

Polymers with perconjugated double bonds, for example those based on pyrrole or thiophene are often only extremely difficult to dissolve and can therefore z. B. on the one hand only clean and analyze with complex methods and others not with simple techniques like the Langmuir Blogett-Ver drive to form thin films. But about the good electrical ones and optoelectric effects of such polymers , it is necessary that they clean themselves well, analyze them and have it processed.

The object of the present invention was therefore both low molecular as well as higher molecular weight soluble polymers to produce perconjugated double bonds.  

The object is achieved by the defi at the beginning substituted zircona aza alkenes. Furthermore, Ver drive for the production of such substituted zirconia aza alkenes, their use for the production of amino groups Polymers and the amino groups available here containing polymers.

The for the preparation of the substituted zirconia according to the invention aza-alkenes butadiene zirconocene can be used in two forms are present as cis-butadiene zirconocene and as trans-butadiene zirconocene. A mixture of these can also be used both forms, as is customary in the manufacture of Butadiene zirconocene occurs.

The production of butadiene zirconocene can be carried out by reacting Zirconocene dichloride with (2-butene-1,4-diyl) magnesium bis (tetra hydrofuran), also called butadiene magnesium. Zircono Cendichloride is usually made by reacting zirconium tetrachloride made with cyclopentadienyl sodium, butadiene Magnesium by reacting tetrahydrofuran with butadiene and Magnesium shavings. These syntheses are known to those skilled in the art knows, so that further explanations are unnecessary.

Suitable nitriles are compounds of the general formula R ¹ -CN (I) or dinitriles of the general formula NC-R ¹ -CN (II). The radicals R ¹ can mean a C ₄ to C ₂₀ heterocyclic system. These heterocyclic nitriles (I) or dinitriles (II) can be mononuclear or polynuclear. The compounds (I) or (II) include substituted or unsubstituted pyrrole nitriles, substituted or unsubstituted thiophenitriles but also substituted or unsubstituted furanitriles. Unsubstituted pyrrole nitriles or thiophene nitriles are preferably used. Among these, particular preference is given to those in which the carbon atoms in the α-position to the heteroatom carry a nitrile group. The following nitriles are very particularly preferably used as compounds (I) and (II):

In addition to heterocyclic nitriles, the compounds (I) and (II) also mean alkynyl nitriles, ie R ¹ in these cases represents a C ₂ -C ₂₀ -alkynyl radical. An example is acetyl nitrile. Propargyl nitrile is preferably used. Like the heterocyclic nitriles, the alkynyl nitriles can have further substituents. The radical R ¹ can also be a C ₂ to C ₁₀ alkenyl radical. Among them, the C ₂ alkenyl radicals are preferred. Acrylonitrile is an example.

The zirkona-aza-alkenes according to the invention can also be carried out Reaction with tetranitriles of the general formula

produce. R ² can mean a C ₂ to C ₂₀ alkenyl or cyclo alkenyl radical. Preferred compounds (III) are:

However, substituted tetranitriles (III) such as 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane was used become.

According to the invention, the nitriles (I) to (III) can be substituted by C ₁ to C ₁₀ alkyl groups, preferably methyl or ethyl. In addition, C ₁ to C ₁₀ alkoxy groups such as methoxy, ethoxy or t-butoxy can be suitable substituents. Phenyl, NO ₂ , F, Cl, Br or CF _{3 are also suitable} as substituents. Examples of substituted nitriles are cyanomethylpyrrole, cyanomethylthiophene, 7,7,8,8-tetracyano-2,3,5,6-tetrachloroquinodimethane or the aforementioned corresponding fluoroquinodimethane.

The nitriles (I) to (III) are either known or can be known methods can be obtained.

For the production of the substituted zirconia aza Alkenes are butadiene zirconocene with the nitriles (I), (II) or (III) implemented, the molar ratio of nitrile to butadiene zirconocene is generally in the range from 5: 1 to 0.2: 1, be preferably from 2: 1 to 1: 1 and the molar ratio of dinitrile to Butadiene zirconocene in the range from 1.5: 1 to 0.3: 1, preferably from 1: 1 to 0.2: 1.

Depending on the molar ratio of nitrile, dinitrile or tetranitrile Various zirconia aza alkenes can be used for butadiene zirconocene will hold. So z. B. the implementation of a nitrile general formula 1 with butadiene zirconocene in a molver ratio of 1: 1 a zirkona-aza-cyclopent-3-en of the general Formula IV

Cp stands for cyclopenta, as is usual in the specialist literature dienyl.

Compounds corresponding to the general formula IV are e.g. B.

If a nitrile of the general formula I is used with butadiene zircon nocene in a molar ratio of 2: 1 µm, for example as a zirkona-diaza-cyclonona-2,5,8-triene of the general Formula V

In the reaction of a dinitrile of the general formula II with butadiene zirconocene in a molar ratio of 2: 1, a zirconium diaza-cyclonona-2,5,8-triene of the general formula VI:

during the implementation of a dinitrile of the general Formula II with butadiene zirconocene in a molar ratio of 1: 1 zirconia aza-alkenes of the general formula VII can deliver:

with n = 1 to 50
and the reaction of a dinitrile of the general formula II with butadiene zirconocene in a molar ratio of 0.5: 1 zirconia aza-alkenes of the general formula VIII:

An example that corresponds to general formula VIII is

Zircona-aza-alkenes of the general formula VIII can now be used equimolar amounts of dinitrile to zirkona aza alkenes of the general my Formula IX are implemented:

Appropriate connections can be made when reacting the tetranitriles can be obtained with butadiene zirconocene. Because of the larger type number of nitrile groups available for the reaction correspondingly many different zirkona-aza- alkenes can be obtained. With a large excess of tetra nitriles (III) generally react (III) only on one of the Nitrile groups with the butadiene zirconocene. The smaller the molar Ratio of tetranitrile to butadiene zirconocene all the more Nitrile groups react per tetranitrile molecule. In this way highly cross-linked zircono-azo-alkenes can be formed.

When reacting nitrile, dinitrile or tetranitrile with buta dienzirkonocen is preferably carried out in such a way that both Nitrile, dinitrile or tetranitrile as well as the butadiene zirconocene mixed with a solvent. This is preferably used same solvents, especially toluene. The two solutions are generally at temperatures from -10 to 100 ° C before combined at temperatures of 0 to 30 ° C. That ent standing substituted zircona-aza-alkene precipitates and becomes filtered.

The substituted zirconia aza alkenes according to the invention can now by hydrolysis to amino group-containing polymers be set.

One can produce the polymers containing amino groups the zircona aza alkenes in a solvent such as tetrahydrofuran Dissolve (THF) and then, preferably at room temperature, add water and the resulting amino group-containing Isolate polymer.

The hydrolysis of zirkona-diaza-cyclonona-2,5,8-trien of all general formula V provides compounds of the general my formula X:

Hydrolyzing zirconia aza alkenes of the general formula VI, see above compounds of the general formula XI can be obtained:  

By hydrolysis of zircona aza alkenes of the general Formula VII one can compounds of the general formula XII he hold:

with n = 1 to 50.

Of course, those can be obtained from the tetranitriles Lichen zirkona aza alkenes analogously hydrolyze ent Talking polymers containing amino groups can be obtained.

By introducing the amino groups into polymers with konju Allied double bonds become soluble. Therefore, they are good to handle and easy to process. You let yourself be for example, doping in solution and so optoelektro African devices are processed further.

Since the zirconia-aza-alkenes according to the invention are polarizable They contain groups such as pyrrole, thiophene or acetylene deal with these groups either chemically, or as preferred will polymerize electrochemically. Then you can Polymers are hydrolyzed, thereby containing amino groups Polymers are obtained.

Examples Reacting butadiene zirconocene with mononitriles example 1

2.45 g (8.9 mmol) of butadiene zirconocene was added to 40 ml of toluene dissolves and then dropwise with a solution of 1.1 ml (15 mmol) Acrylonitrile in 10 ml of toluene. The reaction mixture was Stirred for 15 hours at room temperature. Then the deep red solution filtered, the solvent removed and the red solid dried in vacuo. 3 g (78%) of the were obtained Product

Example 2

Example 1 was repeated, but the reaction mixture Stirred at 50 ° C for 50 hours. 3.2 g (83%) of the product were obtained Product.

Polymerization Example 3

10 g of compound IV ₁ were dissolved in 90 ml of toluene and 2 ml of a 16% strength by weight solution of n-butyllithium in n-hexane were added and the mixture was stirred at 20 ° C. for 5 hours. After the product had precipitated from methanol, 5 g, a polymeric compound with a molecular weight (number average) of 28,000 (determined by means of HPLC and tetrahydrofuran as eluent) were obtained.

Example 4

Example 3 was repeated, using the compound V ₁ instead of IV ₁ . A corresponding polymeric compound with a molecular weight (number average) of 37,000 (determined by means of HPLC and tetrahydrofuran as the eluent) was used.

Hydrolysis of the polymers Example 5

The polymer obtained according to Example 3 was mixed with water in one Weight ratio of 1: 100 and 3 hours at 50 ° C ge stirs. The reaction solution was then filtered, the Solvent removed and the polymer containing amino groups dried in vacuo. Yield 2.9 g. The polymer was in N- Methylpyrrolidone soluble.

Example 6

Example 5 was with the polymer obtained according to Example 4 repeated. 3.4 g of the corresponding amino groups were obtained containing polymer which was soluble in dimethylformamide.

Claims (7)

1. Substituted zircona-aza-alkenes, obtainable by reacting butadiene zirconocene with nitriles of the general formula where R ^{1 is} a C ₄ to C ₂₀ heterocyclic system or a C ₂ to C ₁₀ alkynyl group and R ^{2 is} a C ₂ to C ₂₀ alkenyl or cycloalkenyl radical, these systems, groups or radicals each having C ₁ - to C ₁₀ alkyl groups, C ₁ - to C ₁₀ alkoxy groups, phenyl, NO ₂ , Cl, Br, F, or CF ₃ may be substituted. 2. Substituted zirkona-aza-alkenes according to claim 1, in which the nitriles are selected from 3. Process for the preparation of zirkona-aza-alkenes according to claim 1 or 2, characterized in that zirconocene butadiene with nitriles of the general formula where R ^{1 is} a C ₄ to C ₂₀ heterocyclic system or a C ₂ to C ₁₀ alkynyl group and R ^{2 is} a C ₂ to C ₂₀ alkenyl or cycloalkenyl radical, these systems, groups or radicals each having C ₁ - to C ₁₀ alkyl groups, C ₁ - to C ₁₀ alkoxy groups, phenyl, NO ₂ , Cl, Br, F, or CF ₃ may be substituted. 4. Use of the substituted zirkona-aza-alkenes according to Claim 1 or 2 for the preparation of amino group-containing Polymers and crosslinked amino-containing poly merisates. 5. Amino group-containing polymers, obtainable by hydrolysis the substituted zirkona aza-alkenes according to claim 1 or 2. 6. Crosslinked polymers containing amino groups, obtainable by Polymerization of the substituted zircona aza alkenes according to Claim 1 or 2 and subsequent hydrolysis. 7. Crosslinked polymers containing amino groups according to claim 6, obtainable by electrochemical polymerization of the substi performed zirkona-aza-alkenes.