DE1570760B2 - PROCESS FOR THE PRODUCTION OF POLYMERIZED AND MIXED POLY MERIZED FROM 9 ALKENYL-SUBSTRATED CARBAZOLES - Google Patents

Description

in which η is a value from 1 to 20 and R, R ', R ", R'" and R "" denote hydrogen atoms or aryl, alkyl or substituted alkyl or aryl substituents, optionally in a mixture with one another or in a mixture with other copolymerizable ones Monomers used.

2. The method according to claim 1, characterized in that one pentenylcarbazole of the formula

at 0 to 70 ° C in the presence of a polymerization catalyst containing diethyl aluminum chloride and titanium trichloride polymerized in a hydrocarbon solvent for the hexenyl carbazole.

4. The method according to claim 3, characterized in that one is a mixture of 9- (4-pentenyl) carbazole and 9- (5-hexenyl) carbazole in a ratio of 1 to 100 parts to 100 to 1 part polymerized and terminated the polymerization reaction by adding hydrogen.

5. The method according to any one of the preceding claims, characterized in that the Polymerization to a number average degree of polymerization of 10 to 1000 carries out.

The invention relates to a process for the production of polymers and copolymers of 9-alkenyl-substituted carbazoles in the presence of solvents and polymerization catalysts, which is characterized in that the 9-alkenyl-substituted carbazoles are those of formula

at 0 to 70 ° C in a solvent for the pentenylcarbazole and in the presence of a Ziegler polymerization catalyst, which contains a complex of diethyl aluminum chloride and titanium trichloride in a weight ratio of about 1: 3, polymerized.

in which η is a value from 1 to 20 and R, R ', R ", R'" and R "" denote hydrogen atoms or aryl, alkyl or substituted alkyl or aryl substituents, optionally in a mixture with one another or in a mixture with other copolymerizable ones Monomers.

The new polymers obtainable according to the invention are thus polymers, the monomer units the formula

anhydrous sodium hydride in anhydrous tetrahydrofuran at room temperature to form 9-sodium carbazole implemented. The alkali-substituted carbazole corresponds to the formula

R - C - R '

/ I

MR""

IO

contain, in which n, R, R ', R ", R'" and R "" have the meanings given above, and copolymers, of which at least one of the monomer units corresponds to the above formula.

Appropriate copolymers are those in which each of the monomer units of the specified Formula corresponds. The new polymers and copolymers expediently have a Number-average degree of polymerization from 10 to 1000. You can go in tactical or atactical Form.

A suitable copolymer is, for example, a poly-9- (5-hexenyl) -carbazole and poly-9- (4-pentenyl) -carbazole containing polymer of the formula

in which X is sodium, potassium or lithium.

The one substituted in the 9-position by an alkali metal Carbazole is then monohalogenated under anhydrous, non-oxidizing conditions with a Alkene of formula

55

in which m has a value from 5 to 500 and the ratio of ο to ρ is 1 to 100 to 100 to 1.

The monomers to be used for the process according to the invention, in which the alkenyl substituents contain 5 to 23 carbon atoms, can be prepared from carbazole by first carbazole with an alkali metal compound, preferably a hydride from the group consisting of lithium, sodium and potassium hydride, in the presence of a suitable reaction medium is reacted under anhydrous, non-oxidizing conditions. For example, anhydrous carbazole in anhydrous tetrahydrofuran under a nitrogen atmosphere with R
R '--C

R "

C-

R "'

R ""

• C = CH,

(where η is a value from 2 to 20, A is a chlorine, bromine or iodine atom and R, R ', R ", R'" and R "" are hydrogen atoms or alkyl, aryl or substituted alkyl or aryl substituents), for example with anhydrous 5-bromopentene in anhydrous tetrahydrofuran under suitable reaction conditions, for example, about 70 ⁰ C, to yield the desired 9-position alkenyl Carbazolmonomere, for example 9- (4-pentenyl) -carbazole of the formula

HHH

to obtain.

In the case of carbazoles which are alkenyl-substituted in the 9-position and for which η has the value 1, a different preparation route is necessary in order to avoid the formation of products of the butadiene type instead of the desired 9- (3-butenyl) carbazoles. 9- (3-butenyl) carbazole is z. B. prepared by first reacting an alkali metal substituted carbazole as previously described with a 1,4-dihalogenated butene in which the halogen atoms can be chlorine, bromine or iodine or any two of these three halogen atoms.

The substitution reaction is carried out under anhydrous, non-oxidizing conditions to form a carbazole substituted by a monohalogenated butyl group, such as 9- (4-chlorobutyl) carbazole or 9- (4-bromobutyl) carbazole. Thus, for example, anhydrous Natriumcarbazol in anhydrous tetrahydrofuran under a nitrogen atmosphere with anhydrous 1,4-dichlorobutane in anhydrous tetrahydrofuran at 70 ⁰ C for 18 hours with stirring reacted to prepare 9- (4-chlorobutyl) carbazole.

This product is then, preferably using a metal alkoxide such as Potassium tert-butoxide, and under reflux conditions under anhydrous, non-oxidizing conditions, converted to the desired 9- (3-butenyl) carbazole. For example, anhydrous 9- (4-chlorobutyl) carbazole under a nitrogen atmosphere at reflux temperature in anhydrous tert-butyl alcohol with Potassium converted to 9- (3-butenyl) carbazole. This process can also be applied to 9- (3-butenyl) carbazoles, the substituents, in particular alkyl and / or aryl and / or alkaryl substituents, on the butylene chain according to the formula given above.

Other methods of preparing the 9- (3-butenyl) carbazoles are also possible, for example by produces a dimethylamine derivative from 9- (4-monohalobutyl) carbazole, the amine obtained then oxidized and the oxide formed then pyrolyzed to the desired 9- (3-butenyl) carbazole. ■

Depending on the constituents of the polymerizable material, a homopolymer or a copolymer can be used are formed. In this way, a single type of the above-described 9-aJkenyl-substituted Carbazoles are polymerized to form a homopolymer. However, there can also be two or several kinds of the above-described 9-alkenyl-substituted Carbazoles are copolymerized to form a suitable copolymer. For example naeh ;; the process according to the invention, a copolymer can be produced, the poly-9- (4-pentenyl) -carbazole and poly-9- (5-hexenyl) carbazole in a ratio of 1 to 100 parts to 100 to 1 parts contains.

Block copolymers can also be formed. A block copolymer is a copolymer whose molecules consist of relatively long sections that belong to two chemical types, exist, the sections of one type alternating along the chain with sections of the second type. Accordingly, blocks of one type of the 9-alkenyl-substituted carbazoles described above with blocks of another type of the 9-alkenyl-substituted carbazoles described above along the polymer chain alternate. In a further polymerization reaction, an alkenyl-substituted one in the 9-position can be used Carbazole of the formula mentioned with another copolymerizable monomer, for example Pentene- (l), are reacted to form a copolymer, if desired a Can be block copolymer. The molecules produced by the process according to the invention Polymers can be in tactical or atactical form, depending on the particular one used Polymerization conditions.

The 9-position alkenyl-substituted carbazole is brought into contact with the catalyst and optionally other reaction components while it is dissolved or dispersed in a suitable medium, for example an aromatic solvent such as benzene or toluene, or a paraffinic solvent such as hexane. The polymerization temperature may be any suitable temperature, but it is usually relatively low, for example in the range between about -170 and + 100 ⁰ C, and the polymerization catalyst may be any suitable catalyst.

Substances which produce free radicals, for example, can be used as catalysts for the polymerization reaction Benzoyl peroxide in question. The Friedel-Crafts type catalysts, such as aluminum chloride, Boron fluoride, stannous chloride, are suitable for the process.

The polymerization reaction can also be carried out using Ziegler-Natta type catalysts be made. One such catalyst is a chemical complex made up of a halide a transition metal from the IV. to VIII. Group of the Periodic Table of the Elements and a Metal hydride or metal alkyl of a metal from I. to III. Group of the Periodic Table of the Elements is obtained. A typical example of a Ziegler catalyst is a complex of titanium trichloride and diethyl aluminum chloride. Such catalysts bring about a stereospecific polymerization atmospheric pressure and at a relatively low temperature. For example, diethyl aluminum chloride in a mixture with titanium trichloride in an M oil ratio of 25: 1 in the case of the invention Polymerization processes can be used. The 9-position alkenyl-substituted carbonazole monomer can be in any suitable concentration relative to the catalyst, for example in one Ratio of 10 to 200: 1 to 3 are present.

The polymerization reaction is terminated when the product has the desired average degree of polymerization from 10 to 1000.

The finished polymers are synthetic for a number of purposes, such as insulation Fibers, binders and adhesives, coatings are valuable and can also be used with selected sensitizers to new polymer-containing products, such as improved photoconductors, implemented will.

example 1
Preparation of 9- (4-pentenyl) carbazole

About 8.5 g of sodium carbazole, in 120 ml of anhydrous tetrahydrofuran (previously prepared by reaction of about 8.4 grams of carbazole in the same solvent with about 1.3 grams of sodium hydride 35 ° C for 1.5 hours under anhydrous conditions and under a nitrogen atmosphere) are at reflux temperature under anhydrous conditions and under a nitrogen atmosphere with 9 g of monohalogenated alkene, namely 5-bromopentene- (l), in 20 ml of anhydrous tetrahydrofuran Reacted for 20 hours with agitation, 6 g of 9- (4-pentenyl) carbazole being obtained.

Polymerization

About 4.7 g of this product are after separation from the solvent and unreacted Ingredients placed in 40 ml of benzene, the 2 millimole Contains titanium trichloride and 5 millimoles of ethyl aluminum chloride. The temperature of the reaction components is held for 72 hours at 50 ° C under non-oxidizing, anhydrous conditions until the Degree of polymerization is about 200. About 2.5 g of polymer are obtained. The polymer thus formed is then separated from the catalyst and the reaction medium by the following procedure: The product is added to a mixture of 20 ml of HCl in methanol (10 percent by volume of the product

ducts) and stirred for 5 minutes, after which the product is poured into a large amount of methanol and the mass is filtered. The purified product is a white, powdery, crystalline polymer in tactical form with the following properties: Viscosity number (intrinsic viscosity) = 0.40; Softening point = 170 ^° C .; 95% insoluble in boiling acetone; 95% insoluble in boiling heptane. This polymer is valuable for the production of electrical insulation and for the production of synthetic fibers for fibrous products.

In addition, the polymer can be converted into an improved photoconductor by adding the aromatic nucleus the same with an effective concentration of a sensitizer such as iodine Reaction is brought about; the product shows a sudden change in electrical conductivity Exposure to visible and / or ultraviolet light.

The poly-9- (4-pentenyl) -carbazole can also be sensitized with 2,5-diphenylquinone (in 3 weight percent concentration). In the sensitization reaction, the aromatic units of the polymer combine with the molecules of the sensitizer to form complexes and result in a product that shows a sudden increase in electrical conductivity when exposed to light in the visible range (blue) of the photospectrum. A film applied to an aluminum sheet was charged to 280 volts in the dark with a corona unit. Upon exposure to visible light radiation from a high pressure mercury arc lamp, the film lost 140 volts in 6 milliseconds; 'ti. half of its original span. As a result, this film is an effective photoconductor that acts as a variable resistor photosensitive to visible light.

In a corresponding manner was 9- (4-pentenyl) -carbazole at 50 ⁰ C with a diethyl aluminum chloride and titanium chloride (molar ratio 2: 1) Ziegler catalyst containing polymerized up to a polymerization degree of 500, wherein the weight ratio of the substituted carbazole to the catalyst 100 : 1 was.

45 Example2

Preparation of 9- (5-hexenyl) carbazole

About 55 g of 9-sodium carbazole, in 800 ml of anhydrous tetrahydrofuran (previously prepared by reacting about 55 g of anhydrous carbazole in the same solvent with about 9 g of anhydrous sodium hydride at 25 ^° C. for 3 hours under anhydrous conditions and under a nitrogen atmosphere) are produced at reacted with 65 g of 6-bromo-1-hexene in 100 ml of anhydrous tetrahydrofuran for 20 hours with agitation at about 70 ° C. under anhydrous conditions and under a nitrogen atmosphere to give 36 g of 9- (5-hexenyl) carbazole.

Polymerization

About 5 g of this product, after separation from the solvent and unreacted constituents, are introduced into 40 ml of benzene which contains 2 millimoles of titanium trichloride and 5 millimoles of ethylaluminum chloride as a polymerization catalyst. The reaction components are not held oxidizing, anhydrous conditions at a temperature of 70 ⁰ C for 72 Stunden'unter, amounts until the degree of polymerization about 200th 2.6 g of polymeric product are obtained. The polymer formed in this way is then separated from the catalyst and the reaction medium according to the procedure given in Example 1.

The white powdery product is a crystalline polymer in tactical form with the following properties: viscosity = 0.46; Softening point = 180 ^° C .; 91% insoluble in acetone and heptane. This polymer is valuable for the production of electrical insulation.

In addition, the polymer can be converted into a photoconductor by adding its aromatic core with a selected sensitizer, for example iodine, is made to react, so that the product an increased sensitivity to light in the visible and / or near ultraviolet range of the Has photo spectrum.

Example 3

A mixture of 2.35 g of 9- (4-pentenyl) carbazole and 2.5 g of 9- (5-hexenyl) carbazole is placed in 30 ml of benzene containing 2 millimoles of titanium trichloride and 5 millimoles of ethylaluminum chloride as a polymerization catalyst. The reaction components are kept for 72 hours at a temperature of 50 ° C. under anhydrous, non-oxidizing conditions until the degree of polymerization is about 180. 2.9 g of polymer are obtained. The polymer formed in this way is then separated from the catalyst and the reaction medium according to the procedure given in Example 1. This product is a white powder with the following properties: Softening point = 160 " ¹ C; extremely poorly soluble. This polymer can be used, among other things, for the production of synthetic products, electrical insulation and improved photoconductors.

Example4

5 g of 9- (4-pentenyl) carbazole are introduced into 50 ml of benzene which contains 1% benzoyl peroxide. The mixture is kept at a temperature of 700 ^° C. for 24 hours under anhydrous, non-oxidizing conditions until the degree of polymerization is about 10. 3.5 g of a polymer are obtained, which is separated from the catalyst and the reaction medium by repeated washing with large amounts of ethyl alcohol.

The product is an amorphous atactic polymer with a viscosity number of about 0.03.

Example 5

Preparation of 9- (22-TricosenyI) -carbazole

About 8.5 g of 9-sodium carbazole, in 120 ml of anhydrous tetrahydrofuran (previously prepared by reacting about 8.4 g of carbazole in the same solvent with about 1.3 g of sodium hydride at 23 "C for 1.5 hours under anhydrous, non-oxidizing conditions ) are reacted under anhydrous, non-oxidizing conditions at about 70 ¹ C with 24 g of 23-bromo-1-tricosene, which is in 40 ml of anhydrous tetrahydrofuran, for 20 hours with agitation.

109 582M08

Polymerization

10 g of this product are placed in 80 ml of benzene containing 2 millimoles of titanium chloride and 5 millimoles of ethylaluminum chloride. The reaction components are kept at a temperature of 70 ^° C. under anhydrous, non-oxidizing conditions for 72 hours until the degree of polymerization is about 100. About 6 g of polymer are thus formed, which is then separated off from the catalyst and the reaction medium using a procedure as described in Examples 1 and 2.

Maintained anhydrous, non-oxidizing conditions until the degree of polymerization is about 100. About 2.5 g of polymer are obtained, which is then from the catalyst, the monomers and the The reaction medium is separated off according to the procedure described in Example 1.

The powdery white product is a crystalline polymer in tactical form that the has the following properties: viscosity number ίο = 0.2; extraordinary in common organic solvents difficult to dissolve. This polymer is for the purposes indicated generally in Example 1 useful.

Example 6

About 8.5 g of 9-sodium carbazole, in 120 ml of anhydrous tetrahydrofuran (previously by reacting about 8.4 g of carbazole in the same solvent with about 1.3 g of sodium hydride at 23 ° C for 1.5 hours under anhydrous, non-oxidizing Conditions established) are ^{reacted at about 70 0} C with 18.5 g of 2-phenyl-II-bromundecen- (l), which is present in 60 ml of tetrahydrofuran, for 20 hours with agitation under anhydrous, non-oxidizing conditions, with 12 g of 9- (10-phenyl-10-undecenyl) -carbazole can be obtained.

Polymerization, / " ¹ .

This product is introduced in an amount of about 5 g in 60 ml of methylene chloride, the 0.2 g of boron trifluoride etherate The reaction components are 6 hours at a temperature of -78 ° C ,; kept under anhydrous, non-oxidizing conditions until the degree of polymerization is about 12. The polymerization is then terminated by adding ammonium hydroxide to the reaction mixture. The polymer formed in this way is then affected by the catalyst, the monomer and the reaction medium washed neutral by repeated treatment with methanol and dried. This Polymer is suitable as a component for an improved photoconductor and as a material for electrical Isolations.

Example7 ^ ₅

About 5 g of 9- (4-pentenyl) -carbazole are in 50 ml Introduced n-heptane, the 2 millimoles of titanium trichloride, 5 millimoles of ethylaluminum chloride and 0.05 millimoles Contains zinc diet. The reaction components are 72 hours at a temperature of 50 ° C under

Example 8

Poly-9- (4-pentenyl) -carbazole with a degree of polymerization of about 70 is according to the procedure of Example 7 using the same ingredients and concentrations as prepared with Exception that there is no zinc diet and instead 20 ml (normal pressure) of hydrogen are introduced the reaction being carried out in an autoclave. Under anhydrous, non-oxidizing Conditions, the temperature of the reaction components is kept at 70 ° C for 24 hours, until the monomer multiplication is about 70. About 2 g of polymer are obtained. The cleaned Polymer has a viscosity number of 0.15.

Example 9

A mixture of 2.5 g of 9- (4-pentenyl) carbazole and 2.0 g (1-pentene is placed in 30 ml of benzene and implemented according to the procedure given in Example 3, the same concentrations of the same Catalyst and the same time and temperature are applied. About 2.8 g of product are obtained and cleaned in the manner indicated in Example 3. The purified product has a degree of polymerization of 150 and is a copolymer of poly-9- (4-pentenyl) -carbazole and poly-1-pentene.

The manufacturing process according to the invention is simple and quick and provides the desired polymers Products in high yield. The physical properties of such products can be easily identified Selection of the particular reaction components and reaction parameters are controlled; so can for example the molecular weight under Ziegler-Natta polymerization conditions controlled by the use of hydrogen and zinc diethyl. Other advantages have already been mentioned.

Claims (1)

Patent claims: 1. Process for the preparation of polymers and copolymers of 9-alkenyl-substituted Carbazoles by polymerization of 9-alkenyl-substituted carbazoles in the presence of Solvents and polymerization catalysts, characterized in that 9-alkenyl-substituted carbazoles are those of the formula 3. The method according to claim 1, characterized in that one 9- (5-hexenyl) carbazole the formula