DE2447270A1 - METHOD FOR MANUFACTURING FUNCTIONAL, UNSUBSTITUTED OR SUBSTITUTED 2-ANTHRYLIC MONOMERS AND POLYMERS AND THEIR USE - Google Patents

Description

25 950 i / wa

XEROX CORPORATION, ROCHESTER, N.Y./USA

Process for the production of functional, unsubstituted or substituted 2-anthryl monomers and polymers and their uses

The invention relates to processes for the preparation of functional, unsubstituted or substituted 2-anthryl monomers and polymers, their addition products, their use in electrophotographic imaging elements and imaging methods using the compounds prepared according to the invention. In particular

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The invention relates to a process for the preparation of functional _f unsubstituted or substituted 2-anhydric monomers in high yield. The monomers prepared according to the invention can be polymerized to polymers with high molecular weight (M> 10 with a degree of polymerization of about 40 or higher). These polymers can easily be made into self-supporting films that exhibit specific photoconductivity in the ultraviolet region of the electromagnetic spectrum.

The formation and development of images on the image layers Photoconductive materials using electrostatic devices is known. That commercially the best known technique is commonly known as xerography. This procedure concerns the Formation of an electrostatic latent image on the imaging layer of an imaging member in which first the surface of the imaging layer is evenly charged electrostatically in the dark and then this electrostatically charged surface is exposed to the action of a light and shadow image. The ones struck by the light Areas of the imaging layer are thus made conductive and the electrostatic charge in these is irradiated Areas selectively dispersed. After the photoconductor has been exposed, the electrostatic latent image will appear this, the image-bearing surface through development with finely divided, colored electroscopic material, which is commonly known as "toner", made visible. This toner is basically made up of the areas on the surface carrying the image, which retain the electrostatic charge, so that a visible Powder image arises.

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This developed image can then either be scanned or permanently fixed on the photoconductor and in those cases in which the imaging layer is not to be used repeatedly. The latter practice is generally used with respect to binder-type photoconductive films (i.e., zinc oxide pigment in a film-forming film Insulating resin), in which the photoconductive The imaging layer also constitutes an integral part of the finished copy. In the so-called copier systems with "plain paper {. ' can the latent Imaging developed on the imaging surface of a reusable photoconductor or on another surface, such as a sheet of paper, can be transferred and then developed. When the latent image is on the imaging surface A reusable photoconductor is developed, it is then transferred to another substrate and then permanently fixed on it. Any variation of the known methods can be used to achieve the To permanently fix the toner image on the copy sheet, such as overlaying with transparent films or the solvent or heat fusion of the toner particles onto the substrate carrier.

In the copier systems mentioned above with coated paper Preferably, the materials used in the photoconductive layer should be capable of moving from insulating to conductive Quickly change the isolation state to allow cycling of the imaging layer. The absence of the material to return to the isolation state before the subsequent imaging sequence leads to an increase the dark decay rate of the photoconductor. This phenomenon, aas

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is generally referred to in the literature as "fatigue" has hitherto been avoided by using photoconductive Materials were selected that had the ability to change quickly. Typical materials which are suitable for use in such fast cycling imaging systems are, for example Anthracene, sulfur, selenium, and mixtures thereof (US Pat. No. 2,297,691), selenium being particularly good because of it Photosensitivity is preferred.

Up to now, the use of anthracene in photoconductive insulating layers has been limited exclusively to the use of the crystalline form of this material in a binder, because it has hitherto been practically impossible to produce functional anthracene polymers with a high molecular weight. For example, attempts have been made to synthesize high molecular weight anthracene polymers from 9-vinylanthracene by free radical polymerization processes ₍ but generally only oligomers were obtained. Attempts by cationic polymerization of the same monomers only resulted in low molecular weight materials of questionable structure; probably one Mixture of low molecular weight polymer materials containing structural units of 9-vinyl anthracene and 9,10-dimethylene anthracene. A danionic polymerisation of 9-vinyl anthracene likewise only leads to oligomers with a degree of polymerisation in the range from about 4 to 12. Attempts, 9-vinyl anthracene with other monomers such as styrene, apparently did not improve the Chaneen.polymeric high molecular weight products Obviously, resonance stabilization of the anthracene-free moiety is preferred among those during the

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Polymerization prevailing conditions, the formation of a non-multiplying residue, whereby the further growth of the polymer chain is prevented, see A. Rembaum et al, Macromol Rev. V ₁ 57 (1.967) .-

Attempts to make homopolymers from 2-vinyl anthracene and 1-vinylanthracene, as well as styrene copolymers of it, were equally inconclusive; it only led to low molecular weight Products.

Recently, the synthesis of copolymers from 9-anthryl ethyl acrylate and methyl methacrylate led to limited success; see Vysokomolekulyarne Soedineniya A14 (5): 1127-31 (1972). The anthracene function of these copolymers (generally less than 1%) produces luminescent markings (Scintilators) that study the relaxation properties and support conformational transformation of methyl methacrylate. Other copolymers, the anthracene groups were also produced, such as polycondensates, formaldehyde resins and oligoarylene. All these polymeric products, however, have relatively poor mechanical properties and cannot easily become self-supporting Movies are converted.

The invention is based on the object of eliminating the above-mentioned and related deficiencies in the known systems.

In particular, the object of this invention is a method for the production of anthracene monomers in high yields.

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Another object of the invention is the preparation of anthracene monomers that are easy to high molecular weight functional anthracene polymers are polymerized can.

Another object of the present invention is to provide a process for polymerizing such anthracene monomers to find functional anthracene polymers.

It is a further object of the invention to provide high molecular weight scintillating polymers with an anthracene function.

Finally, a further object of the invention is to provide functional anthracene polymers that are used for Use in photoconductive imaging elements and for electrostatic imaging processes are suitable.

According to the invention are those specified above and the therewith related problems solved in that a process for the production of unsubstituted and substituted functional 2-anthryl monomers of the following formulas: Monomers of the formula

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in which R is hydrogen or an alkyl group with 1 to about 3 carbon atoms, and X and Y independently of one another are hydrogen, chlorine, bromine, an alkyl group with 1 to 4 carbon atoms or the phenyl group, as well as monomers of the formula

O R "

Il I ^

C - C = CH,

in which R _{1 is} hydrogen or an alkyl group having 1 to 6 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms and X and Y are independently hydrogen, chlorine, bromine, an alkyl group having 1 to 4 carbon atoms or the phenyl group.

In this process, a nitrobenzene dispersion, which is a reactive anthracene derivative of the formula

in which X and Y independently of one another are hydrogen, chlorine, bromine, an alkyl group having 1 to 4 carbon atoms or

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represent the phenyl group,

contains, brought into contact with a further solution which contains a complex of an acylating agent and a Lewis acid at a temperature of about 5 to about 50 ^° C. until the acylation of at least part of the reactive anthracene derivative in the 2- Position has taken place. The relative molar ratio of the acylating agent to the Lewis acid in the separate solution is preferably 1: 3 (for the case that the acylating agent is acetic anhydride) or 1: 1 (for the case that the acylating agent is an acid or an acid chloride ). The relative molar ratio of the acylating agent to the reactive anthracene derivative is preferably 2: 1 or slightly above. The acylated anthracene derivative is then further modified at the carbonyl group to produce a functional 2-anthryl or a substituted 2-anthryl addition monomer. The methods and reactants used for such modification will vary with the specific addition monomer desired.

Prior to making such monomers, two separate mixtures are made; one contains the reactive Anthracene derivative and the second contains a complex of a Lewis acid and an acylating agent. The relative Lewis acid to acylating agent molar ratio in such mixtures can range from about 0.5: 1 to vary about 5: 1, with best results being obtained using a slight excess of an equimolar amount the Lewis acid is present. It is essential that one

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constant ratio of Lewis acid to acylating agent maintained in the presence of the reactive anthracene derivative is used to produce reproducible high yields of the acylated Product '. Typical examples of Lewis acids, which can be used in the second solution are, for example, aluminum chloride, aluminum bromide, Phosphorus (III) chloride, iron (III) chloride, tin tetrachloride, Titanium tetrachloride, boron chloride, zirconium tetrachloride and sodium aluminum chloride. Examples of acylating agents which can be suitably interacted with the above-mentioned Lewis acids Can be converted into complexes are, for example, acetic acid, acetic anhydride and acetyl chloride.

The relative molar ratio of acylating agent to reactive anthracene derivative must also be carefully adjusted so that the reaction equation the acylation of the reactive anthracene derivative in favored the 2 position. Good results have been obtained when the molar ratio of acylating agent to reactive Anthracene derivative ranges from about 1: 1 to about 5: 1, and preferably about 2: 1. Recommendable it is also to reduce the volume of nitrobenzene in the reaction medium to the minimum amount required to dissolve the reactive anthracene derivative and the Lewis acid / acylating agent complex is necessary to limit. The presence of excess amounts of nitrobenzene can lead to some loss of acylated product, because of the problems of isolating this product from the solvent. In general, the volume of nitrobenzene preferably to about 600 to about 1500 ml of solvent / 150 g of reactive anthracene derivative limited, this being

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Amount includes the amount of nitrobenzene that is necessary is to get the two solutions, the one being the reactive Anthracene derivative and on the other hand contain the complex of Lewis acid and acylating agent.

In addition to the use of nitrobenzene alone, solvent mixtures which mainly contain nitrobenzene can also be used (in excess of 50% by volume) and other organic liquids can also be used as a medium in which the acylation of the reactive anthracene derivative is carried out. If other solvents are in the reaction medium are introduced, however, the selectivity of the acylation in the 2-position decreases rapidly and progressively. Examples of solvents that can be used in combination with nitrobenzene as a medium for carrying out the acylation of the reactive anthracene derivative Carbon tetrachloride, carbon disulfide and chloroform. However, the yields of the desired product show a noticeable drop. Subsequent to the preparation of the separate solutions, on the one hand the reactive anthracene derivative and on the other hand the complex of Lewis acid and acylating agents, the two solutions are combined by adding the solution containing the Lewis acid / acylating agent complex contains, gradually to the solution containing the reactive anthracene derivative, is added within about 15 minutes to about 60 minutes. After the union of the two solutions is complete, the reactants contained therein are left for an additional period of time react from about 1 to 20 hours. The temperature of this combined solution will be within a range of

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about 5 to about 50 ° C, and preferably within a range from about 10 to about 30 ° C during mixing and reacting of the reactants in the two solutions held.

It is also recommended, although not critical, to carry out the acylation reaction under an inert, non-oxidizing one Atmosphere. Because of the photosensitive The nature of such anthracene substances should also protect the reaction mass from activating electromagnetic radiation to be protected. The acylation reaction is terminated by adding an acylated anthracene reactant / Lewis acid complex from the nitrobenzene solution by adding a solvent in which this complex 'is insoluble, precipitates into the reaction mixture. Solvents suitable for precipitating such materials, are for example benzene, toluene and carbon tetrachloride. The volume of the used to precipitate the complex Solvent must be carefully controlled in order to avoid precipitation of the product in the form of oil to complicate the extraction of the product. The precipitated complex is then decomposed with the aid of aqueous hydrochloric acid and then dried the product. The acylated product thus obtained (hereinafter referred to as intermediate) is made by recrystallization from ethanol, benzene or a further purified using other suitable solvents.

The intermediate prepared as described above can now on carbonyl oxygen through a variety of Reactions can be modified depending on the specific monomer desired. For example, can

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Öj-alkyl vinyl monomers corresponding to formula I, by simply reacting the carbonyl group of the functional anthracene derivative with an alkylidene phosphorane according to the procedures as described by Wittig and co-workers, Ber. 87., 1318 (1954) and Ber. 88_, 1654 (1955) will be made. On the other hand, the intermediate described above can also lead to the corresponding alcohol be reduced, the intermediate product first in a suitable organic solvent, such as lower alkyl alcohols, tetrahydrofuran, ether or diglyme. is dispersed. This dispersion is then with a reducing agent such as sodium borohydride, potassium borohydride, lithium aluminum hydride / Aluminum chloride or lithium aluminum hydride / boron fluoride with the borohydride reducing agents generally preferred. The relative molar concentration of Intermediate product to reducing agent should be at least 1: 1 and preferably with an excess of equimolar Amounts of the reducing agent lie. After completing the addition of the reducing agent to the solution with the intermediate product the resulting mixture is refluxed for about 4 hours heated to boiling and then opened the reflux condenser to remove volatile solvent. The remaining solids in the reaction vessel are after the evaporation of the solvent to room temperature cooled and then brought into contact with aqueous hydrochloric acid in order to remove residual traces of reducing agents may be present in the isolated product. The solid reaction product obtained in this way can be obtained from this acidic solution can be separated either by filtration or by extraction with ether, the solids according to known methods can be isolated from the extractant.

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Monomers corresponding to formula I can be prepared from this anthracene alcohol by at least two suitable processes. For example, the alcohol can first be reacted with a metal halide or an acid halide (i.e. thionyl chloride), the hydroxyl group of the alcohol being replaced by a halogen atom. After such exchange, the obtained functional, halogenated anthracene compound in a basic solution (ie, Li ₂ COo i ⁿ dimethylformamide) is heated for a time sufficient to the elimination of hydrogen halide and thus the formation to cause the vinyl analogs. A second way that can be used to convert the alcohol to the vinyl monomer involves simply heating the alcohol over a palladium catalyst for a period of time sufficient to generate hydrogen; .. to be carried out.

Monomers corresponding to the formula II can be obtained from the above-mentioned anthracene alcohol by condensation d ^ -Älkylacryloylhalogenids with the alcohol in a suitable Solvents such as dioxane can be produced. It is recommended that a small Amount of triethylamine present in the solution is less than that formed during the condensation of these materials To absorb acid and with it the subsequent hydrolysis of the desired reaction product as soon as it has formed. In the event that one or If several of the above-mentioned materials are not readily soluble in the reaction medium, this medium may gradually be heated until all of the reactants are completely dissolved. It is also recommended that the relative

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Concentration of CK / -Alkylacryloylhalogenid to anthracene alcohol is adequate to cause substantially complete condensation of the two materials. Quality Results are obtained when equimolar amounts of the two reactants are present in the solution, and especially if there is a slight molar excess of ck / -alkylacryloyl halide is present. Upon completion of the addition of the reactants to the reaction medium, it begins to form the monomer itself, as evidenced by the appearance of a precipitate at the bottom of the reaction vessel will. The reaction can continue for up to about 24 hours, after which it is stopped by adding water to the reaction medium. The addition of water does one increased failure of monomers). Unresponsive C ^ - Acryloyl halide dissolves in the water and can thus be easily separated from the monomeric product. Monomers Solids can then be obtained from the reaction medium by filtration, dried and made from a mixture of benzene / Hexane are recrystallized.

It is both essential and critical that the monomers prepared according to the methods described above a way can be isolated that the oxidation of the functional groups of the anthracene or substituted Anthracene kept to a minimum. This can be achieved by the failure, the separation and the Recrystallizing these monomers under an atmosphere of an inert, non-oxidizing gas such as Argon or nitrogen. After the desired monomeric materials are obtained, they are either in vacuo or under an inert, non-oxidizing atmosphere

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kept. Before the polymerization of such monomers are they are further purified to remove oxidation products. To guarantee that the monomer is free from Oxidation products of the functional groups of anthracene or of the substituted anthracene are, is one Passed solution of the monomer through a column with activated neutral or basic aluminum oxide, the pure monomers collected and the eluent evaporated therefrom in vacuo. Such cleaning procedures must also be carried out in a non-oxidizing atmosphere.

The vinyl monomers produced (formula I) , produced as described above, can be polymerized in a non-oxidizing atmosphere by means of anion or cation polymerization triggered by free radicals. Initiator compounds suitable for use in such free radical-initiated addition polymerizations are, for example, various peroxides or azobisisobutyronitrile and analogous initiators. Particularly good polymers can also be obtained by anionic polymerization of these monomers. In general, such anion polymerization systems are preferably kept at a temperature below about ⁰ ° C. in order to avoid inhibition processes which generally occur at higher temperatures. In addition, such polymerizations are preferably initiated with the aid of an "addition type" initiator. Cation polymerization is the least preferred polymerization of the three systems because of the relatively low molecular weights of the resulting polymers.

Acrylate monomers corresponding to formula II can according to known addition polymerisation triggered by free radicals

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tion process to be processed into polymers. It understands that the conditions within the reaction vessel should remain essentially free of oxygen until the monomer is substantially completely polymerized. Many of the peroxide initiators traditionally come in by free Free radical initiated polymerization systems are known to reduce the hydrogen secretion of such To influence acrylate polymers, which creates a crosslinking of these materials. That is why it is made by free Radial addition polymerization of these monomers, preferably with azobisobutyronitrile and analogous initiators carried out.

Once the polymer resins are made, they are separated from their respective polymerization media and dried. These resins can then easily be dissolved in a number of organic solvents such as tetrahydrofuran, Dimethylformamide, toluene, cyclohexanone or their corresponding solvent mixtures can be dissolved and the solutions obtained are sprayed, drawn on or onto a suitable (preferably conductive) substrate can be applied by dipping and / or melting. The ease with which such polymers in the above organic solvents mentioned are dissolved, is one of the unique characteristics of the according to the invention Process produced polymers. The amount of polymer that is applied to the substrate can be varied with the intended use of the film. After the substrate is coated with these materials the resulting film is dried until it is essentially free of residual solvent. In the case,

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that the polymer solution by spraying onto the substrate has been applied, the dry film obtained may have a rough surface texture. Such a rough surface can be removed by simply heating this polymer layer until it flows.

The amount of polymer applied to such substrates is carefully controlled to ensure that the coatings obtained are both coherent and have a substantially uniform film on the carrier element form. In general, when applying by dip painting, the film thickness is determined by adjusting the viscosity the coating solution and / or by controlling the temperature and humidity of the conditions after coating In the event that the polymer layer is solvent-poured with a polymer solution onto a carrier element mechanical devices can be used to adjust the viscosity in addition to the Control film thickness of the polymer layer. For example, the 'use of a doctor blade with a Wet gap settings of about 0.0125 cm (0.005 inches) help spread the resin dispersion on a substrate and thus to guarantee that the film thickness of the coating obtained does not exceed a dimension of about 15 microns. Films made from such polymeric materials having a thickness ranging from about 0.1 to about 300 microns, can be used in known electrophotographic imaging elements as either the carrier generating element Element or as an electronically active matrix for the transport of charge carriers by others photoconductive materials are generated, used

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will; is the separation into carrier and transport producer in GB-PS 1 337 228 and 1 343 671.

Practically all commonly used conductive, self-supporting substrates used in the manufacture of electrophotographic imaging members can be effectively associated with such films. Typical examples of conductive materials, which can be used with satisfactory results as substrates for such imaging elements for example aluminum, chrome, stainless steel, brass, copper, berrylic copper, corresponding alloys thereof, metallized plastic films, plastic films coated with metals (i.e. polyethylene terephthalate, coated with aluminum in a vacuum) and glass substrates, which are conductive Have oxide layers.

As indicated above, films made from these polymer preparations are photoconductive in the ultraviolet region of the electromagnetic spectrum. In order to shift the photoreactivity of such materials into the visible region of the spectrum, such polymers can be ^{sensitized by the addition of a dye or an activator (ie an electron donor;} and / or electron acceptor). The concentration of such sensitizers within the polymer must be sufficient to extend the absorption of such materials into the visible range. Generally from about 0.1 to about 10% by weight of such sensitizers is sufficient to effect such enhancement in spectral responsiveness.

To the physical and / or electrical properties

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to reinforce the polymers according to the invention or to It may also be desirable to modify one or more of the above monomers with one not to copolymerize anthracenic monomers. The copolymer obtained will of course vary with the relative reactivity ratio the monomers that are present in the batch and the manner in which such Polymerization is carried out. For example, many can the above-mentioned anthracene polymer segments are copolymerized with elastomers to improve the flexibility of a film reinforce from such materials.

The following examples define, describe and illustrate the various methods according to this invention and the products made in the process even further. The apparatus and process conditions used in these processes, as well as the evaluation of the corresponding products was carried out according to known methods or according to methods as described above. Parts and percentages, those given in the examples are on a weight basis unless otherwise stated.

Example I.

In a 5 l flask containing 150 ml of nitrobenzene were dispersed about 150 grams (0.84 moles) of anthracene. The container and its contents were purged of air with the aid of nitrogen and then cooled to about 15 ° C. In to a separate vessel containing 500 ml of nitrobenzene was given 255 g (1.9 moles) of anhydrous aluminum chloride

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dispersed. This aluminum chloride solution became slow 150 ml (1.6 mol) of acetic anhydride are added. The aluminum chloride solution became during the addition vigorously stirred. The aluminum chloride / acetic anhydride complex that was produced in this way was now mixed with the Anthracene dispersion combined by adding the complex gradually dropwise over about 1 hour was added to the anthracene dispersion. The temperature of the resulting mixture became about 15 ° C after completion the addition held. After 18 hours, the reaction of these materials was stopped by the addition of approximately 1800 ml dry benzene terminated to the combined solution. The reaction mixture was stirred for a further 4 hours, the precipitated complex contained therein, separated from the liquid by filtration, with about 200 ml Washed benzene and then washed again with a larger amount of hexane. The solid complex was now hydrolyzed with the help of a dilute acid solution (2% hydrochloric acid), the product obtained by filtration separated from the hydrolyzed medium until it is neutral Reaction washed with water, dried and, after carbon treatment, from a mixture of benzene and hexane recrystallized. The product thus obtained, namely 2-anthryl methyl ketone was a yellow-green powder with a melting point of 188 ° C. The yield was 98 g.

Example II

The criticality of the formation of the complex between the Lewis acid and the acylating agent prior to admixture

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to demonstrate the anthracene, the procedures of Example I were repeated, except that a separate addition of acetic anhydride and aluminum chloride to the anthracene dispersion was made.

About 150 g of anthracene were placed in a reaction vessel Contained 200 ml nitrobenzene and 150 ml acetic anhydride, dispersed. The mixture was cooled to about 15 ° C and both the reaction vessel and its contents are washed free of air with the aid of nitrogen. In a separate The vessel was dissolved in 255 g of anhydrous aluminum chloride in 500 ml of nitrobenzene. This aluminum chloride solution was added dropwise to the vessel containing the mixture of anthracene and acetic anhydride. During the encore the contents of the reaction vessel were constantly stirred. After completing the addition of the aluminum chloride solution to the Reaction vessel, the contents of the reaction vessel became stirred for a further 18 hours at 15 ° C. The one through the Reaction of the materials formed complex within the reaction vessel was removed from the solution by adding 1800 ml of dry benzene precipitated. After 4 hours, the precipitation of the complex is complete and this has become separated from the reaction medium by means of filtration, dried and, after a carbon treatment, from a mixture recrystallized from benzene and hexane. The melting point was 187 to 188 ° C, the yield was 8 g.

This clearly proves that the separate addition of the Lewis acid and the acylating agent to the reactive Anthracene compound the yield of the to be produced Product dramatically reduced.

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Example III

The procedures according to Example II were repeated and with the same amounts of reactants and under the same conditions. The product obtained had a melting point of 187 to 188 ° C, the yield was 35 g.

Example IV

Example II was repeated with equal amounts of reactants under the same conditions. Of the The melting point of the product thus obtained was 187 bis 188 ° C, the yield was less than 1 g.

A comparison of the results from Examples II, III and IV shows that the reproducibility of the reaction, especially with regard to the yield of the desired product, is not given if the Lewis acid and the acylating agent separately from the reactive one Anthracene derivative can be added.

Example V

The procedure of Example II was essentially repeated, except that for nitrobenzene benzene as Reaction medium was used.

About 89 g (0.5 mol) of anthracene were in a reaction

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vessel containing 500 ml of benzene and 113 ml (1.5 mol) of acetyl chloride contained, dispersed. 200 g of anhydrous aluminum chloride were added in small amounts for about 1 hour added to the reaction vessel. The resulting mixture was stirred in an ice bath for about 90 minutes and then increased the temperature to about 25 ° C. The contents of the reaction vessel were stirred for a further 18 hours, the reaction of the materials terminated by adding ice water, the reaction product with the help of benzene extracted, washed with water and dried. The benzene remaining in the product evaporated during drying; Acetophenone residues remaining in the product were removed in vacuo. The product thus obtained was used twice from a mixture of heptane and benzene in a ratio of 10: 1 with the addition of charcoal and then again twice recrystallized from ethanol. There were 5 g of 2-anthryl methyl ketone obtained with a melting point of 185 to 186 ° C.

It was thus possible to show that the exchange of benzene for nitrobenzene according to Example II also leads to yields leads that are significantly lower than those obtained according to Example I, and that further impurities were present in the product to be manufactured, which had to be specially separated and removed.

Example VI

The procedure according to Example I was repeated, except that instead of 255 g of aluminum chloride only

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127 g of aluminum chloride were used. There were 27.5 g of 2-anthryl methyl ketone with a melting point of Preserved 187 ° C.

This example shows that the relative concentration of aluminum chloride is critical for the yield of the product to be produced Product, since a 50% reduction in aluminum chloride results in an approximately 75% reduction in Yield of the product to be produced led.

Example VII

The procedures according to Example I were repeated, except that the relative concentration of acetic anhydride in the acylation complex was changed and that was, from (150) 155 ml reduced to 80 ml. There were 45 g of 2-anthryl methyl ketone obtained with a melting point of 187 to 188 ° C.

This example shows that the yield of the product is roughly directly proportional to the concentration of the for this formation of the acylating agent complex used is acetic anhydride.

Example VIII

About 53 g of the product obtained according to Example I were placed in a 3 l vessel containing 1800 ml of ethanol,

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the reaction vessel and its contents with the help of Freed of air from nitrogen, heated to boiling under reflux conditions and treated with 25 g of sodium borohydride in 280 ml Water slowly decomposes. The mixture became increasingly homogeneous after about two thirds of the total borohydride solution were admitted. The solution was refluxed for about 2 hours, the volume by evaporating one off Part of the ethanol reduced by a third and the product contained in it by precipitation with the help of a slightly acidic, aqueous solution isolated. The precipitated product was separated off from the reaction medium with the aid of filtration, washed with water, dried and recrystallized from benzene with the addition of charcoal. There were 50 g of 0, - (2-anthryl) ethanol with a melting point of 164 ° C.

About 50 g of (V (2-anthryl) ethanol were dissolved in 600 ml of anhydrous benzene and heated to boiling under reflux conditions. 20 ml of thionyl chloride were added to this boiling solution. The addition of thionyl chloride to the alcohol solution was initially slow and then faster, while the materials began to react. After the addition of thionyl chloride, the reaction vessel was purged with nitrogen and the contents of the vessel heated under nitrogen for a further 3 hours, cooled to room temperature and poured into about 1.2 liters of petroleum ether Ether filtered off, washed with additional amounts of petroleum ether and recrystallized from a solvent mixture of benzene and hexane, giving 46 g of pale green powder of (^ j- (2-anthryl) chloroethane with a melting point of

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170 to 178 ° C (with decomposition) obtained.

350 ml of dimethylformamide, which contained 25 g of lithium carbonate, were mixed with about 45 g of ck> - (2-anthryl) chloroethane. The reaction vessel containing this mixture was purged of air with the aid of nitrogen, heated to 130 ° C. and kept at this temperature for about 4 hours. The contents of the reaction vessel were then poured into a very dilute solution of aqueous hydrochloric acid. The product thus obtained was filtered off from the acidic medium, dried and recrystallized three times from solvent mixtures of benzene and hexane, after treatment with charcoal. 30 g of a yellow powder of 2-vinyl anthracene with a melting point of 210 ° C. were obtained.

After the preparation, the 2-vinylanthracene was recrystallized at least once again from a mixture of benzene and hexane, dissolved in a degassed mixture of benzene and hexane and passed through a column with basic aluminum oxide, which was protected from light, passed through. The monomer is eluted with degassed benzene and that Eluent collected in a light-tight ampoule under an argon atmosphere. The protected ampoule that cleaned it Contained monomers, a vacuum was applied, the solvent evaporated therefrom and the ampule melted and sealed. The monomer can thus be stored without being adversely affected, provided that it is protected from light protected (especially from ultraviolet light).

The monomers in the ampoule (about 1 g) can be added according to known addition-

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polymerization process are polymerized by adding a solution containing 8 ml of xylene (which was previously passed through a column of activated aluminum oxide and cleaned by subsequent degassing) and 0.05 ml of di-t-butyl peroxide To be injected through a side arm of the ampoule * Argon gas is used to infuse the xylene initiator solution back into the ampoule. After infusing the above materials into the ampoule, the The ampoule is placed in liquid nitrogen, after which the solution it contains freezes and the remaining gases inside the ampoule can be removed by means of a vacuum. After the gas has been removed from the ampoule ■ this sealed again and heated for 48 hours at 115 ° C. The vial was then opened and the polymeric product precipitated with the aid of methanol, by filtration recovered, dried and recrystallized from a benzene solution containing methanol. 0.97 g of poly (2-vinylanthracene) obtain; the molecular weight M = 80,000 was determined according to gel permeation chromatography and light scattering methods certainly.

Example IX

The following example illustrates the cation polymerization of a monomer prepared according to Example VIII. Before the polymerization, 20 ml of methylene chloride (previously obtained by passing through a column of activated Alumina and cleaned by degassing) in a vacuum in a sealed, light-tight ampoule containing the contained about 2 g of 2-vinylanthracene, distilled. After this

contains

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the monomer was dissolved, about 1 ml of catalyst solution (0.2 ml of boron trifluoride etherate in 200 ml of methylene chloride, which had been cleaned in a similar way) was also inserted into the ampoule, the ampoule closed again and heating the combined solution to about 35 ° C. After about 48 hours of continuous heating and / or stirring, the polymerization was terminated and polymer solids precipitated by the contents of the ampoule in Methanol was poured. The precipitated solid polymers were filtered off from the methanol and with the aid of methanol reprecipitated again from benzene. 0.6 g of a yellow powder was obtained which had a molecular weight of 18,000 (determined by gel permeation chromatography).

Example X

The procedures according to Example IX were repeated, wherein however, the monomer before the polymerization attempt was exposed to air and diffuse room lighting for about 1 hour was exposed. The monomer could then not be polymerized.

Example XI

The following example illustrates the anion polymerization of a monomer prepared according to Example VIII. Before start the polymerization were 200 ml dry, oxygen-free Tetrahydrofuran was distilled in vacuo into a light-tight ampoule containing 3 g of 2-vinylanthracene. After this

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the monomer was dissolved, the ampoule and its contents were cooled to -78 ° C and about 5 ml of the initiator solution (5-10 mol sodium salt of ou-methylstyrene tetramer in tetrahydrofuran) was injected through a side arm of the ampoule into the ampoule. The polymerization of the monomer occurred when these two solutions were combined. After 5 days of continuous stirring at -78 ° C, the contents of the ampoule were poured into methanol to precipitate the polymer. The polymeric solids were then removed from the methanol by filtration and reprecipitated from benzene by the addition of methanol to remove impurities, residual monomer and low molecular weight fractions. The yield was 3.0 g of a white polymer with a molecular weight of 1,000,000 (M _w = 1,000,000, M _w / Mn 2.87J.

Example XII

The anion polymerization of 2-vinyl anthracene was repeated according to the procedure of Example XI with the following modifications: The polymerization temperature was increased from -78 ° C to -32 ° C and the reaction time was extended from 5 days to 20 days. The yield was 3.0 g of a white polymer with a molecular weight of 2,890,000 (M _w = 2,890,000 M _w / Mn 10.

Example XIII

The anion polymerization of 2-vinylanthracene according to the procedures of Example XI was repeated with the following

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Modifications: Before initiating the polymerization, the monomer was exposed to air and a diffuse one Exposed to room lighting for 1 hour. The monomer could then not be polymerized.

Example XIV Production of 2- (2-anthyl) propylene

16.6 g of triphenylmethylphosphonium bromide and 100 ml of tetrahydrofuran were placed in a 500 ml vessel which had been washed free of air with the aid of nitrogen. After the contents of the vessel had dissolved, the vessel was ^{cooled to 0} ° C. and 21 ml of a butyllithium solution (2.2 mol / l hexane) were added. The combined solution was ^{stirred under nitrogen at 0} ° C. for 16 hours and then slowly warmed to room temperature (about 20 ° C.). About 2 g of 2-anthryl methyl ketone (prepared * the method described in Example I) in 250 ml of tetrahydrofuran was then added to the above solution, the combined solution heated to boiling under reflux conditions and the volume increased by about 250 ml by controlled evaporation of the tetrahydrofuran within a Period of 90 minutes. The dark colored solution that remained in the vessel was cooled to room temperature and poured into an alcoholic solution (50:50 ethanol: water) to precipitate the monomer. Thereafter, "the monomeric solids were removed from the alcoholic solution by means of filtration, dried and reprecipitated from mixtures of hexane and heptane. 8.8 g of crude monomer was obtained. The monomer was obtained

* after

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further purified according to the method described in Example VIII. The monomer obtained, namely 2- (2-anthryl) propylene was obtained as a white powder with a melting point of 153 ° C.

About 100 ml of tetrahydrofuran were distilled in vacuo into a light-tight ampoule containing the above monomer, the ampoule was cooled to the temperature of dry ice (about -40 ° C) and about 5 ml of an initiator solution (5 10 mol of the sodium salt of o * - Methyls tyroltetramer en in Tetrahydrofuran) injected through a side arm of the ampoule into the ampoule. The polymerization of the monomer began when the initiator was introduced into the ampoule. After about 24 hours of continuous stirring at -40 ° C., the contents of the ampoule were placed in a vessel containing methanol, the polymerization reaction being interrupted and the polymer being precipitated. The polymeric solids were recovered from the methanol solution by filtration, dried and reprecipitated from benzene by adding methanol. 8.0 g of a white polymer with a molecular weight of 280,000 were obtained (M _w 280,000, M _w / Mn 1.74).

Example XV Production of poly (1 (2-anthryl) -methyl acid ethyl ester)

About 150 g (0.84 moles) of anthracene were dissolved in 150 ml of nitrobenzene dispersed. This dispersion was prepared in a reaction vessel equipped with an additional funnel, a Thermometer, a feed line for non-oxidizing gas

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and a magnetic stirrer. The dispersion was cooled to about 15 ° C. In a separate Containers were dissolved 255 g (1.9 moles) of aluminum chloride in 480 ml of nitrobenzene. About 155 ml (1.6 moles) of acetic anhydride were added dropwise to the aluminum chloride solution. The aluminum chloride solution became during the addition vigorously stirred. The temperature of this solution was carefully controlled, since the formation of the complex between is strongly exothermic to aluminum chloride and acetic anhydride. After the formation of this complex, the mixture becomes added to the addition funnel. The reaction vessel containing the anthracene dispersion was stirred vigorously and the aluminum chloride / acetic anhydride complex is added dropwise over about 60 minutes. The temperature the anthracene dispersion was kept at 15 ° C during the addition of this complex. About 5 hours after finishing The addition of the complex to the anthracene dispersion increased the reaction of these materials by the addition stopped by 1500 ml of cold (cooled to approximately 8 ° C) dry benzene. The reaction vessel was in an ice bath cooled after the addition of the benzene and held at this temperature for about 4 hours. The red solids which were formed during this reaction were removed from the reaction mass by filtration, with additional Washed amounts of dry benzene and hexane to remove residual nitrobenzene from the solids. The filtration and subsequent washing of the recovered solids should be carried out under low humidity conditions to prevent premature hydrolysis of the solid product obtained. After removal residual traces of nitrobenzene from this product were dissolved in an aqueous solution of hydrochloric acid (200 ml

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concentrated hydrochloric acid / 2 liters of distilled water) hydrolyzed. The solids were then recovered by filtration, washed continuously with distilled water until all traces of acid were removed, dried in a vacuum oven and recrystallized by recrystallization from a solvent mixture of benzene and hexane in a ratio of 1: 1. The product recovered, 2-acetyl-anthracene, was pale green. The yield was 98 g and the melting point was around 188 ° C.

About 53 g of 2-acetylanthracene were dispersed in 1800 ml of ethanol, the dispersion is heated to boiling under reflux conditions and 25 g of sodium borohydride in 280 ml of distilled Water added drop by drop. During the addition of the sodium borohydride, the dispersion was stirred gently and constantly Add about two thirds of the sodium borohydride solution the dispersed material dissolved in the solvent and turned brown. After the addition of the sodium borohydride is complete the resulting solution was refluxed for a further 2 hours. At that point it was the reflux condenser opened and about two thirds of the volatile solvents present in the mixture were evaporated. The product remaining in the reaction vessel was made by hydrolysis with an aqueous solution of hydrochloric acid (200 ml hydrochloric acid / 2 l of distilled water) isolated from the excess of sodium borohydride. After precipitation of the isolated product, this was filtered off, alternating with solutions of aqueous hydrochloric acid and distilled Washed with water, dried and recrystallized from benzene. The product obtained, 1- (2-anthryl) ethanol was white, the yield was 50 g, the melting point was 164 ° C.

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About 50 g of 1- (2-anthryl) ethanol were dissolved in 375 ml of dioxane. 37.5 ml of triethylamine and 27.5 ml of methacryloyl were then added to this solution. The condensation of 1 - (2-anthryl) ■ Ethanol and methacryloyl chloride was carried out for about 24 hours. After this time the re ^ ߧ | tion between the 1 (2-anthryl) ethanol and methacryloyl chloride Addition of water to the reaction medium stopped. A sufficient amount of water was added so as not to to extract reacted methacryloyl chloride from the reaction mass. The precipitate that had formed was removed from the reaction medium by filtration, dried in a vacuum oven, and from a mixed solvent recrystallized from benzene and methanol.

About 25 grams of the monomeric compound and about 0.05 grams of azobisisobutyronitrile (5 ml solution of 0.5 g azobisisobutyronitrile in 50 ml benzene) were in a light-tight resin kettle, containing 300 ml of dry benzene, entered. The reaction vessel was flushed with nitrogen and the Contents heated to 60 ° C with gentle stirring and kept at this temperature for 24 hours. The polymer compound was isolated from the reaction mass by precipitation with methanol and the precipitated solids by filtration separated, washed with methanol and dried. The recovered solids were reprecipitated from acetone Purified to remove low molecular weight polymer fraction and unpolymerized monomer residues. The yield was 26g, the molecular weight of 280,000, as determined by known light scattering methods (Brice Pheonix Light Scattering Photometer).

The polymer produced in this way could now be dissolved in tetrahydrofuran

* Chloride

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dissolved and the resulting solution can be sprayed onto a suitable conductive substrate to remove any unevenness To eliminate in the surface texture of such a film, the coated substrate was placed on a hot plate and gradually heated in a non-oxidizing atmosphere until the coating began to melt and thus all surface irregularities have been eliminated. The fat the dry film of the functional anthracene polymer layer, so produced is on the order of about 15 microns. The obtained plate was in a known Xerox Model D copier evaluated. The first copies made with this plate were of good strength Density development and good resolution.

Example XVI

A smooth Teflon substrate was provided with a film of the polymer produced according to Example XV by spraying on. The coated Teflon substrate was heated under non-oxidizing conditions for a time sufficient so that the polymer could zusammenfHessen ^v and so any irregularities have been eliminated in the surface of the polymer layer. A sufficient amount of polymer is sprayed onto the Teflon substrate to achieve a polymer film thickness of about 50 microns. After the polymer film has cooled, the substrate carrying the film is placed in an evaporator and a photoconductive layer of amorphous selenium is applied to the surface of the polymer film. A sufficient amount of selenium was deposited to provide a photogenerator layer with a thickness

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of about 1 micron. The coated substrate was placed in a second evaporator and a layer of aluminum of 15 microns thick deposited in vacuum on the surface of the selenium layer. The coated substrate was removed from the evaporator and the polymer / selenium / aluminum composition from the Teflon surface of the substrate lifted. This composition is then coated onto a conductive metal plate, the Aluminum layer rests on the surface of the plate. The electrophotographic properties of the compound Layers were then evaluated in a Xerox Model D copier. Such evaluation consisted of charging the Polymer layer of the composite layer in the dark to a positive potential of about 600 volts and then Projection of the image information onto the surface. The illumination source of the image information was white Light. The latent, electrostatic image obtained in this way was developed with the help of cascade development, wherein a mixture of a toner and a carrier material is applied to the surface of the composite layer comprising the latent, electrostatic image has been applied. The developed image was transferred to a sheet of paper and permanently fixed on it with the help of thermal fusion. Toner residues were from the one carrying the picture The surface of the composite layer is removed and the copy cycle repeated. The quality of the copies was good and was reproducible.

Example XVII

A composite layer similar to that of Example XVI

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similar, was made by replacing the selenium an X-metal-free phthalocyanine layer was applied in vacuo became. The quality of the copies was good and reproducible. ■ '

Example XVIII

About 45 g of the polymer prepared according to Example XV and 5 g of X-metal-free phthalocyanine were in one. usual solvent dispersed and the resulting solution sprayed onto a tin oxide coated glass plate (NESA, glass). The polymer coating was on the plate heated until melted so that any surface imperfections in the coating were eliminated. A sufficient amount of polymer / phthalocyanine was added to the Plate deposited to form a substantially uniform layer of binder, the thickness of the dry Film was about 50 microns thick. The electrophotographic Properties of this plate were measured in a Xerox Model D copier according to the type described in Example XVI Way evaluated. Such copies were of good quality and the quality was reproducible.

Example XIX

About 30 mol of the monomer prepared according to Example XV were copolymerized with 70 mol of methyl methacrylate. That arbitrary copolymers so prepared had essentially the same relative monomer content as disclosed in

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the original template was present after separation and purification of the obtained copolymer, it was dissolved in tetrahydrofuran and a suitable conductive one Substrate coated with it by dipping or drawing up. A sufficient amount of copolymer was applied to the substrate to leave a dry film with a Thickness of about 40 microns was created. The electrophotographic Properties of the imaging element so produced were evaluated in a Xerox Model D copier. the The quality of the first copies was good; the quality was reproducible.

Example XX

The procedures according to Example XIX were repeated, except that for the methyl methacrylate monomer, the lauryl methacrylate monomer was used for the production of the copolymer. The evaluation of the films produced in this way from this copolymer gave results equivalent to those of Example XV.

Examples XXI through XXVI

The monomer synthesis according to Example XV was repeated, however, the acetic anhydride has been substituted with the following acylating agents.

Example No. Acylating Agents

XXI formyl chloride

XXII acetyl chloride

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Example no. Acylating agents XXIII Propionyl chloride XXIV Butyryl chloride XXV Valeryl chloride XXVI Caproyl chloride

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Claims (1)

P 24 47 27ο.6 2ο. December 1974 Patent claims 1. Process for the production of anthracene polymers Ren, characterized in that a) a dispersion of one or more reactive Anthracene compounds of the formula: in which X and Y independently of one another are hydrogen, chlorine-bromine, an alkyl group having 1 to 4 carbon atoms or the Bheny! Group represent, is produced in an organic solvent mainly composed of nitrobenzene, b) a solution containing a previously prepared complex of acylating agent and a Lewis acid contains.1 1. is brought into contact with the reactive anthracene derivative, the relative molar ratio of acylating agent to Lewis acid in the solution in the range of 0.5 : 1 to about 5: 1, and the relative molar ratio of acylating agent to reactive anthracene derivative is in the range of about 1: 1 to about 5: 1, c) the monomers acylated in the 2-position by one or more Steps in the carbonyl function is modified, with optionally substituted, functional 2-anthryl monomers be obtained d) isolating the monomer in some way after its formation is that the oxidation of the functional groups of the optionally substituted anthracene derivative on a Minimum is limited, 509835/0983 e) the monomer is purified until essentially all oxidation products have been removed and f) the polymerization of the purified monomer is carried out in a non-oxidizing atmosphere. 2. The method according to claim 1, wherein the modification of the 2-acylated monomer thereby is carried out that the compound is reduced to the corresponding alcohol and then the compound obtained under Formation of the vinyl monomers is dehydrated. 3. The method of claim 1, in which the modification of the monomers acylated in the 2-position is carried out by using a Wittig reaction . Is converted into the corresponding vinyl monomers. 4.. The method of claim 1 in which the modification the monomers acylated in the 2-position is carried out by reducing them to the corresponding alcohol, the hydroxyl group of the alcohol is replaced by a halogen atom and the halides obtained by dehydrohalogenation to the corresponding monomers are converted. 5. The method of claim 1, in which the modification of the monomers acylated in the 2-position is carried out by reducing them to the corresponding alcohols and condensed with acrylic acid or an acrylic acid halide. 6. The method according to claim 1, characterized in that g e k e η η ze Ichnet that the solution containing the previously prepared acylating agent / Lewis acid complex with the reactive Anthracene derivative is brought into contact in that 509835/09 8 3 -ta- the complex is gradually added to the anthracene dispersion over a period of from about 15 minutes to about 60 minutes will. 7. The method according to claim 1, characterized in that the temperature of the solution, which thereby occurs that the dispersion (a) is brought into contact with the complex (b) within a temperature range of about 5 is held until about 5 ° C. 8. The method according to claim 1, characterized in that the temperature of the solution, which thereby is obtained that the dispersion (a) is brought into contact with the complex (b), in a temperature range of about 1o to about 3o C. 9. The method according to claim 1, characterized in that the reactive anthracene compound and the acylating agent / Lewis acid complex for one a further period of time from about 1 to about 20 hours. 10. The method according to claim 1, characterized in that the acylating agent / Lewis acid complex is dissolved in a solvent consisting essentially of nitrobenzene. 11. The method according to claim 1, characterized in that the relative weight ratio of reactive anthracene compound to solvent in the range of about 1: 4 to about 1: 1o. 12. The method according to claim 1, characterized in that the reactive anthracene derivative is unsubstituted anthracene. - 4 509835/0983 - A - 13. The method according to claim 1, characterized in that the reactive anthracene derivative is substituted in the 9- and 1o-position. 14. The method according to claim 1, characterized in that the acylating agent is acetic anhydride is. 15. The method according to claim 1, characterized in that the Lewis acid is aluminum chloride is. 16. The method according to claim 1, characterized in that - k e η indicates that the acylation of the reactive Anthracene compound is carried out in an inert, non-oxidizing atmosphere. 17. ■ The method according to claim 1, characterized in that the for the dispersion of reactive anthracene solvent used consists essentially of nitrobenzene. 18. The method according to claim 1, characterized in that - mark i c hn.e t that the for the manufacture of the Solution containing the previously formed acylating agent / Lewis acid complex contains, the solvent used consists essentially of nitrobenzene. 19. The method according to any one of claims 1 to 18, characterized in that step (f) is a free radical initiated addition polymerization of at least one monomer of the formula - 5 5 0 9835/0983 -.-4fr = CIL in which R is hydrogen or an alkyl group of 1 to about Carbon atoms, and X and Y independently of one another are chlorine, bromine, an alkyl group with 1 to 4 carbon atoms or the Mean phenyl group, is carried out. 2o. Method according to one of Claims 1 to 18, characterized in that step (f) is a cation initiated addition polymerization of at least one monomer of the formula in which R is hydrogen or an alkyl group with 1 to about carbon atoms and X and Y independently of one another are chlorine, Bromine, an alkyl group having 1 to 4 carbon atoms or mean the phenyl group, is carried out. 21. The method according to any one of claims 1 to 18, characterized in that step (f) is an anion-initiated addition polymerization at least one monomer of the formula ⁼⁼ CH, 509835/0983 in which R is hydrogen or an alkyl group with 2 to about 3 Carbon atoms and X and Y independently of one another chlorine, Bromine, an alkyl group having 1 to 4 carbon atoms or the Pheny! group is carried out. - 22. The method according to any one of claims 1 to 18, characterized in that step (f) as an addition polymerization triggered by free radicals at least one monomer of the formula C-O-C-C = CH 2 i in which R _{1 is} hydrogen or an alkyl group having 1 to 6 carbon atoms, R2 is an alkyl group having 1 to 4 carbon atoms and X and Y are independently chlorine ,. Bromine, an alkyl group having 1 to 4 carbon atoms or the phenyl group is carried out. 23.. Polymers with anthracene polymer segments consisting essentially of the addition product of at least one Monomers of the formula X · R ^! = CH in which R is hydrogen or an alkyl group having 1 to about 3 carbon atoms and X and Y are independently chlorine, 5098 3 5/0983 Bromine, an alkyl group having 1 to 4 carbon atoms or the phenyl group, the segments having a degree of polymerization of about 40 or more exist. 24. Polymers with anthracene polymer segments, the essentially from the addition product of at least one monomer of the formula SI ² C-O-C-C = CH in which R. is hydrogen or an alkyl group with 1 to 6 carbon atoms, R _{0 is} an alkyl group with 1 to 4 carbon atoms and X and Y are independently chlorine, bromine, an alkyl group with 1 to 4 carbon atoms or the phenyl group, the polymer segments having a degree of polymerization of about 40 or higher exist. 25. Use of the anthracene polymers according to claim 23 or 24 in an electrophotographic imaging member that the end a) a conductive substrate and b) a polymeric, photoconductive insulating layer, the carrier generator centers and carrier transmission centers having and which is characterized in that the generation centers consist of an anthracene polymer. 509835/098 3 26. Use of the anthracene polymers according to claim 23 or 24 in an electrophotographic imaging member consisting of a photoconductive substrate, a photogenerator layer / covering at least one surface of the substrate and a charge transfer matrix forming the photogenerator layer covered, is characterized in that the charge transfer matrix consists of a functional anthracene polymer consists. 27. Use of the anthracene polymers according to claim 23 or 24 in an electrophotographic imaging element which consists of a conductive substrate and a photoconductive insulating layer in which a charge carrier generator material in a charge transfer matrix is dispersed, characterized in that the charge transfer matrix consists of "functional anthracene polymers. 28. Use of the anthracene polymers according to claim 2 "? Or 24 in an electrophotographic imaging process" in which one a) provides an electrophotographic imaging member that has a conductive substrate and a polymeric, photoconductive ^ insulating layer possesses · which is effectively arranged in relation thereto, and b) a latent electrostatic image on the surface forms the photoconductive insulating layer, characterized in that the photoconductive insulating layer consists of a functional anthracene polymer. r 509835/098 3