DE2366296C2 - Poly-N-vinyldiphenylamines - Google Patents

Description

The present invention relates to the field of electrophotography, namely photosensitive ones polymeric substances based on poly-N-vinyldiphnylamine derivatives, which have photoelectric properties.

It is the use of some poly-N-vinyldiphenylamines known as photosensitive polymeric fabrics and materials for electrophotography

DE-OS 20 07 962 relates to a photoconductive one Material based on N-vinyldiphenylamine. the but does not contain any substituents

Linear stereoregular polymers of N-vinyldiphenylamine are described (P. Longi, Att Accad. Naz. Linsei Rend. Cl. May be. fis .. mat. e natur, 31.273.1961), which also contain no substituents in the benzene rings. The disadvantage of poly-N-vinyldiphenylamine, which is used as an electrophotographic Material used is the high softening point (approx. 300 ° C) (P. Longi, Att. Accad. Naz, Linsei. Rend. Cl. May be. f sharp, mat e natur, 31.273, 1961) and the need. Use plasticizers (DE-OS 20 07 962).

The aim of the present invention is to overcome these drawbacks.

Accordingly, polyN-vinyldiphenylamines are proposed which contain substituents in the benzene rings, namely 4-ethoxy, 4-methoxy, 4-propyloxy, 4-isopropyloxy and 4,4'-dibromodiphenyl wmin

The new polymers do not have a high softening point (60 to 127 ° C) and can be used well in Ketones, aromatic and chlorinated hydrocarbons. Dioxane. Dissolve dimethylformamide, from their Solutions of electrophotosensitive films are formed. Such polymers can be used in electrophotographic and photothermoplastic records of information can be used.

A disadvantage of the known processes for the preparation of poly-N-vinyldiphenylamines by polymerization of the corresponding N-vinylamines is their multistage and complex technological Arrangement in connection with the need to prepare the monomers, separate and carefully to clean. All of these operations make the poly-N-vinyldiphenylamine considerably more expensive. The procedure for the production of poly-N-vinyldiphenylamine after the re-vinylation of the corresponding amines with Vinyl acetate is one-step, which makes it much easier and cheaper because the separation and No more cleaning of the monomers. According to this method, the reagent used is cheap and widely accessible vinyl acetate

ίο A disadvantage of making poly-N-vinyldiphenylamine according to the method described above after the transvinylation of diphenylamine with vinyl acetate is the unstable and low yield of polymers and the use in larger quantities of the toxic

is a mercury catalyst (not less than 5% by weight, based on the diphenylamine). In addition, according to the above method, it is impossible for the production of poly-N-vinyldiphenylamine, acetone and methyl ethyl ketone to use other solvents.

The aim of the present invention is to eliminate the disadvantages mentioned.

In accordance with the aim of this invention, the object was posed of novel poly-N-vinyldiphenylamines provide.

The subject matter of the invention is evident from the preceding claim.

The new polymers can by reacting secondary aromatic amines with vinyl ethers in Presence of acid catalysts in an organic solvent can be obtained, the Implementation of the amines mentioned with vinyl ethers and the implementation of the same amines with the vinyl acetate in The presence of a catalyst is carried out, which consists of mercury ^!) - or lead (IV) salts, water and strong acids.

AK secondary starting amines are used Diphenylamine derivatives that contain bromine, Contain alkoxy groups, and which correspond to the formula listed in the claim.

Vinyl acetate is used as the vinyl ether. Vinyl ethyl. Vinyl butyl ether. However, it can be used as a vinyl ether in addition to the aforementioned vinyl ethers of aliphatic alcohols, e.g. B. the vinyl methyl, vinyl propyl ether and others are used. In terms of lower cost and easier accessibility however, it is preferable to use vinyl ethyl and vinyl butyl ethers. When using Vinyl acetate occurs in the reaction with the amine

so trap comes about when you act as a catalyst at the same time Mercury ^ I) sal / e or lead (IV) salts. strong acid and water used. The optimal amounts of water that are required for the peaction depend on the Nature of the amine introduced into the reaction and the solvent used and are based on empiri chosen path. When using Vinylethyl and vinylbutylether form the polyN-vinylamines even in the presence of an acidic one Catalyst such as sulfur. Chloric acid, iodic acid, hydrogen chloride. ßortnfluoridätherat quickly enough. As a solvent organic compounds of different classes come into question, such as ketones, e.g. B. acetone, methyl ethyl ketone. Chloroalkanes, e.g. B. chloroform. Carbon tetrachloride, aromatic hydrocarbons, e.g. B. benzene, Chlorobenzene, toluene. Xylenes, nitroparaffins, e.g. B. nitromethane, dioxane. Carboxylic acids, e.g. B. acetic acid. In In individual cases, aqueous solutions of acetic acid, acetone, dioxane, nitromethane can be used as solvents

be used. The poly-N-vinylamines formed are separated off as a function of the used solvents in various ways, in in the case of how the polymers obtained are in the solvent in which the reaction is carried out becomes, are soluble, they are separated by the Reaction solution is poured into a precipitant, the latter being alcohols or their aqueous Solutions, paraffinic hydrocarbons, water, aqueous solutions of salts, e.g. B. sodium chloride is used The thereby precipitated polymers are filtered off, washed and dried. When using Solvents in which the polymers that are formed are insoluble and according to the extent to which they are formed Precipitate, they are filtered off after completion of the process, washed and dried

All polymers obtained are colorless or pale colored amorphous powders with a molecular weight of 1000 to 3000, which are readily soluble in ketones, aromatic and chlorinated paraffinic hydrocarbons, in dioxane, dimethylformamide, from the solutions of which films form that are insoluble in water, in alcohols and Paraffinic hydrocarbons are poorly or at all insoluble.

The electrophotographic material in which the polymers obtained according to the invention are used, consists of an electrically conductive base with a layer of the photosensitive layer applied to it polymeric material.

Various known methods have been used for the preparation of the electrophotographic material to cover 'the electrically conductive pads with the polymeric materials. The photosensitive one polymeric material (aHeine or together with additives) one dissolves or disperses in a suitable organic solvent and bring the solution or suspension obtained in this way to the Electrically conductive surface by dousing, with a brush or by spraying. after which the received Layer is dried to remove the solvent. Another variant is to prepare it electrophotographic material by applying a melt of the photoelectric material to the electrically conductive pad.

The thickness of the photosensitive layer thus obtained Depending on the requirements made, materials can be used in each specific case can be changed over a wide range. Good results are achieved with layers of 5 to 30 μm thick, the best layers having a thickness of 10 to 20 μm exhibit. The layers of less than 5 μm thick have poor insulating properties. while the layers whose thickness is greater than the said limit is. require a relatively long exposure time

The layer thicknesses mentioned are based on experimental Ways by changing the amount of the solution. Dispersion or the melt of the photoemp sensitive material selected.

For the production of said electrophotography Materials are used electrically conductive Aluminum, copper, brass. Brun / c represent nder Glass plates and various polymer. · Films. /. B. Polyethylene terephthalate, Polyprop \ lenfilmc and others, with one on this according to the known method. e.g. applied by pre-evaporation in a vacuum Layer of metal. Silver or platinum.

The electrophotographic materials can be used in various fields of electrophotography be used where the discharge of electrostatic charges on the photoconductive layer at the time Exposure to different lengths of electromagnetic waves is required

example 1

Production of poly-N-vinyl-4-ethoxydiphenylamine

2.15 g of 4-ethoxydiphenylamine, 11 ml of acetone 0.1 ml Wesser, 0.04 g of mercury acetate, 0.03 ml of sulfuric acid, 1.8 nl vinyl acetate is stirred for 5 hours at a temperature of 25 ° C. and, by pouring the reaction solution into 300 ml of ethanol, 2.0 g (83.2%) Polymer with a melting point of 60 to 67 ° C. Molecular weight 2,000 to 2,000.

Electrophotographic material based on poly-N-vinyl-4-ethoxydiphenylamine

0.25 g of poly-N-vinyl-4-ethoxydiphenylamine are in 1 ml of benzene or toluene dissolved and applied to a metal base by the pouring method Room temperature, dried for 48 hours One charges in the dark with a Kt; ona charge (the charge potential is 400-7-500 V) and measures the half-time of the original when exposed to polychromatic light Potential, the exposure time is 48 to 50 seconds.

Example 2

Production of poly-N-vinyl-4-propyloxy-diphenylamine

2.27 g of 4-propyloxydiphenylamine, 12 m. ' Acetone, 0.1 ml water, 0.034 g mercury acetate. 0.04 ml of sulfuric acid and 1.8 ml of vinyl acetate are stirred for 3 hours at a temperature of 25 ° C. and obtained by pouring the reaction solution into ethanol. 2.1 g (83%) of polymer having a mp. 78-88 ⁰ C. molecular weight 2,000 to 2,500.

Electrophotographic material based on poly-N-vinyl-4-propyloxydiphenylamine

Made from 0.25 g of poly-N-vinyl-4-propyloxydiphenylamine electrophotographic material is prepared as described in Example 1 in 1 ml of benzene or toluene. That The charge potential is 350 to 400 V, the exposure time 43 to 47 seconds.

Example 3

Production of poly-N-vinyl-4-isopropyloxy-diphenylamine

2.27 g of 4-isopropyloxydiphenylamine, 12 ml of acetone, 0.1 ml of water, 0.064 g of mercury acetate, 0.04 ml of sulfuric acid. 1.8 ml of vinyl acetate are stirred for 3 hours at a temperature of 25 ° C. and obtained by pouring the reaction solution into 300 ml of ethanol. 2.0 g (78%) of polymer having a mp. Of 80 to 90 ⁰ C. molecular weight 2500 to 3000.

Electrophotographic material on the base
of poly-N-vinyl-4-isopropyloxadiphenylamine

From 0.25 g of poly-N-vinyl-Hsopropyloxydiphep.ylamir. one prepares electrophotographic in 1 ml of benzene or toluene Material as described in Example 1. The charge potential is 400 to 450 V, the E ^ pu-sition time 90 to 95 seconds.

Example 4

Production of
Poly-N-vinyi-4,4'-dibromodiphenylamine

3.48 g 4,4'-dibromodiphenylamine, 17.5 ml acetone, 0.1 ml water, 0.053 ml sulfuric acid, 1.8 ml vinyl acetate, 0.052 g of mercury acetate is stirred for 4 hours at a temperature of 20 ° C. and obtained by the Pour reaction solution into 450 ml of ethanol, 2.1 g (56%) of polymer with a melting point of 121 to 127 ° C. Molecular weight 2500 to 3000.

Elekirophoiographic material on the base
of poly-N-vinyI-4,4'-dibromodiphenylamine

From 0.25 g of poly-N-vinyi-4,4-dibrümdiphenyln.min electrophotographic material is prepared as described in Example 1 in 1 ml of benzene or toluene.

The ρ charge potential is 530 to ί, οϋ V, the Exposure time 16 to 20 seconds.

Example 5

Production of
Poly-N-vinyl-4-methoxydiphenylamine

4.9 g of 4-methoxydiphenylamine, 2.5 ml of vinyl acetate, 2.5 ml of acetone, 0.2 ml of water, 0.09 ml of sulfuric acid, 0.098 g of mercury acetate are stirred for 3 hours at a temperature of 25 ° C. and obtained by the reaction solution is poured into 400 ml of ethanol, 2 g (51%) of polymer with a melting point of 118 ° to 128 ° C. Molecular weight 2000 to 2500.

Claims (1)

Claim: Polymeric N-vinyldiphenylamine derivatives, characterized in that they are characterized by Implementation of monomers of the general formula in which X stands for the methoxy, ethoxy, propyloxy and isopropyloxy group for the case that Y is a Represents hydrogen atom, and X is a bromine atom. when Y represents a bromine atom obtained have been.