Patent GB-822932-A (GB)
Title: Improvements in light-sensitive polymers
IPC: C08F20/08
Filed: 1956-09-14
Abstract: Light-sensitive C-vinyl pyridine quaternary salt polymers and copolymers containing on a substantial proportion of the pyridyl nuclei in positions ortho or para to the nitrogen atom substituent groups of the form -CH = CH-A where A represents a heterocyclic group or aromatic carbocyclic group containing 6, 10 or 14 carbon atoms in the nucleus are used in photographic reproduction. Specified comonomers are 1,3-butadiene, vinyl and isopropenyl acetate, butyrate and benzoate, methyl vinyl ketone, methyl vinyl ether, ethylene, isobutylene, styrene, alkyl styrenes, chlorostyrenes, acrylic and methacrylic acids and anhydrides, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, acrylamide, methacrylamide, N-methyl acrylamide, N : N-dimethyl acrylamide, N-methyl methacrylamide, maleic anhydride, maleic and fumaric acids, alkyl esters, nitriles, amides and N-alkyl amides, vinyl chloride and vinylidene chloride. The light-sensitive products may be prepared by condensing vinylpyridine salt polymers having methyl groups ortho or para to the heterocyclic nitrogen atom with aromatic aldehydes, preferably such that A represents <FORM:0822932/IV (a)/1> where m is 1 or 2, R2 is hydrogen, chlorine, bromine, methylene dioxy, cyano, nitro, hydroxyl, C1 to C4 alkyl, C1 to C4 alkoxy, acetamido, -COOR3 or -SO3R3, where R3 is hydrogen, C1 to C4 alkyl or alkali metal, or -N(R4)2, where R4 is C1 to C4 alkyl groups and D represnts atoms necessary to complete phenyl, naphthyl or anthryl nuclei, in the presence of a basic compound, e.g. piperidine or piperidinium ion. Specified aldehydes are benzaldehyde, o-, m- and p-chlorobenzaldehydes and bromobenzaldehydes, o-, m- and p-tolualdehydes and ethyl, propyl and butyl benzaldehydes, 2 : 4- and 2 : 5-dimethyl benzaldehydes, o-, m- and p-methoxybenzaldehyde, p-ethoxybenzaldehyde, 3 : 4 - diethoxybenzaldehyde, p - hydroxybenzaldehyde, 2 : 4 - di-hydroxybenzaldehyde, vanillin, isovanillin, piperonal, o- and p-carboxybenzaldehydes, o-, m- and p-benzaldehyde sulphonic acids and their sodium and potassium salts, p-nitrobenzaldehyde, p - acetaminobenzaldehyde, p-N : N - dimethyl and diethyl aminobenzaldehydes, p - cyanobenzaldehyde, 1 - and 2-naphthaldehydes, 1 : 8 - naphthaldehydic acid, 9-anthraldehyde, furfuraldehyde, cinnamaldehyde, 3 - azidobenzaldehyde, thenaldehyde, 2-, 3- and 4-pyridine aldehydes.  Specified vinyl pyridines are 2-methyl-4-vinyl pyridine, 2-methyl - 5 - vinylpyridine, 2 - methyl - 3 - vinylpyridine, 2 - methyl - 6 - vinylpyridine, 2 : 6-and 2 : 5-dimethyl-4-vinylpyridines, 2 : 3-, 2 : 4-, 2 : 6-, 3 : 6- and 4 : 6-dimethyl-5-vinylpyridines and 2 : 3-, and 2 : 4-dimethyl-6-vinylpyridines, which may be quaternized with alkyl esters of alkyl- and arylsulphonic acids, alkyl halides or perchlorates, e.g. methyl methanesulphonate, methyl benzenesulphonate, methyl and ethyl p-toluenesulphonates, dimethyl, diethyl and dibutyl sulphates, methyl iodide, chloride and bromide, ethyl iodide and bromide, n-propyl bromide and n-butyl bromide, before, during or after polymerization.  The vinylpyridines may be polymerized in bulk, solution or suspension, if desired in the presence of an emulsifying agent such as sodium lauryl sulphate, in the presence of catalysts, e.g. hydrogen peroxide, benzoyl peroxide, acetyl peroxide, ammonium persulphate and potassium persulphate, optionally together with an activator, e.g. an alkali metal bisulphite.