Patent GB-959679-A (GB)
Title: A process for the production of fluorescent polymers
IPC: C07D311/06
Filed: 1960-09-29
Abstract: (1-[4-beta-methacrylolylethyl-sulphonylphenyl] -3-p-chlorophenyl)-pyrazoline of the formula: <FORM:0959679/C2/1> is made by reacting acetyl aminobenzene sulphinic acid to produce beta-hydroxyethyl-(p-acetylamino-phenyl) sulphone which is hydrolyzed to the amine and converted into the corresponding hydrazine derivative. The hydrazine derivative is condensed with p-chlorophenyl-beta-chloroethyl ketone to produce p1-(3-p-chlorophenyl -1-pyrazolyl)-phenyl-beta-hydroxyethyl sulphone (M.P. 224 DEG C.) which i reacted with methacrylic chloride to give the desired compound.  The compound of the formula: <FORM:0959679/C2/2> is made by esterifying 3-p-chlorophenyl -1- p-carboxyphenyl pyrazoline with allyl alcohol. 7-methacryloylaminocoumarin of the formula: <FORM:0959679/C2/3> is made by acylating 7-aminocoumarin with methacrylic chloride.  The compounds of the formula: <FORM:0959679/C2/4> is made by acylating <FORM:0959679/C2/5> acid with methacrylic chloride. 4-methacryloylaminostilbene-2-sulphonic acid of the formula: <FORM:0959679/C2/6> is made by acylating 4-aminostilbene-2-sulphonic acid with methacrylic chloride.  <FORM:0959679/C2/7> of the formula: <FORM:0959679/C2/8> is made by acylating 3-p-chloro-1, 3-diphenyl-pyrazoline-1-p-sulphonic acid-hydroxyethylamide with methacrylic chloride.  4-methacryloylamino-(N-n-butyl-1, 8-naphthalimide) of the formula: <FORM:0959679/C2/9> is made by acylating 4-amino-(N-n-butyl-1, 8-naphthalimide) with methacrylic chloride.  The compound of the formula: <FORM:0959679/C2/100> is made by acylating 3-p-aminophenyl coumarin with methacrylic chloride.  The compound of the formula: <FORM:0959679/C2/111> is made by acylating (3-p-chloro)-1, 3-diphenyl pyrazoline carboxylic acid hydroxyethyl ester with acrylic chloride.  <FORM:0959679/C2/122> of the formula: <FORM:0959679/C2/133> is made by acylating (3-p-chloro)-1, 3-diphenylpyrazoline-1, p-sulphonic hydroxyethylamide with acrylic chloride.ALSO:Fluorescent copolymers are made which contain from 80 to 99.9% by weight of acrylonitrile, 0 to 10% by weight of one or more ethylenic compounds and 0.1 to 10% by weight of a compound containing a radical which shows a blue fluorescence in daylight, e.g. a derivative of coumarin, stilbene, diphenyl pyrazoline, naphthalic acid amide or compound containing an oxdiazole or triazole radical. Specified fluorescent monomers are those of the formulae: <FORM:0959679/C3/1> <FORM:0959679/C3/2> <FORM:0959679/C3/3> <FORM:0959679/C3/4> <FORM:0959679/C3/5> <FORM:0959679/C3/6> <FORM:0959679/C3/7> <FORM:0959679/C3/8> <FORM:0959679/C3/9> <FORM:0959679/C3/100> Other copolymerizable monomers specified are butadiene, isoprene, chlorobutadiene, vinyl and vinylidene chlorides, acrylic and methacrylic acids, methacrylonitrile, methyl methacrylate, styrene, maleic, fumaric and itaconic acids anhydrides, esters, semi-esters, amides and ester amides and methacrylaminobenzene-benzene sulphonimide.  Polymerization may be carried out in bulk, solution or, preferably an aqueous emulsion which may contain emulsifiers such as polyvinyl alcohol, polyalkylene oxides, long chain sulphonates and N-alkyl ammonium salts. As polymerization catalysts there may be employed hydrogen peroxide, persulphates, organic peroxides, azobisisobutyronitrile, and combinations of persulphates with pyrosulphites bisulphites or sulphur dioxide, if desired in the presence of salts of iron and copper. Also present may be complex-forming substances, e.g. ethylene diamine tetra-acetic acid. The copolymers may be used as such to produce shaped structures, or may be incorporated in other polymers, e.g. polystyrene, polyethylene, polyvinyl chloride, polyesters, polyamides and polyurethanes. The examples describe the copolymerization in an aqueous medium of pH3 containing a persulphate-pyrosulphite catalyst of: (1) acrylonitrile, methyl methacrylate, methacrylaminobenzene benzene disulphonimide and the compound of Formula I; and (2) acrylonitrile, methyl methacrylate and each of the compounds of Formulae II to X.