Patent GB-376479-A (GB)
Title: Manufacture of resinous polymerisation products
IPC: C08F8/00
Filed: 1931-06-25
Abstract: The ketone obtained by condensing tetrahydronaphthalene with acetyl chloride by the Friedel-Craft's reaction is reduced to the corresponding alcohol by hydrogen at a raised pressure in the presence of a nickel catalyst.ALSO:Resinous polymerization products are manufactured by polymerizing a non-resinous compound capable of being polymerized and containing a non-conjugated olefinic linkage, such as vinyl esters, ethers and halides, styrene, acrylic acid and its esters and cinnamic acid esters, in admixture with an ethylene-a -b -dicarboxylic acid or an anhydride or other derivative thereof. The proportions of the components may be varied within wide limits, and mixtures of olefinic compounds may be employed instead of single compounds.  The polymerization may be effected by heating, generally to 50-150 DEG  C.  The products are suitable for the manufacture of lacquers, impregnating materials, electrical insulating materials, adhesives and formed articles, and also as assistants in the textile or like industries.  In examples: (1) a mixture of maleic anhydride and styrene is heated on a water bath, producing a slightly yellow to colourless mass; (2) as in (1), using a smaller proportion of maleic anhydride; the product is a light-coloured resin; (3) a mixture of maleic anhydride and vinyl acetate, with the addition of benzoyl superoxide, is passed slowly through a glass or aluminium vessel heated on a water bath to 80-90 DEG  C., yielding a light-coloured transparent resin; the product can be saponified; (4) a mixture of vinyl ethyl ether and maleic anhydride is heated to 110 DEG  C. for 12 hours in an autoclave lined with aluminium, yielding a transparent mass; (5) a mixture of cinnamic acid ethyl ester and maleic anhydride is run slowly into a vessel heated on a water bath, and then heated to 120-140 DEG  C., producing a plastic homogeneous block; (6) a mixture of vinyl chloride and maleic anhydride, with the addition of barium peroxide and acetic anhydride, is heated to 80 DEG  C. for 16 hours in an autoclave lined with aluminium, to produce a white powder; (7) a mixture of methylstyrene and maleic anhydride is polymerized as in (1) in the presence of acetone and benzoyl superoxide, yielding a plastic mass; (8) a mixture of p-hydroxystyrene and citraconic anhydride is refluxed for 10 hours at 120 DEG  C., to produce a transparent, slightly yellow resin; (9) a mixture of maleic sulphonic acid and styrene is heated for 12 hours on a water bath, yielding a brownish-yellow product which is useful as an assistant in the textile industry; (10) a mixture of styrene, vinyl acetate and maleic anhydride, if desired diluted with acetone, is heated to produce a colourless, homogeneous, hard elastic resin, which can be saponified; (11) a mixture of maleic acid diallyl ester (obtainable by heating maleic anhydride with allyl alcohol in the presence of sulphuric acid and copper filings) and styrene is heated for 20 hours at 160 DEG  C.; (12) as in (11), using a larger proportion of maleic acid diallyl ester; a colourless, limpid product is obtained; (13) a mixture of acrolein and the maleic acid ester prepared from maleic acid and the fatty alcohol obtainable from coco nut oil, methyl iodide and magnesium by the Grignard reaction, is heated to 110-120 DEG  C., yielding a colourless glassy mass which is comminuted, subjected to reduced pressure at 40-50 DEG  C. and extracted with alcohol; the yellowish, very elastic mass produced can be used for preparing formed articles; (14) a mixture of styrene and fumaric acid dichloride is refluxed on a water bath, producing a hard, colourless to brownish-yellow block; (15) a mixture of maleic acid monophenyl ester and tetrahydronaphthylvinyl (obtainable by acting with acetyl chloride on tetrahydronaphthalene by the Friedel-Craft's reaction, reducting the ketone formed by hydrogen at a raised pressure in the presence of a nickel catalyst, and splitting off water from the alcohol so obtained by means of phosphorus pentoxide) is heated to 120 DEG  C., then to 140 DEG  C. and finally to 160 DEG  C., yielding a limpid solid product; (16) a mixture of chloromaleic acid, stilbene and 1 : 1-dichloroethane is heated in an autoclave for 10 hours at 70 DEG  C., then 5 hours at 100 DEG  C., and finally for 6 hours at 120 DEG  C., yielding a whitish yellow hard mass; (17) a mixture of phenylmaleic anhydride, vinyl chloride and acetone is heated in an autoclave for 4 hours at 70 DEG  C., then 6 hours at 100 DEG  C. and finally for 10 hours at 120 DEG  C., the contents of the vessel being cooled and comminuted to produce a whitish, crumbly or powdery mass.  The Specification as open to inspection under Sect. 91 (3) (a) comprises also examples of the polymerization of mixtures of: indene and maleic anhydride; coumarone and maleic acid dimethyl ester; vinyl methyl ketone and itaconic acid in the presence of acetone; solvent naphtha (containing styrene, cyclopentadiene, coumarone, indene and their alkyl derivatives) and maleic anhydride.  This subject-matter does not appear in the Specification as accepted.