Patent GB-512463-A (GB)
IPC: C08F240/00
Abstract: 512,463. Condensation products of unsaturated hydrocarbons. JOHNSON, G.W. (I. G. Farbenindustrie Akt.-Ges.). Jan. 31, 1938, No. 3007. [Class 2 (iii)] Drying oils are made by condensing liquid products containing at least 50, preferably at least 70 per cent. of unsaturated hydrocarbons, and obtained by cracking or direct or indirect dehydrogenation of mainly saturated aliphatic carbonaceous substances boiling above about 280C., by treatment with metal halides of the Friedel Crafts type or boron halides together with from 10-35 per cent., calculated on the weight of the products containing unsaturated hydrocarbons, of inorganic acid halides other than boron halides, to form still unsaturated products of higher molecular weight. The initial carbonaceous substances include paraffin wax, ceresin, ozokerite, montan wax, paraffinic petroleum residues, petroleum jelly, lubricating oils or other oils rich in hydrogen obtained from petroleum or brown coal tars by distillation and/or treatment with selective solvents, reduction products of carbon monoxide, voltolization products of hydrocarbons, and destructive hydrogenation products of coals, tars and petroleums. These are usually treated at above 350C., if desired, in the presence of catalysts such as bleaching earths pretreated with acids, e.g., HF or alumina or metals of Group 6 or their compounds. Dehydrogenation may be effected with an addition of sulphur or oxygencontaining gases. Chlorine, bromine, sulphur or oxygen may be introduced, and split off again as hydrogen compounds advantageously in the presence of mild condensing agents, e.g., bleaching earths, and boric, oxalic or ansolvo acids or their salts. The unsaturated hydrocarbons thus obtained may be mixed with diolefines such as allene, butadiene, isoprene, diallyl, piperylene, and corylene, or compounds having triple linkages such as allylene, crotonylene or vinylacetylene, in amounts of from 20-60 per cent. or more. Mixtures of olefines and diolefines may also be formed directly from the initial substances by cracking above 470, e.g., at 500-700C. or by introducing 15-25 per cent. or more of halogen and splitting it off again. Unsaturated aldehydes, ketones, alcohols, acids or anhydrides, e.g., acrolein, crotonaldehyde, phorone, mesityl oxide, furane, geraniol, crotonic, acid or maleic anhydride, may also be added. The condensation is effected at 10-100, e.g. 30-70C., advantageously in the presence of diluents such as chlorinated hydrocarbons, e.g. ethylene chloride or carbon tetrachloride. Metal halides specified are the chlorides of Al, Zn, Fe or Ti. These or boron halides, e.g. BFy, are added in an amount of about 5-35 per cent. to the initial materials, and there is led in while stirring 10-35 per cent. of inorganic acid halide such as phosphene or thionyl chloride or a mixture of carbon monoxide and hydrochloric acid. Sub- .stances retarding the reaction such as zinc oxide or ammonia, may be added or small amounts of cyclic compounds, e.g. benzene, toluene, naphthalene, fluorene, anthracene, pyrene, phenol, phenol ethers, decahydronaphthalene or fractions containing this last obtained in the destructive hydrogenation of mineral coal. The products are used in place'of or in admixture with drying vegetable oils. They dry to hard films especially on heating with an addition of siccatives. In an example, a liquid product of repeated cracking of paraffin wax at 500C., containing 90 per cent. unsaturated hydrocarbons, is dissolved in ethylene chloride, aluminium chloride added, and phosgene led in at 50-60C. Hydrochloric acid is added to dissolve the aluminium chloride, the aqueous layer removed, and the solvent distilled off from the drying oil produced.