Patent GB-542414-A (GB)
Title: Production of new derivatives of hydrocarbons of high molecular weight
IPC: C08F8/34
Filed: 1940-05-30
Abstract: 542,414. Derivatives of high molecular weight aliphatic hydrocarbons. IMPERIAL CHEMICAL INDUSTRIES, Ltd., (Du Pont de Nemours & Co., E. I.). May 30, 1940, No. 9484. [Class 2 (iii)] [Also in Group V] Derivatives of high molecular weight hydrocarbons which contain chlorine, sulphur and oxygen are prepared by treating in the liquid phase with gaseous chlorine and gaseous sulphur dioxide substantially simultaneously one or more aliphatic hydrocarbons of high molecular weight which comprise normally solid or semi-solid substantially saturated olefine polymers derived from mono-or di-olefins the straight chain of which contains not more than five carbon atoms. The treatment is preferably carried out by dissolving or suspending the olefin polymer in an inert organic solvent and passing in gaseous chlorine and gaseous sulphur dioxide substantially simultaneously. The preferred.solvents are carbon tetrachloride and tetrachloroethane. The olefine polymers which may be used include polyisobutylenes and polythenes. The polyisobutylenes may be prepared by methods described in U.S.A. Specification 2,145,350 and Specifications 401,297 and 421,118, and German Specification 641,284 and French Specification 740,407. The polythenes which are high molecular weight straight chain hydrocarbons corresponding in composition to (CH 2 ) n  and of molecular weights from 4000'- 40,000 or higher may be prepared by the polymerization of ethylene as described in Specifications 471,590 and 536,102. Other starting materials mentioned include polymers derived from such mono-olefins as ethylene, propylene, butylene-1, butylene-2, isobutylene, amylenes, and hydrogenated polymers from diolefins such as isoprene and butadiene. The preferred temperature is 60‹-70‹C. The re-action is preferably carried out in the presence of actinic light such as sunlight, light from an incandescent bulb, a carbon arc, ultra violet lamps, ultra red lamps, or monochromatic light. The chlorine and sulphur dioxide may be added separately and simultaneously, but are preferably mixed before introduction. The reaction may be effected either as a continuous or as a batch process and any apparatus suitable for re-acting a liquid with a gas may be employed. In order to reduce the amount of extraneous chlorination it is preferred to use an amount of sulphur dioxide in excess of the amount of chlorine such as up to 20 moles. of sulphur dioxide per mol. of chlorine. The compounds thus prepared are sulphonyl chlorides, and may be hydrolysed by treatment with alkali such as the hydroxides of sodium, potassium, calcium, and ammonium in concentrations of from 5 per cent. to 40 per cent. by weight. The sulphonyl chlorides may be employed as modifying agents for hydrocarbons, and the water soluble salts of the polysulphonic acids obtained on hydrolysis are used as tanning agents for leather, in tanning baths, and as fat liquoring agents. In examples (1) a waxy polythene of mol. wht. about 1.000 prepared according to Specification 536,102 is suspended in carbon tetrachloride and treated at 60‹C. with chlorine and sulphur dioxide for 6¢ hours. The solvent. is removed and the sulphonyl chloride hydrolysed with sodium hydroxide; (2) a polythene of molecular weight 15,000 prepared according to. Specification 471,590 is treated as described in example (1) and the product hydrolysed: (3) polyisobutylene of molecular weight about 7,000 is treated in carbon tetrachloride solution at about 75‹C. for four hours with gaseous sulphur dioxide and chlorine and the product hydrolysed as before ; (4) a semi-solid polythene of molecular weight about 2,400 is treated as described in example (1) and the product similarly worked up. The Provisional Specification includes also an example of the treatment of hydrogenated rubber by the process of the present invention.