Patent GB-684332-A (GB)
Title: Improvements in or relating to a process for the production of organic sulpho-chlorides
IPC: C07C309/78
Filed: 1949-11-17
Abstract: Polyvinyl chloride resins are plasticized by means of esters obtained by the esterification of sulpho-chlorides of hydrogenated mineral oil fractions, wherein the olefines and aromatic and unsaturated alicyclic ring compounds are present in the hydrogenated oil as completely saturated aliphatic and alicyclic compounds.  The production of the sulpho-chlorides is described (see Group IV (b)).ALSO:Sulpho-chlorides are prepared by the sulphochlorination of hydrogenated mineral oil fractions with sulphur dioxide and chlorine, characterized in that olefines and aromatic and unsaturated alicyclic ring compounds originally contained in the mineral oil fractions are present in the hydrogenated oil as completely saturated aliphatic and alicyclic compounds.  The method results in substantial prevention of the formation of carbon-bound chlorine in the product, and of resins and colouring. The resulting mixture of aliphatic and alicyclic sulphochlorides may be reacted with water to form the sulphonic acids, with alkaline compounds to form salts, with alcohols or phenols in presence of alkali to form esters which may be used as plasticizers, and with ammonia to form amides and imides.  In an example, a mineral oil fraction, B.P. 200-300 DEG  C., containing 11 per cent aromatics and 35 per cent naphthenes, is catalytically hydrogenated at 380 DEG  C. and under 250 atmos. hydrogen pressure in presence of a Ni-Mo-S catalyst for 6 hours, constituting a preliminary and the customary refining, and then hydrogenated for 2 hours under 200 atmos. hydrogen pressure at 350 DEG  C. over a Ni-Al catalyst and the product sulphochlorinated while exposed to short-wave light yielding a product in which substantially all the saponifiable chlorine is present as sulpho-chloride.  The product, when saponified, gives a soap free of resin and its esters have plasticizing properties for polyvinyl chloride.  A table gives data comparing the product obtained as above with those obtained by the same sulpho-chlorination in which the hydrocarbon fraction is used unrefined, after sulphuric acid refining, and after refining by partial hydrogenation (the first hydrogenation in the example) respectively.  The Specification as open to inspection under Sect. 91 refers to the refining step as consisting in a customary high-pressure hydrogenation to saturate the olefines followed by further hydrogenation to saturate the aromatic and alicyclic ring systems at 200-450 DEG  C. under 50-400 atm. pressure in the presence of catalysts which preferably contain elements of Groups 3 and 8 of the Periodic Table.  This subject-matter does not appear in the Specification as accepted.ALSO:Mineral oils containing olefines, aromatics and unsaturated alicyclic ring compounds are completely hydrogenated.  In an example, a mineral oil fraction boiling between 200 DEG C and 300 DEG C and containing 11 per cent aromatics and 35 per cent naphthenes is refined by hydrogenation for 6 hours at 380 DEG C under 250 atmos. hydrogen pressure in the presence of a Ni-Mo-S catalyst and then further hydrogenated for 2 hours at 350 DEG C under 200 atmos. hydrogen pressure in the presence of a Ni-Al catalyst. The Specification as open to inspection under Sect. 91, refers to use of the customary hydrogenation to saturate the olefines followed by hydrogenation to saturate the ring compounds at 200 DEG -450 DEG C under 50-400 atmos. pressure in the presence of catalysts preferably containing elements of Groups 3 and 8 of the Periodic Table.  This subject-matter does not appear in the Specification as accepted.