Patent GB-472553-A (GB)
Title: Improvements in the conversion of olefines into valuable products of high molecular weight
IPC: C08F10/00
Filed: 1936-03-27
Abstract: Olefines are polymerized in the presence of an aluminium halide, and of a halogenated hydrocarbon as dispersing agent at a temperature at which the latter does not substantially participate in the reaction. Methylene or ethylene chloride, carbon tetrachloride, ethylene bromide, chlor- or o-dichlor-benzene are suitable halogenated hydrocarbons.  Gaseous olefines, e.g. propylene or a - or b -butylene, or industrial gases containing them may be led upward through a glass filter supporting the catalyst into a reaction vessel containing the dispersing agent and cooled to about -20 to 50 DEG C., preferably 0--20 DEG  C., to form liquid or semi-solid polymers. Ethylene may be polymerized alone if the catalyst is used in larger amounts or previously partly dissolved by treating with a homologue of ethylene, or if elevated temperatures, e.g. 20--60 DEG  C., or pressures, e.g. 5--20 atm., are employed.  Liquid olefines such as pentenes, hexenes, heptenes, octenes, and cyclohexenes may be dropped into the catalytic dispersion while stirring and cooling. Addition of HCl or HBr increases the life of the catalyst. Olefines with terminal double linkages yield viscous polymers of high M.W. which can be heated and drawn into threads or used for addition to lubricating oils.  On heating to 350--500 DEG  C., e.g. by dropping through a packed tube, they split into benzines, middle oils, and lubricating oils.  The relative amounts are varied by regulating reaction conditions or by using catalysts, e.g. aluminium chloride, silica gel, Florida earths, copper, or chromium oxide.  The benzines may be hydrogenated to products also of high octane value.  The split products may be repolymerized to lubricating oils, converted into washing, wetting and emulsifying agents, e.g. by sulphonation as described in Specifications 358,583 and 364,669, or oxidized. Olefines with non-terminal double bonds, and ethylene yield middle and lubricating oils.  In examples: (1) propylene is passed into an ice-cooled vessel containing CCl4 and AlCl3.  Temperature rises to 8--12 DEG  C. a viscous oil being formed; (2) a mixture of 2.2.4-trimethyl-pentene-3 and -4 is dropped into C2H4Cl2 + AlCl3 to give a product resembling spindle oil; (3) a mixture of propene and isobutene is treated with C2H2Cl4 + AlCl3 to yield a lubricating oil; (4) a gas obtained by splitting butane and containing a mixture of olefines is similarly treated; (5) a viscous a -butene polymer is heated at 400 DEG  C., the product yielding benzine and middle oils; (6) a propene polymer is heated with AlCl3 to give benzine, gas oil, and lubricating oil; (7) a propene polymer drops through a tube containing chromic oxide on clay at 480 DEG  C. yielding benzine and middle oil; (8) a middle oil of (5) is hydrogenated and oxidized with air and manganese oleate at 150--160 DEG  C.  It is treated with NaOH to form a soap; (9) a benzine of (7) is condensed with phenol and AlCl3.  The product is converted with H2SO4 or (CH2)2O into wetting and washing agents; (10) a gas obtained by cracking paraffin wax at 520 DEG  C. over copper chips is enriched in olefines, mainly propene and butene, and polymerized as in (1).  The product is depolymerized as in (5) and repolymerized with AlCl3 at 80 DEG  C. to a lubricating oil; (11) the propene polymer of (1) is treated with hydrogen at 200 atm. and 430 DEG  C. in presence of iron oxide giving a saturated middle oil and benzine; (12) ethylene is treated as in (1) at 40 DEG C. giving a lubricating oil.  Specification 447,470 also is referred to.ALSO:Products of the nature of middle oils and lubricating oils are prepared by polymerizing olefines with an aluminium halide in the presence of a halogenated hydrocarbon as dispersing agent at a temperature at which the latter does not substantially participate in the reaction.  Olefines with terminal double linkages yield viscous polymers of high M.W. which can be added to lubricating oils.  On heating to 350--500 DEG  C. they split into benzines, middle and lubricating oils.  The split products may be hydrogenated, or repolymerized to lubricating oils.  Examples of the polymerization of various gaseous or liquid olefines or olefine mixtures, and of the depolymerization of the viscous polymers, are given.