Patent GB-358068-A (GB)
Title: Process for the manufacture of hydrocarbons of higher molecular weight from unsaturated hydrocarbons, in particular of the olefine series
IPC: C08F210/00
Filed: 1930-04-29
Abstract: Motor spirit and similar hydrocarbon liquids are freed from unsaturated resin-forming impurities by treatment with certain catalysts which polymerize the impurities.  The catalysts consist of double compounds obtained by treating metal halides, especially those with a valency of three or more, with polar compounds which form complexes with these halides without decomposing them. Examples of suitable metal halides are those of aluminium, iron, tin, antimony, bismuth, arsenic, molybdenum, tungsten, vanadium, titanium, thorium, zirconium, and mixtures thereof; the Provisional Specifications also mention boron halides.  The polar compounds may be organic compounds, which may be solvents for the metal halides; examples of such compounds are nitrobenzene, nitromethane, acetone, acetophenone, benzophenone, benzoyl chloride, diphenyl sulphone, and mixtures thereof.  The polar compounds may alternatively be inorganic compounds, such as other metal halides, for example, the halides of silver, copper, sodium, calcium, or ammonium.ALSO:Unsaturated hydrocarbons, particularly olefines, are polymerized by treatment at normal or increased pressure with catalysts obtained by treating metal halides, especially those with valencies of three or more, with polar compounds which form complexes with these halides without decomposing them, and which do not substantially combine under the conditions of the reaction with the unsaturated hydrocarbons according to the Friedel-Crafts reaction.  Examples of suitable metal halides are those of aluminium, iron, tin, antimony, bismuth, arsenic, tungsten, vanadium, titanium, thorium, and zirconium; mixtures of these halides may be employed.  The Provisional Specifications also mention boron halides.  The polar compounds used may be organic compounds, which may be solvents for the metal halides; examples of such compounds are nitrobenzene, nitromethane, acetone, acetophenone, benzophenone, benzoyl chloride, diphenyl sulphone, and mixtures thereof.  The complexes formed, which may be solids, as in the case of the compound of aluminium chloride with diphenyl sulphone, or liquids, may be employed dissolved or dispersed in suitable liquids.  In cases where the liquid organic polar compound dissolves the complex formed, the latter may be concentrated or isolated by extracting the excess of organic liquid wholly or partly with a suitable extracting agent.  For example, when aluminium chloride is combined with nitrobenzene, the excess of the latter may be removed by extraction with gasoline.  Instead of organic polar compounds, metal halides which combine with the first metal halides may be employed to form complexes therewith.  The reaction may be carried out at ordinary or lower or higher temperatures, and the reaction temperature may be controlled by external heating.  The conditions for a smooth polymerization should be predetermined according to the nature of the olefines treated and of the product sought.  Thus a polymerization product possessing good lubricating qualities is obtained by using isobutylene and working at -10 to 10 DEG  C.; with propylene higher temperatures are necessary to secure the same end product.  Intimate contact should be ensured between the olefines and the catalytic mass.  The invention may be used to free motor spirit or like hydrocarbon liquids from unsaturated resinforming substances, which may thus be polymerized and removed. Olefines may also be separated from mixtures thereof; for example, ethylene at room temperature is not polymerized by treatment with a solution of aluminium chloride in nitrobenzene, and may thus be separated from a mixture thereof with propylene which is energetically polymerized.  According to examples (1) propylene is polymerized by treatment with a solution of aluminium chloride in nitrobenzene, (2) isobutylene is polymerized with the same catalyst yielding a product the low-boiling fractions of which possess anti-knock properties, (3) di- and tri-isobutylene and higher polymers are obtained by treating isobutylene with the product of mixing aluminium chloride, benzene, and diphenyl sulphone, (4) a viscous oil is formed by the polymerization of isobutylene at 0 DEG C. with the compound of aluminium chloride and nitromethane, (5) propylene is polymerized with the compound of aluminium chloride and nitrobenzene under pressure in a packed metal tube; the product is purified by slaking with dilute lye, dilute sulphuric acid, and water, and is then fractioned with steam.  The residue is suitable as a cylinder oil, (6) isobutylene is polymerized by means of the compound of stannic bromide with nitrobenzene.  The product is steam distilled yielding a benzine and a residue suitable as a lubricating oil, (7) isobutylene is polymerized in the presence of the double chloride of aluminium and silver, and (8) of the double chloride of aluminium and copper, and (9) of the double chloride of aluminium and sodium, (10) isobutylene is polymerized by means of a solution of aluminium and sodium chloride in nitrobenzene; part of the product is suitable as a cylinder oil, (11) isobutylene is passed through a suspension of the double chloride of calcium and aluminium in benzine freed from aromatics; the product freed from benzine and fractionated yields a viscous oil, (12) normal butylene is treated with the double chloride of barium and aluminium mixed with pumice, yielding a product suitable for the manufacture of benzine, (13) technical amylene from cracked gasoline is treated with bromine, converting the amylenes into their dibromides, from which by treatment with alcoholic potash and thereafter with sodium amide suspended in paraffin oil, the corresponding pentines are obtained.  A viscous oil is obtained by polymerizing this mixture of pentines with a solution of aluminium chloride in nitromethane, and (14) isoprene is treated at 0 DEG  C. with a mixture of aluminium chloride, ammonium chloride, and nitrobenzene, yielding a solid polymer having the properties of synthetic rubber.  Similar products can be obtained by polymerizing butadiene with the same catalyst, or by polymerizing isoprene with a mixture of aluminium chloride, ammonium chloride, and nitromethane. Specifications 299,086, 316,701, and 316,951, [all in Class 91, Oils &c.], are referred to.