Patent GB-411894-A (GB)
Title: Improvements in the manufacture and production of high molecular hydrogenation products of rubber, polymersation products of olefines, resins and the like of highly viscous to lubricating oil character
IPC: C10M143/00
Filed: 1932-12-12
Abstract: Hydrogenation products of solid or highly viscous to lubricating oil character which are added to lubricating oils are prepared by partly depolymerizing polymerization products of unsaturated hydrocarbons capable of forming homologous series of compounds or isomerization products thereof by heating in the presence of an organic solvent of high boiling point and hydrogenating the resulting products at a temperature of at least 100 DEG  C. until they contain at least 14,5 parts of hydrogen for each 100 parts of carbon.  The starting materials include rubber, cyclorubber, polymerization products of butadiene or other diolefines or of isobutylene or other olefines, polymerized styrene, and natural and artificial resins.  Mechanical treatment such as rolling or pressing may be employed during the depolymerisation which may be effected at between 50--300 DEG  C., preferably between 100--250 DEG  C., and which is conducted so that the materials are not converted to a substantial extent to products having a molecular weight of less than 500.  The organic solvents used preferably have a boiling point above 150 DEG  C. and include high boiling fractions of tars, mineral oils, or of the products obtained by the distillation or destructive hydrogenation thereof, or of the products obtained by extraction or destructive hydrogenation of coals.  Preferably oils which are saturated and contain no asphalt such as gas oils or lubricating oils are used.  Solvents may also be used in the hydrogenation step, e.g. cyclohexane or the same solvent as used in depolymerization, and where a lubricating oil is used the proportions of the mixture may be regulated so that the hydrogenated product, after separating if desired the middle oil formed, may be directly used as a lubricating oil or as an addition to lubricating oil.  The material may be added to 2 or 3 times the amount of solvent and heated to above 100 DEG  C. preferably 150--200 DEG  C. at ordinary or increased pressure, complete or partial solution taking place with simultaneous partial depolymerization.  Solution may be facilitated by adding hydrocarbon derivatives containing halogen or oxygen such as ethylene chloride, perchlorethane, phenol or benzaldehyde. Hydrogenation may be effected at pressures of 100--200 atmospheres or more and at temperatures of 100--300 DEG  C.; where products of lubricating oil character are desired the heating may be to over 300 DEG  C.  Catalysts such as metals especially of the sixth to the eighth groups or their compounds especially oxides and sulphides, alone or admixed with each other or with zinc oxide, aluminium oxide or other substances, may be used in the hydrogenation.  The catalysts may be arranged rigidly in the reaction chamber, e.g. on carriers.  The products obtained may be used as lubricating oils or added in amounts of 0,5--10 per cent or more to lubricating oils.  In an example, raw rubber is dissolved in a petroleum middle oil, with a boiling point range of 200--300 DEG  C., with heating to 200 DEG  C. and the solution heated to 270 DEG  C. under 200 atmospheres pressure in a tubular preheater with hydrogen and then led over a catalyst of nickel and tungsten sulphide at the same temperature.  The middle oil is distilled from the product and may be used for dissolving fresh amounts of the rubber, and the residue may be added to a machine oil to give an automobile oil. Raw balata or raw guttapercha may be used in place of the rubber. Specification 263,862, [Class 70], is referred to.ALSO:Hydrogenation products of solid or highly viscous to lubricating oil character are prepared by partly depolymerising polymerisation products of unsaturated hydrocarbons capable of forming homologous series or isomerisation products thereof by heating in the presence of an organic solvent of high boiling point and hydrogenating the resulting products at a temperature of at least 100 DEG C. until they contain at least 14,5 parts of hydrogen for each 100 parts of carbon.  The starting materials include rubber, cyclo-rubber, polymerisation products of butadiene or other diolefines or of isobutylene or other olefines, polymerised styrene, and natural and artificial resins. Mechanical treatment such as rolling or pressing may be employed during the depolymerisation which may be effected at between 50--300 DEG C., preferably between 100--250 DEG C., and which is conducted so that the materials are not converted to a substantial extent to products having a molecular weight of less than 500.  The organic solvents used preferably have a boiling point above 150 DEG C. and include high boiling fractions of tars, mineral oils, or of the products obtained by the distillation or destructive hydrogenation thereof, or of the products obtained by extraction or destructive hydrogenation of coals.  Preferably oils which are saturated and contain no asphalt such as gas oils or lubricating oils are used. Solvents may also be used in the hydrogenation step, e.g. cyclohexane or the same solvent as used in depolymerisation, and where a lubricating oil is used the proportions of the mixture may be regulated so that the hydrogenated product, after separating if desired the middle oil formed, may be directly used as a lubricating oil or as an addition to lubricating oil.  The material may be added to 2 or 3 times the amount of solvent and heated to above 100 DEG C. preferably 150--200 DEG C. at ordinary or increased pressure, complete or partial solution taking place with simultaneous partial depolymerisation. Solution may be facilitated by adding hydrocarbon derivatives containing halogen or oxygen such as ethylene chloride, perchlorethane, phenol or benzaldehyde.  Hydrogenation may be effected at pressures of 100--200 atmospheres or more and at temperatures of 100--300 DEG C.; where products of lubricating oil character are desired the heating may be to over 300 DEG C. Catalysts such as metals especially of the sixth to the eighth groups or their compounds especially oxides and sulphides, alone or admixed with each other or with zinc oxide, aluminium oxide or other substances, may be used in the hydrogenation.  The catalysts may be arranged rigidly in the reaction chamber, e.g. on carriers. The products obtained may be used as lubricating oils or added in amounts of 0,5--10 per cent or more to lubricating oils.  In an example, raw rubber is dissolved in a petroleum middle oil, with a boiling point range of 200--300 DEG C., with heating to 200 DEG C., and the solution heated to 270 DEG C. under 200 atmospheres pressure in a tubular preheater with hydrogen and then led over a catalyst of nickel and tungsten sulphide at the same temperature.  The middle oil is distilled from the product and may be used for dissolving fresh amounts of the rubber, and the residue may be added to a machine oil to give an automobile oil.  Raw balata or raw gutta percha may be used in place of the rubber.  Specification 263,862 is referred to.ALSO:Hydrogenation products of solid or highly viscous to lubricating oil character are prepared by partly depolymerising polymerisation products of unsaturated hydrocarbons capable of forming homologous series, or isomerisation products thereof by heating in the presence of an organic solvent of high boiling point and hydrogenating the resulting products at a temperature of at least 100 DEG  C. until they contain at least 14,5 parts of hydrogen for each 100 parts of carbon.  The starting materials include rubber, cyclo-rubber, polymerisation products of butadiene or other diolefines or of isobutylene or other olefines, and polymerised styrene.  Mechanical treatment such as rolling or pressing may be employed during the depolymerisation which may be effected at between 50-300 DEG  C., preferably between 100-250 DEG  C., and which is conducted so that the materials are not converted to a substantial extent to products having a molecular weight of less than 500.  The organic solvents used preferably have a boiling point above 150 DEG C. and include high boiling fractions of tars, mineral oils, or of the products obtained by the distillation or destructive hydrogenation thereof, or of the products obtained by extraction or destructive hydrogenation of coals.  Preferably oils which are saturated and contain no asphalt, such as gas oils or lubricating oils, are used.  The material may be added to 2 or 3 times the amount of solvent and heated to above 100 DEG  C. preferably 150-200 DEG  C. at ordinary or increased pressure, complete or partial solution taking place with simultaneous partial depolymerisation.  Solution may be facilitated by adding hydrocarbon derivatives containing halogen or oxygen such as ethylene chloride, perchlorethane, phenol or benzaldehyde.  In an example, raw rubber, balata or gutta-percha are partly depolymerised by dissolving in a petroleum middle oil, with a boiling point range of 200-300 DEG  C., with heating to 200 DEG  C.  Specification 263,862 is referred to.