GB340513A - Improvements in the polymerisation of olefines - Google Patents

Abstract

Olefines such as ethylene, propylene, and butylene are polymerized in the presence of catalysts composed of acids of phosphorus or their derivatives in a solid or "solid-like," e.g. absorbed, state; examples of such acids are phosphoric acid and metaphosphoric acid. Compounds which furnish such acids under the conditions of the reaction such as esters of the said acids, e.g. triethyl phosphate, or the oxides, e.g. phosphorus pentoxide, which form the basis of the said acids may also be employed either alone or mixed with the said acids. The acids may be employed in the form of their salts; metaphosphates are particularly advantageous. Salts of these acids with aluminium, cerium, chromium, manganese, vanadium, or zinc, or acid sodium phosphate yield good results. Mixtures of these catalysts may be used. Carriers such as active charcoal, Florida earth, and silica gel may be employed. If mixtures of several different olefines are employed, condensation as of ethylene with propylene may occur simultaneously with the polymerization. Diluent gases such as water vapour, hydrogen, nitrogen, carbon dioxide, methane or its homologues may also be present. The reaction may be carried out in a closed vessel or with the initial materials in a state of flow, and it is preferably carried out at an elevated pressure such as 20, 50, 100, 200, 1000 or more atmospheres. The temperatures used lie between 200 and 400 DEG C. but preferably above 240 DEG C. The products obtained vary from butylene to gasolines, middle oils, and lubricating oils, the degree of polymerization being determined by the conditions of working such as the duration of the treatment, the rate of flow of the materials, the pressure and the temperature of the treatment. By working in a closed vessel, a mixture of substances is often obtained. The gasoline-like products are proof against knocking to an extremely high degree when employed in internal-combustion engines. The process can be rendered continuous by distilling off the reaction products, leaving the catalyst in the reaction vessel, so that only a fresh charge of olefine need be introduced. The Provisional Specification refers to the use as catalysts of oxyacids which are not reduced by hydrogen or olefines at temperatures below 500 DEG C., and which are capable of directly forming esters with alcohols or olefines. Acids of boron, and substances giving rise to such acids, are referred to in addition to the phosphorus acids. Specifications 261,393 and 327,382, [both in Class 2 (iii), Dyes &c.], are referred to.ALSO:Olefines such as ethylene, propylene, and butylene are polymerized in the presence of catalysts composed of acids of phosphorus or their derivatives, in a solid or "solid-like," e.g. absorbed, state; examples of such acids are phosphoric acid and metaphosphoric acid. Compounds which furnish such acids under the conditions of the reaction such as esters of the said acids, e.g. triethyl phosphate, or the oxides, e.g. phosphorus pentoxide, which form the basis of the said acids may also be employed either alone or mixed with the said acids. The acids may be employed in the form of their salts; metaphosphates are particularly advantageous. Salts of these acids with aluminium, cerium, chromium, manganese, vanadium, or zinc, or acid sodium phosphate yield good results. Mixtures of these catalysts may be used. Carriers such as active charcoal, Florida earth, and silica gel may be employed. If mixtures of several different olefines are employed, condensation as of ethylene with propylene may occur simultaneously with the polymerization. Diluent gases such as water vapour, hydrogen, nitrogen, carbon dioxide, methane, or its homologues may also be present. The reaction may be carried out in a closed vessel or with the initial materials in a state of flow, and it is preferably carried out at an elevated pressure such as 20, 50, 100, 200, 1000 or more atmospheres. The temperatures used lie between 200 and 400 DEG C. but preferably above 240 DEG C. The products obtained vary from butylene to gasolines, middle oils, and lubricating oils, the degree of polymerization being determined by the conditions of working such as the duration of the treatment, the rate of flow of the materials, the pressure and the temperature of the treatment. By working in a closed vessel, a mixture of substances is often obtained. The gasoline-like products are proof against knocking to an extremely high degree when employed in internal-combustion engines. The process can be rendered continuous by distilling off the reaction products, leaving the catalyst in the reaction vessel, so that only a fresh charge of olefine need be introduced. The Provisional Specification refers to the use as catalysts of oxyacids which are not reduced by hydrogen or olefines at temperatures below 500 DEG C., and which are capable of directly p forming esters with alcohols or olefines. Acids of boron, and substances giving rise to such acids, are referred to in addition to the phosphorus acids. Specifications 261,393 and 327,382, [both in Class 2 (iii), Dyes &c.], are referred to.