Patent GB-820263-A (GB)
Title: Process for the polymerisation of ethylene
IPC: C08F10/00
Filed: 1955-08-11
Abstract: Catalysts used in the polymerization of ethyllene (see Group IV (a)) are formed by reducing a compound of a metal of Group IVa, Va or VIa in the absence of oxygen, moisture and active hydrogen, with a metal or an alloy or mixture of metals (other than aluminium) or a metal hydride (other than aluminium hydride) wherein the metal is an alkali or alkaline earth metal, magnesium or a metal of Group III; or with a complex of an alkali metal hydride with aluminium hydride or a boron compound BR1R11R111 wherein R1, R11 and R111 are alkyl, alkoxy, aryl, aryloxy or hydrogen; or with a compound of an alkali metal and a boron triaryl.  The Group IVa, Va or VIa metal compound may be as disclosed in Specifications 799,392, 799,823 and 801,031, and the reducing agents specified are the rare-earth metals, sodium-potassium alloy, magnesium, aluminium-magnesium alloys (e.g. "Electron" metal); calcium, lithium and lithium aluminium hydrides; sodium boron hydride, sodium hydride/triethyl boron complex, sodium phenyl diethoxy boron hydride, and triphenyl boron sodium.  The catalyst is preferably formed with the aid of an inert material such as sodium chloride, and complex forming compounds, such as ether, t-amines, pyridine and quinoline, may also be included.  Catalyst formation and polymerization are preferably in the presence of an inert diluent such as ether, hexane, benzene, xylene, toluene, decahydronaphthalene, or hydrogenated diesel oil.  Subsequent to the polymerization, catalysts may be decomposed with materials such as methanol, acetone, dilute nitric acid and dilute hydrochloric acid. The use of the catalysts disclosed in Specifications 748,439, 748,583, 748,584, 748,634, 753,349 and 753,350 is disclaimed. Specification 820,264 also is referred to.ALSO:Ethylene is polymerized with a catalyst formed by reducing a compound of a metal of Group IVa, Va or VIa in the absence of oxygen, moisture and active hydrogen, with a metal or an alloy or mixture of metals (other than aluminium) or a metal hydride (other than aluminium hydride) wherein the metal is an alkali or alkaline earth metal, magnesium, or a metal of Group III; or with a complex of an alkali metal hydride with aluminium hydride or a boron compound BR1R11R111, wherein R1, R11 and R111 are alkyl, alkoxy, aryl, aryloxy, or hydrogen; or with a compound of an alkali metal and a boron triaryl.  The Group IVa, Va or VIa metal compound may be as disclosed in Specifications 799,392, 799,823 and 801,031 and in the examples titanium, zirconium, uranium and thorium tetrachlorides, chromic chloride, vanadium oxychloride, zirconium tetraiodide and the corresponding acetyl acetonates are specified. The particular reducing agents used are the rare earth metals, sodium-potassium alloy, magnesium, aluminium-magnesium alloys (e.g. "Electron" metal); calcium, lithium and lithium aluminium hydrides; sodium boron hydride, sodium hydride/triethyl boron complex, sodium phenyl diethoxy boron hydride and triphenyl boron sodium.  The catalyst is preferably formed with the aid of grinding or pulverizing, optionally with the aid of an inert material such as sodium chloride, and complex forming compounds, such as ether, t-amines, pyridine and quinoline, may also be included.  Catalyst formation and polymerization are preferably in the presence of an inert diluent such as ether, hexane, benzene, toluene, xylene, decahydronaphthalene or hydrogenated diesel oil. The ethylene used may, if desired, be diluted with inert gases such as nitrogen, ethane, hydrogen or propane.  The high molecular weight products of the invention may be purified (catalyst decomposed) with the use of materials such as methanol, acetone, dilute nitric acid and dilute hydrochloric acid, and are easily formed into films.  The processes of Specifications 748,439, 748,583, 748,584, 748,634, 753,349 and 753,350 are disclaimed. Specification 820,264, [Group III], also is referred to.