Patent GB-734501-A (GB)
Title: Improvements in or relating to ethylene and/or propylene polymerization
IPC: C08F2/00
Filed: 1952-03-06
Abstract: Polymers of ethylene and propylene are prepared by polymerizing in the presence of a catalyst comprising a subhexavalent compound of molybdenum and oxygen in combination with adsorptive gamma-alumina. Temperatures of 75 DEG  to 325 DEG  C. and pressures of atmospheric to 5000 p.s.i. or higher are employed. Polymerization may be effected in a liquid medium, e.g. benzene, toluene, xylene and other aromatic and aliphatic liquids. Polymers of ethylene, with which the invention is particularly concerned, are produced ranging from greases of molecular weights between 300 and 700, to resins having specific viscosities (X 105) of over 300,000.  Propylene yields oils and greases to high molecular weight rubbery polymers.  The catalyst must contain at least 1 per cent of each of the two ingredients and preferably the subhexavalent molybdenum compound comprises 5 to 35 per cent by weight of total catalyst.  The catalyst is conditioned to obtain the molybdenum compound in the desired state by reducing molybdena on the alumina base with hydrogen or other reducing gas at a temperature of about 300-650 DEG  C.  This conditioning is necessary also for spent catalyst from which the polymer which adheres thereto during polymerization has been removed, preferably by solvents.  The molybdenum compound may also be reduced cobalt molybdate and the catalyst may contain stabilizers and other additives, e.g. silica, aluminium orthophosphate, calcium oxide, zirconia, titania and other oxides except those of alkali metals and iron, and the base may be in the form of a zinc aluminate spinel. The catalyst may be in the form of pellets or powder. The ethylene charging stock may contain inert hydrocarbons and other polymerizable materials, e.g. butylene, acetylene, isoprene, &c.  Oxygen and water should not be present in the system.  A fixed bed reactor with down- or up-flow of ethylene and liquid medium can be used, or a slurry of catalyst in the liquid medium may be passed down through a tower or tubes through the lower portions of which ethylene is injected. Other reactors including autoclaves and reaction coils may also be used.  The polymers may be blended with each other and with hydrocarbon oils, waxes, ester waxes, polybutylenes, and they may be subjected to the usual after-treatments, e.g. halogenation, sulphonation, &c. Specification 471,590 and U.S.A.  Specifications 2,320,147 2,357,332, and 2,388,536 are referred to.ALSO:A catalyst for the polymerization of ethylene and propylene (see Group IV (a)), comprises a subhexavalent compound of molybdenum and oxygen in combination with gamma-alumina.  The molybdenum compound may be molybdena or cobalt molybdate and is conditioned by reducing with hydrogen or other reducing gas, e.g. carbon monoxide, sulphur dioxide, hydrogen sulphide, &c., to form a sub-hexavalent compound on the alumina base.  Reduction is effected at 300-650 DEG  C.  The catalyst may contain stabilizers and other additives, such as silica, aluminium ortho-phosphate, calcium oxide and the oxides of magnesium, nickel, zinc, chromium, vanadium and thorium, in minor amounts, and the base may be in the form of a zinc aluminate spinel and may contain zirconia or titania.  The catalyst, which is generally used in the form of pellets, becomes coated during polymerization with polymer, and this is removed by washing with a solvent at a temperature between the softening and the melting points of the polymer. Suitable solvents are aromatic hydrocarbons, e.g. xylenes, benzene and toluene.  Re-conditioning as above is necessary and it may be necessary first to regenerate the catalyst by burning combustible deposits therefrom with oxygen followed by the reducing step.  A number of references is made to the preparation of the gamma-alumina base from (1) hydrated alumina, (2) an aluminium salt solution from which the gel is precipitated, and (3) from the metal.