Exxon Research and Engineering Company

Other

Harry J Wristers

Terrence Huff

Eugene E Poirot

A titanium trichloride catalyst component containing a minor amount of prepolymerized alpha-olefin and useful in the polymerization of alpha-olefins is produced by reducing titanium tetrachloride with an organoaluminum compound at low temperatures and then treating the resulting reduced solids product with about 1 to 1,000 wt. % alpha-olefin so as to obtain a prepolymerized titanium trichloride reduced solid. The prepolymerized reduced solid can thereafter be activate to a highly active prepolymerized titanium trichloride by treating the prepolymerized reduced solid with a halogenated hydrocarbon and a Lewis base complexing agent or titanium tetrachloride and a Lewis base complexing agent. The prepolymerized reduced solid and the prepolymerized activated titanium trichloride manifests substantially no evidence of friability upon being subjected to mechanical shearing forces. The resulting prepolymerized activated titanium trichloride composition, when employed in combination with an organo-metal compound results in an unexpectedly highly active catalyst obtaining polymers with high heptane insolubles.

Titanium trichloride catalyst component and the process for the

A titanium trichloride catalyst component containing a minor amount of prepolymerized alpha-olifin and useful in the polymerization of alpha-olefins is produced by reducing titanium tetrachloride with an organoaluminum compound at low temperatures and then treating the resulting reduced solids product with about 1 to 1,000 wt. % alpha-olefin so as to obtain a prepolymerized titanium trichloride reduced solid. The prepolymerized reduced solid can thereafter be activated to a highly active prepolymerized titanium trichloride by treating the prepolymerized reduced solid with a halogenated hydrocarbon and a Lewis base complexing agent or titanium tetrachloride and a Lewis base complexing agent. The prepolymerized reduced solid and the prepolymerized activated titanium trichloride manifests substantially no evidence of friability upon being subjected to mechanical shearing forces. The resulting prepolymerized activated titanium trichloride composition, when employed in combination with an organo-metal compound results in an unexpectedly highly active catalyst obtaining polymers with high heptane insolubles.

A titanium trichloride catalyst complex is produced by reducing titanium tetrachloride with an organo-metal compound and then activating the resulting reduced solids by treatment with a chlorinated hydrocarbon and titanium tetrachloride in the presence of a Lewis base complexing agent. The employment of the chlorinated hydrocarbon and titanium tetrachloride in the presence of the Lewis base complexing agent unexpectedly produces a synergistic effect whereby activating conditions, e.g., temperature, time and TiCl.sub.4 concentration can be employed resulting in a titanium trichloride complex having superior alpha-olefin polymerization properties as compared to titanium trichloride catalyst complexes obtained by treatment under the same conditions in the absence of either titanium tetrachloride or chlorinated hydrocarbon. Moreover, unexpectedly high yields of activated catalyst can be recovered without loss of activity.

Titanium trichloride catalyst complex and process for the production

A titanium trichloride catalyst component containing a minor amount of prepolymerized alpha-olefin and useful in the polymerization of alpha-olefins is produced by reducing titanium tetrachloride with an organoaluminum compound at low temperatures and then treating the resulting reduced solids product with about 1 to 1,000 wt. % alpha-olefin so as to obtain a prepolymerized titanium trichloride reduced solid. The prepolymerized reduced solid can thereafter be activated to a highly active prepolymerized titanium trichloride by treating the prepolymerized reduced solid with a halogenated hydrocarbon and a Lewis base complexing agent or titanium tetrachloride and a Lewis base complexing agent. The prepolymerized reduced solid and the prepolymerized activated titanium trichloride manifests substantially no evidence of friability upon being subjected to mechanical shearing forces. The resulting prepolymerized activated titanium trichloride composition, when employed in combination with an organo-metal compound results in an unexpectedly highly active catalyst obtaining polymers with high heptane insolubles.

Large particle size polyolefin is obtained by polymerizing mono-olefins in the presence of a supported olefin catalyst which has been ball milled in the presence of small quantities of polytetrafluoroethylene (PTFE) powder in order to trap, i.e., entangle, the supported catalyst in a web of PTFE submicroscopic fibers.

Supported Ziegler catalysts and method therefor

Solid catalyst particles are made into a form and shape that is easier to handle, without changing their surface area or adversely affecting their activity by 'matting' the catalyst particles with a fibrillatable polymer by mechanical shearing action and subsequently shaping the 'mat', followed by controlled sizing and shaping into the form of pellets, tablets, and the like by known mechanical means. Activity is not impaired, and shaped polymer can be produced in those reactions where the catalyst determines the shape of the product. The practice of this invention is particularly useful to shaped Ziegler-type catalysts.

Shaping and sizing of catalysts

Polyolefins are prepared wherein at least about ninety-five percent of the product is retained on a 100 mesh screen. The polymerization process involves contacting the alpha-olefin with a Ziegler catalyst system wherein the catalyst has been prepared by mixing the active catalytic particles with a fibrillatable polyolefin and a non-fibrillatable polyolefin followed by ballmilling the mixture for a period of time sufficient to cause a fibrous mat to form, entrapping the catalyst particles in the mat which is, in turn, carried by the non-fibrillatable polyolefin.

Preparing polyolefins with a narrow particle size distribution and

Novel TiCl.sub.3 catalytic complexes for the stereospecific polymerization of alpha-olefins and to a process for preparation of these catalytic complexes which are obtained by reduction of TiCl.sub.4 in the presence of a Lewis base which has preferably been complexed with the reducing agent. Furthermore, the present invention relates to a process for improved polymerization of alpha-olefins to crystalline polyolefins in high yields and high stereospecificity using these catalytic complexes.

Reduction of TiCl.sub.4 with reducing agents modified with Lewis bases

Reduction of TiCl.sub.4 with an excess of Et.sub.n AlCl.sub.3-n where n = 1 to 1.95 preferably AlEtCl.sub.2 at -20.degree. to +30.degree. C results in a purple catalyst.

Purple TiCl.sub.3 by direct low temperature reduction

A titanium catalyst for polymerization of olefins is prepared by reduction of TiCl.sub.4 with a mixture of AlEt.sub.2 Cl and AlEt.sub.3, where at high AlEt.sub.3 to AlEt.sub.2 Cl ratios the aluminum reducing agents are added to the TiCl.sub.4 solution. The reduction is performed from -50.degree. to 0.degree. C in a hydrocarbon and the reduced titanium compound is activated by heating to a higher temperature and subsequently is used with a cocatalyst for polymerization of olefins.

Preparation of an active olefin polymerization catalyst

Particle size is increased and particle size range is decreased, e.g. narrower particle size distribution obtained of very tiny inorganic catalyst fines, (particles), particularly olefin catalysts by working these fines with very small quantities of polytetrafluoroethylene (PTFE) powder in order to trap the fines in a web of PTFE submicroscopic fibers.

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Baytown, TX, United States of America

Harry J Wristers