Olefin polymerization process with novel supported titanium catalyst compositions
AssigneeShell Oil Company
InventorsBrian L. Goodall, Adrianus A. van der Nat, Willem Sjardijn
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Abstract
An olefin polymerization process comprises contacting the monomer to be polymerized with a catalyst composition comprising: an organoaluminum compound, a first electron donor, and a product obtained by contacting a solid component comprising a magnesium halide in which the atomic ratio of chlorine to magnesium is at least 1.2, a titanium halide and a second electron donor, with a halohydrocarbon and thereafter with a tetravalent titanium compound.
Claims21
Process for the polymerization of alpha-monoolefins which comprises contacting the monomers to be polymerized with a catalyst composition comprising an organoaluminum compound, a selectivity control agent, or an at least partial reaction product of those two components, and a titanium-containing catalyst component obtained by:
- i contacting with a halohydrocarbon in liquid phase a solid reaction product comprising a magnesium halide in which the atomic ratio of halogen to magnesium is at least 1.2:1, a titanium halide and an electron donor;
- ii optionally washing the resulting solid with an inert diluent to remove liquid remaining from the contacting step;
- iii contacting the resulting solid with a halide of tetravalent titanium in liquid phase;
- and
- iv washing the resulting solid with an inert diluent to remove residual unreacted titanium compound;
- and recovering the resulting olefin polymer.
A process for the polymerization of propylene to isotactic polypropylene which comprises contacting propylene with a catalyst comprising a trialkylaluminum and a selectivity control agent or an at least partial reaction product of those two components, and a titanium-containing catalyst component obtained by:
- i contacting with a halohydrocarbon in liquid phase a solid reaction product comprising a magnesium halide in which the atomic ratio of halogen to magnesium is at least 1.2:1, a titanium halide and an electron donor;
- ii optionally washing the resulting solid with an inert diluent to remove liquid remaining from the contacting step;
- iii contacting the resulting solid with a halide of tetravalent titanium in liquid phase;
- and
- iv washing the resulting solid with an inert diluent to remove residual unreacted titanium compound;
- and recovering polypropylene having a low inorganic ash content.
A process for the polymerization of propylene to isotactic polypropylene which comprises contacting propylene with a catalyst comprising a trialkylaluminum and a selectivity control agent or an at least partial reaction product of those two components, and a solid catalyst component containing titanium and magnesium in the atomic ratio of Ti:Mg in the range from 0.02:1 to 1.5:1, which is obtained by:
- i contacting with a chlorohydrocarbon in liquid phase a solid reaction product comprising a magnesium chloride in which the atomic ratio of chlorine to magnesium is at least 1.5:1, a titanium chloride and, as electron donor, an ether, ester, amine, phenol or phosphine, present in a ratio of 0.01 to 5 mole of said electron donor per atom of magnesium;
- ii optionally washing the resulting solid with an inert diluent to remove liquid remaining from the contacting step;
- iii contacting the resulting solid with a chloride of tetravalent titanium in liquid phase;
- and
- iv washing the resulting solid with an inert diluent to remove residual unreacted titanium compound;
- and recovering polypropylene having a low inorganic ash content.
A process for the polymerization of propylene to isotactic polypropylene which comprises contacting propylene with a catalyst comprising a trialkylaluminum and a selectivity control agent or an at least partial reaction product of those two components, and a solid catalyst component containing titanium and magnesium in an atomic ratio of Ti:Mg in the range from 0.02:1 to 1:1, which is obtained by:
- i contacting with a chlorohydrocarbon in liquid phase a solid reaction product comprising magnesium dichloride, titanium tetrachloride and, as electron donor, an ester of an aromatic carboxylic acid present in a ratio of 0.01 to 5 moles of said ester per atom of magnesium;
- ii optionally washing the resulting solid with an inert diluent to remove liquid remaining from the contacting step;
- iii contacting the resulting solid with titanium tetrachloride in liquid phase;
- and
- iv washing the resulting solid with an inert diluent to remove residual unreacted titanium compound;
- and recovering polypropylene having a low ash content.
Process for the polymerization of alpha-monoolefins which comprises contacting the monomers to be polymerized with a catalyst composition comprising an organoaluminum compound, a selectivity control agent, or an at least partial reaction product of those two components, and a titanium-containing catalyst component obtained by:
- i contacting with a halohydrocarbon in liquid phase a solid reaction product of a magnesium dialkoxide, diaryloxide or dialkyl with titanium tetrachloride and an electron donor, said reaction product comprising magnesium chloride in which the atomic ratio of chlorine to magnesium is at least 1.5:1, titanium chloride and electron donor;
- ii optionally washing the resulting solid with an inert diluent to remove liquid remaining from the contacting step;
- iii contacting the resulting solid with titanium tetrachloride in liquid phase;
- and
- iv washing the resulting solid with an inert diluent to remove residual unreacted titanium compound;
- and recovering the resulting olefin polymer.
A process for the polymerization of propylene to isotactic polypropylene which comprises contacting propylene with a catalyst comprising a trialkylaluminum and a selectivity control agent or an at least partial reaction product of those two components, and a titanium-containing catalyst component obtained by:
- i contacting with a halohydrocarbon in liquid phase a solid reaction product of a magnesium dialkoxide, diaryloxide or dialkyl with titanium tetrachloride and an electron donor, said reaction product comprising magnesium chloride in which the atomic ratio of chlorine to magnesium is at least 1.5:1, titanium chloride and electron donor;
- ii optionally washing the resulting solid with an inert diluent to remove liquid remaining from the contacting step;
- iii contacting the resulting solid with a chloride of tetravalent titanium in liquid phase;
- and
- iv washing the resulting solid with an inert diluent to remove residual unreacted titanium compound;
- and recovering polypropylene having a low inorganic ash content.
A process for the polymerization of propylene to isotactic polypropylene which comprises contacting propylene with a catalyst comprising a trialkylaluminum and a selectivity control agent or an at least partial reaction product of those two components, and a solid catalyst component containing titanium and magnesium in an atomic ratio of Ti:Mg in the range from 0.02:1 to 1:1, which is obtained by:
- i contacting with a chlorohydrocarbon in liquid phase a solid reaction product of a magnesium dialkoxide or diaryloxide with titanium tetrachloride and an ester of an aromatic carboxylic acid as electron donor, said reaction product comprising magnesium dichloride, titanium tetrachloride and said ester present in a ratio of 0.01 to 5 moles of said ester per atom of magnesium;
- ii optionally washing the resulting solid with an inert diluent to remove liquid remaining from the contacting step;
- iii contacting the resulting solid with titanium tetrachloride in liquid phase;
- and
- iv washing the resulting solid with an inert diluent to remove residual unreacted titanium compound;
- and recovering polypropylene having a low ash content.
A process for the polymerization of propylene to isotactic polypropylene which comprises contacting propylene with a catalyst comprising a trialkylaluminum and a selectivity control agent or an at least partial reaction product of those two components, and a solid catalyst component containing titanium and magnesium in an atomic ratio of Ti:Mg in the range from 0.02:1 to 1:1, which is obtained by:
- i contacting with a chlorohydrocarbon in liquid phase a solid reaction product of a dialkyl magnesium compound with titanium tetrachloride and an ester of an aromatic carboxylic acid as electron donor, said reaction product comprising magnesium dichloride, titanium tetrachloride and said ester present in a ratio of 0.01 to 5 moles of said ester per atom of magnesium;
- ii optionally washing the resulting solid with an inert diluent to remove liquid remaining from the contacting step;
- iii contacting the resulting solid with titanium tetrachloride in liquid phase;
- and
- iv washing the resulting solid with an inert diluent to remove residual unreacted titanium compound;
- and recovering polypropylene having a low ash content.
Dependencies are inferred from the claim text.