Olefin polymerization process with novel supported titanium catalyst compositions

Claim 2

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.

Claim 3

An olefin polymerization process according to claim 1 wherein the organoaluminum compound is a trialkylaluminum and said selectivity control agent and said electron donor are esters of aromatic carboxylic acids.

Claim 4

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.

Claim 5

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.

Claim 6

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.

Claim 7

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.

Claim 8

A process according to claim 4 wherein said selectivity control agent and said electron donor are esters of aromatic carboxylic acids and said titanium chloride and said chloride of tetravalent titanium are titanium tetrachloride.

Claim 9

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.

Claim 10

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.

Claim 11

A process according to claim 6 wherein said selectivity control agent is p-ethyl anisate and said electron donor is ethyl benzoate.

Claim 12

A process according to claims 2 or 3 in which said magnesium halide is magnesium dichloride and said titanium halide is titanium tetrachloride.

Claim 13

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.

Claim 14

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.

Claim 15

An olefin polymerization process according to claim 9 wherein the organoaluminum compound is trialkylaluminum and said selectivity control agent and said electron donor are esters of aromatic carboxylic acids.

Claim 16

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.

Claim 17

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.

Claim 18

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.

Claim 19

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.

Claim 20

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.

Claim 21

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.

Claim 22

A process according to claim 12 wherein said selectivity control agent is p-ethyl anisate and said electron donor is ethyl benzoate.

Claim 23

A process according to claim 13 wherein said selectivity control agent is p-ethyl anisate and said electron donor is ethyl benzoate.

Claim 24

A process according to claims 4, 5, 6, 7, 12, 13, 14 or 15 wherein said chlorohydrocarbon is an aliphatic chlorohydrocarbon which has at least two chlorine atoms per molecule.

Claim 25

A process according to claims 4, 5, 6, 7, 12, 13, 14 or 15 wherein said chlorohydrocarbon is carbon tetrachloride.

Claim 26

A process according to claims 4, 5, 6, 7, 12, 13, 14 or 15 wherein said chlorohydrocarbon is chlorobenzene.

Claim 27

An olefin polymerization process according to claims 2, 5, 6, 12 or 13 wherein said trialkyl aluminum is triethylaluminum and said selectivity control agent is p-ethyl anisate, and the atomic ratio of aluminum to titanium in the total catalyst is not in excess of 100:1.

Claim 28

An olefin polymerization process according to claim 19 in which the atomic ratio of aluminum to titanium in the total catalyst is not in excess of 50:1.

Claim 29

A propylene polymerization process according to claims 5, 6 7, 12 or 13 wherein propylene is contacted with said catalyst in a liquid reaction mixture which initially consists essentially of propylene as sole reaction diluent, said catalyst and, optionally, hydrogen.