Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions

• US 4,414,132 A
• Filed: 10/30/1981
• Issued: 11/08/1983
• Est. Priority Date: 05/17/1979
• Status: Expired due to Term

• Current Assignee: Union Carbide Chemicals & Plastics Technology Corporation (Dow, Inc.)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Goodall, Brian L., Sjardijn, Willem, van der Nat, Adrianus A.
• Primary Examiner(s): Garvin, Patrick
• Application Number:
  US06/316,475
• Time in Patent Office: 739 Days
• Field of Search: 252/429 B
• US Class Current: 502/104
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 4/6541 and metals of C08F4/64 or compounds thereof

Abstract

A highly active and stereoselective olefin polymerization catalyst component is obtained by halogenating a magnesium compound of the formula MgR₁ R₂ wherein R₁ is an alkoxide or aryloxide group and R₂ is an alkoxide or aryloxide group or halogen, with a halide of tetravalent titanium in the presence of a halohydrocarbon and an electron donor, and contacting the halogenated product with a tetravalent titanium halide.

Claims

1. An olefin polymerization catalyst composition comprising an organoaluminum compound, a selectivity control agent and a solid component which has been obtained by halogenating a magnesium compound of the formula MgR'"'"'R" wherein R'"'"' is an alkoxide or aryloxide group and R" is an alkoxide or aryloxide group or halogen, with a halide of tetravalent titanium in the presence of a halohydrocarbon and an electron donor, contacting the halogenated product with a tetravalent titanium halide, washing it to remove unreacted titanium compounds, and recovering the solid product.

2. An olefin polymerization catalyst composition according to claim 1 wherein said organoaluminum compound and selectivity control agent are employed as an at least partially prereacted reaction product.

3. A composition according to claim 1 in which the halide of tetravalent titanium and the tetravalent titanium halide are each a titanium tetrahalide, and the selectivity control agent and the electron donor are ethers, esters, amines or phosphines.

4. A composition according to claim 1 in which the halide of tetravalent titanium and the tetravalent titanium halide are each titanium tetrachloride, and the selectivity control agent and the electron donor are esters of aromatic carboxylic acids.

5. A composition according to claim 4 in which the electron donor in the solid component is ethyl benzoate.

6. A composition according to claim 1 in which the atomic ratio of aluminum to titanium is from 10:

1 to 80;

1.

7. A composition according to claim 4 wherein said halohydrocarbon is carbon tetrachloride.

8. A composition according to claim 4 in which said halohydrocarbon is an aliphatic halohydrocarbon of 1 to 12 carbon atoms which has at least two chlorine atoms per molecule.

9. A composition according to claim 4 wherein said halohydrocarbon is chlorobenzene or a dichlorobenzene.

10. A solid component for olefin polymerization catalyst compositions which component has been obtained by halogenating a magnesium compound of the formula MgR'"'"'R" wherein R'"'"' is an alkoxide or aryloxide group and R" is an alkoxide or aryloxide group or halogen, with a halide of tetravalent titanium in the presence of a halohydrocarbon and an electron donor, contacting the halogenated product with a tetravalent titanium halide, washing it to remove unreacted titanium compounds, and recovering the solid product.

11. A composition according to claim 10 in which the halide of tetravalent titanium and the tetravalent titanium halide are each a titanium tetrahalide, and electron donor is an ether, ester, amine or phosphine.

12. A composition according to claim 10 in which the halide of tetravalent titanium and the tetravalent titanium halide are each titanium tetrachloride, and the electron donor is an ester of an aromatic carboxylic acid.

13. A composition according to claim 12 in which the electron donor is ethyl benzoate.

14. A composition according to claim 13 wherein said halohydrocarbon is carbon tetrachloride.

15. A composition according to claim 13 in which said halohydrocarbon is an aliphatic chlorohydrocarbon of 1 to 12 carbon atoms which has at least two chlorine atoms per molcule.

16. A composition according to claim 13 wherein said halohydrocarbon is chlorobenzene or a dichlorobenzene.

17. A solid component for olfin polymerization catalyst compositions, containing titanium and magnesium in an atomic ratio of Ti:

Mg in the range from 0.02;

1 to 1;

1, which component has been obtained by contacting a compound MgR'"'"'R", in which R'"'"' and R" are alkoxy or aryloxy groups of 2 to 8 carbon atoms, in a first contacting step with titanium tetrachloride, a chlorohydrocarbon having 1 to 12 carbon atoms per molecule and an electron donor, resulting in a solid which contains Mg, Ti, Cl and electron donor and which has a Mg;

Cl atomic ratio of at least 1.5, contacting the resulting solid with titanium tetrachloride in a separate contacting step, washing it to remove unreacted titanium compounds, and recovering the solid reaction product.

19. A composition according to claims 17 or 18 in which said chlorohydrocarbon is carbon tetrachloride.

20. A composition according to claims 17 or 18 in which said chlorohydrocarbon is an aliphatic compound which has at least two chlorine atoms per molecule.

21. A composition according to claims 17 or 18 wherein said chlorohydrocarbon is chlorobenzene.

22. An olefin polymerization catalyst composition comprising an organoaluminum compound, a selectivity control agent, and a solid component according to claims 17 or 18 in which the atomic ratio of aluminum to titanium is from 10:

1 to 80;

1.

23. An olefin polymerization catalyst composition according to claim 22 wherein said organoaluminum compound and selectivity control agent are employed as an at least partially prereacted reaction product.

24. An olefin polymerization catalyst composition according to claim 22 wherein the organoaluminum compound is a trialkylaluminum and the selectivity control agent and the electron donor are esters of aromatic carboxylic acids.

25. An olefin polymerization catalyst composition according to claim 24 wherein the organoaluminum compound is triethylaluminum and the selectivity control agent is ethyl anisate.

18. A solid component for olefin polymerization catalyst compositions, containing titanium and magnesium in an atomic ratio of Ti:

Mg in the range from 0.02;

1 to 1;

1, which component has been obtained by converting magnesium diethoxide to magnesium dichloride by reaction with titanium tetrachloride in a molar ratio of magnesium diethoxide;

titanium tetrachloride in the range from 0.01;

1 to 1.0;

1 in a first contacting step in the presence of a chlorohydrocarbon having 1 to 12 carbon atoms per molecule and of an ester of an aromaic caboxylic acid as electron donor, resulting in a solid which contains Mg, Ti, Cl and electron donor, contacting the resulting solid with titanium tetrachloride in a separate contacting step, washing it to remove unreacted titanium compounds, and recovering the solid reaction product.

26. A method for the preparation of a solid component for olefin catalyst compositions, comprising halogenating a magnesium compound of the formula MgR'"'"'R" wherein R'"'"' is an alkoxide or aryloxide group and R" is an alkoxide or aryloxide group or halogen, with a halide of tetravalent titanium in the presence of a halohydrocarbon and an electron donor, separating the solid reaction product from the reaction mixture, optionally washing it with an inert diluent to remove any unreacted material, then contacting the halogenated product with a tetravalent titanium halide, separating the resulting solid from the liquid medium, and washing it with an inert diluent to remove all unreacted titanium compounds.

27. A method for the preparation of a solid component for olefin catalyst compositions, comprising contacting a compound MgR'"'"'R", in which R'"'"' and R" are alkoxy or phenoxy groups of 2 to 8 carbon atoms, in a first contacting step with titanium tetrachloride, a chlorohydrocarbon having 1 to 12 carbon atoms per molecule and an electron donor, resulting in a solid which contains Mg, Ti, Cl and electron donor and which has an Mg:

Cl atomic ratio of at least 1.5, separating the solid reaction product from the reaction mixture, optionally washing it with an inert diluent to remove any unreacted material, then contacting the resulting solid with titanium tetrachloride, separating the resulting solid from the liquid medium, and washing it with an inert diluent to remove all unreacted titanium compounds.

29. A method according to claims 27 or 28 in which said chlorohydrocarbon is carbon tetrachloride.

30. A method according to claims 27 or 28 in which said chlorohydrocarbon is an aliphatic compound which has at least two chlorine atoms per molecule.

31. A method according to claims 27 or 28 in which said chlorohydrocarbon is chlorobenzene.

28. A method for the preparation of a solid component for olefin polymerization catalyst compositions, comprising converting magnesium diethoxide to magnesium dichloride by reaction with titanium tetrachloride in a molar ratio of magnesium diethoxide:

titanium tetrachloride in the range from 0.01;

1 to 1.0;

1 in a first contacting step in the presence of a chlorohydrocarbon having 1 to 12 carbon atoms per molecule and of an ester of an aromatic carboxylic acid as electron donor, resulting in a solid which contains Mg, Ti, Cl and electron donor, separating the solid reaction product from the reaction mixture, optionally washing it with an inert diluent to remove any unreacted material, then contacting the resulting solid with titanium tetrachloride, separating the resulting solid from the liquid medium, and washing it with an inert diluent to remove all unreacted titanium compounds.