Method for the production of olefin polymers and selected catalysts
View Patent ↗A process for preparing olefin homopolymers or copolymers by polymerization of at least one olefin in a hydrocarbon (mixture) in the presence of a molar mass regulator, a mixed catalyst and a substance which increases the electrical conductivity of the hydrocarbon (mixture) and is soluble in the hydrocarbon or the mixture of hydrocarbons or which reacts with components of the mixed catalyst, wherein the mixed catalyst is obtainable by reaction of a magnesium alkoxide with titanium(IV) halide and comprises titanium in the oxidation states four and three and also an organic aluminum compound, where the molar ratio of Ti(IV) to Ti(III) is from 100:1 to 1:100. The process makes it possible to prepare, in particular, polyethylenes having an ultrahigh molecular weight. The formation of deposits on the walls during the polymerization is significantly reduced.
1. A process for preparing olefin homopolymers or copolymers which comprises polymerizing by polymerization of at least one olefin in a hydrocarbon or a mixture of hydrocarbons in the presence of a molar mass regulator, a mixed catalyst and a substance which increases the electrical conductivity of the hydrocarbon or the mixture of hydrocarbons and is soluble in the hydrocarbon or the mixture of hydrocarbons or which reacts with components of the mixed catalyst, wherein the mixed catalyst is obtainable by reaction of a magnesium alkoxide with titanium(IV) halide, and comprises titanium in the oxidation states four and three and also an organoaluminum compound, where the molar ratio of Ti(IV) to Ti(III) is from 100:1 to 1:100 and wherein up to a ratio component of 0.15, soluble organoaluminum compounds which increase the electrical conductivity of the solution are formed.
2. The process as claimed in claim 1 , wherein the molar ratio of Ti(IV) to Ti(III) is from 10:1 to 2:1.
3. The process as claimed in claim 1 , wherein the olefin to be polymerized is propylene or ethylene or a mixture of propylene and ethylene.
4. The process as claimed in claim 3 , wherein the olefin is ethylene.
5. The process as claimed in claim 4 , wherein the polymerization is carried out at temperatures of from 30 to 130° C. and partial pressures of the monomer to be polymerized of from 0.05 to 0.6 mPa.
6. The process as claimed in claim 1 , wherein the substance which increases the electrical conductivity of the hydrocarbon or the mixture of hydrocarbons is selected from the group consisting of oxygen, protic compounds which are soluble in the hydrocarbon or the mixture of hydrocarbons and polyionic compounds which are soluble in the hydrocarbon or the mixture of hydrocarbons.
7. The process as claimed in claim 6 , wherein the substance which increases the electrical conductivity of the hydrocarbon or the mixture of hydrocarbons is a mixture comprising at least one polysulfone and at least one polymeric polyamine.
8. The process as claimed in claim 6 , wherein the substance which increases the electrical conductivity of the hydrocarbon or the mixture of hydrocarbons is water or an alcohol, where the molar ratio of water/aluminum or alcohol/aluminum does not exceed 0.15.
9. The process as claimed in claim 1 , wherein the mixed catalyst is a supported catalyst.
10. The process as claimed in claim 1 , wherein the mixed catalyst is obtainable obtained by reaction of magnesium alkoxide with titanium tetrahalide in a molar ratio of from 1:0.5 to 1:4 in an aliphatic hydrocarbon and subsequent preactivation by means of an organoaluminum compound, with partial conversion of the Ti(IV) component into the Ti(III) component occurring and the molar ratio of Ti(IV) to Ti(III) being from 10:1 to 1:1.
11. The process as claimed in claim 10 , wherein the preactivation is carried out using trimethylaluminum, triethylaluminum or tripropylaluminum with partial conversion of the Ti(IV) component into the Ti(III) component and the molar ratio of Ti(IV) to Ti(III) being from 2.0:1 to 3.0:1.
12. The process as claimed in claim 9 , wherein the catalyst obtained is used for the polymerization of ethylene and the concentration of the organoaluminum compound is from 10 −5 to 10 −4 mol of Al/l.
13. The process as claimed in claim 1 , wherein said titanium(IV) halide is TiCl 4 .
14. The process as claimed in claim 10 , wherein the preactivation is carried out using trimethylaluminum, triethylaluminum or tripropylaluminum with partial conversion of the Ti(IV) component into the Ti(III) component and the molar ratio of Ti(IV) to Ti(III) being from 2.6:1.
15. The process as claimed in claim 9 , wherein the catalyst obtained is used for the polymerization of ethylene and the concentration of the organoaluminum compound is 2×10 −5 to 10 −4 mol of Al/l.