Preparation of supported cocatalysts
View Patent ↗The present invention relates to a process for preparing a supported cocatalyst for olefin polymerization, which comprises reacting A) a support bearing functional groups, B) triethylaluminum and C) a compound of the formula (I), (R 1 ) x —A—OH) y (I) where A is an atom of group 13 or 15 of the Periodic Table, R 1 are identical or different and are each, independently of one another, hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalky, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl, C 7 -C 40 -haloalkylaryl or an OSiR 3 2 group, where R 2 are identical or different and are each hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalkyl, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl or C 7 -C 40 -haloalkylaryl, y is 1 or 2 and x is 3 minus y. In addition, the invention relates to supported cocatalysts obtainable by such a process, to the use of the supported cocatalysts for preparing a catalyst system for the polymerization of olefins, to catalyst systems for the polymerization of olefins obtainable from the supported cocatalysts and to a process for the polymerization of olefins in which these catalyst solids are used.
1. A process for preparing a supported cocatalyst for olefin polymerization, which comprises first reacting
A) support bearing functional groups, with
B) triethylaluminum, thereby producing a reaction product; and subsequently reacting the reaction product with
C) a compound of the formula (I),
where
A is an atom of group 13 or 15 of the Periodic Table;
R 1 are identical or different and are each, independently of one another, hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalky, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl, C 7 -C 40 -haloalkylaryl or an OSiR 2 3 group, where
R 2 are identical or different and are each hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalkyl, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl or C 7 -C 40 -haloalkylaryl;
y is 1 or 2; and
x is 3 minus y.
2. The process as claimed in claim 1 , wherein A in formula (I) is boron.
3. The process as claimed in claim 2 , wherein R 1 in formula (I) is C 6 -C 10 -haloaryl, C 7 -C 20 -alkylaryl or C 7 -C 20 -haloalkylaryl.
4. A supported cocatalyst obtained by a process comprising first reacting
A) support bearing functional groups, with
B) triethylaluminum, thereby producing a reaction product and subsequently reacting the reaction product with
C) a compound of the formula (I),
where
A is an atom of group 13 or 15 of the Periodic Table;
R 1 are identical or different and are each, independently of one another, hydrogen, halogen, C 1 -C 20 -alkyl, C 1 C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalky, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl, C 7 -C 40 haloalkylaryl or an OSiR 2 3 group, where
R 2 are identical or different and are each hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalkyl, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl or C 7 -C 40 -haloalkylaryl;
y is 1 or 2; and
x is 3 minus y.
5. A process comprising preparing a catalyst system for the polymerization of olefins with a supported cocatalyst, the supported cocatalyst being prepared by
first reacting
A) support bearing functional groups, with
B) triethylaluminum, thereby producing a reaction product and subsequently reacting the reaction product with
C) a compound of the formula (I),
where
A is an atom of group 13 or 15 of the Periodic Table;
R 1 are identical or different and are each, independently of one another, hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalky, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl, C 7 -C 40 -haloalkylaryl or an OSiR 2 3 group, where
R 2 are identical or different and are each hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalkyl, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl or C 7 -C 40 -haloalkylaryl;
y is 1 or 2; and
x is 3 minus y.
and then bringing the supported cocatalyst into contact with
D) at least one organic transition metal compound.
6. A catalyst system for the polymerization of olefins, obtained by bringing at least one supported cocatalyst obtained by a process comprising
first reacting
A) support bearing functional groups, with
B) triethylaluminum, thereby producing a reaction product and subsequently reacting the reaction product with
C) a compound of the formula (I),
where
A is an atom of group 13 or 15 of the Periodic Table;
R 1 are identical or different and are each, independently of one another, hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalky, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl, C 7 -C 40 -haloalkylaryl or an OSiR 2 3 group, where
R 2 are identical or different and are each hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalkyl, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl or C 7 -C 40 -haloalkylaryl;
y is 1 or 2; and
x is 3 minus y
into contact with
D) at least one organic transition metal compound.
7. The catalyst system for the polymerization of olefins as claimed in claim 6 , wherein
E) at least one organometallic compound is additionally added in its preparation.
8. The catalyst system for the polymerization of olefins as claimed in claim 7 which is prepared by:
firstly preparing a catalyst solid by bringing the at least one supported cocatalyst into contact with the at least one organic transition metal compound D), then
bringing the catalyst solid into contact with the at least one organometallic compound E) in a second step, thereby forming a mixture and then using the mixture without further work-up for the polymerization.
9. A process comprising polymerizing olefins with a catalyst system obtained by bringing at least one supported cocatalyst obtained by a process comprising
first reacting
A) support bearing functional groups, with
B) triethylaluminum thereby producing a reaction product and subsequently reacting the reaction product with
C) a compound of the formula (I),
where
A is an atom of group 13 or 15 of the Periodic Table;
R 1 are identical or different and are each, independently of one another, hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalky, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl, C 7 -C 40 -haloalkylaryl or an OSiR 3 2 group, where
R 2 are identical or different and are each hydrogen, halogen, C 1 -C 20 -alkyl, C 1 -C 20 -haloalkyl, C 1 -C 10 -alkoxy, C 6 -C 20 -aryl, C 6 -C 20 -haloaryl, C 6 -C 20 -aryloxy, C 7 -C 40 -arylalkyl, C 7 -C 40 -haloarylalkyl, C 7 -C 40 -alkylaryl or C 7 -C 40 -haloalkylaryl;
y is 1 or 2; and
x is 3 minus y
into contact with
D) at least one organic transition metal compound.