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US 7,795,167 B2Granted
Cyclopentadienyl complexes of group 6 substituted by silyl halides
AssigneeBasell Polyolefine GmbH
InventorsShahram Mihan, Markus Enders, Pablo Fernandez
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Abstract
Cyclopentadienyl complexes of group 6 having at least one cyclopentadienyl system which is substituted by at least one silyl group which bears at least one halogen substituent and a catalyst system comprising at least one of the cyclopentadienyl complexes, and also a process for preparing them, the use of the catalyst system for the polymerization or copolymerization of olefins and a process for preparing polyolefins by polymerization or copolymerization of olefins in the presence of the catalyst system.
Claims8
A cyclopentadienyl complex of group 6 comprising at least one silyl group, wherein the silyl group comprises at least one halogen substituent the cyclopentadienyl complex is a monocyclopentadienyl complex comprising a formula of Cp-R15Av-A1A-M1A-XAt, wherein
- Cp-R15Av-A1A is
- E1A-E5A are carbon;
- R1A-R4A are each, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, wherein radicals R1A-R4A can be substituted by at least one halogen, and/or two vicinal radicals R1A-R4A can be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R1A-R4A can be joined to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, with the proviso that at least one R1A-R4A is SiR2D;
- D is fluorine, chlorine, bromine or iodine;
- R are each, independently of one another, hydrogen C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, and arylalkyl comprising from 1 to 16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, wherein radicals R can be substituted by at least one halogen, and/or two radicals R can be joined to form a five-, six- or seven-membered ring;
- R15A is a divalent bridge between A1A and Cp selected tram the group consisting at
- R16A-R19A are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, wherein radicals R16A-R19A can be substituted by at least one halogen, and/or two geminal or vicinal radicals R16A-R19A can be joined to form a five- or six-membered ring:
- A1A in an uncharged donor group —NR23A— or —NR22A2;
- R22A are each, independently of one another, C1-C10-alkyl, C2-C22-alkenyl, C6 C22-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, wherein radicals R22A can be substituted by at least one halogen and/or two radicals R22A can be joined to form a five, six- or seven-membered ring;
- M1A is a metal selected from the group consisting of chromium, molybdenum, and tungsten,
- XA is fluorine, chlorine, bromine, or iodine;
- t is 1 or 2, with the proviso that the cyclopentadienyl complex is uncharged;
- and
- v is 0 or 1.
11 more elements
A catalyst system for olefin polymerization comprising:
- A) at least one cyclopentadienyl complex of group 6 comprising at least one silyl group, wherein the silyl group comprises at least one halogen substituent, the cyclopentadienyl complex is a monocyclopentadienyl complex comprising a formula Cp-R15Av-A1A-M1A-XAt, wherein
- Cp-R15Av-A1A is
- E1A-E5A are carbon;
- R1A-R4A are each, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, wherein radicals R1A-R4A can be substituted by at least one halogen, and/or two vicinal radicals R1A-R4A can be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R1A-R4A can be joined to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, with the proviso that at least one R1A-R4A is SiR2D;
- D is fluorine, chlorine, bromine or iodine;
- R are each, independently of one another, hydrogen, C1-C22alkyl, C2-C22-alkenyl, C6-C22, and arylalkyl comprising from 1 to 16 carbon atoms in the alkyl part and from 6 to 21 carbon atoms in the aryl part, wherein radicals R can be substituted by at least one halogen, and/or two radicals R can be joined to form a five-, six- or seven-membered ring;
- R15A is a divalent bridge between A1A, and Cp selected from the group consisting of
- R16A-R19A are each, independently of one another, hydrogen, C1-C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, wherein radicals R16A-R19A can be substituted by at least one halogen, and/or two geminal or vicinal radicals R16A-R19A can be joined to form a five- or six-membered ring;
- A1A is an uncharged donor group —NR22A— or —NR22A2;
- R22A are each, independently of one another, C1-C10-alkyl, C2-C22-alkenyl, C1-C22-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, wherein radicals R22A can be substituted by at least one halogen and/or two radicals R22A can be joined to form a five-, six- or seven-membered ring;
- M1A is a metal selected from the group consisting of chromium, molybdenum, and tungsten,
- XA is fluorine, chlorine, bromine, or iodine;
- t is 1 or 2, with the proviso that the cyclopentadienyl complex is uncharged;
- and
- v is 0 or 1;
- B) optionally, an organic or inorganic support;
- C) optionally, at least one activating compound,
- D) optionally, at least one additional catalyst suitable for olefin polymerization;
- and
- E) optionally, at least one metal compound comprising a metal of group 1, 2 or 13 of the Periodic Table.
17 more elements
A process for preparing a cyclopentadienyl complex of group 6 comprising at least one cyclopentadienyl system substituted by at least one silyl group, wherein the silyl group comprises at least one halogen substituent, wherein the cyclopentadienyl complex is a monocyclopentadienyl complex comprising formula Cp-R15Av-A1A-M1A-XAt, wherein
- Cp-R15Av-A1A is
- E1A-E5A are carbon;
- R1A-R4A are each, independently of one another, hydrogen, C1-C22-alkyl, C2-C22-alkenyl, C6-C22-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, wherein radicals R1A-R4A can be substituted by at least one halogen, and/or two vicinal radicals R1A-R4A can be joined to form a five-, six- or seven-membered ring, and/or two vicinal radicals R1A-R4A can be joined to form a five-, six- or seven-membered heterocycle comprising at least one atom from the group consisting of N, P, O and S, with the proviso that at leant one R1A-R4A is SiR2D;
- D is fluorine, chlorine, bromine or iodine;
- R are each, independently of one another, hydrogen, C1-C22-alkyl, C2-C22alkenyl, C6-C22-aryl, and arylalkyl comprising from 1 to 16 carbon atom in the alkyl part and from 6 to 21 carbon atoms in the aryl part, wherein radicals R can be substituted by at least one halogen, and/or two radicals R can be joined to form a five-, six- or seven-membered ring:
- R15A is a divalent bridge between A1A, and Cp selected from the group consisting of
- R16A-R19A are each, independently of one another, hydrogen, C1 C20-alkyl, C2-C20-alkenyl, C6-C20-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and 6-20 carbon atoms in the aryl part, wherein radicals R16A-R19A can be substituted by at least one halogen, and/or two geminal or vicinal radicals R16A-R19A can be joined to form a five- or six-membered ring;
- A1A is an uncharged donor group —NR22A— or —NR22A2 system;
- R22A are each, independently of one another, C1-C10-alkyl, C2 C22-alkenyl, C6-C22-aryl, and arylalkyl comprising from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part, wherein radicals R22A can be substituted by at least one halogen and/or two radicals R22A can be joined to form a five-, six- or seven-membered ring;
- M1A is a metal selected from the group consisting of chromium, molybdenum, and tungsten;
- XA is fluorine, chlorine, bromine, or iodine;
- t is 1 or 2, with the proviso that the cyclopentadienyl complex is uncharged;
- and
- v is C or 1;
- wherein the process comprises:
- reacting the cyclopentadienyl complex of group 6 comprising at least one cyclopentadienyl system with a boron trihalide.
13 more elements
Dependencies are inferred from the claim text.