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US 6,451,724 B1Granted
Metallocenes and catalysts for olefin-polymerisation
AssigneeBasell Technology Company BV
InventorsIlya E. Nifant'ev, Vladimir V. Bagrov
Life of this patent
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Abstract
A class of metallocenes of formula (I): (ZR1m)n(Cp)(A)rMLpL′q(I) wherein (ZR1m)n, is a divalent group bridging Cp and A, Cp is a heterocyclic cyclopentadienyl group of formula (II) or (II′), wherein one of X or Y is a single bond, the other being an heteroatom; R2 and R3 are hydrogen, halogen or a hydrocarbon radical, optionally containing heteroatoms; R4 is halogen or an hydrocarbon radical, optionally containing heteroatoms; the group A is a cyclopentadienyl derivative or is equal to Cp; M is Ti, Zr or Hf; m is 1 or 2; n ranges from 0 to 4; r is 0 or 1; p and q range from 0 to 3; and a ranges from 0 to 4. Moreover, are disclosed catalyst systems containing these metallocenes, useful in the polymerization of olefins.
Claims16
A metallocene of formula (I):
- (ZR1m)n(Cp)(A)rMLpL′q (I)
- wherein
- (ZR1m)nis a divalent group bridging Cp and A, Z is selected from the group consisting of C, Si, Ge, N, or P, and each R1 is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, and C7-C20 arylalkyl groups,
- Cp is a heterocyclic cyclopentadienyl group of formula (IIa), (II′a), (IIb), or (II′b), or Cp is a partially hydrogenated derivative of the heterocyclic group of formula (IIa), (II′a), (IIb), or (II′b):
- wherein X or Y is selected from the group consisting of O, S, NR6, and PR6 wherein R6 is selected from the group consisting of hydrogen, a linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, and C7-C20 arylalkyl group, optionally containing one or more atoms belonging to groups 13-16 of the Periodic Table of the Elements;
- R2 and R3, the same or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, —OR6, —OCOR6, —SR6, —NR62, wherein R6 has the meaning reported above;
- or R2 and R3 from together a condensed C5-C7 ring, saturated, unsaturated, or aromatic, optionally containing one or more atoms belonging to groups 13-16 of the Periodic Table of the Elements;
- the substituents R4, the same or different from each other, are selected from the group consisting of halogen, linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, OR6, —OCOR6, —SR6, —NR62, and —PR62, wherein R6 has the meaning reported above;
- a is an integer ranging from 0 to 4;
- A is a substitued or unsubstituted cyclopentadienyl, —NR6 wherein R6 has the meaning reported above, corresponds to formula (IIa), (II′a), (IIb), or (II′b), or corresponds to a partially hydrogenated derivative of formula (IIa), (II′a), (IIb), or (II′b);
- M is a transition metal belonging to group 3, 4, 5, 6 or to the lanthanide or actinide groups of the Periodic Table of the Elements;
- each substituent L is independently a monoanionic sigma ligand selected from the group consisting of hydrogen, halogen, —R6, —OR6, —OCOR6, —OSO2CF3, —SR6, —NR62, and PR62, wherein each R6 group, the same or different from each other, has the meaning reported above;
- each substituent L′ is independently a Lewis base;
- m is 1 or 2, being 1 when Z is N or P, and being 2 when Z is C, Si, or Ge;
- n is an integer ranging from 0 to 4;
- r is 0 when r is 0;
- p and q are integers ranging from 0 to 3, p being equal to the valence of the metal M minus when r=1, and minus 1 when r=0, and p+q being ≦3.
14 more elements
A bridged ligand of formula (IV):
- (ZR1m)n(Cp)(A) (IV)
- wherein
- (ZR1m)n is a divalent group bridging Cp and A, Z is selected from the group consisting of C, Si, Ge, N, and P, and each group is independently selected from the group consisting of hydrogen, linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, and C7-C20 arylalkyl groups;
- Cp is a heterocyclic cyclopentadienyl group of formula (IIa), (II′a), (IIb), or (II′b), or Cp can be a partially hydrogenated derivative of the heterocyclic group of formula (IIa), (II′a), (IIb), or (II′b):
- wherein X or Y is selected from the group consisting of O, S, NR6, and PR6 wherein R6 is selected from the group consisting of hydrogen, a linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, and C7-C20 arylalkyl group, optionally containing one or more atoms belonging to groups 13-16 of the Periodic Table of the Elements;
- R2 and R3, the same or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, —OR6, —OCOR6, —SR6, —NR62, and —PR62, wherein R6 has the meaning reported above;
- or R2 and R3 can form together a condensed C5-C7 ring, saturated, unsaturated, or aromatic, optionally containing one or more atoms belonging to groups 13-16 of the Periodic Table of the Elements;
- the substituents R4, the same or different from each other, are selected from the group consisting of halogen, linear or branched, saturated or unsaturated C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl, C7-C20 arylalkyl, —OR6, —OCOR6, —SR6, —NR62, and —PR62, wherein R6 has the meaning reported above;
- a is an integer ranging from 0 to 4;
- A is a substituted or unsubstituted cyclopentadienyl, —NR6 wherein R6 having the meaning reported above, corresponds to formula (IIa), (II′a), (IIb), or (II′b), or corresponds to a partially hydrogenated derivative of formula (IIa), (II′a), (IIb), or (II′b);
- m is 1 or 2, being 1 when Z is N or P, and being 2 when Z is C, Si, or Ge;
- and
- n is an integer ranging from 1 to 4.
10 more elements
Dependencies are inferred from the claim text.