Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1999-07-08
2002-09-17
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C526S127000, C526S160000, C526S161000, C526S943000, C502S152000, C502S155000, C556S011000, C556S012000, C556S023000, C556S053000
Reexamination Certificate
active
06451724
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a new class of metallocenes, to a catalyst for the polymerization of olefins comprising said metallocenes and to a processes for the polymerization of olefins carried out in the presence of said catalyst. The invention also relates to a novel class of ligands useful as intermediates in the synthesis of said metallocenes.
PRIOR ART DISCLOSURE
Many metallocene compounds known in the state of the art are active as catalyst components in olefin polymerization reactions, in association with suitable cocatalysts, such as alumoxanes or aluminum derivatives. For instance, European patent application EP 0 035 242 discloses a process for the polymerization of ethylene and propylene in the presence of a catalyst system comprising a cyclopentadienyl complex of a transition metal.
European patent application EP 0 129 368 discloses a catalyst system for the polymerization of olefins comprising a bis-cyclopentadienyl coordination complex with a transition metal, wherein the two cyclopentadienyl groups may be linked by a bridging group. Said bridging group is generally a divalent radical containing one or more carbon atoms (such as an ethylene group) or containing heteroatoms (such as a dimethylsilanediyl group).
Bridged metallocene compounds wherein the cyclopentadienyl residue is condensed to one or more aromatic or non aromatic ring are known in the state of the art; for example, European patent application EP 0 604 908 discloses a class of catalysts useful in the polymerization of olefins, in particular in the preparation of high molecular weight atactic polypropylene, comprising a bis-fluorenyl compound bridged by means of a one atom bridge. International application WO 95/27717, in the name of the same Applicant, discloses a class of bridged and unbridged metallocenes useful as catalytic components in the polymerization of ethylene and/or propylene, characterized by the fact that the cyclopentadienyl ligands have two or four adjacent substituents forming one or two alkylenic cycles of 4-8 carbon atoms; examples of these metallocenes are bis(1,2-cyclotetramethyleneinden-1-yl) titaniumdichloride, dimethylsilanediyl-bis(2,3-cyclotetramethylene-inden-1-yl)-zirconium dichloride, dimethylsilanediyl-bis(2,3-octahydrofluorenyl)-zirconium dichloride and isopropyliden-(cyclopentadienyl)(2,3-cyclotetramethyleneinden-1-yl)zirconium dichloride.
The international patent application WO 98/22486, in the name of the same Applicant, describes bridged or unbridged metallocenes comprising at least a coordinating group containing a six 7 electron central radical, directly coordinating a transition metal atom, to which are associated one or more radicals containing at least one non carbon atom selected from B, N, O, Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb and Te. Said metallocenes are useful as catalyst components for the production of polyethylene and polypropylene.
The international patent application WO 98/37106 describes a polymerization catalyst system comprising a catalytic complex formed by activating a transition metal compound which comprises a group 13, 15 or 16 heterocyclic fused cyclopentadienide ligand and a metal selected from the group consisting of Group 3-9 and 10 metals; said heterocyclic fused cyclopentadienide ligand preferably contains, as endocyclic heteroatoms, one or more B, N, P, O or S atoms.
SUMMARY OF THE INVENTION
The Applicant has now unexpectedly found new metallocene compounds useful as catalyst components in the polymerization of olefins. It is an object of the present invention a class of bridged or unbridged metallocenes of formula (I):
(ZR
1
m
)
n
(Cp)(A)
r
ML
p
L′
q
(I)
wherein (ZR
1
m
)
n
is a divalent group bridging Cp and A, Z being C, Si, Ge, N or P, and the R
1
groups, equal or different from each other, being H or linear or branched, saturated or unsaturated C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl or C
7
-C
20
arylalkyl groups;
Cp is a heterocyclic cyclopentadienyl group of formula (II) or (II′):
wherein one of X or Y is a single bond, the other being O, S, NR
6
or PR
6
, R
6
being hydrogen, a linear or branched, saturated or unsaturated C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl or C
7
-C
20
arylalkyl groups, optionally containing one or more atoms belonging to groups 13-16 of the Periodic Table of the Elements (new IUPAC notation), such as B, Al, Si, Ge, N, P, O and S atoms;
R
2
and R
3
, equal or different from each other, are selected from the group consisting of hydrogen, halogen, linear or branched, saturated or unsaturated C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl, C
7
-C
20
arylalkyl, —OR
6
, —OCOR
6
, —SR
6
, PR
6
2
, wherein R
6
has the meaning reported above; or R
2
and R
3
form together a condensed C
5
-C
7
ring, saturated, unsaturated or aromatic, optionally containing one or more atoms belonging to groups 13-16 of the Periodic Table of the Elements (new IUPAC notation), such as B, Al, Si, Ge, N, P, O and S atoms;
the substituents R
4
, equal or different from each other, are selected from the group consisting of halogen, linear or branched, saturated or unsaturated C
1
-C
20
alkyl, C
3
-C
20
cycloalkyl, C
6
-C
20
aryl, C
7
-C
20
alkylaryl, C
7
-
20
arylalkyl, —OR
6
, —OCOR
6
, —SR
6
, —NR
6
2
and —PR
6
2
, wherein R
6
has the meaning reported above, optionally containing one or more atoms belonging to groups 13-16 of the Periodic Table of the Elements (new IUPAC notation), such as B, Al, Si, Ge, N, P, O and S atoms;
a is an integer ranging from 0 to 4;
Cp can be a partially hydrogenated derivative of the heterocyclic cyclopentadienyl group of formula (II) or (II′) reported above;
A is a substituted or unsubstituted cyclopentadienyl, a group —NR
6
, R
6
having the meaning reported above, or corresponds to (II) or (II′), or to a partially hydrogenated derivative of (II) or (II′);
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 (IUPAC version); the substituents L, same or different from each other, are monoanionic sigma ligands selected from the group consisting of hydrogen, halogen, —R
6
, —OR
6
, —OCOR
6
, —OSO
2
CF
3
, —SR
6
, —NR
6
2
and —PR
6
2
, wherein the groups R
6
, same or different from each other, have the meaning reported above and optionally contain Si or Ge atoms;
the substituents L′, same or different from each other, are coordinating molecules, such as Lewis bases;
m is 1 or 2, and more specifically it is 1 when Z is N or P, and it is 2 when Z is C, Si or Ge;
n is an integer ranging from 0 to 4; r is 0 or 1; n 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 2 when r=1, and minus 1 when r=0, and p+q being ≦3.
The present invention further concerns a new class of bridged ligands of formula (IV):
(ZR
1
m
)
n
(CP)(A) (IV)
wherein Cp, A, (ZR
1
m
)
n
, Z, R
1
and m have the meaning reported above and n is an integer ranging from 1 to 4, particularly useful as intermediates in the preparation of the above metallocenes.
Another object of the present invention is a catalyst for the polymerization of olefins comprising said metallocenes and their use in the polymerization of olefins, particularly in the production of homo and copolymers of ethylene.
DETAILED DESCRIPTION OF THE INVENTION
In the metallocenes of formula (I), particularly suitable as catalytic components in the polymerization of olefins, the divalent bridge (ZR
1
m
)
n
is preferably selected from the group consisting of CR
1
2
, SiR
1
2
, GeR
1
2
, NR
1
, PR
1
and (CR
1
2
)
2
, R
1
having the meaning reported above. More preferably, said divalent bridge is Si(CH
3
)
2
, SiPh
2
, CH
2
, (CH
2
)
2
or C(CH
3
)
2
; even more preferably, it is Si(CH
3
)
2
or CH
2
.
m is 1 or 2; n ranges from 0 to 4 and, when n>1, the atoms Z can be the same or different from each
Bagrov Vladimir V.
Nifant'ev Ilya E.
Basell Technology Company BV
Bryan Cave LLP
Harlan R.
Wu David W.
LandOfFree
Metallocenes and catalysts for olefin-polymerisation does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Metallocenes and catalysts for olefin-polymerisation, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Metallocenes and catalysts for olefin-polymerisation will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2829927