Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2000-08-02
2003-10-28
Choi, Ling-Siu (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S103000, C502S117000, C502S104000, C526S160000, C526S127000, C526S943000, C526S352000, C526S348000, C526S161000, C526S126000
Reexamination Certificate
active
06638887
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to certain monocyclopentadienyl metal compounds, to certain catalyst systems comprising such monocyclopentadienyl metal compounds along with an activator, and to a process using such catalyst systems for production of polyolefins, particularly high molecular weight ethylene-&agr;-olefin copolymers having a high level of &agr;-olefin comonomer incorporation.
BACKGROUND OF THE INVENTION
As is well known, various processes and catalysts exist for homopolymerization or copolymerization of olefins. For many applications it is of primary importance for a polyolefin to have a high weight average molecular weight while having a relatively narrow molecular weight distribution. A high weight average molecular weight, when accompanied by a narrow molecular weight distribution, provides a polyolefin or an ethylene-&agr;-olefin copolymer with high strength properties.
U.S. Pat. No. 5,264,504 discloses certain monocyclopentadienyl metal compounds having an amido radical with an aliphatic or alicyclic hydrocarbyl moiety attached thereto through a primary or secondary carbon atom. EPO 416,815 discloses certain monocyclopentadienyl metal compounds which are activated with an alumoxane co-catalyst. U.S. Pat. No. 5,064,802 discloses certain monocyclopentadienyl metal compounds which are activated with a non-coordinating compatible anion of a Bronsted acid salt.
SUMMARY OF THE INVENTION
The present invention is directed to certain monocyclopentadienyl compounds and to catalyst systems which include such monocyclopentadienyl metal compounds along with an activator component. The catalyst systems of the present invention are highly productive for polymerizing ethylene and olefins to produce high molecular weight copolymers having a high content of &agr;-olefin comonomer. More particularly, the present invention relates to certain monocyclopentadienyl metal compounds which include an amido moiety having an alicyclic hydrocarbyl moiety covalently bonded thereto through a tertiary carbon atom. A tertiary carbon atom is defined here as a carbon atom bonded to three other non-hydrogen atoms.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to the discovery of certain monocyclopentadienyl metal compounds which, by reason of the presence therein of ligands of a particular nature, are particularly useful in catalyst systems to provide greatly improved performance characteristics. The monocyclopentadienyl metal compounds of the present invention are represented by the formula:
wherein: M is Zr, Hf or Ti;
(C
5
H
4−x
R
x
) is a cyclopentadienyl ring which is substituted with from zero to four substituent groups R, “x” is 0, 1, 2, 3, or 4 denoting the degree of substitution, and each substituent group R is, independently, a radical selected from C
1
-C
20
hydrocarbyl radicals, substituted C
1
-C
20
hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen radical, an amido radical, a phosphido radical, an alkoxy radical, an aryloxy radical or any other radical containing a Lewis acidic or basic functionality; C
1
-C
20
hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements; halogen radicals; amido radicals; phosphido radicals; alkoxy radicals; alkylborido radicals; or any other radical containing Lewis acidic or basic functionality; or (C
5
H
4−x
R
x
) is a cyclopentadienyl ring in which at least two adjacent R-groups are joined together and along with the carbon atoms to which they are attached form a C
4
-C
20
ring system;
R′ is a radical selected from C
4
-C
30
, preferably C
4
-C
20
, alicyclic hydrocarbyl radicals wherein one or more hydrogen atoms may be replaced by radicals containing Lewis acidic or basic functionalities such as, for example, radicals selected from halogen, amido, phosphido, alkoxy, aryloxy and the like, with the proviso that R′ is covalently bonded to the nitrogen atom through a tertiary carbon atom;
each Q is independently a radical selected from halide; hydride; substituted or unsubstituted C
1
-C
20
hydrocarbyl; alkoxide; aryloxide; amide; or phospide; or both Q together may be an alkylidene or a cyclometallated hydrocarbyl or any other divalent anionic chelating ligand, with the proviso that where any Q is a hydrocarbyl radical, such Q is not a substituted or unsubstituted cyclopentadienyl radical;
T is a covalent bridging group containing a Group IV A or V A element such as, but not limited to, a dialkyl, dialicyclyl, alkylalicyclyl, arylalicyclyl, alkylaryl or diaryl silicon or germanium radical; alkyl and/or aryl phosphine or amine radical; or a substituted or unsubstituted hydrocarbyl radical such as methylene, ethylene and the like which may be substituted with substituents selected from alkyl, alicyclyl and aryl radicals or combinations thereof having from 1 to 20 carbon atoms and silyl atoms.
Such compounds can also include an L
w
complexed thereto wherein L is a neutral Lewis base. Examples of such neutral Lewis bases include but are not limited to diethylether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like. The “w” is a number from 0 to 3. Optionally, L may be covalently bonded to one or both Q provided Q is not hydride or halide.
L can also be a second transition metal compound of the same type such that the two metal centers M and M′ are bridged by Q and Q′, wherein M′ has the same meaning as M, and Q′ has the same meaning as Q. Such dimeric compounds are represented by the formula:
A preferred class of compounds of the present invention are represented by the formula:
wherein:
M is selected from Ti, Hf and Zr;
(C
5
H
4−x
R
x
) is as defined above with respect to Formula I;
each of R
1
and R
2
are independently selected from C
1
-C
20
hydrocarbyl radicals, and may optionally be joined together to form a cyclic ring structure;
T is Si or Ge;
each Q is independently selected from halide, hydride, substituted or unsubstituted C
1
-C
20
hydrocarbyl radicals; alkoxide; amide; and phosphide radicals, with the proviso that Q is not a substituted or unsubstituted cyclopentadienyl radical;
R′ is selected from C
4
-C
20
alicyclic hydrocarbyl radicals with the proviso that R′ is covalently bonded to the nitrogen atom through a tertiary carbon atom; and
L
w
is optional and is as defined above.
A more preferred class of compounds of the present invention are those compounds represented by Formula IV:
wherein:
M is selected from Ti, Zr and Hf;
T is selected from Si or Ge;
each of R
1
and R
2
is independently selected from C
1
-C
20
alkyl, C
6
C
22
aryl, C
3
-C
20
cycloalkyl radicals or combinations thereof and may optionally be joined together to form a cyclic ring structure;
each R
3
is independently selected from hydrogen; C
1
-C
20
alkyl; C
3
-C
20
cycloalkyl; C
6
-C
22
aryl; halogen; amido; phosphido; alkoxy; aryloxy; alkylborido; and the like radicals; or combinations thereof;
each Q is independently selected from hydrogen; halogen; C
1
-C
20
alkyl; C
6
-C
22
aryl; C
3
-C
20
cycloalkyl; alkoxy; aryloxy; amido; and phosphido radicals or combinations thereof;
u is an integer of from 0 to 6, preferably 0 to 4, such as from 1 to 3;
x is 0-4;
each R
4
is independently selected from hydrogen; halogen, C
1
-C
10
alkyl; C
3
-C
10
cycloalkyl; C
6
-C
22
aryl; amido; alkoxy; aryloxy; or combinations thereof and the like radicals; or two R
4
groups along with the carbon atom or atoms to which they are attached, form a saturated or partially saturated alicyclic group or form an aryl group; and
Lw is optional and is as defined above.
Preferred compounds within the scope of Formula IV are those wherein each R
3
is independently selected from C
1
-C
20
alkyl; C
3
-C
20
cycloalkyl; C
6
-C
22
aryl; or combinations thereof; and M is titanium. As utilized herein, the term “alkyl”, alone or in combination, means a straight-chain or branched-chain alkyl radical containing
Choi Ling-Siu
ExxonMobil Chemical Patents Inc.
Schmidt C. Paige
Smith Charles E.
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