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
2000-07-19
2002-04-23
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S117000, C502S152000, C502S155000, C526S127000, C526S160000, C526S943000
Reexamination Certificate
active
06376410
ABSTRACT:
FIELD
This invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization.
BACKGROUND
The use of metallocene compositions in olefin polymerization is well known. Metallocenes containing substituted, bridged indenyl derivatives are noted for their ability to produce isotactic propylene polymers having high isotacticity and narrow molecular weight distribution. Considerable effort has been made toward obtaining metallocene produced propylene polymers having ever-higher molecular weight and melting point, while maintaining suitable catalyst activity.
Toward this end researchers have found that there is a direct relationship between the way in which a metallocene is substituted, and the molecular structure of the resulting polymer. For the substituted, bridged indenyl type metallocenes, it is now well established that the type and arrangement of substituents on the indenyl groups, as well as the type of bridge connecting the indenyl groups, determines such polymer attributes as molecular weight and melting point. Unfortunately, it is impossible at this time to accurately correlate specific substitution patterns with specific polymer attributes, though trends may be identified.
For example, U.S. Pat. No. 5,840,644 describes certain metallocenes containing aryl-substituted indenyl derivatives as ligands, which are said to provide propylene polymers having high isotacticity, narrow molecular weight distribution and very high molecular weight.
Likewise, U.S. Pat. No. 5,936,053 describes certain metallocene compounds said to be useful for producing high molecular weight propylene polymers. These metallocenes have a specific hydrocarbon substituent at the
2
position and an unsubstituted aryl substituent at the
4
position, on each indenyl group of the metallocene compound.
WO 98/40419 and WO 99/42497 both describe certain supported catalyst systems for producing propylene polymers having high melting point. Metallocene compositions and their activators are often combined with a support material in order to obtain a catalyst system that is less likely to cause reactor fouling. However, it is known that supported metallocene catalyst systems tend to result in a polymer having lower melting point than would otherwise be obtained if the metallocene were not supported.
Much of the current research in this area has been directed toward using metallocene catalyst systems under commercially relevant process conditions, to obtain propylene polymers having melting points higher than known metallocene catalyst systems and close to, or as high as, propylene polymers obtained using conventional, Ziegler-Natta catalyst systems, i.e., 160° C. or higher. The present inventors have discovered metallocene compounds that not only have this capability, but retain it upon supportation.
SUMMARY
The present invention relates to novel metallocene compositions capable of providing propylene polymers having high melting point and molecular weight. The present invention further relates to metallocene catalyst systems comprising one or more of these compositions and one or more activators or cocatalysts, and optionally, support material, and to the use of such metallocene catalyst systems in olefin polymerization, particularly propylene polymer polymerization.
DESCRIPTION
The metallocenes of the present invention are represented by the formula:
wherein:
M
1
is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, preferably zirconium, hafnium or titanium, most preferably zirconium;
R
1
and R
2
are identical or different, and are one of a hydrogen atom, a C
1
-C
10
alkyl group, a C
1
-C
10
alkoxy group, a C
6
-C
10
aryl group, a C
6
-C
10
aryloxy group, a C
2
-C
10
alkenyl group, a C
2
-C
40
alkenyl group, a C
7
-C
40
arylalkyl group, a C
7
-C
40
alkylaryl group, a C
8
-C
40
arylalkenyl group, an OH group or a halogen atom; R
1
and R
2
may also be joined together to form an alkanediyl group or a conjugated C
4-40
diene ligand which is coordinated to M
1
in a metallocyclopentene fashion; R
1
and R
2
may also be identical or different conjugated dienes, optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dienes having up to 30 atoms not counting hydrogen and forming a &pgr; complex with M, examples include 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1,3-butadiene, 1,4-bis(trimethylsilyl)-1,3-butadiene, and 1,4-dinaphthyl-1,3-butadiene;
preferably R
1
and R
2
are identical and are a C
1
-C
3
alkyl or alkoxy group, a C
6
-C
8
aryl or aryloxy group, a C
2
-C
4
alkenyl group, a C
7
-C
10
arylalkyl group, a C
7
-C
12
alkylaryl group, or a halogen atom, preferably chlorine;
R
3
are identical or different and are each a hydrogen atom, a halogen atom, a C
1
-C
10
alkyl group which may be halogenated, a C
6
-C
10
aryl group which may be halogenated, a C
2
-C
10
alkenyl group, a C
7
-C
40
-arylalkyl group, a C
7
-C
40
alkylaryl group, a C
8
-C
40
arylalkenyl group, a —NR′
2
, —SR′, —OR′, —OSiR′
3
or —PR′
2
radical, wherein R′ is one of a halogen atom, a C
1
-C
10
alkyl group, or a C
6
-C
10
aryl group; preferably R
3
is not a hydrogen atom;
preferably each R
3
is identical and is a fluorine, chlorine or bromine, atom, a C
1
-C
4
alkyl group which may be halogenated, a C
6
-C
8
aryl group which may be halogenated, a —NR′
2
, —SR′, —OR′, —OSiR′
3
or —PR′
2
radical, wherein R′ is one of a chlorine atom, a C
1
-C
4
alkyl group, or a C
6
-C
8
aryl group;
more preferably, R
3
are identical and are each a C
3
alkyl group, most preferably isopropyl groups;
alternatively, R
3
is a C
1
or C
2
alkyl group;
R
4
to R
7
are identical or different and are hydrogen, or are as defined for R
3
or two or more adjacent radicals R
5
to R
7
together with the atoms connecting them form one or more rings, preferably a 6-membered ring, preferably 4-8 membered ring;
—B(R
14
)—, —Al(R
14
)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO
2
—, —N(R
14
)—, —CO—, —P(R
14
)—, or —P(O)(R
14
)—,
wherein:
R
14
, R
15
and R
16
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
20
branched or linear alkyl group, a C
1
-C
20
fluoroalkyl or silaalkyl group, a C
6
-C
30
aryl group, a C
6
-C
30
fluoroaryl group, a C
1
-C
20
alkoxy group, a C
2
-C
20
alkenyl group, a C
7
-C
40
arylalkyl group, a C
8
-C
40
arylalkenyl group, a C
7
-C
40
alkylaryl group, or R
14
and R
15
, together with the atoms binding them, form a cyclic ring; preferably, R
14
, R
15
and R
16
are identical and are a hydrogen atom, a halogen atom, a C
1
-C
4
alkyl group, a CF
3
group, a C
6
-C
8
aryl group, a C
6
-C
10
fluoroaryl group, more preferably a pentafluorophenyl group, a C
1
-C
4
alkoxy group, in particular a methoxy group, a C
2
-C
4
alkenyl group, a C
7
-C
10
arylalkyl group, a C
8
-C
12
arylalkenyl group, or a C
7
-C
14
alkylaryl group;
or, R
13
is represented by the formula:
wherein:
R
17
to R
24
are as defined for R
1
and R
2
, or two or more adjacent radicals R
17
to R
24
, including R
20
and R
21
, together with the atoms connecting them form one or more rings; preferably, R
17
to R
24
are hydrogen;
M
2
is one or more carbons, silicon, germanium or tin, preferably silicon;
R
13
may also be an amidoborane-type radical such as is described in WO00/20426 (herein fully incorporated by reference);
R
8
, R
10
and R
12
are identical or different and have the meanings stated for R
4
to R
7
; and
R
9
and R
11
are identical or different and are a Group IVA radical having from 1 to 20 carbon atoms or are each primary, secondary or tertiary butyl groups, aryl groups, isopropyl groups, fluoroalkyl groups, trialkyl silyl groups, or other groups of si
Burkhardt Terry J.
Hart James R.
Haygood, Jr. William T.
Kuchta Matthew C.
Li Robert T.
Bell Mark L.
ExxonMobil Chemical Patents Inc.
Pasterczyk J.
Schmidt Paige
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