Bimetallic metallocene catalyst for preparing olefin polymer

Details Bimetallic metallocene catalyst for preparing olefin polymer Bimetallic metallocene catalyst for preparing olefin polymer

1999-06-17

2001-09-11

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S012000, C556S053000, C526S160000, C526S943000, C502S103000, C502S117000

Reexamination Certificate

active

06288254

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel bimetallic metallocene, and more particularly to a novel bimetallic metallocene with a high catalytic activity for preparing olefin polymers having a narrow MWD.
2. Description of the Prior Art
Olefin-based polymers have been used in a wide range of applications. One group of commonly used olefin-based polymers is polyolefins, that is, homopolymers or copolymers of olefins. These polyolefin plastics are typically used in such applications as blow and injection molding, extrusion coating, film and sheeting, pipe, wire and cable.
An example of polyolefin is ethylene-propylene elastomer (ethylene-propylene rubbers, EPR). It has many end-use applications due to its resistance to weather, good heat aging properties and its ability to be compounded with large quantities of fillers and plasticizers. Typical automotive uses are radiator and heater hoses, vacuum tubing, weather stripping and sponge doorseals. Typical industrial uses are sponge parts, gaskets and seals.
Another group of commonly used olefin-based polymers is terpolymers of ethylene, propylene, and a non-conjugated diene, which are generally referred to as EPDM elastomers. EPDM elastomers have outstanding weather and acid resistance, and high and low temperature performance properties. Such properties particularly suit EPDM elastomers for use in hoses, gaskets, belts, bumpers, as blending components for plastics and for tire side walls in the automotive industry, and for roofing applications. Additionally, because of their electrical insulation properties, EPDMs are particularly well suited for use as wire and cable insulation.
To date, many catalyst systems have been developed for olefin polymerization, these mainly being classified into two types: Ziegler-Natta catalyst systems and metallocene catalyst systems.
Ziegler et. al. in U.S. Pat. No. 3,113,115 uses TiCl
4
/AlEtCl
2
catalyst system to produce EPR. Natta et. al. in U.S. Pat. No. 3,300,459 uses VOCl
3
/Al(C
6
H
13
)
3
catalyst system to produce EPR.
Floyd and Hoel in U.S. Pat. Nos. 5,001,205; 4,871,705; and 5,229,478 use metallocenes such as biscyclopentadienyl compounds to produce olefin polymers. The Dow Chemical Company in WO 9,308,221 and European Patent No. 0,416,815 A2 developed monocyclopentadienyl compounds, in which the cyclopentadienyl group is substituted with a constrain-inducing moiety, such as dimethylsilyl. However, synthesis of this particular constained geometry catalyst (CGC) has a low yield (about 30%).
Davis in U.S. Pat. No. 5,372,980 use a bimetallic metallocene as a catalyst to produce olefin polymers. The catalytic activity is below 1.0×10
5
g-polymer/g-metal-hr.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a novel bimetallic metallocene with a high catalytic activity for preparing olefin polymers.
Another object of the present invention is to provide a novel bimetallic metallocene capable of producing an olefin polymer having a narrow MWD.
To achieve the above-mentioned object, a novel bimetallic metallocene is developed in the present invention which is represented by the following formula:
wherein:
M is zirconium, hafnium, or titanium;
R
1
can be the same or different and is independently an alkyl, alkenyl, aryl, alkylaryl or arylakyl group having from 1 to 20 carbon atoms or two adjacent R
1
are joined together to form with the carbon atoms to which they are attached a ring system having from 4 to 20 carbon atoms;
R
2
is
 wherein Y can be the same or different and is carbon or silicon or can be deleted, each R
21
can be the same or different and is hydrogen, an alkyl, aryl, alkylaryl or arylalkyl group having from 1 to 15 carbon atoms or is deleted when Y is deleted, R
22
is a linear, branched or cyclic alkylene having from 1 to 15 carbon atoms;
R
3
is selected from the group consisting of
 wherein R
31
and R
32
can be the same or different and are independently hydrogen, a linear, branched, or cyclic alkyl, aryl, alkylaryl or arylalkyl group having from 1 to 15 carbon atoms, R
33
is an unsubstituted or substituted alkanediyl group having from 2 to 15 carbon atoms wherein the alkanediyl group forms a ring system with the silicon or carbon atom to which it is attached, the substituent being selected from the group consisting of C
1-20
alkyl, C
1-20
alkenyl, C
6-20
aryl, C
7-20
alkylaryl, and C
7-20
arylalkyl;
R
4
can be the same or different and is
AR
41
, A(R
42
)
2
, or
 wherein A is nitrogen, phosphorus, or arsenic, R
41
and R
42
can be the same or different and is independently hydrogen, a linear, branched or cyclic hydrocarbyl group having from 1 to 20 carbon atoms, R
1
is defined as above, and z, which denotes the degree of substitution of the cyclopentadienyl ring, is from 0 to 5;
L is independently an anionic ligand with a −1 valence;
x is 0 or 1;
y, which denotes the degree of substitution of the cyclopentadienyl ring,is from 0 to 4; and
when both R
4
are
x=1 and at least one R
3
is
wherein R
33
is defined as above.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a novel metallic metallocene represented by formula (I).
In formula (I), M is a Group IVB transition metal with an oxidation state of +4, such as titanium, zirconium, and hafnium, preferably zirconium.
R
1
can be the same or different and is independently an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl group having from 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Alternatively, two adjacent R
1
groups can be joined together to form with the carbon atoms to which they are attached a ring system having from 4 to 20 carbon atoms, preferably 4 to 6 carbon atoms. Representative examples of R
1
include methyl, ethyl, propyl, butyl, isobutyl, amyl, isoamyl, hexyl, 2-ethylhexyl, heptyl, octyl, vinyl, allyl, isopropenyl, phenyl, and tolyl.
Specifically, when two adjacent R
1
groups are joined together to form with the carbon atoms to which they are attached a ring system having from 4 to 20 carbon atoms, R
1
can form with the cyclopentadienyl moiety on which they are attached a saturated or unsaturated polycyclic cyclopentadienyl ligand such as an indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl group. Representative examples of such ligands include &eegr;
5
-cyclopentadienyl, &eegr;
5
-methylcyclopentadienyl, &eegr;
5
-tetramethylcyclopentadienyl, &eegr;
5
-pentamethylcyclopentadienyl, &eegr;
5
-n-butylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and octahydrofluorenyl.
R
2
is
wherein Y can be the same or different and is carbon or silicon or can be deleted. Each R
21
can be the same or different and is hydrogen, an alkyl, aryl, alkylaryl or arylalkyl group having from 1 to 15 carbon atoms or is deleted when Y is deleted. R
22
is a linear, branched or cyclic alkylene having from 1 to 15 carbon atoms.
Representative examples of R
22
groups include ethylene, propylene, butylene, amylene, hexylene, heptylene, octylene, nonylene, decylene, phenylene, biphenylene, terphenylene and the like. Suitable R
21
groups include methyl, ethyl, propyl, butyl, t-butyl, isobutyl, amyl, isoamyl, hexyl, 2-ethylhexyl, heptyl, octyl, phenyl, tolyl and the like.
R
3
is selected from the group consisting of
When R
3
is
R
31
and R
32
can be the same or different and are independently hydrogen, a linear, branched, or cyclic alkyl, aryl, alkylaryl or arylalkyl group having from 1 to 15 carbon atoms. Representative examples of R
31
and R
32
include methyl, ethyl, propyl, butyl, t-butyl, isobutyl, amyl, isoamyl, hexyl, 2-ethylhexyl, heptyl, octyl, phenyl, tolyl and the like. Representative examples of R
31
include dimethylsilanediyl, diethylsilanediyl, and dipropylsilanediyl.
When R
3
is
R
33
is an unsubstituted or substituted alkanediyl group having from 2 to 15 carbon atoms, preferably 3 to 8 carbon atoms, wherein the alkanediyl group forms a ring system with the silicon or carbon atom to which it is attached. The substituent can be C

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