Olefin polymerization catalyst, process for preparing olefin...

Details Olefin polymerization catalyst, process for preparing olefin... Olefin polymerization catalyst, process for preparing olefin...

1999-05-20

2001-10-02

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S127000, C526S129000, C526S131000, C526S943000, C526S348200, C526S348000, C502S103000, C502S120000, C502S152000

Reexamination Certificate

active

06297333

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to olefin polymerization catalysts, processes for preparing olefin polymers, and olefin polymers. More particularly, the invention relates to olefin polymerization catalysts which are capable for giving olefin (co)polymers of high molecular weight with extremely high polymerization activities and olefin copolymers having a high comonomer content even if a comonomer is used in a small amount, and also relates to processes for preparing olefin polymers by which olefin (co)polymers of high molecular weight can be obtained with extremely high polymerization activities and olefin copolymers having a high. comonomer content can be obtained even if a comonomer is used in a small amount, and to olefin polymers obtained by the processes.
BACKGROUND OF THE INVENTION
For preparing olefin (co)polymers such as an ethylene homopolymer, an ethylene-&agr;-olefin copolymer, a propylene homopolymer and a propylene-&agr;-olefin copolymer, processes of polymerizing olefins in the presence of a Ziegler catalyst comprising a titanium compound and an organoaluminum compound or a vanadium catalyst comprising a vanadium compound and an organoaluminum compound are conventionally known.
Also known are processes of polymerizing olefins in the presence of a metallocene catalyst comprising a transition metal compound such as zirconocene and an organoaluminum oxy compound (aluminoxane), and it is known that the use of the metallocene catalyst makes it possible to polymerize olefins with high activities and to obtain olefin (copolymers of narrow molecular weight distribution and narrow composition distribution.
Recently, the requirements for properties of the olefin (co)polymers have varied, and olefin (co)polymers of various properties have been desired. Moreover, development of a transition metal compound catalyst component capable of producing such olefin (co)polymers is also desired.
Under the circumstances, Japanese Laid-Open Publication No. 345793/1993 discloses a novel transition metal compound having an indenyl group and a fluorenyl group as ligands serving as an olefin polymerization catalyst component. However, in polymerization of an olefin using this transition metal compound as a catalyst component, the polymerization activity is low so that only a polymer of low molecular weight is produced.
EP0707016A also discloses a transition metal compound having an indenyl group and a fluorenyl group and a catalyst in which a specific aryl group such as a phenyl group or a naphthyl group is introduced into a specific position (4-position) of the indenyl group. However, in polymerization of an olefin using this transition metal compound as a catalyst component, the polymerization activity is also low so that only a polymer of low molecular weight is produced,
The present inventors have studied under such circumstances as mentioned above, and as a result they have found that by the use of a compound wherein a specific substituent is introduced at the specific position of the indenyl group in the above-mentioned transition metal compound, an olefin (co)polymer of high molecular weight can be prepared with high polymerization activities and an olefin copolymer of high comonomer content can be obtained. Further, the present inventors have also sound that an olefin (co)polymer of high molecular weight can be prepared with much higher polymerization activities and an olefin copolymer of much higher comonomer consent can be obtained by introducing a specific substituent at the specific position of the fluorenyl group of the characteristic transition metal compound. Thus, the present invention has been accomplished.
OBJECT OF THE INVENTION
It is an object of the present invention to provide an olefin polymerization catalyst which is capable for giving an olefin (co)polymer having a high molecular weight with extremely high polymerization activities and an olefin copolymer having a high comonomer content. It is another object of the invention to provide a process for preparing an olefin polymer using the catalyst and an olefin polymer obtained by the process.
SUMMARY OF THE INVENTION
The olefin polymerization catalyst according to the present invention comprises:
(A-1) a Group IVB transition metal compound represented by the following formula (I),
(B) (B-1) an organoaluminum oxy-compound, and/or
(B-2) a compound which reacts with the transition metal compound (A-1) to form an ion pair,
 and optionally
(C) an organoaluminum compound;
 wherein M is a transition metal atom of Group IVB of the periodic table;
R
1
's may be the same as or different from each other, at least one Of them is an aryl group of 11 to 20 carbon atoms, an arylalkyl group of 12 to 40 carbon atoms, an arylalkenyl group of 13 to 40 carbon atoms or an alkylaryl group of 12 to 40 carbon atoms, or at least two adjacent groups among groups indicated by R
1
form an aromatic ring or an aliphatic ring together with carbon atoms to which said at least two groups are bonded (in this case the rings formed by R
1
have 4 to 20 carbon atoms as a whole), and the remainder of R
1
is hydrogen atom, a halogen atom or an alkyl group of 1 to 10 carbon atoms,
R
2
's may be the same as or different from each other, 10 they are each hydrogen atom, a halogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, an arylalkenyl group of 8 to 40 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and at least two adjacent groups among groups indicated by R
2
may form an aromatic ring or an aliphatic ring together with carbon atoms to which said at least two groups are bonded (in this case the rings formed by R
2
have 4 to 20 carbon atoms as a whole including carbon atoms to which the R
2
groups are bonded, and the remainder of R
2
is hydrogen atom, a halogen atom or an alkyl group on I to 1i0 carbon atoms),
R
1
and R
2
may be the same as or different from each other,
R
3
and R
4
may be the same as or different from each other, and are each hydrogen atom, a halogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, an arylalkenyl group of 8 to 40 carbon atoms, an alkylaryl group of 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group,
X
1
and X
2
may be the same as or different from each other, and are each hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group, or a combination of X
1
and X
2
may form a stable conjugated diene (a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a silicon-containing group), and
Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, —O—, —CO—, —S—, —SO—, —SO
2
—, —NR
5
—, —P(R
5
)—, —P (O) (R
5
)—, —BR
5
— or —AlR
5
— (R
5
is hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon atoms).
The olefin polymerization catalyst according to the invention includes an embodiment of a solid catalyst wherein at least one of the component (A-1), the component (B-1) the component (B-2) and the component (C) is supported on a fine particle carrier and an embodiment of a prepolymerized catalyst comprising a fine particle carrier, the component (A-1), the component (B-1) (or the component (B-2)), an olefin polymer prod

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