Catalysts for olefin polymer production

Details Catalysts for olefin polymer production Catalysts for olefin polymer production

2000-04-18

2002-05-28

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...

C526S091000, C526S093000, C526S126000, C526S128000, C526S141000, C526S142000, C526S160000, C526S161000, C502S062000, C502S063000, C502S074000, C502S080000, C502S111000, C502S117000, C502S118000, C502S124000, C502S125000, C502S155000, C502S158000

Reexamination Certificate

active

06395846

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to catalysts for olefin polymerization, methods for producing them, and methods for producing olefin polymers. More precisely, the invention relates to high-activity catalysts for olefin polymerization, to efficient methods for producing them, and to methods of using the olefin polymerization catalysts for efficiently producing high-quality olefin polymers.
2. Background Art
Recently, a method has been proposed of using a catalyst comprising a metallocene compound and an aluminoxane for polymerizing olefins in the presence of the catalyst to produce olefin polymers (Japanese Patent Laid-Open Nos. 19309/1983, 167307/1990). It is known that the polymerizing method of using such a catalyst is better than a method of using a conventional Ziegler-Natta catalyst that comprises a titanium or vanadium compound and an organic aluminium compound since the polymerization activity per the transition metal in the former is extremely high and since the former produces polymers having a narrow molecular weight distribution.
Another method has been proposed for polymerizing olefins in the presence of a catalyst that comprises catalytic components of a transition metal compound and an aluminoxane or organic aluminium compound as carried on an inorganic oxide such as silica, alumina or the like (Japanese Patent Laid-Open Nos. 108610/1986, 101303/1989).
However, in order that the methods noted above could have a satisfactory degree of polymerization activity, a large amount of an aluminoxane must be used therein. Therefore, in those methods, the activity per aluminium used is low, and the methods are uneconomical. In addition, since a large amount of aluminium remains in the polymers formed, the methods are further problematic in that the catalyst residue must be removed from the polymers formed therein.
Still another method has been proposed of using clay minerals as catalytic components (Japanese Patent Laid-Open Nos. 25214/1993, 301917/1993, 33814/1995). In this method, however, it is said that the clay minerals to be used must be pre-treated with organic aluminium compounds, especially with methylaluminoxane or trimethylaluminium which is extremely expensive and dangerous. In addition, the method is problematic in that the catalyst activity per aluminium therein is not satisfactory and the amount of the catalyst residue that may remain in the products is large.
In particular, the additional problem with the method of using such clay minerals is that aqueous suspensions of the clay minerals must be repeatedly pre-treated with magnesium chloride or the like and must be thereafter further treated with hydrochloric acid and then washed, and the treatment requires a lot of time.
The present invention has been made in consideration of the problems noted above, and its object is to provide catalysts for olefin polymerization capable of being prepared within a short period of time and to provide methods of using the catalysts for efficiently and inexpensively producing olefin polymers. Specifically, the catalysts do not require a large amount of methylaluminoxane or trimethylaluminium which has poor storage stability and is dangerous and which is therefore not easy to handle. In addition, in the methods of using the catalysts for olefin polymerization, since the amount of the organic aluminium compound to be used in the total polymerization system can be greatly reduced, the metal component that may remain in the polymers produced is much reduced. Therefore, the polymers produced in the methods do not require post-treatment. In particular, the catalysts are especially favorable to producing styrenic polymers having a stereospecifically-controlled syndiotactic structure.
SUMMARY OF THE INVENTION
The present invention encompasses three aspects, which are mentioned in detail hereinunder.
We, the present inventors have found that the object of the invention noted above can be attained by using a polymerization catalyst that comprises catalytic components having been specifically treated, and, on the basis of this finding, we have completed the first aspect of the invention.
Specifically, the first aspect of the invention is to provide a catalyst for olefin polymer production, a method for producing it, and a method of using it for producing olefin polymers, which are as follows:
1. A catalyst for olefin polymer production, which is obtained by contacting a product as prepared by contacting (A) clay, a clay mineral or an ion-exchanging layered compound, (B) an organic silane compound and (C) water with each other, with (D) a transition metal complex containing a transition metal of Groups 4 to 6 or Groups 8 to 10 of the Periodic Table.
2. A catalyst for olefin polymer production, which is obtained by contacting a product as prepared by contacting (A) clay, a clay mineral or an ion-exchanging layered compound, (B) an organic silane compound and (C) water with each other, with (D) a transition metal complex containing a transition metal of Groups 4 to 6 or Groups 8 to 10 of the Periodic Table and (E) an alkylating agent.
3. The catalyst for olefin polymer production of above 1 or 2, wherein the component (A), clay, a clay mineral or an ion-exchanging layered compound is selected from phyllosilicic acid compounds.
4. The catalyst for olefin polymer production of any one of above 1 to 3, wherein the component (B), an organic silane compound has at least one alkyl group directly bonded to the silicon atom of the compound.
5. The catalyst for olefin polymer production of any one of above 1 to 4, wherein the amount of the component (C), water is at least 1% by weight relative to the dry weight of the component (A).
6. The catalyst for olefin polymer production of any one of above 1 to 5, wherein the component (D), a transition metal complex containing a transition metal of Groups 4 to 6 or Groups 8 to 10 of the Periodic Table has a ligand having a carbon-carbon unsaturated bonding group or a carbon-nitrogen unsaturated bonding group.
7. The catalyst for olefin polymer production of any one of above 1 to 6, wherein the component (D), a transition metal complex containing a transition metal of Groups 4 to 6 or Groups 8 to 10 of the Periodic Table is represented by any of the following general formulae (I-1) to (I-4):
Q
1
a
(C
5
H
5−a−b
R
1
b
) (C
5
H
5−a−c
R
2
c
)M
1
X
1
Y
1
  (I-1)
Q
2
a
(C
5
H
5−a−d
R
3
d
)Z
1
M
1
X
1
Y
1
  (I-2)
(C
5
H
5−e
R
4
e
)M
1
X
1
Y
1
W
1
  (I-3)
L
1
L
2
M
2
X
1
Y
1
  (I-4)
where Q
1
represents a bonding group that crosslinks the two conjugated five-membered cyclic ligands (C
5
H
5−a−b
R
1
b
) and (C
5
H
5−a−c
R
2
c
);
Q
2
represents a bonding group that crosslinks the conjugated five-membered cyclic ligand (C
5
H
5−a−d
R
3
d
) and the group Z
1
;
R
1
, R
2
, R
3
and R
4
each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group; and a plurality of these groups, if any, may be the same or different, and may be bonded to each other to form a cyclic structure;
a represents 0, 1 or 2;
b, c and d each represent an integer of from 0 to 5 when a=0, or an integer of from 0 to 4 when a=1, or an integer of from 0 to 3 when a=2;
e represents an integer of from 0 to 5;
M
1
represents a transition metal of Groups 4 to 6 of the Periodic Table;
M
2
represents a transition metal of Groups 8 to 10 of the Periodic Table;
L
1
and L
2
each represent a coordination-bonding ligand;
X
1
, Y
1
, Z
1
and W
1
each represent a covalent-bonding or ionic-bonding ligand; and
L
1
, L
2
, X
1
, Y
1
and W
1
may be bonded to each other to form a cyclic structure.
8. The catalyst for olefin polymer production of any one of above 2 to 7, wherein the component (E), an alkylating agent is an organic aluminium compound.
9

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