Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-10-04
2003-05-13
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...
C526S129000, C526S153000, C526S159000, C526S160000, C526S943000, C502S103000, C502S104000, C502S117000, C502S132000, C502S120000, C204S157620
Reexamination Certificate
active
06562918
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a catalyst for olefin polymerization, a method for producing the catalyst, and a method for producing olefinic polymers. Precisely, it relates to a novel, high-activity metallocene catalyst for olefin polymerization, which has the advantage of high polymerization activity in vapor-phase or slurry polymerization to give olefinic polymers, to a method for producing the catalyst, and to a method of using the catalyst in producing olefinic polymers.
BACKGROUND ART
Heretofore used are Ziegler-Natta catalysts in producing polyolefins. In vapor-phase or slurry polymerization to give substantially granular polymer particles, polyolefins produced could have good morphology since the catalyst used is carried on a carrier such as magnesium chloride or silica gel. Recently, a method of using catalysts that comprise a metallocene compound and an aluminoxane has been proposed for producing polyolefins (Japanese Patent Laid-Open Nos. 019309/1983, 167307/1990, etc.). Being different from conventional Ziegler-Natta catalysts, such metallocene catalysts have enabled polymerization of giving polyolefins uniformly dissolved in solvents such as hydrocarbons, etc., and it is known that their polymerization activity per the transition metal therein is extremely high and they give polymers having a narrow molecular weight distribution. Applying metallocene catalysts that are characterized by such features to ordinary vapor-phase or slurry polymerization, if possible, is preferred, as they will not require any additional investment in plant and equipment. However, metallocene catalysts, if applied to vapor-phase or slurry polymerization, must be carried on carriers. One method of carrying metallocene catalysts on carriers is known, which comprises reacting methylaluminoxane with silica gel followed by carrying a metallocene catalyst on the resulting reaction product (Japanese Patent Laid-Open Nos. 188712/1997, 70227/1995, etc.). However, the method is problematic in that the polymerization activity of the metallocene catalyst carried on such a carrier and used therein is lower than that of a metallocene catalyst in a uniform polymerization system. One example of producing propylene in the presence of a prepolymerized solid catalyst, which is prepared by ultrasonically prepolymerizing an olefin with a catalyst, is disclosed in Japanese Patent Laid-Open No. 120716/1998. However, the prepolymerized solid catalyst is problematic in that it is unstable. At present, metallocene catalysts carried on carriers, which are substantially applicable to vapor-phase or slurry polymerization with no reduction in their activity, could not be obtained. In addition, even in uniform polymerization in which are usedmetallocene catalysts, a large amount of aluminoxanes relative to transition metals must be used. In this, therefore, there are the problems that the polymerization activity per aluminium of the catalysts used is low and that aluminium remains in the polymers produced.
From the viewpoints noted above, we, the inventors have made the present invention, and the object of the invention is to provide a novel high-activity metallocene catalyst for olefin polymerization, of which the activity is high even in vapor-phase or slurry polymerization to give olefinic polymers and which realizes reducing the amount of aluminoxanes to be used along with it, to provide a method for producing the catalyst, and to provide a method for producing olefinic polymers.
DISCLOSURE OF THE INVENTION
We, the present inventors have assiduously studied so as to attain the object as above, and, as a result, have found that a metallocene catalyst for olefin polymerization, which is obtained by subjecting a transition metal compound, an organoaluminiumoxy compound and optionally a carrier to specific treatment, more precisely, a metallocene catalyst for olefin polymerization, which is obtained by contacting a compound of a transition metal compound of Groups 4 to 6 of the Periodic Table, an organoaluminiumoxy compound and optionally a carrier with each other while being exposed to elastic waves, can effectively attain the object. On the basis of this finding, we have completed the present invention. Specifically, the invention provides a catalyst for olefin polymerization, a method for producing it, and a method for producing olefinic polymers, which are as follows:
1. A catalyst for olefin polymerization, which is obtained by contacting (A) a compound of a transition metal of Groups 4 to 6 of the Periodic Table, (B) an organoaluminiumoxy compound, and optionally (C) a carrier with each other, and for which they are exposed to elastic waves at least in any step of contacting them with each other.
2. The catalyst for olefin polymerization of above 1, in which (A) is any of the following general formula (I), (II) or (III):
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
p
Y
1
q
(I)
Q
2
a
(C
5
H
5-a-d
R
3
d
)Z
1
M
1
X
1
p
Y
1
q
(II)
(C
5
H
5-a-d
R
3
d
)M
1
X
1
r
Y
1
s
(III)
wherein 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
and R
3
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; 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; p+q=[(the valency of M
1
)−2]; r+s=[(the valency of M
1
)−1]; M
1
represents a transition metal of Groups 4 to 6 of the Periodic Table; X
1
, Y
1
and Z
1
each represent a covalent-bonding or ionic-bonding ligand; plural X
1
′s and Y
1
′s, if any, may be the same or different, and may be bonded to each other to form a cyclic structure.
3. The catalyst for olefin polymerization of above 1 or 2, in which (C) has a mean particle size of from 1 to 300 &mgr;m, a specific surface area of from 1 to 1000 m
2
/g, and a pore volume of from 0.1 to 5 cm
3
/g.
4. The catalyst for olefin polymerization of any of above 1 to 3, for which the elastic waves are ultrasonic waves.
5. The catalyst for olefin polymerization of any of above 1 to 4, for which the frequency of the ultrasonic waves falls between 1 and 1000 kHz.
6. A method for producing a catalyst for olefin polymerization, which comprises contacting (A) a compound of a transition metal of Groups 4 to 6 of the Periodic Table, (B) an organoaluminiumoxy compound, and optionally (C) a carrier with each other, and in which they are exposed to elastic waves at least in any step of contacting them with each other.
7. A method for producing olefinic polymers, which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst of any of above 1 to 5.
8. A method for producing olefinic polymers, which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst of any of above 1 to 5 and an organoaluminium compound.
BEST MODES OF CARRYING OUT THE INVENTION
The invention is a catalyst for olefin polymerization, which is obtained by contacting (A) a compound of a transition metal of Groups 4 to 6 of the Periodic Table, (B) an organoaluminiumoxy compound, and optionally (C) a carrier with each other, and for which they are exposed to elastic waves at least in any step of contacting them with each other; a method for producing the catalyst; and a method of using the catalyst for producing olefinic polymers. The olefin polymerization catalyst [I]; the method for producing the catalyst [II]; and the method for producing olefinic polymers [III] are described in detail here
Kanamaru Masami
Minami Yutaka
Idemitsu Petrochemical Co. Ltd.
Rabago R.
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