Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-05-14
2001-11-13
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...
C526S160000, C526S346000, C526S347000, C526S943000, C502S080000, C502S104000, C502S117000, C502S152000, C502S232000, C502S239000
Reexamination Certificate
active
06316557
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a catalyst for polymerizing an olefinic monomer, and a method for producing an olefinic polymer or a styrenic polymer, and precisely, it relates to an efficient and inexpensive method for producing an olefinic polymer and a styrenic polymer.
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 Application Laid-Open (JP-A) Sho-58-019309, Hei-2-167307, etc.). 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 (JP-A Sho-61-108610, Hei-1-101303, etc.). 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 (JP-A Hei-5-25214, Hei-5-301917, Hei-7-33814). 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 is that, when styrenic polymers are produced according to the method, the catalyst activity per aluminium is much lower than that in producing other olefins according to it.
The present invention has been made in consideration of the problems noted above, and its object is to provide an efficient and inexpensive method for producing olefinic polymers and also styrenic polymers having a stereospecifically-controlled syndiotactic structure. The method is characterized by using a silane compound, and does 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 method, 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 method do not require post-treatment.
DISCLOSURE OF THE INVENTION
We, the present inventors have found that the object mentioned above can be effectively attained by using a polymerization catalyst that comprises specific catalytic components, and have completed the present invention. Specifically, the invention provides the following:
(1) A catalyst for polymerizing olefinic monomers, which comprises (a) a transition metal compound, (b) at least one member selected from clay, clay minerals and ion-exchanging layered compounds, and (c) a silane compound.
(2) The catalyst for polymerizing olefinic monomers of (1), which further contains (d) an alkylating agent.
(3) A catalyst for polymerizing olefinic monomers, which comprises (a) a transition metal compound, (b) at least one member selected from clay, clay minerals and ion-exchanging layered compounds, (c) a silane compound, and (e) an organic aluminum compound.
(4) The catalyst for polymerizing olefinic monomers of (3), which further contains (d) an alkylating agent.
(5) The catalyst for polymerizing olefinic monomers of any one of (1) to (4), wherein the silane compound (c) is represented by a general formula:
R
n
SiX
4−n
in which R represents a substituent of which the atom in the site directly bonding to Si is carbon, silicon or hydrogen; X represents a substitutent of which the element in the site directly bonding to Si is halogen, oxygen or nitrogen; plural R's and X's, if any, may be the same or different ones, respectively; and n represents 1, 2 or 3.
(6) The catalyst for polymerizing olefinic monomers of (5), wherein n is 1 or 2.
(7) A method for producing olefinic polymers, which comprises homopolymerizing or copolymerizing olefinic monomers in the presence of the catalyst of any one of (1) to (6).
(8) A method for producing styrenic polymers, which comprises homopolymerizing or copolymerizing styrenic monomers in the presence of the catalyst of any one of (1) to (6).
BEST MODES OF CARRYING OUT THE INVENTION
Embodiments of carrying out the invention are described in detail hereinunder.
1. Constituent Components for the Catalyst for Polymerizing Olefinic Monomers:
Transition Metal Compounds for Component (a):
Various type of transition metal compounds are usable as the component (a) in the invention, for which, however, preferred are compounds of transition metals of Groups IV to VI of the Periodic Table and those of Group VIII. In view of their activity, especially preferred are compounds of transition metals of Groups IV to VI of the following general formula (1) to (3); and those of Group VIII of the following general formula (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
p
Y
1
q
(1)
Q
2
a
(C
5
H
5−a−d
R
3
d
)Z
1
M
1
X
1
p
Y
1
q
(2)
M
1
X
2
r
(3)
L
1
L
2
M
2
X
1
p
Y
1
q
(4)
wherein Q
1
represents a bonding group that crosslinks the two conjugated, 5-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, 5-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 a integer of from 0 to 3 when a=2; (p+q) equals the valence number of M
1
minus 2; r equals the valence number of M
1
; M
1
represents a transition metal of Groups IV to VI of the Periodic Table; M
2
represents a transition metal of Group VIII of the Periodic Table; L
1
and L
2
each represent a coordination-bonding ligand; X
1
, Y
1
and Z
1
each represent a covalent-bonding or ionic-bonding ligand; X
2
represents a covalent-bonding ligand; and L
1
, L
2
, X
1
and Y
1
may be bonded to each other to form a cyclic structure.
Specific examples of Q
1
and Q
2
include (1) an alkylene group having from 1 to 4 carbon atoms, or a cycloalkylene group, or the group substituted by a lower alkyl or phenyl group at its side chain, such as a methylene group, an ethylene group, an isopropylene group, a methylphenylmethylene group, a diphenylmethylene group, a cyclohexylene group, etc.; (2) a silylene group, or an oligosilylene group, or the group substituted by a lower alkyl or phenyl group at its side chain, such as a silylene group, a dimethylsilylene group, a methylphenylsilylene group, a diphenylsilylene group, a disilylene group, a tetramethyldisilylene group, etc.; and (3) a hydrocarbon group &l
Abiko Toshiya
Ikeuchi Satoshi
Matsumoto Jun-ichi
Nakashima Harumi
Sato Haruhito
Idemitsu Petrochemical Co. Ltd.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Wu David W.
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