Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1995-12-13
2002-10-08
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, C526S161000, C526S348200, C526S348600, C526S352000, C502S103000, C502S117000, C502S152000, C502S155000
Reexamination Certificate
active
06462154
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a process for preparing an olefin polymer and a catalyst for the polymerization of an olefin. More specifically, the present invention relates to a process for efficiently preparing a homopolymer of an olefin having heretofore unknown characteristics or a copolymer of two or more kinds of olefins by the use of a transition metal complex compound having a specific constrained geometric structure as one of catalytic components, and a catalyst for the polymerization of the olefin.
BACKGROUND ART
Heretofore, it has been known that in a process for preparing an olefin polymer, a transition metal complex compound having a specific constrained geometric structure is used as a catalytic component. For example, Japanese Patent Application Laid-open No. 163088/1991 discloses a method for preparing an olefin polymer in the presence of a catalyst system comprising the combination of a titanium series transition metal compound as a main catalytic component and methyl aluminoxane as a cocatalyst. In this method, however, a large amount of expensive methyl aluminoxane must be used in an aluminum/titanium atomic ratio of 20 to 1000 in order to obtain a sufficient catalytic activity, and so the disclosed method has a drawback that the increase in a catalyst cost is inevitable.
Furthermore, Japanese Patent Application Laid-open No. 139504/1991 discloses a method for preparing an olefin polymer in the presence of a catalyst system comprising the combination of, for example, (t-butylamido)dimethyl(tetramethyl-&eegr;
5
-cyclopentaidenyl)silanetitaniumdimethyl (hereinafter referred to as “M-[alkyl] complex”) and an ionic complex. This M-[alkyl] complex can usually be prepared from a halogen-substituted compound, for example, (t-butylamindo)dimethyl(tetramethyl-&eegr;
5
-cyclopentaidenyl)silanetitanium dichloride, but its manufacturing process is intricate and a reaction yield is low. In consequence, a manufacturing cost increases, and for this reason, the method is not practical. In addition, the method has a disadvantage that a sufficient activity cannot be exerted.
Moreover, in World open Publication WO 94/07927 (published on Apr. 14, 1994), there has been described the improvement of the productivity of an olefin polymer by the use of a catalyst system comprising a compound having a cyclopentadienyl group and a metal in the group 4 of the periodic table, an anion of a Brønsted acid and an organic compound of an element in the group 13 of the same.
DISCLOSURE OF THE INVENTION
Under such circumstances, the present invention has been intended, and an object of the present invention is to provide a process for efficiently preparing a homopolymer of an olefin having heretofore unknown characteristics or a copolymer of two or more kinds of olefins by the use of an inexpensive and highly active catalyst containing, as one catalytic component, a transition metal complex compound having a specific constrained geometric structure. Another object of the present invention is to provide the catalyst for the polymerization of the olefin polymer.
The present inventors have intensively researched with the intention of achieving the above-mentioned objects, and as a result, it has been found that when one or more kinds olefin monomers are polymerized in the presence of catalytic components, i.e., an organic aluminum compound and at least one selected from a transition metal complex compound having a specific structure, an ionic compound capable of reacting with the transition metal complex compound or its derivative to form an ionic complex and a Lewis acid, an olefin polymer can efficiently be obtained, and the molecular weight of this polymer can be regulated under the control of the deterioration of activity and the expansion of a molecular weight distribution of the polymer which has been impossible by conventional techniques, and this polymer can possess the molecular weight distribution having less low-molecular weight and high-molecular weight portions and can have an optional molecular weight. In consequence, the present invention has been completed on the basis of this knowledge.
That is to say, the present invention is directed to a process for preparing an olefin polymer which comprises the step of polymerizing at least one olefin monomer in the presence of (A) a transition metal complex compound represented by the general formula (I)
wherein M is a metallic element in the groups 3 to 10 of the periodic table or a metallic element in a lanthanoide series; L is a &pgr;-bonding ligand; A is a divalent group containing an element selected from elements in the groups 13, 14, 15 and 16 of the periodic table; B is a bonding group containing an element selected from elements in the groups 14, 15 and 16 of the periodic table, and A and B may optionally form a ring together; X is a &sgr;-bonding ligand, a chelating ligand or a Lewis base; and n is an integer of 0 to 6 which varies with the valence of M, and when n is 2 or more, a plurality of Xs may be the same or different, (B) at least one selected from a Lewis acid and an ionic compound capable of reacting with the transition metal complex compound of the component (A) or its derivative to form an ionic complex, and (C) an organic aluminum compound as catalytic components; and a catalyst for the polymerization of an olefin which comprises the above-mentioned catalytic components (A), (B) and (C).
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, a transition metal complex compound represented by the general formula (I)
is used as a catalytic component (A).
In the general formula (I), M is a metallic element in the groups 3 to 10 of the periodic table or a metallic element in a lanthanoide series. L is a &pgr;-bonding ligand, and typical examples of this ligand include an allyl group, cyclopentadienyl groups, substituted cyclopentadienyl groups, cyclopentadienyl groups each having a hetero-atom in a cyclopentadienyl ring, and their substituted cyclopentadienyl groups. A is a divalent group containing an element selected from elements in the groups 13, 14, 15 and 16 of the periodic table, and B is a bonding group containing an element selected from elements in the groups 14, 15 and 16 of the periodic table. The above-mentioned A and B may optionally form a ring together.
Furthermore, X is a &sgr;-bonding ligand, a chelating ligand or a Lewis base, and examples thereof include a hydrogen atom, halogen atoms, organic metalloid groups, alkoxy groups, amino groups, hydrocarbon groups, hetero-atom-containing hydrocarbon groups, amido groups and carboxyl groups.
In the present invention, as the above-mentioned X, there is preferably used HX in which a pKa value is 23 or less, particularly a value in the range of 12 to −10. If the pKa value is more than 23, a manufacturing process is intricate and so a manufacturing cost increases. Typical examples of the preferable X include halogen atoms such as a chlorine atom and a bromine atom, carboxyl groups, sulfonyl groups, thioalkoxy groups, thioaryloxy groups, acetylacetonato groups, acetylacetate groups and malonate groups of the above-mentioned examples. The halogen atom is particularly preferable because of a low manufacturing cost (with regard to the pKa value, refer to “ADVANCED ORGANIC CHEMISTRY: REACTIONS, MECHANISMS, AND STRUCTURE”, Second edition, Jerry March, INTERNATIONAL STUDENT EDITION).
In the general formula, n is an integer of 0 to 6 which varies with the valence of M, and n is preferably in the range of 0 to 4, because the compound in which n is in such a range can be manufactured at a low cost. If n is 2 or more, a plurality of Xs may be the same or different.
In the present invention, preferable examples of the transition metal complex compound represented by the general formula (I) which can be used as the component (A) include (t-butylamido)dimethyl(tetramethyl-&eegr;
5
-cyclopentadienyl)silanetitanium dichloride, (t-butylamido)dimethyl-(tetramethyl-&eegr;
5
-cyclopentadienyl)silanetitanium dibromide, (t-ben
Naganuma Syoji
Watanabe Masami
Idemitsu Kosan Co. Ltd.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Rabago R.
Wu David W.
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