Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-04-21
2003-02-25
Lu, Caixia (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S133000, C526S161000, C526S169000, C502S128000, C502S129000, C502S171000
Reexamination Certificate
active
06525150
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Art
This invention concerns olefin polymerization catalysts and olefin polymer production methods that use the olefin polymerization catalysts. More specifically, this invention concerns olefin polymerization catalysts, which contain prescribed compounds and with which &agr;-olefins can be copolymerized efficiently, and olefin polymer production methods using these polymerization catalysts.
2. Prior Arts and Themes Thereof
Olefin polymers and olefin copolymers, as represented by polyethylene and polypropylene, are excellent in heat resistance, resistance against aging, chemical resistance, and the like, and are used as general-purpose resins in a wide variety of industrial fields, such as automobile parts, and the like. Ziegler-Natta catalysts, as represented by titanium catalysts, which are comprised of a titanium compound and an organic aluminum compound, and vanadium catalysts, which are comprised of a vanadium compound and an organic aluminum compound, are known as catalysts used in the production of such olefin polymers.
However, titanium catalysts are not adequate in polymerization activity. The olefin polymers that are obtained using titanium catalysts are therefore low in molecular weight and wide in molecular weight distribution. Also, olefin copolymers that are obtained using a titanium catalyst are insufficient in terms of random copolymerization, have a broad distribution of composition, and copolymers with adequate mechanical strength are thus difficult to obtain with this type of catalyst. Meanwhile, with vanadium catalysts, though the random copolymerization characteristics are improved, the composition distribution becomes narrow, and though the mechanical characteristics also become improved, these characteristics still cannot be considered to be sufficient.
Metallocene catalysts, comprised of a transition metal compound and an aluminoxane, have been proposed as catalysts that can take the place of Ziegler-Natta catalysts. For example, Japanese Patent Publication No. Hei-4-12283 discloses an olefin polymerization method using a catalyst comprised of a transition metal compound and an aluminoxane. A catalyst comprised of a zirconium hydride compound, having a group with conjugate &pgr; electrons as the ligand, and an aluminoxane is disclosed in Japanese Patent Publication No. Hei-5-80493. This patent publication also discloses a method for producing a polymer or copolymer with a molecular weight distribution (weight average molecular weight
umber average molecular weight) of 1.97 to 2.15 by polymerizing ethylene or propylene or copolymerizing ethylene with an &agr;-olefin of 3 to 10 carbons and a non-conjugated polyene of 5 to 20 carbons under the presence of the abovementioned catalyst.
Besides the abovementioned metallocene catalysts, it is also known that ethylene and an &agr;-olefin can be copolymerized using metallocene compound, having a structure of silicon atoms, and the like, (Japanese Laid-open Patent Publication No. Sho-60-35007 and Japanese Laid-open Patent Publication No. Hei-3-12406), or using a geometrically constrained metallocene compound (CGCT: Japanese Laid-open Patent Publication No. Hei-3-163088).
However, the synthesis of a compound having a metallocene ligand (that is, a compound having a group with a cyclopentadiene ring structure as the ligand) requires a synthesis process of two to five stages. Also, if metallocene catalysts with one cyclopentadienyl group and non-cross-linked metallocene catalysts with two cyclopentadienyl groups are used, which can be synthesized relatively readily, the a-olefin polymerization activity is low and the ethylene—&agr;-olefin copolymer that is produced has a low &agr;-olefin content of approximately 5 weight %.
Besides metallocene catalysts, it is also known that olefins can be polymerized using a transition metal compound that is bonded with oxygen or another heteroatom. For example, Japanese Laid-open Patent Publication No. Hei-2-145606 discloses a method of polymerizing olefins using a product, obtained from bis(2-hydroxy-3-t-butyl-5-methylphenyl) sulfide and vanadium oxytrichloride, and methyl aluminoxane. However, a large quantity of methyl aluminoxane, which is expensive, must be used in this method.
Furthermore, Japanese Laid-open Patent Publication No. Hei-5-230133 and Japanese Laid-open Patent Publication No.Hei-6-192330 disclose methods of polymerizing olefins using 2,2′-thiobis(6-t-butyl-4-methylphenol) titanium dichloride, triisobutylaluminum, and a boron compound. However, a large quantity of triisobutylaluminum must be used in these methods.
SUMMARY OF THE INVENTION
Objects of the Invention
The present invention has been made to solve the above problems and an object thereof is to present olefin polymerization catalysts with which polymers of high molecular weight can be obtained at high yields. In particular, an object of the present invention is to provide olefin polymerization catalysts with which copolymerization of &agr;-olefins with 4 or more carbons and especially 6 or more carbons can be performed at high yield. Another object of this invention is to provide catalysts with which the catalytic.components can be synthesized readily and with which the content of organic aluminum compound is low. Yet another object of this invention is to provide methods of producing olefin polymers using the abovementioned catalysts.
Features of the Invention
The olefin polymerization catalyst of the first aspect of this invention is characterized in containing a compound (a), which is expressed by the general formula (1) indicated below, a below-described compound (b), and a below-described compound (c).
Compound (a):
In formula, (1), each of A
1
and A
2
has an atom which is bonded to M and wherein A
1
and A
2
are selected from a substituted nitrogen atom, an oxygen atom, a substituted silicon atom, a substituted phosphorus atom a sulfur atom and a substituted sulfur atom, and A
1
and A
2
may be the same as or may differ from each other. Each of R
1
and R
2
is a hydrocarbon group with 1 to 20 carbons or a hydrocarbon group with 1 to 20 carbons and containing a heteroatom, R
1
and R
2
may be bonded together and be the same as or may differ from each other. Each of B has an atom which is bonded to the abovementioned R
1
and R
2
and is selected from a substituted nitrogen atom, an oxygen atom, a substituted phosphorus atm, a sulfur atom, a substituted sulfur atom, a substituted silicon atom, rind a carbon atom which is part of a curbonyl group. M is a metal atom of group 5 (VA) of the periodic table. X has an atom which is bonded to M and which is selected from a halogen atom, a carbon atom, a substituted nitrogen atom, an oxygen atom, a substituted silicon atom, a substituted phosphorus atom, a sulfur atom and a substituted sulfur atom.
Compound (b): Compound (b) is at least one type of compound selected from the group consisting of organic aluminum compounds expressed by the general formula (2) indicated below.
(R
3
)
n
AlZ
3−n
(2)
In formula (2), R
3
is a hydrocarbon group with 1 to 20 carbon atoms. Z is the hydrogen atom, a halogen atom, or an alkoxyl group. n takes on a value of 1 to 3.
Compound (c): Compound (c) is an ionized ionic compound.
The olefin polymerization catalyst of the second aspect of this invention is characterized in containing a reaction product (f), which is obtained by reacting a compound (d), expressed by the genera formula (3) indicated below, and a compound (e), expressed by the general formula (4) indicated below, a below-described compound (b), and a below-described compound (c).
Compound (d): M(O)X
3
(3)
In formula (3), M is a metal atom of group 5 (VA) of the periodic table. X has an atom which is bonded to M and which is selected from a halogen atom, a carbon atom, a substituted nitrogen atom, an oxygen atom a substituted silicon atom, a substituted phosphorus atom, a sulfur atom and a substituted sulfur atom.
Compound (e): C
1
—A
1
—R
1
—B—R
2
—A
2
—C
2
(4)
In for
Hayakawa Toshiyuki
Tutumi Fumio
JSR Corporation
Lu Caixia
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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