Process for the polymerization of olefins using a catalyst...

Details Process for the polymerization of olefins using a catalyst... Process for the polymerization of olefins using a catalyst...

1998-12-28

2002-02-26

Wilson, Donald R. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S159000, C526S161000, C526S308000, C526S346000, C526S943000, C502S103000, C502S153000

Reexamination Certificate

active

06350831

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a catalyst component for the polymerization of olefins, a polymerization catalyst containing the component and a process for the polymerization of olefins by using the catalyst, and more particularly, to a catalyst component for the polymerization of olefins which is stable to air, moisture and so on and not corrosive to metal, a polymerization catalyst containing said component, having a high polymerization activity and being capable of producing olefin polymers, and a process for the polymerization of olefins.
BACKGROUND ART
Recently, as a catalyst which can homopolymerize ethylene or copolymerize ethylene and &agr;-olefin with a high polymerization activity, there is proposed a new catalyst for the polymerization of olefins comprising a transition metal compound such as metallocene compound of zirconium and an organic aluminum oxy compound. As a process for the homo-or copolymerization of ethylene by using such catalyst, there has been proposed, for example, in Japanese Patent Application Laid-open Nos. Sho 58(1983)-19309, Sho 60(1985)-35007, etc.
In such a prior art, it has been disclosed that as a transition metal compound component, a metallocene compound is available, which has an alkadienyl radical such as a cyclopentadienyl radical, etc, as a ligand for the transition metal, and further an alkyl radical, a halogen atom, etc.
However, the metallocene compound in such prior arts may show a high polymerization activity as a compound having a halogen atom bound directly to the transition metal atom, but need a treatment with alcohol or water after the polymerization depending on the kind of olefins and the process for the polymerization, so that hydrogen halide may be formed disadvantageously which may occur rusts and corrosions in equipments. Further, a metallocene compound having an alkyl radical bound directly to the metal atom has high polymerization activity relatively and does not form undesirable hydrogen halide, but there are some disadvantages that it is extremely unstable to a little air or moisture, is apt to lower the catalyst activity remarkably by deterioration in the operation or to deteriorate with time in storage, as a result, a special care and equipment to the handling and storage of catalyst component are required. Thus, for example, as seen in Japanese Patent Application Laid-open No. Sho 62(1987)-230802, there has been proposed a process in which the halogen atom or alkyl radical bound to the metal atom is converted to an alkoxy or phenoxy radical to eliminate the formation of hydrogen halide and improve the stability of the metallocene compound. In this case, however, disadvantageously the activity as catalyst for the polymerization of olefins is in general lowered.
Accordingly, it has been strongly desired to develop as a metallocene compound, a transition metal compound, which satisfies at the same time three requirements that it does not contain a halogen atom directly bound to the metal atom, as a result, it does not generate undesirable hydrogen halide, that it is stable to air and moisture so that it may be dealt with easily and has a high storage stability and that it has a high activity on using as a catalyst for the polymerization of olefins. And also it has been strongly desired to provide a process for the polymerization of olefins therewith.
After studying earnestly in view of the present status as mentioned above, it has been found that a metallocene compound may eliminate the disadvantages as mentioned above which has a radical comprising a cyclopentadienyl skeleton coordinated to the transition metal and in which an aromatic ring substituted with a special substituent is bound through an oxygen or a sulphur to the transition metal, and it shows an excellent activity on using it as a catalyst for the polymerization of olefins resulting in the accomplishment of the present invention.
DISCLOSURE OF INVENTION
Accordingly, the present invention relates at first to a catalyst component for the polymerization of olefins which comprises a transition metal compound represented by the general formula [1] or [2]:
(R
a
Cp)
m
(R′
b
Cp)
n
M(—X—AR—Y
c
)
4−(m+n)
  [1]
wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ represent a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, AR represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, a and b each is an integer of 0 to 5, m and n each is an integer of 0 to 3 and that m+n is an integer of 1 to 3, and c is an integer of 1 to 5, proviso Y does not present a hydrogen atom when AR is a benzene ring;
R″(R
d
Cp)(R′
e
Cp)M(—X—AR—Y
c
)
2
  [2]
wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ represent a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, R″ represents a divalent radical which links (R
d
Cp) and (R′
e
Cp) and is selected from an alkylene, an arylalkylene, a dialkylsilylene, a dialkylgermylene, an alkylphosphindiyl or an alkylimino radical, X represents an oxygen or a sulphur atom, AR represents an aromatic radical, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-containing organic radical, an oxygen-containing organic radical or a sulphur-containing organic radical, d and e each represents an integer of 0 to 4, and c is an integer of 1 to 5, proviso that Y is not a hydrogen atom when AR is a benzene ring.
Secondly, the present invention relates to a catalyst for the polymerization of olefins comprising [A] a transition metal compound represented by the above-mentioned general formula [1] or [2], [B] an organic aluminum oxy compound or a cation generator and occasionally [C] an organic aluminum compound, and thirdly to a process for the polymerization of olefins characterized by polymerizing or copolymerizing olefins in the presence of said catalyst for the polymerization of olefins.
The metallocene compound as a catalyst component for the polymerization of olefins has as mentioned-above in general a halogen atom or an alkyl radical as the groupings to bond the transition metal and the polymerization activity thereof is remarkably lowered when all groupings are converted to a phenoxy or thiophenoxy radical. However, the present inventors have found unexpected function in which in case a specified substutient is introduced to an aromatic ring like a phenoxy radical or thiophenoxy radical or the like, a higher polymerization activity is realized without the reduction of activity rather than the metallocene compound to which a halogen atom or an alkyl radical is bound.
The present invention will be illustrated in detail hereinafter, in which the term “polymerization” means the homopolymerization and copolymerization.
The metallocene catalyst component according to the present invention is a transition metal compound represented by any one of the following two general formulae:
(R
a
Cp)
m
(R′
b
Cp)
n
M(—X—AR—Y
c
)
4−(m+n)
  [1]
wherein M represents titanium, zirconium or hafnium, Cp represents a radical having the cyclopentadienyl skeleton, R and R′ represent a hydrogen atom, an alkyl, an alkenyl, an aryl, an alkylaryl, an arylalkyl or an alkylsilyl radical, X represents an oxygen or a sulphur atom, AR represents an aromatic ring, Y represents a hydrogen atom, a hydrocarbon radical, a silyl radical, a halogen atom, a halogenated hydrocarbon radical, a nitrogen-co

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