Olefin polymerization catalyst and process for producing...

Details Olefin polymerization catalyst and process for producing... Olefin polymerization catalyst and process for producing...

1998-10-07

2001-07-03

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...

C526S348600, C556S051000, C502S104000, C502S162000

Reexamination Certificate

active

06255419

ABSTRACT:

TECHNICAL FIELD OF THE ART
The present invention relates to an olefin polymerization catalyst and a process for producing olefin polymers, and more specifically, it relates to an olefin polymerization catalyst which can produce olefin polymers with superior polymerization activity, and to an olefin polymerization process employing the catalyst.
BACKGROUND ART
Olefin(-based) polymers, which include ethylene polymers, ethylene/&agr;-olefin copolymers, ethylene/styrene copolymers, ethylene/cyclic clef in copolymers, propylene polymers and propylene/&agr;-olefin copolymers, are used in various fields because of their excellent rigidity, mechanical strength, chemical resistance, moldability and heat resistance.
As catalysts used to produce these clef in polymers there are known titanium-based catalysts comprising solid titanium catalyst components and organoaluminum compounds, vanadium-based catalysts comprising soluble vanadium compounds and organoaluminum compounds, metallocene-based catalysts comprising metallocene compounds of transitional metals selected from Group 4 of the Periodic Table and organoaluminum oxy-compounds and/or ionizing ionic compounds, etc. In addition, as new olefin polymerization catalyst components there have been proposed metal amide compounds comprising titanium and diamine-based ligands, as represented by the following formulas (Macromolecules 1996, 29, 5241-5243; J. Am. Chem. Soc. 1996, 118. 10008-10009).
wherein R represents 2,6-(iso-Pr)
2
-C
6
H
3
— or 2,6-Me
2
-C
6
H
3
—, and R′ represents —Me or —CH
2
Ph.
These metal amide compounds are used in combination with aluminoxanes or B(C
6
F
5
)
3
, but their polymerization activity is inadequate.
Recently there have also been proposed new olefin polymerization catalysts, for example the olefin polymerization catalysts described in Japanese Laid-open Patent Publication No. 245713/96 comprising a titanium amide compound with a titanium-nitrogen bond and an aluminoxane.
Also, in Organometallics 1996, 15, 562-569 there are described organometallic complexes of Group 4 of the Periodic Table, having bis(borylamide) ligands represented by [Mes
2
BNCH
2
CH
2
NBMes
2
]
−2
, and it is stated that the complexes exhibit slight ethylene polymerization activity.
Incidentally, since olefin polymers generally have excellent mechanical properties, etc., they are used in various fields as different types of molds, but with the diversifying demands for properties of olefin polymers in recent years, olefin polymers with different characteristics have been desired. Improved productivity has also been a goal.
Because of these circumstances, there has been a demand for development of olefin polymerization catalysts with excellent olefin polymerization activity which can give olefin polymers with excellent properties, as well as a process for producing such olefin polymers.
In addition, organoaluminum oxy-compounds (aluminoxanes) used with transition metal compounds for polymerization of olefins are usually produced by contacting an organoaluminum compound such as trialkylaluminum with a metal salt hydrate in a hydrocarbon solvent. The hydrocarbon used here is an aromatic hydrocarbon, especially toluene, which has excellent ability to dissolve the resulting organoaluminum oxy-compound, and such organoaluminum oxy-compounds are usually sold as solutions in toluene, so that they are added to polymerization systems as solutions in toluene when they are used for polymerization. However, addition of an aromatic hydrocarbon such as toluene to a polymerization system raises the problem of residual odor in the polymer, and sometimes problems also arise with respect to working environment conditions. Although there have been methods for distilling toluene out from organoaluminum oxy-compounds for use of the organoaluminum oxy-compounds in solid form, these methods are not industrially convenient.
As a result of diligent research in light of the prior art, the present inventors have completed the present invention upon the finding that when (copolymerization of an olefin is carried out in the presence of a transition metal amide compound and an organoaluminum oxy-compound, addition of the organoaluminum oxy-compound to the polymerization system as an aliphatic or alicyclic hydrocarbon slurry can avoid causing the problems mentioned above and can give better polymerization activity than when the organoaluminum oxy-compound is added to the polymerization system as an aromatic hydrocarbon solution.
DISCLOSURE OF THE INVENTION
One embodiment of the olefin polymerization catalyst of the present invention is a catalyst (olefin polymerization catalyst (1)) comprising
(A) a transition metal amide compound represented by general formula (I) below and at least one compound selected from among
(B)
(B-1) organoaluminum oxy-compounds,
(B-2) compounds which react with the above-mentioned transition metal amide compound (A) to form ion pairs,
 and
(B-3) organometallic compounds.
 where M
1
represents a transition metal of Group 4 or Groups 8 to 10 of the Periodic Table, R
1
represents a hydrocarbon group of 1 to 15 carbon atoms, the multiple (two) R
1
groups being the same or different; and R
2
represents a divalent bonding group represented by general formula (a) or (b) below:
 (where X
1
represents a silicon-containing divalent group, a germanium-containing divalent group, a tin-containing divalent group, —O—, —CO—, —S—, —SO—, —SO
2
—, —C(R
31
)
p
-S-C(R
32
)
q
— (where R
31
and R
32
are each hydrogen atom, the same or different alkyl groups or are linked together to form a ring of 3 to 30 carbon atoms, and p and q are 1 or 2), —N(R
5
)—; —C(R
33
)
r
-N-C(R
34
)
s
— (where R
33
and R
34
are hydrogen atoms, the same or different alkyl groups or are linked together to form a ring of 3 to 30 carbon atoms, and r and s are 1 or 2), —P(R
5
)—, —P(O) (R
5
)—, —B(R
5
)— or —Al(R
5
)—; R
5
and R
6
may be the same or different and each represents a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, a hydrogen atom or a halogen atom; and when R
1
is a (substituted) phenyl group, at least one of the groups represented by R
5
or R
6
is not a hydrogen atom; m is 1 or 2, the multiple R
5
groups and R
6
groups each may be the same or different, 2 or more of the groups R
5
and R
6
may be linked to form a ring; and when m is 1, R
6
is linked to its adjacent R
5
to form a mononuclear or polynuclear aromatic ring), and each R
3
may be the same or different, with each representing a hydrocarbon group of 1 to 15 carbon atoms, a hydrogen atom or a halogen atom, and the multiple R
3
groups being the same or different.
The olefin polymerization catalyst (1) according to the present invention preferably comprises
(A) a transition metal amide compound represented by the aforementioned general formula (I),
(B) (B-1) an organoaluminum oxy-compound and/or (B-2) a compound which reacts with the above-mentioned transition metal amide compound (A) to form an ion pair, and optionally,
(B-3′) an organoaluminum compound.
Preferred as the aforementioned transition metal amide compound (A) is one in which R
1
of the general formula (I) above is a hydrocarbon group with an aromatic ring.
The process for producing the olefin-based polymer of the invention may include embodiments each of which comprises homopolymerizing an olefin, or copolymerizing 2 or more olefins, in the presence of the olefin polymerization catalyst (1).
Use of the olefin polymerization catalyst (1) allows production of olefin polymers by excellent polymerization activity.
Another embodiment of the olefin polymerization catalyst of the present invention is a catalyst (olefin polymerization catalyst (2)) comprising
(A′) a transition metal amide compound represented by general formula (II) below and at least one compound selected from among
(B)
(B-1) organoaluminum oxy-compounds,
(B-2) compounds which react with the above-mentioned transition metal amide compound (A′) to form ion pairs,
 

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