Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1997-12-09
2002-01-22
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S103000, C502S117000, C502S120000, C502S121000, C502S132000, C502S152000, C502S155000
Reexamination Certificate
active
06340652
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to catalysts for polymerization of &agr;-olefin, a process for producing &agr;-olefin polymers, novel transition metal compounds and catalyst components for polymerization of &agr;-olefin.
As catalysts for polymerization of &agr;-olefin, those comprising metallocene and aluminoxane have been proposed (Japanese Patent Application Laid-open (KOKAI) No. 60-35007, Japanese Patent Publication (KOKOKU) No. 4-12283, etc.). However, since the afore-mentioned catalysts are soluble in reaction solvent, the obtained polymer has extremely poor properties in which the polymer has irregular particle shape, has low bulk density and includes a large amount of fine powder therein. Therefore, in the case where these catalysts are applied to a slurry polymerization or a gas-phase polymerization of &agr;-olefin, there have been caused various problems concerning the production of polymers, for example, it has been difficult to conduct safe operations continuously, for the production of polymers.
On the other hand, in order to solve the afore-mentioned problems, there have been proposed catalysts obtained by supporting one or both of a transition metal compound and an organoaluminum on an inorganic oxide such as silica or alumina or an organic substance (Japanese Patent Applications Laid-Open (KOKAI) Nos. 61-108610, 60-135408, 61-296008, 3-74412 and 3-74415, etc.).
However, polymers obtained by using such catalysts have contained a large amount of fine particles or coarse particles, and deteriorated in particle properties such as low bulk density. Further, there arises problems in which the catalysts have a low catalytic activity for the polymerization based on unit weight of solid components thereof, and the obtained polymers have disadvantages such as lower molecular weight or lower stereo regularity as compared to those obtained by using catalysts not supported on a carrier.
SUMMARY OF THE INVENTION
The present invention has been attained for solving the afore-mentioned problems in the prior arts.
It is an object of the present invention to provide catalysts for polymerization of &agr;-olefins, capable of producing &agr;-olefin polymers which are free from poor in properties caused by supporting the catalyst on a carrier such as low molecular weight or low stereo regularity, and which can show not only a narrow composition distribution but also excellent transparency and mechanical strength, and to a process for producing the &agr;-olefin polymer by using the said catalyst.
It is another object of the present invention to provide novel transition metal compounds and catalyst components (catalytically active components) for polymerization of &agr;-olefin.
As a result of the present inventors' earnest studies, it has been found that by using a catalyst comprising a specific transition metal compound and either a specific ion exchangeable layer compound or an inorganic silicate, the above-mentioned objects can be readily achieved.
In a first aspect of the present invention, there is provided a catalyst for polymerization of &agr;-olefin, which comprises:
an essential component (A) of a transition metal compound,
an essential component (B) of an ion exchangeable layer compound except for silicate, or an inorganic silicate, and
an optional component (C) of an organoaluminum compound,
said component (A) being represented by the general formula (I):
wherein A
1
and A
2
are independently a conjugate 5-membered ring ligand with the proviso that A
1
and A
2
may be the same or different in a molecule, and at least one of A
1
and A
2
forms a 7- to 10-membered condensed ring including adjacent two carbon atoms of the conjugate 5-membered ring, which condensed ring is formed by joining two adjacent substituent groups on the conjugate 5-membered ring; Q is a bridging group of the two conjugate 5-membered rings of A
1
and A
2
at optional positions of the 5-membered rings; M is a metal atom selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table; and X and Z are independently a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group.
In a second aspect of the present invention, there is provided a catalyst for polymerization of &agr;-olefin, which comprises:
an essential component (A) of a transition metal compound,
an essential component (D) of an aluminumoxy compound, an ionic compound capable of reacting with the component (A) so as to convert the component (A) to a cation, or a Lewis acid, and
an optional component (E) of a fine particle carrier,
said component (A) being represented by the following general formula (II), (III), (IV), (V) or (VI) included in the above general formula (I).
General formula (II)
wherein R
1
, R
2
, R
4
and R
5
are independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms or halogenated hydrocarbon group having 1 to 18 carbon atoms; R
3
and R
6
are independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms, which forms a condensed ring in cooperation with each of 5-membered rings to which R
3
and R
6
are respectively bonded, with the proviso that at least one of R
3
and R
6
has 5 to 8 carbon atoms and forms a 7- to 10-membered condensed ring having at least one unsaturated bond derived from R
3
or R
6
; R
7
and R
8
are independently a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms with the proviso that at least one of R
7
and R
8
is the halogenated hydrocarbon group having 1 to 20 carbon atoms; m and n are independently an integer of 0 to 20 with the proviso that m and n are not 0 at the same time; Q is a bridging group of the two 5-membered rings, and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a silylene or an oligosilylene group which may have a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms or a germylene group which may have a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms; X and Z are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; and M is a transition metal selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table.
General formula (III)
wherein R
1
, R
2
, R
4
, R
5
, Q, X, and M have the same meanings as defined in the above general formula (II); R
9
, R
10
, R
11
, R
12
, R
13
, R
14
, R
15
and R
16
are independently a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; and Ar is an aryl group which may be substituted, with the proviso that at least one of the two 7-membered rings is bonded to the halogenated hydrocarbon group having 1 to 20 carbon atoms.
General formula (IV)
wherein R
1
and R
4
are independently a hydrocarbon group having 1 to 6 carbon atoms, a silicon-containing hydrocarbon group having 8 to 18 carbon atoms or a halogenated hydrocarbon group having 7 to 12 carbon atoms; R
2
and R
5
are independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms or a halogenated hydro
Aoshima Takayuki
Hayakawa Satoshi
Isobe Eiji
Iwama Naoshi
Kashimoto Masami
Bell Mark L.
Mitsubishi Chemical Corporation
Pasterczyk J.
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