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
1999-04-15
2003-07-15
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...
C502S117000, C526S135000, C526S147000
Reexamination Certificate
active
06593266
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to olefin polymerization catalysts comprising a transition metal compound and to an olefin polymerization process using the olefin polymerization catalysts.
BACKGROUND OF THE INVENTION
As olefin polymerization catalysts, “Kaminsky catalysts” are well known. The Kaminsky catalysts have extremely high polymerization activities, and by the use of them, polymers of narrow molecular weight distribution can be obtained. Transition metal compounds known as components employable for the Kaminsky catalysts are, for example, bis(cyclopentadienyl)zirconium dichloride (see Japanese Patent Laid-Open Publication No. 19309/1983) and ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride (see Japanese Patent Laid-Open Publication No. 130314/1986). It is also known that the olefin polymerization activities or the properties of the resulting polyolefins greatly vary when different transition metal compounds are used in the polymerization. Recently, transition metal compounds having a ligand of diimine structure have been proposed as novel olefin polymerization catalysts (see International Patent Publication No. 9623010).
By the way, polyolefins generally have excellent mechanical properties, so that they are used in many fields such as fields of various molded products. However, with variation of requirements for the polyolefins, polyolefins of various properties have been desired in recent years. Moreover, increase of productivity has been also desired.
Under such circumstances as mentioned above, there has been desired development of an olefin polymerization catalyst having an excellent olefin polymerization activity and capable of producing polyolefins of excellent properties.
OBJECT OF THE INVENTION
It is an object of the invention to provide an olefin polymerization catalyst comprising a transition metal compound and having an excellent olefin polymerization activity and to provide an olefin polymerization process using the catalyst.
SUMMARY OF THE INVENTION
The first olefin polymerization catalyst according to the invention comprises:
(A) a transition metal compound which is obtained by bond-forming reaction of a compound represented by the following formula (a) with a metallic compound represented by the following formula (e) and in which the molar ratio of ligands to metal atoms is in the range of 1 to 6, said ligands being derived from the compound of the formula (a) and bonded to said metal atoms, and optionally
(B) at least one compound selected from the group consisting of:
(B-1) an organometallic compound,
(B-2) an organoaluminum oxy-compound, and
(B-3) a compound which reacts with the transition metal compound (A) to form an ion pair;
wherein
A is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a bonding group —R
5
,
D is —C(R
7
)(R
8
)—, —Si(R
9
)(R
10
)—, —P(O)(R
11
)—, —P(R
12
)—, —SO— or —S—,
Z is a bonding group of N and represents —R
13
and —R
14
, ═C(R
15
)R
16
or ═NR
17
, and
R
1
to R
17
may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residual group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of them may be bonded to each other to form a ring;
MX
k
(e)
wherein
M is a transition metal atom of Group 3 to Group 11 of the periodic table,
k is a number satisfying a valence of M, and
X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residual group, a silicon-containing group, a germanium-containing group or a tin-containing group, and when k is 2 or greater, plural groups X may be the same or different, and may be bonded to each other to form a ring.
The second olefin polymerization catalyst according to the invention comprises:
(A) a transition metal compound which is obtained by bond-forming reaction of a compound represented by the following formula (b) with a metallic compound represented by the above formula (e) and in which the molar ratio of ligands to metal atoms is in the range of 1 to 6, said ligands being derived from the compound of the formula (b) and bonded to said metal atoms, and optionally
(B) at least one compound selected from the group consisting of:
(B-1) an organometallic compound,
(B-2) an organoaluminum oxy-compound, and
(B-3) a compound which reacts with the transition metal compound (A) to form an ion pair;
wherein
A is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a bonding group —R
5
,
D is —C(R
7
)(R
8
)—, —Si(R
9
)(R
10
)—, —P(O)(R
11
)—, —P(R
12
)—, —SO— or —S—, and
R
1
to R
13
may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residual group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of them may be bonded to each other to form a ring.
The third olefin polymerization catalyst according to the invention comprises:
(A) a transition metal compound which is obtained by bond-forming reaction of a compound represented by the following formula (c) with a metallic compound represented by the above formula (e) and in which the molar ratio of ligands to metal atoms is in the range of 1 to 6, said ligands being derived from the compound of the formula (c) and bonded to said metal atoms, and optionally
(B) at least one compound selected from the group consisting of:
(B-1) an organometallic compound,
(B-2) an organoaluminum oxy-compound, and
(B-3) a compound which reacts with the transition metal compound (A) to form an ion pair;
wherein
A is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a bonding group —R
5
,
D is —C(R
7
)(R
8
)—, —Si(R
9
)(R
10
)—, —P(O)(R
11
)—, —P(R
12
)—, —SO— or —S—, and
R
1
to R
13
may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residual group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of them may be bonded to each other to form a ring.
The fourth olefin polymerization catalyst according to the invention comprises:
(A) a transition metal compound which is obtained by bond-forming reaction of a compound represented by the following formula (d) with a metallic compound represented by the above formula (e) and in which the molar ratio of ligands to metal atoms is in the range of 1 to 6, said ligands being derived from the compound of the formula (d) and bonded to said metal atoms, and optionally
(B) at least one compound selected from the group consisting of:
(B-1) an organometallic compound,
(B-2) an organoaluminum oxy-compound, and
(B-3) a compound which reacts with the transition metal compound (A) to form an ion pair;
wherein
A is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom having a bonding group —R
5
,
D is —C(R
7
)(R
8
)—, —Si(R
9
)(R
10
)—, —P(O)(R
11
)—, —P(R
12
)—, —SO— or —S—,
Z is a bonding group of N and represents —R
13
and —R
14
, ═C(R
15
)R
16
or ═NR
17
, and
R
1
to R
17
may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residual group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group
Fujita Terunori
Matsui Shigekazu
Mitani Makoto
Nakano Takashi
Nitabaru Masatoshi
Bell Mark L.
Mitsui Chemicals Inc.
Pasterczyk J.
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