Catalyst for olefin polymerization and method of...

Details Catalyst for olefin polymerization and method of... Catalyst for olefin polymerization and method of...

2000-02-15

2001-11-06

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...

C502S152000, C502S167000, C502S168000

Reexamination Certificate

active

06313243

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a novel olefin olymerization catalyst and a process for olefin olymerization using the olefin polymerization catalyst.
BACKGROUND ART
“Kaminsky catalysts” are well known as olefin polymerization catalysts. The Kaminsky catalysts exhibit extremely high polymerization activity, and by the use of them, polymers of narrow molecular weight distribution can be obtained.
Transition metal compounds known as 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 activity and the properties of the resulting polyolefins greatly vary when different transition metal compounds are used in the polymerization.
Recently, an olefin polymerization catalyst comprising a titanium amide compound having a titanium-nitrogen bond and an aluminoxane has been proposed as a novel olefin polymerization catalyst in, for example, Japanese Patent Laid-Open Publication No. 245713/1996.
Further, an organometallic complex having a metal of Group 4 of the periodic table, which contains a bis (borylamido) ligand represented by (Mes
2
BNCH
2
CH
2
NBMes
2
)
−2
, is described in “Organometallics”, 1996, 15, 562-569. It is also described that this complex slightly exhibits ethylene polymerization activity.
By the way, polyolefins generally have excellent mechanical properties, so that they are used in many fields such as fields of various molded products. With the diversification of requirements for the properties of 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 and a process for olefin polymerization each of which exhibits excellent olefin polymerization activity and is capable of producing polyolefins of excellent properties.
DISCLOSURE OF THE INVENTION
The olefin polymerization catalyst according to the present invention comprises:
(A) a transition metal imine compound represented by the following formula (I), and
(B) at least one compound selected from:
(B-1) an organometallic compound,
(B-2) an organoaluminum oxy-compound, and
(B-3) a compound which reacts with the transition metal imine compound (A) to form an ion pair;
wherein M is a transition metal atom of Group 8 to Group 11 of the periodic table,
R
1
to R
4
may be the same or different and are each a hydrogen atom, a halogen atom, a halogenated hydrocarbon group, a hydrocarbon group, a heterocyclic compound residual group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group or the like,
R
5
and R
6
may be the same or different and are each a halogen atom, a halogenated hydrocarbon group, a hydrocarbon group, a heterocyclic compound residual group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a tin-containing group or the like,
R
1
and R
5
may be bonded to each other to form a ring, R
2
and R
6
may be bonded to each other to form a ring, R
1
and R
3
may be bonded to each other to form a ring, R
2
and R
4
may be bonded to each other to form a ring, and R
3
and R
4
may be bonded to each other to form a ring,
n is a number satisfying a valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or the like, and when n is 2 or greater, plural groups indicated by X may be the same or different, and
Y is an atom of Group 16 of the periodic table.
A preferred example of the transition metal imine compound represented by the formula (I) is a transition metal imine compound represented by the following formula (II):
wherein M is a transition metal atom of Group 8 to Group 11 of the periodic table,
R
7
to R
10
may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residual group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amido group, an imido group, an amino group, an imino group, a sulfonic acid ester group, a sulfonamido group, a cyano group, a nitro group, a carboxyl group, a sulfonyl group, a mercapto group, a hydroxyl group or the like,
R
11
is a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residual group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amido group, an imido group, an amino group, an imino group, a sulfonic acid ester group, a sulfonamido group, a cyano group, a nitro group, a carboxyl group, a sulfonyl group, a mercapto group, a hydroxyl group or the like,
R
7
and R
9
may be bonded to each other to form a ring, R
8
and R
10
may be bonded to each other to form a ring, R
8
and R
11
may be bonded to each other to form a ring, and R
9
and R
10
may be bonded to each other to form a ring,
R
12
to R
16
may be the same or different, and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residual group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amido group, an imido group, an amino group, an imino group, a sulfonate ester group, a sulfonamido group, a cyano group, a nitro group, a carboxyl group, a sulfonyl group, a mercapto group, a hydroxyl group or the like, at least one of R
12
to R
16
is a group other than a hydrogen atom, and two or more of the groups indicated by R
12
to R
16
may be bonded to each other to form a ring,
n is a number satisfying a valence of M,
X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or the like, and when n is 2 or greater, plural groups indicated by X may be the same or different, and
Y is an atom of Group 16 of the periodic table.
Another preferred example of the transition metal imine compound represented by the formula (I) is a transition metal imine compound represented by the following formula (III):
wherein M is a transition metal atom of Group 8 to Group 11 of the periodic table,
R
17
to R
20
may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residual group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester group, an amido group, an imido group, an amino group, an imino group, a sulfonic acid ester group, a sulfonamido group, a cyano group, a nitro group, a carboxyl group, a siilfonyl group, a mercapto group, a hydroxyl group or the like,
R
17
and R
19
may be bonded to each other to form a ring, R
18
and R
20
may be bonded to each other to form a ring, and R
19
and R
20
may be bonded to each other to form a ring,
R
21
to R
30
may be the same or

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