U.S. patent application number 11/092912 was filed with the patent office on 2005-08-04 for transition metal compound, coordinative compound, catalyst for polymerization of olefin, and process for polymerization of olefin using the catalyst.
This patent application is currently assigned to TOSOH CORPORATION. Invention is credited to Hamura, Satoshi, Okada, Takashi, Sato, Morihiko, Tanabiki, Masao, Watanabe, Makoto.
Application Number | 20050171306 11/092912 |
Document ID | / |
Family ID | 18857925 |
Filed Date | 2005-08-04 |
United States Patent
Application |
20050171306 |
Kind Code |
A1 |
Watanabe, Makoto ; et
al. |
August 4, 2005 |
Transition metal compound, coordinative compound, catalyst for
polymerization of olefin, and process for polymerization of olefin
using the catalyst
Abstract
A transition metal compound having a ligand with an azaferrocene
structure or a ferrocene structure. The transition metal compound
is used in combination with an activating cocatalyst, as a catalyst
for polymerization of olefins.
Inventors: |
Watanabe, Makoto;
(Yokkaichi-shi, JP) ; Okada, Takashi; (Kuwana-shi,
JP) ; Sato, Morihiko; (Yokkaichi-shi, JP) ;
Hamura, Satoshi; (Yokkaichi-shi, JP) ; Tanabiki,
Masao; (Yokkaichi-shi, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
TOSOH CORPORATION
Shinnanyo-shi
JP
|
Family ID: |
18857925 |
Appl. No.: |
11/092912 |
Filed: |
March 30, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11092912 |
Mar 30, 2005 |
|
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10022772 |
Dec 20, 2001 |
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Current U.S.
Class: |
526/160 ;
526/170; 526/172; 526/943; 556/16; 556/33 |
Current CPC
Class: |
B01J 31/1805 20130101;
B01J 31/183 20130101; C08F 4/6192 20130101; C08F 10/00 20130101;
C08F 10/00 20130101; C08F 10/02 20130101; C07F 17/02 20130101; C08F
110/02 20130101; C08F 110/02 20130101; B01J 2531/824 20130101; B01J
2531/842 20130101; C08F 10/00 20130101; C08F 10/00 20130101; C08F
210/02 20130101; C08F 10/00 20130101; C08F 210/02 20130101; B01J
31/1815 20130101; B01J 31/2295 20130101; C08F 10/00 20130101; C08F
2500/03 20130101; C08F 10/00 20130101; C08F 4/7006 20130101; C08F
4/50 20130101; C08F 4/7024 20130101; C08F 4/7022 20130101; C08F
2500/03 20130101; C08F 4/7009 20130101; C08F 220/18 20130101; C08F
4/7013 20130101 |
Class at
Publication: |
526/160 ;
526/170; 526/943; 526/172; 556/016; 556/033 |
International
Class: |
C08F 004/44; C07F
017/02 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 20, 2000 |
JP |
2000-391840 |
Claims
1-12. (canceled)
13. A process for polymerization of an olefin, which comprises
polymerizing an olefin in the present of a catalyst comprising a
transition metal compound selected from the group consisting of a
first transition metal compound, a second transition metal
compound, a third transition metal compound and a fourth transition
metal compound, wherein the first transition metal compound is
represented by the following formula (1): 55wherein M represents a
transition metal atom selected from the group consisting of metal
atoms of group 3 to group 12 of the periodic table; X represents a
hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20
carbon atoms, a hydrocarbyloxygroup having 1 to 20 carbon atoms, an
amino group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, a sulfonate group having an organic residue with 1 to
20 carbon atoms, or a non-coordinative anion containing an element
selected from the group consisting of B, Al, P and Sb, and, when q
is an integer of at least 2, Xs may be the same as or different
from each other; A represents a carbon atom, a nitrogen atom or a
phosphorus atom; R.sup.1 represents a hydrogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to
20 carbon atoms and containing at least one halogen atom, or a
ferrocenyl group or a substituted ferrocenyl group; R.sup.2
represents a hydrogen atom, a hydrocarbon group having 1 to 20
carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and
containing at least one atom selected from the group consisting of
halogen, silicon, nitrogen, oxygen and sulfur atoms, or a
ferrocenyl group or a substituted ferrocenyl group; and R and R may
form together a ring; Q represents a hydrogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, an amino group
having one or more hydrocarbon groups each with 1 to 20 carbon
atoms, a phosphino group having one or more hydrocarbon groups each
with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group
with 1 to 20 carbon atoms, a thio group having a hydrocarbon group
with 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20
carbon atoms and containing at least one atom selected from the
group consisting of nitrogen, phosphorus, oxygen and sulfur atoms,
or oxygen or sulfur; and, when Q contains a coordinative atom, Q
can be coordinatively bound to M; R.sup.3 represents a hydrogen
atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon
atoms, a silyl group having one or more hydrocarbon groups each
with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20
carbon atoms and containing at least one atom selected from the
group consisting of nitrogen, oxygen, halogen and sulfur atoms and
one of R.sup.3s adjacent to Q may form a ring together with Q; and,
when m is an integer of at least 2, R.sup.3s may be the same as or
different from each other, and adjacent R.sup.3s may form together
a ring; R.sup.4 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms
and containing at least one atom selected from the group consisting
of nitrogen, phosphorus, oxygen, halogen and sulfur atoms; and,
when n is an integer of at least 2, R.sup.4s may be the same as or
different from each other, and adjacent R.sup.4s may form together
a ring; and R.sup.3 and R.sup.4 may form together a ring; and, when
R.sup.4 contains a heteroatom, R.sup.4 can coordinate with the
transision metal atom M; L is a coordinate bond-forming compound
selected from the group consisting of J electron, ethers, nitrites,
amines and phosphines, and L may be bound to X; m is an integer of
1 to 3, n is an integer of 1 to 5, and p is an integer of 0 or 1;
when Q is sulfur or oxygen, the bond between Q and M is a sigma
bond; when p is 0 and A is a nitrogen atom or a phosphorus atom, A
can be coordinatively bound to M; and q is an integer of 1 to 3 and
r is an integer of 0 to 3, wherein the second transition metal
compound is represented by the following formula (2): 56wherein M
represents a transition metal atom selected from the group
consisting of metal atoms of group 3 to group 12 of the periodic
table; X represents a hydrogen atom, a halogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a sulfonate group having an
organic residue with 1 to 20 carbon atoms, or a non-coordinative
anion containing an element selected from the group consisting of
B, Al, P and Sb, and, when q is an integer of at least 2, Xs may be
the same as or different from each other; R.sup.1 represents a
hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a
hydrocarbon group having 1 to 20 carbon atoms and containing at
least one halogen atom, or a ferrocenyl group or a substituted
ferrocenyl group; R.sup.2 represents a hydrogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to
20 carbon atoms and containing at least one atom selected from the
group consisting of halogen, silicon, nitrogen, oxygen and sulfur
atoms, or a ferrocenyl group or a substituted ferrocenyl group; and
R and R may form together a ring; R.sup.3 represents a hydrogen
atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon
atoms, a silyl group having one or more hydrocarbon groups each
with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20
carbon atoms and containing at least one atom selected from the
group consisting of nitrogen, oxygen, halogen and sulfur atoms and,
when m is an integer of at least 2, R.sup.3s may be the same as or
different from each other, and adjacent R.sup.3s may form together
a ring; R.sup.4 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms
and containing at least one atom selected from the group consisting
of nitrogen, phosphorus, oxygen, halogen and sulfur atoms; and,
when n is an integer of at least 2, R.sup.4s may be the same as or
different from each other, and adjacent R.sup.4s may form together
a ring; and R.sup.3 and R.sup.4 may form together a ring; L is a
coordinate bond-forming compound selected from the group consisting
of n electron, ethers, nitrites, amines and phosphines, and L may
be bound to X; m is an integer of 1 to 3, n is an integer of 1 to
5, q is an integer of 1 to 3 and r is an integer of 0 to 3, wherein
the third transition metal compound is represented by the following
formula (3): 57wherein M represents a transition metal atom
selected from the group consisting of metal atoms of group 3 to
group 12 of the periodic table; X represents a hydrogen atom, a
halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a
hydrocarbyloxygroup having 1 to 20 carbon atoms, an amino group
having one or more hydrocarbon groups each with 1 to 20 carbon
atoms, a sulfonate group having an organic residue with 1 to 20
carbon atoms, or a non-coordinative anion containing an element
selected from the group consisting of B, Al, P and Sb, and, when q
is an integer of at least 2, Xs may be the same as or different
from each other; R.sup.1 represents a hydrogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to
20 carbon atoms and containing at least one halogen atom, or a
ferrocenyl group or a substituted ferrocenyl group; R.sup.2
represents a hydrogen atom, a hydrocarbon group having 1 to 20
carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and
containing at least one atom selected from the group consisting of
halogen, silicon, nitrogen, oxygen and sulfur atoms, or a
ferrocenyl group or a substituted ferrocenyl group; and R and R may
form together a ring; Q represents a hydrogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, an amino group
having one or more hydrocarbon groups each with 1 to 20 carbon
atoms, a phosphino group having one or more hydrocarbon groups each
with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group
with 1 to 20 carbon atoms, a thio group having a hydrocarbon group
with 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20
carbon atoms and containing at least one atom selected from the
group consisting of nitrogen, phosphorus, oxygen and sulfur atoms,
or oxygen or sulfur; and, when Q contains a coordinative atom, Q
can be coordinatively bound to M; R.sup.3 represents a hydrogen
atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon
atoms, a silyl group having one or more hydrocarbon groups each
with 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20
carbon atoms and containing at least one atom selected from the
group consisting of nitrogen, oxygen, halogen and sulfur atoms, and
one of R.sup.3s adjacent to Q may form a ring together with Q; and,
when m is an integer of at least 2, R.sup.3s may be the same as or
different from each other, and adjacent R.sup.3s may form together
a ring; R.sup.4 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms
and containing at least one atom selected from the group consisting
of nitrogen, phosphorus, oxygen, halogen and sulfur atoms; and,
when n is an integer of at least 2, R.sup.4s may be the same as or
different from each other, and adjacent R.sup.4s may form together
a ring; and R.sup.3 and R.sup.4 may form together a ring; and, when
R.sup.4 contains a heteroatom, R.sup.4 can coordinate with the
transition metal atom M; L is a coordinate bond-forming compound
selected from the group consisting of a electron, ethers, nitrites,
amines and phosphines, and L may be bound to X; m is an integer of
1 to 3 and n is an integer of 1 to 5; when Q is sulfur or oxygen,
the bond between Q and M is a sigma bond; and q is an integer of 1
to 3 and r is an integer of 0 to 3, and wherein the fourth
transition metal compound is represented by the following formula
58wherein M represents a transition metal atom selected from the
group consisting of metals of group 3 to group 12 of the periodic
table; X represents a hydrogen atom, a halogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a sulfonate group having an
organic residue with 1 to 20 carbon atoms, or a non-coordinative
anion containing an element selected from the group consisting of
B, Al, P and Sb, and, when q is an integer of at least 2, Xs may be
the same as or different from each other; R.sup.1 represents a
hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a
trifluoromethyl group, a ferrocenyl group or a substituted
ferrocenyl group; R.sup.2 represents a hydrogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to
20 carbon atoms and containing at least one atom selected from the
group consisting of silicon, nitrogen, oxygen and sulfur atoms, or
a ferrocenyl group or a substituted ferrocenyl group; and R.sup.1
and R.sup.2 may form together a ring; R.sup.3 represents a hydrogen
atom, a hydrocarbon group having 1 to 20 carbon atoms or a silyl
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms; and, when m is an integer of at least 2, R.sup.3s may
be the same as or different from each other; R.sup.4 represents a
hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a
silyl group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, a phosphino group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, an oxy group having a
hydrocarbon group with 1 to 20 carbon atoms, a thio group having a
hydrocarbon group with 1 to 20 carbon atoms, or a hydrocarbon group
having 1 to 20 carbon atoms and containing at least one atom
selected from the group consisting of nitrogen, phosphorus, oxygen,
halogen and sulfur atoms; and, when n is an integer of at least 2,
R.sup.4s may be the same as or different from each other, and
adjacent R.sup.4s may form together a ring; R.sup.5 represents a
hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or
an amino group having one or more hydrocarbon groups each with 1 to
20 carbon atoms; L is a coordinate bond-forming compound selected
from the group consisting of .pi. electron, ethers, nitrites,
amines and phosphines, and L may be bound to X; m is an integer of
1 or 2, n is an integer of 1 to 5, q is an integer of 1 to 3 and r
is an integer of 0 to 3.
14. The process according to claim 13, wherein the olefin is
selected from the group consisting of .alpha.-olefins, styrene and
styrene derivatives, conjugated dienes, non-conjugated dienes,
cycloolefins, .alpha.,.beta.-unsaturated carboxylic acids, metal
salts of .alpha.,.beta.-unsaturated carboxylic acids, esters of
.alpha.,.beta.-unsaturated carboxylic acids, vinyl esters,
unsaturated glycidyl esters, vinyl ketones, and
.alpha.,.beta.-unsaturated nitriles.
15. The process according to claim 13, wherein M in the formula (1)
to (4) represents a transition metal atom selected from the group
consisting of metal atoms of group 8 to group 12 of the periodic
table.
16. The process according to claim 15, wherein the olefin is
selected from the group consisting of .alpha.-olefins, styrene and
styrene derivatives, conjugated dienes, non-conjugated dienes,
cycloolefins, .alpha.,.beta.-unsaturated carboxylic acids, metal
salts of .alpha.,.beta.-unsaturated carboxylic acids, esters of
.alpha.,.beta.-unsaturated carboxylic acids, vinyl esters,
unsaturated glycidyl esters, vinyl ketones, and
.alpha.,.beta.-unsaturated nitriles.
17. The process according to claim 13, wherein M in the formula (1)
to (4) represents a transition metal atom selected from the group
consisting of Ni, Pd, Fe and Cu.
18. The process according to claim 17, wherein the olefin is
selected from the group consisting of .alpha.-olefins, styrene and
styrene derivatives, conjugated dienes, non-conjugated dienes,
cycloolefins, .alpha.,.beta.-unsaturated carboxylic acids, metal
salts of .alpha.,.beta.-unsaturated carboxylic acids, esters of
.alpha.,.beta.-unsaturated carboxylic acids, vinyl esters,
unsaturated glycidyl esters, vinyl ketones, and
.alpha.,.beta.-unsaturated nitriles.
19. The process according to claim 13, wherein the polymerization
of an olefin is carried out further in the presence of an
activating cocatalyst.
20. The process according to claim 19, wherein the olefin is
selected from the group consisting of .alpha.-olefins, styrene and
styrene derivatives, conjugated dienes, non-conjugated dienes,
cycloolefins, .alpha.,.beta.-unsaturated carboxylic acids, metal
salts of .alpha.,.beta.-unsaturated carboxylic acids, esters of
.alpha.,.beta.-unsaturated carboxylic acids, vinyl esters,
unsaturated glycidyl esters, vinyl ketones, and
.alpha.,.beta.-unsaturated nitriles.
Description
BACKGROUND OF THE INVENTION
[0001] (1) Field of the Invention
[0002] This invention relates to a transition metal compound, a
coordinative compound, a catalyst for polymerization of an olefin
comprising the transition metal compound, and a process for
polymerizing an olefin using the catalyst.
[0003] (2) Description of the Related Art
[0004] It is known that a homogeneous catalyst comprising a
combination of a transition metal compound containing a metal of
group 4 of the periodic table and having a cyclopentadienyl
derivative as a ligand with an aluminoxane exhibits a high activity
for polymerization of olefins and is used therefor (for example,
Japanese Unexamined Patent Publication [hereinafter abbreviated to
"JP-A"] No. S58-19309). Catalysts comprising an organometalic
complex having a cyclopentadienyl structure as a non-ligand, which
include the above-mentioned homogeneous transition metal catalyst,
are known as giving a polyolefin having a narrow molecular weight
distribution and having a uniform distribution In composition over
the polymer.
[0005] In recent years, to provide an improved homogeneous catalyst
for polymerization of olefins, extensive researches have been made
on homogeneous catalysts comprising an organometallic complex
having a ligand other than that having a cyclopentadienyl
structure, i.e., a ligand containing a heteroatom. For example, as
for catalysts for polymerization of olefins comprising an
organometallic complex of a transition metal compound with a ligand
containing a nitrogen atom, JP-A H.sub.8-176217 and JP-A H8-245713
disclose a catalyst for polymerization of an olefin comprising a
titanium amide compound containing a titanium metal with a
dialkylamine as a ligand. JP-A H10-298216 discloses a catalyst for
polymerization of an olefin comprising a transition metal amide
compound with a crosslinkable aromatic amine compound as a
ligand.
[0006] Catalysts for polymerization of olefins comprising an
organometallic complex with a ligand comprising a nitrogen atom
have also been widely studied from a scientific point of view.
Living polymerization of 1-hexene using a catalyst system
comprising a diamide complex represented by the formula:
[ArN(CH.sub.2).sub.3NAr]TiMe.sub.2, and B(C.sub.6F.sub.5).sub.3 is
described in D. H. McConville et al. J. Am. Chem. Soc. vol. 118, p.
10008 (1996). Living polymerization of 1-hexene using a catalyst
system comprising a diamido complex with a tridentate ligand,
represented by the formula: [(t-BuN-ortho-C.sub.6H.sub-
.4).sub.2O]ZrMe.sub.2 and B(C.sub.6F.sub.5).sub.3, is described in
R. R. Schlock et al., J. Am. Chem. Soc. 119, p. 3830 (1997).
Further, synthesis of a transition metal compound containing a
metal of group 4 with a ligand having a bis(borylamide) structure
such as [Mes.sub.2BNCH.sub.2CH.- sub.2NBMes.sub.2].sup.2- and its
catalytic activity for polymerization of ethylene are described in
Organometallics, vol. 15, p 562 (1996) and Organometallics, vol.
17, p 308 (1998).
[0007] Recently, it has been reported that a catalyst comprising a
bidentate ligand-containing diimine chelete-type nickel complex
gives a polyolefin having a structure with many branches introduced
therein, which is distinct from a structure of the conventional
polyolefins produced by using a metallocene catalyst (for example,
WO96/23010). Further, it has been reported that a catalyst
comprising an aldimine chelete-type group 4 transition metal
complex exhibits greatly enhanced activity for polymerization of an
olefin (for example, EP 874.005 (1998), and J. Am. Chem. Soc., vol.
123, p 6847 (2001)).
SUMMARY OF THE INVENTION
[0008] A primary object of the present invention is to provide a
novel transition metal compound having an azaferrocene or ferrocene
structure, which is useful as a catalyst for polymerization of
olefins.
[0009] Another object is to provide a coordinative compound used
for production of the above-mentioned novel transition metal
compound: and a precursor compound used for production of the
coordinative compound.
[0010] Still another object is to provide a catalyst for
polymerization of an olefin comprising the above-mentioned novel
transition metal compound, and a process for polymerizing an olefin
using the catalyst, by which polyolefins can be produced with an
enhanced efficiency.
[0011] In one aspect of the present invention, there is provided a
transition metal compound represented by the following formula (1):
1
[0012] wherein M represents a transition metal atom selected from
the group consisting of metal atoms of group 3 to group 12 of the
periodic table.
[0013] X represents a hydrogen atom, a halogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1
to 20 carbon atoms, an amino group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, a sulfonate group having an
organic residue with 1 to 20 carbon atoms, or a non-coordinative
anion containing an element selected from the group consisting of
B, Al, P and Sb, and, when q is an integer of at least 2, Xs may be
the same as or different from each other. A represents a carbon
atom, a nitrogen atom or a phosphorus atom.
[0014] R.sup.1 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20
carbon atoms and containing at least one halogen atom, or a
ferrocenyl group or a substituted ferrocenyl group. R.sup.2
represents a hydrogen atom, a hydrocarbon group having 1 to 20
carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and
containing at least one atom selected from halogen, silicon,
nitrogen, oxygen and sulfur atoms, or a ferrocenyl group or a
substituted ferrocenyl group: and R.sup.1 and R.sup.2 may form
together a ring.
[0015] Q represents a hydrogen atom, a hydrocarbon group having 1
to 20 carbon atoms, a silyl group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, an amino group having one or
more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and
containing at least one atom selected from nitrogen, phosphorus,
oxygen and sulfur atoms, or oxygen or sulfur; and, when Q contains
a coordinative atom, Q can be coordinatively bound to M.
[0016] R.sup.3 represents a hydrogen atom, a halogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a silyl group having
one or more hydrocarbon groups each with 1 to 20 carbon atoms, or a
hydrocarbon group having 1 to 20 carbon atoms and containing at
least one atom selected from nitrogen, oxygen, halogen and sulfur
atoms, and one of R.sup.3s adjacent to Q may form a ring together
with Q; and, when m is an integer of at least 2. R.sup.3s may be
the same as or different from each other, and adjacent R.sup.3s may
form together a ring. R.sup.4 represents a hydrogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a silyl group having
one or more hydrocarbon groups each with 1 to 20 carbon atoms, a
phosphino group having one or more hydrocarbon groups each with 1
to 20 carbon atoms, an oxy group having a hydrocarbon group with 1
to 20 carbon atoms, a thio group having a hydrocarbon group with 1
to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon
atoms and containing at least one atom selected from nitrogen,
phosphorus, oxygen, halogen and sulfur atoms; and, when n in an
integer of at least 2, R.sup.4s may be the same as or different
from each other, and adjacent R.sup.4s may form together a ring;
and R.sup.3 and R.sup.4 may form together a ring; and, when R.sup.4
contains a heteroatom, R.sup.4 can coordinate with the transision
metal atom M.
[0017] L is a coordinate bond-forming compound selected from the
group consisting of .pi. electron, ethers, nitriles, ines and
phosphines, and L may be bound to X.
[0018] m is an integer of 1 to 3, n is an Integer of 1 to 5, and p
is an Integer of 0 or 1. When Q is sulfur or oxygen, the bond
between Q and M is a sigma bond. When p is 0 and A is a nitrogen
atom or a phosphorus atom, A can be coordinatively bound to M. q is
an integer of 1 to 3 and r is an integer of 0 to 3.
[0019] In another aspect of the present invention, there is
provided a coordinative compound represented by the following
formula (5): 2
[0020] wherein A represents a carbon atom, a nitrogen atom or a
phosphorus atom;
[0021] R.sup.1 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20
carbon atoms and containing at least one halogen atom, or a
ferrocenyl group or a substituted ferrocenyl group;
[0022] R.sup.2 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20
carbon atoms and containing at least one atom selected from
halogen, silicon, nitrogen, oxygen and sulfur atoms, or a
ferrocenyl group or a substituted ferrocenyl group; and R.sup.1 and
R.sup.2 may form together a ring;
[0023] Q represents a hydrogen atom, a hydrocarbon group having 1
to 20 carbon atoms, a silyl group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, an amino group having one or
more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and
containing at least one atom selected from nitrogen, phosphorus,
oxygen and sulfur atoms, or a hydroxyl group or a thiol group;
[0024] R.sup.3 represents a hydrogen atom, a halogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a silyl group having
one or more hydrocarbon groups each with 1 to 20 carbon atoms, or a
hydrocarbon group having 1 to 20 carbon atoms and containing at
least one atom selected from nitrogen, oxygen, halogen and sulfur
atoms, and one of R.sup.3s adjacent to Q may form a ring together
with Q; and, when m is an integer of at least 2, R.sup.3s may be
the same as or different from each other, and adjacent R.sup.3s may
form together a ring;
[0025] R.sup.4 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms
and containing at least one atom selected from the group consisting
of nitrogen, phosphorus, oxygen, halogen and sulfur atoms; and,
when n is an integer of at least 2, R.sup.4s may be the same as or
different from each other, and adjacent R.sup.4s may form together
a ring; and R.sup.3 and R.sup.4 may form together a rings and
[0026] m is an integer of 1 to 3, n is an integer of 1 to 5, and p
is an integer of 0 or 1.
[0027] In still another aspect of the present invention, there is
provided a compound which is a precursor to the coordinative
compound represented by formula (5), and which is represented by
the following formula (6): 3
[0028] wherein R.sup.3, R.sup.4, m and n are the same as defined
for formula (5), except that, R.sup.4 is not a hydrogen atom, and
when n is an integer of 1, R.sup.4 is not a methyl group, and, when
n is an integer of at least 2, all of the R.sup.4s are not
simultaneously a methyl group.
[0029] In a further aspect of the present invention, there is
provided a catalyst for polymerization of an olefin, which
comprises the transition metal compound of formula (1).
[0030] In a further aspect of the present invention, there is
provided a process for polymerizing an olefin in the presence of a
catalyst comprising the transition metal compound of formula
(1).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0031] In formula (1) representing the transition metal compound of
the present invention, M represents a transition metal atom
selected from metals of group 3 to group 12, preferably metals of
group 8 to group 12, of the periodic table. More preferably M is
selected from Ni, Pd, Fe and Cu.
[0032] X represents a hydrogen atom, a halogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1
to 20 carbon atoms, an amino group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, a sulfonate group having an
organic residue with 1 to 20 carbon atoms, or a non-coordinative
anion containing an element selected from B, Al, P and Sb.
Preferably, X represents a halogen atom, a hydrocarbon group having
1 to 20 carbon atoms, a sulfonate group having an organic residue
with 1 to 20 carbon atoms, or a non-coordinative anion containing
an element selected from B, Al, P and Sb. q is an integer of 1 to
3, and, when q is an integer of 2 or 3, Xs may be the sane as or
different from each other. As specific examples of the halogen atom
for X, there can be mentioned chlorine, bromine and iodine atoms.
Of these, chlorine and bromine atoms are preferable. The
hydrocarbon group having 1 to 20 carbon atoms includes for example,
methyl, ethyl, isopropyl, tert.-butyl, benzyl, allyl, phenyl and
o-tolyl groups. The hydrocarbyloxy group having 1 to 20 carbon
atoms includes, for example, methoxy, ethoxy, isopropoxy,
tert.-butoxy and phenoxy groups. The amino group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms includes, for
example, dialkylamino groups such as dimethylamino, diethylamino
and diisopropylamino groups, diarylamino groups such as a
diphenylamino group, and diaralkylamino groups such as
dibenzylamino groups. The sulfonate group having an organic residue
with 1 to 20 carbon atoms includes, for example,
trifluoromethanesulfonate and p-toluenesulfonate groups. As
specific examples of the non-coordinative anion containing an
element selected from B, Al, P and Sb, there can be mentioned
tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion,
tetrakis(pentafluorophenyl)borate anion,
tetrakis-(pentafluorophenyl)alum- inate anion, SbF.sub.6 anion and
PF.sub.6 anion.
[0033] R.sup.1 in formula (1) represents a hydrogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group
having 1 to 20 carbon atoms and containing at least one halogen
atom, or a ferrocenyl group or a substituted ferrocenyl group. Of
these, a hydrogen atom and a hydrocarbon group having 1 to 20
carbon atoms are preferable. As specific examples of the
hydrocarbon group having 1 to 20 carbon atoms, there can be
mentioned methyl, ethyl, propyl, butyl, isopropyl, tert.-butyl,
benzyl, phenyl, 2-methylphenyl and naphthyl groups. Of these,
methyl and phenyl groups are preferable. As specific examples of
the hydrocarbon group having 1 to 20 carbon atoms and containing at
least one halogen atom, there can be mentioned trifluoromethyl,
trichloromethyl, 2,2,2-trifluoroethyl and difluoromethyl groups. Of
these, a trifluoromethyl group is preferable. As specific examples
of the substituted ferrocenyl group, there can be mentioned
methylferrocenyl, dimethylferrocenyl and tert.-butylferrocenyl
groups.
[0034] R.sup.2 in formula (1) represents a hydrogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group
having 1 to 20 carbon atoms and containing at least one atom
selected from halogen, silicon, nitrogen, oxygen and sulfur atoms,
or a ferrocenyl group or a substituted ferrocenyl group. Of these,
a hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon
group having 1 to 20 carbon atoms and containing at least one atom
selected from halogen, silicon, nitrogen, oxygen and sulfur atoms
are preferable. As specific examples of the hydrocarbon group
having 1 to 20 carbon atoms in R.sup.2, there can be mentioned
methyl, ethyl, propyl, isopropyl, tert.-butyl, benzyl, phenyl,
2-methylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl,
2,6-diisopropylphenyl, 2-tert.butylphenyl, mesityl, 2-biphenyl,
naphthyl and adamantyl groups. Of these, 2-methylphenyl,
2-isopropylphenyl, 2-tert.butylphenyl and 2-biphenyl groups are
preferable. As specific examples of the hydrocarbon group having 1
to 20 carbon atoms and containing at least one atom selected from
halogen, silicon, nitrogen, oxygen and sulfur atoms, there can be
mentioned 2-(trifluoromethyl)phenyl- , 2-(trichloromethyl)phenyl,
2-methyl-4-chlorophenyl, 2-(trimethylsilyl)phenyl,
2,6-di(trimethylsilyl)phenyl, 2-(dimethylaminomethyl)phenyl,
2-(diphenylaminomethyl)phenyl, 2-(methoxymethyl)phenyl,
2-(phenoxymethyl)phenyl, 2-(methylthiomethyl)phe- nyl,
2-(phenylthiomethyl)phenyl, 2-pyridyl, 2-quinolyl,
2-(3-benzyloxypyridyl), 5-(1,3-dimethylpyrazolyl),
2-(methylthio)-5-(trifluoromethyl)phenyl and
2-(1H-pyrrol-1-yl)phenyl groups. Of these, (trifluoromethyl)phenyl,
2-(trichloromethyl)phenyl, 2-methyl-4-chlorophenyl,
2-(trimethylsilyl)phenyl, 2-(diphenylaminomethyl)phenyl and
2-(methoxymethyl)phenyl groups are preferable. AB specific examples
of the substituted ferrocenyl group, there can be mentioned a
methylferrocenyl group, a dimethylferrocenyl group, a
tert.-butylferrocenyl group and a ferrocenyl group having a
tetramethyl-cyclopentadienyl (hereinafter abbreviated to Cp* when
appropriate) group. R.sup.1 and R.sup.2 in formula (1) may form
together a ring.
[0035] Q in formula (1) represents a hydrogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, an amino group
having one or more hydrocarbon groups each with 1 to 20 carbon
atoms, a phosphino group having one or more hydrocarbon groups each
with 1 to 20 carbon atoms, an oxy group having a hydrocarbon group
with 1 to 20 carbon atoms, a thio group having a hydrocarbon group
with 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20
carbon atoms and containing at least one atom selected from
nitrogen, phosphorus, oxygen and sulfur atoms, or oxygen or sulfur.
Of these, an amino group having one or more hydrocarbon groups each
with 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20
carbon atoms and containing at least one nitrogen atom are
preferable. When Q contains a coordinative atom, 0 can be
coordinatively bound to M. As specific examples of the hydrocarbon
group having 1 to 20 carbon atoms in Q, there can be mentioned
methyl, ethyl, tert.-butyl and phenyl group. As specific examples
of the silyl group having one or more hydrocarbon groups each with
1 to 20 carbon atoms, there can be mentioned trimethylsilyl,
tert.-butyldimethylsilyl and triphenylsilyl groups. As specific
examples of the amino group having one or more hydrocarbon groups
each with 1 to 20 carbon atoms, there can be mentioned
dimethylamino, diethylamino, diphenylamino, or a pyridyl group
bound to the adjacent R.sup.2 group or a substituted pyridyl group
bound to the adjacent R.sup.3 group, Of these, a pyridyl group
bound to the adjacent R.sup.3 group and a substituted pyridyl group
bound to the adjacent R.sup.3 group are preferable. As specific
examples of the phosphino group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, there can be mentioned
dimethylphosphino, dicyclohexylphosphino, di-tert.-butylphosphino
and diphenylphosphino; and azaphosphines such as
bis(diisopropylamino)phosphino, bis(pyrrolidinyl)phosphino,
1-(N,N-dimethyl-2,5-diaza-1-phosphinocyclopentyl) and
1-(N,N-diphenyl-2,5-diaza-1-phosphinocyclopentyl) groups. As
specific examples of the oxy group having a hydrocarbon group with
1 to 20 carbon atoms, there can be mentioned methyloxy, phenoxy,
2-methylphenoxy and benzyloxy groups. As specific examples of the
thio group having a hydrocarbon group with 1 to 20 carbon atoms,
there can be mentioned methylthio, phenylthio and
2-methylphenylthio groups. As specific examples of the hydrocarbon
group having 1 to 20 carbon atoms and containing at least one atom
selected from nitrogen, phosphorus, oxygen and sulfur atoms, there
can be mentioned N-phenyliminomethyl, N-(2-tolyl)iminomethyl,
dimethylaminomethyl, diphenyl-aminomethyl, phenylamlnomethyl,
diphenylphosphinomethyl, dicyclohexylphosphinomethyl,
di(tert.-butylphosphino)methyl, methoxymethyl,
(1-methoxymethyl)ethyl, phenoxymethyl, (2-methylphenoxy)methyl,
methylthiomethyl and phenylthiomethyl groups. Of these,
N-phenyliminomethyl and N-(2-tolyl)iminomethyl groups are
preferable. When Q is oxygen or sulfur, Q can be sigma-bound to a
transition metal M. p is an integer of 0 or 1, preferably 0.
[0036] R.sup.3 in formula (1) represents a hydrogen atom, a halogen
atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl
group having one or more hydrocarbon groups Bach with, 1 to 20
carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms
and containing at least one atom selected from nitrogen, oxygen,
halogen and sulfur atoms. Preferably, R.sup.3 represents a hydrogen
atom, a hydrocarbon group having 1 to 20 carbon atoms, or a
hydrocarbon group having 1 to 20 carbon atoms and containing an
oxygen atom. As specific examples of the hydrocarbon having 1 to 20
carbon atoms, there can be mentioned methyl ethyl, butyl,
isopropyl, tert.-butyl, phenyl, 2-methylphenyl and 4-methoxyphenyl.
As specific examples of the silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, there can be
mentioned trimethylsilyl, tert.-butyldimethylsilyl and
triphenylsilyl groups, As specific examples of the hydrocarbon
having 1 to 20 carbon atoms and containing a nitrogen, oxygen,
halogen or sulfur atom, there can be mentioned chloromethyl,
methoxymethyl, dimethylaminomethyl, formyl,
N-(2-methylphenyl)iminomethyl, N-(2-isopropylphenyl)iminomethyl,
methylthiomethyl and phenylthiomethyl groups. Q and one of adjacent
R.sup.3 may bond to each other to form a ring, Such a ring
includes, for example, a pyridine ring. m is an integer of 1 to 3,
and, when m is 2 or 3, two or three R.sup.3s may be either the same
as or different from each other, and adjacent R.sup.3s may bond to
each other to form a ring.
[0037] n of (R.sup.4).sub.n in formula (1) is an integer of 1 to 5,
and, when n is at least 2. R.sup.4s may be the same as or different
from each other. R.sup.4 represents a hydrogen atom, a hydrocarbon
group having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms
and containing at least one atom selected from nitrogen,
phosphorus, oxygen, halogen and sulfur atoms. Of these, a hydrogen
atom, a hydrocarbon group having 1 to 20 carbon atoms, a silyl
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms
and containing at least one atom selected from nitrogen, oxygen and
halogen atoms are preferable. As specific examples of the
hydrocarbon group having 1 to 20 carbon atoms in R.sup.4, there can
be mentioned methyl, ethyl, butyl, isopropyl, tert.-butyl, phenyl,
2-methylphenyl and 4-tert.-butylphenyl groups. As specific examples
of the silyl group having one or more hydrocarbon groups each with
1 to 20 carbon atoms, there can be mentioned trimethylsilyl,
tert.-butyldimethylsilyl and triphenylsilyl groups. As specific
examples of the phosphino group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, there can be mentioned
dimethylphosphino, dicyclohexylphosphino, di-(tert.-butyl)phosphino
and diphenylphosphino groups. As specific examples of the oxy group
having a hydrocarbon group with 1 to 20 carbon atoms, there can be
mentioned methyloxy, phenoxy, 2-methylphenoxy and benzyloxy groups.
As specific examples of the thio group having a hydrocarbon group
with 1 to 20 carbon atoms, there can be mentioned methylthio,
phenylthio and 2-methylphenylthio groups. As specific examples of
the hydrocarbon group having 1 to 20 carbon atoms and containing at
least one atom selected from nitrogen, phosphorus, oxygen, halogen
and sulfur atoms, there can be mentioned
N-(tert.-butyl)iminomethyl, N-phenyliminomethyl,
N-(2-tolyl)iminomethyl, 3-(dimethylaminomethyl)phenyl,
dimethylaminomethyl, 1-(dimethylamino)ethyl, diphenylaminomethyl,
phenylmethylaminomethyl, diphenylphosphinomethyl,
dicyclohexylphosphinome- thyl, di(tert.-butylphosphino)methyl,
4-methoxyphenyl, 3-(methoxymethyl)phenyl, methoxymethyl,
1-(methoxymethyl)ethyl, phenoxymethyl, (2-methylphenoxy)methyl,
4-fluorophenyl, 3-trifluoromethyl)phenyl, 2,2-trifluorethyl
methylthiomethyl and phenylthiomethyl groups.
[0038] When R.sup.4 contains a heteroatom, R.sup.4 can coordinate
with the transision metal atom M.
[0039] L in formula (1) is a coordinate bond-forming compound
selected from .pi. electron, ethers, nitriles, amines and
phosphines. As specific examples of L, there can be mentioned
ethylene, propylene, styrene, dimethyl ether, diethyl ether,
dibutyl ether, acetonitrile, benzonitrile, trimethylamine,
triethylamine, N,N-dimethylaniline, N-methyldiphenylamine,
triphenylphosphine and tricyclohexylphosphine. r is an integer of 0
to 3.
[0040] X and L In formula (1) may be bound together to form a group
such as, for example, .pi.-allyl, 1-methyl-.pi.-allyl,
2-methyl-.pi.-allyl and 1-phenyl-n-allyl groups.
[0041] The transition metal compound of the present invention
having a ligand with an azaferrocene structure or A ferrocene
structure, represented by formula (1), preferably includes those
which are represented by the following formulae (2), (3) and (4).
4
[0042] In formula (4), R.sup.5 represents a hydrogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, or an amino group
having one or more hydrocarbon groups each with 1 to 20 carbon
atoms. As specific examples of the hydrocarbon group having 1 to 20
carbon atoms, there can be mentioned methyl, ethyl, butyl,
isopropyl, tert.-butyl, phenyl and 2-methylphenyl groups. As
specific examples of the amino group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, there can be mentioned
dimethylamino, diethylamino, N-piperazinyl, N-piperidinyl,
N-pyrrolidinyl and diphenylamino groups. m in formula (4) is an
integer of 1 or 2.
[0043] As specific examples of the transition metal compound of the
present invention having a ligand with an azaferrocene structure or
a ferrocene structure, there can be mentioned the transition metal
complexes represented by the following formulae, which by no means
limit the transition metal compound of the present invention. In
the transition metal compound having a ligand with an azaferrocene
structure or a ferrocene structure of the present invention, when
the azaferrocene ring or ferrocene ring has a planar asymmetry, or
when R.sup.2 has an asymmetrical carbon atom, a racemic
modification or an optically active substance may be used.
56789101112131415161718192021222324252627
[0044] The transition metal compound of the present invention
having a ligand with an azaferrocene structure or a ferrocene
structure, represented by formula (1), can be synthesized by a
process wherein a corresponding coorinative compound having a
azaferrocene structure or a ferrocene structure is synthesized and
then the coordinative compound is made into a complex. The
corresponding coorinative compound having a azaferrocene structure
or a ferrocene structure is represented by the following formula
(5). 28
[0045] wherein A represents a carbon atom, a nitrogen atom or a
phosphorus atom;
[0046] R.sup.1 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20
carbon atoms and containing at least one halogen atom, a ferrocenyl
group or a substituted ferrocenyl group:
[0047] R.sup.2 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20
carbon atoms and containing at least one atom selected from
halogen, silicon, nitrogen, oxygen and sulfur atoms, a ferrocenyl
group, or a substituted ferrocenyl group, and R and may form
together a ring;
[0048] Q represents a hydrogen atom, a hydrocarbon group having 1
to 20 carbon atoms, a silyl group having one or more hydrocarbon
groups each with 1 to 20 carbon atoms, an amino group having one or
more hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms and
containing at least one atom selected from nitrogen, phosphorus,
oxygen and sulfur atoms, or a hydroxyl group or a thiol group;
[0049] R.sup.3 represents a hydrogen atom, a halogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a silyl group having
one or more hydrocarbon groups each with 1 to 20 carbon atoms, or a
hydrocarbon group having 1 to 20 carbon atoms and containing at
least one atom selected from nitrogen, oxygen, halogen and sulfur
atoms, and one of R.sup.3 adjacent to Q may form a ring together
with Q; and, when m is an integer of at least 2, R.sup.3s may be
the same as or different from each other, and R.sup.3s may form
together a ring;
[0050] R.sup.4 represents a hydrogen atom, a hydrocarbon group
having 1 to 20 carbon atoms, a silyl group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, a phosphino
group having one or more hydrocarbon groups each with 1 to 20
carbon atoms, an oxy group having a hydrocarbon group with 1 to 20
carbon atoms, a thio group having a hydrocarbon group with 1 to 20
carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms
and containing at least one atom selected from nitrogen,
phosphorus, oxygen, halogen and sulfur atoms; and, when n is an
integer of at least 2, R.sup.4 s may be the same as or different
from each other, and adjacent R.sup.4 s may form together a ring;
and R.sup.3 and R.sup.4 may form together a ring; and
[0051] m is an integer of 1 to 3, n is an integer of 1 to 5, and p
is an integer of 0 or 1.
[0052] Substituents R.sup.1 through R.sup.4 in the coordinative
compound of formula (5) are the same a substituents R.sup.1 through
R.sup.4, respectively, in the transition metal compounds of
formulae (1), (2) and (3).
[0053] As specific examples of the coordinative compound of formula
(5) of the present invention, there can be mentioned compounds
represented by the following formulae. 29303132333435
[0054] Among the coordinative compounds of formula (5) of the
present invention, those in which A is a nitrogen atom can be
synthesized from azaferrocene compounds represented by the
following general formula (6) 36
[0055] wherein R.sup.3 represents a hydrogen atom, a halogen atom,
a hydrocarbon group having 1 to 20 carbon atoms, a silyl group
having one or more hydrocarbon groups each with 1 to 20 carbon
atoms, or a hydrocarbon group having 1 to 20 carbon atoms and
containing at least one atom selected from nitrogen, oxygen,
halogen and sulfur atoms and, when m is an integer of at least 2,
R.sup.3s may be the same as or different from each other, and
adjacent R.sup.3s may form together a ring;
[0056] R.sup.4 represents a hydrocarbon group having 1 to 20 carbon
atoms, a silyl group having one or more hydrocarbon groups each
with 1 to 20 carbon atoms, a, phosphino group having one or more
hydrocarbon groups each with 1 to 20 carbon atoms, an oxy group
having a hydrocarbon group with 1 to 20 carbon atoms, a thio group
having a hydrocarbon group with 1 to 20 carbon atoms, or a
hydrocarbon group having 1 to 20 carbon atoms and containing at
least one atom selected from nitrogen, phosphorus, oxygen, halogen
and sulfur atoms; and, when n is an integer of 1, R.sup.4 is not a
methyl group; and, when n is an integer of at least 2. R.sup.4 s
may be the same as or different from each other, and all of the
R.sup.4s are not simultaneously a methyl group; and adjacent
R.sup.4 s may form together a ring; and R.sup.3 and R.sup.4 may
form together a ring; and
[0057] m is an integer of 1 to 3 and n is an integer of 1 to 5.
[0058] As specific examples of the precursor azaferrocene compounds
of formula (6), there can be mentioned compounds represented by the
following formulae. 373839
[0059] The azaferrocene compound of formula (6) according to the
present invention can be Synthesized by a process described in G.
C. Fu et al, J. Org. Chem., vol. 61, p 7230 (1996) or K. K. Joshi
et al, J. Organomet. Chem., I, p 471 (1964).
[0060] The coordinative compound of formula (5) according to the
present invention can be synthesized from the azaferrocene compound
of formula (6). For example, the azaferrocene compound of formula
(6) is lithiated with a lithiating agent such as n-butyllithium,
and then the obtained organolithium compound is allowed to react
with, for example, N,N-dimethylformamide, benzonitrile or
acetonitrile to introduce a carbonyl-containing group such as a
formyl group or an acetyl group. The lithiation of the azaferrocene
compound can be effected, for example, by a process described in V.
N. Setkina et al, J. Organomet. Chem., vol. 251, C-p 41 (1983). If
the lithiation is carried out in the presence of a chiral diamine
such as (-)-sparteine, then an azaferrocene compound predominantly
comprised of one of the enantiomers, i.e., an optically active
azaferrocene compound can be synthesized. The introduction of a
carbonyl group-containing group can also be carried out by a
Friedel-Crafts acylation using an acid chloride and aluminum
chloride. The coordinative compound of formula (5) according to the
present invention can also be synthesized by a process wherein the
compound having introduced therein a carbonyl-containing group is
subjected to dehydro-condensation with an aromatic amine or an
aliphatic amine to be thereby converted to an imine. The
imine-formation can be carried out by using acetic acid as a
catalyst in ethanol or by using p-toluenesulfonic acid as a
catalyst in toluene.
[0061] Coordinative compounds used as raw materials for producing
the transition metal compound of formula (4) according to the
present invention can be synthesized from a ferrocene derivative
having a pyrimidine ring. The ferrocene derivative having a
pyrindine ring is prepared from pyrindine, for example, by a
process described in G. C. Fu et al. J. Am. Chem. Sac., vol. 123, p
353 (2001). The thus-prepared ferrocene having a pyrindine ring is
lithiated with a lithiating agent such as n-butyllithium, and then
the obtained organolithium compound is allowed to react with, for
example, N,N-dimethylformamide, benzonitrile or acetonitrile to
introduce a carbonyl-containing group such as a formyl group or an
acetyl group. The introduction of a carbonyl group-containing group
can also be carried out by a Friedel-crafts acylation using an acid
chloride and aluminum chloride. The coordinative compound of
formula (5) according to the present invention can be synthesized
by a process wherein the compound having introduced therein a
carbonyl-containing group is subjected to dehydro-condensation with
an aromatic amine or an aliphatic amine to be thereby converted to
an imine. The imine-formation can be carried out by using acetic
acid as a catalyst in ethanol or by using p-toluenesulfonic acid as
a catalyst in toluene.
[0062] Among the coordinative compounds of the present invention
represented by formula (5), those in which A is a carbon atom can
be synthesized from a ferrocene derivative. A ferrocene compound
having two cyolopentadienyl rings (hereinafter abbreviated to "Cp
ring"), each of which has a substituent containing a hetero atom,
is synthesized, for example, by a process wherein a formyl group is
introduced in each Cp ring and then the formyl group-introduced
ferrocene compound is subjected to dehydro-condensation with an
amine whereby an imino group is introduced, which process Is
described in J. Organomet. Chem., vol. 412, p 381 (1991) and
Organometellics, vol. 18, p 1267 (1999). A ferrocene compound
having two cyclopentadienyl rings, at least one of which has two or
more substituents, is synthesized, for example, by a
heteroatom-introducing process as described in Bull. Chem. Soc.
Jpn, vol. 53, p 1138 (1980) and J. Org. Chem., vol. 62, p 6733
(1997). By employing a combination of these processes, various
substituents can be introduced into the two Cp rings. Further, an
asymmetric ferrocene structure can be formed by using a specific
reaction of a substituted cyclopentadienyl alkali metal as
described in J. Organomet. Chem., vol. 598, p 365 (2000).
[0063] The transition metal compound of the present invention,
represented by formula (1), having the above-mentioned azaferrocene
or ferrocene ligand can be synthesized by the conventional
processes employed for synthesis of known complexes. For example, a
process described in WO96/23010 and J. Am. Chem. Soc., vol. 121, p
8728 (1999).
[0064] The transition metal compound of the present invention,
represented by formula (1), having the above-mentioned azaferrocene
or ferrocene ligand is used as a catalyst for polymerization of
olefins. The transition metal compound can be used for the
polymerization catalyst either after it is isolated by an ordinary
procedure in the synthesis process, or as It is synthesized
in-situ.
[0065] By the term "activating Cocatalyst (B)" used in combination
with the above-mentioned transition metal compound of the present
invention, we mean a compound having a function of forming an
activated species capable of polymerizing an olefin by a
cooperative action or reaction with the transition metal compound
or with a reaction product of the transition metal compound with an
organometal compound. The activating cocatalyst provides a compound
which weakly coordinates or exhibits cooperative activity for the
thus-formed activated species, but does not directly react with the
activated species.
[0066] The activating cocatalyst includes, for example,
trialkylaluminums such as triethylaluminum and triisobutylaluminum;
halogenated alkylaluminums such as diethylaluminum chloride and
ethylaluminum sesquichloride; halogenated alkylaluminoxanes such as
1,3-dichloro-1,3-diethylaluminoxane and
1,3-dichloro-1,3-diisopropylalumi- noxane; alkylaluminoxanes which
have been recently widely used as a cocatalyst for a homogeneous
polymerization catalyst system for olefins, ionized ionic compounds
having a non-coordinative anion, and modified clay compounds. But,
the acitivating cocatalyst should not be construed to be limited to
these compounds.
[0067] As preferable examples of the alkylaluminoxane as the
activating cocatalyst (B), there can be mentioned compounds
represented by the following formulae (7) and (a): 40
[0068] wherein R.sup.6s may be the same or different and represents
a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms
such as methyl, ethyl, propyl and tert.-butyl groups, and s is an
integer in the range of 2 to 60. The alkylaluminoxanes may be used
either alone or in combination. The alkylaluminooxanes may contain
a minor amount of an organometallic comound.
[0069] As preferable examples of the ionized ionic compounds having
a non-coordinative anion as the activating cocatalyst, there can be
mentioned protonic acids represented by the following general
formula (9), ionized ionic compounds represented by the following
general formula (10), Lewis acids represented by the following
general formula (11), Lewis acidic compounds represented by the
following general formula (12), and compounds having a structure of
AgbF.sub.6 or AgPF.sub.6.
[HL.sup.1][B(Ar).sub.4] (9)
[AL.sup.2.sub.u][B(Ar).sub.4] (10)
[D][B(AR).sub.4] (11)
B(Ar).sub.3 (12)
[0070] wherein H is a propton, B is a boron atom or an aluminum
atom, L.sup.1 is a Lewis base, L.sup.2 is a Lewis base or a
cyclopentadienyl group, A is a cation of metal selected from
lithium, iron and silver, D is a carbonium cation or a tropylium
cation, Ar is a halogen-substituted aryl group having 6 to 20
carbon atoms, and u is an integer in the range of 0 to 2.
[0071] As specific examples of the protonic acids of formula (9),
there can be mentioned diethyloxonium [tetrakis
3,5-bis(trifluoromethyl)phenyl]- borate, diethyloxonium tetrakis
(pentafluorophenyl)borate, dimethyloxonium
tetrakis-(pantafluorophenyl)borate, tetramethyleneoxonium
tetrakis-(pentafluorophenyl)borate, hydrofuran
tetrakis-(pentafluoropheny- l)borate, N,N-dimethylanilinium
tetrakis-(pentafluorophenyl)borate, tri-N-butylammonium
tetrakis-(pentafluorophenyl)borate, diethyloxonium
tetrakis-(pentafluorophenyl)aluminate, dimethyloxonium
tetrakis-(pentafluorophenyl)aluminate, tetramethyleneoxonium
tetrakis(pentafluorophenyl)aluminate, hydronium
tetrakis-(pantafluorophen- yl) aluminate, N,N-dimethylanilinium
tetrakis-(pentafluorophenyl)aluminate and tri-N-butylammonium
tetrakis(pentafluorophenyl)aluminate. The protonic acids of formula
(9) are not limited to these compounds.
[0072] As specific examples of the ionized ionic compounds of
formula (10), there can be mentioned sodium tetrakis[3,5
bis(trifluoromethyl)phen- yl]borate; lithium salts such as lithium
tetrakis(pentafluorophenyl)borate and lithium
tetrakis(pentafluorophenyl) aluminate, and other complexes thereof:
ferrocenium salts such as ferrocenium tetrakis(pentafluorophenyl-
)borate and ferrocenium tetrakis(pentafluorophenyl)aluminate; and
silver salts such as silver tetrakis(pentafluorophenyl)borate and
silver tetrakis(pentafluorophenyl) aluminate. The ionized ionic
compounds of formula (10) are not limited to these compounds.
[0073] As specific examples of the Lewis acids of formula (11),
there can be mentioned trityl tetrakis(pentafluorophenyl)-borate,
trityl tetrakis(pentafluorophenyl)aluminate, tropyliyum
tetrakis(pentafluorophen- yl)borate and tropylium
tetrakis(pentafluorophenyl)aluminate. The Lewis acids of formula
(11) are not limited to these compounds.
[0074] As specific examples of the Lewis acidic compounds of
formula (12), there can be mentioned
tris[3,5-bis(trifluoromethyl)phenyl]borane,
tris(pentafluorophenyl)-borane,
tris(2,3,5,6-tetrafluorophenyl)borane,
tris(2,3,4,5-tetrafluorophenyl)-borane,
tris(3,4,5-trifluorophenyl)borane- ,
phenyl-bis(perfluorophenyl)borane and
tris(3,4,5-trifluorophenyl)-alumin- ium. The Lewis acidic compounds
of formula (12) are not limited to these compounds.
[0075] Preferable examples of the modified clay compound as the
activating cocatalyst (B) are modified clay compounds having a
cation exchangeability. The modification of the clay compounds for
the activating cocatalyst is preferably effected by subjecting the
clay compound to treatments such as a chemical treatment with an
acid, an alkali or a salt, or a treatment with an organic compound
or an inorganic compound to form a composite.
[0076] As specific examples of the clay compound, there can be
mentioned natural clays including kaoline group such as kaolinite,
dickite and halloysite; smectite group such as montmorillonite,
hectrite, beidellite, saponite, taeniolite and sauconite; mica
group such as muscovite, paragonite and illite; vermiculite group;
brittle mica group such as margarite and clinotnite; chlorite group
such as donbassite, cookeite and clinochlore; sepiolite and
palygorskite; and synthetic clay compounds. The modified clay
compounds are not limited to these compounds.
[0077] The treating agents used for a chemical treatment of the
clay compounds include, for example, acids including br.o
slashed.nsted acids such as hydrochloric acid, sulfuric acid,
nitric acid and acetic acid; alkalis such as sodium hydroxide,
potassium hydroxide and calcium hydroxide; and salts including
inorganic salts which include ionic chlorides such as sodium
chloride, potassium chloride, lithium chloride, magnesium chloride,
aluminum chloride, iron chloride and ammonium chloride, sulfates
such as sodium sulfate, potassium sulfate, aluminum sulfate and
ammonium sulfate, carbonates such as potassium carbonate, sodium
carbonate and calcium carbonate, and phosphates such as sodium
phosphate, potassium phosphate, aluminum phosphate and ammonium
phosphate, and organic acid salts such as sodium acetate, potassium
acetate, potassium oxalate, sodium citrate and sodium tartrate.
[0078] The organic compound used for treating the clay compound to
form an organic composite includes, for example, onium salts,
carbon cation-forming compounds such as trityl chloride and
tropylium bromide, metal complex cation-forming complex compounds
such as ferrocenium salts. The inorganic compound used for treating
the clay compound to form an inorganic composite includes, for
example, hydroxide cation-forming metal hydroxides such as aluminum
hydroxide, zirconium hydroxide and chromium hydroxide.
[0079] Among the modified clay compounds used in the present
invention, an especially preferable modified clay compound is a
clay compound/organic ion composite which it produced by a metal
ion, i.e., an exchangeable cation, present within the clay compound
is exchanged with a specific organic cation. As specific examples
of the organic cation, there can be mentioned ammonium ions
including aliphatic ammonium cations such as butylammonium,
hexylammonium, decylammonium, dodecylammonium
dimethyldecylammonium; and aromatic ammonium cations such as
anilinium, N-methylanilinium; N,N-dimethylanilinium,
N-ethylanilinium, N,N-diethylanilinium, benzylammonium,
toluidinium, dibenzylammonium, tribenzylammonium and
N,N,2,4,6-pentamethylanilinium; and oxonium ions such as
dimethyloxonium and diethyloxonium. The organic cations used are
not limited to these cations.
[0080] The activating cocatalyst (B) used as an ingredient of the
catalyst for polymerization of olefins of the present invention can
also be topotactic reduction products accompanied by transfer of
electrons. Such reduction product include, for example, compounds
represented by the following formula (13):
E.sup.r+(k/r)(L.sup.3).sub.h[G].sup.k- (13)
[0081] wherein [G] is a host compound, k is a quantity of
reduction, E.sup.r+ is a guest cation with a valency of n, L.sup.3
is a Lewis base, and h is a quantity of Lewis base.
[0082] The host compound [G] includes, for example, host compounds
having a three-dimensional structure, host compounds having a
two-dimensional structure, host compounds having a one-dimensional
structure, and host compounds which are molecular solid.
[0083] As specific examples of the host compounds having a
three-dimensional structure, there can be mentioned hexamolybdenum
octasulfide, divanadium pentaoxide, tungsten trioxide, titanium
dioxide, vanadium dioxide, chromium dioxide, manganese dioxide,
tungsten dioxide, ruthenium dioxide, osmium dioxide and iridium
dioxide.
[0084] As specific examples of the host compounds having a
two-dimensional structure, there can be mentioned titanium
disulfide, zirconium disulfide, hafnium disulfide, vanadium
disulfide, niobium disulfide, tantalum disulfide, chromium
disulfide, molybdenum disulfide, tungsten disulfide, rhenium
disulfide, platinum disulfide, tin disulfide, lead disulfide,
phosphomagnesium trisulfide, phosphomanganese trisulfide, tantalum
sulfide carbide, molybdenum trioxide, vanadium pentaoxide gel,
graphite and polyacene.
[0085] As specific examples of the host compounds having a
one-dimensional structure, there can be mentioned titanium
trisulfide and niobium triselenide.
[0086] As specific examples of the molecular solid host compounds,
there can be mentioned tetracyanoquinodimethane and
tetrathiofulvalene.
[0087] As the [G], a mixture of two or more of the above-mentioned
host compounds can be used.
[0088] The value k Is not particularly limited, but, in view of
enhanced catalytic activity for polymerization of olefins, k is
preferably in the range of 0<k.ltoreq.3, and more preferably
0<k.ltoreq.2.
[0089] The L.sup.2 includes Lewis bases capable of coordinating to
E.sup.r+ and a cyclopentadienyl group. As specific examples of the
Lewis bases, there can be mentioned water, amine compounds,
nitrogen-containing heterocyclic compounds, ethers such as ethyl
ether and n-butyl ether, amides such as formamide,
N-methylformamide and N-methylacetamide, alcohols such as methyl
alcohol and ethyl alcohol, and diols such as 1,2-butanediol and
1,3-butanediol. These bases may be used either alone or as a
mixture of at least two threof.
[0090] The value h can be in the range of 0.ltoreq.h.ltoreq.10.
[0091] The guest cation E.sup.r+ includes cations containing at
least one atom selected from atoms of group 1 to group 14 of the
periodic table, and r is in the range of 0<r.ltoreq.10. In view
of enhanced catalytic activity for polymerization of olefins, as
preferable examples of the guest cation E.sup.r+, there can be
mentioned cations represented by the following formulas (14) and
(15).
R.sup.7.sub.2R.sup.8NH.sup.+ (14)
[0092] wherein R.sup.7.sub.2R.sup.8N is an amine compound, and
R.sup.7 independently represents a hydrogen atom or an aliphatic
hydrocarbon group having 1 to 30 carbon atoms and R.sup.8 is a
hydrogen atom, an aliphatic hydrocarbon group having 1 to 30 carbon
atoms or an aromatic hydrocarbon group having 6 to 50 carbon
atoms.
(R.sup.9).sup.+ (15)
[0093] wherein (R.sup.9).sup.+ is a carbonium cation or tropylium
cation, which have 1 to 50 carbon atoms. These guest cations may be
used either alone or in combination.
[0094] As specific examples of the amine compound represented by
formula R.sup.7.sub.2R.sup.8N, there can be mentioned aliphatic
amines such as methylamine, n-propylamine, isopropylamine,
n-butylamine, tert.-butylamine, allylamine,
N-methylcyclohexylamine, N,N-dimethyloctylamine,
N,N-dimethyldodecylamine, N,N-dimethyloctadecylam- ine,
N,N-dioctadecylmethylamine, trihexylamine, triisooctylamine,
tridodecylamine and N,N-dimethylcyclohexylamine; and aromatic
amines such as aniline, N-methylaniline, N-ethylaniline,
N-allylaniline-toludine, p-toluidine, N,N-dimethylaniline,
N-methyl-o-toluidine, N-methyl-m-toluidine and
N-ethyl-o-toluidine.
[0095] As specific examples of the cation of formula (15), there
can be mentioned a triphenylmethyl cation and a tropylium
cation.
[0096] The polymerization of olefins using the catalyst of the
present invention can be carried out by ordinary polymerization
procedures such as slurry polymerization, vapor phase
polymerization, high-pressure polymerization, solution
polymerization and bulk polymerization. By the term
"polymerization" used herein, we mean not only homopolymerization
for producing a homopolymer but also copolymerization for producing
a copolymer.
[0097] The catalyst of the present invention comprising the
above-mentioned transition metal compound and the above-mentioned
activating cocatalyst can be used in combination with an
organometallic compound. The organometallic compound Is preferably
a compound having a function of deactivating ingredients forming a
catalyst poison, and capable of forming an alkyl moiety of the
transition metal compound. As specific examples of the
organometallic compound, there can be mentioned alkyllithium
compounds such as methyllithium and n-butyllithium; Grignard
reagents such as methylmagnesium chloride, ethylmagnesium chloride,
isopropylmagnesium chloride, benzylmagnesium chloride,
methylmagnesium bromide, ethylmagnesium bromide, isopropylmagnesium
bromide and benzylmagnesium bromide; dialkylmagnesiums such as
dimethylmagnesium; dialkylzincs such as dimethylzinc and
diethylzinc; alkylboranes such as trimethylborane and
triethylborane; alkylaluminums such as trimethylaluminum,
triethylaluminum and triisobutylaluminum; and alkylaluminoxanes
such as methylaluminoxane, butylaluminoxane and
tert.-butylaluminoxane.
[0098] As specific examples of the olefin to be polymerized in the
presence of the catalyst of the present invention, there can be
mentioned .alpha.-olefins such as ethylene, propylene, 1-butene,
4-methyl-1-pentene, 1-hexene and 1-otene: styrene and styrene
derivatives; conjugated dienes and non-conjugated dienes such as
butadiene, 1,4-hexadiene, 5-ethylidene-2-norbornene,
dicyclopentadiene, 4-methyl-1,4-hexadiene and
7-methyl-1,6-octadiene; cycloolefins such as cyclobutene and
cyclohexene; .alpha., .beta.-unsaturated carboxylic acids such as
acrylic acid, methacrylic acid, fumaric acid, maleic anhydride,
itaconic acid, itaconic anhydride and
bicyclo(2,2,1)-5-heptene-2,3-dicarb- oxylic acid; metal salts of
.alpha.,.beta.-unsaturated carboxylic acids such as sodium,
potassium, lithium, zinc, magnesium and calcium salts of the
above-recited .alpha.,.beta.-unsaturated carboxylic acids; esters
of .alpha.,.beta.-unsaturated carboxylic acids such as methyl
acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate,
isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl
methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl
methacrylate, n-butyl methacrylate and isobutyl methacrylate; vinyl
esters such as vinyl acetate, vinyl propionate, vinyl caproate,
vinyl caprylate, vinyl laurate, vinyl stearate and vinyl
trifluoroacetate; unsaturated glycidyl eaters such as glycidyl
acrylate, glycidyl methacrylate, glycidyl itaconate and
monoglycidyl itaconate; vinyl ketones such as methyl vinyl ketone,
ethyl vinyl ketone and phenyl vinyl ketone; .alpha.,
.beta.-unsaturated nitriles such as acrylonitrile,
methacrylonitrile and 1-phenylacrylonitrile. These olefins may be
polymerized as a mixture of at least two thereof, such as ethylene
plus propylene, ethylene plus 1-butene, ethylene plus 1-hexene,
ethylene plus 1-octene, ethylene plus vinyl acetate, ethylene plus
methyl acrylate, ethylene plus methyl methacrylate, ethylene plus
propylene plus styrene, ethylene plus 1-hexene plus styrene, and
ethylene plus propylene plus ethylidene norbornene.
[0099] The polymerization of an olefin can be carried out in the
vapor phase or the liquid phase. The liquid medium used in the
liquid phase polymerization is not particularly limited and may be
selected from those which are generally used. The liquid medium
includes, for example, benzene, toluene, xylene, pentane, hexane,
heptane, 2,2,2-trifluoroethanol and hexafluoroisopropyl alcohol.
Olefins themselves such as proplylene, 1-butene, 1-octene and
1-hexene may be used as the liquid medium.
[0100] The polymerization conditions employed for polymerization of
olefins are not particularly limited, but preferably, the
polymerization temperature is in the range of -100.degree. C. to
300.degree. C., the polymerization time is in the range of 10
seconds to 60 hours, and the polymerization pressure is in the
range of normal pressure to 3,000 kg/cm.sup.2G. At polymerization,
the molecular weight can be controlled by using hydrogen. The
polymerization procedure can be any of batchwise, semi-continuous
and continuous manners. The polymerization can be carried out in
two stages under different polymerization conditions. Olefin
polymers are separated for recovery from a polymerization mixture
and dried by a conventional procedure.
[0101] The benefits of the present invention can be summarized as
follows. The transition metal compound having an azaferrocene or
ferrocene structure of the present invention can be easily
synthesized and various substituents can be introduced therein. The
transition metal compound exhibits a high catalytic activity for
polymerization of olefins, and olefins can be polymerized with an
enhanced efficiency by using the catalyst. It is presumed that the
transition metal compound having an azaferrocene or ferrocene
structure of the present Invention can be used as a catalyst for
synthesis of polycarbonate and for asymmetric synthesis, for
example, asymmetric cyclopropane synthesis, as well as a catalyst
for polymerization olefins.
[0102] The invention will now be described by the following working
examples that by no means limit the scope of the invention.
[0103] In the working examples, transition metal compounds were
synthesized by using a Schlenk technique or dry box, and all
operations were carried out in an argon or nitrogen atmosphere. The
solvents used for the preparation of the transition metal compounds
were subjected to deoxygen treatment and dehydration treatment by
the conventional procedure prior to the use thereof. The
polymerization reaction was carried out by using a 1 liter
autoclave at a predetermined temperature for a predetermined time
while ethylene gas was continuously fed therein. The polymerization
mediums used for polymerization were subjected to deoxygen
treatment and dehydration treatment by the conventional procedure
prior to the use for polymerization. As the ethylene gas, that of
polymerization grade was used.
EXAMPLE 1
[0104] Synthesis of Complex A-1:
[0105] [Synthesis of Coordinative Compound]
[0106] By the method described in J. Org. Chem., vol. 62, p 6733
(1997), 1,2-diformylferrocene was synthesized.
[0107] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 625 mg (2.58 mmol) of 1,2-diformylferrocene was
dissolved in 8 ml of ethanol in the flask. Then 493 mg (5.29 mmol)
of aniline was added to the obtained solution, and the mixture was
stirred at room temperature overnight to conduct a reaction. After
completion of the reaction, the reaction mixture was distilled
under a reduced pressure to remove ethanol. To the obtained solid
residue, 20 ml of cyclohexane was added to carry out
recrystallization. The precipitated crystal was filtered and dried
under a reduced pressure to give 620 mg (1.58 mmol) of a deep red
solid. The yield was 61%.
[0108] .sup.1H-NMR (400 MHz, C.sub..delta.D.sub..delta.)
.delta.=3.99(s, 5H), 4.25(t, J=2.6 Hz, 1H), 5.02(d, J=2.6 Hz, 2H),
7.02-7.28(m, 10H), 8.91(s, 2H)
[0109] MS m/z 392(M.sup.+)
[0110] [Synthesis of Complex A-1]
[0111] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 143 mg (0.539 mmol) of
(1,5-cyclooctadiene)PdMeCl and 219 mg (0.558 mmol) of the ligand
prepared by the above-mentioned procedure were placed therein. Then
6 ml of toluene was added in the flask. The mixture was stirred at
room temperature for 20 hours to conduct a reaction. Then the
reaction mixture was concentrated under a reduced pressure and then
washed with 2 ml of toluene. The obtained residue was dried under a
reduced pressure to give 254 mg (0.497 mmol) of a red solid
(complex A-1). The yield was 89%.
[0112] .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) .delta.=0.14(s, 3H),
4.39(s, 5H), 5.12(brs, 1H), 5.22(brs, 2H), 7.10-7.55(m, 6H),
7.65-7.83(m, 4H), 6.56(s, 1H), 8.59(s, 1H)
[0113] MS M/z 549(M.sup.+) 41
EXAMPLE 2
[0114] Synthesis of Complex A-2:
[0115] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 204 mg (0.371 mmol) of complex A-1, prepared in
Example 1, and 129 mg (0.375 mmol) of AgbF.sub.6 were placed
therein. The content was cooled to -50.degree. C., and a solution
of 0.15 ml of acetonitrile in 6 ml of dichloromethane was dropwise
added. The temperature was elevated to -10.degree. C. over a period
of 4 hours, and then obtained slurry was filtered and the extracted
with dichloromethane. The combined dichloromethane solutions were
concentrated under a reduced pressure. The obtained solid residue
was dissolved in 4 ml of dichloromethane, and then 9 ml of pentane
was dropwise added. A clear supernatant liquid was removed, and the
obtained residue was dried under a reduced pressure to give 291 mg
(0.368 mmol) of a deep red solid (complex A-2). The yield was
99%.
[0116] .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) .delta.=0.33(s, 3H),
1.95(s, 3H), 4.47(s, 5H), 5.28(brs, 1H), 5.37(brs, 1H), 5.45(brs,
1H), 7.42-7.75(m, 10H), 8.60(5, 1H), 8.73(s, 1H)
[0117] MS m/z 790(M.sup.+) 42
EXAMPLE 3
[0118] Synthesis of Complex A-3:
[0119] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 90 mg (0.163 mmol) of complex A-1, prepared in
Example 1, and 165 mg (0.187 mmol) of sodium
tetrakis[3,5-bis(trifluoromethyl)phenyl- ]borate were placed
therein. The content was cooled to -50.degree. C., and a solution
of 0.09 ml of acetonitrile in 5 ml of dichloromethane was dropwise
added. The temperature was elevated to -10.degree. C. over a period
of 4 hours, and the obtained slurry was filtered and then extracted
with dichloromethane. The combine a dichloromethane solutions were
concentrated under a reduced pressure. The obtained solid residue
was dissolved in 3 ml of diethyl ether, and then 4 ml of pentane
was dropwise added. A clear supernatant liquid was removed, and the
obtained residue was dried under a reduced pressure to give 135 mg
(0.095 mmol) of a deep red solid (complex A-3). The yield was
58%.
[0120] .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) .delta.=0.34(s, 3H),
1.90(s, 3H), 4.47(s, 5H), 5.25(s, 1H), 5.49(s, 1H), 5.64(s, 1H),
7.40-7.67(m, 10H), 7.58(s, 4H), 7.73(s, 8H), 8.58(s, 1H), 8.69(s,
1H)
[0121] MS m/z 1418(M.sup.+) 43
EXAMPLE 4
[0122] Synthesis of Complex A-4:
[0123] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 1 mg (0.373 mmol) of
(dimethoxyethane)NiBr.sub.2 and 3 ml of dichloromethane were placed
therein. To the thus-obtained suspension, a solution of 153 mg
(0.390 mmol) of the ligand prepared In Example 0.1, in 5 ml of
dichloromethane was added. The mixture was stirred at room
temperature over a period of 3 hours, and the reaction mixture was
filtered and extracted with dichloromethane. The combined
dichloromethane solutions were concentrated under a reduced
pressure. The obtained solid residue was washed with 40 ml of
cyclohexane, and dried under a reduced pressure to give 213 mg
(0.348 mmol) of a deep red solid (complex A-4). The yield was
93%.
[0124] MS m/z 610(M.sup.+) 44
EXAMPLE 5
[0125] Synthesis of Complex B-1:
[0126] [Synthesis of Coordinative Compound]
[0127] By the method described in J. Organomet. Chem., vol. 412, p
381(1991), 1,1'-diformylferrocene was Synthesized.
[0128] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, the flask was charged with 1.04 g (4.30 mmol)
of 1,1'-diformylferrocene, 5 g of molecular sieves 4A, 8 ml of
toluene and 1.26 g (17.2 mmol) of tert.-butylamine. The content was
stirred at room temperature for 15 hours to conduct a reaction. The
reaction mixture was distilled under a reduced pressure to remove
volatile ingredients. The residue was extracted with 20 ml of
diethyl ether, and the extracted material was concentrated and
dried under a reduced pressure to give 1.35 g (3.863 mmol) of a
brown solid. The yield was 89%.
[0129] .sup.1H-NMR (400 MHz, C.sub..delta.D.sub..delta.)
.delta.=1.30(s, 18H), 4.12(t, J=2.2 Hz, 4H), 4.64(d, J=2.2 Hz, 4H),
8.05(s, 2H)
[0130] MS m/z 352(M.sup.+)
[0131] [Synthesis of Complex B-1]
[0132] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 120 mg (0.452 mmol) of
(1,5-cyclooctadiene)PdMeCl and 156 mg (0.443 mmol) of the ligand
prepared by the above-mentioned procedure were placed therein. Then
2.5 ml of toluene was added. The mixture was stirred at room
temperature for 7 hours to conduct a reaction. Then the obtained
slurry was filtered and then washed with 3 ml of toluene. The
obtained residue was dried under a reduced pressure to give 135 mg
(0.265 mmol) of a testaceous solid (complex B-1). The yield was
60%.
[0133] .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) .delta.=0.55(s, 3H),
1.72(s, 18H), 4.55(brs, 4H), 4.82(bra, 2H), 6.02(brs, 2H), 8.15(s,
1H), 8.70(brs, 1H) 45
EXAMPLE 6
[0134] Synthesis of Complex B-2:
[0135] [Synthesis of Coordinative Compound]
[0136] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, the flask was charged with 0.00 g (4.13 mmol)
of 1,1'-diformylferrocene, 25 ml of ethanol, 1.26 g (10.4 mmol) of
2,6-dimethylaniline and 10 mg of acetic acid. The content was
stirred for B hours under heated reflux conditions to conduct a
reaction. The reaction mixture was distilled under a reduced
pressure to remove volatile ingredients. The residue was extracted
with 90 ml of diethyl ether, and the extracted material was
concentrated under a reduced pressure. The obtained solid was
recrystallized from hexane/toluene (5/1), and then filtered and
dried to give 0.90 g (2.00 mmol) of an orange-colored solid. The
yield was 49%.
[0137] .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) .delta.=2.20(s, 12H),
4.23(t. J=2.2 Hz, 4H), 4.70(t, J=2.2 Hz, 4H), 6.96(t, J=7.8 Hz,
2H), 7.05(d, J=7.8 Hz, 4H), 7.70(s, 2H)
[0138] MS m/z 448(M.sup.+)
[0139] [Synthesis of Complex B-2]
[0140] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 148 mg (0.479 mmol) of (dimethoxyethane)
NiBr.sub.2 and 3 ml of dichloromethane. To the suspension, a
solution of 222 mg (0.495 mmol) of the ligand prepared by the
above-mentioned procedure, in 5 ml of dichloromethane was added.
The mixture was stirred at room temperature for 48 hours to conduct
a reaction. Then the obtained slurry was filtered and then
extracted with dichloromethane. The combined dichloromethane
solutions were concentrated under a reduced pressure. The obtained
residue was washed with 20 ml of toluene, and then dried under a
reduced pressure to give 142 mg (0.213 mmol) of a deep red solid
(complex B-2). The yield was 45%.
[0141] MS m/z 667 (M.sup.+) 46
EXAMPLE 7
[0142] [Preparation of Complex Solution]
[0143] The atmosphere within a 100 ml of Schlenk flask was replaced
with nitrogen, and the flask was charged with 59 mg (0.097 mmol) of
complex A-4 synthesized in Example 4, and 40 ml of toluene. The
content was stirred for 30 minutes to prepare a complex
solution.
[0144] [Polymerization of Ethylene]
[0145] Two liter autoclave was charged with 500 ml of toluene, and
methylaluminoxane (PMAO available from Tosoh Akzo K.K., in an
amount of 3.5 ml [equivalent to 10 mmol of aluminum atom]), The
temperature within the autoclave was adjusted to 40.degree. C., and
ethylene was blown therein to a pressure of 10 kg/cm.sup.2G. The
complex solution prepared by the above-mentioned procedure was
pressed into the autoclave, and polymerization was carried out at
40.degree. C. for 1 hour while ethylene was continuously fed
therein at a rate such that the pressure of 10 kg/cm.sup.2G was
maintained. The thus-obtained reaction liquid was treated by the
ordinary procedure to obtain 12.8 g of a liquid polymer.
EXAMPLE 8
[0146] [Polymerization of Ethylene]
[0147] 100 liter glass autoclave was charged with 50 ml of toluene,
and 33.4 mg (0.055 mmol) of complex A-4 prepared in Example 4.
Ethylene was blown therein to a pressure of 10 kg/cm.sup.2G. Then 4
ml of a solution containing 2.9% by weight (0.16 mmol) of
tris(pentafluorophenyl)borane in Isopar-E (available from Tosoh
Akzo K.K.) and 0.07 ml of a solution containing 20% by weight (0.17
mmol) of trimethylaluminum in toluene were added, and
polymerization was carried out at room temperature for 2 hour while
ethylene was continuously fed therein at a rate such that the
pressure of 10 kg/cm.sup.2G was maintained. The thus-obtained
reaction liquid was treated by the ordinary procedure to obtain 1.1
g of a liquid polymer.
EXAMPLE 9
[0148] [Preparation of Complex Solution]
[0149] The atmosphere within a 100 ml of Schlenk flask was replaced
with nitrogen, and the flask was charged with 69 mg (0.11 mmol) of
complex A-4 synthesized in Example 4, and 50 ml of toluene. The
content was stirred for 30 minutes to prepare a complex
solution.
[0150] [Copolymerization of Ethylene/Methyl Acrylate]
[0151] Two liter autoclave was charged with 450 ml of toluene, and
methylaluminoxane (PMAO available from Tosoh Akzo K.K., in an
amount of 4.0 ml [equivalent to 12.8 mmol of aluminum atom]).
Ethylene was blown therein to a pressure of 10 kg/cm.sup.2G. The
complex solution prepared by the above-mentioned procedure was
pressed into the autoclave, and the mixture was stirred for 5
minutes. Then a solution of 5 ml (56 mmol) of methyl acrylate and
0.5 ml of methylaluminoxane in 40 ml of toluene was pressed into
the autoclave, and then polymerization was carried out at room
temperature for 24 hours while ethylene was continuously fed
therein at a rate such that the pressure of 10 kg/cm.sup.2G was
maintained. The thus-obtained reaction liquid was quenched with 350
ml of 0.1N hydrochloric acid, and separated into two phases. The
organic phase was washed with water. Then the organic phase was
concentrated under a reduced pressure. The thus-obtained material
was extracted with hexane. The extract was concentrated under a
reduced pressure to give 1.82 g of a viscous copolymer liquid.
[0152] .sup.1H-NMR (CDCl.sub.3) revealed that the content of methyl
acrylate unit. In the copolymer was 19% by weight. Gel permeation
chromatography (GPC) revealed that the copolymer had a weight
average molecular weight (Mw) of 1.0.times.10.sup.3 and a Mw/number
average molecular weight (Mn) ratio of 1.8.
EXAMPLE 10
[0153] [Copolymerization of Ethylene/Methyl Acrylate]
[0154] The procedures in Example 9 were repeated wherein 67 mg of
complex A-4 and 15 ml of methyl acrylate were used with all other
conditions remaining the same. Thus 1.25 g of a viscous copolymer
liquid was obtained.
[0155] .sup.1H-NMR (CDCl.sub.3) revealed that the content of methyl
acrylate units in the copolymer was 50% by weight. GPC revealed
that the copolymer had a Mw of 1.0.times.10.sup.3 and a Mw/in ratio
of 1.9.
EXAMPLE 11
[0156] [Polymerization of Ethylene]
[0157] The procedures In Example 7 were repeated wherein 59 mg
(0.088 mmol) of complex B-2 and 3.1 ml of methylaluminoxane (PMAO
available from Tosoh Akzo K.K., equivalent to 8.8 mmol of aluminum
atom]). All other conditions remained the same. Thus, 44 mg of a
sold polymer was obtained. The polymer had a melting point of
124.4.degree. C.
EXAMPLE 12
[0158] Synthesis of Complex C-1:
[0159] [Synthesis of Coordinative Compound]
[0160] By the method described in J. Org. Chem., vol. 61, p 7230
(1996), 1',2',3',4',5'-pentamethylazaferrocene was synthesized.
[0161] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 404 mg (1.57 mmol) of
1',2',3',4',5'-pentamethylazaferroce- ne was dissolved in 7 ml of
diethyl ether in the flask. Then 740 mg (3.10 mmol) of
(-)-sparteine was added to the obtained solution, and then 2 ml
(3.2 mmol) of 1.5.9 M n-BuLi solution in hexane was dropwise added
under toe-cooled conditions. The content was stirred for 1 hour
under ice-cooled conditions, and then 240 mg (3.3 mmol) of
N,N-dimethylformamide was added. When 20 minutes elapsed, water was
added to quench the reaction mixture. The reaction mixture was
extracted with diethyl ether, and then, the organic phase was
concentrated under a reduced pressure and the obtained residue was
purified by silica gel column chromatography (solvent: hexane/ethyl
acetate). Thus 350 mg (1.22 mmol) of a deep red liquid was
obtained. The yield was 78%.
[0162] .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) .delta.=1.59(s, 15H),
3.99(s, 1H), 4.63(s, 1H), 4.99(s, 1H), 10.1(s, 1H)
[0163] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, the flask was charged with 341 mg (1.19 mmol)
of 2-formylazaferrocene prepared by the above-mentioned procedure
and 7 ml of ethanol. Then 140 mg (1.31 mmol) of o-toluidine and 10
mg of acetic acid were added. The content was stirred at room
temperature for 2 days, and the reaction mixture was concentrated
under a reduced pressure. The obtained residue was extracted with
hexane, and the extract was concentrated under a reduced pressure
to give 455 mg of a deep red liquid (coordinative compound).
[0164] .sup.1H-NMR (400 MHz, C.sub..delta.D.sub..delta.)
.delta.=1.72(s, 15H), 2.58(s, 3H), 4.07(s, 1H), 4.92(s, 1H),
5.06(s, 1H), 6.90-7.40(m, 4H), 8.54(s, 1).
[0165] [Synthesis of Complex C-1]
[0166] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 152 mg (0.49 mmol) of (DME)NiBr.sub.2 and 2 ml
of dichloromethane were placed therein. With stirring, a solution
of 191 mg of the above-mentioned coordinative compound in 6 ml of
dichloromethane was added by using a cannula. The content was
stirred at room temperature for 2 hours, and the obtained reaction
liquid (slurry) was filtered. The obtained solid was washed with
dichloromethane and then the residue was dried under a reduced
pressure to give 210 mg (0.35 mmol) of a red solid (complex C-1).
The yield was 71%.
[0167] .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) .delta.=-8.15(s,
1H), -7.70(s, 1H), -1.80(s, 1H), 1.48(s, 15H), 1.80(s, 3H),
16.50(s, 1H), 22.85(s, 1H), 23.30(B, 1H), 34.10(s, 2H)
[0168] FAB-MASS: m/z 593(M.sup.+), 513(M.sup.+-Br),
433(M.sup.+-2Br), 374(M.sup.+-NiBr.sub.2) 47
EXAMPLE 13
[0169] Synthesis of Complex C-2:
[0170] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 43.8 mg (0.35 mmol) of iron(II) chloride and 7
ml of tetrahydrofuran (THF) were placed therein. With stirring, a
solution of 157 mg (0.42 mmol) of the coordinative compound,
synthesized in Example 12, in 10 ml of THF was added by using a
cannula. The content was stirred at room temperature for 2 hours,
and the obtained reaction liquid (slurry) was filtered. The
obtained solid was washed with THF and then the residue was dried
under a reduced pressure to give 124 mg (0.25 mmol) of an
orange-red solid (complex C-2). The yield was 71%.
[0171] FAB-MASS; m/z 465(M.sup.+-Cl), 429(M.sup.+-2Cl),
374(M.sup.+-FeCl.sub.2) 48
EXAMPLE 14
[0172] Synthesis of Complex C-3:
[0173] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 45.9 mg (0.32 mmol) of copper(II) chloride and
10 ml of THF were placed therein. With stirring, a solution of 133
mg (0.3636 mmol) of the coordinative compound, synthesized in
Example 12, in 12 ml of THF was added by using a cannula. The
content was stirred at room temperature for 2 hours, and the
obtained homogeneous black reaction liquid was preserved over night
in a freezer. Then the liquid was filtered. The obtained solid was
dried under a reduced pressure to give 47 mg (0.092 mmol) of an
orange-colored solid (complex C-3). The yield was 28%.
[0174] FAB-MASS: m/z 473(M.sup.+-Cl), 437(M.sup.+-2Cl),
374(M.sup.+-CuCl.sub.2) 49
EXAMPLE 15
[0175] Synthesis of Complex C-4:
[0176] [Synthesis of Precursor Compound]
[0177] The atmosphere within a 100 ml Schlenk flask was replaced
with nitrogen, and, 255 mg (2.01 mmol) of iron(II) chloride and 10
ml of THF were placed therein. The atmosphere within a 50 ml
Schlenk flask was replaced with nitrogen, and, 785 mg (1.75 mmol)
of pentaphenylcyclopentadiene and 20 ml of THF were placed in
therein. Then 1.24 ml of a 1.56M (1.93 mmol) n-BuLi solution in
hexane was dropwise added at room temperature Into the 50 ml flask,
followed by stirring for 5 minutes. The thus-obtained solution was
introduced in the slurry of iron(II) chloride in THF by using a
cannula. Then a solution of 216 mg (2.05 mmol) of potassium
pyrrolide in 10 ml of THF was introduced by using a cannula. The
mixture was stirred at room temperature for 2 hours to effect a
reaction, and then 15 ml of water was added to quench the reaction
liquid. The reaction liquid was extracted with 25 ml of
dichloromethane and the obtained organic phase was concentrated
under a reduced pressure. The residue was purified by a silica gel
column chromatography (solvent: dichloromethane, ethyl acetate) to
give 868 mg (1.53 mmol) of an orange solid
(1',2',3',4',5'-pentaphenyl-azaferrocene). The yield was 87%.
[0178] .sup.1H-NMR (400 MHZ, CD.sub.2Cl.sub.2) .delta.=4.71(t,
J=0.7 Hz, 2H), 5.44(t, J=0.7 Hz, 2H), 7.07-7.12(m, 10H),
7.14-7.20(m, 15H)
[0179] [Synthesis of Coordinative Compound]
[0180] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 985 mg (1.73 mmol) of
1',2',3',4',5'-pentaphenylazaferroce- ne was dissolved in 21 ml of
THF in the flask. The solution was cooled to -50.degree. C. and
2.35 ml of 1.59M (3.74 mmol) n-BuLi solution In hexane was dropwise
added; Then the mixture was stirred at -50.degree. C. for 3 hours
and then 264 mg (3.89 mmol) of N,N-dimethylformamide was added. A
reaction was carried out for 40 minutes while the temperature was
gradually elevated, and then water was added to quench the reaction
liquid. The reaction liquid was extracted with ether and the
obtained organic phase was concentrated under a reduced pressure.
The residue was purified by a silica gel column chromatography
(solvent: hexane/dichloromethane, ethyl acetate) to give 743 mg
(1.25 mmol) of an orange liquid. The yield was 72%.
[0181] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 92 mg (0.15 mmol) of the
2-formylazaazaferrocene prepared by the above-mentioned procedures
and 4 ml of ethanol were placed therein. Then 25 mg (0.23 mmol) of
o-toluidine and 5 mg of acetic acid were added. A reaction was
affected at room temperature for one day, and then, the reaction
liquid was concentrated under a reduced pressure. The residue was
washed with hexane and dried under a reduced pressure to give 76 mg
(0.11 mmol) of a red solid (coordinative compound). The yield was
734.
[0182] .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) .delta.=2.31(s, 3H),
4.48(s, 1H), 5.45(s, 1H), 5.55(s, 1H), 6.14(d. J-7.0 Hz, 1H),
6.78-7.06(m, 18H), 7.42(d, J=6.2 Hz, 10H), 8.44(s, 1H)
[0183] [Synthesis of Complex C-4]
[0184] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, the flask was charged with 20 mg (0.065 mmol)
of (DME)NiBr .sub.2 and 2 ml of dichrolomethane. With stirring, a
solution of 40 mg (0.058 mmol) of the coordinative compound,
prepared by the above-mentioned procedures, in 3 ml of
dichloromethane, was added by using a cannula. The mixture was
stirred at room temperature for 3 hours, and the reaction liquid
was filtered and then, extracted with diohloromethane. The combined
dichloromethane solutions were concentrated under a reduced
pressure. The residue was washed with hexane, and then dried under
a reduced pressure to give 44 mg (0.048 mmol) of a reddish brown
solid (complex C-4). The yield was 83%.
[0185] FAB-MASS: m/z 823(M.sup.+-Br), 743(M.sup.+-2Br),
684(M.sup.+-NiBr.sub.2) 50
EXAMPLE 16
[0186] Synthesis of Complex C-5:
[0187] [Synthesis of Coordinative Compound]
[0188] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 291 mg (0.49 mmol) of
1',2',3',4',5'-pentaphenyl-2-formyla- zaferrocene was dissolved in
10 ml of ethanol in the flask. Then 86 mg (0.64 mmol) of
2-isopropylaniline and 10 mg of aoetic acid were added. The mixture
was stirred at room temperature for 2 days, and then, the reaction
liquid was concentrated under a reduced pressure. The residue was
washed with a minor amount of ethanol, and dried under a reduced
pressure to give 289 mg (0.41 mmol) of a red solid (coordinative
compound). The yield was 834.
[0189] .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) .delta.=1.16(d, J=6.4
Hz, 3H), 1.31(d, J=6.4 Hz, 3H), 3.65-3.78(s, 1H), 4.46(s, 1H),
5.47(s, 1H), 5.55(s, 1H), 6.01(d, J=7.0 Hz, 1H), 6.78-7.04(m,
18H)., 7.40(d, J=6.2 Hz, 10), 8.49(s, 1H)
[0190] [Synthesis of Complex C-5]
[0191] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, the flask was charged with 56 mg (0.18 mmol) of
(DME)NiBr.sub.2 and 2 ml of dichrolomethane. With stirring, a
solution of 129 mg (0.18 mmol) of the coordinative compound,
prepared by the above-mentioned procedures, in 6 ml of
dichloromethane, was added by using a cannula. The mixture was
stirred at room temperature for 3 hours, and the reaction liquid
was concentrated under a reduced pressure. The residue was washed
with a minor amount of dichloromethane, and dried under a reduced
pressure to give 160 mg (0.17 mmol) of a red solid (complex C-5).
The yield was 95%.
[0192] FAB-MASS: m/z 712(M.sup.+-NiBr.sub.2) 51
EXAMPLE 17
[0193] Synthesis of Complex C-6:
[0194] [Synthesis of Coordinative Compound]
[0195] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 132 mg (0.22 mmol) of
1',2',3',4',5'-pentaphenyl-2-formyla- zaferrocene was dissolved In
6 ml of ethanol in the flask. Then 49 mg (0.29 mmol) of
2-aminobiphenyl and 5 mg of acetic acid were added. The mixture was
stirred at room temperature for 2 days, and then, the reaction
liquid was concentrated under a reduced pressure. The residue was
washed with a minor amount of ethanol, and dried under a reduced
pressure to give 122 mg (0.16 mmol) of a red solid (coordinative
compound). The yield was 74%.
[0196] .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) .delta.=4.39(s, 1H),
5.29(s, 1H), 5.51(s, 1H), 6.99(d, J=7.6 Hz, 1H), 6.80-7.10(m, 18H),
7.12-7.20(m, 3H), 7.36(d, J=7.0 Hz, 10H), 7.51(d, J=7.0 Hz, 2H),
8.53(s, 1H)
[0197] [Synthesis of Complex C-6]
[0198] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, the flask was charged with 40 mg (0.13 mmol) of
(DME)NiBr .sub.2 and 2 ml of dichrolomethane. With Stirring, a
solution of 105 mg (0.14 mmol) of the coordinative compound,
prepared by the above-mentioned procedures, in 5 ml of
dichloromethane, was added by using a cannula. The mixture was
stirred at room temperature for 3 hours, and the reaction liquid
was concentrated under a reduced pressure. The residue was washed
with hexane, and dried under a reduced pressure to give 110 mg
(0.11 mmol) of a red solid (complex C-6). The yield was 85%.
[0199] FAB-MASS: m/z 885(M.sup.+-Br), 805(M.sup.+-2Br),
747(M.sup.+-NiBr.sub.2) 52
EXAMPLE 18
[0200] [Synthesis of Precursor Compound]
[0201] By the method described in Chem. Commun., p 1889 (1998),
1',2',3',4',5'-penta(p-fluorophenyl)cyclopentadiene was
synthesize.
[0202] The procedures for synthesizing the precursor Compound
described in Example 15 were repeated wherein
1',2',3',4',5'-penta(p-fluorophenyl)cycl- opentadiene was used
instead of 1',2',3',4',5'-pentaphenylcyclopentadiene with all other
conditions remaining the same. Thus an orange-colored solid,
1',2',3',4',5'-penta(p-fluorophenyl)azaferrocene was obtained in a
yield of 47%.
[0203] .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) .delta.=4.08(d, J=0.8
Hz, 2H), 5.10(t, J=0.5 Hz, 2H), 6.58-6.68(m, 10H), 7.00-7.10(m,
10H)
EXAMPLE 19
[0204] [Synthesis of Precursor Compound]
[0205] By the method described in Chem. Commun., p 1889 (1998),
1',2',3',4',5'-penta(p-methoxyphenyl)cyclopentadiene was
synthesized.
[0206] The procedures for synthesizing the precursor compound
described in Example 15 were repeated wherein
1',2',3',4',5'-penta(p-methoxyphenyl)cyc- lopentadiene was used
instead of 1',2',3',4',5'-pentaphenylcyclopentadiene with all other
conditions remaining the same. Thus an orange-colored solid,
1',2',3',5'-penta(p-methoxyphenyl)azaferrocene was obtained in a
yield of 72%.
[0207] .sup.1H-NMR (400 MHz, C.sub.6D.sub.6) .delta.=3.23(s, 15H),
4.47(s, 2H), 5.48(s, 2H), 6.60(d, J=8.8 Hz, 10H), 7.40(d, J=8.8 Hz,
10H)
EXAMPLE 20
[0208] [Preparation of Complex Solution]
[0209] The atmosphere within a 100 ml of Schlenk flask was replaced
with nitrogen, and the flask was charged with 28 mg (47 .mu.mol) of
complex C-1 synthesized in Example 12, and 50 ml of toluene. The
content was stirred for 20 minutes to prepare a complex
solution.
[0210] [Polymerization of Ethylene]
[0211] Two liter autoclave was charged with 500 ml of toluene, and
methylaluminoxane (PMAO available from Tosoh Akzo K.K., in an
amount of 1.6 ml 3[equivalent to 4.6 mmol of aluminum atom]).
Ethylene was blown therein to a pressure of 10 kg/cm.sup.2G. The
complex solution prepared by the above-mentioned procedure was
pressed into the autoclave at room temperature, and polymerization
was carried out for 1 hour while ethylene was continuously fed
therein at a rate such that the pressure of 10 kg/cm.sup.2G was
maintained. Methanol was pressed into the autoclave to quench the
polymerization liquid, and the pressure was released. Methanol was
further added to precipitate a polymer. The polymer was filtered
and then washed with methanol. The polymer was dried under a
reduced pressure to give 82.7 g of a solid polymer. The activity
was 1.7 kg/Ni.mmol.h. Analysis by differential scanning calorimeter
(DSC) revealed that the polymer had a melting point of 77.5.degree.
C. GPC (1,2,4-trichlorobenzene, 140.degree. C.) revealed that the
polymer had Mw of 1.0.times.10.sup.4 and a molecular weight
distribution (Mw/Mn) of 2.2.
EXAMPLES 21-24
[0212] The procedures described in Example 20 were repeated wherein
the transition metal compounds and polymerization temperatures,
shown in Table 1, were employed with all other conditions remaining
the same. The evaluation results of the polymers are shown In Table
1.
1 TABLE 1 Example No. 20 21 22 23 24 Complex C-1 C-1 C-4 C-5 C-6
Amount of complex 47 20 25 24 22 (.mu.mol) Polymerization Room
50.degree. C. Room Room Room temperature temp. temp. temp. temp.
Yield of polymer (g) 82.7 26.4 77.5 94.8 25.2 Activity 1.7 1.3 3.1
3.9 1.1 (kg/N1 .multidot. mmol .multidot. h) GPC Mw
(.times.10.sup.4) 1.0 1.5 6.3 11.0 4.1 Mw/Mn 2.2 3.6 4.9 4.5 2.5
DSC melting point (.degree. C.) 77.5 -- 39.9 31.0 89.0 Al/N1 = 100
(mol ratio), polymerization time: 1 hour
EXAMPLE 25
[0213] [Preparation of Complex Solution]
[0214] The atmosphere within ab 100 ml of Schlenk flask was
replaced with nitrogen, and the flask was charged with 52 mg (0.056
mmol) of complex C-5 synthesized in Example 16, and 60 ml of
toluene. The content was stirred for 20 minutes to prepare a
complex solution.
[0215] [Copolymerization of Ethylene/Methyl Acrylate]
[0216] Two liter autoclave was charged with 450 ml of toluene, and
methylaluminoxane (PMAO available from Tosoh Akzo K.K., in an
amount of 2.0 ml [equivalent to 5.7 mmol of aluminum atom]).
Ethylene was blown therein to a pressure of 1 kg/cm.sup.2G. The
complex solution prepared by the above-mentioned procedure was
pressed into the autoclave, and the mixture was stirred for 5
minutes. Then a solution of 5 ml (56 mmol) of methyl acrylate and
0.5 ml of methylaluminoxane in 40 ml of toluene was pressed into
the autoclave, and then polymerization was carried out at room
temperature for 27 hours while ethylene was continuously fed
therein at a rate such that the pressure of 5 kg/cm.sup.2G was
maintained. The thus-obtained reaction liquid was quenched with 350
ml of 0.1N hydrochloric acid, and separated into two phases. The
organic phase was washed with water and filtered, and then, the
filtrate was concentrated under a reduced pressure to give 4.0 g of
a rubbery viscous solid copolymer.
[0217] .sup.1H-NMR (CDCl.sub.3) revealed that the content of methyl
acrylate units in the copolymer was 74 by weight.
EXAMPLE 26
[0218] Synthesis of Complex C-7:
[0219] The atmosphere within a 100 ml Schlenk flask was replaced
with nitrogen, and, 152 mg (0.21 mmol) of the coordinate compound
prepared in Example 16 and 55.4 mg (0.21 mmol) of
(1,5-cyclooctadiene)Pd(Me)Cl were placed therein, 12 ml of diethyl
ether was added, and the mixture was stirred at room temperature
for 3 hours. A supernatant was removed and the residue was washed
with 6 ml of diethyl other. The obtained solid was dried to give
166 mg (0.19 mmol) of a pink-colored solid (complex C-7). The yield
was 92%.
[0220] .sup.1H-NMR (400 MHz, CD.sub.2Cl.sub.2) .delta.=0.40(s, 3H),
0.86(d, J=6.6 Hz, 3H), 1.26(d, J=6.6 Hz, 3H), 3.34-3.50(m, 1H),
5.29(s, 1H), 5.35(s, 1H), 5.84(s, 1H), 5.90(d, J=8.4 Hz, 1H),
6.93-7.44(m, 28H), 8.23(s, 1H) 53
EXAMPLE 27
[0221] Synthesis of Complex C-8:
[0222] The atmosphere within a 50 ml Schlenk flask was replaced
with nitrogen, and, 71 mg (0.082 mmol) of the transition metal
compound synthesized in Example 26 and 29 mg (0.085 mmol) of AgSbF
were placed therein. The mixture was cooled to -50.degree. C. and 8
ml of diethyl ether was added. A cooling bath was removed, and the
mixture was stirred at room temperature for 1 hour. The reaction
liquid was filtered, and the residue was extracted with 16 ml of a
dichloromethane/diethyl ether (1:1) mixed solution. The extract was
combined with above-mentioned filtrate. The combined liquid was
concentrated to 1.0 ml under a reduced pressure. Then 20 ml of
hexane was added to precipitate a solid. A supernatant was removed,
and the obtained solid was dried to give 76 mg of a reddish-brown
sold (complex C-8). The yield was 81%.
[0223] .sup.1H-NMR (400 MHz, CD.sub.3CN) .delta.=1.13(t, J=7.0 Hz,
6H), 1.20(s, 1.5H), 1.22(s, 1.5H), 2.04-2.30(brs), 3.43(q, J=7.0
Hz, 4H), 5.72(d, J=1.5 Hz, 1H), 5.81(d, J=2.5 Hz, 1H), 6.08(s, 1H),
6.26(d, J=7.7 Hz, 1H), 7.00-7.37(m, 28H), 8.80(s, 1H) 54
* * * * *