U.S. patent application number 10/289310 was filed with the patent office on 2003-06-12 for transition metal compound, addition polymerization catalyst component, addition polymerization catalyst and process for production of olefin polymer.
Invention is credited to Nabika, Masaaki.
Application Number | 20030109730 10/289310 |
Document ID | / |
Family ID | 17672909 |
Filed Date | 2003-06-12 |
United States Patent
Application |
20030109730 |
Kind Code |
A1 |
Nabika, Masaaki |
June 12, 2003 |
Transition metal compound, addition polymerization catalyst
component, addition polymerization catalyst and process for
production of olefin polymer
Abstract
A transition metal compound obtained by reacting (a) a
transition metal compound represented by the following general
formula (1) with (b) a conjugated or non-conjugated diene in the
presence of a compound (c) selected from the group consisting of
alkyllithiums, alkali metals, alkali metal hydrides and Grignard
compounds, and a transition metal compound represented by the
following general formula (2), an addition polymerization catalyst
obtained by contacting the above-mentioned transition metal
compound (2) with a co-catalyst for activation, and a method for
producing an olefin polymer with the addition polymerization
catalyst. 1 (In the general formula (1) or (2), M represents a
titanium atom, zirconium atom or hafnium atom, L represents a group
having an aromatic .pi. electron and is connected to M via the .pi.
electron, D represents a conjugated or non-conjugated diene, R
represents a hydrogen atom, alkyl group, aralkyl group, aryl group
or substituted silyl group, all R's may be the same or different, d
is 1 or 2, p is 1 or 2, m is 0 or 1, and the sum of p and m is
2.).
Inventors: |
Nabika, Masaaki;
(Ichihara-shi, JP) |
Correspondence
Address: |
Thomas P. Pavelko, Esquire
STEVENS, DAVIS, MILLER & MOSHER, L.L.P.
Suite 850
1615 L Street, N.W.
Washington
DC
20036
US
|
Family ID: |
17672909 |
Appl. No.: |
10/289310 |
Filed: |
November 7, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10289310 |
Nov 7, 2002 |
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09672306 |
Sep 29, 2000 |
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6528671 |
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Current U.S.
Class: |
556/9 ;
556/13 |
Current CPC
Class: |
C08F 210/14 20130101;
C08F 2500/10 20130101; Y10S 526/943 20130101; C08F 210/16 20130101;
C08F 4/65912 20130101; C08F 4/65908 20130101; C07F 7/28 20130101;
C08F 210/16 20130101; C08F 210/16 20130101; C08F 2500/17 20130101;
C07F 7/00 20130101; C08F 2500/01 20130101; C08F 4/6592 20130101;
C08F 2500/03 20130101 |
Class at
Publication: |
556/9 ;
556/13 |
International
Class: |
C07F 007/28; C07F
009/22 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 5, 1999 |
JP |
11-283993 |
Claims
What is claimed is:
1. A transition metal compound obtained by reacting a transition
metal compound (a) represented by the following general formula (1)
with a conjugated diene or non-conjugated diene (b) in the presence
of a compound (c) selected from the group consisting of
alkyllithiums, alkali metals, alkali metal hydrides and Grignard
compounds: 6(wherein, M represents a titanium atom, zirconium atom
or hafnium atom; L represents a group having an aromatic .pi.
electron and is connected to M via the .pi. electron; R represents
a hydrogen atom, alkyl group, aralkyl group, aryl group or
substituted silyl group, all R's may be the same or different; p is
1 or 2; m is 0 or 1; and the sum of p and m is 2.).
2. A transition metal compound represented by the following general
formula (2): 7(wherein, M represents a titanium atom, zirconium
atom or hafnium atom; L represents a group having an aromatic .pi.
electron and is connected to M via the .pi. electron; D represents
a conjugated diene or non-conjugated diene; R represents a hydrogen
atom, alkyl group, aralkyl group, aryl group or substituted silyl
group, and all R's may be the same or different; d is 1 or 2; p is
1 or 2, m is 0 or 1; and the sum of p and m is 2.).
3. The transition metal compound according to claim 1, wherein the
compound(b) is a conjugated diene.
4. The transition metal compound according to claim 2, wherein D in
the general formula (2) is a conjugated diene.
5. An addition polymerization catalyst obtained by contacting the
transition metal compound of claim 1 with a co-catalyst for
activation.
6. An addition polymerization catalyst obtained by contacting the
transition metal compound of claim 2 with a co-catalyst for
activation.
7. An addition polymerization catalyst according to claim 5, the
co-catalyst is an organoaluminum compound (B) and/or a boron
compound(C) below: (C) Any boron compound of the following (C1) to
(C3) (C1) A boron compound represented by the general formula
BQ.sup.1Q.sup.2Q.sup.3 (C2) A boron compound represented by the
general formula G.sup.+(BQ.sup.1Q.sup.2- Q.sup.3Q.sup.4).sup.-(C3)
A boron compound represented by the general formula
(L-H).sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4).sup.-(wherein, B is a
boron atom in the trivalent valence state, Q.sup.1 to Q.sup.4 are a
halogen atom, hydrocarbon group, halogenated hydrocarbon group,
substituted silyl group, alkoxy group or di-substituted amino
group, and they may be the same or different. G.sup.+ is an
inorganic or organic cation, L is a neutral Lewis base, and
(L-H).sup.+ is a Br.PHI.nsted acid.).
8. An addition polymerization catalyst according to claim 6, the
co-catalyst is an organoaluminum compound (B) and/or a boron
compound (C) below: (C) Any boron compound of the following (C1) to
(C3) (C1) A boron compound represented by the general formula
BQ.sup.1Q.sup.2Q.sup.3 (C2) A boron compound represented by the
general formula G.sup.+(BQ.sup.1Q.sup.2- Q.sup.3Q.sup.4).sup.-(C3)
A boron compound represented by the general formula
(L-H).sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4).sup.-(wherein, B is a
boron atom in the trivalent valence state, Q.sup.1 to Q.sup.4 are a
halogen atom, hydrocarbon group, halogenated hydrocarbon group,
substituted silyl group, alkoxy group or di-substituted amino
group, and they may be the same or different. G.sup.+ is an
inorganic or organic cation, L is a neutral Lewis base, and
(L-H).sup.+ is a Br.PHI.nsted acid.).
7. The addition polymerization catalyst according to claim 6
wherein as the organoaluminum compound (B), one or more aluminum
compounds selected from the following (B1) to (B3) are used: (B1)
An organoaluminum compound represented by the general formula
E.sup.1.sub.aAlZ.sub.3-a (B2) Cyclic aluminoxane having a structure
represented by the general formula {--Al(E.sup.2)-O--}.sub.b (B3)
Linear aluminoxane having a structure represented by the general
formula E.sup.3{-Al(E.sup.3)-O--}.sub.cAlE.sup- .3.sub.2 (wherein,
each of E.sup.1, E.sup.2 and E.sup.3 is hydrocarbon group, and all
E.sup.1s, all E.sup.2s and all E.sup.3S may be the same or
different respectively. Z represents a hydrogen atom or halogen
atom, and all Zs may be the same or different. a represents a
number satisfying 0<a.ltoreq.3, b is an integer of 2 or more,
and c is an integer of 1 or more.).
9. A process for producing an olefin polymer which comprises
polymerizing one or more of olefins with the addition
polymerization catalyst of claim 7.
10. A process for producing an olefin polymer which comprises
polymerizing one or more of olefins with the addition
polymerization catalyst of claim 8.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a transition metal compound
suitable as an addition polymerization catalyst component, an
addition polymerization catalyst, and a process for producing an
olefin polymer.
[0003] 2. Description of the Relates Arts
[0004] A lot of reports have been made previously regarding a
process for producing an olefin polymer using a transition metal
compound such as a metallocene complex or the like. For example, a
process for producing an olefin polymer using a metallocene complex
and aluminoxane, has been reported in JP-A-58-19309. Further,
regarding an olefin polymerization using a transition metal
compound in which a diene compound is a ligand, a bridging type
monocyclopentadienyl complex in which titanium has a formal
oxidation number of II is disclosed in WO95/00526, and a bridging
type monocyclopentadienyl complex as described above having a
metallacycle structure in which titanium has a formal oxidation
number of IV, is disclosed in WO96/00734. On the other hand,
regarding a non-bridged type monocyclopentadienyl complex,
JP-A-10-502396 discloses that a monocyclopentadienyl titanium
(diphenylbutadiene) complex is useful in stereoregular
polymerization of styrene by combining with various co-catalysts,
and, regarding a polymerization using a monocyclopentadienyl
titanium complex in which a phosphineimine is a ligand,
JP-A-10-338706 discloses that a polymer of high molecular weight
can be produced by conducting solution polymerization of an olefin
at a temperature of 80.degree. C. or more. However, these processes
were not admitted as satisfactory from the standpoint of
polymerization activity.
SUMMARY OF THE INVENTION
[0005] The object of the present invention is to provide a
transition metal compound useful as an addition polymerization
catalyst component which can exhibit high activity, an addition
polymerization catalyst component composed of the above-mentioned
transition metal compound, a highly active addition polymerization
catalyst prepared by using the above-mentioned transition metal
compound, and a process for efficiently producing an olefin polymer
using the above-mentioned addition polymerization catalyst.
[0006] Namely, the present invention relates to a transition metal
compound obtained by reacting a transition metal compound(a)
represented by the following general formula (1) with (b) a
conjugated diene or non-conjugated diene in the presence of (c) a
compound selected from the group consisting of an alkyllithium,
alkali metal, hydrogenated substance of an alkali metal, and
Grignard compound, and to a transition metal compound represented
by the following general formula (2). Further, the present
invention relates to an addition polymerization catalyst composed
of the above-mentioned transition metal compound, an addition
polymerization catalyst obtained by contacting the above-mentioned
transition metal compound with a co-catalyst for activation, and a
method for producing an olefin polymer using the above-mentioned
addition polymerization catalyst. 2
[0007] (wherein, in the general formula (1) or (2), M represents a
titanium atom, zirconium atom or hafnium atom; L represents a group
having an aromatic .pi. electron and is connected to M via the .pi.
electron; D represents a conjugated diene or non-conjugated diene;
R represents a hydrogen atom, alkyl group, aralkyl group, aryl
group or substituted silyl group, and all R's may be the same or
different; d is 1 or 2; p is 1 or 2, m is 0 or 1; and the sum of p
and m is 2.).
[0008] The present invention will be illustrated further in detail
below.
DETAILED DESCRIPTION OF THE INVENTION
[0009] (A) Transition Metal Compound
[0010] The transition metal compound (A) of the present invention
is a transition metal compound obtained by reacting a transition
metal compound (a) represented by the following general formula (1)
with a conjugated diene or non-conjugated diene (b) in the presence
of a compound (c) selected from the group consisting of
alkyllithiums, alkali metals, hydrogenated substances of an alkali
metal and Grignard compounds. 3
[0011] M in the transition metal compound represented by the
above-mentioned general formula (1) represents a titanium atom,
zirconium atom or hafnium atom, and particularly preferably a
titanium atom.
[0012] Examples of the group represented by L having an aromatic
.pi. electron and is connected to M via the .pi. electron include
an .eta..sup.5-cyclopentadienyl group, .eta..sup.5
-methylcyclopentadienyl group, .eta..sup.5-dimethylcyclopentadienyl
group, .eta..sup.5-trimethylcyclopentadienyl group,
.eta..sup.5-tetramethylcyclo- pentadienyl group,
.eta..sup.5-ethylcyclopentadienyl group,
.eta..sup.5-n-propylcyclopentadienyl group,
.eta..sup.5-isopropylcyclopen- tadienyl group,
.eta..sup.5-n-butylcyclopentadienyl group,
.eta..sup.5-sec-butylcyclopentadienyl group,
.eta..sup.5-tert-butylcyclop- entadienyl group,
.eta..sup.5-n-pentylcyclopentadienyl group,
.eta..sup.5-neopentylcyclopentadienyl group,
.eta..sup.5-n-hexylcyclopent- adienyl group,
.eta..sup.5-n-octylcyclopentadienyl group,
.eta..sup.5-phenylcyclopentadienyl group,
.eta..sup.5-naphthylcyclopentad- ienyl group,
.eta..sup.5-trimethylsilylcyclopentadienyl group,
.eta..sup.5-triethylsilylcyclopentadienyl group,
.eta..sup.5-tert-butyldi- methylsilylcyclopentadienyl group,
.eta..sup.5-indenyl group, .eta..sup.5-methylindenyl group,
.eta..sup.5-dimethylindenyl group, .eta..sup.5-ethylindenyl group,
.eta..sup.5-n-propylindenyl group, .eta..sup.5-isopropylindenyl
group, .eta..sup.5-n-butylindenyl group,
.eta..sup.5-sec-butylindenyl group, .eta..sup.5-tert-butylindenyl
group, .eta..sup.5-n-pentylindenyl group,
.eta..sup.5-neopentylindenyl group, .eta..sup.5-n-hexylindenyl
group, .eta..sup.5-n-octylindenyl group, .eta..sup.5-n-decylindenyl
group, .eta..sup.5-phenylindenyl group,
.eta..sup.5-methylphenylindenyl group, .eta..sup.5-naphthylindenyl
group, .eta..sup.5-trimethylsilylindenyl group,
.eta..sup.5-triethylsilylindenyl group,
.eta..sup.5-tert-butyldimethylsilylindenyl group,
.eta..sup.5-tetrahydroindenyl group, .eta..sup.5-fluorenyl group,
.eta..sup.5-methylfluorenyl group, .eta..sup.5-dimethylfluorenyl
group, .eta..sup.5-ethylfluorenyl group,
.eta..sup.5-diethylfluorenyl group, .eta..sup.5-n-propylfluorenyl
group, .eta..sup.5-di-n-propylfluorenyl group,
.eta..sup.5-isopropylfluorenylgroup, .eta..sup.5-diisopropylfluore-
nyl group, .eta..sup.5-n-butylfluorenyl group,
.eta..sup.5-sec-butylfluore- nyl group,
.eta..sup.5-tert-butylfluorenyl group, .eta..sup.5-di-n-butylfl-
uorenyl group, .eta..sup.5-di-sec-butylfluorenyl group,
.eta..sup.5-di-tert-butylfluorenyl group,
.eta..sup.5-n-pentylfluorenyl group, .eta..sup.5-neopentylfluorenyl
group, .eta..sup.5-n-hexylfluorenyl group,
.eta..sup.5-n-octylfluorenyl group, .eta..sup.5-n-decylfluorenyl
group, .eta..sup.5-n-dodecylfluorenyl group,
.eta..sup.5-phenylfluorenyl group, .eta..sup.5-di-phenylfluorenyl
group, .eta..sup.5-methylphenylfluo- renyl group,
.eta..sup.5-naphthylfluorenyl group, .eta..sup.5-trimethylsil-
ylfluorenyl group, .eta..sup.5-bis-trimethylsilylfluorenyl group,
.eta..sup.5-triethylsilylfluorenyl group,
.eta..sup.5-tert-butyldimethyls- ilylfluorenyl group and the like,
and preferable examples thereof include an
.eta..sup.5-cyclopentadienyl group,
.eta..sup.5-methylcyclopentadienyl group,
.eta..sup.5-tert-butylcyclopentadienyl group,
.eta..sup.5-tetramethylcyclopentadienyl group, .eta..sup.5-indenyl
group or .eta..sup.5-fluorenyl group.
[0013] R in the general formula (1) represents ahydrogen atom,
alkyl group, aralkyl group, aryl group or substituted silyl group,
and all R's may be the same or different.
[0014] The alkyl group in the substituent R is preferably an alkyl
group having 1 to 20 carbon atoms, and more preferably an alkyl
group having 4 to 10 carbon atoms, and examples thereof include a
methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl
group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl
group, tert-pentyl group, cyclopentyl group, n-hexyl group,
cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group,
n-pentadecyl group, n-eicosyl group and the like, and more
preferably a n-butyl group, tert-butyl group, neopentyl group,
cyclopentyl group, tert-pentyl group and cyclohexyl group.
[0015] Any of these alkyl groups may also be substituted with a
halogen atom such as a fluorine atom, chlorine atom, bromine atom
or iodine atom. Examples of the alkyl group having 1 to 20 carbon
atoms substituted with a halogen atom include a fluoromethyl group,
difluoromethyl group, trifluoromethyl group, chloromethyl group,
dichloromethyl group, trichloromethyl group, bromomethyl group,
dibromomethyl group, tribromomethyl group, iodomethyl group,
diiodomethyl group, triiodomethyl group, fluoroethylgroup,
difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group,
pentafluoroethyl group, chloroethyl group, dichloroethyl group,
trichloroethyl group, tetrachloroethyl group, pentachloroethyl
group, bromoethyl group, dibromoethyl group, tribromoethyl group,
tetrabromoethyl group, pentabromoethyl group, perfluoropropyl
group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl
group, perfluorooctyl group, perfluorododecyl group,
perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl
group, perchlorobutyl group, perchloropentyl group, perchlorohexyl
group, perchlorooctyl group, perchlorododecyl group,
perchloropentadecyl group, perchloroeicosyl group, perbromopropyl
group, perbromobutyl group, perbromopentyl group, perbromohexyl
group, perbromooctyl group, perbromododecyl group,
perbromopentadecyl group, perbromoeicosyl group and the like.
[0016] Any of these alkyl groups may also be partially substituted
with an alkoxy group such as a methoxy group. ethoxy group or the
like, an aryloxy group such as a phenoxy group or the like, or an
aralkyloxy group such as a benzyloxy group or the like.
[0017] The aralkyl group in the substituent R is preferably an
aralkyl group having 7 to 20 carbon atoms, and examples thereof
include a benzyl group, (2-methylphenyl)methyl group,
(3-methylphenyl)methyl group, (4-methylphenyl)methyl group,
(2,3-dimethylphenyl)methyl group, (2,4-dimethylphenyl)methyl group,
(2,5-dimethylphenyl)methyl group, (2,6-dimethylphenyl)methyl group,
(3,4-dimethylphenyl)methyl group, (3,5-dimethylphenyl)methyl group,
(2,3,4-trimethylphenyl)methyl group, (2,3,5-trimethylphenyl)methyl
group, (2,3,6-trimethylphenyl)methyl group,
(3,4,5-trimethylphenyl)methyl group, (2,4,6-trimethylphenyl)methyl
group, (2,3,4,5-tetramethylphenyl)methyl group,
(2,3,4,6-tetramethylphenyl)methy- l group,
(2,3,5,6-tetramethylphenyl)methyl group, (pentamethylphenyl)methy-
l group, (ethylphenyl)methyl group, (n-propylphenyl)methyl group,
(isopropylphenyl)methyl group, (n-butylphenyl)methyl group,
(sec-butylphenyl)methyl group, (tert-butylphenyl)methyl group,
(n-pentylphenyl)methyl group, (neopentylphenyl)methyl group,
(n-hexylphenyl)methyl group, (n-octylphenyl)methyl group,
(n-decylphenyl)methyl group, (n-tetradecylphenyl)methyl group,
naphthylmethyl group, anthracenylmethyl group and the like, and a
benzyl group is more preferable.
[0018] Any of these aralkyl groups may also be partially
substituted with a halogen atom such as a fluorine atom, chlorine
atom, bromine atom or iodine atom, an alkoxy group such as a
methoxy group, ethoxy group or the like, an aryloxy group such as a
phenoxy group or the like, or an aralkyloxy group such as a
benzyloxy group or the like.
[0019] The aryl group in the substituent R is preferably an aryl
group having 6 to 20 carbon atoms, and more preferably an aryl
group having 7 to 18 carbon atoms. Examples thereof include a
phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group,
2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group,
3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group,
2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group,
2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group,
2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group,
2,3,5,6-tetramethylphenyl group, pentamethylphenyl group,
ethylphenyl group, n-propylphenyl group, isopropylphenyl group,
n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group,
n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group,
n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group,
n-tetradecylphenyl group, naphthyl group, anthracenyl group and the
like, and more preferably a tolyl group, xylyl group,
tert-butylphenyl group, di-tert-butylphenyl group,
tert-butylmethylphenyl group or di-tert-butylmethylphenyl group
[0020] Any of these aryl groups may also be partially substituted
with a halogen atom such as a fluorine atom, chlorine atom, bromine
atom or iodine atom, an alkoxy group such as a methoxy group,
ethoxy group or the like, an aryloxy group such as a phenoxy group
or the like, or an aralkyloxy group such as a benzyloxy group or
the like.
[0021] The substituted silyl group in the substituent R is a silyl
group substituted with a hydrocarbon group, and examples of the
hydrocarbon group include alkyl groups having 1 to 10 carbon atoms
such as a methyl group, ethyl group, n-propyl group, isopropyl
group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl
group, n-pentyl group, n-hexyl group, cyclohexyl group and the
like, aryl groups such as a phenyl group and the like. Examples of
the substituted silyl group having 1 to 20 carbon atoms include
mono-substituted silyl groups having 1 to 20 carbon atoms such as a
methylsilyl group, ethylsilyl group, phenylsilyl group and the
like, di-substituted silyl groups having 2 to 20 carbon atoms such
as a dimethylsilyl group, diethylsilyl group, diphenylsilyl group
and the like, tri-substituted silyl groups having 3 to 20 carbon
atoms such as a triemthylsilyl group, triethylsilyl group,
tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl
group, tri-sec-butyl silyl group, tri-tert-butylsilyl group,
tri-isobutylsilyl group, tert-butyldimethylsilyl group,
tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl
group, triphenylsilyl group and the like, and preferable examples
thereof include a trimethylsilyl group, tert-butyldimethylsilyl
group and triphenylsilyl group.
[0022] Any of these substituted silyl groups may also be partially
substituted with a halogen atom such as a fluorine atom, chlorine
atom, bromine atom or iodine atom, an alkoxy group such as a
methoxy group, ethoxy group or the like, an aryloxy group such as a
phenoxy group or the like, or an aralkyloxy group such as a
benzyloxy group or the like.
[0023] R in the general formula (1) is more preferably an alkyl
group, substituted aryl group or substituted silyl group.
particularly preferably a methyl group, ethylgroup, tert-butyl
group, neopentyl group, cyclopentyl group, cyclohexyl group,
methoxyphenyl group or trimethylsilyl group.
[0024] m in the general formula (1) is 0 or 1, p is 1 or 2, and the
sum of m and p is 2. Particularly preferably, both of m and p
represent 1.
[0025] The transition metal compound (A) of the present invention
is a transition metal compound obtained by reacting a transition
metal compound (a) represented by the above-described general
formula (1) with a conjugated diene or non-conjugated diene (b) in
the presence of a compound (c) selected from the group consisting
of alkyllithiums, alkali metals, alkali metal hydrides and Grignard
compounds.
[0026] The transition metal compound (a) represented by the general
formula (1) is produced, for example, by a method described in
Organometallics, Vol. 18, pp. 1116-1118 (1999) or J. Organometallic
Chem., Vol. 159, pp. 47-52 (1978) or the like. The specific
examples of the transitionmetal compound (a) are those obtained by
replacing the groups corresponding to -(D)p of the specific
examples of the transition metal compound represented by the
general formula (2) described below with Cl.sub.2 (dichloride).
[0027] The conjugated diene or non-conjugated diene (b) is
preferably a conjugated diene or non-conjugated diene having 4 to
40 carbon atoms and more preferably a conjugated diene, and
specific examples thereof include butadiene, 1,3-pentadiene,
isoprene, 1,3-hexadiene, 2,4-hexadiene, 2,3-dimethylbutadiene,
1,3-heptadiene, 2,4-heptadiene, 2,3-dimethyl-1,3-pentadiene,
1,3-octadiene, 2,4-octadiene, 3,5-octadiene,
3,4-dimethyl-2,4-hexadiene, 5,5-dimethyl-1,3-hexadiene,
2,2,7,7-tetramethyl-3,5-octadiene,
2,4,5,7-tetramethyl-3,5-octadiene, 1-phenylbutadiene,
2-phenylbutadiene, 1,4-diphenylbutadiene, 2,3-diphenylbutadiene and
the like, and butadiene, 2,4-hexadiene or 1,4-diphenylbutadiene is
particularly preferable.
[0028] The compound (c) is a compound selected from the group
consisting of alkyllithiums, alkali metals, alkali metal hydrides,
and Grignard compounds.
[0029] The alkyllithium is preferably an alkyllithium having 1 to
10 carbon atoms, and more preferably methyllithium, ethyllithium,
n-propyllithium, n-butyllithium or tert-butyllithium.
[0030] Examples of the alkyl metal include lithium, sodium,
potassium and the like, and lithium or sodium is preferable.
[0031] Examples of the alkali metal hydride include lithium
hydride, sodium hydride, potassium hydride and the like, and
lithium hydride or sodium hydride is preferable.
[0032] The Grignard compound is preferably a compound represented
by the general formula R'MgX' (wherein, Mg represents a magnesium
atom, R' represents a hydrocarbon group having 1 to 20 carbon
atoms, and X' represents a halogen atom). Specific examples of R'
include alkyl, aryl, aralkyl and alkenyl groups having 1 to 20
carbon atoms such as a methyl group, ethyl group, n-propyl group,
isopropyl group, n-butyl group, sec-butyl group, tert-butyl group,
isopentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group,
phenyl group, benzyl group and the like. The Grignard compound is
particularly preferably isopropylmagnesium chloride.
[0033] The amount of the conjugated diene or non-conjugated diene
(b) used is usually 1 to 5-fold by mole based on the amount of the
transition metal compound (a) used in the reaction.
[0034] When the amount of the conjugated diene or non-conjugated
diene (b) used is extremely smaller than that of the transition
metal compound (a), the production yield of the transition metal
compound (A) may lower. Too large amount of the conjugated diene or
non-conjugated diene (b) is uneconomical and not preferable. The
amount thereof is preferably from 1 to 3-fold by mol, and more
preferably from 1 to 1.5-fold by mol.
[0035] The amount used of the compound(c) selected from the group
consisting of alkyllithiums, alkali metals, alkali metal hydrides,
and Grignard compounds (hereinafter, sometime abbreviated as
"compound (c)") is usually from 1-fold to 10-fold mol based on the
amount of the transition metal compound (a) used in the present
reaction.
[0036] When the amount of the compound (c) used is extremely
smaller than that of the transition metal compound (a) used. the
production yield of the transition metal compound (A) may lower.
Too large amount of the compound (c) is uneconomical and not
preferable. The use amount thereof is preferably from 1.5 to 3-fold
by mol, and more preferably from 1.8 to 2.5-fold by mol.
[0037] Regarding the addition order of reagents in the present
reaction, the compound (c) may be added to a mixed solution of the
transition metal compound (a) and the conjugated or non-conjugated
diene (b), or the transition metal compound (a) may be added to a
mixed solution of the conjugated diene or non-conjugated diene (b)
and the compound (c). Alternatively, the reverse order is
permissible.
[0038] The reaction is usually carried out in a solvent inert to
the reagents. Examples of this solvent include aromatic hydrocarbon
solvents such as benzene, toluene, xylene, mesitylene and the like,
aliphatic hydrocarbon solvents such as pentane, hexane, heptane,
octane and the like, ether solvents such as diethyl ether,
tetrahydrofuran and the like. These solvents are used alone or in
combination of two or more, and the use amount thereof is usually
from 1 to 200-fold by weight, preferably from 3 to 50-fold by
weight based on the use amount of the transition metal compound
(a).
[0039] The reaction temperature is not particularly restricted, and
the reaction is conducted at a temperature preferably from
-100.degree. C. to the boiling point of a solvent used in the
reaction, and more preferably from -80 to 150.degree. C. and lower
than the boiling point of the solvent. Industrially, lower
temperature is not preferable, and the reaction is conducted at a
temperature preferably from -20 to 80 and lower than the boiling
point of the solvent.
[0040] The transition metal compound (A) of the present invention
is obtained by the above-mentioned reaction, and for example, when
butadiene is used as the conjugated diene or non-conjugated diene
(b), a transition metal compound (A1) in which the transition metal
atom M has a formal oxidation number of II and a transition metal
compound (A2) in which the transition metal atom M has a formal
oxidation number of IV as described below are usually obtained.
4
[0041] The configuration of butadiene in (A1) is s-trans or s-cis
configuration.
[0042] The transition metal compound (A) in the present invention
is, as one embodiment, a transition metal compound represented by
the following general formula (2) 5
[0043] Wherein, M, L, R, p and m are as defined in the
above-mentioned transition metal compound represents by the general
formula (1), and D represents the above-described conjugated diene
or non-conjugated diene (b), and d is 1 or 2.
[0044] Specific examples of the transition metal compound
represented by the general formula (2) include
(cyclopentadienyl)(trimethylphosphineimin- e)(butadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(1,3-pen-
tadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(isoprene)tit- anium,
(cyclopentadienyl)(trimethylphosphineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(2,3-dimethylbutadiene)titaniu-
m,
(cyclopentadienyl)(trimethylphosphineimine)(1,3-heptadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(2,3-dimethyl-1,3-pentadiene)t-
itanium,
(cyclopentadienyl)(trimethylphosphineimine)(1,3-octadiene)titaniu-
m,
(cyclopentadienyl)(trimethylphosphineimine)(2,4-octadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(3,4-dimethyl-2,4-hexadiene)ti-
tanium,
(cyclopentadienyl)(trimethylphosphineimine)(5,5-dimethyl-1,3-hexad-
iene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(2,7-dimethyl-3,-
5-octadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(4,5-dime-
thyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(2-
,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trimethylpho-
sphineimine)(2,4,5,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(trimethylphosphineimine)(1,4-diphenylbutadiene)titaniu-
m,
(cyclopentadienyl)(trimethylphosphineimine)(2,3-diphenylbutadiene)titan-
ium, (cyclopentadienyl)(triethylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(1,3-pentadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(2,3-dimethylbutadiene)titanium-
,
(cyclopentadienyl)(triethylphosphineimine)(1,3-heptadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(2,3-dimethyl-1,3-pentadiene)ti-
tanium,
(cyclopentadienyl)(triethylphosphineimine)(1,3-octadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(2,4-octadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(3,4-dimethyl-2,4-hexadiene)tit-
anium,
(cyclopentadienyl)(triethylphosphineimine)(5,5-dimethyl-1,3-hexadie-
ne)titanium,
(cyclopentadienyl)(triethylphosphineimine)(2,7-dimethyl-3,5-o-
ctadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(4,5-dimethyl-
-3,5-octadiene)titanium, (cyclopentadienyl)
(triethylphosphineimine)(2,2,7-
,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triethylphosphin-
eimine)(2,4,5,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(triethylphosphineimine)(1,4-diphenylbutadiene)titanium-
,
(cyclopentadienyl)(triethylphosphineimine)(2,3-diphenylbutadiene)titaniu-
m,
(cyclopentadienyl)(tri-n-propylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)
(1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)
(1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2,3-dimethylbutadiene)tita-
nium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(1,3-heptadiene)titani-
um,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2,4-heptadiene)titanium-
,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2,3-dimethyl-1,3-pentadie-
ne)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(1,3-octadiene)-
titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2,4-octadiene)tit-
anium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(3,5-octadiene)titani-
um,
(cyclopentadienyl)(tri-n-propylphosphineimine)(3,4-dimethyl-2,4-hexadi-
ene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(5,5-dimethyl--
1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2,7-
-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphine-
imine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-propy-
lphosphineimine)(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2,4,5,7-tetramethyl-3,5-oc-
tadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(1-phenylb-
utadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2-phenyl-
butadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(1,4-dip-
henylbutadiene)titanium,
(cyclopentadienyl)(tri-n-propylphosphineimine)(2,-
3-diphenylbutadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimin-
e)(butadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)
(1,3-pentadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(- isoprene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(1,3-hexa-
diene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(2,4-hexadie-
ne)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(2,3-dimethylbu-
tadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(1,3-hepta-
diene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(2,4-heptadi-
ene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(2,3-dimethyl--
1,3-pentadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(1,-
3-octadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(2,4-o-
ctadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(3,5-octa-
diene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(3,4-dimethy-
l-2,4-hexadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(5-
,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(triisopropylphosphi-
neimine)(2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisopro-
pylphosphineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(2,2,7,7-tetramethyl-3,5-oc-
tadiene)titanium,
(cyclopentadienyl)(triisopropylphosphineimine)(2,4,5,7-t-
etramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisopropylphosphin-
eimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(triisopropylphosphi-
neimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(triisopropylphosph-
ineimine)(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(triisopropylp-
hosphineimine)(2,3-diphenylbutadiene)titanium,
(cyclopentadienyl)(tri-n-bu- tylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosp-
hineimine)(1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphin- eimine)(isoprene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(1-
,3-hexadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(2,4-h-
exadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(2,3-dimet-
hylbutadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(1,3-h-
eptadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(2,4-hept-
adiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(2,3-dimethy-
l-1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(1-
,3-octadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(2,4-o-
ctadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(3,5-octad-
iene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(3,4-dimethyl--
2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(5,5--
dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineim-
ine)(2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-butylph-
osphineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri--
n-butylphosphineimine)(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(2,4,5,7-tetramethyl-3,5-oct-
adiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(1-phenylbut-
adiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(2-phenylbut-
adiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(1,4-dipheny-
lbutadiene)titanium,
(cyclopentadienyl)(tri-n-butylphosphineimine)(2,3-dip-
henylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(b-
utadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(1,3-pen-
tadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(isoprene-
)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(1,3-hexadiene)t-
itanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(2,4-hexadiene)tit-
anium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(2,3-dimethylbutadie-
ne)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(1,3-heptadien-
e)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(2,4-heptadiene-
)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(2,3-dimethyl-1,-
3-pentadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(1,3-
-octadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(2,4-o-
ctadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(3,5-oct-
adiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(3,4-dimet-
hyl-2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine-
)(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-sec-butylpho-
sphineimine)(2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-s-
ec-butylphosphineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(2,2,7,7-tetramethyl-3,5-o-
ctadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosphineimine)(2,4,5,7-
-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-sec-butylphosp-
hineimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-butylpho-
sphineimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-butylp-
hosphineimine)(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec--
butylphosphineimine)(2,3-diphenylbutadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(1,3-pentadiene)titanium,
(cyclopentadienyl) (triisobutylphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(2,3-dimethylbutadiene)titan-
ium,
(cyclopentadienyl)(triisobutylphosphineimine)(1,3-heptadiene)titanium-
,
(cyclopentadienyl)(triisobutylphosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(2,3-dimethyl-1,3-pentadiene-
)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(1,3-octadiene)tit-
anium,
(cyclopentadienyl)(triisobutylphosphineimine)(2,4-octadiene)titaniu-
m,
(cyclopentadienyl)(triisobutylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(3,4-dimethyl-2,4-hexadiene)-
titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(5,5-dimethyl-1,3-h-
exadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(2,7-dimet-
hyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(-
4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisobutylphosphi-
neimine)(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(2,4,5,7-tetramethyl-3,5-oct-
adiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(1-phenylbut-
adiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(2-phenylbut-
adiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(1,4-dipheny-
lbutadiene)titanium,
(cyclopentadienyl)(triisobutylphosphineimine)(2,3-dip-
henylbutadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(-
butadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)
(1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine-
)(isoprene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(1,3--
hexadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(2,4-h-
exadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(2,3-di-
methylbutadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)-
(1,3-heptadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)-
(2,4-heptadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)-
(2,3-dimethyl-1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-tert-butylph-
osphineimine)(1,3-octadiene)titanium,
(cyclopentadienyl)(tri-tert-butylpho-
sphineimine)(2,4-octadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphos-
phineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosp-
hineimine)(3,4-dimethyl-2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-ter-
t-butylphosphineimine)(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(2,7-dimethyl-3,5-octadie-
ne)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(4,5-dimethyl-
-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(-
2,2,7,7-tetramethyl-3,5-octadiene)titanium, (cyclopentadienyl)
(tri-tert-butylphosphineimine)(2,4,5,7-tetramethyl-3,5-octadiene)titanium-
,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(1-phenylbutadiene)titan-
ium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(2-phenylbutadiene)ti-
tanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(1,4-diphenylbutad-
iene)titanium,
(cyclopentadienyl)(tri-tert-butylphosphineimine)(2,3-diphen-
ylbutadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(butad-
iene)titanium, (cyclopentadienyl)(tri-n-pentylphosphineimine)
(1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(- isoprene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(1,3-hexa-
diene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(2,4-hexadie-
ne)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(2,3-dimethylbu-
tadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(1,3-hepta-
diene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(2,4-heptadi-
ene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(2,3-dimethyl--
1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(1,-
3-octadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(2,4-o-
ctadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(3,5-octa-
diene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(3,4-dimethy-
l-2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(5-
,5-dimethyl-1,3-hexadiene) titanium,
(cyclopentadienyl)(tri-n-pentylphosph-
ineimine)(2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-pe-
ntylphosphineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(2,2,7,7-tetramethyl-3,5-oc-
tadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphineimine)(2,4,5,7-t-
etramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphin-
eimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosphi-
neimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(tri-n-pentylphosph-
ineimine)(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(tri-n-pentylp-
hosphineimine)(2,3-diphenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec--
pentylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(tri-sec-penty-
lphosphineimine)(1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-sec-penty-
lphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosp-
hineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosph-
ineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphi-
neimine)(2,3-dimethylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-pentyl-
phosphineimine)(1,3-heptadiene)titanium,
(cyclopentadienyl)(tri-sec-pentyl-
phosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(tri-sec-pentyl-
phosphineimine)(2,3-dimethyl-1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(1,3-octadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(2,4-octadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(3,4-dimethyl-2,4-hexadie-
ne)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(5,5-dimethyl-
-1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(-
2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphos-
phineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-se-
c-pentylphosphineimine)(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(2,4,5,7-tetramethyl-3,5--
octadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(1-phe-
nylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)(2--
phenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphineimine)-
(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-pentylphosphin-
eimine)(2,3-diphenylbutadiene)titanium,
(cyclopentadienyl)(triisopentylpho-
sphineimine)(butadiene)titanium,
(cyclopentadienyl)(triisopentylphosphinei-
mine)(1,3-pentadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimi- ne)(isoprene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(1,3--
hexadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(2,4-hex-
adiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(2,3-dimeth-
ylbutadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(1,3-h-
eptadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(2,4-hep-
tadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(2,3-dimet-
hyl-1,3-pentadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine-
)(1,3-octadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(2-
,4-octadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(3,5--
octadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(3,4-dim-
ethyl-2,4-hexadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimin-
e)(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(triisopentylpho-
sphineimine)(2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triis-
opentylphosphineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(2,2,7,7-tetramethyl-3,5-oc-
tadiene)titanium,
(cyclopentadienyl)(triisopentylphosphineimine)(2,4,5,7-t-
etramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisopentylphosphin-
eimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(triisopentylphosphi-
neimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(triisopentylphosph-
ineimine)(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(triisopentylp-
hosphineimine)(2,3-diphenylbutadiene)titanium,
(cyclopentadienyl)(tri-tert-
-pentylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(tri-tert-pen-
tylphosphineimine)(pentadiene)titanium,
(cyclopentadienyl)(tri-tert-pentyl-
phosphineimine)(isoprene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosp-
hineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosp-
hineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosp-
hineimine)(2,3-dimethylbutadiene)titanium,
(cyclopentadienyl)(tri-tert-pen-
tylphosphineimine)(1,3-heptadiene)titanium,
(cyclopentadienyl)(tri-tert-pe-
ntylphosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(tri-tert-p-
entylphosphineimine)(2,3-dimethyl-1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimine)(1,3-octadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimine)(2,4-octadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimine)(3,4-dimethyl-2,4-hexadi-
ene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimine)(5,5-dimeth-
yl-1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimin-
e)(2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-pentyl-
phosphineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimine)(2,2,7,7-tetramethyl-3,5-
-octadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimine)(2,4-
,5,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-penty-
lphosphineimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(tri-tert-p-
entylphosphineimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(tri-te-
rt-pentylphosphineimine)(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(tri-tert-pentylphosphineimine)(2,3-diphenylbutadiene)t-
itanium,
(cyclopentadienyl)(trineopentylphosphineimine)(butadiene)titanium-
,
(cyclopentadienyl)(trineopentylphosphineimine)(pentadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(2,3-dimethylbutadiene)tita-
nium,
(cyclopentadienyl)(trineopentylphosphineimine)(1,3-heptadiene)titani-
um,
(cyclopentadienyl)(trineopentylphosphineimine)(2,4-heptadiene)titanium-
,
(cyclopentadienyl)(trineopentylphosphineimine)(2,3-dimethyl-1,3-pentadie-
ne)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(1,3-octadiene)-
titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(2,4-octadiene)tit-
anium,
(cyclopentadienyl)(trineopentylphosphineimine)(3,5-octadiene)titani-
um,
(cyclopentadienyl)(trineopentylphosphineimine)(3,4-dimethyl-2,4-hexadi-
ene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(5,5-dimethyl--
1,3-hexadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(2,7-
-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trineopentylphosphine-
imine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trineopenty-
lphosphineimine)(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(2,4,5,7-tetramethyl-3,5-oc-
tadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(1-phenylb-
utadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(2-phenyl-
butadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(1,4-dip-
henylbutadiene)titanium,
(cyclopentadienyl)(trineopentylphosphineimine)(2,-
3-diphenylbutadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineim-
ine)(butadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(-
1,3-pentadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(-
isoprene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(1,3-he-
xadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(2,4-hex-
adiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(2,3-dime-
thylbutadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(1-
,3-heptadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(2-
,4-heptadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(2-
,3-dimethyl-1,3-pentadiene)titanium,
(cyclopentadienyl)(tricyclopentylphos-
phiheimine)(1,3-octadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosp-
hineimine)(2,4-octadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosph-
ineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphi-
neimine)(3,4-dimethyl-2,4-hexadiene)titanium,
(cyclopentadienyl)(tricyclop-
entylphosphineimine)(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(2,7-dimethyl-3,5-octadie-
ne)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(4,5-dimethyl-
-3,5-octadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(-
2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tricyclopen-
tylphosphineimine)(2,4,5,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(1-phenylbutadiene)titani-
um,
(cyclopentadienyl)(tricyclopentylphosphineimine)(2-phenylbutadiene)tit-
anium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(1,4-diphenylbutadi-
ene)titanium,
(cyclopentadienyl)(tricyclopentylphosphineimine)(2,3-dipheny-
lbutadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(butadie- ne)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(1,3-pentadiene)-
titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2,3-dimethylbutadiene)titan-
ium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(1,3-heptadiene)titanium-
,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2,3-dimethyl-1,3-pentadiene-
)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(1,3-octadiene)tit-
anium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2,4-octadiene)titaniu-
m,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(3,4-dimethyl-2,4-hexadiene)-
titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(5,5-dimethyl-1,3-h-
exadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2,7-dimet-
hyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(-
4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphi-
neimine)(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2,4,5,7-tetramethyl-3,5-oct-
adiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(1-phenylbut-
adiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2-phenylbut-
adiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(1,4-dipheny-
lbutadiene)titanium,
(cyclopentadienyl)(tri-n-hexylphosphineimine)(2,3-dip-
henylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(b-
utadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(1,3-pen-
tadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(isoprene-
)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(1,3-hexadiene)t-
itanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(2,4-hexadiene)tit-
anium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(2,3-dimethylbutadie-
ne)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(1,3-heptadien-
e)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(2,4-heptadiene-
)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(2,3-dimethyl-1,-
3-pentadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(1,3-
-octadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(2,4-o-
ctadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(3,5-oct-
adiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(3,4-dimet-
hyl-2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine-
)(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylpho-
sphineimine)(2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-s-
ec-hexylphosphineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(2,2,7,7-tetramethyl-3,5-o-
ctadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosphineimine)(2,4,5,7-
-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylphosp-
hineimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylpho-
sphineimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec-hexylp-
hosphineimine)(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(tri-sec--
hexylphosphineimine)(2,3-diphenylbutadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(1,3-pentadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(2,3-dimethylbutadiene)titan-
ium,
(cyclopentadienyl)(triisohexylphosphineimine)(1,3-heptadiene)titanium-
,
(cyclopentadienyl)(triisohexylphosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(2,3-dimethyl-1,3-pentadiene-
)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(1,3-octadiene)tit-
anium,
(cyclopentadienyl)(triisohexylphosphineimine)(2,4-octadiene)titaniu-
m,
(cyclopentadienyl)(triisohexylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(3,4-dimethyl-2,4-hexadiene)-
titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(5,5-dimethyl-1,3-h-
exadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(2,7-dimet-
hyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(-
4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisohexylphosphi-
neimine)(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(2,4,5,7-tetramethyl-3,5-oct-
adiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(1-phenylbut-
adiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(2-phenylbut-
adiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(1,4-dipheny-
lbutadiene)titanium,
(cyclopentadienyl)(triisohexylphosphineimine)(2,3-dip-
henylbutadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(-
butadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(1,3-p-
entadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(isopr-
ene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(1,3-hexadie-
ne)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(2,4-hexadien-
e)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(2,3-dimethylb-
utadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(1,3-he-
ptadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(2,4-he-
ptadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(2,3-di-
methyl-1,3-pentadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphine-
imine)(1,3-octadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphinei-
mine)(2,4-octadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineim-
ine)(3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimi-
ne)(3,4-dimethyl-2,4-hexadiene)titanium,
(cyclopentadienyl)(tri-tert-hexyl-
phosphineimine)(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(2,7-dimethyl-3,5-octadie-
ne)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(4,5-dimethyl-
-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(-
2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-he-
xylphosphineimine)(2,4,5,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(1-phenylbutadiene)titani-
um,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(2-phenylbutadiene)tit-
anium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(1,4-diphenylbutadi-
ene)titanium,
(cyclopentadienyl)(tri-tert-hexylphosphineimine)(2,3-dipheny-
lbutadiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(butadie- ne)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)
(1,3-pentadiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(i- soprene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(1,3-hexadi-
ene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2,4-hexadiene)-
titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2,3-dimethylbutadi-
ene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(1,3-heptadiene-
)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2,4-heptadiene)ti-
tanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2,3-dimethyl-1,3-pen-
tadiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(1,3-octadi-
ene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2,4-octadiene)-
titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(3,5-octadiene)tita-
nium,
(cyclopentadienyl)(trineohexylphosphineimine)(3,4-dimethyl-2,4-hexad-
iene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(5,5-dimethyl--
1,3-hexadiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2,7--
dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trineohexylphosphineim-
ine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trineohexylph-
osphineimine)(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2,4,5,7-tetramethyl-3,5-oct-
adiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(1-phenylbut-
adiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2-phenylbut-
adiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(1,4-dipheny-
lbutadiene)titanium,
(cyclopentadienyl)(trineohexylphosphineimine)(2,3-dip-
henylbutadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(b-
utadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(pentadi-
ene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(isoprene) titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(1,3-hexadiene)t-
itanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(2,4-hexadiene)tit-
anium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(2,3-dimethylbutadie-
ne)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(1,3-heptadien-
e)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(2,4-heptadiene-
)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(2,3-dimethyl-1,-
3-pentadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(1,3-
-octadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(2,4-o-
ctadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(3,5-oct-
adiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(3,4-dimet-
hyl-2,4-hexadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine-
)(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl)(tricyclohexylpho-
sphineimine)(2,7-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tricy-
clohexylphosphineimine)(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(2,2,7,7-tetramethyl-3,5-o-
ctadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosphineimine)(2,4,5,7-
-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tricyclohexylphosp-
hineimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(tricyclohexylpho-
sphineimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(tricyclohexylp-
hosphineimine)(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(tricyclo-
hexylphosphineimine)(2,3-diphenylbutadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(1,3-pentadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(2,3-dimethylbutadiene)titaniu-
m,
(cyclopentadienyl)(triphenylphosphineimine)(1,3-heptadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(2,3-dimethyl-1,3-pentadiene)t-
itanium,
(cyclopentadienyl)(triphenylphosphineimine)(1,3-octadiene)titaniu-
m,
(cyclopentadienyl)(triphenylphosphineimine)(2,4-octadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(3,4-dimethyl-2,4-hexadiene)ti-
tanium,
(cyclopentadienyl)(triphenylphosphineimine)(5,5-dimethyl-1,3-hexad-
iene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(2,7-dimethyl-3,-
5-octadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(4,5-dime-
thyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(2-
,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triphenylpho-
sphineimine)(2,4,5,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(triphenylphosphineimine)(1,4-diphenylbutadiene)titaniu-
m,
(cyclopentadienyl)(triphenylphosphineimine)(2,3-diphenylbutadiene)titan-
ium, (cyclopentadienyl)(tritolylphosphineimine)(butadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)
(1,3-pentadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(isoprene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(1,3-hexadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(2,4-hexadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(2,3-dimethylbutadiene)titanium-
,
(cyclopentadienyl)(tritolylphosphineimine)(1,3-heptadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(2,4-heptadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(2,3-dimethyl-1,3-pentadiene)ti-
tanium,
(cyclopentadienyl)(tritolylphosphineimine)(1,3-octadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(2,4-octadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(3,5-octadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(3,4-dimethyl-2,4-hexadiene)tit-
anium,
(cyclopentadienyl)(tritolylphosphineimine)(5,5-dimethyl-1,3-hexadie-
ne)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(2,7-dimethyl-3,5-o-
ctadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(4,5-dimethyl-
-3,5-octadiene)titanium,
(cyclopentadienyl)(tritolylphosphineimine)(2,2,7,-
7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(tritolylphosphine-
imine)(2,4,5,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl)(trit-
olylphosphineimine)(1-phenylbutadiene)titanium,
(cyclopentadienyl)(tritoly-
lphosphineimine)(2-phenylbutadiene)titanium,
(cyclopentadienyl)(tritolylph-
osphineimine)(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl)(tritolylp-
hosphineimine)(2,3-diphenylbutadiene)titanium,
(cyclopentadienyl){tris(tri-
methylsilyl)phosphineimine}(butadiene)titanium,
(cyclopentadienyl){tris(tr-
imethylsilyl)phosphineimine}(1,3-pentadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(isoprene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(1,3-hexadiene)tita-
nium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(2,4-hexadiene-
)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(2,3-dime-
thylbutadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineim-
ine}(1,3-heptadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosp-
hineimine}(2,4-heptadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl-
)phosphineimine}(2,3-dimethyl-1,3-pentadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(1,3-octadiene)tita-
nium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(2,4-octadiene-
)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(3,5-octa-
diene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(3,4-
-dimethyl-2,4-hexadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)p-
hosphineimine}(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(2,7-dimethyl-3,5-o-
ctadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(-
4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl){tris(trimethylsily-
l)phosphineimine}(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(2,4,5,7-tetramethy-
l-3,5-octadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphine-
imine}(1-phenylbutadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)-
phosphineimine}(2-phenylbutadiene)titanium,
(cyclopentadienyl){tris(trimet-
hylsilyl)phosphineimine}(1,4-diphenylbutadiene)titanium,
(cyclopentadienyl){tris(trimethylsilyl)phosphineimine}(2,3-diphenylbutadi-
ene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine}(b-
utadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimi-
ne}(1,3-pentadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)ph-
osphineimine}(isoprene)titanium,
(cyclopentadienyl){tris(butyldimethylsily-
l)phosphineimine}(1,3-hexadiene)titanium,
(cyclopentadienyl){tris(butyldim-
ethylsilyl)phosphineimine}(2,4-hexadiene)titanium,
(cyclopentadienyl){tris-
(butyldimethylsilyl)phosphineimine}(2,3-dimethylbutadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine}(1,3-heptadiene-
)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine}(2,4--
heptadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphinei-
mine}(2,3-dimethyl-1,3-pentadiene)titanium,
(cyclopentadienyl){tris(butyld-
imethylsilyl)phosphineimine}(1,3-octadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine}(2,4-octadiene)-
titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine}(3,5-o-
ctadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimi-
ne}(3,4-dimethyl-2,4-hexadiene)titanium,
(cyclopentadienyl){tris(butyldime-
thylsilyl)phosphineimine}(5,5-dimethyl-1,3-hexadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine}(2,7-dimethyl-3-
,5-octadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphin-
eimine}(4,5-dimethyl-3,5-octadiene)titanium,
(cyclopentadienyl){tris(butyl-
dimethylsilyl)phosphineimine}(2,2,7,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine)
(2,4,5,7-tetramethyl-3,5-octadiene)titanium,
(cyclopentadienyl){tris(buty-
ldimethylsilyl)phosphineimine}(1-phenylbutadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine}(2-phenylbutadi-
ene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)phosphineimine}(1-
,4-diphenylbutadiene)titanium,
(cyclopentadienyl){tris(butyldimethylsilyl)-
phosphineimine}(2,3-diphenylbutadiene)titanium and the like, and
transition metal compounds such as compounds obtained by replacing
titanium on these compounds with zirconium or hafnium and compounds
obtained by replacing cyclopentadienyl on these compounds with
dimethylcyclopentadienyl, trimethylcyclopentadienyl,
tetramethylcyclopentadienyl, n-butylcyclopentadienyl,
tert-butyldimethylsilylcyclopentadienyl, indenyl,
tetrahydroindenyl, fluorenyl or octahydrofluorenyl.
[0045] The transition metal compound (A) of the present invention
is useful as an addition polymerization catalyst component which
can manifest high polymerization activity. The addition
polymerization catalyst of the present invention is an addition
polymerization catalyst which is prepared by using the
above-described transition metal compound (A) and preferably
prepared by contacting the above-described transition metal
compound (A) with a co-catalyst for activation.
[0046] As the co-catalyst for activation, an organoaluminum
compound (B) and/or the following (C) is preferably used. (C) Any
boron compound of the following (C1) to (C3)
[0047] (C1) A boron compound represented by the general formula
BQ.sup.1Q.sup.2Q.sup.3
[0048] (C2) A boron compound represented by the general formula
G.sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4).sup.-
[0049] (C3) A boron compound represented by the general formula
(L-H).sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4).sup.-
[0050] (wherein, B is a boron atom in the trivalent valence state,
Q.sup.1 to Q.sup.4 are a halogen atom, hydrocarbon group,
halogenated hydrocarbon group, substituted silyl group, alkoxy
group or di-substituted amino group, and they may be the same or
different. G.sup.+ is an inorganic or organic cation, L is a
neutral Lewis base, and (L-H).sup.+ is a Br.PHI.nsted acid.).
[0051] (B) Organoaluminum Compound
[0052] The organoaluminum compound (B) is an aluminum compound
having a carbon-aluminum bond, and one or more of aluminum
compounds selected from the following (B1) to (B3) are
preferable.
[0053] (B1) An organoaluminum compound represented by the general
formula E.sup.1.sub.aAlZ.sub.3-a
[0054] (B2) Cyclic aluminoxane hating a structure represented by
the general formula {--Al(E.sup.2)-O--}.sub.b
[0055] (B3) Linear aluminoxane having a structure represented by
the general formula E.sup.3(--Al(E.sup.3)-O--}.sub.cAlE.sup.3.sub.2
(wherein, each of E.sup.1, E.sup.2 and E.sup.3 is hydrocarbon
group, and all E.sup.1's, all E.sup.2's and all E.sup.3's may be
the same or different respectively. Z represents a hydrogen atom or
halogen atom, and all Z's may be the same or different. a
represents a number satisfying 0<a.ltoreq.3, b is an integer of
2 or more, and c is an integer of 1 or more.).
[0056] The hydrocarbon group in E.sup.1, E.sup.2 or E.sup.3 is
preferably a hydrocarbon group having 1 to 8 carbon atoms, and more
preferably an alkyl group.
[0057] Specific examples of the organoaluminum compound (B1)
represented by the general formula E.sup.1.sub.aAlZ.sub.3-a include
trialkylaluminums such as trimethylaluminum, triethylaluminum,
tripropylaluminum, triisobutylaluminum, trihexylaluminum and the
like; dialkylaluminum chlorides such as dimethylaluminum chloride,
diethylaluminum chloride, dipropylaluminum chloride,
diisobutylaluminum chloride, dihexylaluminum chloride and the like;
alkylaluminum dichlorides such as methylaluminum dichloride,
ethylaluminum dichloride, propylaluminum dichloride,
isobutylaluminum dichloride, hexylaluminum dichloride and the like;
dialkylaluminum hydrides such as dimethylaluminum hydride,
diethylaluminum hydride, dipropylaluminum hydride,
diisobutylaluminum hydride, dihexylaluminum hydride and the like;
and so forth.
[0058] The trialkylaluminum is preferable, and triethylaluminum or
triisobutylaluminum is more preferable.
[0059] Specific examples of E.sup.2 and E.sup.3 in (B2) cyclic
aluminoxane having a structure represented by the general formula
{--Al(E.sup.2)-O--}.sub.b and (B3) linear aluminoxane having a
structure represented by the general formula
E.sup.3{-Al(E.sup.3)-O--}.sub.cAlE.sup- .3.sub.2 include alkyl
groups such as a methyl group, ethyl group, n-propyl group,
isopropyl group, n-butyl group, isobutyl group, n-pentyl group,
neopentyl group and the like. b is an integer of 2 or more, c is an
integer of 1 or more. Preferably, E.sup.2 and E.sup.3 represent a
methyl group or isobutyl group, and b is 2 to 40 and c is 1 to
40.
[0060] The above-described aluminoxane is made by various methods.
This method is not particularly restricted, and the aluminoxane may
be produced according to a known method. For example, a solution
prepared by dissolving a trialkylaluminum (for example,
trimethylaluminum and the like) in a suitable organic solvent
(benzene, an aliphatic hydrocarbon or the like) is allowed to
contact with water to produce aluminoxane. Further, there is
exemplified a method in which a trialkylaluminum (for example,
trimethylaluminum and the like) is allowed to contact with a metal
salt containing crystal water (for example, copper sulfate hydrate
and the like) to produce aluminoxane.
[0061] (C) Boron Compound
[0062] As the boron compound (C), any of a boron compound (Cl)
represented by the general formula BQ.sup.1Q.sup.2Q.sup.3, a boron
compound (C2) represented by the general formula
G.sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4)- .sup.-, and a boron
compound (C3) represented by the general formula
(L-H).sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4).sup.- is used.
[0063] In the boron compound (C1) represented by the general
formula BQ.sup.1Q.sup.2Q.sup.3, B is a boron atom in the trivalent
valence state, Q.sup.1 to Q.sup.3 are a halogen atom, hydrocarbon
group, halogenated hydrocarbon group, substituted silyl group,
alkoxy group or di-substituted amino group, and they may be the
same or different. Q.sup.1 to Q.sup.3 are preferably a halogen
atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated
hydrocarbon group having 1 to 20 carbon atoms, substituted silyl
group having 1 to 20 carbon atoms, alkoxy group having 1 to 20
carbon atoms or amino group having 2 to 20 carbon atoms, and more
preferably, Q.sup.1 to Q.sup.3 are a halogen atom, hydrocarbon
group having 1 to 20 carbon atoms, or halogenated hydrocarbon group
having 1 to 20 carbon atoms. Further preferably, Q.sup.1 to Q.sup.4
are a fluorinated hydrocarbon group having 1 to 20 carbon atoms
containing at least one fluorine atom, and particularly preferably,
Q.sup.1 to Q.sup.4 are a fluorinated aryl group having 6 to 20
carbon atoms containing at least one fluorine atom.
[0064] Specific examples of the compound (C1) include
tris(pentafluorophenyl)borane,
tris(2,3,5,6-tetrafluorophenyl)borane,
tris(2,3,4,5-tetrafluorophenyl)borane,
tris(3,4,5-trifluorophenyl)borane,
tris(2,3,4-trifluorophenyl)borane,
phenylbis(pentafluorophenyl)borane and the like, and
tris(pentafluorophenyl)borane is most preferable.
[0065] In the boron compound (C2) represented by the general
formula G.sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4).sup.-, G+ is an
inorganic or organic cation, B is a boron atom in the trivalent
valence state, and Q.sup.1 to Q.sup.4 are as defined for Q.sup.1 to
Q.sup.3 in the above-mentioned (C1).
[0066] Specific examples of the inorganic cation G.sup.+ in a
compound represented by the general formula
G.sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4)- .sup.- include a
ferrocenium cation, alkyl-substituted ferrocenium cation, silver
cation and the like, specific examples of the organic cation
G.sup.+ thereof include a triphenylmethyl cation and the like.
G.sup.+ is preferably a carbenium cation, and particularly
preferably a triphenylmethyl cation. Examples of
(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4).sup.- include
tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6-tetrafluoroph-
enyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate,
tetrakis(3,4,5-trifluorophenyl) borate,
teterakis(2,3,4-trifluorophenyl)b- orate,
phenyltris(pentafluorophenyl)borate,
tetrakis(3,5-bistrifluoromethy- lphenyl) borate and the like.
[0067] As specific combination of them,
ferroceniumtetrakis(pentafluorophe- nyl) borate,
1,1'-dimethylferroceniumtetrakis(pentafluorophenyl)borate,
silvertetrakis(pentafluorophenyl)borate,
triphenylmethyltetrakis(pentaflu- orophenyl) borate,
triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)bo- rate and
the like are listed, and triphenylmethyltetrakis(pentafluoropheny-
l) borate is most preferable.
[0068] In the boron compound (C3) represented by the general
formula (L-H)+(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4), L is a neutral Lewis
base, (L-H).sup.+ is a Broensted acid, B is a boron atom in the
trivalent valence state, and Q.sup.1 to Q.sup.4 are as defined for
Q.sup.1 to Q.sup.3 in the above-mentioned Lewis acid (C1).
[0069] Specific examples of the Broensted acid (L-H).sup.+ in a
compound represented by the general formula
(L-H).sup.+(BQ.sup.1Q.sup.2Q.sup.3Q.su- p.4).sup.- include a
trialkyl-substituted ammonium, N,N-dialkylanilinium,
dialkylammonium, triaryl phosphonium and the like, and as the
(BQ.sup.1Q.sup.2Q.sup.3Q.sup.4).sup.-, the same compounds as
described above are listed.
[0070] As specific combination of them, there are listed
triethylammoniumtetrakis(pentafluorophenyl) borate,
tripropylammoniumtetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate,
N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,
N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,
N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl)borate,
N,N-dimethylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate,
diisopropylammoniumtetrakis(pentafluorophenyl)borate,
dicyclohexylammoniumtetrakis(pentafluorophenyl)borate,
triphenylphosphoniumtetrakis(pentafluorophenyl)borate,
tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate,
tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate and
the like, and tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate
or N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate is most
preferable.
[0071] In the present invention, the above-mentioned transition
metal compound (A), and as the co-catalyst, the organic aluminum
compound (B) and/or the above-mentioned compound (C) can be charged
in any order in polymerization and used, alternatively, a reaction
product obtained by previously contacting these compounds in any
combination may also be used.
[0072] Regarding amounts of catalyst components used, it is
desirable to use the components so that the molar ratio of
organoaluminum compound (B)/transition metal compound (A) is
usually from 0.1 to 10000, preferably from 5 to 2000, and the molar
ratio of boron compound (C)/transition metal compound (A) is
usually from 0.01 to 100, preferably from 0.5 to 10. Regarding the
concentrations when catalyst components are used in the form of a
solution, it is desirable to use the components so that the
concentration of the transition metal compound (A) is usually from
0.0001 to 5 mmol/liter, preferably from 0.001 to 1 mmol/liter, the
concentration of the organoaluminum compound (B) is usually from
0.01 to 500 mmol/liter, preferably from 0.1 to 100 mmol/liter in
terms of an Al atom, and the concentration of the boron compound
(C) is usually from 0.0001 to 5 mmol/liter, preferably from 0.001
to 1 mmol/liter.
[0073] As the olefin which can be applied in polymerization in the
present invention, there can be used olefins having 2 to 20 carbon
atoms, particularly, ethylene, .alpha.-olefins having 3 to 20
carbon atoms, diolefins having 4 to 20 carbon atoms, and the like,
and also, 2 or more of olefins can be used simultaneously. Specific
examples of the olefin include linear olefins such as ethylene,
propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
1-nonene, 1-decene and the like, branched olefins such as
3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene,
5-methyl-1-hexene and the like, vinylcyclohexane and the like, but
the scope of the present invention should not be limited to the
above-mentioned compounds. Specific combinations of olefins in
copolymerization, include ethylene and propylene, ethylene and
1-butene, ethylene and 1-hexene, ethylene and 1-octene, propylene
and 1-butene, and the like, but the scope of the present invention
should not be limited to these combinations.
[0074] The present invention can be applied effectively for
production of copolymers of particularly ethylene with other
.alpha.-olefin, speifically, propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-octene or the like.
[0075] The polymerization process also should not be limited
particularly, and for example, solvent polymerization or slurry
polymerization using as a solvent an aliphatic hydrocarbon such as
butane, pentane, hexane, heptane, octane or the like, an aromatic
hydrocarbon such as benzene, toluene or the like, or a halogenated
hydrocarbon such as methylene dichloride or the like, gas-phase
polymerization in a gaseous monomer, or the like can be used, and
it is possible to select any of continuous polymerization and
batch-wise polymerization.
[0076] The polymerization temperature can be in the range from -50
to 250.degree. C., and particularly, the range from -20 to
100.degree. C. is preferable, and the polymerization pressure is
preferably from normal pressure to 60 kg/cm.sup.2 G. The
polymerization time is appropriately determined depending generally
on the kind of the intended polymer, and the reaction apparatus,
and can be in the range from 1 minute to 20 hours. Further, a chain
transfer agent such as hydrogen or the like can also be added in
the present invention to regulate the molecular weight of a
polymer.
EXAMPLE
[0077] The following examples and comparative examples will
illustrate the present invention further in detail below, but do
not limit the scope of the present invention.
[0078] Properties of polymers in the examples were measured
according to the following methods.
[0079] (1) Intrinsic viscosity [.eta.]: It was measured using a
Ubbellohde viscometer at 135.degree. C. in a tetralin solution.
[0080] (2) .alpha.-Olefin unit content in copolymer: It was
measured by the characteristic absorptions of ethylene and
.alpha.-olefin using an infrared spectrophotometer (IR-810
manufactured by Nippon Bunko Kogyo Ltd.), and represented as the
number of short chain branching (SCB) per 1000 carbons.
[0081] (3) Melting point of polymer: It was measured by using Seiko
SSC-5200 under the following conditions.
[0082] Raising temperature: from 40.degree. C. to 150.degree. C.
(10.degree. C./min.); kept for 5 minutes
[0083] Cooling: from 150.degree. C. to 10.degree. C. (5.degree.
C./min.); kept for 10 minutes
[0084] Measurement: from 10 to 1600 (5.degree. C./min.)
[0085] (4) Molecular weight and molecular weight distribution: The
molecular weight was measured by using gel permeation chromatograph
(150, C manufactured by Waters) under the following conditions.
[0086] Column: TSK gel GMH-HT
[0087] Measurement temperature: set at 145.degree. C.
[0088] Measurement concentration: 10 mg/10
ml-orthodichlorobenzene
[0089] The molecular weight distribution was evaluated as the ratio
(Mw/Mn) of the weight-average molecular weight to the
number-average molecular weight.
Example 1
[0090] (1) Synthesis of
N-trimethylsilyl-tri-tert-butylphosphineimine
[0091] Into a 100 ml four-necked flask equipped with a stirrer and
cooling apparatus was charged 44.8 g (221 mmol) of
tri-tert-butylphosphine and 27.8 g (242 mmol) of
trimethylsilylazide under nitrogen atmosphere. This solution was
heated from 100.degree. C. to 120.degree. C., and stirred from 1.5
hours. Then, 6 g (52 mmol) of trimethylsilylazide was added, and
the mixture was further stirred at 125.degree. C. to 130.degree. C.
for 1 hour. Thus obtained reaction solution was cooled, and 100 ml
of dehydrated acetonitrile was added at 60.degree. C., and the
mixture was cooled to room temperature. To the resulted slurry was
added further 420 ml of dehydrated acetonitrile, and the mixture
was heated to 70.degree. C. to give a solution. This solution was
left to cool to room temperature, and allowed to stand still over
night to obtain a colorless needle-like crystal. This was
filtrated, and further washed with 50 ml of dehydrated
acetonitrile, and dried to obtain 47.8 g (165 mmol) of
N-trimethylsilyl-tri-tert-butylphosphineimine in the form of a
colorless needle-like crystal. The yield was 75%.
[0092] .sup.1H-NMR(CDCl.sub.3): d-0.20 (2, 9H), 1.28 (d, 27H, J=12
Hz)
[0093] .sup.31P-NMR(CDCl.sub.3): d 32.7
[0094] (2) Synthesis of
(cyclopentadienyl)(tri-tert-butylphosphineimine)ti- tanium
dichloride
[0095] In a 100 ml flak equipped with a stirrer, 5.08 g (23.1 mol)
of cyclopentadienyltitanium dichloride was dissolved in 100 ml of
toluene under nitrogen atmosphere. To this was added a solution
prepared by dissolving 7.50 g (26.0 mmol) of
N-triemthylsilyl-tri-tert-butylphosphine- imine synthesized in (1)
above in 30 ml of toluene, slowly at room temperature. The resulted
orange color solution was stirred at room temperature for one day
to obtain a suspension which was filtrated through Celite, and the
filtrate was collected, condensed and cooled for crystallization to
give 6.70 g (16.8 mmol) of (cyclopentadienyl)(tri-tert-
-butylphosphineimine) titanium dichloride in the form of a yellow
plate-like crystal. The yield was 73%.
[0096] .sup.1H-NMR(CDCl.sub.3): d 1.54 (d, 27H, J=13.9 Hz), 6.48
(s, 5H)
[0097] .sup.31P-NMR(CDC1.sub.3): d 48.3
[0098] (3) Synthesis of
(cyclopentadienyl)(tri-tert-butylphosphineimine)(1-
,4-diphenylbutadiene)titanium
[0099] In a 100 ml flak equipped with a stirrer, 1.00 g (2.50 mmol)
of (cyclopentadienyl)(tri-tert-butylphosphineimine)titanium
dichloride synthesized in (2) above and 0.875 g (2.50 mmol) of
1,4-diephnylbutadiene were dissolved in 30 ml of toluene under
nitrogen atmosphere. To this yellow solution was added 3.4 ml of a
1.55 mol/liter n-butyllithium/n-hexane solution at room temperature
dropwise. This solution was heated under reflux for 2 hours, then,
filtrated through Celite, and further condensed to 20 ml, then,
heated to give a dark black solution. This solution was left to
cool to room temperature, then, allowed to stand still at
-20.degree. C. over night to give a dark bright needle-like
crystal. This crystal was filtrated and washed with 5 ml of
n-pentane three times and dried to obtain 0.88 g (1.65 mmol) of
(cyclopentadienyl)(tri-tert-butylphosphineimine)(1,4-diphenylbutadiene)ti-
tanium in the form of a dark bright needle-like crystal. The yield
was 66%.
[0100] .sup.1H-NMR(C.sub.6D.sub.6): d 1.14 (d, 27H, J=13.2 Hz),
4.04 (s, 2H), 5.53 (s, 2H), 6.15 (s, 5H), 6.93-7.59 (m, 10H)
Example 2
[0101] An autoclave having an inner volume of 0.4 liter equipped
with a stirrer was dried in vacuo, purged with argon, then, 190 ml
of toluene was charged as a solvent, and 10 ml of 1-hexene was
charged as an .alpha.-olefin, and the reaction vessel was heated up
to 80.degree. C. After the heating, ethylene was fed while
controlling the ethylene pressure at 6 kg/cm.sup.2, and after the
system was stabilized, 1.0 mmol (mol number in terms of an aluminum
atom; hereinafter the same) of a solution of
methylisobutylaluminoxane in toluene (MMAO 3A, manufactured by
TOSOH-AKZO, hereinafter, simply abbreviated as "MMAO") was charged,
subsequently, 0.5 .mu.mol of
(cyclopentadienyl)(tri-tert-butylphosphineim-
ine)(1,4-diphenylbutadiene)titanium synthesized in the
above-mentioned Example 1 (3) was charged. Polymerization was
conducted for 60 minutes while controlling the temperature at
80.degree. C. The temperature in the polymerization chamber
increased by 8.0 by the initial heat generation in this
procedure.
[0102] As a result of the polymerization, a copolymer of ethylene
with 1-hexene having SCB of 23.1, [.eta.]=5.24 dl/g, molecular
weight (Mw) of 4.9.times.10.sup.5, molecular weight distribution
(Mw/Mn)of 2.8 and melting temperature of 107.7.degree. C. was
produced at a rate of 2.3.times.10.sup.7 g per 1 hour per 1 mol of
a titanium atom.
Example 3
[0103] An autoclave having an inner volume of 0.4 liter equipped
with a stirrer was dried in vacuo, purged with argon, then, 190 ml
of toluene was charged as a solvent, and 10 ml of 1-hexene was
charged as an .alpha.-olefin, and the reaction vessel was heated up
to 80.degree. C. After the heating, ethylene was fed while
controlling the ethylene pressure at 6 kg/cm.sup.2, and after the
system was stabilized, 0.25 mmol of triisobutylaluminum was
charged, subsequently, 0.5 .mu.mol of
(cyclopentadienyl)(tri-tert-butylphosphineimine)(1,4-diphenylbutadiene)ti-
tanium was charged, then, 1.5 .mu.mol of
triphenylmethyltetrakis(pentafluo- rophenyl)borate was charged.
Polymerization was conducted for 60 minutes while controlling the
temperature at 80.degree. C. The temperature in the polymerization
chamber increased by 7.0.degree. C. by the initial heat generation
in this procedure.
[0104] As a result of the polymerization, a copolymer of ethylene
with 1-hexene having SCB of 25.2, [.eta.] of 7.01 dl/g, molecular
weight (Mw) of 5.3.times.10.sup.5, molecular weight distribution
(Mw/Mn) of 3.3 and melting temperature of 106.6.degree. C. was
produced at a rate of 2.4.times.10.sup.7 g per 1 hour per 1 mol of
a titanium atom.
Comparative Example 1
[0105] An autoclave having an inner volume of 0.4 liter equipped
with a stirrer was dried in vacuo, purged with argon, then, 190 ml
of toluene was charged as a solvent, and 10 ml of 1-hexene was
charged as an .alpha.-olefin, and the reaction vessel was heated up
to 80.degree. C. After the heating, ethylene was fed while
controlling the ethylene pressure at 6 kg/cm.sup.2, and after the
system was stabilized, 2.0 mmol of MMAO was charged, subsequently,
1.0 .mu.mol of (cyclopentadienyl)(tri--
tert-butylphosphineimine)titanium dichloride synthesized in the
above-mentioned Example 1 (2) was charged. Polymerization was
conducted for 60 minutes while controlling the temperature at
80.degree. C. The temperature in the polymerization chamber
increased by 14.8.degree. C. by the initial heat generation in this
procedure.
[0106] As a result of the polymerization, a copolymer of ethylene
with 1-hexene having a SCB of 25.8, [.eta.] of 5.23 dl/g, molecular
weight (Mw) of 4.3.times.10.sup.5, molecular weight distribution
(Mw/Mn)=3.7 and melting temperature of 109.6.degree. C. was
produced at a rate of 5.5.times.10.sup.6 g per 1 hour per 1 mol of
a titanium atom.
Comparative Example 2
[0107] An autoclave having a content volume of 0.4 liter equipped
with a stirrer was dried in vacuo, purged with argon, then, 190 ml
of toluene was charged as a solvent, and 10 ml of 1-hexene was
charged as an .alpha.-olefin, and the reaction vessel was heated up
to 80.degree. C. After the heating, ethylene was fed while
controlling the ethylene pressure at 6 kg/cm.sup.2, and after the
system was stabilized, 0.50 mmol of triisobutylaluminum was
charged, subsequently, 1.0 .mu.mol of
(cyclopentadienyl)(tri-tert-butylphosphineimine)titanium dichloride
was charged, then, 3.0 .mu.mol of
triphenylmethyltetrakis(pentafluorophenyl) borate was charged.
Polymerization was conducted for 60 minutes while controlling the
temperature at 80.degree. C. The temperature in the polymerization
chamber increased by 16.8.degree. C. by the initial heat generation
in this procedure.
[0108] As a result of the polymerization, a copolymer of ethylene
with 1-hexene having SCB of 24.2, [.eta.] of 4.88 dl/g, molecular
weight (Mw) of 3.8.times.10.sup.5, molecular weight distribution
(Mw/Mn) of 2.6 and melting temperature of 109.9.degree. C. was
produced at a rate of 7.9.times.10.sup.6 g per 1 hour per 1 mol of
a titanium atom.
[0109] According to the present invention, as described above in
detail, a transition metal compound useful as an addition
polymerization catalyst component which can manifest high activity,
an addition polymerization catalyst component composed of this
transition metal compound, an addition polymerization catalyst
having high activity obtained by using this transition metal
compound, and an efficient method for producing an olefin polymer
using this addition polymerization catalyst are provided.
* * * * *