JP3164417B2 - Novel transition metal compounds and their uses - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel transition metal compound and its use, and more particularly to a novel transition metal compound which can be used as a catalyst component for olefin polymerization having excellent polymerization activity, and a novel transition metal compound. Catalyst component.

[0002]

BACKGROUND OF THE INVENTION Heretofore, a process for producing an α-olefin polymer has been carried out in the presence of a titanium catalyst comprising a titanium compound and an organoaluminum compound or a vanadium catalyst comprising a vanadium compound and an organoaluminum compound. A method for copolymerizing ethylene and an α-olefin is known.

[0003] In general, ethylene
The α-olefin copolymer had a wide molecular weight distribution and composition distribution, and was inferior in transparency, surface non-adhesion, and mechanical properties. In addition, ethylene and vanadium catalysts
α-olefin copolymers have a narrower molecular weight distribution and composition distribution than those obtained with titanium-based catalysts, and have significantly improved transparency, surface non-adhesion, and mechanical properties. However, there is still a need for a catalyst that can provide an α-olefin polymer having improved performance, especially an ethylene / α-olefin copolymer.

On the other hand, a catalyst comprising a zirconium compound and an aluminoxane has recently been proposed as a new Ziegler-type olefin polymerization catalyst. For example, JP-A-58-19309, JP-A-60-35006, JP-A-60-35007, JP-A-60-35
008, JP-A-61-130314 and JP-A-2-41303 disclose transition metal compounds having a pentadienyl group such as a cyclopentadienyl group, an alkyl group and / or a halogen atom as a ligand. It is described that a catalyst system comprising a combination of a metallocene compound and an aluminoxane is highly active in the polymerization of α-olefins and the properties of the obtained polymer are excellent.

[0005] Also, Journal of Organometallic Chemis
try, 363 (1989) The _{C12-C14 Cp 2 Zr (CF} 3 SO 3) 2
(THF) and [Cp ₂ Zr (CF ₃ SO ₃ ) (bipy)] ⁺ CF ₃ SO
₃ ^- are disclosed, the two compounds olefin polymerization activity is low compared to the cyclopentadienyl compound as described above. When the concentration of aluminoxane is low, the olefin polymerization activity is remarkably low.

Under these circumstances, it has been desired to develop a new transition metal compound which is excellent in olefin polymerization activity and can be used as an olefin polymerization catalyst component having excellent properties of the obtained olefin.

[0007]

An object of the present invention is to provide a novel transition metal compound which can be a catalyst component for olefin polymerization having excellent olefin polymerization activity, and to provide a catalyst component comprising the transition metal compound. And

[0008]

SUMMARY OF THE INVENTION The transition metal compound according to the present invention is a novel transition metal compound represented by the following general formula [I].

[0009]

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(In the formula [I], M is a group IVB transition metal, Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton are substituents. And Cp ¹ and Cp ² may be bonded via an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group. R ¹ is substituted with an alkyl group or a halogen atom. X ¹ is OR ¹ , S (O) _q R ¹ , Si is an alkyl group, an aryl group, an aryl group substituted with a halogen atom or an alkyl group.
A R ¹ _3, PR ¹ ₃ or _{^{P (O) R 1 3,}} q is 0, 1
Or 2. ) Such a transition metal compound can be used as an olefin polymerization catalyst in combination with an organic aluminum oxy compound.

The catalyst component for olefin polymerization according to the present invention
Is composed of a transition metal compound represented by the following general formula [II].
It is characterized by that.

[0012]

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(In the formula [II], M is a group IVB transition gold
And Cp ¹ and Cp ^{2 each} have a cyclopentadienyl skeleton.
Which have these cyclopentadienyl skeletons.
To group may have a substituent, and the Cp ¹ and Cp ²
Is an alkylene group, a substituted alkylene group, a silylene group,
It may be bonded through a silylene group. R ² is Al
With a kill group, aryl group, halogen atom or alkyl group
A substituted aryl group, wherein X ² is SO ₃ R ² , R ² ,
_{^{OR 2, NR 2 2, S}} (O) q R 2, SiR 2 3, PR 2 3,
P (O) a R ² _3, or a halogen atom, q is 0, 1
Or 2. )

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the novel transition metal compound according to the present invention and its use will be specifically described. The transition metal compound according to the present invention is a novel transition metal compound represented by the following general formula [I].

[0015]

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(In the formula [I], M is a group IVB transition metal, Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton, and these groups having a cyclopentadienyl skeleton are substituents. And Cp ¹ and Cp ² may be bonded via an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group. R ¹ is substituted with an alkyl group or a halogen atom. alkyl group, an aryl group, an aryl group substituted by a halogen atom or an alkyl group, X ¹ is _{^{oR 1, S (O) q}} R 1, SiR 1 3,
A PR ¹ ₃ or _{^{P (O) R 1 3,}} q is 0, 1 or
2. ) In the above formula [I], M is the periodic table IV
Group B transition metals, specifically, zirconium,
Titanium or hafnium.

Cp ¹ and Cp ² are groups having a cyclopentadienyl skeleton. Examples of the group having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group and an ethylcyclopentadienyl group. Groups, alkyl-substituted cyclopentadienyl groups such as n-butylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, fluorenyl group, etc. can do.

Of these, an alkyl-substituted cyclopentadienyl group and an indenyl group are preferred. These groups having a cyclopentadienyl skeleton may be bonded via an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group. Examples of the alkylene group include an ethylene group and a propylene group. Examples of the substituted alkylene group include an isopropylidene group and a diphenylmethylene group. Examples of the substituted silylene group include a dimethylsilylene group.

R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom or an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and an isopropyl group. And a butyl group, which may be substituted with a halogen atom. Examples of the aryl group include a phenyl group and a tolyl group, which may be substituted with a halogen atom or an alkyl group.

[0020]SO _Three R ¹ The group represented by
Sulfonato group, p-toluenesulfonato group, trifluoro
Methanesulfonato group, benzenesulfonato group, trimethyl
Rubenzenesulfonato group, triisopropylbenzenes
Ruphonato group, p-chlorobenzenesulfonato group, pentaf
And a fluorobenzenesulfonato group. X
¹ Is OR ¹ , S (O) _q R ¹ , SiR ¹ _Three , PR ¹ _Three There
Is P (O) R ¹ _Three And q is 0, 1 or 2.

Examples of the group represented by OR ¹ include a methoxy group, an ethoxy group and a propoxy group. S
The group represented by (O) _q R ^1, methylmercapto group, thiophenyl group, a methyl sulfone group, and the like methyl sulfoxide group. The group represented by SiR ¹ _3, and the like trimethylsilyl group.

[0022] As the group represented by PR ¹ ₃ or P (O) R ¹ ₃ are trimethylphosphine group, such as triphenyl phosphine groups. Such a transition metal compound represented by the general formula [I] has excellent stability and, when used as an olefin polymerization catalyst together with an organic aluminum oxy compound, has excellent olefin polymerization activity.

Specific examples of the transition metal compound represented by the above general formula [I] are shown below. Bis (cyclopentadienyl) -zirconium (IV)-(ethoxy) (trifluoromethanesulfonato) ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato)
Methoxy, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methoxy, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) methylmercapto, ethylenebis (indenyl) -zirconium (IV) -(Methanesulfonate)
Methyl mercapto, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) thiophenyl, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) thiophenyl, ethylenebis (indenyl) -zirconium (IV) -(Trifluoromethanesulfonato) methylsulfone, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methylsulfone, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato)
Methylsulfoxide, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) methylsulfoxide, ethylenebis (indenyl) -zirconium (I
V)-(Trifluoromethanesulfonato) trimethylsilyl, ethylenebis (indenyl) -zirconium (IV)-
(Methanesulfonato) trimethylsilyl, ethylenebis (indenyl) -zirconium (IV)-(trifluoromethanesulfonato) trimethylphosphine, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) trimethylphosphine, ethylenebis (indenyl) ) -Zirconium (IV)-(trifluoromethanesulfonato) triphenylphosphine, ethylenebis (indenyl) -zirconium (IV)-(methanesulfonato) triphenylphosphine and the like.

[Catalyst component] The catalyst component for polymerization according to the present invention is represented by the following general formula [II].
Consisting of a transition metal compound.

[0025]

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(In the formula [II], M is a group IVB transition gold
And Cp ¹ and Cp ^{2 each} have a cyclopentadienyl skeleton.
Which have these cyclopentadienyl skeletons.
To group may have a substituent, and the Cp ¹ and Cp ²
Is an alkylene group, a substituted alkylene group, a silylene group,
It may be bonded through a silylene group. R ² is Al
With a kill group, aryl group, halogen atom or alkyl group
A substituted aryl group, wherein X ² is SO ₃ R ² , R ² ,
_{^{OR 2, NR 2 2, S}} (O) q R 2, SiR 2 3, PR 2 3,
P (O) a R ² _3, or a halogen atom, q is 0, 1
Or 2. ) In the above formula [II], M is a periodic rule.
A transition metal belonging to Group IVB of the Table, specifically, zirconium
, Titanium or hafnium.

Cp ¹ and Cp ^{2 each} have a cyclopentadienyl skeleton
Group having a cyclopentadienyl skeleton
Are, for example, cyclopentadienyl group, methyl
Clopentadienyl group, ethylcyclopentadienyl
Group, n-butylcyclopentadienyl group, dimethylcyclo
Pentadienyl group, trimethylcyclopentadienyl
Groups, pentamethylcyclopentadienyl groups, etc.
Substituted cyclopentadienyl group, indenyl group, fluoro
A phenyl group and the like can be exemplified.

Among these, alkyl-substituted cyclopenes
Tadienyl groups and indenyl groups are preferred. These shiks
The group having a lopentadienyl skeleton is an alkylene group,
Via a substituted alkylene group, a silylene group, or a substituted silylene group
They may be combined. Ethylene as the alkylene group
Group, a propylene group, and the like.
Isopropylidene group, diphenylmethylene group, etc.
And the substituted silylene group is dimethylsilylene.
And the like.

R ² represents an alkyl group, an aryl group, a halogen
An aryl group substituted with an atom or an alkyl group,
Examples of the alkyl group include a methyl group, an ethyl group, and a propyl
Group, isopropyl group, butyl group and the like. Ants
Examples of the phenyl group include a phenyl group and a tolyl group.
Which are substituted with halogen atoms or alkyl groups.
May be.

X ² is SO ₃ R ² , R ² , OR ² , NR ²
_{2, S (O) q R} 2, SiR 2 3, PR 2 3, P (O) R 2 3 Oh
Or q is 0, 1 or 2.
You. The group represented by SO ₃ R ² includes methanesulfonate
G, p-toluenesulfonato, benzenesulfonato
Group, trimethylbenzenesulfonato group, triisopropyl
Benzenesulfonato group, p-chlorobenzenesulfonato
Group, pentafluorobenzenesulfonato group, etc.
It is.

The group represented by OR ² includes methoxy
Group, ethoxy group, propoxy group and the like. NR
Examples of the group represented by ² _2, dimethylamide group, diethyl
Luamide group and the like. S (O) _q represented by R ²
Examples of the group include a methyl mercapto group, a thiophenyl group,
Tylsulfone group, methylsulfoxide group, etc.
You.

[0032] The group represented by SiR ² _3, trimethylene
Tilsilyl group and the like. PR ² ₃ or P (O) R
Examples of the group represented by ² _3, trimethylphosphine group, DOO
And a triphenylphosphine group. halogen
Is fluorine, chlorine, bromine and iodine. Such one
The transition metal compound represented by the general formula [II] has excellent stability.
Together with the organic aluminum oxy compound
When used as a refining polymerization catalyst, olefin polymerization activity
Is excellent.

The transition gold represented by the above general formula [II]
The specific example of a genus compound is shown. Bis (cyclopentadie
Nyl) -zirconium (IV) -bis (methanesulfona
G), bis (cyclopentadienyl) -zirconium (I
V) -bis (p-toluenesulfonato), bis (cyclopen
Tadienyl) -zirconium (IV) -bis (benzenesul
Honato), bis (cyclopentadienyl) -zirconium
(IV) -bis (2,4,6-trimethylbenzenesulfona
G), bis (cyclopentadienyl) -zirconium (I
V) -bis (2,4,6-triisopropylbenzenesulfona
G), bis (cyclopentadienyl) -zirconium (I
V) -bis (pentafluorobenzenesulfonato), bis
(Cyclopentadienyl) -zirconium (IV) -benze
Bisulfonatomonochloride, bis (cyclopentadienyl)
Le) -zirconium (IV) -2,4,6-trimethylbenzenes
Ruphonatomonochloride, bis (cyclopentadienyl)
-Zirconium (IV) -2,4,6-triisopropylbenzene
Sulfonatomonochloride, bis (cyclopentadienyl)
Le) -zirconium (IV) -pentafluorobenzenesul
Honatomonochloride, bis (1,3-dimethylcyclopenta
Dienyl) -zirconium (IV) -bis (benzenesulfo
Nato), bis (1,3-dimethylcyclopentadienyl)-
Zirconium (IV) -bis (p-toluenesulfonato),
Bis (1,3-dimethylcyclopentadienyl) -zirconi
(IV) -bis (2,4,6-trimethylbenzenesulfona
G), bis (1,3-dimethylcyclopentadienyl) -di
Ruconium (IV) -bis (2,4,6 -triisopropylben
Zensulfonato), bis (1,3-dimethylcyclopentadi)
Enyl) -zirconium (IV) -bis (pentafluorobe
Nsensulfonato), bis (1,3-dimethylcyclopentane)
Dienyl) -zirconium (IV) -benzenesulfonatomo
Nochloride, bis (1,3-dimethylcyclopentadienyl
Le) -zirconium (IV) -2,4,6-trimethylbenzenes
Ruphonatomonochloride, bis (1,3-dimethylcyclopen
Tadienyl) -zirconium (IV) -2,4,6-triisopro
Pyrbenzenesulfonatomonochloride, bis (1,3-dimethyl
Tylcyclopentadienyl) -zirconium (IV) -pen
Tafluorobenzenesulfonatomonochloride, ethylene
Bis (indenyl) -zirconium (IV) -bis (methane
Sulfonato), ethylenebis (indenyl) -zirconi
(IV) -bis (p-toluenesulfonato), ethylene
Bis (indenyl) -zirconium (IV) -bis (p-chloro
Rubenzenesulfonato), ethylenebis (indenyl)
-Zirconium (IV) -methanesulfonatomonochloride,
Ethylene bis (indenyl) -zirconium (IV) -p-to
Ruensulfonatomonochloride, ethylene bis (indene
Nyl) -zirconium (IV)-(methanesulfonato) methyl
, Ethylenebis (indenyl) -zirconium (IV)-
(Trifluoromethanesulfonato) phenyl, ethylene
Bis (indenyl) -zirconium (IV)-(methanesulfur
(Honato) phenyl, ethylenebis (indenyl) -zyl
Conium (IV)-(methanesulfonato) methoxy, ethi
Lenbis (indenyl) -zirconium (IV)-(methane
Sulfonato) dimethylamide, ethylene bis (indeni
Le) -zirconium (IV)-(methanesulfonato) methyl
Mercapto, ethylenebis (indenyl) -zirconium
(IV)-(methanesulfonato) thiophenyl, ethyl
Nbis (indenyl) -zirconium (IV)-(methanes
Ruphonato) methyl sulfone, ethylene bis (indeni
Le) -zirconium (IV)-(methanesulfonato) methyl
Sulfoxide, ethylenebis (indenyl) -zirconi
(IV)-(methanesulfonato) trimethylsilyl,
Ethylenebis (indenyl) -zirconium (IV)-(meth
Tansulfonato) trimethylphosphine, ethylenebis
(Indenyl) -zirconium (IV)-(methanesulfona
G) triphenylphosphine, ethylene bis (indeni
Le) -zirconium (IV) -bis (benzenesulfona
G), ethylenebis (indenyl) -zirconium (I
V) -bis (2,4,6-trimethylbenzenesulfonato), d
Tylene bis (indenyl) -zirconium (IV) -bis
(2,4,6-triisopropylbenzenesulfonato), ethyl
Lenbis (indenyl) -zirconium (IV) -bis (pe
N-fluorobenzenesulfonato), ethylenebis (a
Ndenyl) -zirconium (IV) -benzenesulfonatomo
Nochloride, ethylenebis (indenyl) -zirconium
(IV) -2,4,6-trimethylbenzenesulfonatomonoc
Chloride, ethylenebis (indenyl) -zirconium (I
V)-2,4,6-triisopropyl Baie emissions Zen sulfonato mono click
Chloride, ethylenebis (indenyl) -zirconium (I
V) -pentafluorobenzenesulfonatomonochloride,
Ethylene bis (indenyl) -hafnium (IV) -bis
(Methanesulfonato), ethylenebis (indenyl)-
Hafnium (IV) -bis (p-toluenesulfonato), d
Tylene bis (indenyl) -hafnium (IV) -bis (p-
Chlorobenzenesulfonato), ethylenebis (indene)
Le) -hafnium (IV) -methanesulfonatomonochloride
De, ethylenebis (indenyl) -hafnium (IV) -p-
Toluenesulfonatomonochloride, ethylenebis (in
Denenyl) -titanium (IV) -bis (methanesulfonato), d
Tylene bis (indenyl) -titanium (IV) -bis (p-tolu
Ensulfonato), ethylenebis (indenyl) -tita
(IV) -bis (p-chlorobenzenesulfonato), ethyl
Lenbis (indenyl) -titanium (IV) -methanesulfona
Tomonochloride, ethylenebis (indenyl) -titanium
(IV) -p-toluenesulfonatomonochloride, dimethyl
Silylbis (indenyl) -zirconium (IV) -bis
(Methanesulfonato), dimethylsilylbis (indeni
Le) -zirconium (IV) -bis (p-toluenesulfona
G), dimethylsilylbis (indenyl) -zirconium
(IV) -bis (p-chlorobenzenesulfonato),
Tylsilylbis (indenyl) -zirconium (IV) -meth
Tansulfonatomonochloride, dimethylsilylbis (I
Ndenyl) -zirconium (IV) -p-toluenesulfonate
Monochloride, dimethylsilylbis (indenyl) -di
Ruconium (IV) -bis (benzenesulfonato)
Tylsilylbis (indenyl) -zirconium (IV) -bi
(2,4,6-trimethylbenzenesulfonato), dimethyl
Silylbis (indenyl) -zirconium (IV) -bis
(2,4,6-triisopropylbenzenesulfonato),
Tylsilylbis (indenyl) -zirconium (IV) -bi
(Pentafluorobenzenesulfonato), dimethyl
Rilbis (indenyl) -zirconium (IV) -benzene
Sulfonatomonochloride, dimethylsilylbis (indene
Nyl) -zirconium (IV) -2,4,6-trimethylbenzene
Sulfonatomonochloride, dimethylsilylbis (indene
Nyl) -zirconium (IV) -2,4,6-triisopropyl
Nsensulfonatomonochloride, dimethylsilylbis
(Indenyl) -zirconium (IV) -pentafluorobe
Nsensulfonatomonochloride, diphenylsilylbis
(Indenyl) -zirconium (IV) -bis (benzenes
Ruphonato), diphenylsilylbis (indenyl) -di
Ruconium (IV) -bis (2,4,6-trimethylbenzenes
Ruphonato), diphenylsilylbis (indenyl) -di
Ruconium (IV) -bis (2,4,6-triisopropylben
Sensulfonato), diphenylsilylbis (indene)
) -Zirconium (IV) -bis (pentafluorobenzene)
Sulfonato), diphenylsilylbis (indenyl)
-Zirconium (IV) -benzenesulfonatomonochlory
Do, diphenylsilylbis (indenyl) -zirconium
(IV) -2,4,6-trimethylbenzenesulfonatomonoc
Loride, diphenylsilylbis (indenyl) -zirco
Bromide (IV)-2,4,6-Toriisopu b pill benzenesulfonyl
Natomonochloride, diphenylsilylbis (indeni
Le) -zirconium (IV) -pentafluorobenzenesul
Honatomonochloride, diphenylmethylenebis (indene
Nyl) -zirconium (IV) -bis (methanesulfona
G), diphenylmethylenebis (indenyl) -zirco
(IV) -bis (p-toluenesulfonato), dife
Nylmethylenebis (indenyl) -zirconium (IV)-
Bis (p-chlorobenzenesulfonato), diphenylmethyl
Lenbis (indenyl) -zirconium (IV) -methanes
Ruphonatomonochloride, diphenylmethylenebis (in
Denenyl) -zirconium (IV) -p-toluenesulfonatomo
Nochloride and the like.

[Production Method] The novel transition metal compound according to the present invention includes, for example, a compound represented by the following general formula [III]:

[0035]

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(In the formula [III] , M and Cp ¹ , Cp
² is the same as in the formula [I], and Cp ¹ and Cp ² may be bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like. Y ¹ is a halogen atom, Y ² is OR ¹ similar to X ^{1 in the} formula [I] ,
_{^{S (O) q R 1,}} SiR 1 3, a PR ¹ ₃ or P (O) R ¹ _3. ) From a sulfonic acid derivative represented by the following general formula [IV] , R ³ SO ₃ Z ... [IV] (In the formula [IV] , R ³ is the same alkyl group and halogen atom as R ^{1 in the} formula [I].) Is an alkyl group, an aryl group, an aryl group substituted with a halogen atom or an alkyl group, and Z is an alkali metal such as Ag or Na or K, or a triatom such as triethylammonium or tri (n-octyl) ammonium. It is an alkyl ammonium group.) It can be produced according to the following reaction formula.

[0037]

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In the above formula [I], X ¹ is Y ^{2
Similar, OR 1, S (O)} q R 1, SiR 1 3, PR 1 3 Ah and
Rui is P (O) R ¹ _3. Transition metal used in the present invention
Compound [II] is represented by the general formula [III]
In the compound, Y ² is the same as R ² or OR as X ^{2 of the} formula [II].
_{^{2, NR 2 2, S (}} O) q R 2, SiR 2 3, PR 2 3, P
(O) a R ² _3, or a halogen atom, the general formula
In the sulfonic acid derivative represented by [IV], R ³ is a group represented by the formula
The same alkyl group, aryl group and halogen group as R ^{2 in} [II]
Is an aryl group substituted with an alkyl atom or an alkyl group
Except that, the same as the new transition metal compound [I]
It can be manufactured by a manufacturing method.

The reaction conditions in this reaction vary depending on the composition of the compound [I] or [II] to be obtained. Usually, the compound [IV] is 1 to 10 moles, preferably 1 to 10 times the mole of the compound [III] . It is used in an amount of 1 to 3 moles. The reaction temperature is -20 to 180 ° C, preferably 0 to 13 ° C.
The reaction temperature is desirably 0 ° C., and the reaction time is desirably 0.5 to 48 hours, preferably 2 to 12 hours.

The solvent used in the reaction includes aliphatic hydrocarbons such as hexane and decane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride; acetone; Ketones such as methyl isobutyl ketone and acetonitrile are used. Of these, toluene and xylene are particularly preferred. Such a hydrocarbon solvent is generally used in an amount of 1 to 1000 times the amount of the compound [III] ,
Preferably, it is used in an amount of 50 to 500 times.

According to the above-described production method, a desired transition metal compound can be produced in a high yield. The transition metal compound thus obtained can be filtered, and the obtained filtrate can be concentrated under reduced pressure and recrystallized, or isolated and purified by a method such as sublimation.

[Catalyst] The transition metal compound represented by the above general formula [I] or [II]
The product can be used as an olefin polymerization catalyst in combination with an organic aluminum oxy compound. In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" includes not only homopolymers but also copolymers. It may be used for the purpose.

[0043] The [A] [B] an organic aluminum oxy compound used as an olefin polymerization catalyst together with the transition metal compound may be a conventionally known aluminoxane, also exemplified in JP-A-2-78687 It may be a benzene-insoluble organic aluminum oxy compound as described above. A conventionally known aluminoxane can be produced, for example, by the following method.

(1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous chloride water A method of adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium such as a hydrate and reacting the suspension to recover a hydrocarbon solution.

(2) A method in which water, ice or steam is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover a hydrocarbon solution. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in the solvent. Specific examples of the organoaluminum compound used in producing aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum,
trialkylaluminum such as sec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum chloride Dialkylaluminum halides such as diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; diethyl Dialkyl aluminum Ally Loki Sid such Rumi iodonium phenoxide and the like.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred.
Further, as the organoaluminum compound, the following general formula
Isoprenyl aluminum represented by [V] can also be used. _{(I-C 4 H 9)} X Al y (C 5 H 10) Z ... [V] in (formula [V], x, y, z are positive numbers, z ≧
2x. ) The above-mentioned organoaluminum compounds are used alone or in combination.

Solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrocarbons, cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil or the above aromatic hydrocarbons, aliphatic hydrocarbons,
A hydrocarbon solvent such as an alicyclic hydrocarbon halide, especially a chlorinated product or a brominated product, may be used. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

Such an olefin polymerization catalyst containing [A] a transition metal compound and [B] an organoaluminum oxy compound has excellent olefin polymerization activity. The transition metal compound [A] and / or the organic aluminum oxy compound [B] as described above may be used by being supported on a carrier. [Polymerization method] In the olefin polymerization method according to the present invention, the olefin is polymerized in the presence of the above-mentioned [A] transition metal compound and [B] an organoaluminum oxy compound. In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.

In the liquid phase polymerization, an inert hydrocarbon solvent or olefin itself can be used as a solvent. Specific examples of the hydrocarbon medium include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane Hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and petroleum fractions such as gasoline, kerosene and light oil.

In the present invention, when carrying out the slurry polymerization method, the polymerization temperature is usually in the range of -50 to 100 ° C, preferably 0 to 90 ° C. When carrying out the liquid phase polymerization method, the polymerization temperature is preferably in the range of usually 0 to 250 ° C, preferably 20 to 200 ° C.
When the gas phase polymerization method is carried out, the polymerization temperature is usually 0.
To 120 ° C, preferably 20 to 100 ° C.

In the present invention, when polymerizing an olefin by a slurry polymerization method, a solution polymerization method or a gas phase polymerization method,
[A] The transition metal compound has a concentration of the transition metal atom in the polymerization reaction system of usually 10 ^-8 to 10 ^-1 gram atom / liter, preferably 10 ^{-7 to} 5 × 10 ^-2 gram atom / liter. Preferably, it is used in an amount. [A] Atomic ratio of transition metal in transition metal compound to aluminum in [B] organoaluminum oxy compound (Al / transition metal)
Is usually 10 to 10000, preferably 20 to 5000
It is desirable that

The polymerization pressure is usually from normal pressure to 100 kg.
/ Cm ² , preferably normal pressure to 50 kg / cm ² , and the polymerization can be carried out in any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

The olefins that can be polymerized by the olefin polymerization method according to the present invention include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, and 4-olefin. Methyl-1
-Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 3 to 20 carbon atoms, for example, cyclopentene, cycloheptene, norbornene, 5- Methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. . Further, styrene, vinylcyclohexane, diene and the like can be used.

In the present invention, an α-olefin may be preliminarily polymerized on the olefin polymerization catalyst during the polymerization of the olefin. In the prepolymerization, the olefin polymer is
0.05 to 500 g, preferably 0.1 to 300 g, more preferably 0.2 to 10 g per gram of the olefin polymerization catalyst.
It is desirable to prepolymerize in an amount of 0 g.

Examples of the olefin for prepolymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene,
Examples thereof include 1-tetradecene, 3-methyl-1-butene, and 3-methyl-1-pentene. Preferred among these are olefins used during polymerization.

[0057]

The novel transition metal compound according to the present invention
Transition metallization used as [I] or a polymerization catalyst component
The compound [II] shows excellent polymerization activity when used as an olefin polymerization catalyst together with an organoaluminum oxy compound, and has excellent properties of the obtained polymer.

[0058]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition,
In the present invention, the melt flow rate (MFR), intrinsic viscosity [η], stereoregularity (mm triad fraction), ethylene content, and reduced specific viscosity (RSV) are measured as follows.

[Melt Flow Rate (MFR)] Measured at 190 ° C. under a load of 2.16 kg according to ASTM D785. [Intrinsic viscosity [η]] It was measured in decalin at 135 ° C. and expressed in dl / g. [Stereoregularity (mm triad fraction)] The isotactic fraction (mm triad fraction) in the propylene chain was measured by ¹³ C-NMR.

For ¹³ C-NMR, about 150 mg of a sample is dissolved in a mixed solution of hexachlorobutadiene and deuterated benzene (0.5 ml and 0.1 ml, respectively), and the mixture is usually dissolved in a JEOLGX-50.
Using an apparatus, the measurement was performed at a measurement frequency of 125.65 MHz, a spectrum width of 8800 Hz, a pulse repetition time of 4.0 seconds, a pulse angle of 45 °, and a measurement temperature of 95 to 110 ° C. [Ethylene content] The ethylene content of the copolymer was determined by measuring the ¹³ C-NMR spectrum of a sample in which about 200 mg of the copolymer was uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube, at a measurement temperature of 120 ° C. , Measurement frequency 25.05MH
z, spectrum width 1500 Hz, pulse repetition time 4.2
The measurement was performed under the measurement conditions of a second and a pulse width of 6 μsec.

[Reduced specific viscosity (RSV)] Measured by dissolving in decalin at 135 ° C. at a concentration of 0.1 dl / g, and expressed in dl / g. [Synthesis of transition metal compound]

[0062]

Example 1 [Production of bis (cyclopentadienyl) -zirconium (IV) -bis (methanesulfonato) (Compound No. 100)] Dry acetonitrile was placed in a glass reactor having an internal volume of 300 ml which had been sufficiently purged with nitrogen. 100 ml and 1.24 g (4.25 mmol) of zirconocene dichloride were charged and stirred at room temperature until homogeneous. 50 ml of acetonitrile solution of 1.74 g (8.57 mmol) of silver methanesulfonate was added dropwise to this reaction solution at room temperature over 10 minutes, and the reaction was continued at room temperature for 2 hours. The produced salt was filtered with a glass filter under a stream of nitrogen, and the obtained filtrate was concentrated under reduced pressure.
The obtained solid was recrystallized from toluene to give 1.04 g of colorless needle crystals (yield; 60%, melting point: 145 to 145).
148 ° C).

The ¹ H-NM of the thus obtained crystal
Table 1 shows the results of R spectrum and elemental analysis.

[0064]

Example 2 [Production of bis (cyclopentadienyl) -zirconium (IV) -bis (p-toluenesulfonato) (Compound No. 101)] Dried in a glass reactor having an internal volume of 200 ml and sufficiently purged with nitrogen. 50 ml of acetonitrile and 1.05 g (3.6 mmol) of zirconocene dichloride were charged and stirred at room temperature until homogeneous. To this reaction solution was added a solution of 2.04 g (7.3 mmol) of silver p-toluenesulfonate in acetonitrile 1
After dropwise adding 00 ml at room temperature for 10 minutes, the reaction was continued at 60 ° C. for 2 hours. The produced salt was filtered with a glass filter under a stream of nitrogen, and the obtained filtrate was concentrated under reduced pressure.
The obtained solid was recrystallized from toluene to obtain 1.39 g of pale yellow needle-like crystals (yield: 69%, melting point: 2).
13-216 ° C).

The ¹ H-NM of the crystal thus obtained was
Table 1 shows the results of R spectrum and elemental analysis.

[0066]

Example 3 [Production of bis (cyclopentadienyl) -zirconium (IV) -bis (2,4,6-trimethylbenzenesulfonato) (Compound No. 104)] A glass having an inner volume of 500 ml sufficiently purged with nitrogen. 100 ml of dry acetonitrile and bis (cyclopentadienyl) -zirconium (IV) -dichloride.
58 g (5.4 mmol) were charged and stirred at room temperature until homogeneous. To this reaction solution, a solution of 3.70 g (10.8 mmol) of silver 2,4,6-trimethylbenzenesulfonate in 50 ml of acetonitrile was added dropwise over 30 minutes. After the completion of the dropwise addition, the temperature was raised to 60 ° C., and the reaction was continued for 2 hours, then, cooled to room temperature, and the generated salt was filtered. 300 ml of acetonitrile was added to the obtained salt, and the mixture was stirred under reflux for 30 minutes, and filtered while hot to remove silver chloride. The filtrate was concentrated under reduced pressure, and recrystallized by adding 100 ml of toluene to obtain 1.2 g of needle crystals (yield: 38%, melting point: 250 to 251 ° C).

The ¹ H-NM of the thus obtained crystal
Table 1 shows the results of R spectrum and elemental analysis.

[0068]

Example 4 [Production of bis (cyclopentadienyl) -zirconium (IV)-(ethoxy) (trifluoromethanesulfonato) (Compound No. 302)] In a glass reactor having an inner volume of 500 ml sufficiently purged with nitrogen. , 350 ml of dry toluene and 5.27 g of bis (cyclopentadienyl) -zirconium (IV) -dichloride
And stirred at room temperature until uniform. After adding 1.16 ml of ethyl alcohol to the reaction solution, triethylamine (3.77 ml) was slowly added. 50 ℃
Then, after reacting for 1 hour, the mixture was cooled to room temperature, and the generated salt was removed by filtration. After concentrating the obtained filtrate under reduced pressure, 40 ml of hexane was added and the mixture was cooled to -20 ° C, and bis (cyclopentadienyl) was recovered from the hexane layer.
4.00 g of white plate crystals of -zirconium (IV)-(ethoxy) chloride were obtained (yield; 74%).

Into a glass reactor having an internal volume of 500 ml which was sufficiently purged with nitrogen, 200 ml of dry toluene and 4.00 g of bis (cyclopentadienyl) -zirconium (IV)-(ethoxy) chloride were charged, and the mixture was made uniform. Up to 6
Stirred at 0 ° C. To this reaction solution was added a solution of silver trifluoromethanesulfonate in toluene (0.16 mmol / ml).
4.4 ml were added dropwise over 1 hour. After continuing the reaction for an additional hour, the mixture was cooled to room temperature, and the generated salt was removed by filtration.
After concentrating the obtained filtrate under reduced pressure, 50 ml of hexane was used.
Was added and the mixture was cooled to −20 ° C., and 2.40 g of white crystals were obtained from the hexane layer (yield; 44%, melting point; 99 to 100 ° C. (decomposition)).

The ¹ H-NM of the crystal thus obtained was
Table 1 shows the results of R spectrum and elemental analysis.

[0071]

[Table 1]

[Polymerization of ethylene]

[0073]

In Example 5 See prolonged polymerization activity purpose, the catalyst preparation method such that the supported catalyst to maintain a good suspension over a long time, was adopted polymerization method. 5.5% by weight of water was adsorbed on fine-particle silica (F-948 manufactured by Fuji Devison Co., Ltd. baked at 700 ° C. for 7 hours), and 1/2 mole of aluminoxane of silica (manufactured by Schering Co., Ltd.) was adsorbed. Methylaluminoxane was dried and redissolved in toluene) and reacted in toluene at 80 ° C. for 3 hours to obtain an aluminoxane component.

A 1-liter glass flask with an internal volume of 1 liter, which is sufficiently purged with nitrogen, is charged with 1 liter of purified n-decane, and heated to 75 ° C. while flowing hydrogen at 0.3 to 2 liter / hr and ethylene at 250 liter / hr. Hold for 10 minutes. Then, the bis (cyclopentadienyl)-obtained in Example 1 was obtained by adding 0.5 mg atom of triisobutylaluminum in terms of aluminum atom and 5.0 mg atom of the aluminoxane component prepared above in terms of aluminum atom. Zirconium (IV) -bis (methanesulfonate)
(Compound No. 100) was calculated to be 0.0 in terms of zirconium atom.
Two milligram atoms were charged. After polymerization at 75 ° C. for 2 hours, the polymerization was stopped by adding a small amount of isobutanol.

A small amount of diluted hydrochloric acid was added to the obtained polymer suspension, and the mixture was filtered through a glass filter to remove n-decane as a solvent, washed with hexane and dried at 80 ° C. overnight.
The resulting polyethylene weighed 8.8 g and had a polymerization activity of 2
20 g / mmol-Zr / hr and an MFR of 0.45
g / 10 minutes.

[0076]

Reference Examples 1 to 4 Example 5 was repeated except that the zirconium compounds shown in Table 2 were used instead of bis (cyclopentadienyl) -zirconium (IV) -bis (methanesulfonato) (Compound No. 100). Was polymerized in the same manner as described above. The yield and physical properties of the polymer thus obtained are shown in Table 2.

[0077]

[Table 2]

[Polymerization of ethylene-propylene]

[0079]

EXAMPLE 6 500 ml of purified toluene was charged into a 500-liter glass reactor which had been sufficiently purged with nitrogen.
A mixed gas of ethylene and propylene (ethylene / propylene = 40/60 (mol%)) was passed, and the mixture was kept at 40 ° C. for 10 minutes while stirring at 800 rpm. Then
Methylaluminoxane (Methylaluminoxane manufactured by Schering Co., Ltd., which was dried and redissolved in toluene) was charged with 1.25 mg of atoms in terms of aluminum atoms. Further, 0.0005 mg of bis (cyclopentadienyl) -zirconium (IV) -bis (p-toluenesulfonato) (Compound No. 101) obtained in Example 2 was charged in terms of zirconium atoms. After conducting polymerization at 40 ° C. and normal pressure for 30 minutes, a small amount of isobutanol was added to terminate the polymerization.

After the reaction, the reaction solution was poured into an aqueous solution of diluted hydrochloric acid to remove the catalyst residue, and the toluene layer was concentrated.
It dried under reduced pressure at ℃ overnight. Table 3 shows the yield and physical properties of the copolymer thus obtained.

[0081]

Reference Examples 5 to 7 The procedure was carried out except that the zirconium compounds described in Table 3 were used instead of bis (cyclopentadienyl) -zirconium (IV) -bis (p-toluenesulfonato) (compound No. 101). Copolymerization of ethylene and propylene was carried out in the same manner as in Example 6 . Table 3 shows the yield and physical properties of the copolymer thus obtained.

[0082]

[Table 3]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Mitsuaki Mukoyama 1-15-18 Minamiogikubo, Suginami-ku, Tokyo (56) References Special Tables Sho 63-501962 (JP, A) US Patent 3782917 (US, A) "J. Chem. Soc., Chem. Commun.," (1991), No. 2, pages 134-136 "Organometallics," (1990), Vol. 9, No. 4, pages 1290-1295 "Organometallics," (1989), Vol. 8, No. 2, pages 324-330, "J. Organomet. Chem.," (1986), Vol. 302, No. 2, pages 201-210, "J. Organomet. Chem.," (1986), Vol. 302, No. 2, pages 193-200 "J. Organomet. Chem.," (1985), Vol. 284, No. 3, pages 395-402, "J. Inst. Chem. (India)," (1982), Vol. 54, No. 3, pages 143-145, "J. Organomet. Chem.," (1981), vol. 206, No. 1, pages 69-75 "Z. Kristrallog r.," (1980), Vol. 153, No. 3-4, pages 307-315 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07F 17/00 C08F 4/642 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A novel transition metal compound represented by the following general formula [I]. Embedded image (In the formula [I], M is a group IVB transition metal,
p ¹ and Cp ² are groups having a cyclopentadienyl skeleton; these groups having a cyclopentadienyl skeleton may have a substituent; and Cp ¹ and Cp ² are an alkylene group, They may be bonded via an alkylene group, a silylene group, or a substituted silylene group. R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom or an alkyl group, X ¹ is _{^{OR 1, S (O) q}} R 1, SiR 1 3, PR ¹ ₃ Oh
Rui is _{^{P (O) R 1 3,}} q is 0, 1 or 2. ) 2. An olefin polymerization catalyst component comprising a transition metal compound represented by the following general formula [II] . Embedded image (In the formula [II] , M is a group IVB transition metal,
p ¹ and Cp ² are groups having a cyclopentadienyl skeleton; these groups having a cyclopentadienyl skeleton may have a substituent; and Cp ¹ and Cp ² are an alkylene group, They may be bonded via an alkylene group, a silylene group, or a substituted silylene group. R ² is kill group, an
Substituted with a reel group, a halogen atom or an alkyl group
X ² is an SO ₃ R ² , R ² , OR ² , N ^{2
_{R 2 2, S (O)}} q R 2, SiR 2 3, PR 2 3, P (O) R 2 3
Alternatively, it is a halogen atom, and q is 0, 1 or 2. )