JPH0812718A - Catalyst component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain a catalyst component which enables an olefin polymer having a high mol.wt. and a relatively wide mol.wt. distribution to be produced at a high yield with a small amt. of a modified aluminum compd. used. CONSTITUTION:A catalyst component for olefin polymn. is prepd. by bringing a compd. of the formula: Me<1>R<1>p(OR<2>)qXr(OSiR<3>R<4>R<-5>)4-p-q-r (wherein R<1>, R<2>, R<3>, R<4> and R<5> are each independently a 1-24C hydrocarbon group; X is halogen; Me<1> is Zr, Ti, or Hf; and p, q, and r are each an integer satisfying the relations: 0:Sp<4, 0<q<4, 0<=r<4, and 0<=p+q<4), a compd. of the formula: Me<2>R(OR ')nXz-m-n, (wherein R and R' are each independently a 1-24C hydrocarbon group; X is halogen; Me<2> is an element of the group I, II, or III; z is the valency of Me<2>; and m and n are each an integer satisfying the relations: 0<=m<=z, 0<=n<=z, and 0<=m+n<=z), and a cyclic org. compd. having at least two conjugated double bonds into contact with each other.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is used for polymerizing or copolymerizing olefins, and has high catalytic efficiency, small amount of modified organoaluminum compound, high molecular weight of the polymer produced, and molecular weight distribution. Relates to a catalyst component for polymerizing olefins, in which a polymer having a relatively wide range and a narrow composition distribution in the case of a copolymer can be produced, and the molecular weight and the molecular weight distribution can be easily controlled. The present invention also relates to a catalyst using this catalyst component and a method for producing an olefin polymer by the catalyst. Here, the olefin polymer is a generic term for a homopolymer and a copolymer of olefins.

[0002]

2. Description of the Related Art Recently, a catalyst comprising a zirconium compound and an aluminoxane has been proposed as a means for obtaining an ethylene polymer having a narrow molecular weight distribution and a narrow composition distribution in an ethylene polymer or an ethylene / α-olefin copolymer ( JP-A-58-19309). By such a method, an ethylene-based copolymer can be obtained in a high yield, and a physical property thereof has a narrow molecular weight distribution, and a copolymer having a narrow composition distribution can be obtained, but a drawback is that the resulting polymer has a low molecular weight. Another drawback is that the amount of aluminoxane used is large.

JP-A-63-234005 proposes to improve the molecular weight of a polymer obtained by using a transition metal compound having a 2,3- and 4-substituted cyclopentadienyl group. Further, JP-A-2-22307 proposes to improve the molecular weight of a polymer by using a hafnium compound having a ligand bonded to at least two bridged conjugated cycloalkadienyl groups. However, the use of hafnium as the transition metal also has the disadvantage that the yield of the obtained polymer is low.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to produce an olefin polymer in a high yield under the condition that the molecular weight distribution is high and the molecular weight distribution is relatively wide, and the amount of the modified organoaluminum compound such as methylaluminoxane used is small. It is intended to provide a catalyst component, a catalyst and a method for producing a polymer using the catalyst.

[0005]

That is, the present invention is as follows.
(1) General formula Me ¹ R ¹ _p (OR ² ) _q X _r (OSiR
_{^{3 R 4 R 5) 4-}} p-q-r compounds represented by (wherein,
R ¹ , R ² , R ³ , R ⁴ and R ⁵ individually have 1 to 1 carbon atoms.
24 hydrocarbon groups, which may be the same or different, X is a halogen atom, Me ¹ is Zr, Ti or Hf, and p, q and r are 0 ≦ p <4, 0 respectively.
≦ q <4, 0 ≦ r <4, 0 ≦ p + q + r <4 integer), (2) General formula Me ² R _m (OR ′) _n X
a compound represented by _z-mn (wherein R and R'are individually a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom,
Me ² is an element of Group I to III of the periodic table, z is the valence of Me ² , and m and n are 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively.
, And 0 ≦ m + n ≦ z), and (3)
The present invention relates to a catalyst component for olefin polymerization, which is obtained by bringing organic compounds which are cyclic and have two or more conjugated double bonds into contact with each other.

The present invention also provides (1) Me ¹ R ¹ _p (OR
_{^{2) q X r (OSiR 3}} R 4 R 5) 4-p-q-r compounds represented by ^{(wherein, R 1, R 2, R} 3, R 4 and R
⁵ are individually hydrocarbon groups having 1 to 24 carbon atoms, which may be the same or different, and X is a halogen atom or Me.
¹ represents Zr, Ti or Hf, and p, q and r are 0 ≦ p <4, 0 ≦ q <4, 0 ≦ r <4 and 0 ≦ p +, respectively.
q + r <4 is an integer), (2) General formula Me ² R
_m (OR ′) _n X _z-m-n (wherein
R and R ′ are independently a hydrocarbon group having 1 to 24 carbon atoms, X
Is a halogen atom, Me ² is an element of Group I to III of the periodic table, z is the valence of Me ² , and m and n are each 0 ≦.
m ≦ z, an integer of 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z), (3) a cyclic organic compound having two or more conjugated double bonds, and (4) an organic aluminum compound and water. The invention relates to a catalyst for polymerization of olefins obtained by bringing modified organoaluminum compounds having an Al-O-Al bond obtained by the above reaction into contact with each other.

The present invention also relates to a method for producing an olefin polymer or copolymer, which comprises polymerizing or copolymerizing an olefin in the presence of the above catalyst.

The olefin polymerization catalyst of the present invention has high catalytic efficiency, a small amount of a modified organoaluminum compound such as aluminoxane, and a high molecular weight polymer.
A polymer having a relatively wide molecular weight distribution and a narrow composition distribution in the case of a copolymer can be produced. Further, when molding a polymer produced by using the olefin polymerization catalyst of the present invention, there is no stickiness in either the inflation method or the T-die method, high-speed molding is possible, and the moldability is extremely good. Is. Further, the formed film is excellent in transparency, anti-blocking property and strength both in the inflation method and in the T-die method, and particularly excellent in the mouth opening property in the inflation method.

The present invention will be described in detail below. First, the component (1) is a compound represented by the following. General formula Me ¹ R
¹ _p (OR ² ) _q X _r (OSiR ³ R ⁴ R ⁵ )
_4-p-q-r Formula WHEREIN: R < ¹ >, R < ² >, R < ³ >, R < ⁴ > and R.
⁵ independently represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 and more preferably 1 to 8 and may be the same or different, and the hydrocarbon group may be a methyl group. , Ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group,
Alkyl groups such as tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group; vinyl group, allyl group Alkenyl groups such as; phenyl groups, tolyl groups, xylyl groups, mesityl groups, indenyl groups, naphthyl groups and other aryl groups; benzyl groups, trityl groups, phenethyl groups, styryl groups, benzhydryl groups,
Examples thereof include aralkyl groups such as phenylbutyl group, phenylpropyl group, and neophyll group. These may have branches. X is a halogen atom of fluorine, iodine, chlorine and bromine, Me ¹ is Zr, Ti or Hf,
Zr is preferred. p, q and r are each 0 ≦
p <4, 0 ≦ q <4, 0 ≦ r <4, 0 ≦ p + q + r <4
Is an integer.

Specific examples of the compound represented by the above general formula include zirconium tri (methoxy) mono (trimethylsilanolate), zirconium tri (methoxy) mono (triethylsilanolate), zirconium tri (methoxy) mono ( Triisopropylsilanolate), zirconium tri (methoxy) mono (tributylsilanolate), zirconium tri (methoxy) mono (tripentylsilanolate), zirconium tri (methoxy) mono (triphenylsilanolate), zirconium tri (methoxy) mono (Tribenzylsilanolate), zirconium tri (methoxy) mono (trinaphthylsilanolate), zirconium tri (methoxy) mono (dimethylethylsilanolate), zirconium tri (methoxy) mono (methyldiethyl) Lanolates),

Zirconium tri (ethoxy) mono (trimethylsilanolate), zirconium tri (ethoxy)
Mono (triethylsilanolate), zirconium tri (ethoxy) mono (triisopropylsilanolate),
Zirconium tri (ethoxy) mono (tributylsilanolate), zirconium tri (ethoxy) mono (tripentylsilanolate), zirconium tri (ethoxy)
Mono (triphenylsilanolate), zirconium tri (ethoxy) mono (tribenzylsilanolate), zirconium tri (ethoxy) mono (trinaphthylsilanolate), zirconium tri (ethoxy) mono (dimethylethylsilanolate), zirconium tri ( Ethoxy)
Mono (methyldiethylsilanolate),

Zirconium tri (propoxy) mono (trimethylsilanolate), zirconium tri (propoxy) mono (triethylsilanolate), zirconium tri (propoxy) mono (triisopropylsilanolate), zirconium tri (propoxy) mono (tributylsilanolate) ), Zirconium tri (propoxy) mono (tripentyl silanolate), zirconium tri (propoxy) mono (triphenylsilanolate), zirconium tri (propoxy) mono (tribenzylsilanolate), zirconium tri (propoxy) mono (trinaphthyl) Silanolate), zirconium tri (propoxy) mono (dimethylethylsilanolate), zirconium tri (propoxy) mono (methyldiethylsilanolate),

Zirconium tri (butoxy) mono (trimethylsilanolate), zirconium tri (butoxy)
Mono (triethylsilanolate), zirconium tri (butoxy) mono (triisopropylsilanolate),
Zirconium tri (butoxy) mono (tributylsilanolate), zirconium tri (butoxy) mono (tripentylsilanolate), zirconium tri (butoxy)
Mono (triphenylsilanolate), zirconium tri (butoxy) mono (tribenzylsilanolate), zirconium tri (butoxy) mono (trinaphthylsilanolate), zirconium tri (butoxy) mono (dimethylethylsilanolate), zirconium tri ( Butoxy)
Mono (methyldiethylsilanolate),

Zirconium tri (phenoxy) mono (trimethylsilanolate), zirconium tri (phenoxy) mono (triethylsilanolate), zirconium tri (phenoxy) mono (triisopropylsilanolate), zirconium tri (phenoxy) mono (tributylsilanolate) ), Zirconium tri (phenoxy) mono (tripentyl silanolate), zirconium tri (phenoxy) mono (triphenylsilanolate), zirconium tri (phenoxy) mono (tribenzylsilanolate), zirconium tri (phenoxy) mono (trinaphthyl) Silanolate), zirconium tri (phenoxy) mono (dimethylethylsilanolate), zirconium tri (phenoxy) mono (methyldiethylsilanolate),

Zirconium di (methoxy) di (trimethylsilanolate), zirconium di (methoxy) di (triethylsilanolate), zirconium di (methoxy)
Di (triisopropylsilanolate), zirconium di (methoxy) di (tributylsilanolate), zirconium di (methoxy) di (tripentylsilanolate),
Zirconium di (methoxy) di (triphenylsilanolate), zirconium di (methoxy) di (tribenzylsilanolate), zirconium di (methoxy) di (trinaphthylsilanolate), zirconium di (methoxy)
Bis (dimethylethylsilanolate), zirconium di (methoxy) bis (methyldiethylsilanolate),

Zirconium di (ethoxy) di (trimethylsilanolate), zirconium di (ethoxy) di (triethylsilanolate), zirconium di (ethoxy)
Di (triisopropylsilanolate), zirconium di (ethoxy) di (tributylsilanolate), zirconium di (ethoxy) di (tripentylsilanolate),
Zirconium di (ethoxy) di (triphenylsilanolate), zirconium di (ethoxy) di (tribenzylsilanolate), zirconium di (ethoxy) di (trinaphthylsilanolate), zirconium di (ethoxy)
Bis (dimethylethylsilanolate), zirconium di (ethoxy) bis (methyldiethylsilanolate),

Zirconium di (propoxy) di (trimethylsilanolate), zirconium di (propoxy) di (triethylsilanolate), zirconium di (propoxy) di (triisopropylsilanolate), zirconium di (propoxy) di (tributylsilanolate) ),
Zirconium di (propoxy) di (tripentyl silanolate), zirconium di (propoxy) di (triphenylsilanolate), zirconium di (propoxy) di (tribenzylsilanolate), zirconium di (propoxy) di (trinaphthylsilanolate) ), Zirconium di (propoxy) bis (dimethylethylsilanolate), zirconium di (propoxy) bis (methyldiethylsilanolate),

Zirconium di (butoxy) di (trimethylsilanolate), zirconium di (butoxy) di (triethylsilanolate), zirconium di (butoxy)
Di (triisopropylsilanolate), zirconium di (butoxy) di (tributylsilanolate), zirconium di (butoxy) di (tripentylsilanolate),
Zirconium di (butoxy) di (triphenylsilanolate), zirconium di (butoxy) di (tribenzylsilanolate), zirconium di (butoxy) di (trinaphthylsilanolate), zirconium di (butoxy)
Di (dimethylethylsilanolate), zirconium di (butoxy) di (methyldiethylsilanolate),

Zirconium di (phenoxy) di (trimethylsilanolate), zirconium di (phenoxy) di (triethylsilanolate), zirconium di (phenoxy) di (triisopropylsilanolate), zirconium di (phenoxy) di (tributylsilanolate) ),
Zirconium di (phenoxy) di (tripentyl silanolate), zirconium di (phenoxy) di (triphenylsilanolate), zirconium di (phenoxy) di (tribenzylsilanolate), zirconium di (phenoxy) di (trinaphthylsilanolate) ), Zirconium di (phenoxy) bis (dimethylethylsilanolate), zirconium di (phenoxy) bis (methyldiethylsilanolate),

Zirconium (methoxy) tris (trimethylsilanolate), zirconium (methoxy) tris (triethylsilanolate), zirconium (methoxy) tris (triisopropylsilanolate), zirconium (methoxy) tris (tributylsilanolate), zirconium ( Methoxy) tris (tripentylsilanolate), zirconium (methoxy) tris (triphenylsilanolate), zirconium (methoxy)
Tris (tribenzylsilanolate), zirconium (methoxy) tris (trinaphthylsilanolate), zirconium (methoxy) tri (dimethylethylsilanolate), zirconium (methoxy) tri (methyldiethylsilanolate),

Zirconium (ethoxy) tris (trimethylsilanolate), zirconium (ethoxy) tris (triethylsilanolate), zirconium (ethoxy) tris (triisopropylsilanolate), zirconium (ethoxy) tris (tributylsilanolate), zirconium ( Ethoxy) tris (tripentylsilanolate), zirconium (ethoxy) tris (triphenylsilanolate), zirconium (ethoxy)
Tris (tribenzylsilanolate), zirconium (ethoxy) tris (trinaphthylsilanolate), zirconium (ethoxy) tri (dimethylethylsilanolate), zirconium (ethoxy) tri (methyldiethylsilanolate),

Zirconium (propoxy) tris (trimethylsilanolate), zirconium (propoxy) tris (triethylsilanolate), zirconium (propoxy) tris (triisopropylsilanolate), zirconium (propoxy) tris (tributylsilanolate), zirconium ( Propoxy) tris (tripentylsilanolate), zirconium (propoxy) tris (triphenylsilanolate), zirconium (propoxy) tris (tribenzylsilanolate), zirconium (propoxy) tris (trinaphthylsilanolate), zirconium (propoxy) Tri (dimethylethylsilanolate), zirconium (propoxy) tri (methyldiethylsilanolate),

Zirconium (butoxy) tris (trimethylsilanolate), zirconium (butoxy) tris (triethylsilanolate), zirconium (butoxy) tris (triisopropylsilanolate), zirconium (butoxy) tris (tributylsilanolate), zirconium (butyr). Butoxy) tris (tripentyl silanolate), zirconium (butoxy) tris (triphenyl silanolate), zirconium (butoxy)
Tris (tribenzylsilanolate), zirconium (butoxy) tris (trinaphthylsilanolate), zirconium (butoxy) tri (dimethylethylsilanolate), zirconium (butoxy) tri (methyldiethylsilanolate),

Zirconium (phenoxy) tris (trimethylsilanolate), zirconium (phenoxy) tris (triethylsilanolate), zirconium (phenoxy) tris (triisopropylsilanolate), zirconium (phenoxy) tris (tributylsilanolate), zirconium (phenoxy) tris (tributylsilanolate) Phenoxy) tris (tripentylsilanolate), zirconium (phenoxy) tris (triphenylsilanolate), zirconium (phenoxy) tris (tribenzylsilanolate), zirconium (phenoxy) tris (trinaphthylsilanolate), zirconium (phenoxy) Tri (dimethylethylsilanolate), zirconium (phenoxy) tri (methyldiethylsilanolate),

Zirconium trimethyl mono (trimethylsilanolate), zirconium trimethyl mono (triethylsilanolate), zirconium trimethylmono (triisopropylsilanolate), zirconium trimethylmono (tributylsilanolate), zirconium trimethylmono (tripentylsilanolate), Zirconium trimethyl mono (triphenyl silanolate), zirconium trimethyl mono (tribenzyl silanolate), zirconium trimethyl mono (trinaphthyl silanolate), zirconium trimethyl mono (dimethyl ethyl silanolate), zirconium trimethyl mono (methyl diethyl silanolate),

Zirconium triethyl mono (trimethylsilanolate), zirconium triethylmono (triethylsilanolate), zirconium triethylmono (triisopropylsilanolate), zirconium triethylmono (tributylsilanolate), zirconium triethylmono (tripentylsilanolate), Zirconium triethyl mono (triphenylsilanolate), zirconium triethylmono (tribenzylsilanolate), zirconium triethylmono (trinaphthylsilanolate), zirconium triethylmono (dimethylethylsilanolate), zirconium triethylmono (methyldiethylsilanolate),

Zirconium tripropyl mono (trimethylsilanolate), zirconium tripropyl mono (triethylsilanolate), zirconium tripropylmono (triisopropylsilanolate), zirconium tripropylmono (tributylsilanolate), zirconium tripropylmono (tri) Pentyl silanolate),
Zirconium tripropyl mono (triphenylsilanolate), zirconium tripropylmono (tribenzylsilanolate), zirconium tripropylmono (trinaphthylsilanolate), zirconium tripropylmono (dimethylethylsilanolate), zirconium tripropylmono (methyl) Diethyl silanolate),

Zirconium tributyl mono (trimethylsilanolate), zirconium tributylmono (triethylsilanolate), zirconium tributylmono (triisopropylsilanolate), zirconium tributylmono (tributylsilanolate), zirconium tributylmono (tripentylsilanolate), Zirconium tributyl mono (triphenylsilanolate), zirconium tributylmono (tribenzylsilanolate), zirconium tributylmono (trinaphthylsilanolate), zirconium tributylmono (dimethylethylsilanolate), zirconium tributylmono (methyldiethylsilanolate),

Zirconium triphenyl mono (trimethylsilanolate), zirconium triphenylmono (triethylsilanolate), zirconium triphenylmono (triisopropylsilanolate), zirconium triphenylmono (tributylsilanolate), zirconium triphenylmono (tri) Pentyl silanolate),
Zirconium triphenyl mono (triphenylsilanolate), zirconium triphenylmono (tribenzylsilanolate), zirconium triphenylmono (trinaphthylsilanolate), zirconium triphenylmono (dimethylethylsilanolate), zirconium triphenylmono (methyl) Diethyl silanolate),

Zirconium tribenzyl mono (trimethylsilanolate), zirconium tribenzyl mono (triethylsilanolate), zirconium tribenzyl mono (triisopropylsilanolate), zirconium tribenzylmono (tributylsilanolate), zirconium tribenzylmono (tri) Pentyl silanolate),
Zirconium tribenzyl mono (triphenylsilanolate), zirconium tribenzylmono (tribenzylsilanolate), zirconium tribenzylmono (trinaphthylsilanolate), zirconium tribenzylmono (dimethylethylsilanolate), zirconium tribenzylmono (methyl) Diethyl silanolate),

Zirconium dimethyldi (trimethylsilanolate), zirconium dimethyldi (triethylsilanolate), zirconium dimethyldi (triisopropylsilanolate), zirconium dimethyldi (tributylsilanolate), zirconium dimethyldi (tripentylsilanolate), Zirconium dimethyldi (triphenylsilanolate), zirconium dimethyldi (tribenzylsilanolate), zirconium dimethyldi (trinaphthylsilanolate), zirconium dimethylbis (dimethylethylsilanolate), zirconium dimethylbis (methyldiethylsilanolate),

Zirconium diethyldi (trimethylsilanolate), zirconium diethyldi (triethylsilanolate), zirconium diethyldi (triisopropylsilanolate), zirconium diethyldi (tributylsilanolate), zirconium diethyldi (tripentylsilanolate), Zirconium diethyldi (triphenylsilanolate), zirconium diethyldi (tribenzylsilanolate), zirconium diethyldi (trinaphthylsilanolate), zirconium diethylbis (dimethylethylsilanolate), zirconium diethylbis (methyldiethylsilanolate),

Zirconium dipropyl di (trimethylsilanolate), zirconium dipropyl di (triethylsilanolate), zirconium dipropyldi (triisopropylsilanolate), zirconium dipropyldi (tributylsilanolate), zirconium dipropyldi (tri) Pentyl silanolate), zirconium dipropyl di (triphenyl silanolate), zirconium dipropyl di (tribenzyl silanolate), zirconium dipropyl di (trinaphthyl silanolate), zirconium dipropyl bis (dimethylethyl silanolate), zirconium Dipropylbis (methyldiethylsilanolate),

Zirconium dibutyldi (trimethylsilanolate), zirconium dibutyldi (triethylsilanolate), zirconium dibutyldi (triisopropylsilanolate), zirconium dibutyldi (tributylsilanolate), zirconium dibutyldi (tripentylsilanolate), Zirconium dibutyldi (triphenylsilanolate), zirconium dibutyldi (tribenzylsilanolate), zirconium dibutyldi (trinaphthylsilanolate), zirconium dibutylbis (dimethylethylsilanolate), zirconium dibutylbis (methyldiethylsilanolate),

Zirconium diphenyldi (trimethylsilanolate), zirconium diphenyldi (triethylsilanolate), zirconium diphenyldi (triisopropylsilanolate), zirconium diphenyldi (tributylsilanolate), zirconium diphenyldi (tripentylsilanolate), Zirconium diphenyldi (triphenylsilanolate), zirconium diphenyldi (tribenzylsilanolate), zirconium diphenyldi (trinaphthylsilanolate), zirconium diphenylbis (dimethylethylsilanolate), zirconium diphenylbis (methyldiethylsilanolate),

Zirconium dibenzyldi (trimethylsilanolate), zirconium dibenzyldi (triethylsilanolate), zirconium dibenzyldi (triisopropylsilanolate), zirconium dibenzyldi (tributylsilanolate), zirconium dibenzyldi (tri) Pentyl silanolate), zirconium dibenzyldi (triphenylsilanolate), zirconium dibenzyldi (tribenzylsilanolate), zirconium dibenzyldi (trinaphthylsilanolate), zirconium dibenzylbis (dimethylethylsilanolate), zirconium Dibenzylbis (methyldiethylsilanolate),

Zirconium methyl tris (trimethylsilanolate), zirconium methyl tris (triethyl silanolate), zirconium methyl tris (triisopropyl silanolate), zirconium methyl tris (tributyl silanolate), zirconium methyl tris (tripentyl silanolate), Zirconium methyl tris (triphenyl silanolate), zirconium methyl tris (tribenzyl silanolate), zirconium methyl tris (trinaphthyl silanolate), zirconium methyl tri (dimethylethyl silanolate), zirconium methyl tri (methyl diethyl silanolate),

Zirconium ethyl tris (trimethylsilanolate), zirconium ethyl tris (triethyl silanolate), zirconium ethyl tris (triisopropyl silanolate), zirconium ethyl tris (tributyl silanolate), zirconium ethyl tris (tripentyl silanolate), Zirconium ethyl tris (triphenyl silanolate), zirconium ethyl tris (tribenzyl silanolate), zirconium ethyl tris (trinaphthyl silanolate), zirconium ethyl tri (dimethyl ethyl silanolate), zirconium ethyl tri (methyl diethyl silanolate),

Zirconium propyl tris (trimethylsilanolate), zirconium propyl tris (triethyl silanolate), zirconium propyl tris (triisopropyl silanolate), zirconium propyl tris (tributyl silanolate), zirconium propyl tris (tripentyl silanolate), Zirconium propyl tris (triphenyl silanolate), zirconium propyl tris (tribenzyl silanolate), zirconium propyl tris (trinaphthyl silanolate), zirconium propyl tri (dimethylethyl silanolate), zirconium propyl tri (methyl diethyl silanolate),

Zirconium butyl tris (trimethylsilanolate), zirconium butyl tris (triethylsilanolate), zirconium butyl tris (triisopropylsilanolate), zirconium butyl tris (tributylsilanolate), zirconium butyl tris (tripentylsilanolate), Zirconium butyl tris (triphenyl silanolate), zirconium butyl tris (tribenzyl silanolate), zirconium butyl tris (trinaphthyl silanolate), zirconium butyl tri (dimethyl ethyl silanolate), zirconium butyl tri (methyl diethyl silanolate),

Zirconium phenyl tris (trimethylsilanolate), zirconium phenyl tris (triethyl silanolate), zirconium phenyl tris (triisopropyl silanolate), zirconium phenyl tris (tributyl silanolate), zirconium phenyl tris (tripentyl silanolate), Zirconium phenyl tris (triphenyl silanolate), zirconium phenyl tris (tribenzyl silanolate), zirconium phenyl tris (trinaphthyl silanolate), zirconium phenyl tri (dimethylethyl silanolate), zirconium phenyl tri (methyl diethyl silanolate),

Zirconium benzyl tris (trimethylsilanolate), zirconium benzyl tris (triethyl silanolate), zirconium benzyl tris (triisopropyl silanolate), zirconium benzyl tris (tributyl silanolate), zirconium benzyl tris (tripentyl silanolate), Zirconium benzyl tris (triphenyl silanolate), zirconium benzyl tris (tribenzyl silanolate), zirconium benzyl tris (trinaphthyl silanolate), zirconium benzyl tri (dimethylethyl silanolate), zirconium benzyl tri (methyl diethyl silanolate),

Zirconium phenylmethoxydi (trimethylsilanolate), zirconium phenylbenzyldi (triethylsilanolate),

Zirconium chlorotris (trimethylsilanolate), zirconium chlorotris (triethylsilanolate), zirconium chlorotris (triisopropylsilanolate), zirconium chlorotris (tributylsilanolate), zirconium chlorotris (tripentylsilanolate), Zirconium chlorotris (triphenylsilanolate), zirconium chlorotris (tribenzylsilanolate), zirconium chlorotris (trinaphthylsilanolate), zirconium chlorotri (dimethylethylsilanolate), zirconium chlorotri (methyldiethylsilanolate),

Zirconium bromotris (trimethylsilanolate), zirconium bromotris (triethylsilanolate), zirconium bromotris (triisopropylsilanolate), zirconium bromotris (tributylsilanolate), zirconium bromotris (tripentylsilanolate), Zirconium bromotris (triphenylsilanolate), zirconium bromotris (tribenzylsilanolate), zirconium bromotris (trinaphthylsilanolate), zirconium bromotri (dimethylethylsilanolate), zirconium bromotri (methyldiethylsilanolate),

Zirconium iodotris (trimethylsilanolate), zirconium iodotris (triethylsilanolate), zirconium iodotris (triisopropylsilanolate), zirconium iodotris (tributylsilanolate), zirconium iodotris (tripentylsilanolate), Zirconium iodotris (triphenylsilanolate), zirconium iodotris (tribenzylsilanolate), zirconium iodotris (trinaphthylsilanolate), zirconium iodotri (dimethylethylsilanolate), zirconium iodotri (methyldiethylsilanolate),

Zirconium dichlorodi (trimethylsilanolate), zirconium dichlorodi (triethylsilanolate), zirconium dichlorodi (triisopropylsilanolate), zirconium dichlorodi (tributylsilanolate), zirconium dichlorodi (tripentylsilanolate), Zirconium dichlorodi (triphenylsilanolate), zirconium dichlorodi (tribenzylsilanolate), zirconium dichlorodi (trinaphthylsilanolate), zirconium dichlorobis (dimethylethylsilanolate), zirconium dichlorobis (methyldiethylsilanolate),

Zirconium dibromodi (trimethylsilanolate), zirconium dibromodi (triethylsilanolate), zirconium dibromodi (triisopropylsilanolate), zirconium dibromodi (tributylsilanolate), zirconium dibromodi (tripentylsilanolate), Zirconium dibromodi (triphenylsilanolate), zirconium dibromodi (tribenzylsilanolate), zirconium dibromodi (trinaphthylsilanolate), zirconium dibromobis (dimethylethylsilanolate), zirconium dibromobis (methyldiethylsilanolate),

Zirconium diiododi (trimethylsilanolate), zirconium diiododi (triethylsilanolate), zirconium diiododi (triisopropylsilanolate), zirconium diiododi (tributylsilanolate), zirconium diiododi (tri) Pentyl silanolate), zirconium diiododi (triphenylsilanolate), zirconium diiododi (tribenzylsilanolate), zirconium diiododi (trinaphthylsilanolate), zirconium diiodobis (dimethylethylsilanolate), zirconium Diiodobis (methyldiethylsilanolate),

Zirconium trichloromono (trimethylsilanolate), zirconium trichloromono (triethylsilanolate), zirconium trichloromono (triisopropylsilanolate), zirconium trichloromono (tributylsilanolate), zirconium trichloromono (tripentylsilanolate), Zirconium trichloromono (triphenylsilanolate), zirconium trichloromono (tribenzylsilanolate), zirconium trichloromono (trinaphthylsilanolate), zirconium trichloromono (dimethylethylsilanolate), zirconium trichloromono (methyldiethylsilanolate),

Zirconium tribromomono (trimethylsilanolate), zirconium tribromomono (triethylsilanolate), zirconium tribromomono (triisopropylsilanolate), zirconium tribromomono (tributylsilanolate), zirconium tribromomono (tri). Pentyl silanolate), zirconium tribromomono (triphenylsilanolate), zirconium tribromomono (tribenzylsilanolate), zirconium tribromomono (trinaphthylsilanolate), zirconium tribromomono (dimethylethylsilanolate), zirconium Tribromomono (methyldiethylsilanolate),

Zirconium triiodomono (trimethylsilanolate), zirconium triiodomono (triethylsilanolate), zirconium triiodomono (triisopropylsilanolate), zirconium triiodomono (tributylsilanolate), zirconium triiodomono (tri). Pentyl silanolate), zirconium triiodomono (triphenylsilanolate), zirconium triiodomono (tribenzylsilanolate), zirconium triiodomono (trinaphthylsilanolate), zirconium triiodomono (dimethylethylsilanolate), zirconium Triiodomono (methyldiethylsilanolate),

Zirconium tetra (trimethylsilanolate), zirconium tetra (triethylsilanolate), zirconium tetra (triisopropylsilanolate), zirconium tetra (tributylsilanolate), zirconium tetra (tripentylsilanolate), zirconium tetra (triphenyl) Silanolate), zirconium tetra (tribenzylsilanolate), zirconium tetra (trinaphthylsilanolate), zirconium tetra (dimethylethylsilanolate), zirconium tetra (methyldiethylsilanolate),

Zirconium chloromethyldi (trimethylsilanolate), zirconium chloromethyldi (triethylsilanolate), zirconium chloromethyldi (tributylsilanolate), zirconium chloromethyldi (tridodecylsilanolate),

Zirconium chloroethyldi (trimethylsilanolate), zirconium chloroethyldi (triethylsilanolate), zirconium chloroethyldi (tributylsilanolate), zirconium chloroethyldi (tridodecylsilanolate),

Zirconium bromomethyldi (trimethylsilanolate), zirconium bromomethyldi (triethylsilanolate), zirconium bromomethyldi (tributylsilanolate), zirconium bromomethyldi (tridodecylsilanolate),

Zirconium bromoethyldi (trimethylsilanolate), zirconium bromoethyldi (triethylsilanolate), zirconium bromoethyldi (tributylsilanolate), zirconium bromoethyldi (tridodecylsilanolate),

Zirconium iodomethyldi (trimethylsilanolate), zirconium iodomethyldi (triethylsilanolate), zirconium iodomethyldi (tributylsilanolate), zirconium iodomethyldi (tridodecylsilanolate),

Zirconium iodoethyldi (trimethylsilanolate), zirconium iodoethyldi (triethylsilanolate), zirconium iodoethyldi (tributylsilanolate), zirconium iodoethyldi (tridodecylsilanolate),

Zirconium chlorodimethyl mono (trimethylsilanolate), zirconium chlorodimethylmono (triethylsilanolate), zirconium chlorodimethylmono (tributylsilanolate), zirconium chlorodimethylmono (tridodecylsilanolate),

Zirconium chlorodiethyl mono (trimethylsilanolate), zirconium chlorodiethylmono (triethylsilanolate), zirconium chlorodiethylmono (tributylsilanolate), zirconium chlorodiethylmono (tridodecylsilanolate),

Zirconium bromodimethyl mono (trimethylsilanolate), zirconium bromodimethylmono (triethylsilanolate), zirconium bromodimethylmono (tributylsilanolate), zirconium bromodimethylmono (tridodecylsilanolate),

Zirconium bromodiethyl mono (trimethylsilanolate), zirconium bromodiethylmono (triethylsilanolate), zirconium bromodiethylmono (tributylsilanolate), zirconium bromodiethylmono (tridodecylsilanolate),

Zirconium iododimethyl mono (trimethylsilanolate), zirconium iododimethylmono (triethylsilanolate), zirconium iododimethylmono (tributylsilanolate), zirconium iododimethylmono (tridodecylsilanolate),

Zirconium iododiethyl mono (trimethylsilanolate), zirconium iododiethylmono (triethylsilanolate), zirconium iododiethylmono (tributylsilanolate), zirconium iododiethylmono (tridodecylsilanolate),

Zirconium methylbutyl di (trimethylsilanolate), zirconium methylbutyldi (triethylsilanolate), zirconium methylbutyldi (tributylsilanolate), zirconium methylbutyldi (tridodecylsilanolate),

Zirconium methyl ethyl di (trimethylsilanolate), zirconium methyl ethyl di (triethyl silanolate), zirconium methyl ethyl di (tributyl silanolate), zirconium methyl ethyl di (tridodecyl silanolate),

Zirconium methylethoxydi (trimethylsilanolate), zirconium methylethoxydi (triethylsilanolate), zirconium methylethoxydi (tributylsilanolate), zirconium methylethoxydi (tridodecylsilanolate),

Zirconium methyl butoxide di (trimethylsilanolate), zirconium methyl butoxide di (triethyl silanolate), zirconium methyl butoxide di (tributyl silanolate), zirconium methyl butoxide di (tridodecyl silanolate),

Zirconium ethyl ethoxydi (trimethylsilanolate), zirconium ethylethoxydi (triethylsilanolate), zirconium ethylethoxydi (tributylsilanolate), zirconium ethylethoxydi (tridodecylsilanolate),

Zirconium ethyl butoxydi (trimethylsilanolate), zirconium ethylbutoxydi (triethylsilanolate), zirconium ethylbutoxydi (tributylsilanolate), zirconium ethylbutoxydi (tridodecylsilanolate),

Zirconium butylethoxydi (trimethylsilanolate), zirconium butylethoxydi (triethylsilanolate), zirconium butylethoxydi (tributylsilanolate), zirconium butylethoxydi (tridodecylsilanolate),

Zirconium butylbutoxydi (trimethylsilanolate), zirconium butylbutoxydi (triethylsilanolate), zirconium butylbutoxydi (tributylsilanolate), zirconium butylbutoxydi (tridodecylsilanolate),

Zirconium methyl ethyl butyl mono (trimethylsilanolate), zirconium methyl ethyl butyl mono (triethyl silanolate), zirconium methyl ethyl butyl mono (tributyl silanolate), zirconium methyl ethyl butyl mono (tridodecyl silanolate),

Zirconium methyl ethyl butoxy mono (trimethylsilanolate), zirconium methyl ethyl butoxy mono (triethyl silanolate), zirconium methyl ethyl butoxy mono (tributyl silanolate), zirconium methyl ethyl butoxy mono (tridodecyl silanolate),

Zirconium ethyl ethoxy butoxy mono (trimethylsilanolate), zirconium ethyl ethoxy butoxy mono (triethyl silanolate), zirconium ethyl ethoxy butoxy mono (tributyl silanolate), zirconium ethyl ethoxy butoxy mono (tridodecyl silanolate),

Zirconium butyl ethoxy butoxy mono (trimethylsilanolate), zirconium butyl ethoxy butoxy mono (triethyl silanolate), zirconium butyl ethoxy butoxy mono (tributyl silanolate), zirconium butyl ethoxy butoxy mono (tridodecyl silanolate),

Titanium tri (methoxy) mono (trimethylsilanolate), titanium tri (methoxy) mono (triethylsilanolate), titanium tri (methoxy) mono (triisopropylsilanolate), titanium tri (methoxy) mono (tributylsilanolate) ),
Titanium tri (methoxy) mono (tripentyl silanolate), titanium tri (methoxy) mono (triphenylsilanolate), titanium tri (methoxy) mono (tribenzylsilanolate), titanium tri (methoxy) mono (trinaphthylsilanolate) ), Titanium tri (methoxy) mono (dimethylethylsilanolate), titanium tri (methoxy) mono (methyldiethylsilanolate),

Titanium tri (ethoxy) mono (trimethylsilanolate), titanium tri (ethoxy) mono (triethylsilanolate), titanium tri (ethoxy) mono (triisopropylsilanolate), titanium tri (ethoxy) mono (tributylsilanolate) ),
Titanium tri (ethoxy) mono (tripentyl silanolate), titanium tri (ethoxy) mono (triphenylsilanolate), titanium tri (ethoxy) mono (tribenzylsilanolate), titanium tri (ethoxy) mono (trinaphthylsilanolate) ), Titanium tri (ethoxy) mono (dimethylethylsilanolate), titanium tri (ethoxy) mono (methyldiethylsilanolate),

Titanium tri (propoxy) mono (trimethylsilanolate), titanium tri (propoxy)
Mono (triethylsilanolate), Titanium tri (propoxy) mono (triisopropylsilanolate), Titanium tri (propoxy) mono (tributylsilanolate), Titanium tri (propoxy) mono (tripentylsilanolate), Titanium tri (propoxy) Mono (triphenylsilanolate), Titanium tri (propoxy) mono (tribenzylsilanolate), Titanium tri (propoxy) mono (trinaphthylsilanolate), Titanium tri (propoxy) mono (dimethylethylsilanolate), Titanium tri ( Propoxy) mono (methyldiethylsilanolate),

Titanium tri (butoxy) mono (trimethylsilanolate), titanium tri (butoxy) mono (triethylsilanolate), titanium tri (butoxy) mono (triisopropylsilanolate), titanium tri (butoxy) mono (tributylsilanolate) ),
Titanium tri (butoxy) mono (tripentyl silanolate), titanium tri (butoxy) mono (triphenyl silanolate), titanium tri (butoxy) mono (tribenzyl silanolate), titanium tri (butoxy) mono (trinaphthyl silanolate) ), Titanium tri (butoxy) mono (dimethylethylsilanolate), titanium tri (butoxy) mono (methyldiethylsilanolate),

Titanium tri (phenoxy) mono (trimethylsilanolate), titanium tri (phenoxy)
Mono (triethylsilanolate), Titanium tri (phenoxy) mono (triisopropylsilanolate), Titanium tri (phenoxy) mono (tributylsilanolate), Titanium tri (phenoxy) mono (tripentylsilanolate), Titanium tri (phenoxy) Mono (triphenylsilanolate), Titanium tri (phenoxy) mono (tribenzylsilanolate), Titanium tri (phenoxy) mono (trinaphthylsilanolate), Titanium tri (phenoxy) mono (dimethylethylsilanolate), Titanium tri ( Phenoxy) mono (methyldiethylsilanolate),

Titanium di (methoxy) di (trimethylsilanolate), titanium di (methoxy) di (triethylsilanolate), titanium di (methoxy) di (triisopropylsilanolate), titanium di (methoxy) di (tributylsilanolate) ), Titanium di (methoxy) di (tripentyl silanolate), titanium di (methoxy) di (triphenylsilanolate), titanium di (methoxy) di (tribenzylsilanolate), titanium di (methoxy) di (trinaphthyl) Silanolate), titanium di (methoxy) bis (dimethylethylsilanolate), titanium di (methoxy) bis (methyldiethylsilanolate),

Titanium di (ethoxy) di (trimethylsilanolate), titanium di (ethoxy) di (triethylsilanolate), titanium di (ethoxy) di (triisopropylsilanolate), titanium di (ethoxy) di (tributylsilanolate) ), Titanium di (ethoxy) di (tripentyl silanolate), titanium di (ethoxy) di (triphenylsilanolate), titanium di (ethoxy) di (tribenzylsilanolate), titanium di (ethoxy) di (trinaphthyl) Silanolate), titanium di (ethoxy) bis (dimethylethylsilanolate), titanium di (ethoxy) bis (methyldiethylsilanolate),

Titanium di (propoxy) di (trimethylsilanolate), titanium di (propoxy) di (triethylsilanolate), titanium di (propoxy)
Di (triisopropylsilanolate), titanium di (propoxy) di (tributylsilanolate), titanium di (propoxy) di (tripentylsilanolate), titanium di (propoxy) di (triphenylsilanolate), titanium di (propoxy) ) Di (tribenzylsilanolate), titanium di (propoxy) di (trinaphthylsilanolate), titanium di (propoxy) di (dimethylethylsilanolate), titanium di (propoxy) di (methyldiethylsilanolate),

Titanium di (butoxy) di (trimethylsilanolate), titanium di (butoxy) di (triethylsilanolate), titanium di (butoxy) di (triisopropylsilanolate), titanium di (butoxy) di (tributylsilanolate) ), Titanium di (butoxy) di (tripentyl silanolate), titanium di (butoxy) di (triphenylsilanolate), titanium di (butoxy) di (tribenzylsilanolate), titanium di (butoxy) di (trinaphthyl) Silanolate), titanium di (butoxy) bis (dimethylethylsilanolate), titanium di (butoxy) bis (methyldiethylsilanolate),

Titanium di (phenoxy) di (trimethylsilanolate), titanium di (phenoxy) di (triethylsilanolate), titanium di (phenoxy)
Di (triisopropylsilanolate), titanium di (phenoxy) di (tributylsilanolate), titanium di (phenoxy) di (tripentylsilanolate), titanium di (phenoxy) di (triphenylsilanolate), titanium di (phenoxy) ) Di (tribenzylsilanolate), titanium di (phenoxy) di (trinaphthylsilanolate), titanium di (phenoxy) bis (dimethylethylsilanolate), titanium di (phenoxy) bis (methyldiethylsilanolate),

Titanium (methoxy) tris (trimethylsilanolate), titanium (methoxy) tris (triethylsilanolate), titanium (methoxy) tris (triisopropylsilanolate), titanium (methoxy) tris (tributylsilanolate), titanium ( Methoxy) tris (tripentyl silanolate),
Titanium (methoxy) tris (triphenylsilanolate), titanium (methoxy) tris (tribenzylsilanolate), titanium (methoxy) tris (trinaphthylsilanolate), titanium (methoxy) tri (dimethylethylsilanolate), titanium ( Methoxy) tri (methyldiethylsilanolate),

Titanium (ethoxy) tris (trimethylsilanolate), titanium (ethoxy) tris (triethylsilanolate), titanium (ethoxy) tris (triisopropylsilanolate), titanium (ethoxy) tris (tributylsilanolate), titanium ( Ethoxy) tris (tripentyl silanolate),
Titanium (ethoxy) tris (triphenylsilanolate), titanium (ethoxy) tris (tribenzylsilanolate), titanium (ethoxy) tris (trinaphthylsilanolate), titanium (ethoxy) tri (dimethylethylsilanolate), titanium ( Ethoxy) tri (methyldiethylsilanolate),

Titanium (propoxy) tris (trimethylsilanolate), titanium (propoxy) tris (triethylsilanolate), titanium (propoxy) tris (triisopropylsilanolate), titanium (propoxy) tris (tributylsilanolate), titanium ( Propoxy) tris (tripentyl silanolate), titanium (propoxy) tris (triphenyl silanolate), titanium (propoxy)
Tris (tribenzylsilanolate), titanium (propoxy) tris (trinaphthylsilanolate), titanium (propoxy) tri (dimethylethylsilanolate), titanium (propoxy) tri (methyldiethylsilanolate),

Titanium (butoxy) tris (trimethylsilanolate), titanium (butoxy) tris (triethylsilanolate), titanium (butoxy) tris (triisopropylsilanolate), titanium (butoxy) tris (tributylsilanolate), titanium (butanol) Butoxy) tris (tripentyl silanolate),
Titanium (butoxy) tris (triphenylsilanolate), Titanium (butoxy) Tris (tribenzylsilanolate), Titanium (butoxy) Tris (trinaphthylsilanolate), Titanium (butoxy) tri (dimethylethylsilanolate), Titanium ( Butoxy) tri (methyldiethylsilanolate),

Titanium (phenoxy) tris (trimethylsilanolate), titanium (phenoxy) tris (triethylsilanolate), titanium (phenoxy) tris (triisopropylsilanolate), titanium (phenoxy) tris (tributylsilanolate), titanium (phen) Phenoxy) tris (tripentyl silanolate), titanium (phenoxy) tris (triphenyl silanolate), titanium (phenoxy)
Tris (tribenzylsilanolate), titanium (phenoxy) tris (trinaphthylsilanolate), titanium (phenoxy) tri (dimethylethylsilanolate), titanium (phenoxy) tri (methyldiethylsilanolate),

Titanium trimethyl mono (trimethylsilanolate), titanium trimethylmono (triethylsilanolate), titanium trimethylmono (triisopropylsilanolate), titanium trimethylmono (tributylsilanolate), titanium trimethylmono (tripentylsilanolate), Titanium trimethyl mono (triphenylsilanolate), titanium trimethylmono (tribenzylsilanolate), titanium trimethylmono (trinaphthylsilanolate), titanium trimethylmono (dimethylethylsilanolate),
Titanium trimethyl mono (methyl diethyl silanolate),

Titanium triethyl mono (trimethylsilanolate), titanium triethylmono (triethylsilanolate), titanium triethylmono (triisopropylsilanolate), titanium triethylmono (tributylsilanolate), titanium triethylmono (tripentylsilanolate), Titanium triethyl mono (triphenylsilanolate), titanium triethylmono (tribenzylsilanolate), titanium triethylmono (trinaphthylsilanolate), titanium triethylmono (dimethylethylsilanolate),
Titanium triethylmono (methyldiethylsilanolate),

Titanium tripropyl mono (trimethylsilanolate), titanium tripropyl mono (triethylsilanolate), titanium tripropylmono (triisopropylsilanolate), titanium tripropylmono (tributylsilanolate), titanium tripropylmono (tri) Pentyl silanolate), titanium tripropyl mono (triphenyl silanolate), titanium tripropyl mono (tribenzyl silanolate), titanium tripropyl mono (trinaphthyl silanolate), titanium tripropyl mono (dimethylethyl silanolate), titanium Tripropylmono (methyldiethylsilanolate),

Titanium tributyl mono (trimethylsilanolate), titanium tributylmono (triethylsilanolate), titanium tributylmono (triisopropylsilanolate), titanium tributylmono (tributylsilanolate), titanium tributylmono (tripentylsilanolate), Titanium tributyl mono (triphenylsilanolate), titanium tributylmono (tribenzylsilanolate), titanium tributylmono (trinaphthylsilanolate), titanium tributylmono (dimethylethylsilanolate),
Titanium tributyl mono (methyldiethylsilanolate),

Titanium triphenyl mono (trimethylsilanolate), titanium triphenylmono (triethylsilanolate), titanium triphenylmono (triisopropylsilanolate), titanium triphenylmono (tributylsilanolate), titanium triphenylmono (tri) Pentyl silanolate), titanium triphenyl mono (triphenyl silanolate), titanium triphenyl mono (tribenzyl silanolate), titanium triphenyl mono (trinaphthyl silanolate), titanium triphenyl mono (dimethylethyl silanolate), titanium Triphenylmono (methyldiethylsilanolate),

Titanium tribenzyl mono (trimethylsilanolate), titanium tribenzylmono (triethylsilanolate), titanium tribenzylmono (triisopropylsilanolate), titanium tribenzylmono (tributylsilanolate), titanium tribenzylmono (tri) Pentyl silanolate), titanium tribenzyl mono (triphenyl silanolate), titanium tribenzyl mono (tribenzyl silanolate), titanium tribenzyl mono (trinaphthyl silanolate), titanium tribenzyl mono (dimethylethyl silanolate), titanium Tribenzyl mono (methyldiethylsilanolate),

Titanium dimethyldi (trimethylsilanolate), titanium dimethyldi (triethylsilanolate), titanium dimethyldi (triisopropylsilanolate), titanium dimethyldi (tributylsilanolate), titanium dimethyldi (tripentylsilanolate), Titanium dimethyldi (triphenylsilanolate), titanium dimethyldi (tribenzylsilanolate), titanium dimethyldi (trinaphthylsilanolate), titanium dimethylbis (dimethylethylsilanolate), titanium dimethylbis (methyldiethylsilanolate),

Titanium diethyldi (trimethylsilanolate), titanium diethyldi (triethylsilanolate), titanium diethyldi (triisopropylsilanolate), titanium diethyldi (tributylsilanolate), titanium diethyldi (tripentylsilanolate), Titanium diethyldi (triphenylsilanolate), titanium diethyldi (tribenzylsilanolate), titanium diethyldi (trinaphthylsilanolate), titanium diethylbis (dimethylethylsilanolate), titanium diethylbis (methyldiethylsilanolate),

Titanium dipropyl di (trimethylsilanolate), titanium dipropyl di (triethyl silanolate), titanium dipropyl di (triisopropyl silanolate), titanium dipropyl di (tributyl silanolate), titanium dipropyl di (tri) Pentyl silanolate), titanium dipropyl di (triphenyl silanolate), titanium dipropyl di (tribenzyl silanolate), titanium dipropyl di (trinaphthyl silanolate), titanium dipropyl bis (dimethylethyl silanolate), titanium Dipropylbis (methyldiethylsilanolate),

Titanium dibutyl di (trimethylsilanolate), titanium dibutyl di (triethyl silanolate), titanium dibutyl di (triisopropyl silanolate), titanium dibutyl di (tributyl silanolate), titanium dibutyl di (tripentyl silanolate), Titanium dibutyl di (triphenyl silanolate), titanium dibutyl di (tribenzyl silanolate), titanium dibutyl di (trinaphthyl silanolate), titanium dibutyl bis (dimethyl ethyl silanolate), titanium dibutyl bis (methyl diethyl silanolate),

Titanium diphenyldi (trimethylsilanolate), titanium diphenyldi (triethylsilanolate), titanium diphenyldi (triisopropylsilanolate), titanium diphenyldi (tributylsilanolate), titanium diphenyldi (tripentylsilanolate), Titanium diphenyldi (triphenylsilanolate), titanium diphenyldi (tribenzylsilanolate), titanium diphenyldi (trinaphthylsilanolate), titanium diphenylbis (dimethylethylsilanolate), titanium diphenylbis (methyldiethylsilanolate),

Titanium dibenzyl di (trimethylsilanolate), titanium dibenzyl di (triethyl silanolate), titanium dibenzyl di (triisopropyl silanolate), titanium dibenzyl di (tributyl silanolate), titanium dibenzyl di (tri) Pentylsilanolate), titanium dibenzyldi (triphenylsilanolate), titanium dibenzyldi (tribenzylsilanolate), titanium dibenzyldi (trinaphthylsilanolate), titaniumdibenzylbis (dimethylethylsilanolate), titanium Dibenzylbis (methyldiethylsilanolate),

Titanium methyl tris (trimethylsilanolate), titanium methyl tris (triethyl silanolate), titanium methyl tris (triisopropyl silanolate), titanium methyl tris (tributyl silanolate), titanium methyl tris (tripentyl silanolate), Titanium methyl tris (triphenyl silanolate), titanium methyl tris (tribenzyl silanolate), titanium methyl tris (trinaphthyl silanolate), titanium methyl tri (dimethylethyl silanolate), titanium methyl tri (methyl diethyl silanolate),

Titanium ethyl tris (trimethylsilanolate), titanium ethyl tris (triethyl silanolate), titanium ethyl tris (triisopropyl silanolate), titanium ethyl tris (tributyl silanolate), titanium ethyl tris (tripentyl silanolate), Titanium ethyl tris (triphenyl silanolate), titanium ethyl tris (tribenzyl silanolate), titanium ethyl tris (trinaphthyl silanolate), titanium ethyl tri (dimethyl ethyl silanolate), titanium ethyl tri (methyl diethyl silanolate),

Titanium propyl tris (trimethylsilanolate), titanium propyl tris (triethyl silanolate), titanium propyl tris (triisopropyl silanolate), titanium propyl tris (tributyl silanolate), titanium propyl tris (tripentyl silanolate), Titanium propyl tris (triphenyl silanolate), titanium propyl tris (tribenzyl silanolate), titanium propyl tris (trinaphthyl silanolate), titanium propyl tri (dimethylethyl silanolate), titanium propyl tri (methyl diethyl silanolate),

Titanium butyl tris (trimethylsilanolate), titanium butyl tris (triethyl silanolate), titanium butyl tris (triisopropyl silanolate), titanium butyl tris (tributyl silanolate), titanium butyl tris (tripentyl silanolate), Titanium butyl tris (triphenyl silanolate), titanium butyl tris (tribenzyl silanolate), titanium butyl tris (trinaphthyl silanolate), titanium butyl tri (dimethylethyl silanolate), titanium butyl tri (methyl diethyl silanolate),

Titanium phenyl tris (trimethylsilanolate), titanium phenyl tris (triethyl silanolate), titanium phenyl tris (triisopropyl silanolate), titanium phenyl tris (tributyl silanolate), titanium phenyl tris (tripentyl silanolate), Titanium phenyl tris (triphenyl silanolate), titanium phenyl tris (tribenzyl silanolate), titanium phenyl tris (trinaphthyl silanolate), titanium phenyl tri (dimethylethyl silanolate), titanium phenyl tri (methyl diethyl silanolate),

Titanium benzyl tris (trimethylsilanolate), titanium benzyl tris (triethyl silanolate), titanium benzyl tris (triisopropyl silanolate), titanium benzyl tris (tributyl silanolate), titanium benzyl tris (tripentyl silanolate), Titanium benzyl tris (triphenyl silanolate), titanium benzyl tris (tribenzyl silanolate), titanium benzyl tris (trinaphthyl silanolate), titanium benzyl tri (dimethylethyl silanolate), titanium benzyl tri (methyl diethyl silanolate),

Titanium methylethoxydi (trimethylsilanolate), titanium methylbutyldi (triethylsilanolate), titanium phenylmethoxydi (trimethylsilanolate), titanium phenylbenzyldi (triethylsilanolate),

Titanium chlorotris (trimethylsilanolate), titanium chlorotris (triethylsilanolate), titanium chlorotris (triisopropylsilanolate), titanium chlorotris (tributylsilanolate), titanium chlorotris (tripentylsilanolate), Titanium chlorotris (triphenylsilanolate), titanium chlorotris (tribenzylsilanolate), titanium chlorotris (trinaphthylsilanolate), titanium chlorotri (dimethylethylsilanolate), titanium chlorotri (methyldiethylsilanolate),

Titanium bromotris (trimethylsilanolate), titanium bromotris (triethylsilanolate), titanium bromotris (triisopropylsilanolate), titanium bromotris (tributylsilanolate), titanium bromotris (tripentylsilanolate), Titanium bromotris (triphenylsilanolate), titanium bromotris (tribenzylsilanolate), titanium bromotris (trinaphthylsilanolate), titanium bromotri (dimethylethylsilanolate), titanium bromotri (methyldiethylsilanolate),

Titanium iodotris (trimethylsilanolate), titanium iodotris (triethylsilanolate), titanium iodotris (triisopropylsilanolate), titanium iodotris (tributylsilanolate), titanium iodotris (tripentylsilanolate), Titanium iodotris (triphenylsilanolate), titanium iodotris (tribenzylsilanolate), titanium iodotris (trinaphthylsilanolate), titanium iodotri (dimethylethylsilanolate), titanium iodotri (methyldiethylsilanolate),

Titanium tetra (trimethylsilanolate), titanium tetra (triethylsilanolate),
Titanium tetra (triisopropylsilanolate),
Titanium tetra (tributylsilanolate), titanium tetra (tripentylsilanolate), titanium tetra (triphenylsilanolate), titanium tetra (tribenzylsilanolate), titanium tetra (trinaphthylsilanolate), titanium tetra (dimethylethylsilano) Rate), titanium tetra (methyldiethylsilanolate),

Titanium chloromethyldi (trimethylsilanolate), titanium chloroethyldi (triethylsilanolate),

Titanium bromomethyldi (trimethylsilanolate), titanium bromoethyldi (triethylsilanolate),

Titanium iodomethyldi (trimethylsilanolate), titanium iodoethyldi (triethylsilanolate),

Titanium chlorodimethyl (trimethylsilanolate), titanium chlorodiethyl (triethylsilanolate),

Titanium bromodimethyl (trimethylsilanolate), titanium bromodiethyl (triethylsilanolate),

Titanium iododimethyl (trimethylsilanolate), titanium iododiethyl (triethylsilanolate),

Hafnium tri (methoxy) mono (trimethylsilanolate), hafnium tri (methoxy) mono (triethylsilanolate), hafnium tri (methoxy) mono (triisopropylsilanolate), hafnium tri (methoxy) mono (tributylsilanolate) ),
Hafnium tri (methoxy) mono (tripentyl silanolate), Hafnium tri (methoxy) mono (triphenylsilanolate), Hafnium tri (methoxy) mono (tribenzylsilanolate), Hafnium tri (methoxy) mono (trinaphthylsilanolate) ), Hafnium tri (methoxy) mono (dimethylethylsilanolate), hafnium tri (methoxy) mono (methyldiethylsilanolate),

Hafnium tri (ethoxy) mono (trimethylsilanolate), hafnium tri (ethoxy) mono (triethylsilanolate), hafnium tri (ethoxy) mono (triisopropylsilanolate), hafnium tri (ethoxy) mono (tributylsilanolate) ),
Hafnium tri (ethoxy) mono (tripentyl silanolate), Hafnium tri (ethoxy) mono (triphenylsilanolate), Hafnium tri (ethoxy) mono (tribenzylsilanolate), Hafnium tri (ethoxy) mono (trinaphthylsilanolate) ), Hafnium tri (ethoxy) mono (dimethylethylsilanolate), hafnium tri (ethoxy) mono (methyldiethylsilanolate),

Hafnium tri (propoxy) mono (trimethylsilanolate), hafnium tri (propoxy)
Mono (triethylsilanolate), hafnium tri (propoxy) mono (triisopropylsilanolate), hafnium tri (propoxy) mono (tributylsilanolate), hafnium tri (propoxy) mono (tripentylsilanolate), hafnium tri (propoxy) Mono (triphenylsilanolate), hafnium tri (propoxy) mono (tribenzylsilanolate), hafnium tri (propoxy) mono (trinaphthylsilanolate), hafnium tri (propoxy) mono (dimethylethylsilanolate), hafnium tri ( Propoxy) mono (methyldiethylsilanolate),

Hafnium tri (butoxy) mono (trimethylsilanolate), hafnium tri (butoxy) mono (triethylsilanolate), hafnium tri (butoxy) mono (triisopropylsilanolate), hafnium tri (butoxy) mono (tributylsilanolate) ),
Hafnium tri (butoxy) mono (tripentyl silanolate), Hafnium tri (butoxy) mono (triphenylsilanolate), Hafnium tri (butoxy) mono (tribenzylsilanolate), Hafnium tri (butoxy) mono (trinaphthylsilanolate) ), Hafnium tri (butoxy) mono (dimethylethylsilanolate), hafnium tri (butoxy) mono (methyldiethylsilanolate),

Hafnium tri (phenoxy) mono (trimethylsilanolate), hafnium tri (phenoxy)
Mono (triethylsilanolate), hafnium tri (phenoxy) mono (triisopropylsilanolate), hafnium tri (phenoxy) mono (tributylsilanolate), hafnium tri (phenoxy) mono (tripentylsilanolate), hafnium tri (phenoxy) Mono (triphenylsilanolate), hafnium tri (phenoxy) mono (tribenzylsilanolate), hafnium tri (phenoxy) mono (trinaphthylsilanolate), hafnium tri (phenoxy) mono (dimethylethylsilanolate), hafnium tri ( Phenoxy) mono (methyldiethylsilanolate),

Hafnium di (methoxy) di (trimethylsilanolate), hafnium di (methoxy) di (triethylsilanolate), hafnium di (methoxy) di (triisopropylsilanolate), hafnium di (methoxy) di (tributylsilanolate), hafnium di ( Methoxy) di (tripentyl silanolate), hafnium di (methoxy) di (triphenylsilanolate), hafnium di (methoxy) di (tribenzylsilanolate), hafnium di (methoxy) di (trinaphthylsilanolate), hafnium di (methoxy) Bis (dimethylethylsilanolate), hafnium di (methoxy) bis (methyldiethylsilanolate),

Hafnium di (ethoxy) di (trimethylsilanolate), hafnium di (ethoxy) di (triethylsilanolate), hafnium di (ethoxy) di (triisopropylsilanolate), hafnium di (ethoxy) di (tributylsilanolate), hafnium di ( Ethoxy) di (tripentyl silanolate), hafnium di (ethoxy) di (triphenylsilanolate), hafnium di (ethoxy) di (tribenzylsilanolate), hafnium di (ethoxy) di (trinaphthylsilanolate), hafnium di (ethoxy) Bis (dimethylethylsilanolate), hafnium di (ethoxy) bis (methyldiethylsilanolate),

Hafnium di (propoxy) di (trimethylsilanolate), hafnium di (propoxy) di (triethylsilanolate), hafnium di (propoxy)
Di (triisopropylsilanolate), hafnium di (propoxy) di (tributylsilanolate), hafnium di (propoxy) di (tripentylsilanolate), hafnium di (propoxy) di (triphenylsilanolate), hafnium di (propoxy) di (tri) Benzylsilanolate), hafniumdi (propoxy) di (trinaphthylsilanolate), hafniumdi (propoxy) bis (dimethylethylsilanolate), hafniumdi (propoxy) bis (methyldiethylsilanolate),

Hafnium di (butoxy) di (trimethylsilanolate), hafnium di (butoxy) di (triethylsilanolate), hafnium di (butoxy) di (triisopropylsilanolate), hafnium di (butoxy) di (tributylsilanolate), hafnium di ( Butoxy) di (tripentylsilanolate), hafnium di (butoxy) di (triphenylsilanolate), hafnium di (butoxy) di (tribenzylsilanolate), hafnium di (butoxy) di (trinaphthylsilanolate), hafnium di (butoxy) Bis (dimethylethylsilanolate), hafnium di (butoxy) bis (methyldiethylsilanolate),

Hafnium di (phenoxy) di (trimethylsilanolate), hafnium di (phenoxy) di (triethylsilanolate), hafnium di (phenoxy)
Di (triisopropylsilanolate), hafnium di (phenoxy) di (tributylsilanolate), hafnium di (phenoxy) di (tripentylsilanolate), hafnium di (phenoxy) di (triphenylsilanolate), hafnium di (phenoxy) di (tri) Benzylsilanolate), hafniumdi (phenoxy) di (trinaphthylsilanolate), hafniumdi (phenoxy) bis (dimethylethylsilanolate), hafniumdi (phenoxy) bis (methyldiethylsilanolate),

Hafnium (methoxy) tris (trimethylsilanolate), hafnium (methoxy) tris (triethylsilanolate), hafnium (methoxy) tris (triisopropylsilanolate), hafnium (methoxy) tris (tributylsilanolate), hafnium ( Methoxy) tris (tripentyl silanolate),
Hafnium (methoxy) tris (triphenylsilanolate), hafnium (methoxy) tris (tribenzylsilanolate), hafnium (methoxy) tris (trinaphthylsilanolate), hafnium (methoxy) tri (dimethylethylsilanolate), hafnium ( Methoxy) tri (methyldiethylsilanolate),

Hafnium (ethoxy) tris (trimethylsilanolate), hafnium (ethoxy) tris (triethylsilanolate), hafnium (ethoxy) tris (triisopropylsilanolate), hafnium (ethoxy) tris (tributylsilanolate), hafnium ( Ethoxy) tris (tripentyl silanolate),
Hafnium (ethoxy) tris (triphenylsilanolate), hafnium (ethoxy) tris (tribenzylsilanolate), hafnium (ethoxy) tris (trinaphthylsilanolate), hafnium (ethoxy) tri (dimethylethylsilanolate), hafnium ( Ethoxy) tri (methyldiethylsilanolate),

Hafnium (propoxy) tris (trimethylsilanolate), hafnium (propoxy) tris (triethylsilanolate), hafnium (propoxy) tris (triisopropylsilanolate), hafnium (propoxy) tris (tributylsilanolate), hafnium ( Propoxy) tris (tripentyl silanolate), hafnium (propoxy) tris (triphenyl silanolate), hafnium (propoxy)
Tris (tribenzylsilanolate), hafnium (propoxy) tris (trinaphthylsilanolate), hafnium (propoxy) tri (dimethylethylsilanolate), hafnium (propoxy) tri (methyldiethylsilanolate),

Hafnium (butoxy) tris (trimethylsilanolate), hafnium (butoxy) tris (triethylsilanolate), hafnium (butoxy) tris (triisopropylsilanolate), hafnium (butoxy) tris (tributylsilanolate), hafnium ( Butoxy) tris (tripentyl silanolate),
Hafnium (butoxy) tris (triphenylsilanolate), hafnium (butoxy) tris (tribenzylsilanolate), hafnium (butoxy) tris (trinaphthylsilanolate), hafnium (butoxy) tri (dimethylethylsilanolate), hafnium ( Butoxy) tri (methyldiethylsilanolate),

Hafnium (phenoxy) tris (trimethylsilanolate), hafnium (phenoxy) tris (triethylsilanolate), hafnium (phenoxy) tris (triisopropylsilanolate), hafnium (phenoxy) tris (tributylsilanolate), hafnium ( Phenoxy) tris (tripentyl silanolate), hafnium (phenoxy) tris (triphenyl silanolate), hafnium (phenoxy)
Tris (tribenzylsilanolate), hafnium (phenoxy) tris (trinaphthylsilanolate), hafnium (phenoxy) tri (dimethylethylsilanolate), hafnium (phenoxy) tri (methyldiethylsilanolate),

Hafnium trimethyl mono (trimethylsilanolate), hafnium trimethyl mono (triethyl silanolate), hafnium trimethyl mono (triisopropyl silanolate), hafnium trimethyl mono (tributyl silanolate), hafnium trimethyl mono (tripentyl silanolate), Hafnium trimethyl mono (triphenylsilanolate), hafnium trimethylmono (tribenzylsilanolate), hafnium trimethylmono (trinaphthylsilanolate), hafnium trimethylmono (dimethylethylsilanolate),
Hafnium trimethyl mono (methyldiethylsilanolate),

Hafnium triethylmono (trimethylsilanolate), hafnium triethylmono (triethylsilanolate), hafnium triethylmono (triisopropylsilanolate), hafnium triethylmono (tributylsilanolate), hafnium triethylmono (tripentylsilanolate), Hafnium triethyl mono (triphenylsilanolate), hafnium triethylmono (tribenzylsilanolate), hafnium triethylmono (trinaphthylsilanolate), hafnium triethylmono (dimethylethylsilanolate),
Hafnium triethylmono (methyldiethylsilanolate),

Hafnium tripropyl mono (trimethylsilanolate), hafnium tripropyl mono (triethylsilanolate), hafnium tripropylmono (triisopropylsilanolate), hafnium tripropylmono (tributylsilanolate), hafnium tripropylmono (tri) Pentyl silanolate), hafnium tripropyl mono (triphenyl silanolate), hafnium tripropyl mono (tribenzyl silanolate), hafnium tripropyl mono (trinaphthyl silanolate), hafnium tripropyl mono (dimethylethyl silanolate), hafnium Tripropylmono (methyldiethylsilanolate),

Hafnium tributyl mono (trimethylsilanolate), hafnium tributylmono (triethylsilanolate), hafnium tributylmono (triisopropylsilanolate), hafnium tributylmono (tributylsilanolate), hafnium tributylmono (tripentylsilanolate), Hafnium tributyl mono (triphenylsilanolate), hafnium tributylmono (tribenzylsilanolate), hafnium tributylmono (trinaphthylsilanolate), hafnium tributylmono (dimethylethylsilanolate),
Hafnium tributyl mono (methyldiethylsilanolate),

Hafnium triphenyl mono (trimethylsilanolate), hafnium triphenylmono (triethylsilanolate), hafnium triphenylmono (triisopropylsilanolate), hafnium triphenylmono (tributylsilanolate), hafnium triphenylmono (tri) Pentyl silanolate), hafnium triphenyl mono (triphenyl silanolate), hafnium triphenyl mono (tribenzyl silanolate), hafnium triphenyl mono (trinaphthyl silanolate), hafnium triphenyl mono (dimethyl ethyl silanolate), hafnium Triphenylmono (methyldiethylsilanolate),

Hafnium tribenzyl mono (trimethylsilanolate), hafnium tribenzyl mono (triethylsilanolate), hafnium tribenzyl mono (triisopropylsilanolate), hafnium tribenzyl mono (tributylsilanolate), hafnium tribenzyl mono (tri) Pentyl silanolate), hafnium tribenzyl mono (triphenyl silanolate), hafnium tribenzyl mono (tribenzyl silanolate), hafnium tribenzyl mono (trinaphthyl silanolate), hafnium tribenzyl mono (dimethylethyl silanolate), hafnium Tribenzyl mono (methyldiethylsilanolate),

Hafnium dimethyldi (trimethylsilanolate), hafnium dimethyldi (triethylsilanolate), hafnium dimethyldi (triisopropylsilanolate), hafnium dimethyldi (tributylsilanolate), hafnium dimethyldi (tripentylsilanolate), Hafnium dimethyldi (triphenylsilanolate), hafnium dimethyldi (tribenzylsilanolate), hafnium dimethyldi (trinaphthylsilanolate), hafnium dimethylbis (dimethylethylsilanolate), hafnium dimethylbis (methyldiethylsilanolate),

Hafnium diethyldi (trimethylsilanolate), hafnium diethyldi (triethylsilanolate), hafnium diethyldi (triisopropylsilanolate), hafnium diethyldi (tributylsilanolate), hafnium diethyldi (tripentylsilanolate), Hafnium diethyldi (triphenylsilanolate), hafnium diethyldi (tribenzylsilanolate), hafnium diethyldi (trinaphthylsilanolate), hafnium diethylbis (dimethylethylsilanolate), hafnium diethylbis (methyldiethylsilanolate),

Hafnium dipropyl di (trimethylsilanolate), hafnium dipropyl di (triethyl silanolate), hafnium dipropyl di (triisopropyl silanolate), hafnium dipropyl di (tributyl silanolate), hafnium dipropyl di (tri) Pentyl silanolate), hafnium dipropyl di (triphenyl silanolate), hafnium dipropyl di (tribenzyl silanolate), hafnium dipropyl di (trinaphthyl silanolate), hafnium dipropyl bis (dimethyl ethyl silanolate), hafnium Dipropylbis (methyldiethylsilanolate),

Hafnium dibutyl di (trimethylsilanolate), hafnium dibutyl di (triethyl silanolate), hafnium dibutyl di (triisopropyl silanolate), hafnium dibutyl di (tributyl silanolate), hafnium dibutyl di (tripentyl silanolate), Hafnium dibutyldi (triphenylsilanolate), hafnium dibutyldi (tribenzylsilanolate), hafnium dibutyldi (trinaphthylsilanolate), hafniumdibutylbis (dimethylethylsilanolate), hafniumdibutylbis (methyldiethylsilanolate),

Hafnium diphenyldi (trimethylsilanolate), hafnium diphenyldi (triethylsilanolate), hafnium diphenyldi (triisopropylsilanolate), hafnium diphenyldi (tributylsilanolate), hafnium diphenyldi (tripentylsilanolate), Hafnium diphenyldi (triphenylsilanolate), hafnium diphenyldi (tribenzylsilanolate), hafnium diphenyldi (trinaphthylsilanolate), hafnium diphenylbis (dimethylethylsilanolate), hafnium diphenylbis (methyldiethylsilanolate),

Hafnium dibenzyldi (trimethylsilanolate), hafnium dibenzyldi (triethylsilanolate), hafnium dibenzyldi (triisopropylsilanolate), hafnium dibenzyldi (tributylsilanolate), hafnium dibenzyldi (tri) Pentyl silanolate), hafnium dibenzyldi (triphenylsilanolate), hafnium dibenzyldi (tribenzylsilanolate), hafnium dibenzyldi (trinaphthylsilanolate), hafnium dibenzylbis (dimethylethylsilanolate), hafnium Dibenzylbis (methyldiethylsilanolate),

Hafnium methyl tris (trimethylsilanolate), hafnium methyl tris (triethyl silanolate), hafnium methyl tris (triisopropyl silanolate), hafnium methyl tris (tributyl silanolate), hafnium methyl tris (tripentyl silanolate), Hafnium methyl tris (triphenyl silanolate), hafnium methyl tris (tribenzyl silanolate), hafnium methyl tris (trinaphthyl silanolate), hafnium methyl tri (dimethylethyl silanolate), hafnium methyl tri (methyl diethyl silanolate),

Hafnium ethyl tris (trimethylsilanolate), hafnium ethyl tris (triethyl silanolate), hafnium ethyl tris (triisopropyl silanolate), hafnium ethyl tris (tributyl silanolate), hafnium ethyl tris (tripentyl silanolate), Hafnium ethyl tris (triphenyl silanolate), hafnium ethyl tris (tribenzyl silanolate), hafnium ethyl tris (trinaphthyl silanolate), hafnium ethyl tri (dimethyl ethyl silanolate), hafnium ethyl tri (methyl diethyl silanolate),

Hafnium propyl tris (trimethylsilanolate), hafnium propyl tris (triethyl silanolate), hafnium propyl tris (triisopropyl silanolate), hafnium propyl tris (tributyl silanolate), hafnium propyl tris (tripentyl silanolate), Hafnium propyl tris (triphenyl silanolate), hafnium propyl tris (tribenzyl silanolate), hafnium propyl tris (trinaphthyl silanolate), hafnium propyl tri (dimethylethyl silanolate), hafnium propyl tri (methyl diethyl silanolate),

Hafnium butyl tris (trimethylsilanolate), hafnium butyl tris (triethyl silanolate), hafnium butyl tris (triisopropyl silanolate), hafnium butyl tris (tributyl silanolate), hafnium butyl tris (tripentyl silanolate), Hafnium butyl tris (triphenyl silanolate), hafnium butyl tris (tribenzyl silanolate), hafnium butyl tris (trinaphthyl silanolate), hafnium butyl tri (dimethylethyl silanolate), hafnium butyl tri (methyl diethyl silanolate),

Hafnium phenyl tris (trimethylsilanolate), hafnium phenyl tris (triethyl silanolate), hafnium phenyl tris (triisopropyl silanolate), hafnium phenyl tris (tributyl silanolate), hafnium phenyl tris (tripentyl silanolate), Hafnium phenyl tris (triphenyl silanolate), hafnium phenyl tris (tribenzyl silanolate), hafnium phenyl tris (trinaphthyl silanolate), hafnium phenyl tri (dimethylethyl silanolate), hafnium phenyl tri (methyl diethyl silanolate),

Hafnium benzyl tris (trimethylsilanolate), hafnium benzyl tris (triethyl silanolate), hafnium benzyl tris (triisopropyl silanolate), hafnium benzyl tris (tributyl silanolate), hafnium benzyl tris (tripentyl silanolate), Hafnium benzyl tris (triphenyl silanolate), hafnium benzyl tris (tribenzyl silanolate), hafnium benzyl tris (trinaphthyl silanolate), hafnium benzyl tri (dimethylethyl silanolate), hafnium benzyl tri (methyl diethyl silanolate),

Hafnium methylethoxydi (trimethylsilanolate), hafnium methylbutyldi (triethylsilanolate), hafnium phenylmethoxydi (trimethylsilanolate), hafniumphenylbenzyldi (triethylsilanolate),

Hafnium chlorotris (trimethylsilanolate), hafnium chlorotris (triethylsilanolate), hafnium chlorotris (triisopropylsilanolate), hafnium chlorotris (tributylsilanolate), hafnium chlorotris (tripentylsilanolate), Hafnium chlorotris (triphenylsilanolate), hafnium chlorotris (tribenzylsilanolate), hafnium chlorotris (trinaphthylsilanolate), hafnium chlorotri (dimethylethylsilanolate), hafnium chlorotri (methyldiethylsilanolate),

Hafnium bromotris (trimethylsilanolate), hafnium bromotris (triethylsilanolate), hafnium bromotris (triisopropylsilanolate), hafnium bromotris (tributylsilanolate), hafnium bromotris (tripentylsilanolate), Hafnium bromotris (triphenylsilanolate), hafnium bromotris (tribenzylsilanolate), hafnium bromotris (trinaphthylsilanolate), hafnium bromotri (dimethylethylsilanolate), hafnium bromotri (methyldiethylsilanolate),

Hafnium iodotris (trimethylsilanolate), hafnium iodotris (triethylsilanolate), hafnium iodotris (triisopropylsilanolate), hafnium iodotris (tributylsilanolate), hafnium iodotris (tripentylsilanolate), Hafnium iodotris (triphenylsilanolate), hafnium iodotris (tribenzylsilanolate), hafnium iodotris (trinaphthylsilanolate), hafnium iodotri (dimethylethylsilanolate), hafnium iodotri (methyldiethylsilanolate),

Hafnium tetra (trimethylsilanolate), hafnium tetra (triethylsilanolate),
Hafnium tetra (triisopropylsilanolate),
Hafnium tetra (tributylsilanolate), hafnium tetra (tripentylsilanolate), hafnium tetra (triphenylsilanolate), hafnium tetra (tribenzylsilanolate), hafnium tetra (trinaphthylsilanolate), hafnium tetra (dimethylethylsilanoate) Rate), hafnium tetra (methyldiethylsilanolate),

Hafnium chloromethyldi (trimethylsilanolate), hafnium chloroethyldi (triethylsilanolate), hafnium bromomethyldi (trimethylsilanolate), hafnium bromoethyldi (triethylsilanolate), hafnium iodomethyldi (trimethylsilanolate) Rate), hafnium iodoethyldi (triethylsilanolate), hafnium chlorodimethyl (trimethylsilanolate), hafnium chlorodiethyl (triethylsilanolate), hafnium bromodimethyl (trimethylsilanolate), hafnium bromodiethyl (triethylsilanolate), hafnium iodo Dimethyl (trimethylsilanolate), hafnium iododiethyl (triethylsilanolate),

And so on. Of course, in these compounds exemplified as the above-mentioned component (1), R and R ′ are not only n- but also iso-, s-, t-, ne.
It also includes the case of various structural isomer groups such as o-. Among these specific compounds, zirconium tetra (trimethylsilanolate), zirconium tetra (triethylsilanolate), zirconium tetra (triisopropylsilanolate), zirconium (methoxy) tri (dimethylethylsilanolate), zirconium (methoxy) tri ( Methyldiethylsilanolate),
Zirconium (ethoxy) tris (trimethylsilanolate) and zirconium (ethoxy) tris (triethylsilanolate) are preferable. These compounds can be used as a mixture of two or more kinds.

Component (2) is a compound represented by the following general formula. Me ² R _m (OR ′) _n X _{z-m-n In the} formula, Me ² represents any one of Group I to III elements of the periodic table, and includes lithium, sodium, potassium, magnesium, calcium and zinc. , Boron, aluminum and the like. R and R'represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 and more preferably 1 to 8, which includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, and a butyl group. Group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group,
Alkyl groups such as decyl group and dodecyl group; alkenyl groups such as vinyl group, allyl group, phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, aryl groups such as naphthyl group; benzyl group, trityl group, phenethyl group And aralkyl groups such as styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group, and neophyll group. These may have branches.
X represents halogen such as fluorine, iodine, chlorine or bromine. z represents the valence of Me ² . m is 0 ≦ m ≦ z, n is 0
≦ n ≦ 1, and 0 ≦ m + n ≦ z, preferably 0 <m
+ N ≦ z.

Specific examples of the compound usable as the component (2) include methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, t-butyllithium, pentyllithium, octyllithium, phenyllithium and benzyllithium. , Dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, di-t-butyl magnesium, dipentyl magnesium, dioctyl magnesium, diphenyl magnesium, dibenzyl magnesium, methyl magnesium chloride, ethyl magnesium chloride,
Propyl magnesium chloride, isopropyl magnesium chloride, butyl magnesium chloride, t
-Butyl magnesium chloride, pentyl magnesium chloride, octyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium bromide, propyl magnesium iodide, isopropyl magnesium Bromide, Isopropyl magnesium iodide, Butyl magnesium bromide, Butyl magnesium iodide, t-Butyl magnesium bromide, t-Butyl magnesium iodide, Pentyl magnesium bromide, Pentyl magnesium iodide, Octyl magnesium bromide, Octyl mag Nitrosium iodide, phenyl magnesium bromide, phenyl magnesium iodide, benzyl bromide, benzyl magnesium iodide,

Dimethyl zinc, diethyl zinc, dipropyl zinc, diisopropyl zinc, di-n-butyl zinc, di-t-
Butyl zinc, dipentyl zinc, dioctyl zinc, diphenyl zinc, dibenzyl zinc, trimethylboron, triethylboron, tripropylboron, triisopropylboron, tributylboron, tri-t-butylboron, tripentylboron, trioctylboron, triphenylboron, tri Benzylboron, trimethylaluminum,
Triethyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum fluoride, diethyl aluminum iodide, ethyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum diiodide, tripropyl aluminum, dipropyl aluminum chloride , Dipropyl aluminum bromide, dipropyl aluminum fluoride, dipropyl aluminum iodide,

Propyl aluminum dichloride, propyl aluminum dibromide, propyl aluminum difluoride, propyl aluminum diiodide, triisopropyl aluminum, diisopropyl aluminum chloride, diisopropyl aluminum bromide, diisopropyl aluminum fluoride,
Diisopropyl aluminum iodide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, propyl aluminum sesquichloride,
Propyl aluminum sesquibromide, butyl aluminum sesquibromide, butyl aluminum sesquibromide, isopropyl aluminum dichloride, isopropyl aluminum dibromide, isopropyl aluminum difluoride, isopropyl aluminum diiodide, tributyl aluminum, dibutyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum fluoride Ride, dibutyl aluminum iodide, butyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum difluoride, butyl aluminum diiodide, tri sec-butyl aluminum, di sec-butyl aluminum chloride, di sec-bryl aluminum bromide, sec- butyl aluminum fluoride, di-sec- butyl aluminum iodide,
sec-Butyl aluminum dichloride, sec-butyl aluminum dibromide, sec-butyl aluminum difluoride, sec-butyl aluminum diiodide, tri-tert-butyl aluminum, di-tert-butyl aluminum chloride, di-tert.
-Butyl aluminum bromide, di-tert-butyl aluminum fluoride, di-tert-butyl aluminum iodide,

Tert-Butyl aluminum dichloride, tert-butyl aluminum dibromide, te
rt-Butyl aluminum difluoride, tert-
Butyl aluminum diiodide, triisobutyl aluminum, diisobutyl aluminum chloride, diisobutyl aluminum bromide, diisobutyl aluminum fluoride, diisobutyl aluminum iodide, isobutyl aluminum dichloride, isobutyl aluminum dibromide, isobutyl aluminum difluoride, isobutyl aluminum diiodide, tri Hexyl aluminum, dihexyl aluminum chloride, dihexyl aluminum bromide, dihexyl aluminum fluoride, dihexyl aluminum iodide, hexyl aluminum dichloride, hexyl aluminum dibromide, hexyl aluminum difluoride, hexyl aluminum diiodide, Pentyl aluminum, dipentyl aluminum chloride, dipentyl aluminum bromide, dipentyl aluminum fluoride, dipentyl aluminum iodide, pentyl aluminum dichloride, pentyl aluminum dibromide,
Pentyl aluminum difluoride and pentyl aluminum diiodide, methyl aluminum methoxide, methyl aluminum ethoxide, methyl aluminum propoxide, methyl aluminum butoxide, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, dimethyl aluminum propoxide, dimethyl aluminum butoxide, Ethyl aluminum methoxide,

Ethyl aluminum ethoxide, ethyl aluminum propoxide, ethyl aluminum butoxide, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, propyl aluminum methoxide, propyl aluminum ethoxide,
Propyl aluminum propoxide, propyl aluminum butoxide, dipropyl aluminum methoxide,
Dipropyl aluminum ethoxide, dipropyl aluminum butoxide, dipropyl aluminum butoxide, butyl aluminum methoxide, butyl aluminum ethoxide, butyl aluminum propoxide, butyl aluminum butoxide, dibutyl aluminum methoxide, dibutyl aluminum ethoxide, dibutyl aluminum propoxide , Dibutyl aluminum butoxide and the like.

As the component (3), a cyclic organic compound having two or more conjugated double bonds is used. Ingredient (3)
Includes two or more, preferably 2 to 4 conjugated double bonds,
More preferably, a cyclic hydrocarbon compound having 1 or 2 or more rings having 2 to 3 and having a total carbon number of 4 to 24, preferably 4 to 12; and the cyclic hydrocarbon compound is partially 1 to 6 Hydrocarbon residues (typically having 1 to 1 carbon atoms)
A cyclic hydrocarbon compound substituted with 12 alkyl groups or aralkyl groups); having 1 or 2 or more rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. , The total carbon number is 4 to 24, preferably 4
An organosilicon compound having a cyclic hydrocarbon group of 1 to 12; an organosilicon compound in which the cyclic hydrocarbon group is partially substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium salt or lithium salt). Is included. Particularly preferably, one having a cyclopentadiene structure in any of the molecules is desirable.

Incidentally, as a preferred example of the cyclic hydrocarbon compound, compounds represented by the following general formula can be mentioned.

[0170]

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In Formula 1, R ¹ , R ² , R ³ , and R ⁴
Is hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, and any ^{two of} R ¹ , R ² , R ³ and R ⁴ may be combined to form a cyclic hydrocarbon group. As the hydrocarbon residue, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, an alkyl group such as an octyl group, an aryl group such as a phenyl group,
An alkoxy group such as a methoxy group, an ethoxy group and a propoxy group, an aryloxy group such as a phenoxy group, an aralkyl group such as a benzyl group, and a cyclic hydrocarbon when any two of them jointly form a cyclic hydrocarbon group. Examples of the skeleton of the group include cycloheptatriene, aryl and condensed rings thereof. As the compound represented by Chemical formula 1, cyclopentadiene, indene,
Examples include azulene, or an alkyl, aryl, aralkyl, alkoxy or aryloxy derivative thereof. Further, a compound in which the compound represented by Chemical formula 1 is bonded (crosslinked) via an alkylene group (its carbon number is usually 2 to 8, preferably 2 to 3) is also suitably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A ₁ SiR _4-L wherein A represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, the cyclic hydrocarbon group exemplified by the substituted indenyl group, and R represents a methyl group, an ethyl group, Alkyl groups such as propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; aryl groups such as phenyl group; phenoxy group etc. An aryloxy group of: a hydrocarbon residue or hydrogen having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, as exemplified by an aralkyl group such as a benzyl group, L is 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound usable as the component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene,
t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene,
1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, 4,5,
Cyclohexyl having 7 to 24 carbon atoms such as 6,7-tetrahydroindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, methylcyclooctatetraene, azulene, methylazulene, ethylazulene, fluorene and methylfluorene. Polyene or substituted cyclopolyene,

Monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadienylsilane, tetrakiscyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclo Pentadienyldimethylsilane, Monocyclopentadienyldiethylsilane, Monocyclopentadienyltrimethylsilane, Monocyclopentadienyltriethylsilane, Monocyclopentadienylmonomethoxysilane, Monocyclopentadienylmonoethoxysilane, Monocyclo Pentadienylmonophenoxysilane,

Biscyclopentadienylmonomethylsilane, biscyclopentadienylmonoethylsilane, biscyclopentadienyldimethylsilane, biscyclopentadienyldiethylsilane, biscyclopentadienylmethylethylsilane, biscyclopentadienyl Dipropylsilane, biscyclopentadienylethylpropylsilane, biscyclopentadienyldiphenylsilane,
Biscyclopentadienylphenylmethylsilane, Biscyclopentadienylmonomethoxysilane, Biscyclopentadienylmonoethoxysilane, Triscyclopentadienylmonomethylsilane, Triscyclopentadienylmonoethylsilane, Triscyclopentadienylmonosilane Methoxysilane, triscyclopentadienyl monoethoxysilane, 3-methylcyclopentadienylsilane, bis-3-methylcyclopentadienylsilane, 3-
Methylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclopentadienylsilane, 1,2,3,4 -Tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane,

Monoindenylsilane, bisindenylsilane, trisindenylsilane, tetrakisindenylsilane, monoindenylmonomethylsilane, monoindenylmonoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindene. Nyltrimethylsilane, monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane, monoindenylmonophenoxysilane, bisindenylmonomethylsilane, bisindenylmonoethylsilane, bisindenyldimethylsilane, Bisindenyldiethylsilane, bisindenylmethylethylsilane, bisindenyldipropylsilane, bisindenylethylpropylsilane, bisindenyldiphenylsilane, bisyne Cycloalkenyl phenylmethyl silane, bis indenyl monomethoxy silane, bis indenyl mono-ethoxysilane,

Trisindenyl monomethylsilane, trisindenyl monoethylsilane, trisindenyl monomethoxysilane, trisindenyl monoethoxysilane, 3-methylindenylsilane, bis-3-methylindenylsilane, 3-methylindenyl. Methylsilane,
1,2-dimethylindenylsilane, 1,3-dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane, pentamethylindenylsilane, etc. is there.

Any one of the above compounds may be an alkylene group (the carbon number of which is usually 2-8, preferably 2
A compound bound via 3) can also be used as the component (3) of the present invention. For example, bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl)
Ethane, 1,3-propanedinyl bisindene, 1,3
-Propandinylbis (4,5,6,7-tetrahydro) indene, propylenebis (1-indene), isopropyl (1-indenyl) cyclopentadiene, diphenylmethylene (9-fluorenyl) cyclopentadiene, isopropylcyclopentadienyl All such as -1-fluorene isopropylbiscyclopentadiene are compounds that can be used as the component (3) of the present invention.

The catalyst component of the present invention comprises the above-mentioned three components, namely, (1) the general formula Me ¹ R ¹ , _p (OR ² ) _q X _r.
^{(OSiR 3 R 4 R 5)} 4-p-q-r compounds represented by (component (1)), (2) the general formula ^Me 2 _R m (OR ')
By bringing the compound represented by _n X _z-m-n (component (2)) and the organic compound (component (3)) which is (3) cyclic and has two or more conjugated double bonds (component (3)) into contact with each other. can get.

As the contact ratio, the usual component (1) is used.
With respect to 1 mol, the lower limit of the component (2) is 0.01 mol, preferably 0.1 mol, more preferably 0.5 mol, and the upper limit is 1000 mol, preferably 100 mol, further preferably 50 mol. The lower limit of (3) is 0.01 mol, preferably 0.1 mol, more preferably 0.5 mol, and the upper limit is 1000 mol, preferably 100 mol, more preferably 50 mol, in contact with each other. Is prepared by. In this case, the lower limit of the component (3) is 0.001 mol, preferably 0.01 mol, more preferably 0.1 mol, and the upper limit is 1000 mol, preferably 100 mol, relative to 1 mol of the component (2). It is desirable to contact them at a ratio of preferably 10 mol.

The contact order of the three components is arbitrary,
As a suitable method, for example, the catalyst components of the present invention can be obtained by contacting each component with the following method. A method of simultaneously contacting the components (1), (2) and (3). A method of adding component (3) in the presence of component (1) and then contacting component (2). A method of adding component (2) in the presence of component (1) and then contacting component (3). A method of adding component (3) in the presence of component (2) and then contacting component (1). A method of contacting the component (3) after adding the component (1) in the presence of the component (2). A method of adding component (2) and then contacting component (1) in the presence of component (3). Examples include a method of contacting the component (2) after adding the component (1) in the presence of the component (3). Particularly, the components (1), (2) and (3) are contacted at the same time. Method. A method of adding component (3) in the presence of component (1) and then contacting component (2). A method of adding component (3) in the presence of component (2) and then contacting component (1). A method of adding the component (2) in the presence of the component (3) and then contacting the component (1) is preferable.

Although the method of contacting the three components is arbitrary,
Component (1), component (2) and component (3) are contacted in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene and xylene, usually in an inert atmosphere such as nitrogen or argon. It is preferable. The temperature conditions in this case are usually in the range of -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C, and the contact time is 30 minutes to
It is in the range of 50 hours, preferably 2 hours to 24 hours.
When each component is contacted in an inert hydrocarbon solvent, the produced catalyst component can be directly subjected to polymerization together with the solvent, and once taken out as a solid catalyst component by means of precipitation, drying, etc., It can also be used for polymerization. Of course, each component may be contacted multiple times.

The catalyst component of the present invention obtained by bringing the components (1) to (3) into contact with each other as described above is usually combined with a further promoter-like catalyst component to polymerize or copolymerize olefins. It becomes a useful catalyst. As the promoter-like catalyst component, any one kind or a combination of two or more kinds may be used as long as it does not impair the object of the present invention and the performance of the catalyst part. For this, the following modified organoaluminum compounds are used.

Modified Organoaluminum Compound (Component (4)) The modified organoaluminum compound which can be used in the present invention is a reaction product of an organoaluminum compound and water, which is 1 to 100 in the molecule, preferably Is 1
It contains 50 Al-O-Al bonds. The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.

The organoaluminum compound used for preparing the modified organoaluminum compound has the general formula R ⁶ _a AlX ′.
_3-a (In the formula, R ⁶ has 1 to 18 carbon atoms, preferably 1 to
12 are hydrocarbon groups such as an alkyl group, an alkenyl group, an aryl group, and an aralkyl group; X ′ is a hydrogen atom or a halogen atom; and a is an integer of 1 ≦ a ≦ 3. Although usable, trialkylaluminum is preferably used. The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Is particularly preferable.

The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, and particularly preferably 0.5 / 1 to 1/1. The reaction temperature is usually -70 to 100 ° C, preferably -20 to 20 ° C.
Is in the range. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, so-called water can be used, and also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like can be used.

According to the present invention, olefins are homopolymerized or polymerized in the presence of a catalyst composed of the above catalyst component and a promoter-like catalyst component exemplified by the modified organoaluminum compound (component (4)). Copolymerized.
In this case, the catalyst component and the modified organoaluminum compound are
It can be fed separately or previously mixed or contacted into the polymerization reaction system. When the catalyst component and the modified organoaluminum compound are mixed or contacted in advance,
In addition to the case of simply contacting or mixing the catalyst component and the modified organoaluminum compound obtained by bringing the components (1) to (3) into contact with each other, by further bringing the components (1) to (4) into contact with each other. It also includes a method of obtaining a catalyst.

The contact order of the four components is arbitrary,
As a suitable method, for example, the catalyst components of the present invention can be obtained by contacting each component with the following method. A method of adding component (3) in the presence of component (1), then contacting component (2) and adding component (4). A method of adding component (2) in the presence of component (1), then contacting component (3) and adding component (4). After adding the component (3) in the presence of the component (2), the component (1) is brought into contact with the component (4).
How to add. A method of adding component (1) in the presence of component (2), then contacting component (3) and adding component (4). A method of adding component (2) in the presence of component (3), then contacting component (1) and adding component (4). A method of adding component (1) in the presence of component (3), and then contacting component (2) and adding component (4). A method of adding component (3) in the presence of component (1), then contacting component (4) and adding component (2). After adding the component (2) in the presence of the component (1), the component (4) is brought into contact with the component (3).
How to add. A method of adding component (3) in the presence of component (2), then contacting component (4) and adding component (1). A method of adding component (1) in the presence of component (2), then contacting component (4) and adding component (3). A method of adding component (1) after adding component (2) in the presence of component (3) and then contacting component (4). A method of adding component (1) in the presence of component (3), and then contacting component (4) with component (2). In the presence of component (1), component (4)
The method of contacting the component (2) after the addition of the above, and then adding the component (3). After adding component (4) in the presence of component (1),
A method of contacting the component (3) and adding the component (2). A method of adding component (4) in the presence of component (2), then contacting component (1) and adding component (3). A method of adding component (4) in the presence of component (2), then contacting component (3) and adding component (1). After adding the component (4) in the presence of the component (3), the component (1) is brought into contact with the component (2).
How to add. A method of adding component (4) in the presence of component (3), and then contacting component (2) with component (1).
A method of adding component (3) in the presence of component (4), then contacting component (2) and adding component (1). A method in which the component (2) is added in the presence of the component (4), and then the component (3) is brought into contact with the component (1). A method of adding component (3) in the presence of component (4), then contacting component (1) and adding component (2). After adding the component (1) in the presence of the component (4), the component (3) is brought into contact with the component (2).
How to add. A method in which after adding the component (2) in the presence of the component (4), the component (1) is contacted and the component (3) is added. Examples of the method include adding the component (1) in the presence of the component (4), and then contacting the component (2) with the component (3). Particularly, in the presence of the component (1), the component (1) After adding 3), the component (2) is contacted and the component (4) is added. A method of adding component (3) in the presence of component (2), then contacting component (1) and adding component (4). A method of adding component (2) in the presence of component (3), then contacting component (1) and adding component (4). A preferred method is to add the component (3) in the presence of the component (1), then contact the component (4) and add the component (2).

The contact method of the four components is also optional,
The presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene or xylene for component (1), component (2), component (3) and component (4), usually in an inert atmosphere such as nitrogen or argon. Lower, usually -100 ° C to 200
It is possible to employ a method of contacting at 30 ° C., preferably −50 ° C. to 100 ° C. for 30 minutes to 50 hours, preferably 2 hours to 24 hours.

When the components are brought into contact with each other in an inert hydrocarbon solvent, the produced catalyst may be directly subjected to the polymerization in a solution state after the completion of all the catalytic reactions, or, if possible, precipitated. Alternatively, the solid catalyst component may be once taken out by a means such as drying, and then used for polymerization. of course,
The contact reaction of each component may be performed multiple times. Further, the catalyst component, the promoter-like catalyst component or the catalyst can be used by supporting them on an inorganic carrier represented by alumina or silica and / or mainly on a particulate polymer carrier. In any case, the proportion of the catalyst component and the modified organoaluminum compound used is such that the atomic ratio of aluminum in the modified organoaluminum compound to the transition metal in the catalyst component is 1 to 1.
It is selected to be in the range of 0,000, preferably 5 to 1,000.

In the catalyst of the present invention, components (1) to (4)
The following combinations are mentioned as one of the preferable combinations of. Of the component (1), zirconium tri (methoxy) mono (trimethylsilanolate), zirconium tri (ethoxy) mono (tributylsilanolate), zirconium tri (alkoxy) mono (trialkylsilanolate) compounds or zirconium tetra (trimethyl) Silanolate), zirconium tetra (tributylsilanolate), zirconium tetra (tripropylsilanolate), and other zirconium tetra (trialkylsilanolate) compounds, among components (2) triethylaluminum, triisobutylaluminum, trihexylaluminum or tri Trialkyl aluminum compounds such as decyl aluminum or halogen-containing alkyls such as diethyl aluminum chloride or ethyl aluminum dichloride Luminium compounds, indene derivatives such as indene, methylindene or trimethylsilylindene among the components (3); cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene; bisindenylethane or A compound in which an indene derivative such as isopropylbiscyclopentadiene or a cyclopentadiene derivative is bonded through an alkylene group, or a compound represented by the above general formula A _L SiR _4-L such as dimethylsilylbiscyclopentadiene;
And methylaluminoxane among the components (4).

The following combinations are mentioned as one of the other suitable combinations. Zirconium trialkylmono (trialkylsilanolate) compounds such as zirconium trimethylmono (trimethylsilanolate), zirconium tributylmono (tributylsilanolate), zirconium triethylmono (triethylsilanolate) among the components (1); zirconium tribenzylmono (Tribenzylsilanolate) or zirconium tris (trityl) mono (tristritylsilanolate) or other zirconium triaralkylmono (trialalkylsilanolate) compounds, or zirconium triphenylmono (triphenylsilanolate), zirconium tristrirylmono (tris) Zirconium triaryl mono (triarylsilanolate) compounds such as trilylsilanolate), trimethylaluminum among the components (2) Um, triethylaluminum, triisobutylaluminum, tri-alkyl aluminum compound such as tri-hexyl aluminum or tridecyl aluminum or diethyl aluminum chloride, halogen-containing alkylaluminum compounds such as ethylaluminum dichloride,
Indene derivatives such as indene, methylindene or trimethylsilylindene among components (3); cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene; bisindenylethane or isopropylbiscyclo A compound in which an indene derivative such as pentadiene or a cyclopentadiene derivative is bonded via an alkylene group, a compound represented by the above general formula A _L SiR _4-L such as dimethylsilylbiscyclopentadiene, and methylaluminoxane among the components (4) .

The following combinations are mentioned as one of the other suitable combinations. Diukonium halogen tris (trialkylsilanolate) compounds such as zirconium chlorotris (trimethylsilanolate) or zirconium bromotris (tributylsilanolate) among the components (1), and triethylaluminum, triisobutylaluminum among the components (2). , A trialkylaluminum compound such as trihexylaluminum or tridecylaluminum, or an alkylaluminum alkoxide compound such as diethylaluminum butoxide, ethyldibutoxyaluminum, or diethylethoxyaluminum, indene, methylindene or Indene derivatives such as trimethylsilylindene; cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethyl Formula A, such as a compound bisindenylethane or indene derivative or cyclopentadiene derivative such as isopropyl bis cyclopentadiene is bonded via an alkylene group or a dimethylsilyl bis cyclopentadiene; cyclopentadiene derivatives, such as cyclopentadiene or trimethylsilyl cyclopentadiene _L SiR
A compound represented by _4-L , and methylaluminoxane among the components (4).

The following combinations are mentioned as one of the other suitable combinations. Among the component (1), titanium tri (methoxy) mono (trimethylsilanolate), titanium tri (ethoxy) mono (tributylsilanolate), titanium tri (phenoxy) mono (triisopropylsilanolate) and other titanium tri (alkoxy) mono (Trialkylsilanolate) compounds or titanium tetra (trialkylsilanolate) compounds such as titanium tetra (trimethylsilanolate), titanium tetra (tributylsilanolate) and titanium tetra (tripropylsilanolate), among the components (2) Alkyllithium compounds such as butyllithium or methyllithium or alkylmagnesium compounds such as dibutylmagnesium, ethylmagnesium bromide or butylmagnesium chloride, Minute (3)
Of indene derivatives such as indene, methylindene or trimethylsilylindene; cyclopentadiene,
Cyclopentadiene derivatives such as methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene; Compounds in which an indene derivative or cyclopentadiene derivative such as bisindenylethane or isopropylbiscyclopentadiene is bound via an alkylene group or dimethylsilyl A compound represented by the above general formula A _L SiR _4-L , such as biscyclopentadiene, and methylaluminoxane among the components (4).

The following combinations are mentioned as one of the other suitable combinations. Titanium trialkylmono (trialkylsilanolate) compounds such as titanium trimethylmono (trimethylsilanolate), titanium tributylmono (tributylsilanolate), and titanium triethylmono (triethylsilanolate) among the components (1); (Tribenzylsilanolate) or titanium tris (trityl) mono (tristritylsilanolate) or other titanium triaralkylmono (trialalkylsilanolate) compounds or titanium triphenylmono (triphenylsilanolate), titaniumtristrirylmono (tris) Titanium triaryl mono (triarylsilanolate) compounds such as tolylsilanolate), trimethylaluminum and triethylalanol among the components (2) Trialkylaluminum compounds such as minium, triisobutylaluminum, trihexylaluminum or tridecylaluminum, or halogen-containing alkylaluminum compounds such as diethylaluminum chloride or ethylaluminum dichloride, among components (3) such as indene, methylindene or trimethylsilylindene Indene derivative; cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene, etc. cyclopentadiene derivative; indene derivative such as bisindenylethane or isopropylbiscyclopentadiene or cyclopentadiene derivative through an alkylene group Bound compound or di Formula A _L SiR compound represented by the _4-L, such as chill bis cyclopentadiene, and methylaluminoxane of the components (4).

The following combinations are mentioned as one of the other suitable combinations. Hafnium halogen tris (trialkylsilanolate) compounds such as hafnium chlorotris (trimethylsilanolate) or hafconium bromotris (tributylsilanolate) among the components (1), triethylaluminum, triisobutylaluminum among the components (2), Trialkylaluminum compounds such as trihexylaluminum or tridecylaluminum or halogen-containing alkylaluminum compounds such as diethylaluminum chloride or ethylaluminum dichloride; indene derivatives such as indene, methylindene or trimethylsilylindene among the components (3); cyclopentadiene, Methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilyl Formula A, such as a compound bisindenylethane or indene derivative or cyclopentadiene derivative such as isopropyl bis cyclopentadiene is bonded via an alkylene group or a dimethylsilyl bis cyclopentadiene; cyclopentadiene derivatives, such as cyclopentadiene
A compound represented by _L SiR _4-L , and methylaluminoxane among the components (4).

The olefins used in the present invention include α-olefins, cyclic olefins, dienes, trienes and styrene analogs. The α-olefins include those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically, ethylene, propylene, butene-1,
Hexene-1, 4-methylpentene-1 and the like are exemplified. The α-olefins can be homopolymerized by using the catalyst component of the present invention, and also two or more kinds of α-olefins can be copolymerized. The copolymerization is alternating copolymerization, random copolymerization. It does not matter whether it is polymerization or block copolymerization.

For the copolymerization of α-olefins, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, such as ethylene and carbon number 3 to 12, preferably. Is 3 to 8
-When copolymerizing with an olefin, propylene and butene-1, propylene and 4-methylpentene-1, propylene and 4-methylbutene-1, propylene and hexene-
1, such as propylene and octene-1, the case of copolymerizing propylene with an α-olefin having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms is included. When ethylene or propylene is copolymerized with other α-olefin, the amount of the other α-olefin can be arbitrarily selected within the range of 90 mol% or less of all monomers, but generally ethylene copolymer is used. In the case of a polymer, it is 40 mol% or less, preferably 30
Mol% or less, more preferably 20 mol% or less,
In the propylene copolymer, it is selected in the range of 1 to 90 mol%, preferably 5 to 90 mol%, and more preferably 10 to 70 mol%.

The cyclic olefin has 3 to 2 carbon atoms.
4, preferably 3 to 18 can be used in the present invention, for example cyclopentene, cyclobutene,
Cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, norbornene, 5-methyl-2-norbornene, 5-ethyl-
2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6
-Trimethyl-2-sorbone and the like are included. The cyclic olefin is usually copolymerized with the above-mentioned α-olefin, and in that case, the amount of the cyclic olefin is 50 mol% or less of the copolymer, usually 1 to 50 mol%, preferably 2 to 50 mol. It is in the range of%.

The dienes and trienes usable in the present invention are polyenes having 4 to 26 carbon atoms, preferably 6 to 26 carbon atoms. Specifically, butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene,
1,4-hexadiene, 1,5-hexadiene, 1,3
-Cyclohexadiene, 1,4-cyclohexadiene,
1,9-decadiene, 1,13-tetradecadiene,
2,6-Dimethyl-1,5-heptadiene, 2-methyl-2,7-octadiene, 2,7-dimethyl-2,6-
Octadiene, 2,3-dimethylbutadiene, ethylidene norbornene, dicyclopentadiene, isoprene,
Examples include 1,3,7-octatriene and 1,5,9-decatriene. When a chain diene or triene is used in the present invention, it is usually copolymerized with the above-mentioned α-olefin, but the content of diene and / or triene in the copolymer is generally 0. 0.1 to 50 mol%, preferably 0.2 to 10 mol%.

Styrene analogs that can be used in the present invention are styrene and styrene derivatives, and examples of the derivatives include t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene and 1,1-diphenyl. Examples thereof include ethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like. The catalyst component of the present invention can also be suitably used in the case where a homopolymer or copolymer of olefins is further polymerized with a polar monomer to modify the homopolymer or copolymer. Examples of polar monomers include unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, monomethyl maleate, diethyl fumarate, and dimethyl itaconate. it can. The polar monomer content of the modified copolymer is usually 0.1 to 10 mol%, preferably 0.2 to
It is in the range of 2 mol%.

The polymerization reaction can be carried out by slurry polymerization, solution polymerization or gas phase polymerization in the presence of the above-mentioned catalyst. In particular, slurry polymerization or gas phase polymerization is preferable, and in a state where the enzyme, water and the like are substantially cut off, hexane, heptane and other aliphatic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons, cyclohexane, methylcyclohexane and the like. The olefin is polymerized in the presence or absence of an inert hydrocarbon solvent selected from the alicyclic hydrocarbons.
The polymerization conditions at this time are 20 to 200 ° C., preferably 5
It is in the range of 0 to 100 ° C., pressure normal pressure to 70 kg / cm ² G, preferably normal pressure to 20 kg / cm ² G, and the polymerization time is 5 minutes to 10 hours, preferably 5 minutes to 5 hours. It is normal to The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is possible to more effectively control the molecular weight by adding hydrogen to the polymerization reaction system. it can. Further, by using the catalyst of the present invention, it is possible to carry out a two-step or multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature without any trouble.

The catalyst component or catalyst of the present invention can be used by being carried on a carrier, preferably an inorganic carrier and / or a particulate polymer carrier. The inorganic carrier used in the present invention, in the step of preparing the catalyst of the present invention,
As long as it retains its original shape, it may have any shape such as powder, granules, flakes, foil, or fibrous shape, but in any shape, the maximum length is usually 5 to 5.
Those in the range of 200 μm, preferably 10 to 100 μm are suitable. The inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m ² / g.
The pore volume is preferably in the range of 0.05 to ³ cm ³ .

As the inorganic carrier of the present invention, a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof can be used, and these are usually 200 to 90.
It is used after being baked at 0 ° C. in air or in an inert gas such as nitrogen or argon.

Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Further, as the metal oxide, the periodic table I to VI is used.
Group II single oxides or complex oxides may be mentioned, for example, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , T.
iO ₂ , ZrO ₂ , Fe ₂ O ₃ , SiO ₂ · Al
₂ O ₃ , Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, A
l ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · Si
O ₂ , Al ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ ,
Examples thereof include Al ₂ O ₃ .NiO and SiO ₂ .MgO. In addition, the above formula represented by an oxide is not a molecular formula but represents only a composition, that is, the structure and the component ratio of the multiple oxide used in the present invention are not particularly limited. The metal oxide used in the present invention may adsorb a small amount of water, or may contain a small amount of impurities.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples thereof include magnesium carbonate, calcium carbonate and barium carbonate. Examples of the carbonaceous material include carbon black and activated carbon. Although any of the above inorganic carriers can be preferably used in the present invention, it is particularly preferable to use a metal oxide.

On the other hand, as the particulate polymer carrier, either a thermoplastic resin or a thermosetting resin can be used as long as it does not melt and remains solid during catalyst preparation and polymerization reaction. The particle size is usually 5-2000μ
m, preferably in the range of 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can exist as a solid substance at the time of catalyst preparation and polymerization reaction, and can be arbitrarily selected from low molecular weight to ultra high molecular weight. It is possible to use it, and it depends on the kind of polymer, but it is usually desirable to have a molecular weight of 1000 to 3,000,000. Specifically, various polyolefins (preferably having 2 to 12 carbon atoms) represented by particulate ethylene polymers, ethylene / α-olefin copolymers, propylene polymers or copolymers, poly-1-butene, and the like, Polyester, polyamide, polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate, polystyrene, polynorbornene, as well as various natural polymers and mixtures thereof can be used as polymer carriers.

The above-mentioned inorganic carrier and particulate polymer carrier can of course be used as they are, but as a pretreatment, these carriers are treated with trimethylaluminum, triethylaluminum, triisobutylaluminum,
Organic aluminum compounds such as tri-n-hexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylmonoethoxyaluminum and triethoxyaluminum, and Al-O-Al
A modified organoaluminum compound containing a bond (this compound will be described later) or a silane compound may be used after being contact-treated.

Further, regarding the inorganic carrier, it may be an alcohol, an active hydrogen-containing compound such as aldehyde, an electron-donating compound such as ester or ether, an alkoxide group such as tetraalkoxysilicate, tetraalkoxyaluminum, or transition metal tetraalkoxy. A method of contacting with a compound or the like in advance and then using it is also preferably used.

As such a preliminary contact treatment method, aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, heptane, etc. are usually used in an inert atmosphere such as nitrogen or argon. Compound for pretreatment of carrier in the presence of liquid inert hydrocarbon such as aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as hexane, decane, dodecane, cyclohexane, with or without stirring The method of contacting with is mentioned. It is desirable that this contact be performed at a temperature of usually -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C for 30 minutes to 50 hours, preferably 1 hour to 24 hours.

This catalytic reaction is carried out in a solvent in which the above-mentioned pretreatment compound is soluble, that is, benzene, toluene,
It is preferable to carry out in an aromatic hydrocarbon such as xylene or ethylbenzene (usually having a carbon number of 6 to 12). In this case, after the catalytic reaction, this is used as it is without preparing the solvent to prepare the catalyst component of the present invention. Can be used for Further, in the contact reaction product concerned, a liquid inert hydrocarbon in which the pretreatment compound is insoluble or sparingly soluble (for example, when the pretreatment compound is a modified organoaluminum compound, pentane, hexane, decane, dodecane, cyclohexane). Or an aliphatic or alicyclic hydrocarbon) to precipitate a carrier as a solid component and dry it, or a part of or all of the aromatic hydrocarbon that is a solvent at the time of pretreatment is dried. It is also possible to take out the carrier as a solid component after removing it by.

The ratio of the inorganic carrier and / or particulate polymer carrier to be subjected to the pretreatment and the pretreatment compound is as follows:
There is no particular limitation as long as the object of the present invention is not impaired, but it is usually selected within the range of 1 to 10000 mmol, preferably 5 to 1500 mmol (however, the Al atom concentration in the modified aluminum compound) per 1 g of the carrier. .

The contact ratio of the carrier is 0.001 wt% to 100% of the transition metal in the component (1) with respect to 1 g of the carrier.
It is desirable that the contact is made so as to be in a wt% range, preferably 0.01 wt% to 50 wt%, and more preferably 0.1 wt% to 10 wt%. Further, the carrier can be used in each stage of preparation of the catalyst component or catalyst of the present invention.

[0214]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but prior to that, preparation of modified organoaluminum compounds and catalyst components used in Examples and Comparative Examples will be described. Modified organoaluminum compound (methylaluminoxane)
Preparation of 13 g of copper sulfate pentahydrate was placed in a three-necked flask with a capacity of 300 ml equipped with an electromagnetic induction stirrer and suspended with 50 ml of toluene. Then, 150 ml of a solution of trimethylaluminum having a concentration of 1 mmol / ml was added dropwise to the above suspension under the temperature condition of 0 ° C. over 2 hours, and after the addition was completed, the temperature was raised to 25 ° C. and the reaction was performed at that temperature for 24 hours. Let Thereafter, the reaction product was filtered to remove toluene in the liquid containing the reaction product, and 4 g of white crystalline methylaluminoxane (MAO) was obtained.
I got The physical properties of the polymers obtained in Examples and Comparative Examples were evaluated by the following methods. Melt Index (MI) ASTM D 1238-57T 190 ° C, 2.16
It was measured based on the kg load.

Density: Measured according to ASTM D 1505-68. Melting point measurement by differential scanning calorimeter (DSC) Using a DSC-20 type melting point measuring device manufactured by Seiko Instruments Inc., a 5 mg sample was held at 180 ° C. for 3 minutes,
Then, the melting point was measured by cooling to 0 ° C. at 10 ° C./min, holding at 0 ° C. for 10 minutes, and then raising the temperature at 10 ° C./min. Measurement of Mw / Mn Using a 150C type GPC apparatus manufactured by Waters Co., a column Toyo Soda GMH-6, a solvent O-dichlorobenzene, a temperature of 135 ° C., and a flow rate of 1.0 ml / min were measured, and Mw / Mn was measured. Mn was determined.

Example 1 100 ml of purified toluene was added to a 300 CC three-necked flask under a nitrogen atmosphere, then 4.9 g of zirconium tributoxymono (triethylsilanolate) and 9.3 g of indene were added, and the mixture was stirred at room temperature and then gradually stirred. 21.8 ml of triethylaluminum was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. A 3 L capacity stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and 200 g of dried salt was added, and further 1 mg as a catalyst component Zr and 1 part of methylaluminoxane.
1 ml of mM / ml solution was added and heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was added at 9 kgf / cm ^2.
Polymerization was started by injecting so as to become G, and a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio
0.05) is continuously supplied and the total pressure is 9 kgf / c.
Polymerization was carried out for 1 hour while maintaining m ² G. After the completion of the polymerization, the excess mixed gas was discharged, the mixture was cooled and the sodium chloride was removed to obtain 190 g of a white polymer. Catalyst efficiency is 190kg / gZr
And the MI of the obtained polymer was 1.1 g / 10 mi.
n, density 0.9225 g / cm ³ , melting point 114.6
° C. MW / Mn 4.3

Example 2 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, 4 g of zirconium chlorotris (triphenylsilanolate) and 5.3 g of cyclopentadiene were added, and the mixture was stirred at room temperature and then gradually added. 40 ml of triisobutylaluminum was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. 1 as the catalyst component Zr in a 50 CC flask under a nitrogen atmosphere
After introducing mg, methylaluminoxane 1 mM / ml
1 ml of the solution was added and stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) was continuously supplied and the total pressure was maintained at 9 kgf / cm ² G to carry out polymerization for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 148 g of a white polymer. The catalyst efficiency was 148 kg / gZr, the MI of the obtained polymer was 5.6 g / 10 min, and the density was 0.9235 g.
/ Cm ³ and the melting point was 114.8 ° C. Mw / Mn
4.1

Example 3 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, and then 6.4 g of zirconium tribenzyl mono (triphenylsilanolate) and 7.4 g of 1,3 dimethylcyclopentadiene were added at room temperature. After being stirred at 34.4% of trihexylaluminum.
ml was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. After introducing 1 mg of the above catalyst component Zr into a 50 CC flask under a nitrogen atmosphere, 1 ml of a methylaluminoxane 1 mM / ml solution was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was added at 9 kgf / cm.
Polymerization was started by injecting so as to be ² G, and the total pressure was 9 kgf / c while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05).
Polymerization was carried out for 1 hour while maintaining m ² G. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 240 g of a white polymer. Catalyst efficiency is 240kg / gZr
And the MI of the obtained polymer was 0.08 g / 10 m.
in, density 0.9219 g / cm ³ , melting point 114.
It was 3 ° C. Mw / Mn 3.8

Example 4 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, 6.2 g of zirconium diprocoxydi (tributylsilanolate) and 10.3 g of ethylenebisindene were added, and the mixture was stirred at room temperature. Then, 20.5 ml of triethylaluminum was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. The above catalyst component Zr was placed in a 50 CC flask under a nitrogen atmosphere.
As a result, 1 mg of methylaluminoxane was introduced.
1 ml of the M / ml solution was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) is continuously supplied and the total pressure is maintained at 9 kgf / cm ² G.
Polymerization was carried out for a period of time. After the polymerization was completed, the excess mixed gas was discharged, cooled and the salt was removed to obtain 231 g of a white polymer. The catalyst efficiency was 231 kg / gZr, the MI of the obtained polymer was 0.6 g / 10 min, and the density was 0.92.
It was 11 g / cm ³ and the melting point was 114.2 ° C. Mw
/ Mn 3.7

Example 5 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, 4 g of zirconium tributoxymono (trimethylsilanolate) and 6.4 g of methylcyclopentadiene were added, and the mixture was stirred at room temperature and then gradually stirred. Then, 9.7 ml of trimethylaluminum was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. The above catalyst component Zr was placed in a 50 CC flask under a nitrogen atmosphere.
As a result, 1 mg of methylaluminoxane was introduced.
1 ml of the M / ml solution was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) is continuously supplied and the total pressure is maintained at 9 kgf / cm ² G.
Polymerization was carried out for a period of time. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 221 g of a white polymer. The catalyst efficiency was 221 kg / gZr, the MI of the obtained polymer was 0.2 g / 10 min, and the density was 0.92.
The melting point was 38 g / cm ³ and the melting point was 115.0 ° C. Mw
/ Mn 4.9

Example 6 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, then 4.5 g of zirconium tetra (trimethylsilanolate) and 9.3 g of indene were added, and the mixture was stirred at room temperature, and then gradually added with a triton. Hexylaluminum (68.8 ml) was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. Under nitrogen atmosphere 50
After introducing 1 mg of the above catalyst component Zr into a CC flask, 1 ml of a methylaluminoxane 1 mM / ml solution was introduced.
Was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then ethylene and butene-1
The mixed gas (butene-1 / ethylene molar ratio 0.25) was charged to 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05 ) Was continuously supplied, the total pressure was maintained at 9 kgf / cm ² G, and polymerization was carried out for 1 hour.
After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 180 g of a white polymer. Catalyst efficiency is 180
kg / gZr, and the MI of the obtained polymer was 0.9.
It was g / 10 min, the density was 0.9240 g / cm ³ , and the melting point was 115.3 ° C. Mw / Mn4.5

Example 7 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, 6 g of zirconium ethyl butoxide di (tridodecyl silanolate) and 6.6 g of cyclopentadiene were added, and the mixture was stirred at room temperature and then gradually stirred. Then, 0.2 mol of dibutylmagnesium was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. 1 as the catalyst component Zr in a 50 CC flask under a nitrogen atmosphere
After introducing mg, methylaluminoxane 1 mM / ml
1 ml of the solution was added and stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) was continuously supplied and the total pressure was maintained at 9 kgf / cm ² G to carry out polymerization for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 138 g of a white polymer. The catalyst efficiency was 138 kg / gZr, the MI of the obtained polymer was 1.7 g / 10 min, and the density was 0.9227 g.
/ Cm ³ and the melting point was 114.9 ° C. Mw / Mn
5.1

Example 8 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, and then 2.9 g of zirconium trichloromono (trimethylsilanolate) and indene 1 were added.
After adding 8.6 g and stirring at room temperature, 0.01 mol of methyllithium was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. Under nitrogen atmosphere 50
After introducing 1 mg of the above catalyst component Zr into a CC flask, 1 ml of a methylaluminoxane 1 mM / ml solution was introduced.
Was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then ethylene and butene-1
The mixed gas (butene-1 / ethylene molar ratio 0.25) was charged to 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05 ) Was continuously supplied, the total pressure was maintained at 9 kgf / cm ² G, and polymerization was carried out for 1 hour.
After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the common salt was removed to obtain 122 g of a white polymer. The catalyst efficiency is 122
kg / gZr, and the MI of the obtained polymer was 48.
It was 6 g / 10 min, the density was 0.9288 g / cm ³ , and the melting point was 115.9 ° C. Mw / Mn5.2

Example 9 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, 4.2 g of zirconium dibutoxide di (trimethylsilanolate) and 3.3 g of cyclopentadiene were added, and the mixture was stirred at room temperature, 12.5 ml of diethylaluminum chloride was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. The above catalyst component Z was placed in a 50 CC flask under a nitrogen atmosphere.
After introducing 1 mg as r, methylaluminoxane 1
1 ml of mM / ml solution was added and stirred at room temperature. After adding 200 g of dried salt to a 3 L stainless steel autoclave equipped with a stirrer and replacing with nitrogen,
The entire amount of this solution was added, and the mixture was heated to 60 ° C under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) is continuously supplied while maintaining the total pressure at 9 kgf / cm ² G,
Polymerization was carried out for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 138 g of a white polymer. The catalyst efficiency was 138 kg / gZr, the MI of the obtained polymer was 2.2 g / 10 min, and the density was 0.9.
It was 202 g / cm ³ and the melting point was 114.6 ° C. M
w / Mn 4.7

Example 10 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, 4 g of zirconium tributoxymono (trimethylsilanolate) and 120 g of butylcyclopentadiene were added, and the mixture was stirred at room temperature and then gradually added to dibutyl. 20 ml of butoxyaluminum was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. The above catalyst component Z was placed in a 50 CC flask under a nitrogen atmosphere.
After introducing 1 mg as r, methylaluminoxane 1
1 ml of mM / ml solution was added and stirred at room temperature. After adding 200 g of dried salt to a 3 L stainless steel autoclave equipped with a stirrer and replacing with nitrogen,
The entire amount of this solution was added, and the mixture was heated to 60 ° C under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) is continuously supplied while maintaining the total pressure at 9 kgf / cm ² G,
Polymerization was carried out for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, cooled and the salt was removed to obtain 185 g of a white polymer. The catalyst efficiency was 185 kg / gZr, the MI of the obtained polymer was 2.8 g / 10 min, and the density was 0.9.
The melting point was 255 g / cm ³ and the melting point was 114.3 ° C. M
w / Mn 4.8

Example 11 50 ml of purified toluene was added to a 100 CC three-necked flask under a nitrogen atmosphere, 8.1 g of zirconium butoxytris (tributylsilanolate) and 10.4 g of methylindene were added, and the mixture was stirred at room temperature, and then gradually stirred. Then, 22 ml of diethoxybutylaluminum was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. The above catalyst component Zr was placed in a 50 CC flask under a nitrogen atmosphere.
As a result, 1 mg of methylaluminoxane was introduced.
1 ml of the M / ml solution was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) is continuously supplied and the total pressure is maintained at 9 kgf / cm ² G.
Polymerization was carried out for a period of time. After the polymerization was completed, the excess mixed gas was discharged, cooled and the salt was removed to obtain 193 g of a white polymer. The catalyst efficiency was 193 kg / gZr, the MI of the obtained polymer was 0.3 g / 10 min, and the density was 0.92.
The melting point was 24 g / cm ³ and the melting point was 114.8 ° C. Mw
/ Mn 4.3

Example 12 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, and then 3.9 g of zirconium tributyl mono (triethylsilanolate) and 1 methyl-3.
After adding 10.9 g of butylcyclopentadiene and stirring at room temperature, 15 ml of ethyl aluminum dichloride was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. After introducing 1 mg of the above catalyst component Zr into a 50 CC flask under a nitrogen atmosphere, 1 ml of a methylaluminoxane 1 mM / ml solution was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a stainless steel autoclave with a stirrer and a volume of 3 L, and the atmosphere was replaced with nitrogen.
Heated to ° C. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was added at 9 kgf /
cm ² G was introduced to initiate polymerization, and while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05), the total pressure was 9 kgf /
It was maintained at cm ² G and polymerization was carried out for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 135 g of a white polymer. Catalyst efficiency is 135kg / gZ
and MI of the obtained polymer was 8.2 g / 10 m.
in, density 0.9266 g / cm ³ , melting point 115.
It was 4 ° C. Mw / Mn 4.4

Example 13 50 ml of purified toluene was added to a 100 CC three-necked flask under a nitrogen atmosphere, 3.7 g of titanium tributoxymono (trimethylsilanolate) and 5.3 g of cyclopentadiene were added, and the mixture was stirred at room temperature. Gradually, 13.6 ml of triethylaluminum was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. The above catalyst component Ti was placed in a 50 CC flask under a nitrogen atmosphere.
As a result, 1 mg of methylaluminoxane was introduced.
2 ml of the M / ml solution was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) is continuously supplied and the total pressure is maintained at 9 kgf / cm ² G.
Polymerization was carried out for a period of time. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 140 g of a white polymer. The catalyst efficiency was 140 kg / gTi, the MI of the obtained polymer was 0.4 g / 10 min, and the density was 0.92.
The melting point was 18 g / cm ³ and the melting point was 98.6 ° C. Mw /
Mn 4.2

Example 14 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, 5 g of hafnium tributoxymono (trimethylsilanolate) and 5.3 g of cyclopentadiene were added, and the mixture was stirred at room temperature and then gradually stirred. 13.6 ml of triethylaluminum was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. 1 as the above catalyst component Hf in a 50 CC flask under a nitrogen atmosphere
After introducing mg, methylaluminoxane 1 mM / ml
0.56 ml of the solution was added and stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) was continuously supplied and the total pressure was maintained at 9 kgf / cm ² G to carry out polymerization for 1 hour. After the completion of the polymerization, the excess mixed gas was discharged, cooled and the salt was removed to obtain 56 g of a white polymer. The catalyst efficiency was 56 kg / gHf, the MI of the obtained polymer was 0.04 g / 10 min, and the density was 0.92.
The melting point was 31 g / cm ³ , and the melting point was 114.9 ° C. Mw
/ Mn 4.9

Example 15 100 ml of purified toluene was added to a 300 CC three-necked flask under a nitrogen atmosphere, 4.9 g of zirconium tributoxymono (triethylsilanolate) and 9.3 g of indene were added, and the mixture was stirred at room temperature, and then gradually stirred. 21.8 ml of triethylaluminum was added dropwise to the mixture at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. After introducing 1 mg of the above catalyst component Zr into a 50 CC flask under a nitrogen atmosphere, 1 ml of a methylaluminoxane 1 mM / ml solution was added and the mixture was stirred at room temperature. 200 g of dried salt
Was added to a 3 L stainless steel autoclave equipped with a stirrer and purged with nitrogen, then the whole amount of this solution was added and heated to 60 ° C. under stirring. Then ethylene 9k
Polymerization is started by sticking it in so as to be gf / cm ² G,
While continuously supplying ethylene, the total pressure is 9 kgf / cm
^It was maintained at ² G and polymerization was carried out for 1 hour. After the completion of the polymerization, the excess mixed gas was discharged, the mixture was cooled and the common salt was removed to obtain 65 g of a white polymer. The catalyst efficiency was 65 kg / gZr, and the MI of the obtained polymer was 0.09 g / 10 mi.
n, density 0.9510 g / cm ³ , melting point 135.2
° C. Mw / Mn 4.9

Example 16 Under a nitrogen atmosphere, 50 ml of purified toluene was added to a 100 CC three-necked flask, 4 g of zirconium tributoxymono (trimethylsilanolate) and 6.4 g of methylcyclopentadiene were added, and the mixture was stirred at room temperature and then gradually stirred. Trimethylaluminum (9.7 ml) was added dropwise thereto at room temperature.
Further, this solution was stirred at room temperature to obtain a reaction solution. After introducing 1 mg of the above catalyst component Zr into a 50 CC flask under a nitrogen atmosphere, methylaluminoxane 1 mM / m
1 ml of 1 solution was added and stirred at room temperature. A 3 L capacity stainless steel autoclave equipped with a stirrer was replaced with nitrogen, 1 L of purified toluene was added thereto, and then the whole amount of this solution was added. The system was maintained at 20 ° C., propylene was fed thereinto so as to be 4 kgf / cm ² G to start the polymerization, and while continuously supplying propylene, the total pressure was maintained at 4 kgf / cm ² G for 2 hours. Was polymerized.
After the completion of the polymerization, the excess mixed gas was discharged and the contents were taken out by cooling to obtain 190 g of a white polymer. Catalyst efficiency is 1
It was 90 kg / gZr. The obtained polymer has a melting point of 141 ° C. and an MFR (measured at 230 ° C.) of 100 g.
It was / 10 min.

Comparative Example 1 100 ml of purified toluene was added to a 300 CC three-necked flask under a nitrogen atmosphere, 3.8 g of zirconium tetra-normalbutoxide and 9.3 g of indene were added, and the mixture was stirred at room temperature and then gradually added to triethylaluminum. 21.8 ml of was added dropwise at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. 50CC under nitrogen atmosphere
After introducing 1 mg of the catalyst component Zr into the flask, 1 ml of a methylaluminoxane 1 mM / ml solution was added and the mixture was stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was added to 9
Polymerization was started by injecting so as to be kgf / cm ² G, and a total pressure was 9 kgf / cm while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05). ^It was maintained at ² G and polymerization was carried out for 1 hour.
After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 90 g of a white polymer. Catalyst efficiency is 90kg
/ GZr, MI of the obtained polymer is 1.5 g /
10m1n, density 0.9221g / cm ³ , melting point 1
It was 14.9 ° C.

Comparative Example 2 100 ml of purified toluene was added to a 300 CC three-necked flask under a nitrogen atmosphere, and then 21.8 ml of triethylaluminum was added dropwise to 4.9 g of zirconium tributoxymono (triethylsilanolate) at room temperature. Further, this solution was stirred at room temperature to obtain a reaction solution. 1m as the above catalyst component Zr in a 50CC flask under a nitrogen atmosphere
After introducing g, 1 ml of a methylaluminoxane 1 mM / ml solution was added and the mixture was stirred at room temperature. Dried salt 2
After adding 00 g to a 3 L stainless steel autoclave equipped with a stirrer and purging with nitrogen, the whole amount of this solution was added and heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) was continuously supplied and the total pressure was maintained at 9 kgf / cm ² G to carry out polymerization for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 2 g of a white polymer. The catalytic efficiency is 2 kg / gZr.

Comparative Example 3 Under a nitrogen atmosphere, 100 ml of purified toluene was added to a 300 CC three-necked flask, then 4.9 g of zirconium tributoxymono (triethylsilanolate) and 9.3 g of indene were added, and the reaction solution was stirred at room temperature. Got After introducing 1 mg of the above catalyst component Zr into a 50 CC flask under a nitrogen atmosphere, methylaluminoxane 1 mM / m
1 ml of 1 solution was added and stirred at room temperature. 200 g of dried salt was added to a 3 L stainless steel autoclave equipped with a stirrer and the atmosphere was replaced with nitrogen. Then, the entire amount of this solution was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) was continuously supplied and the total pressure was maintained at 9 kgf / cm ² G to carry out polymerization for 1 hour. After the polymerization is completed, the surplus mixed gas is discharged,
After cooling and removing the salt, 35 g of a white polymer was obtained. The catalyst efficiency was 35 kg / gZr, the MI of the obtained polymer was 8.6 g / 10 min, and the density was 0.9344 g /
It had a cm ³ and a melting point of 115.9 ° C.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for producing a catalyst of the present invention.

Claims (3)

[Claims] 1. A general formula Me ¹ R ¹ _p (OR ² ) _{q.
^{X r (OSiR 3 R 4 R}} 5) 4-p-q-r compounds represented by ^(wherein, carbonization of ^{R 1, R 2, R 3} , R 4 and ^{R 5} are independently 1 to 24 carbon atoms Hydrogen groups, which may be the same or different, X is a halogen atom, and Me ¹ is Z
r, Ti or Hf, where p, q and r are 0 ≦ p <4, 0 ≦ q <4, 0 ≦ r <4, 0 ≦ p + q + r, respectively.
<Is an integer of 4), (2) General formula Me ² R _m (O
R ′) _n X _z-m-n (wherein R and R ′ are independently a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, and Me ² is I to I in the periodic table). Group III element, z is the valence of Me ² , m and n are 0 ≦ m ≦ z,
0 ≦ n ≦ z, and 0 ≦ m + n ≦ z),
And (3) a catalyst component for olefin polymerization, which is obtained by bringing an organic compound which is cyclic and has two or more conjugated double bonds into contact with each other. 2. (1) The general formula Me ¹ R ¹ _p (OR ² ) _{q.
^{X r (OSiR 3 R 4 R}} 5) 4-p-q-r compounds represented by ^(wherein, carbonization of ^{R 1, R 2, R 3} , R 4 and ^{R 5} are independently 1 to 24 carbon atoms Hydrogen groups, which may be the same or different, X is a halogen atom, and Me ¹ is Z
r, Ti or Hf, where p, q and r are 0 ≦ p <4, 0 ≦ q <4, 0 ≦ r <4, 0 ≦ p + q + r, respectively.
<Is an integer of 4), (2) General formula Me ² R _m (O
R ′) _n X _z-m-n (wherein R and R ′ are independently a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, and Me ² is I to I in the periodic table). Group III element, z is the valence of Me ² , m and n are 0 ≦ m ≦ z,
O ≦ n ≦ z, and 0 ≦ m + n ≦ z),
(3) A cyclic organic compound having two or more conjugated double bonds,
And (4) an olefin polymerization catalyst obtained by bringing a modified organoaluminum compound containing an Al-O-Al bond obtained by a reaction of an organoaluminum compound and water into contact with each other. 3. A method for producing an olefin polymer or copolymer, which comprises polymerizing or copolymerizing olefins in the presence of the catalyst according to claim 2.