JP2000230024A - Copolymer, its manufacture, and molding therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copolymer capable of taking a structure contg. no halogen regarded questionable from a view point of environmental pollution, transparent, and excellent in flexibility and heat resistance, an efficient manufacturing method of the copolymer, and moldings transparent and excellent in flexibility and heat resistance. SOLUTION: This copolymer is prepared by copolymerising ethylene and/or an α-olefin, a cyclic olefin, and an alkenyl arom. hydrocarbon, and it contains 0.01-66 mol % cyclic olefin, 3-99 mol % alkenyl arom. hydrocarbon, and more than half as much alkenyl arom. hydrocarbon as the cyclic olefin. In this manufacturing method of the copolymer, ethylene and/or the α-olefin, the cyclic olefin, and the alkenyl arom. hydrocarbon are copolymerised in the presence of a catalyst formed using the following (A), and (B) and/or (C). (A) a specific transition metal complex, (B) an org. aluminum compd., (C) a boron compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymer suitable for a film, a sheet or a pipe, a method for producing the same, and a molded article comprising the same. More specifically, the present invention
The present invention relates to a copolymer suitable as a substitute for polyvinyl chloride (for example, a film, a sheet or a pipe), a method for producing the same, and a molded article comprising the same.

[0002]

2. Description of the Related Art Copolymers generally used as stretch films and wrap films are required to have elastic recovery, transparency and mechanical strength as found in polyvinyl chloride. However, polyvinyl chloride has been viewed as a problem with respect to environmental pollution such as harmful substances may be generated during combustion. At present, substitution of polyvinyl chloride by various polymers is being studied, but in reality, satisfactory properties in terms of viscoelasticity and transparency have not been obtained.

[0003] In recent years, in the field of polymerization of olefins such as ethylene and propylene, the emergence of catalysts using transition metal compounds such as so-called metallocenes and non-metallocenes has made it possible to produce polymers having properties different from conventional ones. Advances have been made such that large amounts of polymers can be produced with very small amounts of catalyst.

It has been proposed to apply such a catalyst to the copolymerization of alkenyl aromatic hydrocarbons represented by styrene with ethylene, for example, see Patent Publication No. 262307.
No. 0 describes a pseudo-random copolymer of ethylene and styrene (a methine carbon atom having a phenyl group bonded thereto) obtained using a so-called homogeneous Ziegler-Natta catalyst comprising a specific transition metal compound and an organoaluminum compound. (A random copolymer characterized in that they are always separated from each other by two or more methylene groups).
The copolymer is excellent in viscoelastic properties and transparency,
Although it is expected as a substitute for polyvinyl chloride, there are problems in that the solvent resistance is low and the heat resistance is not sufficient. Further, the copolymer obtained by the production method may cause a decrease in transparency due to by-products of syndiotactic polystyrene.

For the copolymerization of ethylene with a cyclic olefin represented by norbornene, the use of such a metallocene catalyst has been proposed.
In JP-A-2, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride is used, and in JP-A-5-194641, (tert-butylamido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride is used as a catalyst component. A method for copolymerizing norbornene and ethylene has been disclosed. The copolymer obtained by these methods has high solvent resistance, and,
Although it is useful as a heat-resistant resin because of its extremely high glass transition point, it is inferior to a copolymer of ethylene and styrene in flexibility.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a copolymer which is transparent, excellent in flexibility and excellent in heat resistance, and can have a structure containing no halogen which is regarded as a problem from the viewpoint of environmental pollution. It is a further object of the present invention to provide a method for efficiently producing the copolymer, and a molded article comprising the copolymer which is transparent and excellent in flexibility and heat resistance.

[0007]

Means for Solving the Problems In order to achieve the above objects, the present inventors have earnestly focused on the production of a copolymer based on a production method using a transition metal compound represented by a metallocene as a catalyst component. We continued our research and completed the present invention.

That is, according to the present invention, ethylene and / or α
An olefin, a cyclic olefin, and an alkenyl aromatic
A copolymer obtained by copolymerizing a hydrocarbon with the hydrocarbon;
The copolymer composition of the olefin is 0.01 to 66 mol%,
Copolymer composition of alkenyl aromatic hydrocarbon is 3-99mo
1%, and the copolymer composition of the alkenyl aromatic hydrocarbon is
More than half the copolymer composition of cyclic olefin
Such is the case. The present invention also relates to a method for producing the copolymer.
The method comprising the steps of (A), (B) and / or
(C) in the presence of a catalyst comprising ethylene and / or
Or an α-olefin, a cyclic olefin,
A method for producing a copolymer by copolymerizing an aromatic hydrocarbon,
And a molded article comprising the copolymer.
You. (A): represented by the following general formula [I], [II] or [III]
Transition metal complexes(In the above general formulas [I] to [III], M¹
Represents a transition metal atom of Group 4 of the periodic table of the element, and A represents
An atom of Group 16 of the periodic table of the element is shown, and J is the circumference of the element.
Shows the atoms of Group 14 of the Periodic Table. Cp¹Is cyclopenta
It shows a group having a diene-type anion skeleton. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is German
First, hydrogen atom, halogen atom, alkyl group, aralkyl
Group, aryl group, substituted silyl group, alkoxy group, ara
Alkyloxy, aryloxy or disubstituted amino
Represents a group. X^ThreeIndicates an atom belonging to Group 16 of the Periodic Table of the Elements
You. R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is optional
They may combine to form a ring. General formula [II] or [II
I]¹, A, J, Cp¹, X¹, X^Two ,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is it
They may be the same or different. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
(B3) General formula E^Three｛-Al (E^Three) -O-｝_cAl
E^Three _TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
And all E¹, All E^TwoAnd all E^ThreeIs the same
It may be the same or different. Z is a hydrogen atom or
Represents a halogen atom, all Z are the same or different
May be. a is a number satisfying 0 <a ≦ 3, b is 2
And c represents an integer of 1 or more. (C): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-Represented by
(C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)
^-(Where B is a boron atom in a trivalent valence state, and Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated carbon
Hydrogen, substituted silyl, alkoxy or disubstituted amino
And they may be the same or different
No. G⁺Is an inorganic or organic cation, and L is neutral
A Lewis base, (LH)⁺Is Bronsted acid
is there. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in more detail. The copolymer of the present invention is a copolymer obtained by copolymerizing ethylene and / or an α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon,
The copolymer composition of the cyclic olefin is 0.01 to 66 mol.
%, The copolymer composition of the alkenyl aromatic hydrocarbon is 3 to 9
The copolymer is 9 mol%, and the copolymer composition of the alkenyl aromatic hydrocarbon is more than half of the copolymer composition of the cyclic olefin.

The ethylene used in the present invention and / or
Alternatively, the α-olefin is any one of ethylene alone, α-olefin only, and a mixture of ethylene and α-olefin, and is particularly preferably ethylene.

The α-olefin referred to here is preferably an olefin having 3 to 20 carbon atoms. Specific examples of such α-olefin include propylene, butene-1, pentene-1, hexene-1, and hexene-1. Heptene-
Linear olefins such as 1, octene-1, nonene-1, and decene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, and 5-methyl-hexene-1; Examples include branched olefins and vinylcyclohexane. More preferred α-olefins are propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 4-methylpentene-1,
Or vinylcyclohexane, particularly preferably propylene. In the present invention, such α-olefin is used alone or in combination.

The cyclic olefin used in the present invention may have various substituents, four or more carbon atoms form a ring, and one carbon-carbon double bond is formed in the ring. It is a compound containing. Examples of such cyclic olefins include monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene; substituted monocyclic olefins such as 3-methylcyclopentene, 4-methylcyclopentene, and 3-methylcyclohexene; norbornene, 1,2-dihydro Examples include polycyclic olefins such as dicyclopentadiene and tetracyclododecene; and substituted polycyclic olefins such as 5-methylnorbornene.

Among these, preferred cyclic olefins are
It is a compound represented by the following general formula [IV]. (Wherein, R ^{7 to} R ¹⁸ are each independently a hydrogen atom, a hydroxyl group, an amino group, a phosphino group, or a group having 1 to 2 carbon atoms.
0 is an organic group, and R ¹⁶ and R ¹⁷ may form a ring.
m represents an integer of 0 or more. )

Here, the substituent has 1 to 1 carbon atoms.
Specific examples of the organic group of 20 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and a dodecyl group; an aryl group such as a phenyl group, a tolyl group and a naphthyl group; An aralkyl group such as a phenethyl group; an alkoxy group such as a methoxy group and an ethoxy group;
Aryloxy groups such as phenoxy groups; acyl groups such as acetyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; aryloxycarbonyl groups or aralkyloxycarbonyl groups; acyloxy groups such as acetyloxy groups; methoxysulfonyl groups;
An alkoxysulfonyl group such as an ethoxysulfonyl group, an aryloxysulfonyl group or an aralkyloxysulfonyl group; a substituted silyl group such as a trimethylsilyl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; a carboxyl group; a cyano group; Groups in which part of the hydrogen atoms of an aryl group and an aralkyl group are substituted with a hydroxyl group, an amino group, an acyl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a substituted silyl group, an alkylamino group, or a cyano group be able to.

R ^{7 to} R ¹⁸ are preferably each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carbon atom. An acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, 1 to 1 carbon atom
An acyloxy group of 20 or a disubstituted silyl group having 1 to 20 carbon atoms.

M is an integer of 0 or more, preferably 0 ≦
It is an integer in the range of m ≦ 3.

Specific examples of preferred cyclic olefins represented by the general formula [IV] include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, and tetracyclonorbornene. Dodecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, Methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8
-Methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene and the like can be mentioned.

In the polymerization, these cyclic olefins are used alone or in combination.

The alkenyl aromatic hydrocarbon used in the present invention is preferably a compound represented by the following general formula [V]. (In the formula, R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 25 carbon atoms.)

R ¹⁹ is a hydrogen atom or a group having 1 to 20 carbon atoms.
Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group. Preferably, it is a hydrogen atom or a methyl group.

Ar is an aromatic hydrocarbon group having 6 to 25 carbon atoms, and specific examples thereof include phenyl, tolyl, xylyl, tertiary butylphenyl, vinylphenyl, naphthyl, and phenanthryl. , Anthracenyl group, benzyl group and the like. Preferably, it is a phenyl group, a tolyl group, a xylyl group, a tertiary butylphenyl group, a vinylphenyl group or a naphthyl group.

Specific examples of such alkenyl aromatic hydrocarbons include alkenylbenzenes such as styrene, 2-phenylpropylene, 2-phenylbutene and 3-phenylpropylene; p-methylstyrene, m-methylstyrene,
o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3- Methyl-5-
Ethyl styrene, p-tertiary butyl styrene, p-second
Alkyl styrene such as normal butyl styrene; alkenyl naphthalene such as 1-vinyl naphthalene; and the like. The alkenyl aromatic hydrocarbon used in the present invention is preferably styrene, p-methylstyrene, m
-Methylstyrene, o-methylstyrene, p-tertiary butylstyrene, 2-phenylpropylene or 1-vinylnaphthalene, particularly preferably styrene.

In the polymerization, other vinyl compounds can be copolymerized in addition to the above. Specific examples of such vinyl compounds include methyl vinyl ether, ethyl vinyl ether, acrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate and the like.

In the copolymer of the present invention, the copolymer composition of the cyclic olefin is 0.01 to 66 mol%. When the copolymerization composition of the cyclic olefin is within this range, it is particularly excellent in solvent resistance and heat resistance, which is preferable. A more preferred copolymer composition of the cyclic olefin is 0.1 to 40 mol%,
Particularly preferred cyclic olefin copolymer composition is 1 to 30 m.
ol%. The copolymer composition of such a cyclic olefin,
^It can be easily obtained from a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

In the copolymer of the present invention, the copolymer composition of the alkenyl aromatic hydrocarbon is 3 to 99 mol%. When the copolymer composition of the alkenyl aromatic hydrocarbon is in this range, particularly heat resistance, excellent flexibility, high refractive index,
preferable. A more preferred copolymer composition of the alkenyl aromatic hydrocarbon is 3 to 55 mol%, and a particularly preferred copolymer composition of the alkenyl aromatic hydrocarbon is 5 to 45 mol%.
It is. The copolymer composition of such an alkenyl aromatic hydrocarbon can be easily determined from a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

In the copolymer of the present invention, the copolymer composition of the alkenyl aromatic hydrocarbon is more than half of the copolymer composition of the cyclic olefin. When the copolymer composition is in this range, the balance between heat resistance and elastic recovery is excellent. When the copolymerization composition of the alkenyl aromatic hydrocarbon is less than half the copolymerization composition of the cyclic olefin, the elastic recovery may be particularly reduced. More preferably, the copolymer composition of the alkenyl aromatic hydrocarbon of the copolymer of the present invention is equal to or greater than the copolymer composition of the cyclic olefin.

As the copolymer of the present invention, a copolymer having a high refractive index can be obtained. Such a copolymer is hardly impaired in transparency even when a filler or the like is used for improving rigidity.

From the viewpoint of transparency, the copolymer of the present invention is
It is preferably an amorphous copolymer having no crystallinity. Lack of crystallinity is due to differential scanning calorimetry (DS
This can be confirmed by the fact that the melting point measured in C) does not substantially show the melting point.

In the copolymer of the present invention, the sum of the copolymer composition of the alkenyl aromatic hydrocarbon and the copolymer composition of the cyclic olefin is preferably at least 10 mol%. When the sum of the copolymer compositions is within this range, the copolymer becomes amorphous and is excellent in transparency.

Glass transition point (Tg) of the copolymer of the present invention
Is usually −20 to 170 ° C. Preferably Tg is -2
0 to 140 ° C., more preferably Tg
Is a copolymer at 30 to 100 ° C. Particularly preferably, T
g is a copolymer having a temperature of 35 ° C. or more and less than 60 ° C. Here, Tg is measured by a differential scanning calorimeter (DSC).

The copolymer of the present invention is, for example,
Using (A) and (B) and / or (C)
Ethylene and / or α-olefin in the presence of a catalyst
And a cyclic olefin and an alkenyl aromatic hydrocarbon
It can be produced with high polymerization activity by copolymerization.
(A): represented by the following general formula [I], [II] or [III]
Transition metal complexes(In the above general formulas [I] to [III], M¹
Represents a transition metal atom of Group 4 of the periodic table of the element, and A represents
An atom of Group 16 of the periodic table of the element is shown, and J is the circumference of the element.
Shows the atoms of Group 14 of the Periodic Table. Cp¹Is cyclopenta
It shows a group having a diene-type anion skeleton. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is German
First, hydrogen atom, halogen atom, alkyl group, aralkyl
Group, aryl group, substituted silyl group, alkoxy group, ara
Alkyloxy, aryloxy or disubstituted amino
Represents a group. X^ThreeIndicates an atom belonging to Group 16 of the Periodic Table of the Elements
You. R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is optional
They may combine to form a ring. General formula [II] or [II
I]¹, A, J, Cp¹, X¹, X^Two ,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is it
They may be the same or different. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
(B3) General formula E^Three｛-Al (E^Three) -O-｝_cAl
E^Three _TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
And all E¹, All E^TwoAnd all E^ThreeIs the same
It may be the same or different. Z is a hydrogen atom or
Represents a halogen atom, all Z are the same or different
May be. a is a number satisfying 0 <a ≦ 3, b is 2
And c represents an integer of 1 or more. (C): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-Represented by
(C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)
^-(Where B is a boron atom in a trivalent valence state, and Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated carbon
Hydrogen, substituted silyl, alkoxy or disubstituted amino
And they may be the same or different
No. G⁺Is an inorganic or organic cation, and L is neutral
A Lewis base, (LH)⁺Is Bronsted acid
is there. Hereinafter, the production method will be described in more detail.

(A) Transition metal complex In the general formulas [I], [II] and [III], the transition metal atom represented by M ¹ is the periodic table of elements (IUPA).
C, a transition metal element of Group 4 of the inorganic chemical nomenclature revised edition 1989), such as a titanium atom, a zirconium atom, and a hafnium atom. Preferably it is a titanium atom or a zirconium atom.

The atom of Group 16 of the periodic table of the element represented by A in the general formulas [I], [II] or [III] includes, for example, an oxygen atom, a sulfur atom, a selenium atom and the like. Is an oxygen atom.

In the general formulas [I], [II] and [III], examples of the atom belonging to Group 14 of the periodic table of the element represented by J include a carbon atom, a silicon atom, and a germanium atom. Is a carbon atom or a silicon atom. In the present invention, J is particularly preferably a carbon atom.

Examples of the group having a cyclopentadiene type anion skeleton represented by the substituent Cp ¹ include, for example, η
^5- (substituted) cyclopentadienyl group, η ^5- (substituted)
Indenyl group, η ^5- (substituted) fluorenyl group and the like. If specifically exemplified, for example, eta ⁵ - cycloalkyl Bae Ntajieniru group, eta ⁵ - methylcyclopentadienyl group, eta
⁵ - dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, η ⁵
- isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ^{5-n-Penchirushikurope} Antadienyl group, η ⁵ -neopentylcyclopentadienyl group, η ⁵ -n-hexylcyclopentadienyl group, η ⁵
-N- octyl cycloalkyl Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - Nafuchirushikuro Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ⁵ - triethylsilyl cycloalkyl Bae Ntajieniru group, eta ^5-tert. - butyldimethylsilyl cycloalkyl Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group, eta ⁵ - dimethyl indenyl group, eta ⁵ - ethyl indenyl group, eta ^5-n-propyl indenyl group, eta
⁵ - isopropylindenyl group, eta ^5-n-butyl indenyl group, eta ^5-sec-butyl indenyl group, eta ⁵ -
tert- butyl indenyl group, eta ^5-n-pentyl indenyl group, eta ⁵ - neopentyl indenyl group, eta ⁵ -
n- hexyl indenyl group, eta ^5-n-octyl indenyl group, eta ^{5-n-Deshiruindeniru} group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group,
eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group,
eta ^{5-tert-butyldimethylsilyl} indenyl group,
eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ^{5-n-propyl-fluorenyl} group, eta ⁵ - di-n-propyl-fluorenyl group, eta ⁵ - isopropyl fluorenyl group, eta ⁵ - diisopropyl fluorenyl group, eta ^{5-n-Buchirufuruore} Nil group, η ⁵ −
sec- butyl fluorenyl group, eta ^{5-tert-butyl-fluorenyl} group, eta ⁵ - di -n- butyl fluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ -
Di -tert- butyl-fluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorenyl group, eta ^{5-n-hexyl-fluorenyl} group, eta ^{5-n-octyl-fluorenylmethoxycarbonyl} alkenyl group, eta ^{5-n-decyl-fluorenyl} group, eta ^{5-n-dodecyl-fluorenyl} group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - di - phenyl fluorenyl group, eta ⁵ - methylphenyl fluorenyl group, eta ⁵ - naphthyl fluorenyl group, eta ⁵ - trimethylsilyl fluorenyl group, eta ⁵ - bis - trimethylsilyl fluorenyl group, eta ⁵ - triethylsilyl fluorenyl group, eta ⁵ -t
tert-butyldimethylsilylfluorenyl group and the like, preferably η ⁵ -cyclopentadienyl group, η
⁵ -methylcyclopentadienyl group, η ⁵ -tert-
Butylcyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - indenyl group or eta,
⁵ -Fluorenyl group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^4, as the halogen atom in R ⁵ or R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom are exemplified, preferably a chlorine atom or a bromine atom, more preferably chlorine atom.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^{As the} alkyl group for ⁴ , R ⁵ or R ^6, an alkyl group having 1 to 20 carbon atoms is preferable, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
-Butyl group, sec-butyl group, tert-butyl group,
n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group , An ethyl group, an isopropyl group, a tert-butyl group or an amyl group.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl group, iodomethyl group, diiodomethyl group,
Triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl , Dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like. All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^4, The aralkyl group in R ⁵ or R ^6, preferably an aralkyl group having 7 to 20 carbon atoms, such as benzyl group, (2-methylphenyl) methyl group, (3-
A (methylphenyl) methyl group, a (4-methylphenyl) methyl group, a (2,3-dimethylphenyl) methyl group,
(2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethyl Phenyl) methyl group, (2,
3,4-trimethylphenyl) methyl group, (2,3,5
-Trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3 , 4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) methyl group, (2,3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl Group,
(Ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group,
(N-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) Methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, (n-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl group, etc. And more preferably a benzyl group. All of these aralkyl groups are a fluorine atom, a chlorine atom, a bromine atom,
It may be partially substituted with a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^{As the} aryl group for ⁴ , R ⁵ or R ^6, an aryl group having 6 to 20 carbon atoms is preferable, for example, a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group,
2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group,
3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-
Trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3
4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, Isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group ,
Examples include an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, an anthracenyl group and the like, and a phenyl group is more preferable. All of these aryl groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
The substituted silyl group represented by ⁴ , R ⁵ or R ⁶ is a silyl group substituted with a hydrocarbon group, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, -Alkyl groups having 1 to 10 carbon atoms such as -butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group, and aryl groups such as phenyl group. Can be Examples of the substituted silyl group having 1 to 20 carbon atoms include 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group and a phenylsilyl group.
Substituted silyl group, dimethylsilyl group, diethylsilyl group,
A disubstituted silyl group having 2 to 20 carbon atoms such as a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group,
Tri-n-propylsilyl group, triisopropylsilyl group, tri-n-butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri- Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as an n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, and a triphenylsilyl group.
It is a t-butyldimethylsilyl group or a triphenylsilyl group. All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^{As the} alkoxy group for ⁴ , R ⁵ or R ^6, an alkoxy group having 1 to 20 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group , Te
rt-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-icosoxy group and the like, more preferably methoxy group and ethoxy group ,
Or a tert-butoxy group. All of these alkoxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^4, The aralkyloxy group in R ⁵ or R ^6, preferably an aralkyl group having 7 to 20 carbon atoms, for example, benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group,
(4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) Methoxy group,
(3,4-dimethylphenyl) methoxy group, (3,5-
(Dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl)
Methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4,6-tetramethylphenyl)
Methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (N-butylphenyl) methoxy group, (sec-
(Butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy And a naphthylmethoxy group and an anthracenylmethoxy group, and more preferably a benzyloxy group. All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^{As the} aryloxy group for ⁴ , R ⁵ or R ^6, an aryloxy group having 6 to 20 carbon atoms is preferable, for example, a phenoxy group, a 2-methylphenoxy group,
3-methylphenoxy group, 4-methylphenoxy group,
2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group,
3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5
-A trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group,
2,3,4,5-tetramethylphenoxy group, 2,3
4,6-tetramethylphenoxy group, 2,3,5,6-
Tetramethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group, n-propylphenoxy group,
Isopropylphenoxy group, n-butylphenoxy group,
sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. All of these aryloxy groups are
Partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. You may.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R
^4, the 2-substituted amino group in R ⁵ or R ⁶ a amino group substituted with two hydrocarbon groups, as herein hydrocarbon group such as methyl group, ethyl group, n- propyl group, isopropyl Group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, carbon atom such as alkyl group having 1 to 10 carbon atoms such as cyclohexyl group and phenyl group Examples thereof include an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 10 carbon atoms. 1 to 10 carbon atoms
Examples of the disubstituted amino group substituted with a hydrocarbon group of dimethylamino group, diethylamino group, di-n-
Propylamino group, diisopropylamino group, di-n-
Butylamino group, di-sec-butylamino group, di-t
tert-butylamino group, di-isobutylamino group, t
tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group and the like. And preferably a dimethylamino group or a diethylamino group. Each of these disubstituted amino groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyl group such as a benzyloxy group. Part may be substituted with an oxy group or the like.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily linked to form a ring.

Preferably, R ¹ is an alkyl group, an aralkyl group, an aryl group or a substituted silyl group. Preferably, X ¹ and X ² are each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, and more preferably a halogen atom or an alkoxy group.

In the general formula [II] or [III], X ³
Examples of the atom of Group 16 of the periodic table of the element represented by include an oxygen atom, a sulfur atom, and a selenium atom, and an oxygen atom is preferable.

Examples of the transition metal complex represented by the general formula [I] include methylene (cyclopentadienyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2)
-Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Phenyl-2-phenoxy)
Titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Methylene (tert
-Butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tert) -Butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadiene) Enil) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy)
Titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride , Methylene (tetramethylcyclopentadienyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-
2-phenoxy) titanium dichloride,

Methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) ) (3-tert-butyldimethylsilyl-5
Methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene Riden (methylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Isopropylidene (methylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-
Phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (t
tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2)
-Phenoxy) titanium dichloride,

Isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl- 2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2
-Phenoxy) titanium dichloride,

The isopropylidene (fluorenyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2
-Phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene Cyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl- 2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenyl Methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (ter
t-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopenta Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride and the like, compounds obtained by changing titanium to zirconium or hafnium, dibromide to dichloride, diiodide, bis (dimethylamide), bis (diethylamide), -A compound changed to n-butoxide or diisopropoxide,
(Cyclopentadienyl) is replaced by (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n
-Butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl) or a compound modified to (indenyl), (3,5-dimethyl-2-
Phenoxy) to (2-phenoxy), (3-methyl-2)
-Phenoxy), (3,5-di-tert-butyl-2)
-Phenoxy), (3-phenyl-5-methyl-2-phenoxy), (3-tert-butyldimethylsilyl-
2-phenoxy) or (3-trimethylsilyl-2)
A transition metal complex wherein J in the general formula [I] is a carbon atom, such as a compound changed to -phenoxy);

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-
2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl)
(3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride,
Dimethylsilylene (methylcyclopentadienyl) (3
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy)
Titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl- 2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamyl-2-
Phenoxy) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n- Butylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta Dienyl) (5-methyl-3
-Phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (5-
Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta Dienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-
Butylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butyl) Butylcyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,
5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-
2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl- 5
-Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5
-Diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta Dienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta Dienyl) (5-
Methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadiene) Enil) (3,
5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,
5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-
2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5)
-Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5
-Diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-
Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5
-Chloro-2-phenoxy) titanium dichloride,
Dimethylsilylene (indenyl) (3,5-diamyl-
2-phenoxy) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-
Phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3
-Tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl)
(3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl Dimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl)) (1-naphthoxy) -2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds is (dimethylcyclopentadienyl),
(Trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (se
c-butylcyclopentadienyl), (isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl), or (phenylindenyl) Compound changed, (2-phenoxy) changed to (3-phenyl 2-phenoxy), (3-trimethylsilyl-2-phenoxy), or compound changed to (3-tert-butyldimethylsilyl-2-phenoxy), dimethylsilylene Is changed to diethylsilylene, diphenylsilylene, or dimethoxysilylene, a compound is changed to titanium, zirconium or hafnium, dichloride is dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide Or J in the general formula [I] such compound was changed to di isopropoxide include transition metal complexes is a Group 14 atoms of the Periodic Table of the Elements other than carbon atoms.

The transition metal complex represented by the above general formula [I] can be produced, for example, by the method described in WO 97/03992. In addition, the above general formula [II] or [II
The transition metal complex represented by the formula [I] is produced by reacting the transition metal complex represented by the general formula [I] with 0.5 times or 1 times the amount of water, respectively. At that time, a method of directly reacting the required amount of water with the transition metal complex represented by the general formula [I], the method represented by the general formula [I] in a solvent such as a hydrocarbon containing the required amount of water. The transition metal complex represented by the above general formula [I] is introduced into a solvent such as a dried hydrocarbon, and an inert gas containing a necessary amount of water is passed through. A method or the like can be adopted.

(B) Aluminum Compound The aluminum compound (B) used in the present invention is at least one aluminum compound selected from the following (B1) to (B3). (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) Cyclic aluminoxane having a structure represented by the general formula （-Al (E ² ) -O-｝ _b (B3) General formula E ³ ｛-Al (E ³ ) -O-｝ _c Al
E ³ linear aluminoxane having a structure represented by ₂ (wherein, E ^1, E ^2, and E ³ are each a hydrocarbon group, all of E ^1, all E ² and all E ³ are the same Z represents a hydrogen atom or a halogen atom, and all Zs may be the same or different. A is a number satisfying 0 <a ≦ 3, and b is An integer of 2 or more, and c represents an integer of 1 or more.) As the hydrocarbon group for E ¹ , E ² , or E ³ ,
A hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable.

Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride Dimethylal Examples thereof include dialkylaluminum hydrides such as minium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum or triisobutylaluminum.

[0078] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 Specific examples of E ² and E ^{3 in} the linear aluminoxane (B3) having the structure shown include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl, neopentyl An alkyl group such as a group can be exemplified. b is 2
And c is an integer of 1 or more. Preferably, E ² and E ³ are a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

The above aluminoxane can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

(C) Boron Compound In the present invention, the boron compound (C) includes (C1)
General formula BQ¹Q^TwoQ ^ThreeA boron compound represented by the formula (C
2) General formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-Represented by
Boron compound, (C3) general formula (LH)⁺(BQ¹
Q^TwoQ^ThreeQ^Four) ^-One of the boron compounds represented by
Can be used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, 1
A halogenated hydrocarbon group containing from 20 to 20 carbon atoms,
A substituted silyl group containing 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms, and more preferred Q ^{1 to} Q ³ are a halogen atom, A hydrocarbon group containing 20 carbon atoms or a halogenated hydrocarbon group containing 1 to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably Q ^{1 to} Q 4
⁴ is a fluorinated aryl group having 6 to 20 carbon atoms, each containing at least one fluorine atom.

As specific examples of the compound (C1), tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. an atom, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above (C1).

[0084] formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
Tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluoro) Phenyl) borate, tetrakis (2,3,4-
Trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5
-Bistrifluoromethylphenyl) borate and the like.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q
^{In the} boron compound (C3) represented by ³ Q ⁴ ) ^- , L is a neutral Lewis base, (LH) ⁺ is a Bronsted acid, and B is a boron atom in a trivalent valence state. in and, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

Formula (LH) ⁺ (BQ ¹ Q ² Q
³ Q ^{4) -} is a Brønsted acid in the compound represented by (as the L-H) ⁺ Examples of include trialkyl-substituted ammonium, N, N-dialkyl anilinium, dialkyl ammonium, triarylphosphonium Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include the same as described above.

As specific combinations of these, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned, and most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

[Polymerization] In the present invention, the above transition metal complex (A) is combined with the above (B) and / or (C)
Is used.
When an olefin polymerization catalyst comprising two components (A) and (B) is used, the cyclic aluminoxane (B2) and / or the linear aluminoxane (B) may be used as (B).
3) is preferred. As another preferred embodiment of the olefin polymerization catalyst, an olefin polymerization catalyst using the above (A), (B) and (C) is exemplified. ) Easy to use.

The amount of each component used is usually such that the molar ratio of (B) / (A) is 0.1 to 10000, preferably 5 to 200.
It is desirable to use each component so that the molar ratio of 0, (C) / (A) is 0.01 to 100, preferably 0.5 to 10. When each component is used in a solution state or a suspension state in a solvent, the concentration is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. .01-500 μmol
/ G, more preferably 0.05 to 100 μmol /
g, more preferably 0.05 to 50 μmol / g,
(B) is usually 0.01 to 10,000 in terms of Al atom.
μmol / g, more preferably 0.1 to 5000 μm
mol / g, more preferably 0.1 to 2000 μm
ol / g, (C) is usually 0.01 to 500 μmol /
g, more preferably 0.05 to 200 μmol /
g, more preferably 0.05 to 100 μmol / g
It is desirable to use each component so as to fall within the range.

The catalyst used in the present invention may further include Si
A particulate carrier including an inorganic carrier such as O ₂ and Al ₂ O _{3 and} an organic polymer carrier such as a polymer such as ethylene and styrene may be used in combination.

In carrying out the method of the present invention, the polymerization method is not particularly limited, and examples thereof include a batch or continuous gas phase polymerization method, a bulk polymerization method, a solution polymerization method using a suitable solvent, and a slurry polymerization method. Any method can be used. When a solvent is used, various solvents can be used provided that they do not deactivate the catalyst. Examples of such a solvent include hydrocarbons such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; And halogenated hydrocarbon groups such as styrene chloride.

The polymerization temperature is not particularly limited, and is generally -100 to 250 ° C, preferably -50 to 200 ° C. The pressure is not limited, but is generally 10 MPa or less, preferably 0.2 MPa to 5 MPa.
a. In addition, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

The copolymer of the present invention can be used for molded articles such as films, sheets, pipes and containers, but is particularly suitable for films, sheets and pipes.

The film, sheet or pipe is, for example,
Inflation molding to extrude the molten resin from a circular die and winding the film expanded into a cylindrical shape, T-die molding and calendering to extrude the molten resin from a linear die and wind a film or sheet, It can be obtained by blow molding, injection molding, profile extrusion molding, or the like.

The molded article of the present invention has excellent flexibility and elastic recovery. Such flexibility and elastic recovery can be examined by obtaining a hysteresis curve by a tensile test.

The copolymer of the present invention can be used in the form of a multilayer film, sheet or pipe of two or more layers with other materials. At this time, the film, sheet or pipe can be manufactured by various known laminating methods such as a co-extrusion method, a dry lamination method, a sandwich lamination method, and an extrusion lamination method. Other materials include paper, paperboard, aluminum thin film, cellophane,
Known materials such as nylon, polyethylene terephthalate (PET), polypropylene, polyvinylidene chloride, ethylene-vinyl alcohol copolymer (EVOH), and various adhesive resins can be used.

The molded article of the present invention may contain, if necessary, an antioxidant, a weathering agent, a lubricant, an anti-blocking agent, an antistatic agent,
Known additives such as anti-fogging agents, drip-free agents, pigments, and fillers can be contained. Further, known polymer substances such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-α-olefin copolymer elastomer, and polypropylene may be blended. The film or sheet of the present invention can be subjected to known post-treatments such as corona discharge treatment, plasma treatment, ozone treatment, ultraviolet irradiation, and electron beam irradiation.

[0099]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited by these Examples. In addition, the property of the polymer in an Example was measured by the following method.

The intrinsic viscosity [η] was measured at 135 ° C. using tetralin as a solvent using an Ubbelohde viscometer.

The glass transition point was measured using a DSC (SSC-5200 manufactured by Seiko Instruments Inc.) under the following conditions, and determined from the inflection point. Temperature rise 20 ° C to 200 ° C (20 ° C / min) 10 minutes hold Cooling 200 ° C to -50 ° C (20 ° C / min) hold 10 minutes Measurement -50 ° C to 300 ° C (20 ° C / min)

The molecular weight and molecular weight distribution were measured by gel permeation chromatography (Waters 15
0-CV) under the following conditions. Column Shodex 806M / S Measurement temperature 145 ° C Measurement solvent Orthodichlorobenzene Measurement concentration 1mg / ml

The styrene unit copolymer composition in the polymer and the structure of the polymer were determined by ¹ H-NMR and ¹³ C-NMR analyses. ¹ H-NMR device JNM-EX270 manufactured by JEOL Ltd. Measurement solvent dichloromethane-d2 Measurement temperature room temperature ¹³ C-NMR device AC250 manufactured by BRUKER Measurement solvent 8 of orthodichlorobenzene and heavy benzene
5:15 (volume ratio) mixed solution Measurement temperature 135 ° C

The solid viscoelasticity of the polymer is measured by a spectrometer.
(DMS200 of SDM5600H manufactured by Seiko Denshi Kogyo)
Was determined under the following conditions. Specimen 20mm × 3.0mm × 0.3mm press sheet Frequency 5Hz Heating rate 2 ° C / min Displacement amplitude 10μm

The hysteresis curve of the polymer was determined by using Strograph-T (manufactured by Toyo Seiki Seisaku-sho, Ltd.) under the following conditions. Test piece 120 mm x 20 mm x 0.3 mm press sheet Tension speed 200 mm / min Tension magnification 2 times Distance between chucks 60 mm

The refractive index of the polymer was determined by preheating at 180 ° C. for 3 minutes and then hot pressing at 180 ° C. under a pressure of 3 to 5 MPa for 3 minutes to form a 100 μm thick film.
As a test piece cut into a size of mm × 30 mm, the test piece was examined using an Abbe refractometer type 3 (manufactured by Atago Co., Ltd.).

The total haze of the polymer was measured for a 0.3 mm-thick press sheet obtained by preheating for 5 minutes in a hot press at 150 ° C., pressing for 5 minutes, and cooling with a cooling press at 35 ° C. And ASTM-D-1003.

Example 1 A toluene solution of 11.4 ml of styrene and norbornene was placed in a 400 ml autoclave replaced with argon.
After charging 20 ml (5 mol / l) and 105 ml of dehydrated toluene, ethylene was charged at 0.8 MPa. A solution of 15.5 mg of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride in 15 ml of dehydrated toluene and a toluene solution of triisobutylaluminum [Tosoh Akzo Co., Ltd. , 1 mol / l], 2.5 ml of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
1 mg dissolved in 47 ml of dehydrated toluene was added,
The reaction was stirred at 60 ° C. for 1 hour. Thereafter, the reaction solution was poured into a mixture of 5 ml of hydrochloric acid (12N) and 1000 ml of acetone, and the precipitated white solid was filtered off. The solid was washed with acetone and dried under reduced pressure to obtain 26.85 g of a polymer. [Η] of this polymer was 1.30 dl / g, the number average molecular weight was 154,000, the molecular weight distribution (weight average molecular weight / number average molecular weight) was 1.9, the glass transition point was 35 ° C.,
The copolymer composition of norbornene was 15 mol%, and the copolymer composition of styrene was 16 mol%. Of the resulting polymer
FIG. 1 shows the ¹³ C-NMR spectrum, FIG. 2 shows the solid viscoelasticity data, and FIG. 3 shows the hysteresis curve. After the measurement of the hysteresis curve, the test piece recovered almost 100% to the state before the measurement. The press sheet prepared for the measurement was very transparent.

Example 2 A toluene solution of 114 ml of styrene and norbornene was placed in a 400 ml autoclave replaced with argon.
After charging 20 ml (5 mol / l) and 6 ml of dehydrated toluene, 0.8 MPa of ethylene was charged. Isopropylidene (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride
A solution of 11.6 mg in 12 ml of dehydrated toluene and a toluene solution of triisobutylaluminum [Tosoh Corporation]
3.0 ml of Akzo Co., Ltd., 1 mol / l] was previously mixed and charged, followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 72.0 ml.
mg was dissolved in 45 ml of dehydrated toluene, and the reaction solution was stirred at 60 ° C. for 1 hour. Then, the reaction solution was added with hydrochloric acid.
The mixture was poured into a mixture of 5 ml of (12N) and 1000 ml of acetone, and the precipitated white solid was collected. The solid was washed with acetone and dried under reduced pressure to obtain 18.34 g of a polymer. [Η] of this polymer was 1.25 dl / g, the number average molecular weight was 162,000, the molecular weight distribution (weight average molecular weight / number average molecular weight) was 2.0, the glass transition point was 55 ° C.,
The copolymer composition of norbornene was 15 mol%, and the copolymer composition of styrene was 36 mol%. FIG. 4 shows the solid viscoelasticity of the obtained polymer. The total haze of the obtained polymer was 11.8%, and the refractive index was 1.57.

Example 3 27 ml of styrene and a toluene solution of norbornene (5 ml) were previously placed in a 400 ml autoclave purged with argon.
(mol / l) 48 ml and dehydrated toluene 13 ml were charged, and then ethylene was charged at 0.8 MPa. Isopropylidene (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride
A solution prepared by dissolving 3.0 mg in 6 ml of dehydrated toluene and 2.0 ml of a toluene solution of triisobutylaluminum (1 mol / l, manufactured by Tosoh Akzo Co., Ltd.) were mixed in advance, and then charged, followed by N, N-dimethylanilinium. 19.2 mg of tetrakis (pentafluorophenyl) borate
Was dissolved in 24 ml of dehydrated toluene, and the reaction solution was stirred at 60 ° C. for 1 hour. Thereafter, the reaction solution was treated with hydrochloric acid (1
2N) into a mixture of 2 ml of acetone and 500 ml of acetone,
The precipitated white solid was filtered off. The solid was washed with acetone and dried under reduced pressure to obtain 1.43 g of a polymer. The glass transition point of this polymer is 123 ° C., the copolymer composition of norbornene is 28 mol%, and the copolymer composition of styrene is 19 m.
ol%.

Example 4 A toluene solution of 114 ml of styrene and norbornene was placed in a 400 ml autoclave purged with argon.
(5 mol / l) 4 ml and dehydrated toluene 34 ml were charged, and then ethylene was charged at 0.8 MPa. Isopropylidene (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride
A solution of 15.5 mg in 15 ml of dehydrated toluene and a toluene solution of triisobutylaluminum [Tosoh
3.0 ml of Akzo Co., Ltd., 1 mol / l] was previously mixed and charged, followed by N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 96.1.
mg was dissolved in 30 ml of dehydrated toluene, and the reaction solution was stirred at 60 ° C. for 2 hours. Then, the reaction solution was added with hydrochloric acid.
The mixture was poured into a mixture of 5 ml of (12N) and 1000 ml of acetone, and the precipitated white solid was collected. The solid was washed with acetone and dried under reduced pressure to obtain 28.04 g of a polymer. The glass transition point of this polymer is 39 ° C., the copolymer composition of norbornene is 3 mol%, and the copolymer composition of styrene is 4
It was 8 mol%.

Example 5 A toluene solution of 114 ml of styrene and norbornene was placed in a 400 ml autoclave purged with argon.
(5mol / l) After charging 40ml, ethylene was added to 0.8M
Pa was charged. A solution of 15.5 mg of isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride in 15 ml of dehydrated toluene and a toluene solution of triisobutylaluminum [Tosoh Akzo Co., Ltd. Made, 1mo
1 / l] 3.0 ml was mixed in advance and charged.
96.1 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added to dehydrated toluene 3
A solution dissolved in 0 ml was added, and the reaction solution was stirred at 60 ° C. for 2 hours. Thereafter, the reaction solution was poured into a mixture of 5 ml of hydrochloric acid (12N) and 1000 ml of acetone, and the precipitated white solid was filtered off. The solid was washed with acetone and dried under reduced pressure to obtain 34.86 g of a polymer. The glass transition point of this polymer is 83 ° C., and the copolymer composition of norbornene is 21 mo.
1%, and the copolymer composition of styrene was 46 mol%.

[0113]

As described above, according to the present invention,
There is provided a copolymer which is transparent and has excellent flexibility, heat resistance, and solvent resistance, which can have a configuration containing no halogen which is regarded as a problem from the viewpoint of environmental pollution. Furthermore, according to the present invention, there is provided a method for producing the copolymer extremely efficiently, and a molded article comprising the copolymer, which is transparent, flexible, heat-resistant, and excellent in solvent resistance. The utility value is very large.

[Brief description of the drawings]

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph showing ¹³ C- of the copolymer obtained in Example 1.
It is an NMR spectrum.

FIG. 2 is data obtained by measuring the solid viscoelasticity of the copolymer obtained in Example 1.

FIG. 3 is a hysteresis curve of the copolymer obtained in Example 1.

FIG. 4 is data obtained by measuring the solid viscoelasticity of the copolymer obtained in Example 2.

Claims (8)

[Claims] 1. A copolymer obtained by copolymerizing ethylene and / or an α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon, wherein the copolymer composition of the cyclic olefin is 0.01 to 66 mol. %, The copolymer composition of the alkenyl aromatic hydrocarbon is 3 to 99 mol%,
A copolymer characterized in that the copolymer composition of the alkenyl aromatic hydrocarbon is more than half the copolymer composition of the cyclic olefin. 2. The copolymer according to claim 1, wherein the copolymer composition of the alkenyl aromatic hydrocarbon is not less than the copolymer composition of the cyclic olefin. 3. The copolymer according to claim 1, wherein the copolymer has no crystallinity. 4. The copolymer according to claim 1, which has a glass transition point of -20 to 140 ° C. 5. The copolymer according to claim 1, which has a glass transition point of 35 ° C. or more and less than 60 ° C. 6. The process for producing a copolymer according to claim 1, wherein the catalyst comprises the following (A), (B) and / or (C): , An ethylene and / or α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon. (A): a transition metal complex represented by the following general formula [I], [II] or [III] (In the above general formulas [I] to [III], M ¹
Represents a transition metal atom of Group 4 of the periodic table of the element, A represents an atom of Group 16 of the periodic table of the element, and J represents an atom of Group 14 of the periodic table of the element. Cp ¹ represents a group having a cyclopentadiene-type anion skeleton. X ¹ , X ² ,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy Represents a group or a disubstituted amino group. X ³ represents an atom belonging to Group 16 of the periodic table of the elements. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring. General formula [II] or [II
I], M ¹ , A, J, Cp ¹ , X ¹ , X ² ,
X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different. (B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by general formula E ¹ _a AlZ _3-a (B2) General formula ｛-Al (E cyclic aluminoxane having the structure represented by the ²⁾ -O-} _b (B3) formula ^{E 3 {-Al (E 3)} -O-} c Al
E ³ linear aluminoxane having a structure represented by ₂ (wherein, E ^1, E ² and E ³ are each a hydrocarbon group, all of E ^1, all E ² and all E ³ are the same Z represents a hydrogen atom or a halogen atom, all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, b is 2
And c represents an integer of 1 or more. (C): a boron compound of any of the following (C1) to (C3): (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a general formula G ⁺ (BQ ¹ Q ² Q ³ Q ^{4) -} boron compound represented by, (C3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4)
^- the boron compound represented (where, B is a boron atom in the trivalent valence state, Q
^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, and (LH) ⁺ is a Bronsted acid. ) 7. A molded article comprising the copolymer according to any one of claims 1 to 5. 8. The molded article according to claim 7, wherein the molded article is a film, a sheet or a pipe.