JPH1180233A - Propylene copolymer, production of propylene copolymer, compounding ingredient for polyolefin resin and thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene copolymer which gives a thermoplastic resin compsn. excellent in softness by copolymerizing propylene, an α-olefin having a specified number of carbon atoms and ethylene in the presence of a catalyst comprising a transition metal complex and an aluminum compd. and/or a boron compd. SOLUTION: A catalyst comprising a complex represented by formula I, II or III and a compd. represented by formula IV, V or VI and/or a compd. represented by formula VII, VIII or IX is used. In the formulas, M<1> is a group 4 atom; A is a group 16 atom; J is a group 14 atom; Cp<1> is a group contg. an anionic backbone of a cyclopentadiene type; R<1> to R<6> are each alkyl, aralkyl, aryl, substd. silyl or the like; X<1> and X<2> are each pref. halogen or alkoxy; X<3> is a group 16 atom; E<1> to E<3> are each a hydrocarbon group; Z is H or halogen: B is trivalent boron; Q<1> to Q<4> are each esp. pref. a 1-20C fluorohydrocarbon group; G<+> is a cation; L is a neutral Lewis base; and (L-H)<+> is a brϕnsted acid. The α-olefin used is a 4-20C α-olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a propylene-based copolymer, a method for producing a propylene-based copolymer, a compounding agent for a polyolefin-based resin, and a thermoplastic resin composition. More specifically, the present invention relates to a novel propylene-based copolymer which gives a thermoplastic resin composition having excellent flexibility when mixed with a resin such as polypropylene, a method for producing the propylene-based copolymer, The present invention relates to a compounding agent for a polyolefin resin using a copolymer and a thermoplastic resin composition.

[0002]

2. Description of the Related Art Polypropylene resin is used as a general-purpose resin having excellent rigidity, heat deformation temperature, surface hardness and the like in various applications, but has drawbacks in impact resistance and flexibility.
As a method of improving these disadvantages, a method of blending a polypropylene resin with an ethylene-propylene copolymer or a low-crystalline ethylene-α-olefin copolymer such as an ethylene-1-butene copolymer is well known. . JP 5
Japanese Patent Application No. 98095 discloses that a thermoplastic resin composition obtained by blending a specific ethylene-propylene-1-butene copolymer with a polypropylene resin together with an inorganic filler is excellent in impact resistance and surface hardness.

[0003] On the other hand, propylene-based copolymers are obtained by copolymerizing ethylene and α-olefin with propylene using a solid titanium catalyst to obtain transparency, impact resistance, heat sealability, etc., which cannot be achieved with homopolypropylene. Become an excellent material, automotive materials, building materials, industrial materials,
Widely used for electric wire materials, polyolefin modified materials, packaging film applications, etc. Among them, particularly as a polyolefin-based resin modifying material, the demand for uses of polypropylene to improve flexibility, impact resistance and heat sealability is increasing. However, in the case of conventional polyolefin materials modified with a propylene-based copolymer or a propylene copolymer, the composition distribution of the propylene copolymer affects the material, and the material which does not necessarily reach the required level in terms of flexibility and transparency. It wasn't. Japanese Patent Application Laid-Open No. 9-12635 discloses a propylene-1-butene-ethylene copolymer obtained by using a specific metallocene compound catalyst component. These propylene-1-butene-ethylene copolymers have a narrow molecular weight distribution and contain 1-butene and ethylene at a specific ratio, so that they can be compared with propylene copolymers obtained with conventional solid titanium catalysts. It is introduced that it is excellent in transparency, rigidity, heat sealability and shock absorption, and can be a suitable material as a compounding material for resin. JP-A-8-301934 also discloses a propylene-ethylene-α-olefin copolymer synthesized using a metallocene catalyst. These propylene-ethylene-α-olefin copolymers have a narrow molecular weight distribution and composition distribution, and contain a specific ratio of ethylene and α-olefin, so that the conventional propylene-ethylene-olefin-synthesized with a solid titanium catalyst. A propylene-ethylene-α-olefin copolymer exhibiting excellent strength and low permanent elongation and having good transparency compared to α-olefin copolymers is introduced. It is also shown that a polyolefin material having excellent heat resistance can be provided as a modified material of a polyolefin resin.

[0004] In recent years, however, there has been an increasing demand for the use of polyolefin materials in fields where soft vinyl chloride resins and the like have been used. In terms of properties and the like, higher performance is required, such as a method of blending a low-crystalline ethylene-α-olefin copolymer with a polypropylene resin, JP-A-9-12635 and JP-A-8-128
The propylene copolymer disclosed in JP-A-301934 and a polyolefin material using such a propylene copolymer as a compounding agent are not necessarily materials that reach the required level.

In view of such prior art, the present inventors have conducted intensive studies on propylene copolymers. As a result, polyolefins containing a propylene copolymer obtained by using a specific metallocene catalyst as a compounding agent were used. It has been found that a material having excellent flexibility can be obtained.

[0006]

Under these circumstances, the problem to be solved by the present invention is to provide a novel propylene-based resin which, when mixed with a resin such as polypropylene, gives a thermoplastic resin composition having excellent flexibility. Another object of the present invention is to provide a copolymer, a method for producing the propylene-based copolymer, a compounding agent for a polyolefin-based resin using the propylene-based copolymer, and a thermoplastic resin composition.

[0007]

Means for Solving the Problems That is, according to the present invention,
The first invention comprises propylene, one or more kinds of carbon having 4 to 2 carbon atoms.
0 α-olefin and ethylene, the following (A)
Using the following (B) and / or the following (C)
Propylene, one or more types in the presence of a refin polymerization catalyst
Of α-olefin having 4 to 20 carbon atoms and ethylene
Propylene copolymer characterized by being obtained by
It is related. (A): transition gold represented by the following general formulas [I] to [III]
At least one of the genus complexes(In the above general formulas [I] to [III], M¹Is
Represents a transition metal atom of Group 4 of the Periodic Table of the Elements, where A is an element
Indicates an atom belonging to Group 16 of the Periodic Table,
Shows the atoms of Group 14 of the Rule. Cp¹Is cyclopentadi
A group having an ene-type anion skeleton is shown. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are each independently water
Element atom, halogen atom, alkyl group, aralkyl group,
Reel group, substituted silyl group, alkoxy group, aralkyl group
It represents a xy group, an aryloxy group or a disubstituted amino group.
X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements. R¹, R
^Two, R^Three, R^Four, R^FiveAnd R⁶Are optionally linked to form a ring
You may. Two M¹, A, J, Cp¹, X¹, X^Two,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are the same for each
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
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
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)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. )

[0008] The second invention of the present invention relates to a method for producing propylene,
The present invention relates to a method for producing a propylene-based copolymer which polymerizes at least one kind of α-olefin having 4 to 20 carbon atoms and ethylene.

A third aspect of the present invention relates to a compounding agent for a polyolefin resin comprising the propylene copolymer of the first aspect.

A fourth aspect of the present invention relates to a thermoplastic resin composition containing 3 to 95% by weight of the propylene copolymer of the first aspect and 97 to 5% by weight of a polyolefin resin. It is.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Propylene copolymer of the present invention
Is propylene, at least one α-O having 4 to 20 carbon atoms
It consists of refin and ethylene, the following (A) and the following
(B) and / or olefin using the following (C)
In the presence of a polymerization catalyst, propylene, one or more carbon atoms
Obtained by polymerizing 4 to 20 α-olefins and ethylene.
The propylene copolymer is characterized in that: (A): transition gold represented by the following general formulas [I] to [III]
At least one of the genus complexes(In the above general formulas [I] to [III], M¹Is
Represents a transition metal atom of Group 4 of the Periodic Table of the Elements, where A is an element
Indicates an atom belonging to Group 16 of the Periodic Table,
Shows the atoms of Group 14 of the Rule. Cp¹Is cyclopentadi
A group having an ene-type anion skeleton is shown. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are each independently water
Element atom, halogen atom, alkyl group, aralkyl group,
Reel group, substituted silyl group, alkoxy group, aralkyl group
It represents a xy group, an aryloxy group or a disubstituted amino group.
X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements. R¹, R
^Two, R^Three, R^Four, R^FiveAnd R⁶Are optionally linked to form a ring
You may. Two M¹, A, J, Cp¹, X¹, X^Two,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are the same for each
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
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
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)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. )

The α-olefin having 4 to 20 carbon atoms includes linear and branched α-olefins. Specifically, linear α-olefins include 1-butene and 1-butene. Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1
-Dodecene, 1-tridecene, 1-tetradecene, 1-
Pentadecene, 1-hexadecene, 1-heptadecene,
Examples thereof include 1-octadecene, 1-nanodecene, and 1-eicosene. Examples of the branched α-olefin include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, -Ethyl-1-hexene, 2,
2,4-trimethyl-1-pentene and the like are exemplified.

Hereinafter, the above manufacturing method will be described in more detail.

(A) The transition metal complex will be described.

The transition metal complex (A) has the general formula [I] or [I
I] or [III].

In the general formulas [I], [II] and [III], the transition metal atom represented by M ¹ is a transition metal of Group 4 of the Periodic Table of the Elements (Revised edition of IUPAC inorganic chemical nomenclature 1989). A metal element, such as a titanium atom, a zirconium atom, or 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 atoms 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.

Examples of the group having a cyclopentadiene-type anion skeleton represented by the substituent Cp ¹ include, for example, η
⁵ - (substituted) cyclopentadienyl group, eta ⁵ - (substituted) indenyl group, eta ⁵ - and the like (substituted) fluorenyl group. Specific examples include, for example, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η 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, eta ⁵ −
Isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ^{5-n-Penchirushikuro} Bae Ntajieniru A group, η ⁵ -neopentylcyclopentadienyl group,
η ⁵ -n-hexylcyclopentadienyl group, η ⁵ -n-
Octylcyclopropane 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 Nyl group, η ⁵ -isopropylindenyl group, η ⁵ -n-butylindenyl group, η ⁵
-Sec-butylindenyl group,? ⁵ -tert-butylindenyl group,? ^5- n-pentylindenyl group,? ⁵
-Neopentylindenyl group,? ^5- n-hexylindenyl group,? ^5- n-octylindenyl group,? ^5- n-
Decylindenyl group, η ⁵ -phenylindenyl group, η 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-butyl-fluorenyl} group, eta ^{5-sec-butylfluorenyl} group,
η ⁵ -tert-butylfluorenyl group, η ⁵ -di-n-
Butylfluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -tert- butyl-fluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorescens N-yl, η ⁵ -n-hexylfluorenyl, η ⁵ -n-octylfluorenyl, η ⁵ -n-decylfluorenyl, η ⁵ -n-dodecylfluorenyl, η ^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, such as eta ^{5-tert-butyldimethylsilyl-fluorenyl} group and the like, preferably eta ⁵ - cyclopentadienyl group, eta ⁵ - Mechirushiku Pentadienyl, η ⁵ -
tert- butyl cyclopentadienyl group, eta ⁵ - fluorenyl group - tetramethylcyclopentadienyl group, eta ⁵ - indenyl group, or eta ^5.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} halogen atom for ⁵ or R ⁶ , a fluorine atom,
Examples thereof include a chlorine atom, a bromine atom, and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkyl group for ⁵ or R ⁶ has 1 to 1 carbon atoms.
Preferred are 20 alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n- Hexyl group,
n-octyl group, n-decyl group, n-dodecyl group, n-
Examples thereof include a pentadecyl group and an n-eicosyl group, and more preferably a methyl group, an ethyl group, an isopropyl group, and a t-group.
tert-butyl or amyl.

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 , R
The aralkyl group for ⁵ or R ⁶ has 7 carbon atoms.
~ 20 aralkyl groups are preferred, for example, benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl,
(2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl Phenyl) methyl group, (4,6
-Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) ) Methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl,
(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,
Examples include an anthracenylmethyl group, and more preferably a benzyl group.

All of these aralkyl 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; It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} aryl group for ⁵ or R ^6, C ^{6 to} C 6
Preferred are 20 aryl groups such as phenyl, 2
-Tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group,
2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,
3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group,
3,4,5-trimethylphenyl group, 2,3,4,5-
Tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-
Propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert
-Butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, Examples include an anthracenyl group, and more preferably a phenyl group.

All of these aryl groups include halogen atoms such as fluorine, chlorine, bromine and iodine, alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy and benzyloxy. It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The substituted silyl group represented by ⁵ or R ⁶ is a silyl group substituted by a hydrocarbon group, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, tert-
Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group and a cyclohexyl group, and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group and the like. A disubstituted silyl group having 2 to 20 carbon atoms,
Trimethylsilyl group, 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-
n-pentylsilyl group, tri-n-hexylsilyl group,
Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as a tricyclohexylsilyl group and a triphenylsilyl group, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is preferable.

In all of these substituted silyl groups, the hydrocarbon group 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, or an aryloxy group such as a phenoxy group. Alternatively, it may be partially substituted with an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkoxy group for ⁵ or R ⁶ has 1 carbon atom
~ 20 alkoxy groups are preferred, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-
Butoxy group, n-pentoxy group, neopentoxy group, n
-Hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadeoxy group, n-icosoxy group and the like, and more preferably methoxy group, ethoxy group or tert-butoxy group.

All of these alkoxy groups include halogen atoms such as fluorine, chlorine, bromine and iodine, alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy and benzyloxy. It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyloxy group for ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group. 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)
A methoxy group, a (2,3,5-trimethylphenyl) methoxy group, a (2,3,6-trimethylphenyl) methoxy group, a (2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy, (penta (Methylphenyl) 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-
Examples thereof include an (octylphenyl) methoxy group, a (n-decylphenyl) methoxy group, a (n-tetradecylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and more preferably a benzyloxy group.

Each of these aralkyloxy groups is
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 , R
^The aryloxy group for ⁵ or R ⁶ is preferably an aryloxy group having 6 to 20 carbon atoms, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 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-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 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.

Each of these aryloxy groups is 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 ⁴ , R
^The disubstituted amino group in ⁵ or R ⁶ is an amino group substituted with two hydrocarbon groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, isobutyl group, n-pentyl group, n
A hexyl group, a cyclohexyl group or the like having 1 to 1 carbon atoms
10 to 6 carbon atoms such as an alkyl group and a phenyl group
And an aralkyl group having 7 to 10 carbon atoms. Examples of such a disubstituted amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, Di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino Groups, a diphenylamino group, a bistrimethylsilylamino group, a 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 optionally bonded to form a ring.

Preferred examples of R ¹ include an alkyl group, an aralkyl group, an aryl group and a substituted silyl group.

Preferred X ¹ and X ² each independently include a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group and a disubstituted amino group. More preferred are a halogen atom and An alkoxy group can be mentioned.

In the general formula [II] or [III], the atoms of Group 16 of the periodic table of the element represented by X ³ include:
For example, an oxygen atom, a sulfur atom, a selenium atom and the like can be mentioned, and an oxygen atom is preferable.

The transition metal complex represented by the general formula [I] includes, for example, methylene (cyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-ter
t-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-t
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-butyldimethyl Silyl-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 (t
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 (te
rt-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-butylcyclopentadienyl) (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-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-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 (trimethylsilylcyclopentadienyl)
(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 -T
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-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-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-ter
t-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-yl) 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 (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 (tert
-Butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (te
rt-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-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadiene) Enil) (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, 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-te
rt-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-butyl Dimethylsilyl-
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, diphenylmethylene (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-tert-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-butyldimethyl Silyl-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 (tert-butylcyclopentadienyl) (3-te
rt-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
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (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-tert-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-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-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, etc., and titanium of these compounds is zirconium or hafnium The compound in which dichloride was changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide, and (cyclopentadienyl) was changed to (dimethylcyclopentadiene) Enyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl),
(Tert-butyldimethylsilylcyclopentadienyl) or a compound changed to (indenyl), (3,5
-Dimethyl-2-phenoxy) to (2-phenoxy),
(3-methyl-2-phenoxy), (3,5-di-te)
rt-butyl-2-phenoxy), (3-phenyl-5
J in the general formula [I] such as a compound modified to -methyl-2-phenoxy), (3-tert-butyldimethylsilyl-2-phenoxy), or (3-trimethylsilyl-2-phenoxy) is a carbon atom. Transition metal complex, dimethylsilyl (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2)
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5
-Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert -Butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (Methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl -
2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ( 5-methyl-3-phenyl-
2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-
Butyldimethylsilyl-5-methyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-ter
t-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-diamyl-
2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (n-butylcyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl ( n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) Titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (Tert-butylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (ter
t-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2- Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyldimethyl Cyril-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) ( 3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium Dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (Tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadiene) Enyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) ) (5-
Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) )
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopenta Dienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-di-
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl -5-chloro-
2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-2- Phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride Dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl)
(3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds are (Dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl) , (Isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl),
(Methylindenyl) or a compound in which (phenylindenyl) is changed, (2-phenoxy) is converted to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethyl) A compound in which dimethylsilyl is changed to diethylsilyl, diphenylsilyl, or dimethoxysilyl, a compound in which titanium is replaced with zirconium,
Or a compound of the general formula [I] such as a compound in which hafnium has been changed, or a compound in which dichloride has been changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide.
Wherein J is a group 14 atom of the periodic table of elements other than carbon atoms.

Examples of the transition metal complex represented by the general formula [II] include μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride} and μ-oxobis {isopropylidene (cyclopentadiene). Enyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene ( Cyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (methyl) Cyclopentadienyl) (2-
Phenoxy) titanium methoxide {, μ-oxobis} isopropylidene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} isopropylidene (methylcyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium methoxide, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethylcyclo) Pentadienyl) (2
-Phenoxy) titanium methoxide {, μ-oxobis} isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethyl) Cyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (cyclopentane) Dienyl) (2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride｝, μ-
Oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide},
μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium chloride｝, μ-oxobis ｛dimethylsilylene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (tetramethylcyclopentadienyl) (2
-Phenoxy) titanium chloride {, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ
-Oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-
Phenoxy) titanium methoxide, and the like.

Examples of the transition metal complex represented by the general formula [III] include di-μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium} and di-μ-oxobis {isopropylidene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis} isopropylidene (methylcyclopentadienyl)
(2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (Tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis} dimethylsilylene (cyclopentadienyl) ) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl)
(2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (Tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium}, and the like.

The transition metal complex represented by the general formula [I] can be produced, for example, by the method described in WO 97/03992. The transition metal complex represented by the general formula [II] or [III] can be produced by reacting the transition metal complex represented by the general formula [I] with one or two equivalents of water.

The (B) aluminum compound will be described.

The aluminum compound (B) is at least one aluminum compound selected from the following (B1) to (B3). (B1) the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B2) general formula {-Al (E ²⁾ -O-} cyclic aluminoxane (B3) having a structure represented by _b the formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ^2, and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 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, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, 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, more preferably, triethylaluminum or triisobutylaluminum.

[0050] 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 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include an alkyl group such as an isobutyl group, a normal pentyl group, and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ²
And E ³ is a methyl group or an isobutyl group, and b is 2
-40 and c are 1-40.

The above aluminoxane is 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 or the like) in a suitable organic solvent (benzene or 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.

The (C) boron compound will be described.

Examples of the boron compound (C) include (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ and (C2)
A boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
Any of the boron compounds represented by the following formulas can be used.

General formula BQ¹Q^TwoQ^ThreeBoration represented by
In the compound (C1), B is boron in a trivalent valence state
Atom, Q¹~ Q^ThreeRepresents a halogen atom, a hydrocarbon group,
A hydrogenated hydrocarbon group, a substituted silyl group, an alkoxy group or
Disubstituted amino groups, which are the same or different
May be. Q¹~ Q^ThreeIs preferably a halogen atom,
A hydrocarbon group containing 1-20 carbon atoms, 1-20
Halogenated hydrocarbon groups containing carbon atoms, from 1 to 20 carbon atoms
Substituted silyl groups containing 1 to 20 carbon atoms
An alkoxy group or an amino containing 2 to 20 carbon atoms
And more preferred Q¹~ Q^ThreeIs a halogen atom, 1 to
A hydrocarbon group containing 20 carbon atoms, or 1-20
It is a halogenated hydrocarbon group containing a carbon atom. More preferred
Or Q ¹~ Q^FourIs at least one fluorine source
A fluorinated hydrocarbon group having 1 to 20 carbon atoms containing
And particularly preferably Q¹~ Q^FourIs at least 1 each
Fluorinated carbon atoms having 6 to 20 carbon atoms containing two fluorine atoms
It is a reel group.

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. And Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (C1) above.

[0057] 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, particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) 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,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and most preferably triphenylmethyltetrakis (pentafluorophenyl) borate.

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

[0060] formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^{-, the same} as those described above can be mentioned.

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,
Examples thereof include tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the copolymerization, the transition metal complex (A)
And an olefin polymerization catalyst comprising the above (B) and / or the above (C). When an olefin polymerization catalyst comprising two components (A) and (B) is used, the above-mentioned cyclic aluminoxane (B2) and / or linear aluminoxane (B3) are preferred as (B). Another preferred embodiment of the olefin polymerization catalyst is an olefin polymerization catalyst comprising the above (A), (B) and (C). ) Easy to use.

The amount of each component used is usually such that the molar ratio of (B) / (A) is from 0.1 to 10,000, preferably from 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.

The concentration when each component is used in the form of a solution or a suspension in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. , Usually 0.01 to 500 μmol / g,
More preferably, 0.05 to 100 μmol / g, still more preferably, 0.05 to 50 μmol / g, (B)
Usually, in terms of Al atom, 0.01 to 10000 μmol /
g, more preferably 0.1 to 5000 μmol /
g, more preferably 0.1 to 2000 μmol / g,
(C) is usually from 0.01 to 500 μmol / g, preferably from 0.05 to 200 μmol / g, and more preferably from 0.05 to 100 μmol / g. desirable.

To produce a propylene-based copolymer, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as methylene dichloride are used. Solvent polymerization using hydrogen as a solvent, or slurry polymerization, gas-phase polymerization in a gaseous monomer and the like are possible,
Further, either continuous polymerization or batch polymerization can be used.
The polymerization temperature can take a range of -50 to 200 ° C, and particularly preferably a range of -20 to 100 ° C, and the polymerization pressure is
Normal pressure to 60 kg / cm ² G is preferable. The polymerization time is generally appropriately determined depending on the type of the catalyst to be used and the reactor, but can range from 1 minute to 20 hours. Further, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

The propylene copolymer of the present invention has a temperature of 1
The intrinsic viscosity [η] of the tetralin solvent at 35 ° C. is preferably 0.3 to 10, more preferably 0.5 to 10.
To 7, more preferably 0.7 to 5. If the intrinsic viscosity is too low, the resulting thermoplastic resin composition may have poor flexibility and scratch resistance. When the intrinsic viscosity is too high, the flexibility of the obtained thermoplastic resin composition may be poor. The intrinsic viscosity [η] is measured in tetralin at 135 ° C. using an Ubbelohde viscometer. Sample is 3
Dissolve 00mg in 100ml tetralin and add 3mg / m
1 solution was prepared. Further, the solution was １ ／, ３,
Dilute to 1/5 and measure each in a constant temperature water bath at 70 ° C (± 0.1 ° C). The measurement is repeated three times at each concentration, and the obtained values are averaged and used.

The propylene copolymer of the present invention preferably has a molecular weight distribution (Mw / Mn) of 5 or less, more preferably 4 or less, as measured by gel permeation chromatography (GPC). Preferably it is 3 or less. When the molecular weight distribution is too wide, when the copolymer is used as a modifier, the resulting thermoplastic resin composition may have poor flexibility. The molecular weight distribution is measured by gel permeation chromatography (GPC) (for example, 150C / GPC apparatus manufactured by Waters). The elution temperature is 140 ° C., and the column used is, for example, Sodex Packed Column manufactured by Showa Denko KK
A-80M, a molecular weight standard substance uses polystyrene (for example, Tosoh Corporation, molecular weight 68-8,400,000). The obtained polystyrene equivalent weight average molecular weight (M
w), number average molecular weight (Mn), and this ratio (Mw / M
Let n) be the molecular weight distribution. As a measurement sample, about 5 mg of a polymer was dissolved in 5 ml of o-dichlorobenzene, and about 1 mg was dissolved.
/ Ml concentration. 400μ of the obtained sample solution
and the elution solvent flow rate was 1.0 ml /
min and detected by a refractive index detector.

The propylene copolymer of the present invention preferably has an ethylene content of 80 mol% or less, more preferably 75 mol% or less, and still more preferably 7 mol% or less.
0 mol% or less, particularly preferably 65 mol% or less. Outside this range, the propylene-based copolymer may contain crystals derived from ethylene, and the resulting thermoplastic resin composition may be inferior in flexibility.

The propylene-based copolymer of the present invention is used as a modifier for a polyolefin resin, and the thermoplastic resin composition obtained is required to have flexibility, transparency, scratch resistance, etc. When used as a PVC substitute material, the constituent composition of the propylene copolymer preferably satisfies the relationship of the following formula. [Y / (100−x)] ≧ 0.45 More preferably, [y / (100−x)] ≧ 0.47, and still more preferably, [y / (100−x)] ≧ 0.
50.

If the ratio is outside the above range, the flexibility, transparency and scratch resistance of the obtained thermoplastic resin composition may be poor. In the above formula, x represents the molar content of propylene in the copolymer, and y represents 4 carbon atoms in the copolymer.
Represents the sum of the molar contents of ２０20 α-olefins.

The propylene copolymer of the present invention is used as a modifier for a polyolefin resin, and when the resulting thermoplastic resin composition is used for applications requiring flexibility, for example, when it is used as a substitute for soft PVC. 1J based on the melting of the crystal as measured by a differential scanning calorimeter (DSC).
It is preferred that the compound does not have any of a peak of 1 J / g or more and a peak of 1 J / g or more based on crystallization. When it has such a peak, the flexibility of the obtained thermoplastic resin composition may be poor. The differential scanning calorimeter uses, for example, DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd., and performs measurement at a rate of 10 ° C./min in both the temperature raising and constant temperature processes.

The propylene-based copolymer of the present invention is used as a modifier for a polyolefin resin, and when the obtained thermoplastic resin composition is used for applications requiring flexibility, for example, when used as a substitute for soft PVC. A propylene-based copolymer in which the flexural modulus (S) of the homopolypropylene, the added parts by weight (T) of the homopolypropylene and the flexural modulus (U) of the obtained thermoplastic resin composition have the following relationship. Preferably, there is. U ≦ S × [(T / 100) × V] ²

At this time, V is preferably 1.1, more preferably 1.0, more preferably 0.9, particularly preferably 0.8. If the ratio is out of the range, the flexibility of the obtained thermoplastic resin composition may be poor.

The propylene-based copolymer of the present invention is used as a modifier for a polyolefin resin. When the obtained thermoplastic resin composition is used for applications requiring flexibility, for example, when it is used as a substitute for soft PVC, , Propylene and / or α-olefin side chains preferably have an atactic structure. Propylene and / or carbon number 4 ~
When the orientation of the side chain of the propylene chain in the copolymer is an atactic structure, the number of carbon atoms in the copolymer is 4 when the orientation of the side chain of the α-olefin of No. 20 is an atactic structure.
When the orientation of the side chain of the α-olefin chain of -20 to 20 is an atactic structure, propylene / carbon number 4 in the copolymer
The case where the orientation of the side chain of the α-olefin complex chain of -20 is an atactic structure is shown. The fact that the propylene-based copolymer of the present invention has an atactic structure means that, for example, when the homopolypropylene is polymerized using the transition metal complex used for the polymerization of the propylene-based copolymer of the present invention, the obtained homopolymer is obtained. The intensity of each signal [mm], [mr] and each of the polypropylene, which can be determined from the ¹³ C NMR spectrum and is assigned to mm, mr and rr of propylene methyl carbon.
It can be confirmed from the structure that the F (1) value defined by the following formula using [rr] is 40 or more and 60 or less, preferably 43 or more and 57 or less, and more preferably 45 or more and 55 or less. F (1) = 100 × [mr] / ([mm] + [mr] + [r
r])

Similarly, regarding the propylene copolymer of the present invention, the signals of mm, mr and rr assigned to mm, mr and rr of propylene methyl carbon, branched methylene carbon of α-olefin, methyl terminal carbon of branched α-olefin, etc. When the value corresponding to F (1) obtained using the strength is in the above range, it can be confirmed that the structure is an atactic structure. When the propylene-based copolymer does not have an atactic structure, the resulting thermoplastic resin composition may have poor flexibility. The assignment of mm, mr, and rr signals of propylene methyl carbon, branched methylene carbon of α-olefin, methyl terminal carbon of α-olefin, and the like are described in, for example, Asakura, Macromolecule
s, Vol. 24, p. 2334 (1991), and Kinokuniya Publishing Co., Ltd., New Handbook of Polymer Analysis (1995).

The propylene copolymer of the present invention is used as a modifier for a polyolefin resin, and the resulting thermoplastic resin composition is required to have rigidity, impact resistance, balance between rigidity and impact resistance, and the like. Applications, such as bumpers,
When used as interior and exterior parts of automobiles such as malls, front grilles, instrument panels, and exterior parts of electric equipment, it is preferable that the constituent composition of the propylene copolymer satisfy the following relationship. [Y / (100-x)] <0.45

In the above formula, x represents the molar content of propylene in the copolymer, and y represents the total molar content of α-olefins having 4 to 20 carbon atoms in the copolymer.

The propylene copolymer of the present invention preferably has a propylene content of less than 90 mol%, more preferably less than 80 mol%, especially when low temperature resistance is required. And more preferably less than 70 mol%, particularly preferably less than 6 mol%,
Most preferably it is less than 50 mol%. Outside the range, the propylene copolymer and the obtained thermoplastic resin composition may be inferior in low-temperature impact resistance.

The propylene copolymer of the present invention preferably has an α-olefin content of 10 mol% or more, more preferably 15 mol%, particularly when low-temperature resistance is required. % Or more, more preferably 20%
Mol% or more, and particularly preferably 25 mol% or more. Outside of this range, the resulting thermoplastic resin composition may be inferior in low-temperature impact resistance.

The α-olefin component of the propylene copolymer of the present invention has 4 to 20 carbon atoms, preferably α-olefin component.
The olefin is 1-butene, 1-hexene, 1-octene or 1-decene.

The propylene copolymer of the present invention is optimally used as a compounding agent for a polyolefin resin. Polyolefin resins include high density polyethylene, medium density polyethylene, low density polyethylene, LLDPE (linear low density polyethylene), polypropylene resin, poly-4
-Methyl-pentene-1 and the like. Preferably, it is a polypropylene resin.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition containing 3 to 95% by weight of the above-mentioned propylene copolymer of the present invention and 97 to 5% by weight of a polyolefin resin.

Polyolefin resins include high density polyethylene, medium density polyethylene, low density polyethylene, LL
DPE (linear low-density polyethylene), polypropylene resin, poly-4-methyl-pentene-1 and the like. Preferably, it is a polypropylene resin.

The polypropylene resin used in the composition of the present invention is a crystalline polypropylene resin, and is a homopolymer of propylene or a random or block copolymer of propylene and a small amount of α-olefin. When the polypropylene resin is a copolymer, in the case of a random copolymer, the other α-olefin copolymerization ratio in the copolymer is generally 10% by weight or less, preferably 0.5% by weight or less. In the case of a block copolymer, the copolymerization ratio of the other α-olefin in the copolymer is generally 1 to 40% by weight, preferably 1 to 25% by weight, and Is 2 to 20% by weight, particularly preferably 3 to 15% by weight. These polypropylene-based polymers may be a combination of two or more polymers. As an index of the crystallinity of polypropylene, for example,
Melting point, heat of crystal fusion, etc. are used.
It is preferable that the heat of crystal fusion at 176 ° C. is in the range of 60 to 120 J / g. If the melting point of the crystal is too low or the heat of fusion is too low, the heat resistance of the material will be poor.

As a method for producing a polypropylene-based resin, generally, a Ziegler-type compound using a combination of a so-called titanium-containing solid transition metal component and an organometallic component is used.
Using a Natta type catalyst, or a metallocene catalyst comprising a transition metal compound belonging to Groups 4A to 6A of the Periodic Table having at least one cyclopentadienyl skeleton and a promoter component,
Slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization, or the like, or a polymerization method combining these, in one step or in multiple steps, to obtain a propylene homopolymer by homopolymerizing propylene, or propylene and a carbon number of 2 or 4 to 12 α
A method of obtaining a propylene-α-olefin copolymer by copolymerizing an olefin, preferably ethylene, in one or more stages. Note that commercially available products may be used.

The thermoplastic resin composition of the present invention contains 3 to 95% by weight of the propylene copolymer (A) and 97 to 5% by weight of the polyolefin resin (B) ((A) + (B) = 100).
% By weight. ). Preferably, the content is 10 to 80% by weight of the olefin copolymer and 90 to 20% by weight of the polyolefin resin, and more preferably 30 to 70% by weight of the olefin copolymer and 70 to 30% by weight of the polyolefin resin. . If the amount of the olefin copolymer is too large (the amount of the polyolefin resin is too small), the fluidity becomes low, and the molding processability is poor, the strength is insufficient, and the heat resistance is poor. If the amount is too small (the amount of the polyolefin-based resin is too large), the flexibility is poor or the scratch resistance is poor.

Further, the propylene-based copolymer of the present invention comprises:
Used as a modifier of polyolefin resin, the resulting thermoplastic resin composition is required to have rigidity, impact resistance, and balance between rigidity and impact resistance, such as bumpers, moldings, front grills, instrument panels. When used as interior and exterior parts of automobiles and exterior parts of electric equipment, it is preferable that the constituent composition of the propylene copolymer satisfies the relationship of the following formula as described above. [Y / (100-x)] <0.45

In the above formula, x represents the molar content of propylene in the copolymer, and y represents the total molar content of α-olefins having 4 to 20 carbon atoms in the copolymer. In the above-mentioned range, when the flexibility of the thermoplastic resin composition is particularly required, 30 to 95% by weight of the propylene copolymer and 70 to 5% by weight of the polyolefin resin ((A)
+ (B) = 100% by weight. ) Is preferable. In addition, more preferably, the propylene-based copolymer 4
0 to 90% by weight and polyolefin resin 60 to 10% by weight, more preferably propylene copolymer 5
0 to 85% by weight and 50 to 15% by weight of a polyolefin-based resin, and particularly preferably a propylene-based copolymer 60.
-80 wt% and 40-20 wt% polyolefin resin. If the propylene-based copolymer is too large (the polyolefin-based resin is too small), the fluidity will be low and the molding processability will be poor, the strength will be insufficient, and the heat resistance will be poor. If the amount is too small (the amount of the polyolefin resin is too large), the flexibility is poor.

In the thermoplastic resin composition containing the propylene copolymer of the present invention, in addition to the essential components of the propylene copolymer and the polyolefin resin, other rubber components such as ethylene -Propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, ethylene-1-butene copolymer rubber, polybutadiene, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber ,
Styrene-butadiene random copolymer rubber, partially hydrogenated styrene-butadiene-styrene block copolymer rubber, partially hydrogenated styrene-butadiene random copolymer rubber, styrene-isoprene block copolymer rubber, partially hydrogenated styrene-isoprene Block copolymer rubber, acrylonitrile-butadiene copolymer rubber, partially hydrogenated acrylonitrile-butadiene copolymer rubber, butyl rubber,
Chloroprene rubber, fluorine rubber, chlorosulfonated polyethylene, silicone rubber, urethane rubber, and the like may be added. If necessary, a crosslinking reaction can be carried out by adding a peroxide. Further, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a pigment, a filler, and a flame retardant may be added.

In the thermoplastic resin composition containing the propylene copolymer of the present invention, in addition to the essential components of the propylene copolymer and the polyolefin resin, if necessary, other resin components such as rosin A resin, a polyterpene resin, a synthetic petroleum resin, a chroman resin, a phenol resin, a xylene resin, a styrene resin, an isoprene resin, a cyclic olefin resin, or the like may be added.

As a method for obtaining the thermoplastic resin composition containing the propylene-based copolymer of the present invention, a method in which each component is melt-kneaded with a twin-screw extruder, a Banbury mixer or the like can be mentioned.

The thermoplastic resin composition containing the olefin copolymer of the present invention can be prepared by a known method such as extrusion molding, injection molding, compression molding, blow molding, vacuum molding, powder molding, and calendar molding. It is formed by the method described above. Examples of the powder molding method include a slush molding method, a flow immersion method, an electrostatic coating method, a powder spraying method, a powder rotational molding method, and the like.

The thermoplastic resin composition containing the olefin-based copolymer of the present invention can be optimally used for home electric appliances, automobile parts, miscellaneous goods, etc. by utilizing its excellent characteristics. In automotive parts, it can be suitably used for interior skins of instrument panels, doors, pillars, etc., airbag covers, and the like.

[0094]

The present invention will be described in more detail with reference to the following examples, which are for illustrative purposes only and should not be construed as limiting the present invention.

[I] Measurement method The measurement was performed as follows.

(1) Intrinsic viscosity [η] The viscosity was measured in tetralin at 135 ° C. using an Ubbelohde viscometer. For the sample, 300 mg was dissolved in 100 ml of tetralin to prepare a 3 mg / ml solution. The solution was further diluted to 1/2, 1/3, and 1/5, and each was diluted to 135 ° C.
(± 0.1 ° C.) in a constant temperature oil bath. The measurement was repeated three times at each concentration, and the obtained values were averaged and used.

(2) Differential scanning calorimeter (DSC) measurement Differential scanning calorimeter (DSC220 manufactured by Seiko Instruments Inc.)
Using C), the measurement was performed at a rate of 10 ° C./min in both the temperature increasing and temperature decreasing processes.

(3) Measurement of molecular weight distribution Gel permeation chromatography (GPC) method (W
aters company, 150C / GPC apparatus). The elution temperature is 140 ° C and the column used is Showa Denko S
Odex Packed Column A-80M, molecular weight standard substance is polystyrene (manufactured by Tosoh Corporation, molecular weight 68
-8,400,000). The obtained polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (M
n), and this ratio (Mw / Mn) is used as the molecular weight distribution.
As a measurement sample, about 5 mg of a polymer is dissolved in 5 ml of o-dichlorobenzene, and the concentration is about 1 mg / ml. 400 μl of the obtained sample solution was injected. The elution solvent flow rate was 1.0 ml / min, and detection was performed with a refractive index detector.

(4) Measurement of the content of each monomer unit in the copolymer The content of each monomer unit in the propylene-based copolymer was calculated from the measurement results of an infrared spectrometer according to the following method.

(A) Preparation of Calibration Curve Mixtures of propylene homopolymer and ethylene-1-butene copolymer at various mixing ratios were each hot pressed to form a 0.05 mm thick film. Using an infrared spectrometer, a peak derived from propylene units (wave number 1150c
m ^-1 ) and a peak derived from a 1-butene unit (wave number 770 c
m ^-1 ), and the propylene and 1-butene unit content in the mixture was plotted against the absorbance. A regression line was determined from these plots and used as a calibration curve. In addition, propylene homopolymer and ethylene-
The mixture of 1-butene copolymers was dissolved in toluene, methanol was added, and the resulting precipitate was dried and used.

(B) Measurement of propylene / 1-butene content The olefin copolymer was hot-pressed to form a 0.05 mm-thick film, and the peak derived from the propylene unit and the 1- The absorbance with the peak derived from the butene unit was determined, and the propylene and 1-butene unit content in the olefin copolymer was calculated from the calibration curve obtained by the above method.

[II] Polymerization of Propylene Copolymer Example 1 A 2 l separable flask reactor was equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, and the pressure was reduced.
Replace with nitrogen. 1 liter of dry toluene in this flask
Was introduced as a polymerization solvent. Where ethylene 2NL / m
in, propylene 4NL / min, 1-butene 1NL /
min was continuously fed at normal pressure, and the solvent temperature was 30 ° C. After adding 0.75 mmol of triisobutylaluminum (hereinafter abbreviated as TIBA) to the polymerization tank, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride of the following chemical formula is added. 0.0015 mmol was added to the polymerization vessel. After 15 seconds, triphenylmethyltetrakis (pentafluorophenyl) borate 0.0
075 mmol was added to the polymerization tank to initiate polymerization. 1
As a result of polymerization for 0 minutes, 86.4 g of a propylene-1-butene-ethylene copolymer was obtained.

Examples 2 to 7 and Comparative Example 1 The copolymer was prepared in basically the same manner as in Example 1 except that the amounts of the monomers and the catalyst were changed as shown in Tables 1 to 3. Obtained. Detailed results are summarized in Tables 1 to 3.

Reference Example 1 A separable flask reactor having a capacity of 2 liters was equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, and the pressure was reduced.
Replace with nitrogen. 1 liter of dry toluene in this flask
Was introduced as a polymerization solvent. Here propylene 8NL /
min was continuously fed at normal pressure, and the solvent temperature was 30 ° C. After adding 1.25 mmol of TIBA to the polymerization tank, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 0.00 was used as a polymerization catalyst.
5 mmol was added to the polymerization vessel. Fifteen seconds later, 0.025 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added to the polymerization tank to start polymerization. After 10 minutes of polymerization, homopropylene
6 g were obtained. The resulting homopolypropylene is ¹³ C
Intensities of signals attributable to mm, mr and rr of propylene methyl carbon, which can be determined from NMR spectra
[mm], [mr] and [rr] are 17: 51: 3, respectively.
The intensity ratio was 2. Using these values, the F (1) value defined by the following formula was 51, and it was confirmed that the obtained homopolypropylene had an atactic structure. F (1) = 100 × [mr] / ([mm] + [mr] + [r
r])

[III] Evaluation of thermoplastic resin composition The blends shown in Tables 4 to 6 were preliminarily kneaded for 2 minutes at a temperature of 200 ° C. and a screw rotation speed of 10 rpm using a plastic coder PLV151 type manufactured by Brabender. After 80r
Kneading was performed at pm for 10 minutes. The composition was pressed at 200 ° C. to form a 2 mm thick sheet. In the physical property test, a test piece was punched out of a press sheet and measured. The results are shown in Tables 4 to 6.

Various properties of the propylene copolymer compositions described in Examples and Comparative Examples were measured by the following methods. (1) Hardness: ASTM D2240 (2) Bending test: JIS K7203 (3) Scratch resistance test: 2 mm thickness of a sample with a scratching needle loaded with a load of 500 g using a surface property measuring device Tribogear (manufactured by Shinto Kagaku) The press sheet was scratched by scratching at a constant speed. The depth of the scratch was measured with a contact type surface roughness meter Surfcom (manufactured by Tokyo Seimitsu) on a scale of μm order. (4) Haze: Measurement was performed on a JIS K7105 2 mm-thick press sheet. (5) Differential scanning calorimeter (DSC): Using a differential scanning calorimeter (DSC220C manufactured by Seiko Instruments Inc.), any of the temperature raising and constant temperature processes Was also measured at a rate of 10 ° C./min.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

[Table 3] A-10: VESTOPLAST 520 (manufactured by Huls) ethylene-propylene-1-butene copolymer * 1 (a): triisobutylaluminum * 2 (b): triphenylmethyltetrakis (pentafluorophenyl) borate * 3 (c ): Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride * 4 (d): ethylenebis (indenyl) hafnium dichloride

[0110]

[Table 4]

[0111]

[Table 5]

[0112]

[Table 6] B-1: 230 ° C., 2.16 kg load MI is 14 (g)
/ 10 min) homopolypropylene

[0113]

As described above, according to the present invention, a novel propylene-based copolymer which gives a thermoplastic resin composition having excellent flexibility when mixed with a resin such as polypropylene, and the propylene-based copolymer , A compounding agent for a polyolefin-based resin using the propylene-based copolymer, and a thermoplastic resin composition.

[Brief description of the drawings]

FIG. 1 is a flowchart showing an example of a process for producing a propylene-based copolymer of the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23/14 C08L 23/14 23/16 23/16 23/18 23/18

Claims (16)

[Claims] 1. Propylene, one or more carbon atoms having 4 to 2 carbon atoms
0 α-olefin and ethylene, the following (A)
Using the following (B) and / or the following (C)
Propylene, one or more types in the presence of a refin polymerization catalyst
Of α-olefin having 4 to 20 carbon atoms and ethylene
A propylene-based copolymer obtained by: (A): transition gold represented by the following general formulas [I] to [III]
At least one of the genus complexes(In the above general formulas [I] to [III], M¹Is
Represents a transition metal atom of Group 4 of the Periodic Table of the Elements, where A is an element
Indicates an atom belonging to Group 16 of the Periodic Table,
Shows the atoms of Group 14 of the Rule. Cp¹Is cyclopentadi
A group having an ene-type anion skeleton is shown. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are each independently water
Element atom, halogen atom, alkyl group, aralkyl group,
Reel group, substituted silyl group, alkoxy group, aralkyl group
It represents a xy group, an aryloxy group or a disubstituted amino group.
X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements. R¹, R
^Two, R^Three, R^Four, R^FiveAnd R⁶Are optionally linked to form a ring
You may. Two M¹, A, J, Cp¹, X¹, X^Two,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are the same for each
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
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
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)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. ) 2. The propylene-based copolymer according to claim 1, wherein A in the general formula [I], [II] or [III] is an oxygen atom. 3. X in the general formula [II] or [III]
^3. The propylene-based copolymer according to claim 1, wherein ³ is an oxygen atom. 4. The propylene copolymer according to claim 1, wherein R ¹ in the general formula [I], [II] or [III] is an alkyl group, an aralkyl group, an aryl group or a substituted silyl group. 5. X ¹ and X ² in the general formulas [I], [II] or [III] each independently represent a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group. The propylene-based copolymer according to claim 1. 6. The propylene copolymer according to claim 1, wherein the compound (B) is triethylaluminum, triisobutylaluminum or methylaluminoxane. 7. The propylene copolymer according to claim 1, wherein the compound (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. 8. The propylene copolymer according to claim 1, wherein the intrinsic viscosity [η] of the tetralin solvent at a temperature of 135 ° C. is 0.3 to 10. 9. A molecular weight distribution (Mw / M) measured by gel permeation chromatography (GPC).
2. The propylene copolymer according to claim 1, wherein n) is 5 or less. 10. The method according to claim 1, which has neither a peak of 1 J / g or more based on melting of the crystal nor a peak of 1 J / g or more based on crystallization as measured by a differential scanning calorimeter (DSC). Propylene copolymer. 11. The propylene-based copolymer according to claim 1, which satisfies the following relationship: [Y / (100−x)] ≧ 0.45 (x represents the content (mol%) of propylene in the copolymer, and y represents the content of α-olefin having 4 to 20 carbon atoms in the copolymer. Amount (mol%).) 12. The propylene copolymer according to claim 1, wherein the relationship represented by the following formula is satisfied. [Y / (100−x)] <0.45 (x represents the content (mol%) of propylene in the copolymer, and y represents the content of α-olefin having 4 to 20 carbon atoms in the copolymer. Amount (mol%).) 13. A method for producing a propylene-based copolymer in which propylene, one or more α-olefins having 4 to 20 carbon atoms and ethylene are polymerized in the presence of the olefin polymerization catalyst according to claim 1. 14. A compounding agent for a polyolefin resin comprising the propylene copolymer according to claim 1. 15. A thermoplastic resin composition containing 3 to 95% by weight of the propylene copolymer according to claim 1 and 97 to 5% by weight of a polyolefin resin. 16. The thermoplastic resin composition according to claim 15, wherein the polyolefin resin is a crystalline polypropylene resin.