JP2007254576A - Manufacturing method of cycloolefin copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a cycloolefin copolymer, the one formed by copolymerizing a cycloolefin, an alkenyl aromatic hydrocarbon and an α-olefin, which method gives a higher molecular weight copolymer. <P>SOLUTION: The method manufactures the cycloolefin copolymer which has monomer units based on a cycloolefin, monomer units based on an alkenyl aromatic hydrocarbon and monomer units based on an α-olefin and in which the content of the monomer units based on the cycloolefin is 10-50 mol% and the content of the monomer units based on the alkenyl aromatic hydrocarbon is 1-50 mol%. In the method the cycloolefin, alkenyl aromatic hydrocarbon and α-olefin are copolymerized in the presence of a polymerization catalyst using a specific transition metal complex as a polymerization catalyst component. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a cyclic olefin copolymer.

  Copolymers of cyclic compounds such as norbornene and styrene and α-olefins such as ethylene and propylene are used as optical materials such as lenses, optical fibers, and recording media because they are excellent in optical properties. Examples of the method for producing the copolymer include isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride or dimethylsilylene (tetramethylcyclopentadienyl). A method of copolymerizing norbornene and ethylene, a method of copolymerizing styrene and ethylene, etc. using a polymerization catalyst having (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride as a polymerization catalyst component is proposed. (For example, refer to Patent Document 1).

JP-A-9-183809

However, when a cyclic olefin, an alkenyl aromatic hydrocarbon, and an α-olefin are copolymerized by the above production method, the resulting copolymer is not sufficiently satisfactory in terms of high molecular weight.
Under such circumstances, the problem to be solved by the present invention is a method for producing a cyclic olefin copolymer obtained by copolymerizing a cyclic olefin, an alkenyl aromatic hydrocarbon and an α-olefin, and has a higher molecular weight. Another object of the present invention is to provide a method for producing a high-copolymer.

（上記一般式［Ｉ］〜［III］において、Ｍは元素の周期律表の第４族の遷移金属原子を表し、Ａは元素の周期律表の第１６族の原子を表し、Ｊは元素の周期律表の第１４族の原子を表す。Ｃｐはシクロペンタジエン形アニオン骨格を有する基を表す。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｘ¹、Ｘ²はそれぞれ独立に水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、置換シリル基、２置換アミノ基、アルコキシ基、アラルキルオキシ基またはアリールオキシ基を表し、該アルキル基、該アラルキル基、該アリール基、該置換シリル基の炭化水素基、２置換アミノ基の炭化水素基、該アルコキシ基、該アラルキルオキシ基および該アリールオキシ基は、ハロゲン原子で置換されていてもよく、アルコキシ基で置換されていてもよく、アリールオキシ基で置換されていてもよく、アラルキルオキシ基で置換されていてもよい。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は任意に結合して環を形成してもよい。Ｒ⁵、Ｒ⁶はエチル基を表す。Ｘ³は元素の周期律表の第１６族の原子を表す。一般式［II］および［III］における二つのＭ、Ａ、Ｊ、Ｃｐ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｘ¹、Ｘ³はそれぞれ同じであっても異なっていてもよい。） That is, the present invention includes a monomer unit based on a cyclic olefin, a monomer unit based on an alkenyl aromatic hydrocarbon, and a monomer unit based on an α-olefin. The total content of the monomer unit based on the alkenyl aromatic hydrocarbon and the content of the monomer unit based on the α-olefin is 100 mol%, and the content of the monomer unit based on the cyclic olefin is 10 A method for producing a cyclic olefin copolymer having a monomer unit content based on an alkenyl aromatic hydrocarbon of 1 to 50 mol%, wherein the following component (A) is a polymerization catalyst component: The present invention relates to a method for producing a cyclic olefin copolymer in which a cyclic olefin, an alkenyl aromatic hydrocarbon and an α-olefin are copolymerized in the presence of a polymerization catalyst.
(A): transition metal complex represented by the following general formula [I], [II] or [III]

(In the above general formulas [I] to [III], M represents a transition metal atom of Group 4 of the periodic table of elements, A represents an atom of Group 16 of the periodic table of elements, and J represents an element. And Cp represents a group having a cyclopentadiene type anion skeleton, R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² are each independently a hydrogen atom, Represents a halogen atom, alkyl group, aralkyl group, aryl group, substituted silyl group, disubstituted amino group, alkoxy group, aralkyloxy group or aryloxy group, the alkyl group, the aralkyl group, the aryl group, the substituted silyl group The hydrocarbon group, the hydrocarbon group of the 2-substituted amino group, the alkoxy group, the aralkyloxy group and the aryloxy group may be substituted with a halogen atom, or may be substituted with an alkoxy group. May be substituted with aryloxy group, an optionally substituted aralkyl group ^{.R 1, R 2, R 3} , R 4 MAY form a ring optionally .R ^5, R ⁶ represents an ethyl group, X ³ represents an atom of group 16 of the periodic table of the elements, and two M, A, J, Cp, R ¹ , R ² , in general formulas [II] and [III], R ³ , R ⁴ , X ¹ and X ³ may be the same or different.)

  According to the present invention, there is provided a method for producing a cyclic olefin copolymer obtained by copolymerizing a cyclic olefin, an alkenyl aromatic hydrocarbon and an α-olefin, and a method for producing a copolymer having a higher molecular weight. be able to. Moreover, this invention is excellent in the polymerization activity of a polymerization catalyst. Furthermore, the cyclic olefin copolymer obtained by the present invention is excellent in the balance between heat resistance and strength, and optical properties.

（上記一般式［Ｉ］〜［III］において、Ｍは元素の周期律表の第４族の遷移金属原子を表し、Ａは元素の周期律表の第１６族の原子を表し、Ｊは元素の周期律表の第１４族の原子を表す。Ｃｐはシクロペンタジエン形アニオン骨格を有する基を表す。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｘ¹、Ｘ²はそれぞれ独立に水素原子、ハロゲン原子、アルキル基、アラルキル基、アリール基、置換シリル基、２置換アミノ基、アルコキシ基、アラルキルオキシ基またはアリールオキシ基を表し、該アルキル基、該アラルキル基、該アリール基、該置換シリル基の炭化水素基、２置換アミノ基の炭化水素基、該アルコキシ基、該アラルキルオキシ基および該アリールオキシ基は、ハロゲン原子で置換されていてもよく、アルコキシ基で置換されていてもよく、アリールオキシ基で置換されていてもよく、アラルキルオキシ基で置換されていてもよい。Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴は任意に結合して環を形成してもよい。Ｒ⁵、Ｒ⁶はエチル基を表す。Ｘ³は元素の周期律表の第１６族の原子を表す。一般式［II］および［III］における二つのＭ、Ａ、Ｊ、Ｃｐ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｘ¹、Ｘ³はそれぞれ同じであっても異なっていてもよい。） The polymerization catalyst used in the present invention comprises the following component (A) as a polymerization catalyst component.
(A): transition metal complex represented by the following general formula [I], [II] or [III]

(In the above general formulas [I] to [III], M represents a transition metal atom of Group 4 of the periodic table of elements, A represents an atom of Group 16 of the periodic table of elements, and J represents an element. And Cp represents a group having a cyclopentadiene type anion skeleton, R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² are each independently a hydrogen atom, Represents a halogen atom, alkyl group, aralkyl group, aryl group, substituted silyl group, disubstituted amino group, alkoxy group, aralkyloxy group or aryloxy group, the alkyl group, the aralkyl group, the aryl group, the substituted silyl group The hydrocarbon group, the hydrocarbon group of the 2-substituted amino group, the alkoxy group, the aralkyloxy group and the aryloxy group may be substituted with a halogen atom, or may be substituted with an alkoxy group. May be substituted with aryloxy group, an optionally substituted aralkyl group ^{.R 1, R 2, R 3} , R 4 MAY form a ring optionally .R ^5, R ⁶ represents an ethyl group, X ³ represents an atom of group 16 of the periodic table of the elements, and two M, A, J, Cp, R ¹ , R ² , in general formulas [II] and [III], R ³ , R ⁴ , X ¹ and X ³ may be the same or different.)

  In the general formula [I], [II] or [III], M represents a transition metal atom of Group 4 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revision 1989), for example, a titanium atom, a zirconium atom, And hafnium atoms. A titanium atom or a zirconium atom is preferred.

  In the general formula [I], [II] or [III], A represents a group 16 atom in the periodic table of the elements, and examples thereof include an oxygen atom, a sulfur atom, and a selenium atom, preferably an oxygen atom. is there.

  In the general formula [I], [II] or [III], J represents an atom belonging to Group 14 of the periodic table of elements, such as a carbon atom, silicon atom, germanium atom, etc. It is a silicon atom.

In general formula [I], [II] or [III], Cp represents a group having a cyclopentadiene-type anion skeleton, such as η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, and η ^5- (substituted) fluorenyl group. In more specific examples, for example, eta ⁵ - cycloalkyl Bae Ntajieniru group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, 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 group, eta ⁵ - neopentyl cycloalkyl Bae Ntajieniru group, eta ^{5-n-hexylcyclopentadienyl} Bae Ntajieniru group, eta ^5-n-octyl cyclopentane 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 - methyl Indenyl group, η ⁵ -dimethylindenyl group, η ⁵ -ethylindenyl group, η ⁵ -n-propylindenyl group, η ⁵ -isopropylindenyl group, η ⁵ -n-butylindenyl group, η ⁵ -sec- butyl indenyl group, eta ^5-tert-butyl indenyl group, eta ^5-n-pentyl indenyl group, eta ⁵ - neopentyl indenyl group, eta ^5-n-hexyl indenyl group, eta ⁵ - n- octyl indenyl group, eta ^{5-n-Deshiruindeniru} group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - Na Fuchiruindeniru 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, eta ^5-tert. - butylfluorenyl group, eta ⁵ - di -n- butyl fluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -tert- butyl-fluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorenyl group, eta ^{5-n-hexyl-fluorenyl} group, eta ^{5-n-octyl-fluorenyl} group, eta ^{5-n-Deshirufuruore} Nyl group, η ⁵ -n-dodecylfluorenyl group, η ⁵ -phenylfluorenyl group, η ⁵ -diphenylfluorenyl group, η ⁵ -methylphenylfluorenyl group, η ⁵ -naphthylfluorenyl 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 - methylcyclopentadienyl group, eta ^{5-tert-butylcyclopentadienyl} group, eta ⁵ - dimethyl cyclopentadienyl group, eta ⁵ Trimethyl cyclopentadienyl group, eta ⁵ - indenyl group, eta ⁵ - fluorenyl group, particularly preferably eta ⁵ - cyclopentadienyl group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - indenyl group, eta ⁵ -Fluorenyl group.

In the general formula [I], [II] or [III], R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group or an aryl group. Represents a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a disubstituted amino group.

Examples of the halogen atom in R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, and more Preferably it is a chlorine atom.

The alkyl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² is preferably an alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, 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 a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or a tert-pentyl group is more preferable.

The alkyl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² may be substituted with a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, 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 group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, tetrafluoroethyl group, pentafluoroethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group Perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl Group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group, perbromobutyl group, perbromopentyl group, perbromohexyl group, perbromooctyl group, perbromododecyl group, perbromododecyl group Examples thereof include a bromopentadecyl group and a perbromoeicosyl group.
In addition, the alkyl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² is an alkoxy group such as a methoxy group or an ethoxy group; an aryloxy group such as a phenoxy group; an aralkyloxy group such as a benzyloxy group It may be substituted with.

The aralkyl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² is preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, (2-methylphenyl) methyl group, (3 -Methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, ( 2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (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 group, (2,3,5,6-tetramethylphenyl) methyl group, (Pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl Group, (n-dodecylphenyl) methyl group, (n-tetradecylphenyl) methyl group, naphthylmethyl group, anthracenylmethyl And the like, more preferably a benzyl group.
The aralkyl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² is a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom; an alkoxy group such as methoxy group or ethoxy group; a phenoxy group An aryloxy group such as benzyloxy group and the like, and an aralkyloxy group such as a benzyloxy group.

The aryl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, 2-tolyl group, 3-tolyl group, 4 -Tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3 4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,6 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, -Butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl Group, n-tetradecylphenyl group, naphthyl group, anthracenyl group and the like, and a phenyl group is more preferable.
The aryl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² is a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom; an alkoxy group such as methoxy group or ethoxy group; a phenoxy group An aryloxy group such as benzyloxy group and the like, and an aralkyloxy group such as a benzyloxy group.

The substituted silyl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² is a silyl group substituted with a hydrocarbon group, and examples of the hydrocarbon group include a methyl group and an ethyl group Alkyl groups having 1 to 10 carbon atoms such as n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group An aryl group such as a phenyl group; As the substituted silyl group, a substituted silyl group having 1 to 20 carbon atoms is preferable. For example, a monosubstituted silyl group having 1 to 20 carbon atoms such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group, a dimethylsilyl group, and a diethylsilyl group. , Disubstituted silyl groups having 2 to 20 carbon atoms such as diphenylsilyl group, 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, tricyclohexylsilyl group, triphenylsilyl group, etc. And trisubstituted silyl groups having 3 to 20 carbon atoms. Properly is trimethylsilyl group, tert- butyldimethylsilyl group or triphenylsilyl group.
The substituted silyl group in R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² is such that the hydrocarbon group is a halogen atom such as a fluorine atom, chlorine atom, bromine atom, iodine atom; methoxy group, ethoxy group, etc. An aryloxy group such as an alkoxy group or a phenoxy group; and an aralkyloxy group such as a benzyloxy group.

The disubstituted amino group in R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² is an amino group substituted with two hydrocarbon groups, and the hydrocarbon group is, for example, methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. An alkyl group having 10 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group; and an aralkyl group having 7 to 10 carbon atoms. The disubstituted amino group is preferably a disubstituted amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms. For example, 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 , A di-n-decylamino group, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert-butyldimethylsilylamino group, and the like, preferably a dimethylamino group or a diethylamino group.
These disubstituted amino groups have a hydrocarbon group such as 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; a benzyloxy group May be partially substituted with an aralkyloxy group such as

As the alkoxy group in R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ^2, an alkoxy group having 1 to 20 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group N-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, n-eicosoxy group, etc. More preferred is a methoxy group, an ethoxy group, or a tert-butoxy group.
The alkoxy group in R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² is a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom; an alkoxy group such as methoxy group or ethoxy group; a phenoxy group An aryloxy group such as benzyloxy group and the like, and an aralkyloxy group such as a benzyloxy group.

The aralkyloxy group in R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² is preferably an aralkyloxy group having 7 to 20 carbon atoms, such as a benzyloxy group or a (2-methylphenyl) methoxy group. , (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy Group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2 , 3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group, (2,4,5-trimethylphenyl) methoxy Group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) methoxy group, (2,3,4,5-tetramethylphenyl) methoxy group, (2,3,4) , 6-tetramethylphenyl) methoxy group, (2,3,5,6-tetramethylphenyl) methoxy group, (pentamethylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (Isopropylphenyl) methoxy group, (n-butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-octylphenyl) methoxy Group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy group, naphthylmethoxy group And anthracenylmethoxy group, more preferably a benzyloxy group.
Aralkyloxy groups in R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group and ethoxy group; phenoxy An aryloxy group such as a group; and an aralkyloxy group such as a benzyloxy group.

The aryloxy group in R ¹ , R ² , R ³ , R ⁴ , X ¹ , X ² is preferably an aryloxy group having 6 to 20 carbon atoms, such as a phenoxy group, 2-methylphenoxy group, 3-methyl Phenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3 , 5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4 , 6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetra Lamethylphenoxy 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.
These aryloxy 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; an aralkyloxy group such as a benzyloxy group; May be substituted.

R ¹ , R ² , R ³ and R ⁴ are preferably an alkyl group, an aralkyl group, an aryl group or a substituted silyl group.

X ¹ and X ² are preferably each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, and more preferably a halogen atom or an alkoxy group.

R ¹ , R ² , R ³ , and R ⁴ may be optionally combined to form a ring.

In general formula [I], [II] or [III], R ⁵ and R ⁶ each represent an ethyl group.

In the general formula [II] or [III], X ³ represents an atom of Group 16 of the periodic table of elements, and examples thereof include an oxygen atom, a sulfur atom, and a selenium atom, and preferably an oxygen atom.

  Examples of the transition metal complex represented by the general formula [I] include the compounds exemplified below.

  Diethylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylmethylene (cyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylmethylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, die Lumethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride .

  Diethylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylmethylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylmethylene (methylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phen Xyl) titanium dichloride, diethylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylmethylene (methylcyclopentadienyl) (3-tert-butyl-5- (Chloro-2-phenoxy) titanium dichloride.

  Diethylmethylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diethylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, diethylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (tert-butylcyclo Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylmethylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride.

  Diethylmethylene (dimethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylmethylene (dimethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylmethylene (dimethyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (dimethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylmethylene (dimethylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (dimethylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, diethylmethylene (dimethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylmethylene (dimethylcyclopentadienyl) (3-tert-butyl) -5-chloro-2-phenoxy) titanium dichloride.

  Diethylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylmethylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylmethylene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (trimethylsilylcyclo) Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylmethylene (trimethylsilylcyclo) Pentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride.

  Diethylmethylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylmethylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylmethylene (indenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylmethylene (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diethylmethylene (indenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (indenyl) (3-tert-butyl-5-methoxy 2-phenoxy) titanium dichloride, diethylmethylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride.

  Diethylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylmethylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylmethylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diethylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylmethylene (fluorenyl) (3-tert-butyl) 5-methoxy-2-phenoxy) titanium dichloride, diethylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride.

  Diethylsilylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, die Lucylylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride .

  Diethylsilylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (methylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phen Xyl) titanium dichloride, diethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5- (Chloro-2-phenoxy) titanium dichloride.

  Diethylsilylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, Diethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, diethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (tert-butylcyclo) Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride.

  Diethylsilylene (dimethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (dimethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (dimethyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (dimethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (dimethylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (dimethylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, diethylsilylene (dimethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (dimethylcyclopentadienyl) (3-tert-butyl) -5-chloro-2-phenoxy) titanium dichloride.

  Diethylsilylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (trimethylsilylcyclo) Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diethylsilylene (trimethylsilylcyclo) Pentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride.

  Diethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (indenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diethylsilylene (indenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (indenyl) (3-tert-butyl-5-methoxy) 2-phenoxy) titanium dichloride, diethyl silylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride.

  Diethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diethylsilylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diethylsilylene (fluorenyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diethylsilylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diethylsilylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diethylsilylene (fluorenyl) (3-tert-butyl) 5-methoxy-2-phenoxy) titanium dichloride, diethyl silylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride.

  In addition, in the above compounds, compounds in which titanium is zirconium or hafnium can be given.

  In addition, in the above compounds, compounds in which dichloride is dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide can be exemplified.

  Moreover, the compound which changed (cyclopentadienyl) into (n-butylcyclopentadienyl) and (tert-butyldimethylsilylcyclopentadienyl) in the said compound can be mention | raise | lifted.

  In the above compound, (3,5-dimethyl-2-phenoxy) is replaced with (2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), Examples thereof include (3-phenyl-5-methyl-2-phenoxy), (3-tert-butyldimethylsilyl-2-phenoxy), and (3-trimethylsilyl-2-phenoxy).

  The transition metal complex represented by the general formula [I] is produced by a known method, for example, a method described in the published specification of WO 97/03992.

  In addition, the transition metal complex represented by the general formula [II] is obtained by reacting the transition metal complex represented by the general formula [I] with 0.5 times molar amount of water with respect to the transition metal complex. The produced transition metal complex represented by the general formula [III] is produced by reacting the transition metal complex represented by the general formula [I] with a 1-fold molar amount of water with respect to the transition metal complex. Is done. In the reaction between the transition metal complex and water, a method of directly reacting the transition metal complex with a required amount of water, a method of introducing the transition metal complex into a solvent such as a hydrocarbon containing the required amount of water, For example, a method in which the transition metal complex is added to a dried solvent such as hydrocarbon and an inert gas containing a necessary amount of water is circulated can be employed.

  Examples of the polymerization catalyst used in the present invention include a contact-treated product obtained by contacting the component (A) with the following component (B) and / or component (C).

(B): One or more aluminum compounds selected from the group consisting of the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {- Cyclic aluminoxane represented by Al (E ² ) —O—} _b (B3) General formula E ³ {—Al (E ³ ) —O—} _c Linear aluminoxane represented by AlE ³ ₂ (wherein , A represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, E ¹ , E ² and E ³ represent a hydrocarbon group, and the hydrocarbon group May be substituted with a halogen atom, and the plurality of E ¹ , the plurality of E ^2, and the plurality of E ³ may be the same or different, Z represents a hydrogen atom or a halogen atom, Z may be the same or different.)

(C): one or more boron compounds selected from the group consisting of the following (C1) to (C3) (C1) boron compounds represented by the general formula BQ ¹ Q ² Q ³ (C2) the general formula G ⁺ (BQ Boron compound represented by ¹ Q ² Q ³ Q ⁴ ) ^- (C3) Boron compound represented by general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (wherein B is 3 Represents a boron atom in a valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ each independently represents a halogen atom, a hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, groups are optionally .G ⁺ is substituted with a halogen atom represents an inorganic or organic cation, L represents a neutral Lewis base, represents the (L-H) ⁺ is a Bronsted acid.)

In the general formula of the organoaluminum compound (B1), E ¹ represents a hydrocarbon group, preferably a hydrocarbon group having 1 to 8 carbon atoms, and more preferably an alkyl group.

Specific examples of the organoaluminum compound (B1) include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutyl. Dialkylaluminum chlorides such as aluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride; dimethylaluminum hydride and diethylaluminium Hydride, dipropyl aluminum hydride, diisobutylaluminum hydride, there can be mentioned dialkyl aluminum hydride such as dihexyl aluminum hydride.
Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.

In the general formulas of the aluminoxane of (B2) and (B3), E ² and E ³ represent a hydrocarbon group, preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably a methyl group or an ethyl group. , Alkyl groups such as normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group and neopentyl group, more preferably methyl group and isobutyl group.

  In the general formula of the aluminoxane of (B2) and (B3), b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, b is 2 to 40 and c is 1 to 40.

  As a method for producing the aluminoxane of (B2) and (B3), a known method is used. For example, a solution obtained by dissolving a trialkylaluminum (for example, trimethylaluminum) in an appropriate organic solvent (benzene, aliphatic hydrocarbon, etc.) is brought into contact with water. Moreover, the method of making a trialkylaluminum (for example, trimethylaluminum etc.) contact the metal salt (for example, copper sulfate hydrate etc.) containing crystal water can be illustrated.

In the general formula of the boron compound of (C1) to (C3), Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a halogen atom, a hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group. The hydrocarbon group may be substituted with a halogen atom. Q ¹ , Q ² , Q ³ and Q ⁴ are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Or an amino group having 2 to 20 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom, more preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, The hydrocarbon group may be substituted with a halogen atom, more preferably a halogenated hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably a fluorinated hydrocarbon group having 1 to 20 carbon atoms. And most preferably a fluorinated aryl group having 6 to 20 carbon atoms.

In the general formula of the boron compound of (C2), G ⁺ represents an inorganic or organic cation, and specific examples include inorganic cations such as ferrocenium cation, alkyl-substituted ferrocenium cation, and silver cation; Organic cations such as methyl cation are listed. A carbenium cation is preferable, and a triphenylmethyl cation is more preferable.

In the general formulas of the boron compounds of (C2) and (C3), (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl). ) Borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris ( Pentafluorophenyl) borate, tetrakis (3,5-bistrifluoromethylphenyl) borate and the like.

In the general formula of the boron compound of (C3), L is a neutral Lewis base, (L—H) ⁺ is a Bronsted acid, and specific examples of (L—H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium and the like can be mentioned.

  Specific examples of the boron compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-tetrafluorophenyl). Examples include borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and preferably tris (pentafluoro). Phenyl) borane.

  Specific examples of the boron compound (C2) include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, tri Examples thereof include phenylmethyltetrakis (pentafluorophenyl) borate and triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and triphenylmethyltetrakis (pentafluorophenyl) borate is preferable.

  Specific examples of the boron compound (C3) include 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-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate , Diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri ( Dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like, preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate It is.

  When a contact-treated product obtained by contacting the component (A) and the component (B) is used as the polymerization catalyst, the component (B) includes the cyclic aluminoxane of (B2) and / or the linear of (B3). It is preferable to use aluminoxane. Moreover, when using the contact treatment thing which contacts a component (A), a component (B), and a component (C) as a polymerization catalyst, the organoaluminum compound of (B1) is used as a component (B). Cheap.

  The method for contacting each polymerization catalyst component may be any method in which each polymerization catalyst component is in contact, and may be contacted in the presence of a hydrocarbon solvent or in gas. When three or more polymerization catalyst components are used, any two polymerization catalyst components may be brought into contact with each other in advance and then another catalyst component may be brought into contact with each other. Alternatively, they may be charged separately in order, or any two or more catalyst components that have been contacted in advance may be charged into the polymerization reactor and contacted in the polymerization reactor.

  As the contact treatment amount of each polymerization catalyst component, the Al atom / component (A) (molar ratio) of the component (B) is usually 0.1 to 10,000, preferably 5 to 2,000. Moreover, component (C) / component (A) (molar ratio) is 0.01-100, Preferably it is 0.5-10.

  The concentration in the case of using each polymerization catalyst component in a solution state or in a suspended state in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each polymerization catalyst component to the polymerization reaction apparatus. The concentration of A) is usually 0.01 to 500 μmol / g, preferably 0.05 to 100 μmol / g, more preferably 0.05 to 50 μmol / g. Moreover, the density | concentration of a component (B) is 0.01-10000 micromol / g normally in conversion of Al atom, Preferably it is 0.1-5000 micromol / g, More preferably, it is 0.1-2000 micromol / g. . The density | concentration of a component (C) is 0.01-500 micromol / g normally, Preferably it is 0.05-200 micromol / g, More preferably, it is 0.05-100 micromol / g.

As the polymerization catalyst used in the present invention, a particulate carrier including an inorganic carrier such as SiO ₂ and Al ₂ O _{3 and} an organic polymer carrier such as polyethylene and polystyrene may be used in combination.

  The cyclic olefin used in the present invention is a compound having a ring formed of 4 or more carbon atoms and having one carbon-carbon double bond in at least one of the rings.

  Examples of cyclic olefins include unsubstituted monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene; substituted monocyclic olefins such as 3-methylcyclopentene, 4-methylcyclopentene, and 3-methylcyclohexene; norbornene, 1,2-dihydrodi Examples include unsubstituted polycyclic olefins such as cyclopentadiene and tetracyclododecene; substituted polycyclic olefins such as 5-methylnorbornene.

（上記一般式において、ｍは０以上の整数を表す。Ｒ⁷〜Ｒ¹⁸は、それぞれ独立に、水素原子、水酸基、アミノ基、ホスフィノ基、アルキル基、アリール基、アラルキル基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アラルキルオキシカルボニル基、アシルオキシ基、アルコキシスルホニル基、アリールオキシスルホニル基、アラルキルオキシスルホニル基、置換シリル基、ジアルキルアミノ基、カルボキシル基、シアノ基を表し、該アルキル基、該アリール基および該アラルキル基は、水酸基、アミノ基、アシル基、カルボキシル基、アルコキシ基、アルコキシカルボニル基、アシルオキシ基、置換シリル基、アルキルアミノ基もしくはシアノ基で置換されていてもよい。Ｒ⁷〜Ｒ¹⁸は、任意に結合して環を形成してもよい。） The cyclic olefin is preferably a compound represented by the following general formula [IV].

(In the above general formula, m represents an integer of 0 or more. R ^{7 to} R ¹⁸ are each independently a hydrogen atom, a hydroxyl group, an amino group, a phosphino group, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryl group. Oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, acyloxy group, alkoxysulfonyl group, aryloxysulfonyl group, aralkyloxysulfonyl group, substituted silyl group, dialkylamino group, carboxyl group, cyano group The alkyl group, the aryl group and the aralkyl group are substituted with a hydroxyl group, an amino group, an acyl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a substituted silyl group, an alkylamino group or a cyano group. which may be .R ⁷ R ¹⁸ may be bonded to form a ring optionally.)

  m is an integer of 0 or more, preferably an integer of 0 ≦ m ≦ 3.

R ^{7 to} R ¹⁸ in the general formula [IV] are each independently a hydrogen atom, a hydroxyl group, an amino group, a phosphino group, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, or an alkoxycarbonyl group. Represents an aryloxycarbonyl group, an aralkyloxycarbonyl group, an acyloxy group, an alkoxysulfonyl group, an aryloxysulfonyl group, an aralkyloxysulfonyl group, a substituted silyl group, a dialkylamino group, a carboxyl group, a cyano group, the alkyl group, the aryl The group and the aralkyl group may be substituted with a hydroxyl group, amino group, acyl group, carboxyl group, alkoxy group, alkoxycarbonyl group, acyloxy group, substituted silyl group, alkylamino group or cyano group.

R ^{7 to} R ¹⁸ are preferably a hydrogen atom or a group having 20 or less carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the aryloxy group include a phenoxy group, examples of the acyl group include an acetyl group, examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group, and examples of the acyloxy group include an acetyloxy group. Examples of the alkoxysulfonyl group include a methoxysulfonyl group, an ethoxysulfur group, and the like. Mentioned alkenyl group. Examples of the substituted silyl group, a trimethylsilyl group and the like, as the dialkylamino group, dimethylamino group, diethylamino group and the like.

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

  Examples of the cyclic olefin represented by the general formula [IV] include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, tetracyclododecene, tricyclodecene, Tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetylnorbornene, 5-acetyloxynorbornene, 5-methoxycarbonylnorbornene, 5-ethoxy Carbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetrasic Or the like can be mentioned dodecene. One or more of these cyclic olefins are used. The cyclic olefin is preferably norbornene or tetracyclododecene, more preferably tetracyclododecene.

（上記一般式において、Ｒ¹⁹は水素原子または炭素原子数１〜２０のアルキル基を表し、Ａｒは炭素原子数６〜２５の芳香族炭化水素基を表す。） Examples of the alkenyl aromatic hydrocarbon used in the present invention include compounds represented by the following general formula [V].

(In the above general formula, R ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 25 carbon atoms.)

In the general formula [V], R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group and the like. R ¹⁹ is preferably a hydrogen atom or a methyl group.

  In the general formula [V], Ar is an aromatic hydrocarbon group having 6 to 25 carbon atoms, and Ar includes a phenyl group, a tolyl group, a xylyl group, a tertiary butylphenyl group, a vinylphenyl group, and a naphthyl group. Phenanthryl group, anthracenyl group, benzyl group and the like. Preferred are phenyl group, tolyl group, xylyl group, tertiary butylphenyl group, vinylphenyl group, and naphthyl group.

  Examples of the alkenyl aromatic hydrocarbon include alkenylbenzene such as styrene, 2-phenylpropylene, 2-phenylbutene, and 3-phenylpropylene; p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m -Ethyl styrene, o-ethyl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,4-dimethyl styrene, 3,5-dimethyl styrene, 3-methyl-5-ethyl styrene, p-third Examples thereof include alkyl styrene such as primary butyl styrene and p-secondary butyl styrene; alkenyl naphthalene such as 1-vinylnaphthalene. Preferred are styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tertiary butylstyrene, 2-phenylpropylene and 1-vinylnaphthalene, and more preferred is styrene.

Examples of the α-olefin used in the present invention include compounds represented by the following general formula [VI].
^{_{CH 2 = CH-R 20 [}} VI]
(In the above general formula, R ²⁰ represents a hydrogen atom or a saturated hydrocarbon group.)

  As the α-olefin, linear olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene; 3-methyl-1 Examples include branched olefins such as -butene, 3-methyl-1-pentene, 4-methyl-1-pentene, and 5-methyl-1-hexene, and these are used in one or more kinds.

  The α-olefin is preferably an α-olefin having 2 to 20 carbon atoms, more preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, more preferably ethylene and propylene, and particularly preferably ethylene.

  In the copolymerization of the cyclic olefin, the alkenyl aromatic hydrocarbon and the α-olefin, other vinyl compounds may be copolymerized in addition to the cyclic olefin, the alkenyl aromatic hydrocarbon and the α-olefin. Specific examples of such vinyl compounds include methyl vinyl ether, ethyl vinyl ether, acrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, vinyl acetate and the like.

  In the present invention, a cyclic olefin, an alkenyl aromatic hydrocarbon, and an α-olefin are copolymerized in the presence of a polymerization catalyst having the above-described component (A) as a polymerization catalyst component. There is no restriction | limiting in particular as a polymerization method, For example, arbitrary methods, such as a gas phase polymerization method, a block polymerization method, a solution polymerization method, a slurry polymerization method, can be used. When a solvent is used, a solvent that does not deactivate the catalyst can be used. Examples of such a solvent include hydrocarbons such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; halogens such as dichloromethane and styrene dichloride. Hydrocarbons can be mentioned. The polymerization method may be a batch method or a continuous method.

  There is no restriction | limiting in particular about superposition | polymerization temperature, Generally -100-250 degreeC, Preferably -50-200 degreeC is employ | adopted. The pressure is not limited, but is generally 10 MPa or less, preferably 0.2 MPa to 5 MPa. A chain transfer agent such as hydrogen can also be added to adjust the molecular weight of the copolymer.

In the cyclic olefin copolymer obtained by the present invention, the content of the monomer unit based on the cyclic olefin is the same as the content of the monomer unit based on the cyclic olefin in the cyclic olefin copolymer and the alkenyl aromatic carbonization. From the viewpoint of increasing the balance between the heat resistance and strength of the copolymer and the solvent resistance, the total of the content of monomer units based on hydrogen and the content of monomer units based on α-olefin is 100 mol%, It is 10-50 mol%, Preferably it is 15-35 mol%, More preferably, it is 25-35 mol%. The content of the monomer unit based on the cyclic olefin is determined by a proton nuclear magnetic resonance ( ¹ H-NMR) spectrum or a carbon nuclear magnetic resonance ( ¹³ C-NMR) spectrum.

In the cyclic olefin copolymer, the content of the monomer unit based on the alkenyl aromatic hydrocarbon depends on the content of the monomer unit based on the cyclic olefin in the cyclic olefin copolymer and the alkenyl aromatic hydrocarbon. From the viewpoint of improving the optical properties of the copolymer, the total content of the monomer units based on the α-olefin and the content of the monomer units based on the α-olefin is 100 mol%, preferably 5 to 5 mol%. It is -40 mol%, More preferably, it is 5-30 mol%, More preferably, it is 10-25 mol%, Most preferably, it is 15-25 mol%. The content of the monomer unit based on the alkenyl aromatic hydrocarbon is determined by a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

  The cyclic olefin copolymer is preferably an amorphous copolymer having no crystallinity from the viewpoint of enhancing transparency. The absence of crystallinity can be confirmed by the substantial absence of a peak derived from the melting point in the melting curve measured with a differential scanning calorimeter (DSC).

  The glass transition point (Tg) of the cyclic olefin copolymer is usually -20 to 300 ° C. Preferably, it is a copolymer having a Tg of 30 to 200 ° C, more preferably a copolymer having a Tg of 30 to 170 ° C, more preferably a copolymer having a Tg of 50 to 150 ° C, particularly preferably. Tg is 100 to 150 ° C. Tg here is measured with a differential scanning calorimeter (DSC).

  The intrinsic viscosity ([η]) of the cyclic olefin copolymer is usually 0.6 to 3 dl / g. From the viewpoint of increasing the strength of the copolymer, it is preferably 0.7 dl / g or more.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In addition, the property of the copolymer in an Example was measured with the following method.

(1) Intrinsic viscosity ([η], unit: dl / g)
An Ubbelohde viscometer was used and measured at 135 ° C. using tetralin as a solvent.

(2) Glass transition point (Tg, unit: ° C)
Using a differential scanning calorimeter (SSC-5200, manufactured by Seiko Denshi Kogyo Co., Ltd.), an endothermic curve was measured under the following conditions and obtained from the inflection point.
Temperature rise 20 ° C. to 200 ° C. (10 ° C./min) Hold for 10 minutes Cooling 200 ° C. to 30 ° C. (10 ° C./min) Hold for 10 minutes Measurement 30 ° C. to 200 ° C. (10 ° C./min)

(3) Monomer unit content in copolymer [ ¹ H-NMR]
Equipment AC250 manufactured by BRUKER
Measurement solvent Tetrachloroethane-d2
Measurement temperature 135 ℃
[ ¹³ C-NMR]
Equipment AC250 manufactured by BRUKER
Measurement solvent Orthodichlorobenzene and orthodichlorobenzene-d4 80:20 (volume ratio) liquid mixture Measurement temperature 135 ° C

(4) Tensile strength at break of film (unit: MPa)
A strip-shaped test piece having a width of 20 mm, a length of 100 mm, and a thickness of about 0.1 mm was prepared from a sheet obtained by press-molding the copolymer at 230 ° C. The strip-shaped specimen was pulled and measured by a tensile tester (UNIVERSAL TESTING MACHINE manufactured by Orientec Co., Ltd.) under conditions of a distance between chucks of 40 mm and a tensile test speed of 5 mm / min.

[Example 1]
In a 400 ml autoclave purged with argon, 24.1 ml styrene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (hereinafter referred to as tetracyclododecene) in toluene (5 mol / l) (66 ml) and dehydrated toluene (47.7 ml) were added. After raising the temperature to 50 ° C., 0.4 MPa of ethylene was charged. Toluene solution of triisobutylaluminum [manufactured by Tosoh Finechem Co., Ltd., 1 mol / l] 2 ml, diethylsilylene (3-methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 4 .5 mg dissolved in dehydrated toluene 2.2 ml, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 16 mg mixed in dehydrated toluene 4 ml were sequentially charged, and the reaction solution was stirred at 50 ° C. for 2 hours. . Thereafter, the reaction solution was stirred and mixed with 150 ml of hydrochloric acid (2%), separated, and then poured into 500 ml of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 6.57 g of a copolymer was obtained. [Η] of this copolymer is 0.78 dl / g, glass transition point is 124 ° C., content of tetracyclododecene unit is 35 mol%, content of styrene unit is 23 mol%, content of ethylene unit The amount was 42 mol%. The tensile strength at break of the film was 58 MPa. The polymerization activity per 1 mol of the transition metal complex and the unit time was 330 kg / (mol · hour).

[Example 2]
In a 400 ml autoclave substituted with argon, 24.1 ml of styrene, 63.6 ml of a toluene solution of tetracyclododecene (5 mol / l) and 50.1 ml of dehydrated toluene were charged. After raising the temperature to 50 ° C., 0.4 MPa of ethylene was charged. Toluene solution of triisobutylaluminum [manufactured by Tosoh Finechem Co., Ltd., 1 mol / l] 2 ml, diethylsilylene (3-methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 4 .5 mg dissolved in dehydrated toluene 2.2 ml, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate 16 mg mixed in dehydrated toluene 4 ml were sequentially charged, and the reaction solution was stirred at 50 ° C. for 2 hours. . Thereafter, the reaction solution was stirred and mixed with 150 ml of hydrochloric acid (2%), separated, and then poured into 500 ml of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 6.12 g of a copolymer was obtained. [Η] of this copolymer is 0.74 dl / g, glass transition point is 124 ° C., tetracyclododecene unit content is 34 mol%, styrene unit content is 23 mol%, ethylene unit content The amount was 43 mol%. The tensile strength at break of the film was 47 MPa. Further, 1 mol of the transition metal complex and the polymerization activity per unit time were 310 kg / (mol · hour).

[Example 3]
In a 400 ml autoclave substituted with argon, 15.5 ml of styrene, 33 ml of a toluene solution of tetracyclododecene (5 mol / l) and 89.9 ml of dehydrated toluene were charged. After raising the temperature to 50 ° C., 0.6 MPa of ethylene was charged. 2 ml of a toluene solution of triisobutylaluminum [manufactured by Tosoh Finechem Co., Ltd., 1 mol / l], 6.5 mg of diethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride A solution dissolved in 1.6 ml of dehydrated toluene and a mixture of 24 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in 4 ml of dehydrated toluene were sequentially added, and the reaction solution was stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution was stirred and mixed with 150 ml of hydrochloric acid (2%), separated, and then poured into 500 ml of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 7.44 g of a copolymer was obtained. [Η] of this copolymer is 0.76 dl / g, glass transition point is 122 ° C., tetracyclododecene unit content is 31 mol%, styrene unit content is 19 mol%, ethylene unit content The amount was 50 mol%. The tensile strength at break of the film was 43 MPa. The polymerization activity per 1 mol of the transition metal complex and the unit time was 250 kg / (mol · hour).

[Example 4]
In a 400 ml autoclave substituted with argon, 13.4 ml of styrene, 33 ml of a toluene solution of tetracyclododecene (5 mol / l) and 91.4 ml of dehydrated toluene were charged. After raising the temperature to 50 ° C., 0.6 MPa of ethylene was charged. 2 ml of a toluene solution of triisobutylaluminum [manufactured by Tosoh Finechem Co., Ltd., 1 mol / l], 4.3 mg of diethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride A solution dissolved in 2.2 ml of dehydrated toluene and 16 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate mixed with 4 ml of dehydrated toluene were sequentially charged, and the reaction solution was stirred at 50 ° C. for 2 hours. Thereafter, the reaction solution was stirred and mixed with 150 ml of hydrochloric acid (2%), separated, and then poured into 500 ml of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and then dried under reduced pressure. As a result, 4.93 g of a copolymer was obtained. [Η] of this copolymer is 0.77 dl / g, glass transition point is 124 ° C., tetracyclododecene unit content is 30 mol%, styrene unit content is 17 mol%, ethylene unit content The amount was 53 mol%. The tensile strength at break of the film was 46 MPa. The polymerization activity per 1 mol of the transition metal complex and the unit time was 250 kg / (mol · hour).

[Comparative Example 1]
The amount of dehydrated toluene was changed to 48.4 ml, and “diethylsilylene (3-methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 4.5 mg was dissolved in dehydrated toluene 2.2 ml. "Dimethylsilylene (3-methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 6.3 mg dissolved in dehydrated toluene 1.6 ml" Was used in the same manner as in Example 1 except that N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was changed to 24 mg, to obtain 5.57 g of a copolymer. [Η] of this copolymer is 0.65 dl / g, glass transition point is 127 ° C., tetracyclododecene unit content is 36 mol%, styrene unit content is 22 mol%, ethylene unit content The amount was 42 mol%. The tensile strength at break of the film was 42 MPa. The polymerization activity per 1 mol of the transition metal complex and the unit time was 190 kg / (mol · hour).

[Comparative Example 2]
The amount of dehydrated toluene was changed to 50.8 ml. “Diethylsilylene (3-methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 4.5 mg was dissolved in dehydrated toluene 2.2 ml. "Dimethylsilylene (3-methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 6.3 mg dissolved in dehydrated toluene 1.6 ml" Was used in the same manner as in Example 2 except that N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was changed to 24 mg, to obtain 6.54 g of a copolymer. [Η] of this copolymer is 0.62 dl / g, glass transition point is 128 ° C., tetracyclododecene unit content is 33 mol%, styrene unit content is 22 mol%, ethylene unit content The amount was 45 mol%. The tensile strength at break of the film was 34 MPa. The polymerization activity per 1 mol of the transition metal complex and the unit time was 220 kg / (mol · hour).

[Comparative Example 3]
The amount of dehydrated toluene was changed to 89.5 ml, and “diethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 6.5 mg dissolved in dehydrated toluene 1.6 ml Instead of “dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride dissolved in 2 ml of dehydrated toluene”, N, N— The same procedure as in Example 3 was conducted except that dimethylanilinium tetrakis (pentafluorophenyl) borate was changed to 32 mg. Thus, 5.72 g of a copolymer was obtained. [Η] of this copolymer is 0.63 dl / g, glass transition point is 124 ° C., tetracyclododecene unit content is 33 mol%, styrene unit content is 18 mol%, ethylene unit content The amount was 49 mol%. The tensile strength at break of the film was 42 MPa. The polymerization activity per 1 mol of the transition metal complex and the unit time was 140 kg / (mol · hour).

[Comparative Example 4]
The amount of dehydrated toluene was changed to 91.6 ml, and “diethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 4.3 mg dissolved in dehydrated toluene 2.2 ml Instead of “dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride dissolved in 2 ml of dehydrated toluene”, N, N— The same procedure as in Example 4 was carried out except that dimethylanilinium tetrakis (pentafluorophenyl) borate was changed to 32 mg, to obtain 5.04 g of a copolymer. [Η] of this copolymer is 0.60 dl / g, glass transition point is 128 ° C., tetracyclododecene unit content is 32 mol%, styrene unit content is 16 mol%, ethylene unit content The amount was 53 mol%. The tensile strength at break of the film was 32 MPa. Further, 1 mol of the transition metal complex and the polymerization activity per unit time were 130 kg / (mol · hour).

Claims (3)

Monomer unit based on cyclic olefin, monomer unit based on alkenyl aromatic hydrocarbon, monomer unit based on α-olefin, content of monomer unit based on cyclic olefin, and alkenyl aromatic The sum of the content of monomer units based on hydrocarbons and the content of monomer units based on α-olefins is 100 mol%, and the content of monomer units based on cyclic olefins is 10 to 50 mol%. And a method for producing a cyclic olefin copolymer having a monomer unit content based on an alkenyl aromatic hydrocarbon of 1 to 50 mol%, wherein a polymerization catalyst having the following component (A) as a polymerization catalyst component is present A method for producing a cyclic olefin copolymer, comprising copolymerizing a cyclic olefin, an alkenyl aromatic hydrocarbon and an α-olefin.
(A): transition metal complex represented by the following general formula [I], [II] or [III]

(In the above general formulas [I] to [III], M represents a transition metal atom of Group 4 of the periodic table of elements, A represents an atom of Group 16 of the periodic table of elements, and J represents an element. And Cp represents a group having a cyclopentadiene type anion skeleton, R ¹ , R ² , R ³ , R ⁴ , X ¹ and X ² are each independently a hydrogen atom, Represents a halogen atom, alkyl group, aralkyl group, aryl group, substituted silyl group, disubstituted amino group, alkoxy group, aralkyloxy group or aryloxy group, the alkyl group, the aralkyl group, the aryl group, the substituted silyl group The hydrocarbon group, the hydrocarbon group of the 2-substituted amino group, the alkoxy group, the aralkyloxy group and the aryloxy group may be substituted with a halogen atom, or may be substituted with an alkoxy group. May be substituted with aryloxy group, an optionally substituted aralkyl group ^{.R 1, R 2, R 3} , R 4 MAY form a ring optionally .R ^5, R ⁶ represents an ethyl group, X ³ represents an atom of group 16 of the periodic table of the elements, and two M, A, J, Cp, R ¹ , R ² , in general formulas [II] and [III], R ³ , R ⁴ , X ¹ and X ³ may be the same or different.) The method for producing a cyclic olefin copolymer according to claim 1, wherein the polymerization catalyst is a contact-treated product obtained by contacting the component (A) with the following component (B) and / or component (C).
(B): One or more aluminum compounds selected from the group consisting of the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {- Cyclic aluminoxane represented by Al (E ² ) —O—} _b (B3) General formula E ³ {—Al (E ³ ) —O—} _c Linear aluminoxane represented by AlE ³ ₂ (wherein , A represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, c represents an integer of 1 or more, E ¹ , E ² and E ³ represent a hydrocarbon group, and the hydrocarbon group May be substituted with a halogen atom, and the plurality of E ¹ , the plurality of E ^2, and the plurality of E ³ may be the same or different, Z represents a hydrogen atom or a halogen atom, Z may be the same or different.)
(C): one or more boron compounds selected from the group consisting of the following (C1) to (C3) (C1) boron compounds represented by the general formula BQ ¹ Q ² Q ³ (C2) the general formula G ⁺ (BQ Boron compound represented by ¹ Q ² Q ³ Q ⁴ ) ^- (C3) Boron compound represented by general formula (L-H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- (wherein B is 3 Represents a boron atom in a valence state, and Q ¹ , Q ² , Q ³ and Q ⁴ each independently represents a halogen atom, a hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, The group may be substituted with a halogen atom, G ⁺ represents an inorganic or organic cation, L represents a neutral Lewis base, and (L—H) ⁺ represents a Bronsted acid.) The method for producing a cyclic olefin copolymer according to claim 1 or 2, wherein the cyclic olefin is a compound represented by the following general formula [IV].

(In the above general formula, m represents an integer of 0 or more. R ^{7 to} R ¹⁸ are each independently a hydrogen atom, a hydroxyl group, an amino group, a phosphino group, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryl group. Oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, acyloxy group, alkoxysulfonyl group, aryloxysulfonyl group, aralkyloxysulfonyl group, substituted silyl group, dialkylamino group, carboxyl group, cyano group The alkyl group, the aryl group and the aralkyl group are substituted with a hydroxyl group, an amino group, an acyl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a substituted silyl group, an alkylamino group or a cyano group. which may be .R ⁷ R ¹⁸ may be bonded to form a ring optionally.)