JP2006057105A - Method for producing copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a copolymer transparent, excellent in flexibility and heat resistance and capable of containing no halogen viewed with suspicion from a viewpoint of environmental pollution. <P>SOLUTION: The method for producing a copolymer obtained by copolymerization of ethylene and/or an α-olefin, a cyclic olefin and an alkenyl aromatic hydrocarbon is provided, wherein the copolymerization composition of the cyclic olefin is 0.01-66 mol %, the copolymerization composition of the alkenyl aromatic hydrocarbon is 3-99 mol %, and copolymerization composition of alkenyl aromatic hydrocarbon is more than a half of the cyclic olefin copolymerization composition, and the ethylene and/or α-olefin, the cyclic olefin and the alkenyl aromatic hydrocarbon are copolymerized in the presence of a catalyst comprising below-mentioned (A) and (B) and/or (C). (A): a specific transition metal complex: (B) an organoaluminum compound: (C) a boron compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a copolymer suitable for a film, sheet or pipe. More specifically, the present invention relates to a method for producing a copolymer suitable as a substitute for polyvinyl chloride (for example, a film, a sheet, or a pipe).

  In general, a copolymer used as a stretch film or a wrap film is required to have elastic recovery, transparency, and mechanical strength as found in polyvinyl chloride. However, polyvinyl chloride is regarded as a problem with respect to environmental pollution, such as the possibility of generating harmful substances during combustion. At present, substitution of polyvinyl chloride by various polymers is being studied, but the reality is that satisfactory ones in terms of viscoelastic properties and transparency have not been obtained.

  In recent years, in the field of polymerization of olefins such as ethylene and propylene, with the advent of catalysts using transition metal compounds such as metallocene and nonmetallocene, polymers with properties different from conventional ones can be produced, or very small amounts can be produced. Progress has been made in that large quantities of polymers can be produced with these catalysts.

  The application of such a catalyst has also been proposed for the copolymerization of alkenyl aromatic hydrocarbons typified by styrene and ethylene. For example, Patent Document 1 discloses a so-called method using a specific transition metal compound and an organoaluminum compound. A pseudo-random copolymer of ethylene and styrene obtained by using a homogeneous Ziegler-Natta catalyst (characterized in that methine carbon atoms bonded with phenyl groups are always separated by two or more methylene groups. Random copolymers). The copolymer is excellent in viscoelastic properties and transparency, and is expected as a substitute for polyvinyl chloride. However, there are problems in that the solvent resistance is low and the heat resistance is not sufficient. there were. Moreover, the copolymer obtained by this manufacturing method may cause the transparency fall by the byproduct of syndiotactic polystyrene.

  Application of such a metallocene catalyst has also been proposed for copolymerization of cyclic olefins represented by norbornene and ethylene. For example, Patent Document 2 discloses isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, Patent Document 3 discloses. A method of copolymerizing norbornene and ethylene using (tertiary butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride as a catalyst component is disclosed. Copolymers obtained by these methods have high solvent resistance and a very high glass transition point and are useful as heat-resistant resins. However, in terms of flexibility, a copolymer of ethylene and styrene is used. Inferior to polymers.

Japanese Patent No. 2623070 JP-A-2-173112 Japanese Patent Laid-Open No. 5-194641

  The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a method for efficiently producing a transparent, flexible, and heat-resistant copolymer that can take a halogen-free configuration, which is regarded as a problem from the viewpoint of environmental pollution. There is.

  ADVANTAGE OF THE INVENTION According to this invention, the transparent copolymer which can take the structure which does not contain the halogen regarded as a problem from a viewpoint of environmental pollution, and was excellent in the softness | flexibility, heat resistance, and solvent resistance is provided. Furthermore, according to the present invention, there is provided a method for producing the copolymer extremely efficiently, and a molded article having excellent transparency, flexibility, heat resistance, and solvent resistance, comprising the copolymer. The utility value is great.

  In order to achieve the above-mentioned object, the inventors of the present invention have intensively studied on the production of a copolymer based on a production method using a transition metal compound typified by metallocene as a catalyst component, thereby completing the present invention. It came to.

（上記一般式［Ｉ］〜［III］においてそれぞれ、Ｍ¹ は元素の周期律表の第４族の遷移金属原子を示し、Ａは元素の周期律表の第１６族の原子を示し、Ｊは元素の周期律表の第１４族の原子を示す。Ｃｐ¹ はシクロペンタジエン形アニオン骨格を有する基を示す。Ｘ¹ 、Ｘ² 、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＲ⁶ 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、アルコキシ基、アラルキルオキシ基、アリールオキシ基または２置換アミノ基を示す。Ｘ³ は元素の周期律表の第１６族の原子を示す。Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＲ⁶ は任意に結合して環を形成してもよい。一般式［II］または［III］における二つのＭ¹ 、Ａ、Ｊ、Ｃｐ¹ 、Ｘ¹ 、Ｘ² 、Ｘ³ 、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＲ⁶ はそれぞれ同じであっても
異なっていてもよい。）
（Ｂ）：下記（Ｂ１）〜（Ｂ３）から選ばれる１種以上のアルミニウム化合物
（Ｂ１）一般式 Ｅ¹ _aＡｌＺ_3-a で示される有機アルミニウム化合物
（Ｂ２）一般式 ｛−Ａｌ（Ｅ² ）−Ｏ−｝_b で示される構造を有する環状のアルミノキサン
（Ｂ３）一般式 Ｅ³ ｛−Ａｌ（Ｅ³ ）−Ｏ−｝_c ＡｌＥ³ ₂で示される構造を有する線状のアルミノキサン
（但し、Ｅ¹ 、Ｅ² およびＥ³ は、それぞれ炭化水素基であり、全てのＥ¹ 、全てのＥ² および全てのＥ³ は同じであっても異なっていても良い。Ｚは水素原子またはハロゲン原子を表し、全てのＺは同じであっても異なっていても良い。ａは０＜ａ≦３を満足する数を、ｂは２以上の整数を、ｃは１以上の整数を表す。）
（Ｃ）：下記（Ｃ１）〜（Ｃ３）のいずれかのホウ素化合物
（Ｃ１）一般式 ＢＱ¹ Ｑ² Ｑ³ で表されるホウ素化合物、
（Ｃ２）一般式 Ｇ⁺ （ＢＱ¹ Ｑ² Ｑ³ Ｑ⁴ ）^- で表されるホウ素化合物、
（Ｃ３）一般式 （Ｌ−Ｈ）⁺ （ＢＱ¹ Ｑ² Ｑ³ Ｑ⁴ ）^- で表されるホウ素化合物
（但し、Ｂは３価の原子価状態のホウ素原子であり、Ｑ¹ 〜Ｑ⁴ はハロゲン原子、炭化水素基、ハロゲン化炭化水素基、置換シリル基、アルコキシ基または２置換アミノ基であり、それらは同じであっても異なっていても良い。Ｇ⁺ は無機または有機のカチオンであり、Ｌは中性ルイス塩基であり、（Ｌ−Ｈ）⁺ はブレンステッド酸である。） That is, the present invention is a copolymer obtained by copolymerizing ethylene and / or α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon, and the copolymer composition of the cyclic olefin is 0.01 to 66 mol. %, The copolymer composition of the alkenyl aromatic hydrocarbon is 3 to 99 mol%, and the copolymer composition of the alkenyl aromatic hydrocarbon is more than half the copolymer composition of the cyclic olefin, Copolymerization of copolymerizing ethylene and / or α-olefin, cyclic olefin and alkenyl aromatic hydrocarbon in the presence of a catalyst comprising the following (A) and (B) and / or (C) This relates to a method for producing a coalescence.
(A): transition metal complex represented by the following general formula [I], [II] or [III]

(In the general formulas [I] to [III], M ¹ represents a group 4 transition metal atom in the periodic table of elements, A represents a group 16 atom in the periodic table of elements, and J Represents an atom belonging to Group 14 of the periodic table of elements, Cp ¹ represents a group having a cyclopentadiene-type anion skeleton, X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, or a disubstituted amino group, and X ³ represents an element period. It represents an atom belonging to group 16 of the table, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be optionally combined to form a ring, represented by the general formula [II] or [III ], M ¹ , A, J, Cp ¹ , X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different.
(B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having a structure represented by _b (B3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ 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 may be the same or different, Z is a hydrogen atom or a halogen atom And all Z's may be the same or different, a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)
(C): a boron compound of any one of (C1) to (C3) below (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ,
(C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
(C3) A boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (where B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ Are halogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, substituted silyl groups, alkoxy groups or disubstituted amino groups, which may be the same or different, G ⁺ is an inorganic or organic cation. Yes, L is a neutral Lewis base and (L—H) ⁺ is a Bronsted acid.)

Hereinafter, the present invention will be described in more detail.
The copolymer of the present invention is a copolymer obtained by copolymerizing ethylene and / or α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon, and the copolymer composition of the cyclic olefin is 0. It is a copolymer having a copolymer composition of 01 to 66 mol%, a copolymer composition of the alkenyl aromatic hydrocarbon of 3 to 99 mol%, and a copolymer composition of the alkenyl aromatic hydrocarbon of more than half of the copolymer composition of the cyclic olefin.

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

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

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

（式中、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、または炭素原子数１〜２０の有機基であり、Ｒ¹⁶とＲ¹⁷は環を形成してもよい。ｍは０以上の整数を示す。） Among these, preferred cyclic olefins are compounds represented by the following general formula [IV].

Wherein R ^{7 to} R ¹⁸ are each independently a hydrogen atom, a hydroxyl group, an amino group, a phosphino group, or an organic group having 1 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ may form a ring. M is an integer of 0 or more.

  Specific examples of the organic group having 1 to 20 carbon atoms, which is a member of the substituent, include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group; phenyl group, Aryl groups such as tolyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; acyl groups such as acetyl group; methoxycarbonyl group and ethoxy Alkoxycarbonyl groups such as carbonyl groups, aryloxycarbonyl groups or aralkyloxycarbonyl groups; acyloxy groups such as acetyloxy groups; alkoxysulfonyl groups such as methoxysulfonyl groups and ethoxysulfonyl groups; aryloxysulfonyl groups or aralkyloxysulfonyl groups; trimethylsilyl Substituted silyl groups such as: dialkylamino groups such as dimethylamino groups and diethylamino groups; carboxyl groups; cyano groups; and some of the hydrogen atoms of the above alkyl groups, aryl groups and aralkyl groups are hydroxyl groups, amino groups, acyl groups, carboxyl groups And a group substituted with a group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a substituted silyl group, an alkylamino group or a cyano group.

R ^{7 to} R ¹⁸ are preferably each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 1 carbon atom. They are 20 acyl groups, C2-C20 alkoxycarbonyl groups, C1-C20 acyloxy groups, or C1-C20 disubstituted silyl groups.

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

  Specific examples of preferable cyclic olefins 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-ethoxycarbonylnorbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-cyanonorbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8- It is possible to enumerate anode tetracyclododecene and the like.

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

（式中、Ｒ¹⁹は水素原子または炭素原子数１〜２０のアルキル基であり、Ａｒは炭素原子数６〜２５の芳香族炭化水素基を示す。） The alkenyl aromatic hydrocarbon used in the present invention is preferably a compound represented by the following general formula [V].

(In the formula, R ¹⁹ 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.)

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

  Ar is an aromatic hydrocarbon group having 6 to 25 carbon atoms, and specific examples thereof include phenyl group, tolyl group, xylyl group, tertiary butylphenyl group, vinylphenyl group, naphthyl group, phenanthryl group, anthracenyl group. And benzyl group. A phenyl group, a tolyl group, a xylyl group, a tertiary butylphenyl group, a vinylphenyl group or a naphthyl group is preferable.

  Specific examples of such alkenyl aromatic hydrocarbons include alkenylbenzenes such as styrene, 2-phenylpropylene, 2-phenylbutene and 3-phenylpropylene; p-methylstyrene, m-methylstyrene, o-methylstyrene, p- Ethyl styrene, 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, Alkyl styrene such as p-tertiary butyl styrene and p-secondary butyl styrene; alkenyl naphthalene such as 1-vinylnaphthalene and the like can be listed. The alkenyl aromatic hydrocarbon used in the present invention is preferably styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tertiary butylstyrene, 2-phenylpropylene, or 1-vinylnaphthalene. Yes, particularly preferably styrene.

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

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

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

  In the copolymer of the present invention, the copolymer composition of the alkenyl aromatic hydrocarbon is more than half of the copolymer composition of the cyclic olefin. When the copolymer composition is within this range, the balance between heat resistance and elastic recovery is excellent. When the copolymerization composition of the alkenyl aromatic hydrocarbon is less than half of the copolymerization composition of the cyclic olefin, the elastic recovery property may be lowered. More preferably, the copolymer composition of the alkenyl aromatic hydrocarbon of the copolymer of the present invention is not less than the copolymer composition of the cyclic olefin.

  As the copolymer of the present invention, a copolymer having a high refractive index is obtained. Such copolymers are less likely to lose transparency even when fillers are used to improve rigidity.

  The copolymer of the present invention is preferably an amorphous copolymer having no crystallinity from the viewpoint of transparency. The absence of crystallinity can be confirmed by substantially not showing the melting point in the melting curve measured with a differential scanning calorimeter (DSC).

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

  The glass transition point (Tg) of the copolymer of the present invention is usually -20 to 170 ° C. Preferably, it is a copolymer having a Tg of -20 to 140 ° C, and more preferably a copolymer having a Tg of 30 to 100 ° C. Particularly preferred is a copolymer having a Tg of 35 ° C. or more and less than 60 ° C. Tg here is measured with a differential scanning calorimeter (DSC).

（上記一般式［Ｉ］〜［III］においてそれぞれ、Ｍ¹ は元素の周期律表の第４族の遷移金属原子を示し、Ａは元素の周期律表の第１６族の原子を示し、Ｊは元素の周期律表の第１４族の原子を示す。Ｃｐ¹ はシクロペンタジエン形アニオン骨格を有する基を示す。Ｘ¹ 、Ｘ² 、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＲ⁶ 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、アルコキシ基、アラルキルオキシ基、アリールオキシ基または２置換アミノ基を示す。Ｘ³ は元素の周期律表の第１６族の原子を示す。Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＲ⁶ は任意に結合して環を形成してもよい。一般式［II］または［III］における二つのＭ¹ 、Ａ、Ｊ、Ｃｐ¹ 、Ｘ¹ 、Ｘ² 、Ｘ³ 、Ｒ¹ 、Ｒ² 、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ およびＲ⁶ はそれぞれ同じであっても異なっていてもよい。）
（Ｂ）：下記（Ｂ１）〜（Ｂ３）から選ばれる１種以上のアルミニウム化合物
（Ｂ１）一般式 Ｅ¹ _aＡｌＺ_3-a で示される有機アルミニウム化合物
（Ｂ２）一般式 ｛−Ａｌ（Ｅ² ）−Ｏ−｝_b で示される構造を有する環状のアルミノキサン
（Ｂ３）一般式 Ｅ³ ｛−Ａｌ（Ｅ³ ）−Ｏ−｝_c ＡｌＥ³ ₂で示される構造を有する線状のアルミノキサン
（但し、Ｅ¹ 、Ｅ² およびＥ³ は、それぞれ炭化水素基であり、全てのＥ¹ 、全てのＥ² および全てのＥ³ は同じであっても異なっていても良い。Ｚは水素原子またはハロゲン原子を表し、全てのＺは同じであっても異なっていても良い。ａは０＜ａ≦３を満足する数を、ｂは２以上の整数を、ｃは１以上の整数を表す。）
（Ｃ）：下記（Ｃ１）〜（Ｃ３）のいずれかのホウ素化合物
（Ｃ１）一般式 ＢＱ¹ Ｑ² Ｑ³ で表されるホウ素化合物、
（Ｃ２）一般式 Ｇ⁺ （ＢＱ¹ Ｑ² Ｑ³ Ｑ⁴ ）^- で表されるホウ素化合物、
（Ｃ３）一般式 （Ｌ−Ｈ）⁺ （ＢＱ¹ Ｑ² Ｑ³ Ｑ⁴ ）^- で表されるホウ素化合物
（但し、Ｂは３価の原子価状態のホウ素原子であり、Ｑ¹ 〜Ｑ⁴ はハロゲン原子、炭化水素基、ハロゲン化炭化水素基、置換シリル基、アルコキシ基または２置換アミノ基であり、それらは同じであっても異なっていても良い。Ｇ⁺ は無機または有機のカチオンであり、Ｌは中性ルイス塩基であり、（Ｌ−Ｈ）⁺ はブレンステッド酸である。）
以下、該製造方法についてさらに詳しく説明する。 Such a copolymer of the present invention includes, for example, ethylene and / or α-olefin, cyclic olefin, alkenyl in the presence of a catalyst comprising the following (A) and (B) and / or (C): It can be produced with high polymerization activity by copolymerizing with an aromatic hydrocarbon.
(A): transition metal complex represented by the following general formula [I], [II] or [III]

(In the general formulas [I] to [III], M ¹ represents a group 4 transition metal atom in the periodic table of elements, A represents a group 16 atom in the periodic table of elements, and J Represents an atom belonging to Group 14 of the periodic table of elements, Cp ¹ represents a group having a cyclopentadiene-type anion skeleton, X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, or a disubstituted amino group, and X ³ represents an element period. It represents an atom belonging to group 16 of the table, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be optionally combined to form a ring, represented by the general formula [II] or [III ], M ¹ , A, J, Cp ¹ , X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different.
(B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having a structure represented by _b (B3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ 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 may be the same or different, Z is a hydrogen atom or a halogen atom And all Z's may be the same or different, a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)
(C): a boron compound of any one of (C1) to (C3) below (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ,
(C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
(C3) A boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (where B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ Are halogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, substituted silyl groups, alkoxy groups or disubstituted amino groups, which may be the same or different, G ⁺ is an inorganic or organic cation. Yes, L is a neutral Lewis base and (L—H) ⁺ is a Bronsted acid.)
Hereinafter, the production method will be described in more detail.

(A) Transition metal complex In the general formula [I], [II] or [III], the transition metal atom represented by M ¹ is the fourth element of the periodic table of elements (IUPAC inorganic chemical nomenclature revised edition 1989). A transition metal element belonging to the group, for example, a titanium atom, a zirconium atom, and a hafnium atom. A titanium atom or a zirconium atom is preferred.

  Examples of the group 16 atom in the periodic table of the element represented by A in the general formula [I], [II] or [III] include an oxygen atom, a sulfur atom, and a selenium atom, preferably an oxygen atom. It is.

  Examples of the group 14 atom in the periodic table of the element represented by J in the general formula [I], [II] or [III] include a carbon atom, a silicon atom, a germanium atom, and preferably a carbon atom. Or it is a silicon atom. In the present invention, J is particularly preferably a carbon atom.

Examples of the group having a cyclopentadiene-type anion skeleton represented by the substituent Cp ¹ include η ^5- (substituted) cyclopentadienyl group, η ^5- (substituted) indenyl group, η ^5- (substituted) fluorenyl group, and the like. is there. If specifically exemplified, for example, eta ⁵ - cycloalkyl Bae Ntajieniru group, eta ⁵ - methylcyclopentadienyl group, eta ⁵ - dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetra methylcyclopentadienyl 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-Hekishirushikurope} Ntajieniru group, eta ^5-n-octyl cyclopentane Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - Na Fuchirushikuro Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ⁵ - triethylsilyl cycloalkyl Bae Ntajieniru group, eta ^{5-tert-butyldimethylsilyl} cycloalkyl Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group , eta ⁵ - dimethyl indenyl group, eta ⁵ - ethyl indenyl group, eta ^5-n-propyl indenyl group, eta ⁵ - isopropylindenyl group, eta ^5-n-butyl indenyl group, eta ^5-sec- Butyl indenyl group, η ⁵ -tert-butyl indenyl group, η ⁵ -n-pentyl indenyl group, η ⁵ -neopentyl indenyl group, η ⁵ -n-hexyl indenyl group, η ⁵ -n-octyl indenyl group, eta ^{5-n-Deshiruindeniru} group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - naphthyl Indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group, eta ^{5-tert-butyldimethylsilyl} indenyl group, eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ^{5-n-propyl-fluorenyl} group, eta ⁵ - di-n- propyl fluorenyl group, eta ⁵ - isopropyl fluorenyl group, eta ⁵ - diisopropyl fluorenyl group, eta ^{5-n-butyl-fluorenyl} group, eta ^{5-sec-butylfluorenyl} group, eta ^5-tert. -Butyl fluorenyl group, η ⁵ -di-n-butyl fluorenyl group, η ⁵ -di-sec-butyl fluorenyl group, η ⁵ -di-tert-butyl fluorenyl group, η 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-decyl fluorenyl group, eta ^{5-n-dodecyl-fluorenyl} group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - di - phenyl fluorenyl group, eta ⁵ - methylphenyl fluorenyl group, eta ⁵ - naphthyl fluorenyl group, η ⁵ -trimethylsilylfluorenyl group, η ⁵ -bis-trimethylsilylfluorenyl group, η ⁵ -triethylsilylfluorenyl group, η ⁵ -tert-butyldimethylsilylfluorenyl group, and the like, preferably η ⁵ - cyclopentadienyl group, eta ⁵ - methylcyclopentadienyl group, eta ^{5-tert-butylcyclopentadienyl} group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ Fluorenyl group - indenyl group or eta ^5,.

Examples of the halogen atom in the substituent X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably chlorine An atom or a bromine atom, more preferably a chlorine atom.

As the alkyl group in the substituent X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an alkyl group having 1 to 20 carbon atoms is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n -Dodecyl group, n-pentadecyl group, n-eicosyl group, etc. are mentioned, More preferably, they are a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, or an amyl group.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or 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 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 include a bromopentadecyl group and a perbromoeicosyl group.
Any 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.

As the aralkyl group for the substituent X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aralkyl group having 7 to 20 carbon atoms is preferable. 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-trimethyl) Methylphenyl) 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 And anthracenylmethyl group and the like, more preferably a benzyl group.
These aralkyl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

As the aryl group in the substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aryl group having 6 to 20 carbon atoms is preferable, for example, 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, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl Group, n-propylphenyl group, iso Propylphenyl 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, anthracenyl group, and the like, more preferably a phenyl group.
These aryl groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group or aralkyloxy groups such as benzyloxy group Etc. may be partially substituted.

The substituted silyl group in the substituent X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is a silyl group substituted with a hydrocarbon group, where Is, for example, carbon such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, etc. Examples thereof include an alkyl group having 1 to 10 atoms and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include 1-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group, and phenylsilyl group, dimethylsilyl group, diethylsilyl group, and diphenylsilyl group. 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 3 -carbon atoms such as -butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, triphenylsilyl group 20 trisubstituted silyl groups and the like, preferably trimethyl Lil group, a tert- butyldimethylsilyl group or triphenylsilyl group.
All of these substituted silyl 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, or a benzyloxy group. A part thereof may be substituted with an aralkyloxy group such as a group.

As the alkoxy group in the substituent X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an alkoxy group having 1 to 20 carbon atoms is preferable, for example, a methoxy group, an ethoxy group, n-propoxy group, 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 Group, n-icosoxy group and the like, more preferably methoxy group, ethoxy group, or tert-butoxy group.
These alkoxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. Etc. may be partially substituted.

As the aralkyloxy group for the substituent X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aralkyloxy group having 7 to 20 carbon atoms is preferable. (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-trimethyl) (Tilphenyl) 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-octyl) Phenyl) methoxy group, (n-decylphenyl) methoxy group, (n-tetradecylphenyl) methoxy , Naphthylmethoxy group, anthracenylmethoxy methoxy group and the like, more preferably a benzyloxy group.
These aralkyloxy groups are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group, and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

As the aryloxy group in the substituent X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ^6, an aryloxy group having 6 to 20 carbon atoms is preferable, for example, a phenoxy group, 2 -Methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3 , 4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5 -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 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 are all halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. A part thereof may be substituted with a group or the like.

The disubstituted amino group in the substituent X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is an amino group substituted with two hydrocarbon groups, Examples of the hydrogen group include 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, and cyclohexyl group. And an alkyl group having 1 to 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. Examples of the 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 Group, diphenylamino group, bistrimethylsilylamino group, bis-tert-butyldimethylsilylamino group, and the like, preferably dimethylamino group or diethylamino group.
All of these disubstituted amino groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyl such as benzyloxy group. A part thereof 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 combined to form a ring.

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

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

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

Methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methyl Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene ( tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-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 (tetramethyl Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) tita Um 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 (trimethylsilylcyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5 -Chloro-2-phenoxy) titanium dichloride,

Methylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methyl) -2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-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-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadiene) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, iso Ropyridene (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 (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopenta Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phen Xyl) 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 (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclo) Ntadienyl) (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 (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-to Methylsilyl-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 (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Ntadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclo) Pentadienyl) (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-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadi) Enyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3 -Tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride Id, 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 (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopenta Dienyl) (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-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert- Tilcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (Tetramethylcyclopentadienyl) (3-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 (tetramethyl) Cyclopentadienyl) (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 (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopenta) Dienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethyl) Rylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenyl Methylene (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- ert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, etc., and titanium or hafnium of these compounds. Compound changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, or diisopropoxide, (cyclopentadienyl) changed to (dimethylcyclopentadiene) A compound changed to (enyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), or (indenyl), (3,5-dimethyl-2 − Enoxy) to (2-phenoxy), (3-methyl-2-phenoxy), (3,5-di-tert-butyl-2-phenoxy), (3-phenyl-5-methyl-2-phenoxy), ( 3-tert-butyldimethylsilyl-2-phenoxy) or a transition metal complex in which J in the general formula [I] is a carbon atom, such as a compound changed to (3-trimethylsilyl-2-phenoxy), and the like,

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

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, Dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium Dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2- Phenoxy) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride Dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert -Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylene) Cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopenta) Dienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2 Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethyl) Silyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-) - phenoxy) titanium dichloride, dimethylsilylene (tert- butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium Chloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl) -2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl -5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Rushiriren (tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

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

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (indenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (I Denyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamil) -2-phenoxy) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethyl Silylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5 -Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl)) (1-naphthoxy-2-yl) titanium dichloride, and (cyclohexane) of these compounds Ntadienyl) to (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclo) Compound changed to (pentadienyl), (isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl), or (phenylindenyl), A compound in which (2-phenoxy) is changed to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl-2-phenoxy), dimethylsilylene is diethylsilylene, Diphenylsilylene or dimethyl Compound changed to toxylylene, compound changed to titanium or hafnium, compound changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, or diisopropoxide Examples include transition metal complexes in which J in the general formula [I] is an atom of Group 14 of the periodic table of elements other than carbon atoms.

  The transition metal complex represented by the above general formula [I] is produced, for example, by the method described in the published specification of WO 97/03992. Moreover, the transition metal complex represented by the above general formula [II] or [III] is obtained by converting the transition metal complex represented by the above general formula [I] into 0.5 molar amount or 1 molar amount of water, respectively. Produced by reacting. At that time, the method of directly reacting the transition metal complex represented by the above general formula [I] with a necessary amount of water, the solvent represented by the above general formula [I] in a solvent such as a hydrocarbon containing the necessary amount of water. The transition metal complex is added, the transition metal complex represented by the above general formula [I] is introduced into a dried hydrocarbon solvent, and an inert gas containing a necessary amount of water is circulated. A method etc. can be adopted.

(B) Aluminum compound The aluminum compound (B) used in the present invention is one or more aluminum compounds selected from the following (B1) to (B3).
(B1) General formula E ¹ _a Organoaluminum compound represented by AlZ _3-a (B2) General formula {-Al (E ² ) -O—} Cyclic aluminoxane (B3) having the structure represented by _b General formula E ³ {-Al (E ³ ) —O—} _c Linear aluminoxane having a structure represented by AlE ³ ₂ (where E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ² and all E ³ may be the same or different, Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different. (A number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)
As the hydrocarbon group in E ^1, E ² or E ^3,, preferably a hydrocarbon group having 1 to 8 carbon atoms, 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 trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; dimethylaluminum chloride Dialkylaluminum chloride such as diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichloride such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride; Yes Examples thereof include dialkylaluminum hydrides such as dride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride.
Trialkylaluminum is preferable, and triethylaluminum or triisobutylaluminum is more preferable.

Cyclic aluminoxane (B2) having a structure represented by the general formula {-Al (E ² ) —O—} _b , a structure represented by the general formula E ³ {—Al (E ³ ) —O—} _c AlE ³ ₂ Specific examples of E ² and E ^{3 in} the linear aluminoxane (B3) having a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, a neopentyl group, etc. An alkyl group can be illustrated. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ² and E ³ are a methyl group or an isobutyl group, b is 2 to 40, and c is 1 to 40.

  The above aluminoxane can be made by various methods. There is no restriction | limiting in particular about the method, What is necessary is just to make according to a well-known method. 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.

(C) Boron Compound As the boron compound (C) in the present invention, (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- a boron compound represented by, (C3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - can be used either the boron compound represented.

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

  Specific examples of the compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane, Examples include tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, and most preferably tris (pentafluoro). Phenyl) 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 a boron atom in a trivalent valence state. , Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (C1) above.

Specific examples of G ⁺ which is an inorganic cation in the compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include ferrocenium cation, alkyl-substituted ferrocenium cation, silver cation, etc. However, examples of G ⁺ that is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ includes 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-bistri) Fluoromethylphenyl) borate and the like.

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

In the boron compound (C3) represented by the general formula (L—H) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , L is a neutral Lewis base, and (L—H) ⁺ is a slashed.nsted acid, B are boron atoms 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).

Specific examples of (LH) ⁺ which is a Bronsted acid in the compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include trialkyl-substituted ammonium, N, N - dialkylanilinium, dialkylammonium and triarylphosphonium ^{mentioned, (BQ 1 Q 2 Q 3} Q 4) - as include the same as described above.

  Specific combinations of these 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, most preferably tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl). ) Borate.

[polymerization]
In the present invention, an olefin polymerization catalyst comprising the above transition metal complex (A) and the above (B) and / or (C) is used. When an olefin polymerization catalyst comprising two components (A) and (B) is used, the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) are preferred as (B). Other preferred olefin polymerization catalysts include olefin polymerization catalysts using the above (A), (B), and (C), and the (B) at that time is the above (B1). ) Easy to use.

  The amount of each component used is usually a molar ratio of (B) / (A) of 0.1 to 10,000, preferably 5 to 2000, and a molar ratio of (C) / (A) of 0.01 to 100. It is desirable to use each component so that it is preferably in the range of 0.5 to 10. The concentration in the case of using each 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 component to the polymerization reactor, but in general, (A) is usually 0. 0.01 to 500 μmol / g, more preferably 0.05 to 100 μmol / g, still more preferably 0.05 to 50 μmol / g, and (B) is usually 0.01 to 10,000 μmol / g in terms of Al atom. More preferably, it is 0.1 to 5000 μmol / g, more preferably 0.1 to 2000 μmol / g, and (C) is usually 0.01 to 500 μmol / g, more preferably 0.05 to 200 μmol. / G, more preferably, it is desirable to use each component so that it is in the range of 0.05 to 100 μmol / g.

As the 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 a polymer such as ethylene and styrene may be used in combination.

  In carrying out the method of the present invention, the polymerization method is not particularly limited. For example, a batch or continuous gas phase polymerization method, a bulk polymerization method, a solution polymerization method or a slurry polymerization method using an appropriate solvent, etc. Can be used. When a solvent is used, various solvents can be used under the condition that the catalyst is not deactivated. Examples of such solvents include hydrocarbons such as benzene, toluene, pentane, hexane, heptane, cyclohexane; Examples thereof include halogenated hydrocarbon groups such as chlorinated styrene.

  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 polymer.

  Such a copolymer of the present invention can be used for a molded article such as a film, a sheet, a pipe or a container, but is particularly suitable for a film, a sheet or a pipe.

  The film, sheet or pipe is, for example, an extrusion molding process in which a molten resin is extruded from a circular die and the film expanded in a cylindrical shape is wound, or a molten resin is extruded from a linear die and the film or sheet is wound up. It can be obtained by die molding, calendar molding, blow molding, injection molding, or profile extrusion molding.

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

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

The molded article of the present invention may contain known additives such as antioxidants, weathering agents, lubricants, anti-blocking agents, antistatic agents, antifogging agents, drip-free agents, pigments, fillers, etc., if necessary. it can. In addition, known polymer substances such as radical polymerization method low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α-olefin copolymer elastomer, and polypropylene may be blended.
The film or sheet of the present invention can be subjected to known post-treatments such as corona discharge treatment, plasma treatment, ozone treatment, ultraviolet irradiation, and electron beam irradiation.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited the range by this Example. In addition, the property of the polymer in an Example was measured with the following method.

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

The glass transition point was measured under the following conditions using DSC (SSC-5200, manufactured by Seiko Denshi Kogyo Co., Ltd.) and determined from the inflection point.
Temperature rising 20 ° C. to 200 ° C. (20 ° C./min) 10 minutes holding cooling 200 ° C. to −50 ° C. (20 ° C./min) 10 minutes holding measurement −50 ° C. to 300 ° C. (20 ° C./min)

The molecular weight and molecular weight distribution were determined under the following conditions using a gel permeation chromatograph (150-CV manufactured by Waters).
Column shodex 806M / S
Measurement temperature 145 ℃
Measurement solvent Orthodichlorobenzene measurement concentration 1mg / ml

The styrene unit copolymer composition in the polymer and the structure of the polymer were determined by ¹ H-NMR and ¹³ C-NMR analysis.
¹ H-NMR apparatus JNM-EX270 manufactured by JEOL Ltd.
Measuring solvent Dichloromethane-d2
Measurement temperature Room temperature
¹³ C-NMR apparatus BRUKER AC250
Measuring solvent 85:15 (volume ratio) mixture of orthodichlorobenzene and heavy benzene Measuring temperature 135 ° C

The solid viscoelasticity of the polymer was determined under the following conditions using a spectrometer (DMS200 of SDM5600H manufactured by Seiko Denshi Kogyo).
Test piece 20 mm x 3.0 mm x 0.3 mm press sheet frequency 5 Hz
Temperature rising rate 2 ℃ / min Displacement amplitude 10μm

The hysteresis curve of the polymer was determined under the following conditions using Strograph-T (manufactured by Toyo Seiki Seisakusho).
Test piece 120 mm × 20 mm × 0.3 mm press sheet pulling speed 200 mm / min pulling magnification 2 times distance between chucks 60 mm

  The refractive index of the polymer was pre-heated at 180 ° C. for 3 minutes and then heat-pressed at 180 ° C. under a pressure of 3 to 5 MPa for 3 minutes to cut a 100 μm-thick film into a size of 10 mm × 30 mm as a test piece. , Using an Abbe refractometer type 3 (manufactured by Atago Co., Ltd.).

  The total haze of the polymer was determined by ASTM- about a 0.3 mm thick press sheet obtained by preheating for 5 minutes with a 150 ° C hot press machine, pressing for 5 minutes, and cooling with a 35 ° C cooling press machine. It measured based on D-1003.

Example 1
Into a 400 ml autoclave substituted with argon, 11.4 ml of styrene, 20 ml of a toluene solution of norbornene (5 mol / l) and 105 ml of dehydrated toluene were charged in advance, and then 0.8 MPa of ethylene was charged. Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 15.5 mg dissolved in 15 ml of dehydrated toluene and a toluene solution of triisobutylaluminum [Tosoh Akzo Co., Ltd. Made, 1 mol / l] 2.5 ml was mixed in advance and charged, and then 80.1 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate dissolved in 47 ml of dehydrated toluene was added. Stir at 1 ° C. for 1 hour. Thereafter, the reaction solution was poured into a mixture of 5 ml of hydrochloric acid (12N) and 1000 ml of acetone, and the precipitated white solid was collected. The solid was washed with acetone and then dried under reduced pressure to obtain 26.85 g of a polymer. [Η] of this polymer is 1.30 dl / g, number average molecular weight is 154,000, molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.9, glass transition point is 35 ° C., norbornene The polymerization composition was 15 mol%, and the copolymerization composition of styrene was 16 mol%.
FIG. 1 shows the ¹³ C-NMR spectrum of the obtained polymer, FIG. 2 shows the solid viscoelasticity data, and FIG. 3 shows the hysteresis curve. After the measurement of the hysteresis curve, the test piece recovered almost 100% to the state before the measurement. Further, the press sheet prepared for measurement was very transparent.

Example 2
Into a 400 ml autoclave substituted with argon, 114 ml of styrene, 20 ml of a norbornene toluene solution (5 mol / l) and 6 ml of dehydrated toluene were charged in advance, and then 0.8 MPa of ethylene was charged. Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 11.6 mg dissolved in 12 ml of dehydrated toluene and toluene solution of triisobutylaluminum [Tosoh Akzo Co., Ltd. Manufactured, 1 mol / l] 3.0 ml was mixed in advance and charged with 72.0 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate dissolved in 45 ml of dehydrated toluene. Stir at 1 ° C. for 1 hour. Thereafter, the reaction solution was poured into a mixture of 5 ml of hydrochloric acid (12N) and 1000 ml of acetone, and the precipitated white solid was collected. The solid was washed with acetone and then dried under reduced pressure. As a result, 18.34 g of a polymer was obtained. [Η] of this polymer is 1.25 dl / g, number average molecular weight is 162,000, molecular weight distribution (weight average molecular weight / number average molecular weight) is 2.0, glass transition point is 55 ° C., norbornene The polymerization composition was 15 mol%, and the copolymerization composition of styrene was 36 mol%.
The solid viscoelasticity of the obtained polymer is shown in FIG. The obtained polymer had a total haze of 11.8% and a refractive index of 1.57.

Example 3
Into a 400 ml autoclave substituted with argon, 27 ml of styrene, 48 ml of a norbornene toluene solution (5 mol / l) and 13 ml of dehydrated toluene were charged in advance, and then 0.8 MPa of ethylene was charged. Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 3.0 mg dissolved in dehydrated toluene 6 ml and toluene solution of triisobutylaluminum [Tosoh Akzo Co., Ltd. Manufactured, 1 mol / l] 2.0 ml was mixed in advance and charged, and then 19.2 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate dissolved in 24 ml of dehydrated toluene was added, and the reaction solution was added to 60 ml. Stir at 1 ° C. for 1 hour. Thereafter, the reaction solution was poured into a mixture of 2 ml of hydrochloric acid (12N) and 500 ml of acetone, and the precipitated white solid was collected. The solid was washed with acetone and then dried under reduced pressure. As a result, 1.43 g of a polymer was obtained. This polymer had a glass transition point of 123 ° C., a norbornene copolymer composition of 28 mol%, and a styrene copolymer composition of 19 mol%.

Example 4
Into a 400 ml autoclave substituted with argon, 114 ml of styrene, 4 ml of a toluene solution of norbornene (5 mol / l) and 34 ml of dehydrated toluene were charged in advance, and then 0.8 MPa of ethylene was charged. Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 15.5 mg dissolved in 15 ml of dehydrated toluene and a toluene solution of triisobutylaluminum [Tosoh Akzo Co., Ltd. Manufactured, 1 mol / l] 3.0 ml was mixed in advance and charged, and then 96.1 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate dissolved in 30 ml of dehydrated toluene was added. Stir for 2 hours at ° C. Thereafter, the reaction solution was poured into a mixture of 5 ml of hydrochloric acid (12N) and 1000 ml of acetone, and the precipitated white solid was collected. The solid was washed with acetone and then dried under reduced pressure. As a result, 28.04 g of a polymer was obtained. The polymer had a glass transition point of 39 ° C., a norbornene copolymer composition of 3 mol%, and a styrene copolymer composition of 48 mol%.

Example 5
In a 400 ml autoclave substituted with argon, 114 ml of styrene and 40 ml of norbornene in toluene (5 mol / l) were added in advance, and then 0.8 MPa of ethylene was charged. Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 15.5 mg dissolved in 15 ml of dehydrated toluene and a toluene solution of triisobutylaluminum [Tosoh Akzo Co., Ltd. Manufactured, 1 mol / l] 3.0 ml was mixed in advance and charged, and then 96.1 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate dissolved in 30 ml of dehydrated toluene was added. Stir for 2 hours at ° C. Thereafter, the reaction solution was poured into a mixture of 5 ml of hydrochloric acid (12N) and 1000 ml of acetone, and the precipitated white solid was collected. The solid was washed with acetone and then dried under reduced pressure. As a result, 34.86 g of a polymer was obtained. This polymer had a glass transition point of 83 ° C., a norbornene copolymer composition of 21 mol%, and a styrene copolymer composition of 46 mol%.

1 is a ¹³ C-NMR spectrum of the copolymer obtained in Example 1. FIG.

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

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

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

Claims (4)

A copolymer obtained by copolymerizing ethylene and / or α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon, wherein the cyclic olefin has a copolymer composition of 0.01 to 66 mol%, and the alkenyl aromatic The copolymer composition of the aromatic hydrocarbon is 3 to 99 mol%, and the copolymer composition of the alkenyl aromatic hydrocarbon is more than half the copolymer composition of the cyclic olefin, comprising the following (A) and , (B) and / or (C), in the presence of a catalyst, copolymerizing ethylene and / or α-olefin, cyclic olefin, and alkenyl aromatic hydrocarbon Manufacturing method of coalescence.
(A): transition metal complex represented by the following general formula [I], [II] or [III]

(In the general formulas [I] to [III], M ¹ represents a group 4 transition metal atom in the periodic table of elements, A represents a group 16 atom in the periodic table of elements, and J Represents an atom belonging to Group 14 of the periodic table of elements, Cp ¹ represents a group having a cyclopentadiene-type anion skeleton, X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently represents a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group, or a disubstituted amino group, and X ³ represents an element period. It represents an atom belonging to group 16 of the table, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be optionally combined to form a ring, represented by the general formula [II] or [III ], M ¹ , A, J, Cp ¹ , X ¹ , X ² , X ³ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different.
(B): One or more aluminum compounds selected from the following (B1) to (B3) (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) General formula {-Al (E ² ) -O-} cyclic aluminoxane having a structure represented by _b (B3) a linear aluminoxane having a structure represented by the general formula E ³ {-Al (E ³ ) -O—} _c AlE ³ 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 may be the same or different, Z is a hydrogen atom or a halogen atom And all Z's may be the same or different, a represents a number satisfying 0 <a ≦ 3, b represents an integer of 2 or more, and c represents an integer of 1 or more.)
(C): a boron compound of any one of (C1) to (C3) below (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ ,
(C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
(C3) A boron compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ (where B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ Are halogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, substituted silyl groups, alkoxy groups or disubstituted amino groups, which may be the same or different, G ⁺ is an inorganic or organic cation. Yes, L is a neutral Lewis base and (L—H) ⁺ is a Bronsted acid.)   The method for producing a copolymer according to claim 1, wherein the copolymer composition of the alkenyl aromatic hydrocarbon of the copolymer is not less than the copolymer composition of the cyclic olefin.   The method for producing a copolymer according to claim 1 or 2, wherein the copolymer has no crystallinity. The method for producing a copolymer according to any one of claims 1 to 3, wherein the glass transition point of the copolymer is -20 to 140 ° C.

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