JP2009209336A - Catalytic component for addition polymerization, catalyst for addition polymerization and method for producing addition polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalytic component for addition polymerization capable of producing an addition polymer having a high molecular weight and a catalyst for addition polymerization and to provide a method for producing the addition polymer. <P>SOLUTION: The catalytic component for addition polymerization includes modified particles obtained by bringing (a) a compound represented by formula [1]: M<SP>1</SP>L<SP>1</SP><SB>m</SB>into contact with (b) a specific benzene-based compound, (c) a compound represented by formula [3]: R<SP>3</SP><SB>t-2</SB>TH<SB>2</SB>and (d) solid particles, wherein when the molar ratio of amounts of these compounds (a), (b) and (c) used for contact is represented by the formula (a):(b):(c)=1:y:z, y and z satisfy the formula (i): 0.6≤y≤1.0 and the formula (ii): -0.625y+1.275≤z≤-0.875y+1.625. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an addition polymerization catalyst component capable of producing a higher molecular weight addition polymer, an addition polymerization catalyst, and a method for producing the addition polymer.

  Olefin polymers such as polypropylene and polyethylene are widely used in various molded products because they are excellent in mechanical properties and chemical resistance, and are inexpensive and economical.

  In recent years, olefin polymers have undergone addition polymerization of olefins using a so-called single-site catalyst, which is a combination of a transition metal compound (for example, a metallocene complex or a nonmetallocene compound) and an organic metal component (for example, aluminoxane). Manufactured.

  When a single-site catalyst is applied to polymerization in which an olefin-based addition polymer forms particles, such as slurry polymerization or gas phase polymerization, for example, as described in Patent Document 1, specific particles are used. It is known to be used as one of the catalyst components.

International Patent Publication No. 02/051878

In the production of an olefin polymer, the molecular weight of the obtained olefin polymer is adjusted with hydrogen gas. Generally, when the concentration of hydrogen in the polymerization system is increased, the molecular weight of the olefin polymer is decreased. However, when a conventional single site catalyst is used, the molecular weight of the olefin polymer is low even under polymerization conditions where the hydrogen concentration is not so high, and the molecular weight of the olefin polymer is designed by controlling the hydrogen concentration. It was difficult to do. Therefore, from the viewpoint of designing an olefin polymer, if a high molecular weight addition polymer is obtained under polymerization conditions with a high hydrogen concentration, the hydrogen concentration can be easily controlled and the molecular weight of the olefin polymer can be easily designed. Therefore, it is preferable.
Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention, is an addition polymerization catalyst component capable of producing a higher molecular weight addition polymer under polymerization conditions having a higher hydrogen concentration. It is to provide a catalyst for use and a method for producing an addition polymer.

ｃ）下式［３］で表される化合物
Ｒ³ _t-2ＴＨ₂ ［３］
（ただし、上式［１］〜［３］において、Ｍ¹は元素の周期表第１族、第２族、第１２族、第１４族または第１５族の典型金属原子を表し、ｍはＭ¹の原子価に相当する数を表す。Ｌ¹は水素原子、ハロゲン原子または炭化水素基を表し、Ｌ¹が複数存在する場合、複数のＬ¹は互いに同じであっても異なっていてもよい。Ｒ¹は電子吸引性基または電子吸引性基を含有する基を表し、Ｒ¹は互いに同じであっても異なっていてもよく、隣接する炭素原子にそれぞれ結合する２つのＲ¹は、互いに連結してベンゼン環に隣接した縮合環構造を形成してもよい。Ｒ^３は炭化水素基またはハロゲン化炭化水素基を表す。Ｔはそれぞれ独立に元素の周期表第１５族または第１６族の非金属原子を表し、ｔはそれぞれの化合物のＴの原子価に相当する数を表す。）
０．６≦ｙ≦１．０ （ｉ）
−０．６２５ｙ＋１．２７５≦ｚ≦−０．８７５ｙ＋１．６２５ （ｉｉ）；
（２）固体粒子（ｄ）が無機物質粒子または有機ポリマー粒子である上記（１）に記載の付加重合用触媒成分；
（３）無機物質粒子が無機酸化物、粘土または粘土鉱物である上記（１）に記載の付加重合用触媒成分；
（４）上記（１）〜（３）のいずれかに記載の改質された粒子からなる付加重合用触媒成分（Ａ）および元素の周期表第３族〜第１１族またはランタノイド系列の遷移金属化合物（Ｂ）を接触させて得られる付加重合用触媒；
（５）上記（１）〜（３）のいずれかに記載の改質された粒子からなる付加重合用触媒成分（Ａ）、元素の周期表第３族〜第１１族またははランタノイド系列の遷移金属化合物（Ｂ）および有機アルミニウム化合物（Ｃ）を接触させて得られる付加重合用触媒；
（６）元素の周期表第３族〜第１１族またはランタノイド系列の遷移金属化合物（Ｂ）が、少なくとも一つのシクロペンタジエン形アニオン骨格を有する遷移金属化合物である上記（４）または（５）に記載の付加重合用触媒；
（７）上記（４）〜（６）のいずれかに記載の付加重合用触媒を用いる付加重合体の製造方法；
（８）付加重合体がオレフィン重合体である上記（７）に記載の付加重合体の製造方法；
ならびに
（９）付加重合体がエチレンとα−オレフィンとの共重合体である上記（８）に記載の付加重合体の製造方法。 The present invention provides the following inventions in order to solve the above problems.
(1) A catalyst component for addition polymerization comprising modified particles obtained by contacting the following compounds (a), (b), (c) and solid particles (d), wherein the compound (a ), (B), and (c) are used in a molar ratio of (a) :( b) :( c) = 1: y: z, y and z are represented by the following formulas (i) and (ii) Catalyst component for addition polymerization satisfying
(A) Compound M ¹ L ¹ _m [1] represented by the following formula [1]
(B) Compound represented by the following formula [2]

c) Compound R ³ _t-2 TH ₂ [3] represented by the following formula [3]
(In the above formulas [1] to [3], M ¹ represents a typical metal atom of Group 1, Group 2, Group 12, Group 14 or Group 15 of the periodic table of elements; ¹ valence .L ¹ which represents a number corresponding to a hydrogen atom, a halogen atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, R ¹ may be the same as or different from each other, and two R ¹ bonded to adjacent carbon atoms are And may be linked to form a condensed ring structure adjacent to the benzene ring, R ³ represents a hydrocarbon group or a halogenated hydrocarbon group, and each T independently represents Group 15 or Group 16 of the periodic table of elements. Represents a non-metallic atom, and t is a number corresponding to the valence of T of each compound. It is.)
0.6 ≦ y ≦ 1.0 (i)
−0.625y + 1.275 ≦ z ≦ −0.875y + 1.625 (ii);
(2) The catalyst component for addition polymerization according to the above (1), wherein the solid particles (d) are inorganic substance particles or organic polymer particles;
(3) The catalyst component for addition polymerization according to the above (1), wherein the inorganic substance particles are inorganic oxide, clay or clay mineral;
(4) Addition polymerization catalyst component (A) comprising the modified particles according to any one of the above (1) to (3), and Group 3 to Group 11 or lanthanoid series transition metals of the periodic table of elements A catalyst for addition polymerization obtained by contacting the compound (B);
(5) Addition polymerization catalyst component (A) comprising the modified particles according to any one of (1) to (3) above, transition of Group 3 to Group 11 or lanthanoid series of the periodic table of elements A catalyst for addition polymerization obtained by contacting the metal compound (B) and the organoaluminum compound (C);
(6) In the above (4) or (5), the transition metal compound (B) of Group 3 to Group 11 of the periodic table of elements or the lanthanoid series is a transition metal compound having at least one cyclopentadiene type anion skeleton. The catalyst for addition polymerization as described;
(7) A method for producing an addition polymer using the addition polymerization catalyst according to any one of (4) to (6) above;
(8) The method for producing an addition polymer according to (7), wherein the addition polymer is an olefin polymer;
And (9) The method for producing an addition polymer as described in (8) above, wherein the addition polymer is a copolymer of ethylene and α-olefin.

  According to the present invention, there are provided an addition polymerization catalyst component, an addition polymerization catalyst and a method for producing an addition polymer, which can produce a higher molecular weight addition polymer under polymerization conditions having a higher hydrogen concentration.

The compound (a) is a compound represented by the following formula [1].
M ¹ L ¹ _m [1]
M ¹ in the above formula [1] represents a typical metal atom of Group 1, 2, 12, 14 or 15 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). M ¹ in the formula [1] is, for example, lithium atom, sodium atom, potassium atom, rubidium atom, cesium atom, beryllium atom, magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, cadmium atom, mercury atom , Germanium atoms, tin atoms, lead atoms, antimony atoms, and bismuth atoms. Among them, preferred is a magnesium atom, calcium atom, strontium atom, barium atom, zinc atom, germanium atom, tin atom or bismuth atom, particularly preferred is a magnesium atom, zinc atom, tin atom or bismuth atom, and most preferred. Is a zinc atom. Also, m in the formula [1] represents the number corresponding to the valence of M ^1, for example, when M ¹ is a zinc atom and m is 2.

The halogen atom of L ¹ in the formula [1] includes, for example, fluorine atom, chlorine atom, bromine atom, and iodine atom. The hydrocarbon group for L ¹ is preferably an alkyl group, an aryl group, or an aralkyl group.

As the alkyl group as the hydrocarbon group in L ¹ , an alkyl group having 1 to 20 carbon atoms is preferable. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, tert-butyl, isobutyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl, and n-eicosyl Among them, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group or an isobutyl group is more preferable.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, and a tetrafluoroethyl group. , Pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group, 1H, 1H-perfluoropropyl group, 1H, 1H-perfluorobutyl group, 1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl 1H, 1H-par Le Oro pentadecyl group, and IH, 1H-perfluoro eicosyl group, and can be exemplified an alkyl group where fluoro is changed to the alkyl groups chloro, bromo or iodo.
Any of these alkyl groups may be substituted with an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aryl group as the hydrocarbon group in L ¹ 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, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4-trimethylphenyl, 2,3, 5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2 , 3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenol Group, sec-butylphenyl group, tert-butylphenyl group, isobutylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n- Examples thereof include a dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group, and among them, a phenyl group is more preferable.
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 or aralkyloxy groups such as benzyloxy group. It may be substituted with a group or the like.

The aralkyl group 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-dimethyl) Phenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethyl) Phenyl) methyl group, (3,4,5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) Nyl) 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, (isobutylphenyl) methyl Group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group, (n-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group, naphthylmethyl group, And anthracenylmethyl group. Among them, a benzyl group is more preferable.
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. It may be substituted with a group or the like.

L ¹ in the above formula [1] is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group.

また、化合物（ｃ）は下記式［３］で表される化合物である。
Ｒ³ _t-2ＴＨ₂ ［３］
上記式［２］または［３］におけるＴはそれぞれ独立に、元素の周期律表（ＩＵＰＡＣ無機化学命名法改訂版１９８９）の第１５族または第１６族の非金属原子を表す。式［２］におけるＴと式［３］におけるＴとは同じであっても異なっていてもよい。第１５族の非金属原子の具体例としては、窒素原子、リン原子などが、第１６族の非金属原子の具体例としては、酸素原子、硫黄原子などが挙げられる。Ｔとして好ましくは、それぞれ独立に窒素原子または酸素原子であり、特に好ましくはＴは酸素原子である。
上記式［２］または［３］におけるｔはそれぞれのＴの原子価に相当する数を表す。ｔは、Ｔが第１５族非金属原子の場合は３であり、Ｔが第１６族非金属原子の場合は２である。 The compound (b) is a compound represented by the following formula [2].

Compound (c) is a compound represented by the following formula [3].
R ³ _t-2 TH ₂ [3]
T in the above formula [2] or [3] independently represents a non-metal atom of Group 15 or Group 16 of the Periodic Table of Elements (IUPAC Inorganic Chemical Nomenclature Revised Edition 1989). T in Formula [2] and T in Formula [3] may be the same or different. Specific examples of the Group 15 nonmetallic atom include a nitrogen atom and a phosphorus atom, and specific examples of the Group 16 nonmetallic atom include an oxygen atom and a sulfur atom. T is preferably each independently a nitrogen atom or an oxygen atom, and particularly preferably T is an oxygen atom.
T in the above formula [2] or [3] represents a number corresponding to the valence of each T. t is 3 when T is a Group 15 nonmetallic atom, and t is 2 when T is a Group 16 nonmetallic atom.

R ¹ in the above formula [2] represents an electron-withdrawing group or a group containing an electron-withdrawing group, and three R ¹ may be the same or different from each other, and optionally two R ¹ Together may be linked to an adjacent position of the benzene ring to form a condensed ring structure. As an index of electron withdrawing property, for example, Hammett's rule substituent constant σ is known, and a functional group having a positive substituent constant σ can be exemplified as an electron withdrawing group.

Examples of the electron-withdrawing group represented by R ¹ in the formula [2] include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. Examples of the group containing an electron-withdrawing group represented by R ¹ in the formula [2] include a halogenated alkyl group, a halogenated aryl group, a (halogenated alkyl) aryl group, a cyanated aryl group, a nitrated aryl group, and an ester. A group (alkoxycarbonyl group, aralkyloxycarbonyl group or aryloxycarbonyl group), an acyl group, and an acyl halide group.

Examples of the halogenated alkyl group of R ¹ in the above formula [2] include, for example, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, 2,2,3,3, 3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 1H, 1H- Perfluorobutyl group, 1H, 1H-perfluoropentyl group, 1H, 1H-perfluorohexyl group, 1H, 1H-perfluorooctyl group, 1H, 1H-perfluorododecyl group, 1H, 1H-perfluoropentadecyl group And 1H, 1H-perfluoroeicosyl group, and fluoro of these halogenated alkyl groups are chloro, bromo or It can be exemplified alkyl groups that have changed over de.

Examples of the halogenated aryl group of R ¹ in the above formula [2] include, for example, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl. Group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluoro Phenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1 A naphthyl group, a perfluoro-2-naphthyl group, and a 4,5,6,7,8-pentafluoro-2-naphthyl group, and these And halogenated aryl groups in which the fluoro of the halogenated aryl group is changed to chloro, bromo or iodo.

As the (halogenated alkyl) aryl group of R ¹ in the above formula [2], for example, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl) phenyl group 2,6-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, and 2,4,6-tris (trifluoromethyl) phenyl group, and their (halogenated) Mention may be made of (alkyl halide) aryl groups in which the fluoro of the alkyl) aryl group has been changed to chloro, bromo or iodo.

Examples of the cyanated aryl group represented by R ¹ in the formula [2] include a 2-cyanophenyl group, a 3-cyanophenyl group, and a 4-cyanophenyl group.

Examples of the nitrated aryl group for R ¹ in the above formula [2] include a 2-nitrophenyl group, a 3-nitrophenyl group, and a 4-nitrophenyl group.

Examples of the ester group of R ¹ in the above formula [2] include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, a phenoxycarbonyl group, a trifluoromethoxycarbonyl group, and a pentafluorophenoxycarbonyl. The group can be mentioned.

Examples of the acyl group and the acyl halide of R ¹ in the above formula [2] include a formyl group, an ethanoyl group, a propanoyl group, a butanoyl group, a trifluoroethanoyl group, a benzoyl group, a pentafluorobenzoyl group, and a perfluoroethano group. Yl group, perfluoropropanoyl group, perfluorobutanoyl group, perfluoropentanoyl group, perfluorohexanoyl group, perfluoroheptanoyl group, perfluorooctanoyl group, perfluorononanoyl group, perfluorodecanoyl group , Perfluoroundecanoyl group, and perfluorododecanoyl group.

R ¹ in the formula [2] is preferably a halogen atom, a halogenated alkyl group, a halogenated aryl group, a cyano group, a cyanated alkyl group, a cyanated aryl group, a nitro group, a nitrated alkyl group, or a nitrated aryl group. Or it is an ester group, More preferably, they are a halogen atom, a halogenated alkyl group, or a halogenated aryl group. More preferably, fluorine atom, fluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2, 2-trifluoro-1-trifluoromethylethyl group, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluoro Phenyl group, 2,4-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 3,4, 5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2,3,5,6-tetrafluoro-4- Trifluoromethylphenyl group, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenyl group, perfluoro-1-naphthyl group, perfluoro-2-naphthyl group, chloromethyl group, dichloromethyl group, trichloro Methyl group, 2,2,2-trichloroethyl group, 2,2,3,3,3-pentachloropropyl group, 2,2,2-trichloro-1-trichloromethylethyl group, 1,1-bis (trichloro Methyl) -2,2,2-trichloroethyl group, 4-chlorophenyl group, 2,6-dichlorophenyl group, 3.5-dichlorophenyl group, 2,4,6-trichlorophenyl group, or pentachlorophenyl group, especially Preferred is a fluorine atom, a fluoroalkyl group or a fluoroaryl group, and most preferred is a fluorine atom .

R ² in the above formula [3] represents a hydrocarbon group or a halogenated hydrocarbon group. The hydrocarbon group for R ³ in the formula [3] is preferably an alkyl group, an aryl group or an aralkyl group, and examples of the group exemplified as L ¹ in the formula [1] can be given. Examples of the halogenated hydrocarbon group for R ³ include a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group. The electron-withdrawing group for R ¹ in the above formula [2] And a halogenated alkyl group, a halogenated aryl group, and a (halogenated alkyl) aryl group exemplified as above.

R ² in the general formula [3] is preferably a halogenated hydrocarbon group, and more preferably a fluorinated hydrocarbon group.

Examples of the compound (a) when M ¹ is a zinc atom include dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-n-hexyl zinc; Dinaphthyl zinc and diaryl zinc such as bis (pentafluorophenyl) zinc; dialkenyl zinc such as diallyl zinc; bis (cyclopentadienyl) zinc; methyl zinc chloride, ethyl zinc chloride, propyl zinc chloride, n-butyl zinc chloride, Isobutyl zinc chloride, n-hexyl chloride, methyl zinc bromide, ethyl zinc bromide, propyl zinc bromide, n-butyl zinc bromide, isobutyl zinc bromide, n-hexyl bromide zinc, methyl zinc iodide, iodine Ethyl zinc iodide, propyl zinc iodide, n-butyl zinc iodide, isobutyl zinc iodide, and iodine Of n- alkyl halides zinc hexyl zinc; zinc fluoride, zinc chloride, zinc bromide, and zinc halides such as zinc iodide.

  The compound (a) is preferably dialkyl zinc, more preferably dimethyl zinc, diethyl zinc, dipropyl zinc, di n-butyl zinc, diisobutyl zinc or di n-hexyl zinc, particularly preferably dimethyl zinc or diethyl. Zinc.

  Examples of the compound (b) include phenol, thiophenol, naphthol, naphthylthiol, amine, and phosphine compound. Examples of the phenol, naphthol, thiophenol, and naphthylthiol compounds of the compound (b) include pentafluorophenol, pentakis (trifluoromethyl) phenol, pentakis (pentafluorophenyl) phenol, and pentakis (3,4,5-trimethyl). Fluorophenyl) phenol, 2,3,5,6-tetrafluoro-4-trifluoromethylphenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, 2,3,5,6-tetra Fluoro-4- (3 ′, 4 ′, 5′-trifluorophenyl) phenol, 2,3,4,5,6,7,8-heptafluoro-1-naphthol, 1,3,4,5,6 , 7,8-heptafluoro-2-naphthol, 2,3,5,6-tetrafluoro-4-nitrof Nord, 2,3,5,6-tetrafluoro-4-cyanophenol, and, fluoro these phenols chloro, mention may be made of phenol was replaced by bromo or iodo. Moreover, the thiophenol compound which replaced the oxygen atom of the said phenol compound with the sulfur atom can be mentioned similarly. These thiophenol compounds are compounds represented by replacing “phenol” in the above phenol compounds with “thiophenol” (in the case of naphthol, compounds represented by replacing “naphthol” with “naphthylthiol”), etc. It is. In addition, a hydrogen atom at the 2-6 position of the above phenol compound (in the case of naphthol or naphthylthiol, a hydrogen atom at the 1-3 position) is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, A phenol compound substituted with an isobutyl group, a tert-butyl group, or a phenyl group, or a thiophenol compound can be similarly exemplified.

  Examples of the amine and phosphine compound of the compound (b) include bis (pentafluorophenyl) amine, bis (pentakis (trifluoromethyl) phenyl) amine, bis (pentakis (pentafluorophenyl) phenyl) amine, and bis (pentakis ( 3,4,5-trifluorophenyl) phenyl) amine, bis (2,3,5,6-tetrafluoro-4-trifluoromethyl) amine, bis (2,3,5,6-tetrafluoro-4- Pentafluorophenylmethyl) amine, bis (2,3,4,5,6,7,8-heptafluoro-1-naphthyl) amine, and amines in which the fluoro of these amines has been replaced with chloro, bromo or iodo Can be mentioned. Moreover, the phosphine compound which substituted the nitrogen atom of the said amine compound with the phosphorus atom can be mentioned similarly. These phosphine compounds are compounds represented by substituting “amine” of “amine compound” with “phosphine”.

  Preferably as the compound (b), the phenol is pentafluorophenol, pentakis (trifluoromethyl) phenol, pentakis (pentafluorophenyl) phenol, 2,3,5,6-tetrafluoro-4-pentafluorophenylphenol, 2,3,4,5,6,7,8-heptafluoro-1-naphthol or 1,3,4,5,6,7,8-heptafluoro-2-naphthol, amines include bis (penta Fluorophenyl) amine, bis (pentakis (trifluoromethyl) phenyl) amine, bis (pentakis (pentafluorophenyl) phenyl) amine, bis (2,3,5,6-tetrafluoro-4-pentafluorophenylmethyl) amine , (2,3,4,5,6,7,8-heptafluoro-1-na Chill) amine or bis (1,3,4,5,6,7,8- heptafluoro-2-naphthyl) amine.

  More preferably, the compound (b) is pentafluorophenol, 1,3,4,5,6,7,8-heptafluoro-2-naphthol, bis (pentafluorophenyl) amine, or bis (1,3,4). , 5,6,7,8-heptafluoro-2-naphthyl) amine, particularly preferably pentafluorophenol.

  Examples of the compound (c) include water, hydrogen sulfide, amine, and aniline compounds. Examples of the amine include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, isopentylamine, and n-hexyl. Alkylamines such as amine, n-octylamine, n-decylamine, n-dodecylamine, n-pentadecylamine, and n-eicosylamine, aralkylamines such as allylamine, cyclopentadienylamine, and benzylamine, fluoro Methylamine, difluoromethylamine, trifluoromethylamine, 2,2,2-trifluoroethylamine, 2,2,3,3,3-pentafluoropropylamine, 2,2,2-trifluoro-1-trifluoro Methylethylamine, 1,1-bis (trifluoromethyl) -2,2,2-trifluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluoro Mention may be made of dodecylamine, perfluoropentadecylamine and perfluoroeicosylamine and halogenated alkylamines in which the fluoro of these amines has been replaced by chloro, bromo or iodo.

  Examples of the aniline compound of the compound (c) include aniline, naphthylamine, anthracenylamine, 2-tolylamine, 3-tolylamine, 4-tolylamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4-xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6-trimethylaniline, 2,4,6 -Trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline, penta Methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-diethylaline Phosphorus, 2,4-diethylaniline, 2,5-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline, 3,5-diethylaniline, 2,3,4-triethylaniline, 2,3, 5-triethylaniline, 2,3,6-triethylaniline, 2,4,6-triethylaniline, 3,4,5-triethylaniline, 2,3,4,5-tetraethylaniline, 2,3,4,6 -Tetraethylaniline, 2,3,5,6-tetraethylaniline, and pentaethylaniline, and these ethyls as n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, Alkyla substituted with n-hexyl, n-octyl, n-decyl, n-dodecyl, or n-tetradecyl Phosphorus, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline , And halogenated anilines such as pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-di (trifluoromethyl) aniline, 3,5-di (trifluoromethyl) aniline, and 2,4,6-tri (trifluoromethyl) aniline, and (halogenated alkyl) anilines where these fluoros are replaced by chloro, bromo or iodo Can do.

  The compound (c) is preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2, 6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine, perfluoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, Perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoro Oroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3 -(Trifluoromethyl) aniline, 4- (trifluoromethyl) aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline or 2,4,6-tris (tri Fluoromethyl) aniline, particularly preferably water, trifluoromethylamine, perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2, 6-difluoroaniline, 3,5-difluoroa Phosphorus, 2,4,6-trifluoroaniline, 3,4,5-trifluoroaniline, pentafluoroaniline, 2- (trifluoromethyl) aniline, 3- (trifluoromethyl) aniline, 4- (trifluoromethyl) ) Aniline, 2,6-bis (trifluoromethyl) aniline, 3,5-bis (trifluoromethyl) aniline, or 2,4,6-tris (trifluoromethyl) aniline, most preferably water or penta Fluoroaniline.

  The solid particles (d) are not particularly limited as long as they are solid substances that are insoluble in the solvent or polymerization solvent used in the production of the modified particles (A), but those generally used as carriers are preferably used. A porous material having a uniform particle diameter is preferable, an inorganic material or an organic polymer is preferably used, and an inorganic material is more preferably used.

  The solid particles (d) are preferably 2.5 or less, more preferably 2.0 as the volume standard geometric standard deviation of the particle size of the solid particles (d) from the viewpoint of the particle size distribution of the resulting addition polymer. Hereinafter, it is more preferably 1.7 or less.

Examples of the inorganic substance of the solid particles (d) include inorganic oxides, clays, and clay minerals. A mixture of these plural inorganic substances may be used.
Examples of the inorganic oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , and mixtures thereof, SiO ₂ —MgO, SiO. Mention may be made of _2- Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , and SiO ₂ —TiO ₂ —MgO. Among these inorganic oxides, SiO ₂ and / or Al ₂ O ₃ are preferable, and SiO ₂ (that is, silica) is particularly preferable. The inorganic oxide is a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _2. Carbonic acid salts such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

Examples of the clay or clay mineral include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, vylophilite, talc, ummo group, smectite, montmorillonite group, hectorite, laponite, saponite, vermiculite, ryokdeite stone. Group, palygorskite, kaolinite, nacrite, dickite, halloysite.
Among these, preferred are smectite, montmorillonite, hectorite, laponite and saponite, and more preferred are montmorillonite and hectorite.

  Among these inorganic substances, inorganic oxides are preferably used. These inorganic substances are preferably dried and substantially free of moisture, and those dried by heat treatment are preferred. The heat treatment is usually performed at a temperature of 100 to 1500 ° C., preferably 100 to 1000 ° C., more preferably 200 to 800 ° C. for an inorganic substance whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method in which an inert gas (for example, nitrogen or argon) dried during heating is circulated and dried at a constant flow rate, and a method in which heat drying is performed under reduced pressure. Can do.

  In addition, a hydroxyl group is usually generated and present on the surface of the inorganic oxide, but as the inorganic oxide, modified inorganic oxides in which active hydrogen of the surface hydroxyl group is substituted with various substituents may be used. . Examples of the modified inorganic oxide include trialkylchlorosilanes such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilanes such as triphenylchlorosilane, dialkyldichlorosilanes such as dimethyldichlorosilane, and diaryldichlorosilanes such as diphenyldichlorosilane. Alkyltrichlorosilanes such as methyltrichlorosilane, aryltrichlorosilanes such as phenyltrichlorosilane, trialkylalkoxysilanes such as trimethylmethoxysilane, triarylalkoxysilanes such as triphenylmethoxysilane, and dialkyldialkoxysilanes such as dimethyldimethoxysilane , Diaryl dialkoxysilanes such as diphenyldimethoxysilane, and alkyls such as methyltrimethoxysilane Aryltrialkoxysilanes such as trialkoxysilane, phenyltrimethoxysilane, tetraalkoxysilanes such as tetramethoxysilane, alkyldisilazanes such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, methanol And inorganic oxides obtained by contact treatment with alcohols such as ethanol, phenols, dibutylmagnesium, butylethylmagnesium, dialkylmagnesiums such as butyloctylmagnesium, and alkyllithiums such as butyllithium.

  Furthermore, after contact with trialkylaluminum, inorganic oxides contacted with dialkylamines such as diethylamine and diphenylamine, alcohols such as methanol and ethanol, and phenol can be exemplified.

  In addition, the strength of the inorganic oxide itself may increase due to hydrogen bonding between hydroxyl groups. In that case, if all the active hydrogens of the surface hydroxyl group are substituted with various substituents, the particle strength may be lowered. Therefore, it is not always necessary to substitute all the active hydrogens on the surface hydroxyl groups of the inorganic oxide, and the substitution rate of the surface hydroxyl groups may be determined as appropriate. The method for changing the substitution rate of the surface hydroxyl group is not particularly limited. Examples of the method include a method of changing the amount of the compound used for the contact treatment.

Although the average particle diameter of an inorganic substance is not specifically limited, Usually, it is 1-5000 micrometers, Preferably, it is 5-1000 micrometers, More preferably, it is 10-500 micrometers, More preferably, it is 10-100 micrometers. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 to 10 ml / g. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 100 to 500 m ² / g.

  Any organic polymer may be used as the organic polymer of the solid particles (d), and a mixture of a plurality of types of organic polymers may be used. The organic polymer is preferably a polymer having a functional group having active hydrogen or a non-proton-donating Lewis basic functional group.

  The functional group having active hydrogen is not particularly limited as long as it has active hydrogen. Examples of the functional group include a primary amino group, secondary amino group, imino group, amide group, hydrazide group, amidino group, hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, Mention may be made of sulfinic acid groups, sulfenic acid groups, thiol groups, thioformyl groups, pyrrolyl groups, imidazolyl groups, piperidyl groups, indazolyl groups and carbazolyl groups. Among them, preferred is a primary amino group, a secondary amino group, an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group, or a thiol group, and particularly preferred is a primary amino group. Group, secondary amino group, amide group or hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The non-proton donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base portion having no active hydrogen atom. Examples of the functional group include a pyridyl group, an N-substituted imidazolyl group, an N-substituted indazolyl group, a nitrile group, an azide group, an N-substituted imino group, an N, N-substituted amino group, and an N, N-substituted aminooxy group. Group, N, N, N-substituted hydrazino group, nitroso group, nitro group, nitrooxy group, furyl group, carbonyl group, thiocarbonyl group, alkoxy group, alkyloxycarbonyl group, N, N-substituted carbamoyl group, thioalkoxy group , Substituted sulfinyl groups, substituted sulfonyl groups, and substituted sulfonic acid groups. Preferred is a heterocyclic group, and more preferred is an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

  The content of the functional group having active hydrogen or the non-proton donating Lewis basic functional group in the polymer as the organic polymer is not particularly limited. The amount used is preferably 0.01 to 50 mmol / g, more preferably 0.1 to 20 mmol / g as the molar amount of the functional group per unit gram of the polymer.

  Examples of the method for producing a polymer having the functional group include homopolymerization of a monomer having a functional group having active hydrogen or a non-proton donating Lewis basic functional group and one or more polymerizable unsaturated groups. And a method of copolymerizing the monomer with another monomer having a polymerizable unsaturated group. At this time, it is preferable to copolymerize together a crosslinkable monomer having two or more polymerizable unsaturated groups.

Examples of the polymerizable unsaturated group include alkenyl groups such as a vinyl group and an allyl group, and alkynyl groups such as an ethyne group.
Examples of the monomer having a functional group having active hydrogen and one or more polymerizable unsaturated groups include a vinyl group-containing primary amine, a vinyl group-containing secondary amine, a vinyl group-containing amide compound, and a vinyl group-containing compound. Mention may be made of hydroxy compounds. Specific examples of the monomer include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methyl. Amine, 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-butene-1- Oars.
Examples of the monomer having a functional group having a Lewis base having no active hydrogen atom and one or more polymerizable unsaturated groups include vinyl pyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted). ) Indazole can be mentioned.

Examples of the other monomer having a polymerizable unsaturated group include ethylene, α-olefin, aromatic vinyl compound and cyclic olefin compound. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, styrene, norbornene, and dicyclopentadiene. Of these, ethylene or styrene is preferable. Two or more of these monomers may be used.
Specific examples of the crosslinking polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene.

Although it does not specifically limit as an average particle diameter of an organic polymer, Usually, it is 1-5000 micrometers, Preferably it is 5-1000 micrometers, More preferably, it is 10-500 micrometers. Although it does not specifically limit as pore volume, Preferably it is 0.1 ml / g or more, More preferably, it is 0.3-10 ml / g. Although it does not specifically limit as a specific surface area, Preferably it is 10-1000 m < ² > / g, More preferably, it is 50-500 m < ² > / g.

  These organic polymers are preferably dried and substantially free of moisture, and those dried by heat treatment are preferred. The heat treatment is usually carried out at a temperature of 30 to 400 ° C., preferably 50 to 200 ° C., more preferably 70 to 150 ° C. for an organic polymer whose moisture cannot be visually confirmed. The heating time is not particularly limited, but is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Examples of the heat drying method include a method in which a dried inert gas (for example, nitrogen or argon) is circulated and dried at a constant flow rate during heating, and a method in which heat drying is performed under reduced pressure. be able to.

In order to obtain the modified particles (B) of the present invention, the order in which the above components (a), (b), (c) and (d) are contacted is not particularly limited. The following order can be given.
<1> A contact object obtained by contacting (a) and (b) with (c) and a contact object obtained by bringing (c) into contact with each other.
<2> A contact object obtained by bringing (a) and (b) into contact with each other and a contact object obtained by bringing (d) into contact with each other.
<3> A contact object obtained by bringing (a) and (c) a contact object into contact with (b) is brought into contact with (d).
<4> A contact object obtained by bringing (a) and (c) into contact with each other and (d) in contact with (b).
<5> A contact product obtained by contacting (b) with a contact product between (a) and (d) and (c) are brought into contact with each other.
<6> A contact object obtained by bringing (a) and (d) into contact with (c) and a contact object obtained by bringing (c) into contact with each other.
<7> A contact object obtained by bringing (b) and (c) into contact with each other and a contact object obtained by bringing (a) into contact with each other.
<8> A contact product obtained by contacting (b) with the contact product between (b) and (c) and (a) are brought into contact with each other.
<9> A contact product obtained by contacting (b) with the contact product between (b) and (d) and (c) are brought into contact with each other.
<10> The contact product obtained by bringing (b) and (d) into contact with each other and (c) with the contact product are brought into contact with each other.
<11> A contact object obtained by contacting (a) with a contact object between (c) and (d) and (b) are brought into contact with each other.
<12> A contact product obtained by contacting (b) with a contact product between (c) and (d) and (a) are contacted.
The contact order is preferably <1>, <2>, <3>, <5>, <11> or <12>. Particularly preferred is <2> or <5>.

  Such contact treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Such treatment may use a solvent, or may directly contact these compounds without using a solvent.

  As a solvent, the solvent which does not react with the said component (a), (b), (c), (d), and those contacts is used. However, as described above, when each component is brought into contact in stages, even if the solvent reacts with a certain component at a certain stage, if the solvent does not react with each component at another stage, The solvent can be used in other stages. That is, the solvents in each stage are the same or different from each other. Examples of the solvent include nonpolar solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, and halide solvents, ether solvents, alcohol solvents, phenol solvents, carbonyl solvents, phosphoric acid derivatives, Examples include polar solvents such as nitrile solvents, nitro compounds, amine solvents, and sulfur compounds. Specific examples include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, 2,2,4-trimethylpentane, and cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, dichloromethane, Such as difluoromethane, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, bromobenzene, and o-dichlorobenzene Halide solvent, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl-ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, Ether solvents such as trahydrofuran and tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclo Hexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, alcohol solvents such as glycerin, phenol solvents such as phenol and p-cresol, acetone, ethylmethyl Ketones, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl Carbonyl solvents such as 2-pyrrolidone, phosphoric acid derivatives such as hexamethylphosphoric triamide and triethyl phosphate, nitrile solvents such as acetonitrile, propionitrile, succinonitrile, and benzonitrile, nitro such as nitromethane and nitrobenzene Examples include compounds, amine solvents such as pyridine, piperidine, and morpholine, and sulfur compounds such as dimethyl sulfoxide and sulfolane.

  When contacting the contact product (e) obtained by contacting the components (a), (b) and (c) with the solid particles (d), that is, the above <1>, <3>, <7 In each of the methods, the solvent (s1) in the case of producing the contact product (e) is preferably the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent or ether solvent.

On the other hand, a polar solvent is preferable as the solvent (s2) when the contact product (e) and the solid particles (d) are contacted. As an index representing the polarity of the solvent, E _T ^N value (C.Reichardt, "Solvents and Solvents Effects in Organic Chemistry", 2nd ed., VCH Verlag (1988).) And the like are known, 0.8 ≧ A solvent satisfying the range of E _T ^N ≧ 0.1 is particularly preferable. Examples of the polar solvent include dichloromethane, dichlorodifluoromethane chloroform, 1,2-dichloroethane, 1,2-dibromoethane, 1,1,2-trichloro-1,2,2-trifluoroethane, tetrachloroethylene, chlorobenzene, Bromobenzene, o-dichlorobenzene, dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol Cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol, triethylene glycol, acetone, ethyl methyl ketone, cyclohexanone, acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromethane, nitrobenzene, Mention may be made of ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide and sulfolane. More preferably, the solvent (s2) is dimethyl ether, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl-tert-butyl ether, anisole, 1,4-dioxane, 1,2-dimethoxyethane, bis (2-methoxyethyl). ) Ether, tetrahydrofuran, tetrahydropyran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol, cyclohexanol, benzyl alcohol, Ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol or triethylene glycol, particularly preferably di-n-butyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 3-methyl-1-butanol or cyclohexanol And most preferably tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.

Moreover, as said solvent (s2), the mixed solvent of these polar solvents and hydrocarbon solvents can also be used. As the hydrocarbon solvent, the aliphatic hydrocarbon solvent and aromatic hydrocarbon solvent exemplified above are used. Examples of the mixed solvent of the polar solvent and the hydrocarbon solvent include hexane / methanol mixed solvent, hexane / ethanol mixed solvent, hexane / 1-propanol mixed solvent, hexane / 2-propanol mixed solvent, heptane / methanol mixed solvent, heptane. / Ethanol mixed solvent, heptane / 1-propanol mixed solvent, heptane / 2-propanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, toluene / 1-propanol mixed solvent, toluene / 2-propanol mixed solvent, xylene And xylene / ethanol mixed solvent, xylene / 1-propanol mixed solvent, and xylene / 2-propanol mixed solvent. Preferably in hexane / methanol mixed solvent, hexane / ethanol mixed solvent, heptane / methanol mixed solvent, heptane / ethanol mixed solvent, toluene / methanol mixed solvent, toluene / ethanol mixed solvent, xylene / methanol mixed solvent, xylene / ethanol mixed solvent is there. More preferred are a hexane / methanol mixed solvent, a hexane / ethanol mixed solvent, a toluene / methanol mixed solvent or a toluene / ethanol mixed solvent. Most preferred is a toluene / ethanol mixed solvent.
The preferable range of the ethanol fraction in the toluene / ethanol mixed solvent is 10 to 50% by volume, more preferably 15 to 30% by volume.

  A method of contacting the contact product (e) obtained by contacting the components (a), (b) and (c) with (d), that is, <1>, <3> and <7> above In each method, a hydrocarbon solvent can be used as both the solvent (s1) and the solvent (s2). In this case, after the components (a), (b) and (c) are contacted, it is preferable that the time until the obtained contact product (e) and the solid particles (d) are contacted is short. The time is preferably 0 to 5 hours, more preferably 0 to 3 hours, and most preferably 0 to 1 hour. The temperature when the contact product (e) and the solid particles (d) are contacted is usually −100 ° C. to 40 ° C., preferably −20 ° C. to 20 ° C., and most preferably −10 ° C. -10 ° C.

  In the case of <2>, <5>, <6>, <8>, <9>, <10>, <11>, <12> above, any of the above nonpolar solvents and polar solvents may be used. it can. Preferably, it is a nonpolar solvent. This is because the contact product of (a) and (c) and the contact product of (a) and (b) and the contact product of (c) are generally dissolved in a nonpolar solvent. This is because it is considered that the contact product produced is deposited on the surface of (d) and is more easily immobilized when (d) is present in the reaction system when these contact products are formed. is there.

About the usage-amount of the said compound (a), (b), and (c), the molar ratio of the usage-amount of the compound (a), (b), (c) used for a contact is set to (a) :( b) :( c ) = 1: When y: z, y and z satisfy the following formulas (i) and (ii).
0.6 ≦ y ≦ 1.0 (i)
−0.625y + 1.275 ≦ z ≦ −0.875y + 1.625 (ii)
(In the above formulas (i) and (ii), m represents a number corresponding to the valence of M ¹ of component (a).)
The molar ratio y of the usage amount of the compound (b) with respect to the usage amount of the compound (a) and the molar ratio z of the usage amount of the compound (c) with respect to the usage amount of the component (a) are expressed by the above formulas (i) and (ii). There are no particular restrictions as long as you are satisfied. When the value of y does not satisfy the relational expression (i), an addition polymer having a higher molecular weight cannot be obtained under the polymerization conditions where the hydrogen concentration is the object of the present invention. When the value of z is smaller than the range represented by the relational expression (ii), the polymerization activity is lowered, while when the value of z is larger than the range represented by the relational expression (ii), it is an object of the present invention. In addition, a higher molecular weight addition polymer cannot be obtained under higher polymerization conditions.

  The amount of the compound (a) and the solid particles (d) used is such that the typical metal atoms derived from the compound (a) contained in the modified particles (A) are converted to the moles of typical metal atoms contained in 1 g of the obtained particles. The amount is preferably 0.05 mmol or more, more preferably 0.1 to 20 mmol.

  In order to make the reaction proceed faster, it is preferable to add a heating step at a higher temperature after the contact treatment as described above. In the heating step, it is preferable to use a solvent having a high boiling point in order to obtain a higher temperature. In performing the heating step, the solvent used in the contact step may be replaced with another solvent having a higher boiling point.

  In the modified particles (A) of the present invention, as a result of such contact treatment, the starting compounds (a), (b), (c) and / or (d) remain as unreacted substances. May be. However, it is preferable to perform a washing process for removing unreacted substances in advance. The solvent at that time may be the same as or different from the solvent at the time of contact. Such cleaning treatment is preferably carried out in an inert gas atmosphere. The treatment temperature is usually −100 to 300 ° C., preferably −80 to 200 ° C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.

  Further, after such contact treatment or washing treatment, it is preferable to distill off the solvent from the product, and then to dry under reduced pressure for 1 to 24 hours at a temperature of 0 ° C. or higher. More preferably, it is 1 hour to 24 hours at a temperature of 0 ° C. to 200 ° C., more preferably 1 hour to 24 hours at a temperature of 10 ° C. to 200 ° C., particularly preferably 2 at a temperature of 10 ° C. to 160 ° C. Time to 18 hours, most preferably 4 to 18 hours at a temperature of 15 ° C to 160 ° C.

Specific examples of the method for producing modified particles of the present invention are as follows: M ¹ is a zinc atom, compound (b) is 3,4,5-trifluorophenol, compound (c) is water, The case where the particles (d) are silica is shown in more detail below. Tetrahydrofuran is used as a solvent, and a hexane solution of diethylzinc is added thereto, followed by cooling to 3 ° C., and an equimolar amount of 3,4,5-trifluorophenol is added dropwise thereto relative to diethylzinc for 10 minutes at room temperature. After stirring for 24 hours, 0.75-fold molar amount of water is further added dropwise to diethyl zinc, and the mixture is stirred at room temperature for 10 minutes to 24 hours. Thereafter, the solvent is distilled off, followed by drying at 120 ° C. under reduced pressure for 8 hours. Tetrahydrofuran and silica are added to the solid component obtained by the above operation, and the mixture is stirred at 40 ° C. for 2 hours. The solid component is washed with tetrahydrofuran and then dried at 120 ° C. under reduced pressure for 8 hours. Thus, the modified particles of the present invention can be produced.

  The transition metal compound (B) used in the addition polymerization catalyst of the present invention is added by using it together with the modified particles (A) described below (or further together with the organoaluminum compound (C)). Although it will not specifically limit if it is a transition metal compound which shows polymerization activity, Usually, the transition metal compound which forms a single site catalyst is used. The single-site catalyst in the present invention is a catalyst that is distinguished from conventional solid catalysts, and includes not only a single-site catalyst in a narrow sense that can produce an addition polymer with a narrow molecular weight distribution and high homogeneity, but also a single site in a narrow sense. It also means a catalyst which can be produced by a production method similar to the catalyst and which can produce an addition polymer having a broad molecular weight distribution and low homogeneity.

As the transition metal compound (B), a transition metal compound of Group 3 to 11 of the Periodic Table of the Elements or a lanthanoid series is usually used, and a transition metal compound represented by the following formula [4] or a μ-oxo type thereof is used. Dimers of transition metal compounds are preferred.
L ² _a M ² X ¹ _b [4]
(Wherein M ² represents a transition metal atom of Group 3 to 11 of the Periodic Table of Elements or a lanthanoid series. L ² represents a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of L ² may be linked directly to each other, or may be linked via a residue containing a carbon atom, silicon atom, nitrogen atom, oxygen atom, sulfur atom or phosphorus atom, X ¹ is a halogen atom, carbonized Represents a hydrogen group (excluding a group having a cyclopentadiene-type anion skeleton) or a hydrocarbon oxy group, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8. Represents.)

As M ^{2 in the} formula [4], for example, scandium atom, yttrium atom, titanium atom, zirconium atom, hafnium atom, vanadium atom, niobium atom, tantalum atom, chromium atom, iron atom, ruthenium atom, cobalt atom, rhodium atom Nickel atom, palladium atom, samarium atom, ytterbium atom and the like. Among them, preferred is a titanium atom, zirconium atom, hafnium atom, vanadium atom, chromium atom, iron atom, cobalt atom or nickel atom, more preferred is a titanium atom, zirconium atom or hafnium atom, and particularly preferred is a zirconium atom. It is.

Examples of the group having a cyclopentadiene-type anion skeleton of L ^{2 in} the formula [4] include (substituted) cyclopentadienyl group, (substituted) indenyl group, and (substituted) fluorenyl group. Specifically, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, tert-butylcyclopentadienyl group, 1,2-dimethylcyclopenta Dienyl group, 1,3-dimethylcyclopentadienyl group, 1-methyl-2-ethylcyclopentadienyl group, 1-methyl-3-ethylcyclopentadienyl group, 1-tert-butyl-2-methyl Cyclopentadienyl group, 1-tert-butyl-3-methylcyclopentadienyl group, 1-methyl-2-isopropylcyclopentadienyl group, 1-methyl-3-isopropylcyclopentadienyl group, 1-methyl -2-n-butylcyclopentadienyl group, 1-methyl -3-n-butylcyclopentadienyl group, eta ⁵ -1 2,3-trimethyl cyclopentadienyl group, eta ^{5-1,2,4-trimethyl} cyclopentadienyl group, tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, indenyl group, 4,5, 6,7-tetrahydroindenyl group, 2-methylindenyl group, 3-methylindenyl group, 4-methylindenyl group, 5-methylindenyl group, 6-methylindenyl group, 7-methylindenyl group 2-tert-butylindenyl group, 3-tert-butylindenyl group, 4-tert-butylindenyl group, 5-tert-butylindenyl group, 6-tert-butylindenyl group, 7-tert- Butyl indenyl group, 2,3-dimethyl indenyl group, 4,7-dimethyl indenyl group, 2,4,7-trimethyl indenyl group, -Methyl-4-isopropylindenyl group, 4,5-benzindenyl group, 2-methyl-4,5-benzindenyl group, 4-phenylindenyl group, 2-methyl-5-phenylindenyl group, 2-methyl- Examples thereof include 4-phenylindenyl group, 2-methyl-4-naphthylindenyl group, fluorenyl group, 2,7-dimethylfluorenyl group and 2,7-di-tert-butylfluorenyl group. .

The polydentate η of the group having a cyclopentadiene type anion skeleton used for L ² in the above formula [4] is not particularly limited, and may be any value that can be taken by the group having a cyclopentadiene type anion skeleton. For example, 5 seats, 4 seats, 3 seats, 2 seats and single seats are mentioned, preferably 5 seats, 3 seats or single seats, more preferably 5 seats or 3 seats.

Examples of the hetero atom in the group containing the L ² hetero atom in the formula [4] include an oxygen atom, a sulfur atom, a nitrogen atom and a phosphorus atom. Examples of such a group include an alkoxy group and an aryloxy group. , A thioalkoxy group, a thioaryloxy group, an alkylamino group, an arylamino group, an alkylphosphino group, an arylphosphino group, a chelating ligand, or a ring of oxygen, sulfur, nitrogen and / or phosphorus atoms An aromatic heterocyclic group or an aliphatic heterocyclic group is preferable.

Examples of the group containing a hetero atom of L ² in the formula [4] include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a 2-methylphenoxy group, a 2,6-dimethylphenoxy group, 2, 4,6-trimethylphenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6-diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group Group, 2,6-di-sec-butylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2,6-di-tert-butylphenoxy group, 4-methoxyphenoxy group, 2,6-dimethoxyphenoxy group Group, 3,5-dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group 4-nitrophenoxy group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothiophenoxy group, 2,3,6-trichlorophenoxy group, 2,4,6-trifluorophenoxy group, thiomethoxy group, Dimethylamino group, diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catechol, Resorcinol, 4-isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-biphenyldiol group, 1,1′-bi-2-naphthol group, 2,2′-dihydroxy-6,6′-dimethylbiphenyl group, 4,4 ′, 6 6'-tetra -tert- butyl 2,2 'methylenedianiline phenoxy group, and 4,4', mention may be made of 6,6'-tetramethyl-2,2'-isobutenyl dust Denji phenoxy group.

Moreover, as group containing the said hetero atom, group represented by following formula [5] can also be mentioned, for example.
R ³ ₃ P = N− [5]
(In the formula, each R ³ independently represents a hydrogen atom, a halogen atom or a hydrocarbon group, and the plurality of R ³ may be the same or different from each other, and any two of the plurality of R ³ may be selected. The above may be bonded to each other and may form a ring structure.)

Specific examples of R ³ in the formula [5] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert- Examples thereof include a butyl group, a cyclopropyl group, a cyclobutyl group, a cycloheptyl group, a cyclohexyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a benzyl group.

（式中、Ｒ⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭化水素基、ハロゲン化炭化水素基、炭化水素オキシ基、シリル基またはアミノ基を表し、複数のＲ⁴は互いに同じであっても異なっていてもよく、複数のＲ⁴のうち、任意の２つ以上が互いに結合していてもよく、環構造を形成していてもよい。） Further, examples of the group containing a heteroatom include a group represented by the following formula [6].

(In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon oxy group, a silyl group or an amino group, and the plurality of R ⁴ are the same as each other. And any two or more of R ⁴ may be bonded to each other and may form a ring structure.)

Specific examples of R ⁴ in the above formula [6] include hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl group, 1-naphthyl group, 2-naphthyl group, tert-butyl group, 2,6- Dimethylphenyl group, 2-fluorenyl group, 2-methylphenyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-pyridyl group, cyclohexyl group, 2-isopropylphenyl group, benzyl group, methyl group, triethyl Examples thereof include silyl group, diphenylmethylsilyl group, 1-methyl-1-phenylethyl group, 1,1-dimethylpropyl group, 2-chlorophenyl group, and pentafluorophenyl group.

The chelating ligand of L ² in the formula [4] refers to a ligand having a plurality of coordination sites. Examples of the ligand include acetylacetonate, diimine, oxazoline, bisoxazoline, Mention may be made of terpyridine, acyl hydrazones, diethylenetriamine, triethylenetetramine, porphyrin, crown ether, and cryptate.

Examples of the heterocyclic group represented by L ² in the formula [4] include a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and among them, a pyridyl group is preferable.

In the formula [4], when a plurality of L ² are linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom (that is, a cyclopentadiene anion When a group having a skeleton is linked through the residue, a group containing a hetero atom is linked through the residue, or a group having a cyclopentadiene anion skeleton and a hetero atom If the group containing is connected through the said residues), as preferably the residues, two L ² and the atoms connecting the carbon atom, silicon atom, nitrogen atom, oxygen, sulfur or It is a phosphorus atom and is a divalent residue having a minimum atomic number of 3 or less for bonding two L ² . Examples of the residue include alkylene groups such as methylene group, ethylene group and propylene group; substituted alkylene groups such as dimethylmethylene group (isopropylidene group) and diphenylmethylene group; silylene group, dimethylsilylene group, diethylsilylene group and diphenylsilylene group. And substituted silylene groups such as tetramethyldisilylene group and dimethoxysilylene group; and heteroatoms such as nitrogen atom, oxygen atom, sulfur atom and phosphorus atom. Among these, a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), a diphenylmethylene group, a dimethylsilylene group, a diethylsilylene group, a diphenylsilylene group, or a dimethoxysilylene group is particularly preferable.

Examples of the halogen atom represented by X ¹ in the formula [4] include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group for X ¹ include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. Among them, an alkyl group having 1 to 20 carbon atoms, preferably 7 to 7 carbon atoms is preferable. A aralkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkenyl group having 3 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, and n-pentyl group. , Neopentyl group, amyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, and n-eicosyl group, and more preferably methyl. Group, ethyl group, isopropyl group, tert-butyl group, isobutyl group or amyl group.
Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, and a perfluorobutyl group. Mention may be made of fluorohexyl, perfluorooctyl, perchloropropyl, perchlorobutyl and perbromopropyl groups.
These alkyl groups may be substituted with an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, and (2,3-dimethyl). (Phenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, 3,5-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, , 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, naphthylmethyl group, and anthracenylmethyl group More preferably, it is a benzyl group.
These aralkyl groups include 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 substituted.

Examples of the aryl group having 6 to 20 carbon atoms include 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, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butyl Enyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl, and anthracenyl Group, and more preferably a phenyl group.
These aryl groups are fluorine atoms, chlorine atoms, bromine atoms, halogen atoms such as iodine atoms, alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

  Examples of the alkenyl group having 3 to 20 carbon atoms include an allyl group, a methallyl group, a crotyl group, and a 1,3-diphenyl-2-propenyl group, and more preferably an allyl group or a methallyl group. It is.

Examples of the hydrocarbon oxy group represented by X ¹ in the general formula [4] include an alkoxy group, an aralkyloxy group, and an aryloxy group. Among these, an alkoxy group having 1 to 20 carbon atoms is preferable, An aralkyloxy group having 7 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.

Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, and neopentoxy. Group, n-hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadesoxy group, and n-icosoxy group, and among them, preferably methoxy group, ethoxy group, isopropoxy group, or tert. -Butoxy group.
These alkoxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

Examples of the aralkyloxy group having 7 to 20 carbon atoms include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3 -Dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2,6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group , (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) methoxy group, (2,3,6-trimethylphenyl) methoxy group , (2,4,5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethyl) Ruphenyl) 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, naphthylmethoxy group, and anthracenylmethoxy group Among them, a benzyloxy group is more preferable.
These aralkyloxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,3-dimethylphenoxy group, and 2,4-dimethylphenoxy group. Group, 2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert- Butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group, 2-tert-butyl-6-methylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy Group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethyl Ruphenoxy group, 2-tert-butyl-3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6- Di-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,4,5-trimethylphenoxy group Group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl- 3,4,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,4-dimethylphenoxy group, 2,3,5,6-tetramethylphenoxy group Group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-di-tert-butyl-3,5-dimethylphenoxy 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 And anthracenoxy group.
These aryloxy groups include fluorine atoms, chlorine atoms, halogen atoms such as bromine atoms and iodine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups, and aralkyloxy groups such as benzyloxy groups. May be substituted.

X ¹ in the formula [4] is more preferably a chlorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n -Butoxy group, trifluoromethoxy group, phenyl group, phenoxy group, 2,6-di-tert-butylphenoxy group, 3,4,5-trifluorophenoxy group, pentafluorophenoxy group, 2,3,5,6 -Tetrafluoro-4-pentafluorophenylphenoxy group or benzyl group.

In the formula [4], a is a number satisfying 0 <a ≦ 8, b is a number satisfying 0 <b ≦ 8, and is appropriately selected according to the valence of M ² . When M ² is a titanium atom, a zirconium atom or a hafnium atom, a is preferably 2, and b is also preferably 2.

  Examples of the compound represented by the formula [4] in which the transition metal atom is a titanium atom, a zirconium atom or a hafnium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, Bis (ethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dichloride, bis (tert-butylcyclopentadienyl) titanium dichloride, bis (1,2-dimethylcyclopentadienyl) titanium Dichloride, bis (1,3-dimethylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-ethylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) titanium dichloride , Screw (1 Methyl-2-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) titanium dichloride, bis (1-methyl-2-isopropylcyclopentadienyl) titanium dichloride Bis (1-methyl-3-isopropylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-2-methylcyclopentadienyl) titanium dichloride, bis (1-tert-butyl-3-methylcyclopenta) Dienyl) titanium dichloride, bis (1,2,3-trimethylcyclopentadienyl) titanium dichloride, bis (1,2,4-trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) titanium Dichloride, bis (pentameth Lucyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, bis (2-phenylindenyl) titanium dichloride ,

Bis [2- (bis-3,5-trifluoromethylphenyl) indenyl] titanium dichloride, bis [2- (4-tert-butylphenyl) indenyl] titanium dichloride, bis [2- (4-trifluoromethylphenyl) Indenyl] titanium dichloride, bis [2- (4-methylphenyl) indenyl] titanium dichloride, bis [2- (3,5-dimethylphenyl) indenyl] titanium dichloride, bis [2- (pentafluorophenyl) indenyl] titanium dichloride , Cyclopentadienyl (pentamethylcyclopentadienyl) titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride , Pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) titanium dichloride, cyclopentadienyl (2-phenylindenyl) titanium dichloride, pentamethylcyclopentadienyl (2-phenylindene) Nil) titanium dichloride,

Dimethylsilylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2-n- Butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4 -Dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,4-dimethylcyclopentadienyl) Titanium dichloride, dimethylsilylene bis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,5-ethylmethylcyclo) Pentadienyl) titanium dichloride, dimethylsilylene bis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (2, 3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylene bis (tetramethylcyclopentadienyl) titanium dichloride,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, dimethylsilylenebis (2-tert-butylindenyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylindenyl) titanium Dichloride, dimethylsilylene bis (2,4,7-trimethylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-isopropylindenyl) titanium dichloride, dimethylsilylene bis (4,5-benzindenyl) titanium dichloride, dimethyl Silylene bis (2-methyl-4,5-benzindenyl) titanium dichloride, dimethylsilylene bis (2-phenylindenyl) titanium dichloride, dimethylsilylene bis (4-phenyl) Indenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-5-phenylindenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-naphthyl) Indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (tetra Methylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, dimethylsilyl (Indenyl) (fluorenyl) titanium dichloride, dimethylsilylenebis (fluorenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (fluorenyl) ) Titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamido) titanium dichloride, cyclopentadienyl (phenoxy) titanium dichloride, cyclopentadienyl (2,6-dimethylphenyl) ) Titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-tert-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethyl) Phenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-tert-butylphenyl) thi Njikuroraido, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl -2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2) -Phenoxy Titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-chloro-) 2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride Id, dimethylsilylene (cyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3 5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) 5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methyl) Cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilyl Down (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (1-naphthoxy-2-yl) 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- Tilcyclopentadienyl) (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-butylcyclopentadienyl) ( 3,5-diamil- -Phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (1-naphthoxy-2-yl) 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 Chloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5) -Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (tert-butylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (1-naphthoxy-2-yl) 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 dichloride, dimethyl Len (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, dimethylsilylene (tetramethylcyclopentadieni) ) (3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (1- Naphthoxy-2-yl) 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 Chloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2) -Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy) -2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethyl Lucylylene (trimethylsilylcyclopentadienyl) (3,5-diamil-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadi) Enyl) (1-naphthoxy-2-yl) 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 (indenyl) (3-tert-butyl) Rudimethylsilyl-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 (indenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (1-naphthoxy-2-yl) 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, dimethylsilylene (fluorenyl) ( -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-diamil-2-phenoxy) ) Titanium dichloride, dimethylsilylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (1-naphthoxy-2-yl) titanium dichloride,

(Tert-Butylamide) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl- 1,2-ethanediyl titanium dichloride,
(Tert-Butylamide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert- Butylamido) indenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyltitanium dichloride, (tert- Butylamido) indenyldimethylsilane titanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilane titanium dichloride (Tert- butylamido) fluorenyl dimethylsilane titanium dichloride,

(Dimethylaminomethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyl titanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyl titanium (III) dichloride (N-pyrrolidinylethyl) tetramethylcyclopentadienyl titanium dichloride, (B-dimethylaminoborabenzene) cyclopentadienyl titanium dichloride, cyclopentadienyl (9-mesitylboraanthracenyl) titanium dichloride,

2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride, 2,2′-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2′- Thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2'-thiobis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl-6-tert-butylphenoxy) ) Titanium dichloride, 2,2'-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2, 2 ′-(4,4 ′, 6,6′-tetra-tert-butyl-1,1 ′ biphenol Shi) titanium dichloride, (di -tert- butyl-1,3-propane diamide) titanium dichloride, (dicyclohexyl-1,3-propane diamide) titanium dichloride,

[Bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl) -1,3 -Propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-di-tert-butylphenyl) -1,3-propanediamide] Titanium dichloride, [bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [hydrotris (3,5 Dimethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium trichloride, [tris (3 5-dimethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, and [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, and these A compound in which titanium in the compound of the above is replaced with zirconium or hafnium, (2-phenoxy) is replaced with (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl-2) -Fenoki ), A compound in which dimethylsilylene is replaced with methylene, ethylene, dimethylmethylene (isopropylidene), diphenylmethylene, diethylsilylene, diphenylsilylene, or dimethoxysilylene, dichloride is difluoride, dibromide, diiodide, dimethyl, diethyl, Compounds in which diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di (n-propoxide), di (isopropoxide), diphenoxide, or di (pentafluorophenoxide) are substituted, and trichloride is trifluoride, tribromide, Triiodide, trimethyl, triethyl, triisopropyl, triphenyl, tribenzyl, trimethoxide, triethoxide, tri (n-propoxy Sid), tri (isopropoxide), triphenoxide, or tri (pentafluorophenoxide).

  Examples of the compound represented by the formula [4] in which the transition metal atom is a nickel atom include 2,2′-methylenebis [(4R) -4-phenyl-5,5′-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-di-n -Propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diisopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl- 5,5′-dicyclohexyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′- Methoxyoxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diethoxyoxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl- 5,5′-diphenyloxazoline] nickel dibromide,

2,2′-methylenebis [(4R) -4-methyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5, 5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2 , 2′-methylenebis [(4R) -4-methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-methyl-5,5 -Di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-methyl-5,5-di- (4-methoxyphenyl) Xazoline] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4 -Methyloxazoline-5,1'-cyclopentane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-methyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di-n-propyloxazoline], 2,2′-methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5- Diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4- Sopropyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) o Oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isopropyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2 '-Methylenebis [(4R) -4-isobutyl-5,5-diethyloxazoline] Ckell dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl- 5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)- 4-isobutyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2, 2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxa Phosphorus] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) — 4-isobutyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methoxyphenyl) oxazoline ] Nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-diethyloxazo ] Nickel dibromide, 2,2'-methylenebis [(4R) -4--4-tert-butyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2, 2'-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- ( 2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl -5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4-methylphenyl) oxazoline ] Nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-tert-butyl-5,5-di- (4 -Methoxyphenyl) oxazoline] nickel dibromide,

2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyl Oxazoline-5,1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2 '-Methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2′-methylenebis [(4R) -4-phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-fur Nyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-phenyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-diethyloxazoline] nickel dibromide Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5 -Di-isopropyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl -5,5-diphenyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzene Dil-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel Dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl -5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel di Bromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide Ido,

2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5, 1′-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro { (4R) -4-benzyloxazoline-5,1′-cycloheptane}] nickel dibromide, and the enantiomers of the above compounds, the asymmetric carbon configuration of one oxazoline ring of the bisoxazoline type compound is reversed. As well as dibromide, dichloride, diiodide, dimethide Can diethyl, diisopropyl, diphenyl, dibenzyl, dimethoxide, diethoxide, di -n- propoxide, diisopropoxide, diphenoxide or compounds obtained by replacing the di (pentafluorophenyl phenoxide), and the like.

（式中、Ｒ⁵ とＲ⁶ はいずれも２，６−ジイソプロピルフェニル基を表し、Ｒ⁷ およびＲ⁸ はそれぞれ独立に水素原子またはメチル基あるいはＲ⁷ とＲ⁸ とが互いに結合したアセナフテン基を表し、Ｘ² はそれぞれ独立に、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、フェニル基、ベンジル基、メトキシ基、エトキシ基、またはフェノキシ基を表す。）
また、上記のニッケル化合物において、ニッケルをパラジウム、コバルト、ロジウム、またはルテニウムに置き換えた化合物も同様に例示することができる。 Examples of the compound represented by the formula [4] in which the transition metal atom is a nickel atom include compounds represented by the following structural formula.

(In the formula, R ⁵ and R ⁶ are both 2,6-diisopropylphenyl groups, and R ⁷ and R ⁸ are each independently a hydrogen atom or a methyl group or an acenaphthene group in which R ⁷ and R ⁸ are bonded to each other. X ² represents each independently a fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, phenyl group, benzyl group, methoxy group, ethoxy Represents a group or a phenoxy group.)
In addition, in the above nickel compound, compounds in which nickel is replaced with palladium, cobalt, rhodium, or ruthenium can be exemplified as well.

  Examples of the compound represented by the formula [4] whose transition metal atom is iron include 2,6-bis- [1- (2,6-dimethylphenylimino) ethyl] pyridine iron dichloride, 2,6- Bis- [1- (2,6-diisopropylphenylimino) ethyl] pyridine iron dichloride and 2,6-bis- [1- (2-tert-butyl-phenylimino) ethyl] pyridine iron dichloride, and these Mention may be made of compounds in which the dichloride of the compound is replaced by difluoride, dibromide, diiodide, dimethyl, diethyl, dimethoxide, diethoxide, or diphenoxide.

  Examples of the μ-oxo type transition metal compound of the transition metal compound represented by the formula [4] include μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis. [Isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy ) Titanium chloride], μ-oxobis [iso Ropyridene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ -Oxobis [dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride ], [Mu] -oxobis [dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (2 -Phenoxy) Titanium And [mu] -oxobis [dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], and chlorides of these compounds to fluoride, bromide, iodide , Methyl, ethyl, isopropyl, phenyl, benzyl, methoxide, ethoxide, n-propoxide, isopropoxide, phenoxide, or pentafluorophenoxide.

As the transition metal compound (B) other than the compound represented by the formula [4], [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, and [Hydrotris (3,5-di-tert-butylpyrazolyl) borate] Nickel chloride and compounds in which the chloride of these compounds is replaced with bromide, iodide, methyl, ethyl, allyl, methallyl, methoxide, or ethoxide be able to.
In addition, in the above nickel compound, a compound in which nickel is replaced with iron or cobalt can be similarly exemplified.

  Examples of the compound in which the transition metal atom is a nickel atom include nickel chloride, nickel bromide, nickel iodide, nickel sulfate, nickel nitrate, nickel perchlorate, nickel acetate, nickel trifluoroacetate, nickel cyanide, Nickel oxalate, nickel acetylacetonate, bis (allyl) nickel, bis (1,5-cyclooctadiene) nickel, dichloro (1,5-cyclooctadiene) nickel, dichlorobis (acetonitrile) nickel, dichlorobis (benzonitrile) Nickel, carbonyltris (triphenylphosphine) nickel, dichlorobis (triethylphosphine) nickel, diacetbis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, dichloro [1,2-bi (Diphenylphosphino) ethane] nickel, bis [1,2-bis (diphenylphosphino) ethane] nickel, dichloro [1,3-bis (diphenylphosphino) propane] nickel, bis [1,3-bis (diphenyl) Mention may be made of phosphino) propane] nickel, tetraamine nickel nitrate, tetrakis (acetonitrile) nickel tetrafluoroborate, and nickel phthalocyanine.

Similarly, examples of the compound whose transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride, and vanadium oxytrichloride.
Examples of the compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran.
Examples of the compound in which the transition metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.

  These transition metal compounds may be used alone or in combination of two or more.

Of the transition metal compounds exemplified above, the transition metal compound (B) used in the present invention is preferably a transition metal compound represented by the above formula [4]. Among them, a transition metal compound in which M ² in the above formula [4] is a Group 4 atom is preferable, and in particular, a transition metal compound having at least one group having a cyclopentadiene-type anion skeleton as L ² in the formula [4]. preferable. Among them, a zirconium compound is more preferable, and L ² in the formula [4] has two groups having a cyclopentadiene type anion skeleton, and L ² contains a carbon atom, a silicon atom, an oxygen atom, a sulfur atom or a phosphorus atom. Zirconium compounds linked via the containing residues are particularly preferred.

  The transition metal compound represented by the formula [4] can be produced by a production method described in JP-A-6-340684, JP-A-7-258321, International Patent Publication No. 95/00562, and the like.

A known organoaluminum compound can be used as the organoaluminum compound (C). An organoaluminum compound represented by the following formula [7] is preferable.
R ⁸ _d AlY _3-d [7]
(In the formula, R ⁸ represents a hydrocarbon group, and all R ⁸ may be the same or different. Y represents a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, or an aralkyloxy group. And all Y may be the same or different, and d represents a number satisfying 0 <d ≦ 3.)

R ⁸ in the above formula [7] is preferably a hydrocarbon group having 1 to 24 carbon atoms, more preferably an alkyl group having 1 to 24 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, n-hexyl group, 2-methylhexyl group, and n-octyl group. An ethyl group, n-butyl group, isobutyl group, n-hexyl group or n-octyl group is preferred.

Moreover, as a halogen atom in Y, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, for example, Preferably it is a chlorine atom.
The alkoxy group for Y is preferably an alkoxy group having 1 to 24 carbon atoms, and specifically, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a sec-butoxy group. , Tert-butoxy group, n-pentoxy group, and n-icosoxy group, preferably methoxy group, ethoxy group, or tert-butoxy group.

  The aryloxy group for Y is preferably an aryloxy group having 6 to 24 carbon atoms. Examples of the aryloxy group include 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 , 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, and anthracenoxy group.

  The aralkyloxy group for Y is preferably an aralkyloxy group having 7 to 24 carbon atoms. Examples of the aralkyloxy group include benzyloxy group, (2-methylphenyl) methoxy group, (3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, and (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, (2,4,4) 5-trimethylphenyl) methoxy group, (2,4,6-trimethylphenyl) methoxy group, (3,4,5-trimethylphenyl) meth Si group, (2,3,4,5-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, preferably benzyloxy It is a group.

  Examples of the organoaluminum compound (C) represented by the formula [7] include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, And trialkylaluminum such as tri-n-octylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, and di-n-hexylaluminum chloride Dialkylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n- Alkyl aluminum dichlorides such as til aluminum dichloride, isobutyl aluminum dichloride, and n-hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, and di Dialkylaluminum hydrides such as n-hexylaluminum hydride, methyl (dimethoxy) aluminum, methyl (diethoxy) aluminum, and alkyl (dialkoxy) aluminum such as methyl (di-tert-butoxy) aluminum, dimethyl (methoxy) aluminum, dimethyl (Ethoxy) aluminum and dimethyl ( alkyl (diaryloxy) aluminum such as dialkyl (alkoxy) aluminum such as ert-butoxy) aluminum, methyl (diphenoxy) aluminum, methylbis (2,6-diisopropylphenoxy) aluminum, and methylbis (2,6-diphenylphenoxy) aluminum, Moreover, dialkyl (aryloxy) aluminum, such as dimethyl (phenoxy) aluminum, dimethyl (2,6-diisopropylphenoxy) aluminum, and dimethyl (2,6-diphenylphenoxy) aluminum, and the like can be given.

Among them, preferred is trialkylaluminum, more preferred is trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum, particularly preferred. Triisobutylaluminum or tri-n-octylaluminum.
These organoaluminum compounds may be used alone or in combination of two or more.

The amount of component (B) used is usually 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol, preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol, relative to 1 g of component (A). Moreover, the usage-amount of a component (C) is 0.01-10 as molar ratio (C) / (B) of the aluminum atom of a component (C) organoaluminum compound with respect to the transition metal atom of a component (B) transition metal compound. 000 is preferable, 0.1 to 5,000 is more preferable, and 1 to 2,000 is most preferable.

  As the addition polymerization catalyst of the present invention, a reaction product obtained by bringing the component (A) and the component (B), and optionally the component (C) into contact with each other in advance may be used. It may be used after being put in. When components (A), (B) and (C) are used, any two of them may be contacted in advance and then another component may be contacted.

  The method for supplying each catalyst component to the catalyst preparation reactor or the polymerization reactor is not particularly limited. A method of supplying each component in a solid state, a method of supplying a solution dissolved in a hydrocarbon solvent from which components for deactivating catalyst components such as moisture and oxygen are sufficiently removed, or a method of supplying in a suspended or slurry state Etc. Examples of the solvent at this time include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbons such as methylene chloride. Hydrocarbons or aromatic hydrocarbons are preferred.

  When supplying each catalyst component in a solution state or in a suspended or slurry state, the concentration of the component (A) is usually 0.01 to 1000 g / liter, preferably 0.1 to 500 g / liter. The concentration of the component (C) is usually 0.0001 to 100 mol / liter, preferably 0.01 to 10 mol / liter in terms of Al atoms.

  The polymerization method is not particularly limited, and gas phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization, and the like are possible. Solvents used for solution polymerization or slurry polymerization include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, and octane, aromatic hydrocarbon solvents such as benzene and toluene, or halogenated hydrocarbon solvents such as methylene chloride. It is also possible to use olefin itself as a solvent (bulk polymerization). The polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages with different reaction conditions. In general, the polymerization time is appropriately determined depending on the kind of the target olefin polymer and the reaction apparatus, but can be in the range of 1 minute to 20 hours.

The present invention is particularly suitably applied to polymerization involving formation of addition polymer particles (for example, slurry polymerization, gas phase polymerization, bulk polymerization, etc.).
The slurry polymerization may be performed according to a known slurry polymerization method and polymerization conditions, but is not limited thereto. A preferred polymerization method in the slurry process is a continuous reactor in which monomers (and comonomers), feeds, diluents, etc. are continuously added as required, and the polymer product is continuously or at least periodically removed. included. Examples of the reactor include a method using a loop reactor, a plurality of stirred reactors having different reactors or different reaction conditions in series or in parallel, or a combination thereof.

  As the diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature in the polymerization reactor or reaction zone can usually range from about 0 ° C to about 150 ° C, preferably from 30 ° C to 100 ° C. The pressure can usually be changed from about 0.1 MPa to about 10 MPa, preferably 0.5 MPa to 5 MPa. A pressure can be applied to maintain the catalyst in suspension, maintain the medium and at least some of the monomer and comonomer in a liquid phase, and allow the monomer and comonomer to contact. Accordingly, the medium, temperature, and pressure may be selected such that the addition polymer is produced as solid particles and recovered in that form.

The molecular weight of the addition polymer can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen.
Each catalyst component, monomer (and comonomer) can be added to the reactor or reaction zone in any order by any known method. For example, a method of simultaneously adding each catalyst component and monomer (and comonomer) to the reaction zone, a method of adding them sequentially, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere prior to contact with the monomer (and comonomer).

The gas phase polymerization may be performed according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto. As the gas phase polymerization reaction apparatus, a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion is used. There is no problem even in a reactor equipped with a stirring blade in the reaction vessel.
As a method for supplying each component to the polymerization tank, a solution or a slurry is usually supplied using an inert gas such as nitrogen or argon, hydrogen, ethylene or the like in the absence of moisture, or dissolved or diluted in a solvent. A method such as supplying in a state can be used. Each catalyst component may be supplied individually, or may be supplied by contacting arbitrary components in advance in an arbitrary order.

  As polymerization conditions, the temperature is less than the temperature at which the polymer melts, preferably 0 ° C. to 150 ° C., particularly preferably 30 ° C. to 100 ° C. Furthermore, hydrogen may be added as a molecular weight regulator for the purpose of adjusting the melt fluidity of the final product. In the polymerization, an inert gas may coexist in the mixed gas.

  In the present invention, preliminary polymerization may be performed before such polymerization (main polymerization) is performed.

The method for producing an addition polymer of the present invention is a method for producing an addition polymer in which addition-polymerizable monomers are subjected to addition polymerization in the presence of the aforementioned catalyst for addition polymerization of the present invention.
Examples of the monomer used for polymerization include olefins having 2 to 20 carbon atoms, diolefins, cyclic olefins, alkenyl aromatic hydrocarbons, polar monomers, and the like, and two or more monomers can be used at the same time.

  Specific examples thereof include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene, 1-octene and 1-nonene. Olefins such as 1-decene; 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 4-methyl-1, 4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2- Norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphth Diolefins such as len, 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclooctadiene, 1,3-cyclohexadiene; 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-cyanonorbo Cyclic olefins such as nene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene; styrene, 2-phenylpropylene, 2-phenylbutene, 3-phenylpropylene Alkenylbenzene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3 , 4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butyl styrene, alkyl styrene such as p-secondary butyl styrene, bisalkenyl benzene such as divinylbenzene, Alkenes such as 1-vinylnaphthalene and other alkenylnaphthalenes Nyl aromatic hydrocarbons; α, β such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid -Unsaturated carboxylic acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, acrylic acid Α-β-unsaturated carboxylic acid esters such as 2-ethylhexyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, maleic acid, itaconic acid, etc. Unsaturated dicarboxylic acid, vinyl acetate, vinyl propionate, capro Polar monomers such as vinyl esters such as vinyl acid, vinyl caprate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate, unsaturated carboxylic acid glycidyl ester such as glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, etc. Is mentioned.

  The present invention is applied to homopolymerization or copolymerization of these monomers. Specific examples of the monomer constituting the copolymer include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, and propylene and 1-butene. It should not be limited to these.

  The addition polymerization catalyst of the present invention is particularly suitable as an olefin polymerization catalyst, and is preferably used in a method for producing an olefin polymer. Such an olefin polymer is particularly preferably a copolymer of ethylene and an α-olefin, and particularly preferably a copolymer of ethylene and an α-olefin having a polyethylene crystal structure. The α-olefin herein is preferably an α-olefin having 3 to 8 carbon atoms, and specific examples include 1-butene, 1-hexene, 1-octene and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these. The measured value of each item in an Example was measured with the following method.

(1) The content of the repeating unit derived from α-olefin in the copolymer is a calibration curve from the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation). And expressed as the number of short chain branches per 1000 carbon atoms (SCB).

(2) Melt flow rate = MFR: Melt flow rate value measured at 190 ° C. under a load of 21.18 N (2.16 kg) according to the method defined in JIS K7210-1995 (unit: g / 10 minutes) .

(3) Swell ratio = SR: A value obtained by dividing the strand diameter obtained at the time of MFR measurement by 2.095 mm which is the inner diameter of the die.

(4) Melt flow rate ratio = MFRR: According to the method defined in JIS K7210-1995, the melt flow rate value measured at 190 ° C. and a load of 211.82 N (21.60 kg) was calculated as a load of 21.18 N (2. It is a value divided by the melt flow rate value (MFR) measured at 16 kg).
For all the melt flow rate measurements, a polymer containing 1000 ppm of an antioxidant in advance was used.

(5) Elemental analysis zinc: A sample was poured into a sulfuric acid aqueous solution (1 M), and then ultrasonic waves were applied to extract metal components. The obtained liquid portion was quantified by ICP emission spectrometry.
A combustion gas generated by burning a sample in a flask filled with fluorine: oxygen was absorbed in an aqueous sodium hydroxide solution (10%), and the obtained aqueous solution was quantified by an ion electrode method.

[Example 1]
(1) Treatment of silica
In a reactor equipped with a nitrogen-replaced stirrer, 1200 ml of toluene as a solvent, heat-treated silica at 300 ° C. under a nitrogen stream (Sypolol 948 manufactured by Devison; average particle size = 55 μm; pore volume = 1.67 ml / g; 205 g of specific surface area = 325 m ² / g) was added and stirred. Then, after cooling to 5 ° C., a mixed solution of 85 ml of 1,1,1,3,3,3-hexamethyldisilazane and 125 ml of toluene was added dropwise over 30 minutes while keeping the temperature of the reactor at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 95 ° C. for 3 hours. Thereafter, the obtained solid product was washed 4 times with 1200 ml of toluene and 3 times with 1200 ml of hexane. The obtained solid product was dried at 40 ° C. under reduced pressure for 1.5 hours to obtain 228 g of solid particles (d).

(2) Preparation of modified particles (B) In a reactor equipped with a nitrogen-replaced stirrer, 39 ml of toluene as a solvent and 12.5 ml of a 2.0 mol / l diethylzinc hexane solution as a compound (a) were added. Charged and stirred. Then, after cooling to 5 ° C., 12.5 ml of a toluene solution of pentafluorophenol prepared as a compound (b) at a concentration of 2.0 mol / l was added for 15 minutes while maintaining the temperature of the reactor contents at 5 ° C. or less. It was dripped at. The molar ratio y of the compound (b) to the compound (a) corresponds to 1.00. After completion of dropping, the mixture was stirred at 5 ° C for 0.5 hour and at 40 ° C for 1 hour. Thereafter, after cooling to 5 ° C., 5.6 g of the modified silica obtained in Example 1 (1) was added as solid particles (d), and 5.0 ml of toluene was used with the solid content adhering to the reactor wall surface as a solvent. Washed off. After stirring at 5 ° C. for 5 minutes, 0.34 ml of water was added dropwise as compound (c) over 20 minutes while maintaining the temperature of the reactor contents at 5 ° C. or lower. The molar ratio z of the compound (c) to the compound (a) corresponds to 0.75. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 80 ° C. for 1 hour. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is visible, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. 50 ml of toluene was added. Then, it heated up at 95 degreeC and stirred for 1 hour. Thereafter, the mixture was allowed to stand at 95 ° C. with 50 ml of toluene four times and at room temperature with 50 ml of hexane three times to precipitate the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion was visible. The upper slurry portion was removed, and then the remaining liquid components were removed with a filter. The solid component was dried at 23 ° C. under reduced pressure for 1 hour to obtain 7.9 g of modified particles (B).

(3) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure was 0.023 MPa, And 695 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 1.03 mol% and 1-butene = 2.98 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml is added as the transition metal compound (A), and then the above Example 1 is used as the solid catalyst component. 9.7 mg of the solid catalyst component (B) obtained in (2) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.35 mol%) so as to keep the total pressure constant. As a result, 84 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 8670 g / g solid catalyst component. The obtained olefin polymer had SCB = 15.6, MFR = 0.19 g / 10 min, MFRR = 149, SR = 1.15.

[Example 2]
(1) Preparation of modified particles (B) In a reactor equipped with a nitrogen-substituted stirrer, 39 ml of toluene as a solvent and 12.3 ml of a 2.0 mol / l diethylzinc hexane solution as a compound (a) were added. Charged and stirred. Then, after cooling to 5 ° C., 5.3 ml of a toluene solution of pentafluorophenol prepared as a compound (b) at a concentration of 2.0 mol / l was added for 15 minutes while maintaining the temperature of the reactor contents at 5 ° C. or less. It was dripped at. The molar ratio y of the compound (b) to the compound (a) corresponds to 0.60. After completion of dropping, the mixture was stirred at 5 ° C for 0.5 hour and at 40 ° C for 1 hour. Then, after cooling to 5 ° C., 5.5 g of the modified silica obtained in Example 1 (1) was added as particles (d), and the solid content adhering to the reactor wall surface was washed off with 5.0 ml of toluene as a solvent. It was. After stirring at 5 ° C. for 5 minutes, 0.49 ml of water was added dropwise as compound (c) over 20 minutes while keeping the temperature of the reactor contents at 5 ° C. or lower. The molar ratio z of the compound (c) to the compound (a) corresponds to 1.10. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 80 ° C. for 1 hour. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is visible, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. 50 ml of toluene was added. Then, it heated up at 95 degreeC and stirred for 1 hour. Thereafter, the mixture was allowed to stand at 95 ° C. with 50 ml of toluene four times and at room temperature with 50 ml of hexane three times to precipitate the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion was visible. The upper slurry portion was removed, and then the remaining liquid components were removed with a filter. The solid component was dried at 23 ° C. for 1 hour under reduced pressure to obtain 7.6 g of modified particles (B).

(2) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure was 0.015 MPa, and 1-butene was used as a comonomer. 60 g and 690 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was as follows: hydrogen = 1.15 mol% and 1-butene = 2.55 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml is added as the transition metal compound (A), and then the above Example 2 is used as the solid catalyst component. 7.4 mg of the solid catalyst component (B) obtained in (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.31 mol%) so as to keep the total pressure constant. As a result, 58 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 7840 g / g solid catalyst component. The obtained olefin polymer had SCB = 16.3, MFR = 0.11 g / 10 min, MFRR = 164, SR = 1.06.

[Example 3]
(1) Preparation of modified particles (B) In a reactor equipped with a nitrogen-replaced stirrer, 39 ml of toluene as a solvent and 12.4 ml of a 2.0 mol / l diethylzinc hexane solution as a compound (a) were added. Charged and stirred. Then, after cooling to 5 ° C., 5.4 ml of a toluene solution of pentafluorophenol prepared as a compound (b) at a concentration of 2.0 mol / l was added for 15 minutes while maintaining the temperature of the reactor contents at 5 ° C. or less. It was dripped at. The molar ratio y of the compound (b) to the compound (a) corresponds to 0.60. After completion of dropping, the mixture was stirred at 5 ° C for 0.5 hour and at 40 ° C for 1 hour. Thereafter, after cooling to 5 ° C., 5.5 g of modified silica obtained in Example 1 (1) was added as solid particles (d), and 5.0 ml of toluene was used with the solid content adhering to the reactor wall surface as a solvent. Washed off. After stirring at 5 ° C. for 5 minutes, 0.40 ml of water as compound (c) was added dropwise over 20 minutes while maintaining the temperature of the reactor contents at 5 ° C. or lower. The molar ratio z of the compound (c) to the compound (a) corresponds to 0.90. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 80 ° C. for 1 hour. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is visible, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. 50 ml of toluene was added. Then, it heated up at 95 degreeC and stirred for 1 hour. Thereafter, the mixture was allowed to stand at 95 ° C. with 50 ml of toluene four times and at room temperature with 50 ml of hexane three times to precipitate the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion was visible. The upper slurry portion was removed, and then the remaining liquid components were removed with a filter. The solid component was dried at 23 ° C. under reduced pressure for 1 hour to obtain 9.2 g of modified particles (B). As a result of elemental analysis, zinc was 2.1 mmol / g and fluorine was 5.3 mmol / g.

(2) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure was 0.015 MPa, and 1-butene was used as a comonomer. 60 g and 690 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.93 mol% and 1-butene = 3.03 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml is added as the transition metal compound (A), and then the solid catalyst component of Example 3 above is used. 9.6 mg of the solid catalyst component (B) obtained in (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.31 mol%) so as to keep the total pressure constant. As a result, 56 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 5830 g / g solid catalyst component. Moreover, the obtained olefin polymer was SCB = 16.3, MFR = 0.06g / 10min, MFRR = 153, SR = 1.07.

[Comparative Example 1]
(1) Preparation of modified particles (B) In a reactor equipped with a nitrogen-substituted stirrer, 39 ml of toluene as a solvent and 12.7 ml of a 2.0 mol / l diethylzinc hexane solution as a compound (a) were added. Charged and stirred. Then, after cooling to 5 ° C., 4.6 ml of a toluene solution of pentafluorophenol prepared as a compound (b) at a concentration of 2.0 mol / l was added for 15 minutes while maintaining the temperature of the reactor contents at 5 ° C. or less. It was dripped at. The molar ratio y of the compound (b) to the compound (a) corresponds to 0.50. After completion of dropping, the mixture was stirred at 5 ° C for 0.5 hour and at 40 ° C for 1 hour. Thereafter, after cooling to 5 ° C., 5.6 g of the modified silica obtained in Example 1 (1) was added as solid particles (d), and 5.0 ml of toluene was used with the solid content adhering to the reactor wall surface as a solvent. Washed off. After stirring at 5 ° C. for 5 minutes, 0.55 ml of water as compound (c) was added dropwise over 20 minutes while keeping the temperature of the reactor contents at 5 ° C. or lower. The molar ratio z of the compound (c) to the compound (a) corresponds to 1.20. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 80 ° C. for 1 hour. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is visible, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. 50 ml of toluene was added. Then, it heated up at 95 degreeC and stirred for 1 hour. Thereafter, the mixture was allowed to stand at 95 ° C. with 50 ml of toluene four times and at room temperature with 50 ml of hexane three times to precipitate the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion was visible. The upper slurry portion was removed, and then the remaining liquid components were removed with a filter. The solid component was dried at 23 ° C. under reduced pressure for 1 hour to obtain 7.8 g of modified particles (B).

(2) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure was 0.023 MPa, and 1-butene was used as a comonomer. And 695 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.97 mol% and 1-butene = 2.57 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added as the transition metal compound (A), and then the above Comparative Example 1 was used as a solid catalyst component. 8.1 mg of the solid catalyst component (B) obtained in (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.35 mol%) so as to keep the total pressure constant. As a result, 55 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 6830 g / g solid catalyst component. Moreover, the obtained olefin polymer was SCB = 16.0, MFR = 1.0 g / 10min, MFRR = 78, SR = 1.37.

[Comparative Example 2]
(1) Preparation of modified particles (B) In a reactor equipped with a nitrogen-substituted stirrer, 39 ml of toluene as a solvent and 12.7 ml of a 2.0 mol / l diethylzinc hexane solution as a compound (a) were added. Charged and stirred. Then, after cooling to 5 ° C., 4.6 ml of a toluene solution of pentafluorophenol prepared as a compound (b) at a concentration of 2.0 mol / l was added for 15 minutes while maintaining the temperature of the reactor contents at 5 ° C. or less. It was dripped at. The molar ratio y of the compound (b) to the compound (a) corresponds to 0.50. After completion of dropping, the mixture was stirred at 5 ° C for 0.5 hour and at 40 ° C for 1 hour. Thereafter, after cooling to 5 ° C., 5.6 g of the modified silica obtained in Example 1 (1) was added as solid particles (d), and 5.0 ml of toluene was used with the solid content adhering to the reactor wall surface as a solvent. Washed off. After stirring at 5 ° C. for 5 minutes, 0.34 ml of water was added dropwise as compound (c) over 20 minutes while maintaining the temperature of the reactor contents at 5 ° C. or lower. The molar ratio z of the compound (c) to the compound (a) corresponds to 0.75. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 80 ° C. for 1 hour. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is visible, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. 50 ml of toluene was added. Then, it heated up at 95 degreeC and stirred for 1 hour. Thereafter, the mixture was allowed to stand at 95 ° C. with 50 ml of toluene four times and at room temperature with 50 ml of hexane three times to precipitate the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion was visible. The upper slurry portion was removed, and then the remaining liquid components were removed with a filter. The solid component was dried at 23 ° C. under reduced pressure for 1 hour to obtain 8.9 g of modified particles (B).

(2) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure was 0.023 MPa, and 1-butene was used as a comonomer. And 695 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.93 mol% and 1-butene = 2.90 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added as the transition metal compound (A), and then the above Comparative Example 1 was used as a solid catalyst component. 9.7 mg of the solid catalyst component (B) obtained in (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.35 mol%) so as to keep the total pressure constant. As a result, 69 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 7130 g / g solid catalyst component. Moreover, the obtained olefin polymer was SCB = 16.1, MFR = 0.67g / 10min, MFRR = 73, SR = 1.31.

[Comparative Example 3]
(1) Preparation of modified particles (B) In a reactor equipped with a nitrogen-substituted stirrer, 39 ml of toluene as a solvent and 12.5 ml of a 2.0 mol / l diethylzinc hexane solution as a compound (a) were added. Charged and stirred. Then, after cooling to 5 ° C., 9.0 ml of a pentafluorophenol toluene solution prepared as a compound (b) at a concentration of 2.0 mol / l was added for 15 minutes while maintaining the temperature of the reactor contents at 5 ° C. or less. It was dripped at. The molar ratio y of the compound (b) to the compound (a) corresponds to 1.00. After completion of dropping, the mixture was stirred at 5 ° C for 0.5 hour and at 40 ° C for 1 hour. Thereafter, after cooling to 5 ° C., 5.5 g of modified silica obtained in Example 1 (1) was added as solid particles (d), and 5.0 ml of toluene was used with the solid content adhering to the reactor wall surface as a solvent. Washed off. After stirring at 5 ° C. for 5 minutes, 0.54 ml of water was added dropwise as compound (c) over 20 minutes while maintaining the temperature of the reactor contents at 5 ° C. or lower. The molar ratio z of the compound (c) to the compound (a) corresponds to 1.20. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 80 ° C. for 1 hour. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is visible, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. 50 ml of toluene was added. Then, it heated up at 95 degreeC and stirred for 1 hour. Thereafter, the mixture was allowed to stand at 95 ° C. with 50 ml of toluene four times and at room temperature with 50 ml of hexane three times to precipitate the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion was visible. The upper slurry portion was removed, and then the remaining liquid components were removed with a filter. The solid component was dried at 23 ° C. under reduced pressure for 1 hour to obtain 7.0 g of modified particles (B).

(2) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure was 0.023 MPa, and 1-butene was used as a comonomer. And 695 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.92 mol% and 1-butene = 2.98 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added as the transition metal compound (A), and then the above Comparative Example 1 was used as a solid catalyst component. 8.9 mg of the solid catalyst component (B) obtained in (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.35 mol%) so as to keep the total pressure constant. As a result, 36 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 4030 g / g solid catalyst component. Moreover, the obtained olefin polymer was SCB = 16.1, MFR = 1.8g / 10min, MFRR = 47, SR = 1.35.

[Comparative Example 4]
(1) Preparation of modified particles (B) In a reactor equipped with a nitrogen-replaced stirrer, 39 ml of toluene as a solvent and 12.4 ml of a 2.0 mol / l diethylzinc hexane solution as a compound (a) were added. Charged and stirred. Then, after cooling to 5 ° C., 9.0 ml of a pentafluorophenol toluene solution prepared as a compound (b) at a concentration of 2.0 mol / l was added for 15 minutes while maintaining the temperature of the reactor contents at 5 ° C. or less. It was dripped at. The molar ratio y of the compound (b) to the compound (a) corresponds to 1.00. After completion of dropping, the mixture was stirred at 5 ° C for 0.5 hour and at 40 ° C for 1 hour. Thereafter, after cooling to 5 ° C., 5.5 g of modified silica obtained in Example 1 (1) was added as solid particles (d), and 5.0 ml of toluene was used with the solid content adhering to the reactor wall surface as a solvent. Washed off. After stirring at 5 ° C. for 5 minutes, 0.13 ml of water as compound (c) was added dropwise over 20 minutes while maintaining the temperature of the reactor contents at 5 ° C. or lower. The molar ratio z of the compound (c) to the compound (a) corresponds to 0.30. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and at 80 ° C. for 1 hour. Then, the mixture is allowed to stand, and the solid component is allowed to settle. When the interface between the precipitated solid component layer and the upper slurry portion is visible, the upper slurry portion is removed, and then the remaining liquid components are removed with a filter. 50 ml of toluene was added. Then, it heated up at 95 degreeC and stirred for 1 hour. Thereafter, the mixture was allowed to stand at 95 ° C. with 50 ml of toluene four times and at room temperature with 50 ml of hexane three times to precipitate the solid component, and when the interface between the precipitated solid component layer and the upper slurry portion was visible. The upper slurry portion was removed, and then the remaining liquid components were removed with a filter. The solid component was dried at 23 ° C. under reduced pressure for 1 hour to obtain 7.0 g of modified particles (B).

(2) Polymerization After drying under reduced pressure, the inside of an autoclave with a stirrer with an internal volume of 3 liters substituted with argon was evacuated, hydrogen was added as a molecular weight regulator so that its partial pressure was 0.023 MPa, and 1-butene was used as a comonomer. And 695 g of butane as a polymerization solvent were charged, and the temperature was raised to 70 ° C. Thereafter, ethylene was added as a monomer so that the partial pressure became 1.6 MPa, and the inside of the system was stabilized. As a result of gas chromatography analysis, the gas composition in the system was hydrogen = 0.90 mol% and 1-butene = 2.91 mol%. To this was added 0.9 ml of a hexane solution of triisobutylaluminum adjusted to a concentration of 1 mmol / ml as the organoaluminum compound (C). Next, 0.5 ml of a toluene solution of racemic-ethylenebis (1-indenyl) zirconium dichloride adjusted to a concentration of 2 μmol / ml was added as the transition metal compound (A), and then the above Comparative Example 1 was used as a solid catalyst component. 8.9 mg of the solid catalyst component (B) obtained in (1) was added. Polymerization was carried out at 70 ° C. for 1 hour while feeding an ethylene / hydrogen mixed gas (hydrogen 0.32 mol%) so as to keep the total pressure constant. As a result, 9 g of an olefin polymer was obtained. The polymerization activity per solid catalyst component was 930 g / g solid catalyst component. Moreover, the obtained olefin polymer was SCB = 13.5, MFR = 0.63 g / 10min, MFRR = 54, SR = 1.23.

  As described above in detail, according to the present invention, an addition polymerization catalyst component and an addition polymerization catalyst capable of producing a higher molecular weight addition polymer under polymerization conditions having a higher hydrogen concentration, and a higher molecular weight. A method for producing the addition polymer is provided.

Claims (9)

A catalyst component for addition polymerization comprising modified particles obtained by contacting the following compounds (a), (b), (c) and solid particles (d), wherein the compounds (a), ( When the molar ratio of the amount of b) and (c) used is (a) :( b) :( c) = 1: y: z, y and z satisfy the following formulas (i) and (ii) Polymerization catalyst component.
(A) Compound M ¹ L ¹ _m [1] represented by the following formula [1]
(B) Compound represented by the following formula [2]

(C) Compound R ³ _t-2 TH ₂ [3] represented by the following formula [3]
(In the above formulas [1] to [3], M ¹ represents a typical metal atom of Group 1, Group 2, Group 12, Group 14 or Group 15 of the periodic table of elements; ¹ valence .L ¹ which represents a number corresponding to a hydrogen atom, a halogen atom or a hydrocarbon group, if L ¹ there are a plurality, a plurality of L ¹ may be different be the same as each other R ¹ represents an electron-withdrawing group or a group containing an electron-withdrawing group, R ¹ may be the same as or different from each other, and two R ¹ bonded to adjacent carbon atoms are And may be linked to form a condensed ring structure adjacent to the benzene ring, R ³ represents a hydrocarbon group or a halogenated hydrocarbon group, and each T independently represents Group 15 or Group 16 of the periodic table of elements. Represents a non-metallic atom, and t is a number corresponding to the valence of T of each compound. It is.)
0.6 ≦ y ≦ 1.0 (i)
−0.625y + 1.275 ≦ z ≦ −0.875y + 1.625 (ii)   The catalyst component for addition polymerization according to claim 1, wherein the solid particles (d) are inorganic particles or organic polymer particles.   The addition polymerization catalyst component according to claim 1, wherein the inorganic substance particles are inorganic oxide, clay, or clay mineral.   A catalyst component for addition polymerization (A) comprising the modified particles according to any one of claims 1 to 3 and a transition metal compound of group 3 to group 11 or a lanthanoid series of an element periodic table (B) are contacted. Catalyst for addition polymerization obtained.   A catalyst component for addition polymerization (A) comprising the modified particles according to any one of claims 1 to 3, a group 3 to group 11 element of the periodic table of elements or a lanthanoid series transition metal compound (B) and organic A catalyst for addition polymerization obtained by contacting an aluminum compound (C).   The catalyst for addition polymerization according to claim 4 or 5, wherein the transition metal compound (B) of Group 3 to Group 11 or the lanthanoid series of the periodic table of elements is a transition metal compound having at least one cyclopentadiene type anion skeleton. .   The manufacturing method of the addition polymer using the catalyst for addition polymerization in any one of Claims 4-6.   The method for producing an addition polymer according to claim 7, wherein the addition polymer is an olefin polymer.   The method for producing an addition polymer according to claim 8, wherein the addition polymer is a copolymer of ethylene and an α-olefin.