JP5339567B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst having high activity, free from problems of the adhesion of polymer to a reactor, etc., and producing a powdery polyolefin having excellent particle form and enabling easy separation from a solvent and provide a method for the polymerization of an olefin. <P>SOLUTION: The olefin polymerization catalyst is composed of (A) a carrier composed of an oxide of a specific element and essentially free from hydroxy group by removing hydroxy group from the surface of a precursor of the carrier (A) by the chemical treatment with a specific organic aluminum compound or a specific organic magnesium compound, (B) a specific transition metal compound containing a transition metal having a cyclic anion ligand bonded through &eta;-bond, (C) an activated compound containing a cation and a compatible non-coordinated anion and capable of forming a metal complex having catalytic activity by reacting with the transition metal compound (B), and (D) an organic aluminum compound, wherein the activated compound (C) is added to a reactor through a sintered filter having a nominal degree of filtration of &ge;0.01&mu;m and &le;5&mu;m. The invention further relates to an olefin polymerization method by using the catalyst. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a solid catalyst for olefin polymerization and an olefin polymerization method using the catalyst. Specifically, the catalyst for olefin polymerization can be applied to suspension polymerization (slurry polymerization) of olefins and gas phase polymerization, and can produce a polymer having excellent powder properties with very high production efficiency, In particular, the present invention provides a catalyst for ethylene polymerization, and relates to a method for polymerizing ethylene using the same.

  Conventionally, a so-called Ziegler-Natta type catalyst composed of a titanium compound and an organoaluminum compound is known as a catalyst for producing an olefin polymer or copolymer. On the other hand, in recent years, ethylene homopolymerization or copolymerization of ethylene with other α-olefins, aluminoxane which is a kind of soluble halogen-containing transition metal compounds such as bis (cyclopentadienyl) zirconium dichloride and organoaluminum oxy compounds. A technique for polymerizing with high activity by using a catalyst consisting of the following has been found (see, for example, Patent Documents 1 and 2).

On the other hand, as a catalyst system using an activator other than an organoaluminum oxy compound, [Cp ₂ TiMe (THF)] ⁺ [B (Ph) ₄ ] ⁻ (Cp: cyclopentadienyl group, Me: methyl group, Ph Polymerization of ethylene has been reported using a compound represented by: phenyl group, THF: tetrahydrofuran (see Non-Patent Document 1). It has also been reported that a zirconium complex represented by [Cp ₂ ZrR (L)] ⁺ (R: methyl group or benzyl group, L: Lewis base) polymerizes ethylene (see Non-Patent Document 2).
Patent Document 3 and Patent Document 4 disclose a method of polymerizing an olefin using a catalyst comprising a cyclopentadienyl metal compound and an ionic compound capable of stabilizing a cyclopentadienyl metal cation. ing.

  In addition, a catalyst system using an organoaluminum compound and clay, clay mineral, ion-exchange layered compound or the like as an activator is disclosed in Patent Documents 5 to 8, and the like. However, the catalyst systems proposed in these conventional techniques are often soluble in the reaction system, and reflecting this, the olefin polymer obtained by slurry polymerization or gas phase polymerization has an irregular particle shape. In addition, there is a problem that the bulk density is small and there are a lot of fine powders and the particle properties are extremely bad, and the polymer adheres to the wall surface of the reactor, the stirring blade, etc., and cannot be used as it is industrially. For this reason, the production process is usually limited to the solution polymerization method. However, in the solution polymerization method, when an attempt is made to produce a high molecular weight polymer, the viscosity of the solution containing the polymer becomes extremely high and the productivity is greatly increased. There is a problem of lowering, and it cannot be said that it is a preferable method in terms of cost, and there is a big problem in industrial application.

  The above activating compound has low solubility in a nonpolar hydrocarbon solvent such as hexane which is generally used as a solvent for preparing the catalyst. On the other hand, when preparing a catalyst for use in slurry polymerization or gas phase polymerization, in order to solidify the catalyst, the catalyst is prepared by adding these activating compounds to the nonpolar hydrocarbon solvent slurry of the carrier. It is common to prepare. Patent Documents 10 and 11 disclose a technique in which the catalyst component is supported on a carrier and used in a slurry method. However, with these technologies, although the powder does not adhere to the wall surface or further agglomerate in the polymerization vessel to prevent stable production, these activating compounds are solidified in the reactor or become sticky liquids. The powder obtained from the catalyst whose entire support surface is covered with the activating compound floats in a nonpolar hydrocarbon solvent, making it difficult to separate the solvent from the powder by centrifugation. There was a problem.

Japanese Examined Patent Publication No. 4-12283 West German Patent Application Publication No. 3127133 JP-T-1-501950 Japanese translation of PCT publication No. 1-502036 Japanese Patent Laid-Open No. 5-301917 Japanese Patent Laid-Open No. 6-136047 JP-A-9-59310 Japanese Patent Laid-Open No. 11-269222 JP-A-9-194520 WO03 / 035704 pamphlet International Publication No. 99-028353 Pamphlet Taube, et al., J. Organomet. Chem., 347, C9 (1988) Jordan, et al., J. Am. Chem. SoE-109, 4111 (1987)

  Therefore, it is desired to develop a catalyst capable of producing polyolefin powder having high activity, capable of polymerizing a polymer without causing adhesion to a reactor, etc., excellent particle properties, and easy separation from a solvent by centrifugation. The present invention provides such a novel olefin polymerization catalyst and an olefin polymerization method using the same.

In view of the current situation, the present inventors have developed a highly active polyolefin powder that does not cause a phenomenon such as adhesion to a reactor during polymerization, has excellent powder properties, and is easily separated from a solvent. Thus, the present invention has been reached through intensive studies to find a method for obtaining a novel catalyst system that can be produced effectively and efficiently.
That is, the present invention is an olefin polymerization catalyst and an olefin polymerization method using the same as described below.

（式中、Ｍ ^５ は、形式酸化数が＋２、＋３または＋４であるチタンを表し、Ｒ ^１０ は、各々独立して、水素原子、炭素数１以上８以下の炭化水素基、シリル基、ゲルミル基、シアノ基、ハロゲン原子、およびこれらの複合基からなる群より選ばれる置換基を表し、ただし、該置換基Ｒ ^１０ が炭素数１以上８以下の炭化水素基、シリル基またはゲルミル基である時、場合によっては２つの隣接する置換基Ｒ ^１０ が互いに結合して２価の基を形成し、これにより該２つの隣接する該置換基Ｒ ^１０ にそれぞれ結合するシクロペンタジエニル環の２つの炭素原子間の結合と共働して環を形成し、Ｘ ^７ は、各々独立して、ハロゲン原子、炭素数１以上２０以下の炭化水素基、炭素数１以上１８以下のヒドロカルビルオキシ基、炭素数１以上１８以下のヒドロカルビルアミノ基、シリル基、炭素数１以上１８以下のヒドロカルビルアミド基、炭素数１以上１８以下のヒドロカルビルフォスフィド基、炭素数１以上１８以下のヒドロカルビルスルフィド基およびこれらの複合基からなる群より選ばれる置換基を表し、ただし、場合によっては２つの置換基Ｘ ^７ が共働して炭素数４以上〜３０以下の中性共役ジエンまたは２価の基を形成し、Ｙは、−Ｏ−、−Ｓ−、−ＮＲ ^＊ −または−ＰＲ ^＊ −を表し、ただし、Ｒ ^＊ は、水素原子、炭素数１以上１２以下の炭化水素基、炭素数１以上８以下のヒドロカルビルオキシ基、シリル基、炭素数１以上８以下のハロゲン化アルキル基、炭素数６以上２０以下のハロゲン化アリール基、またはこれらの複合基を表し、ＺはＳｉＲ ^＊ _２ 、ＣＲ ^＊ _２ 、ＳｉＲ ^＊ _２ ＳｉＲ ^＊ _２ 、ＣＲ ^＊ _２ ＣＲ ^＊ _２ 、ＣＲ ^＊ ＝ＣＲ ^＊ 、ＣＲ ^＊ _２ ＳｉＲ ^＊ _２ またはＧｅＲ ^＊ _２ を表し、但し、Ｒ ^＊ は上で定義した通りであり、ｒは１、２または３である）。
［Ｃ］カチオンおよび相溶性の非配位性アニオンを含み、かつ遷移金属化合物［Ｂ］と反応して触媒活性を有する金属錯体を形成することが可能である下記の一般式（９）で表される活性化化合物、
［Ｌ ^２ ―Ｈ］ ^＋ ［ＢＱ ^２ _３ Ｑ ^３ ］ ⁻ ・・・・・（９）
（式中、Ｌ ^２ は中性のルイス塩基を表し、［Ｌ ^２ ―Ｈ］ ^＋ はプロトン供与性のブレンステッド酸を表し、［ＢＱ ^２ _３ Ｑ ^３ ］ ⁻ は相溶性の非配位性アニオンであり、Ｑ ^２ はペンタフルオロフェニル基であり、残る１つのＱ ^３ は置換基としてＯＨ基を１つ有する炭素数６以上２０以下の置換アリール基である。）
及び
［Ｄ］ 有機アルミニウム化合物
を触媒調製用反応器内で反応させるオレフィン重合用触媒の製造方法であって、下記工程を含むことを特徴とし、下記工程２において工程１により生成した化合物の添加が、公称ろ過精度０．０１μｍ以上５μｍ以下の焼結フィルターを介して行われることを特徴とするオレフィン重合用触媒の製造方法。
工程１：活性化化合物［Ｃ］と有機アルミニウム化合物［Ｄ］とを接触させる工程
工程２：担体[Ａ]と工程１により生成した化合物とを接触させる工程
工程３：遷移金属化合物［Ｂ］と工程２により生成した化合物とを接触させる工程
（２） 一般式（１）で表される有機アルミニウム化合物が、トリエチルアルミニウムである（１）に記載のオレフィン重合用触媒の製造方法。
（３） 遷移金属化合物［Ｂ］が、［（Ｎ−ｔ−ブチルアミド）（テトラメチル−η ^５ −シクロペンタジエニル）ジメチルシラン］チタニウム−１，３−ペンタジエンである（１）または（２）記載のオレフィン重合用触媒の製造方法。
（４） 活性化化合物［Ｃ］が、ビス（水素化タロウアルキル）メチルアンモニウム−トリス（ペンタフルオロフェニル）（４−ヒドロキシフェニル）ボレートである（１）〜（３）のいずれかに記載のオレフィン重合用の触媒。
（５） （１）〜（４）のいずれかに記載の製造方法により製造されることを特徴とするオレフィン重合用触媒。
（６） （１）〜（４）のいずれかに記載の製造方法により製造されるオレフィン重合用触媒の存在下で、オレフィンを重合または共重合させることを特徴とするポリオレフィンの重合方法。 (1) [A] A silica carrier and a hydroxyl group is substantially removed from the surface of the precursor of the carrier [A] by chemical treatment using an organoaluminum compound represented by the following general formula (1). A carrier having no hydroxyl group,
AlR ¹ _a X ¹ _3-a (1)
(In the formula, each R ¹ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ¹ is independently And represents a halide, hydride or an alkoxide group having 1 to 10 carbon atoms, and a is 1, 2 or 3.
[B] a transition metal compound represented by the following general formula ( 7 ),

( Wherein M ⁵ represents titanium having a formal oxidation number of +2, +3, or +4, and R ¹⁰ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a gel mill, Represents a substituent selected from the group consisting of a group, a cyano group, a halogen atom, and a composite group thereof, provided that the substituent R ¹⁰ is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, or a germyl group. In some cases, two adjacent substituents R ¹⁰ are bonded to each other to form a divalent group, whereby two of the cyclopentadienyl rings that are respectively bonded to the two adjacent substituents R ¹⁰ In combination with a bond between carbon atoms to form a ring , each X ⁷ independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, carbon Number 1 to 18 Selected from the group consisting of a hydrocarbylamino group, a silyl group, a hydrocarbylamide group having 1 to 18 carbon atoms, a hydrocarbyl phosphide group having 1 to 18 carbon atoms, a hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a composite group thereof. Provided that, in some cases, two substituents X ⁷ cooperate to form a neutral conjugated diene having 4 to 30 carbon atoms or a divalent group, and Y is —O—, -S-, -NR ^* -or -PR ^* - , wherein R ^* is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, represents a number 1 to 8 of the halogenated alkyl group carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms or a composite group thereof,, Z is ^SiR _* 2, ^CR _* 2, _{^{iR * 2 SiR * 2, CR}} * 2 CR * 2, CR * = CR *, CR * 2 SiR * 2 , or represents ^GeR _{* 2,} where, ^{R *} is as defined above, r is 1, 2 or 3).
[C] A compound represented by the following general formula (9) which contains a cation and a compatible non-coordinating anion and can form a metal complex having catalytic activity by reacting with the transition metal compound [B]. activating compound,
[L ² −H] ⁺ [BQ ² ₃ Q ³ ] ⁻ (9)
(Wherein, ^{L 2} represents a neutral Lewis ^base, [L 2 ^{-H] +} represents a proton donating Bronsted _{^{acid, [BQ 2 3 Q 3]}} - is a non-coordinating anion compatible Q ² is a pentafluorophenyl group, and the remaining one Q ³ is a substituted aryl group having 6 to 20 carbon atoms and having one OH group as a substituent.
And [D] A method for producing an olefin polymerization catalyst in which an organoaluminum compound is reacted in a catalyst preparation reactor, comprising the following steps, wherein the addition of the compound produced in step 1 in step 2 below is performed: The method for producing an olefin polymerization catalyst, which is performed through a sintered filter having a nominal filtration accuracy of 0.01 μm or more and 5 μm or less.
Step 1: Step of bringing activated compound [C] into contact with organoaluminum compound [D] Step 2: Step of bringing carrier [A] into contact with the compound produced in Step 1 Step 3: With transition metal compound [B] (2) The method for producing the olefin polymerization catalyst according to (1), wherein the organoaluminum compound represented by the general formula (1) is triethylaluminum.
(3) The transition metal compound [B] is [(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (1) or (2) The manufacturing method of the catalyst for olefin polymerization of description.
(4) The olefin according to any one of (1) to (3), wherein the activating compound [C] is bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate Catalyst for polymerization.
(5) An olefin polymerization catalyst produced by the production method according to any one of (1) to (4) .
(6) A polyolefin polymerization method characterized by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst produced by the production method according to any one of (1) to (4) .

  The catalyst for olefin polymerization of the present invention not only has a high polymerization activity but also an olefin polymer excellent in powder properties by suspension polymerization (slurry polymerization) or gas phase polymerization, and the inner wall of the polymerization vessel, stirring blade The polyolefin powder can be produced efficiently and effectively without being attached to the solvent, and the obtained polyolefin powder can be easily separated from the solvent.

Hereinafter, the present invention will be specifically described.
The carrier [A] having substantially no hydroxyl group used in the present invention removes a hydroxyl group from the surface of the precursor of the carrier [A] from a solid material (hereinafter referred to as “precursor of carrier [A]”). It can obtain by attaching | subjecting to the process for.

  In the present invention, the precursor of the carrier [A] is an oxide of an element belonging to the group consisting of Group 2, Group 3, Group 4, Group 13, and Group 14 of the periodic table. Specifically, it is preferably a solid material selected from the group consisting of silica, alumina, magnesia, zirconia, titania, boron oxide, calcium oxide, zinc oxide, barium oxide, vanadium pentoxide, chromium oxide, thorium oxide, A mixture thereof or a composite oxide thereof may be used. Among these, silica, alumina, and a composite oxide of silica and an oxide of an element selected from elements belonging to the group consisting of Groups 2 and 13 of the periodic table are preferably selected. Silica, silica-magnesia, Silica-alumina is more preferred.

  The shape of silica, silica-magnesia, silica-alumina used as a precursor of the carrier [A] is not particularly limited, and silica, silica-magnesia, silica-alumina are granular, spherical, agglomerated, fumed, etc. Any shape is possible. Preferred examples of commercially available silica products include SD3216.30, SP-9-10046, Syloid ™ 245, Devison 948 or Devison 952 [all above, WR Devison, Inc. (US branch)), Aerosil 812 [Degusa AG (Germany)], ES70X [Crossfield (USA)], P-6 and P-10 [Fuji Silysia (Japan)], etc. Is mentioned.

B. of the precursor of the carrier [A] used in the present invention; E. T. T. et al. The specific surface area determined by the nitrogen gas adsorption method by (Brunauer-Emmett-Teller) is not particularly limited, but is preferably 10 m ² / g or more and 1000 m ² / g or less, more preferably 100 m ² / g or more and 600 m ^2. / G or less, more preferably 250 m ² / g or more and 600 m ² / g or less. When the specific surface area is 10 m ² / g or more, the catalytic activity is sufficiently high, and when the specific surface area is 1000 m ² / g or less, the strength of the support [A] is sufficiently high. One typical example of the carrier [A] having such a high specific surface area is a porous material having many pores.

In the present invention, the pore volume of the precursor of the carrier [A] obtained by the nitrogen gas adsorption method is not particularly limited, but is preferably 0.1 cm ³ / g or more and 5 cm ³ / g or less, more preferably 0.8. 1 cm ³ / g or more and 3 cm ³ / g or less, more preferably 0.2 cm ³ / g or more and 2 cm ³ / g or less. The catalyst activity is sufficiently high at 0.1 cm ³ / g or more, and the strength of the carrier [A] is sufficiently high at 5 cm ³ / g or less.

In the present invention, the carrier [A] having substantially no hydroxyl group can be obtained by chemically treating the precursor of the carrier [A] to remove the hydroxyl group from the surface of the precursor of the carrier [A]. In the present invention, “the solid component has substantially no hydroxyl group” means that the hydroxyl group is not detected on the surface of the carrier [A] in the measurement by the method (i) described below.
In the method (i), a predetermined excess amount of ethoxydiethylaluminum is added to a slurry obtained by dispersing the support [A] in a nonpolar hydrocarbon solvent, and the surface hydroxyl group of the support [A] is converted to ethoxydiethyl. React with aluminum. The amount of ethane gas generated by this reaction is measured using a gas burette, and then the amount of surface hydroxyl groups on the carrier [A] is determined based on the amount of ethane gas generated. This method is based on the reaction of a hydroxyl group with ethoxydiethylaluminum represented by the following reaction formula:
S—OH + Al (Et) ₂ (OEt) → S—OAlEt (OEt) + EtH
(In the formula, S represents the carrier [A], S—OH represents the hydroxyl group on the surface of the carrier [A], and Et represents the ethyl group).

  In the present invention, specific examples of the nonpolar hydrocarbon solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclo Examples thereof include alicyclic hydrocarbons such as pentane; aromatic hydrocarbons such as benzene, toluene and xylene; or mixtures thereof. Aliphatic hydrocarbons and alicyclic hydrocarbons are preferred.

  In the present invention, after the carrier [A] precursor is heat-treated and dehydrated, it is further chemically treated to remove all hydroxyl groups from the surface of the carrier [A] precursor to obtain the carrier [A]. preferable. In the present invention, the heat treatment of the precursor of the carrier [A] is, for example, in an inert atmosphere or a reducing atmosphere, preferably at a temperature of 150 ° C. to 1,000 ° C., more preferably 250 ° C. to 800 ° C. Therefore, it can be performed by a treatment of 1 hour to 50 hours.

In the present invention, the precursor of the carrier [A] is obtained by chemical treatment using an organoaluminum compound represented by the following general formula (1) or an organomagnesium compound represented by the following general formula (2). A hydroxyl group is removed from the surface of the precursor of [A], and a carrier having substantially no hydroxyl group is obtained.
AlR ¹ _a X ¹ _3-a (1)
(In the formula, each R ¹ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ¹ is independently And represents a halide, hydride or an alkoxide group having 1 to 10 carbon atoms, and a is 1, 2 or 3.

Examples of the group R ^{1 in} the general formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, and a tolyl group. Examples of the group X ¹ in the general formula (1) include a methoxy group, an ethoxy group, a butoxy group, a hydrogen atom, and a chlorine atom.
MgR ² _b X ² _2-b (2)
(In the formula, each R ² independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ² is each independently A halide, a hydride, or an alkoxide group having 1 to 10 carbon atoms, and b is 1 or 2.
Examples of the group R ^{2 in} the general formula (2) include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, and a tolyl group. Examples of groups X ² in the general formula (2), a methoxy group, an ethoxy group, a butoxy group, a hydrogen atom, a chlorine atom.

  Specific examples of the organoaluminum compound represented by the general formula (1) used for the chemical treatment of the precursor of the carrier [A] include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tri And trialkylaluminum compounds such as decylaluminum, and reaction products of these trialkylaluminum compounds with alcohols (eg, methyl alcohol, ethyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, decyl alcohol). .

  Examples of such reaction products include methoxydimethylaluminum, ethoxydiethylaluminum, butoxydibutylaluminum and the like. When producing such a reaction product, the ratio of trialkylaluminum to alcohol is preferably in the range of 0.3 or more and 20 or less in terms of Al / OH molar ratio, and in the range of 0.5 or more and 5 or less. More preferably, it is in the range of 0.8 or more and 3 or less. In addition, the compound represented by the said General formula (1) may be used independently, and may mix and use two or more.

Specific examples of the organic magnesium compound represented by the general formula (2) used for the chemical treatment of the precursor of the carrier [A] include diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium, butyl octyl magnesium and the like.
The compound represented by the general formula (2) may be used alone or in combination of two or more.

When the precursor of the carrier [A] is chemically treated, the organoaluminum compound or organomagnesium compound described above may be used in a mixed state.
When the support [A] is obtained by subjecting the precursor of the support [A] to chemical treatment, the organometallic compound is present in an amount equal to or greater than the molar amount of hydroxyl groups present on the surface of the precursor of the support [A]. Used. The upper limit of the organometallic compound used for the chemical treatment is usually preferably 10 times the molar amount of the hydroxyl group present on the surface of the support [A] precursor, more preferably 5 times the amount, and even more preferably 2 times the amount. The amount is particularly preferably 1.5 times, and most preferably 1.3 times.

Next, the transition metal compound [B] used in the present invention will be described. The transition metal compound [B] is a transition metal compound represented by the following general formula (3).
L ¹ _c W _d M ¹ X ³ _e X ⁴ _f (3)
(In the formula, each L ¹ independently represents η selected from the group consisting of a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, a tetrahydrofluorenyl group, and an octahydrofluorenyl group. Represents a ^5- bonded cyclic anion ligand, and the ligand optionally has 1 to 8 substituents, each of which is independently a hydrocarbon group having 1 to 20 carbon atoms. A halogen atom, a halogen-substituted hydrocarbon group having 1 to 12 carbon atoms, an aminohydrocarbyl group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, and a dihydrocarbylamino group having 1 to 12 carbon atoms , Hydrocarbylphosphino group having 1 to 12 carbon atoms, silyl group, aminosilyl group, hydrocarbyloxysilyl having 1 to 12 carbon atoms A substituent selected from the group consisting of a group and a halosilyl group, wherein M ¹ is a transition metal selected from the group of transition metals belonging to Group 4 of the periodic table having a formal oxidation number of +2, +3, or +4, and at least 1 Represents a transition metal bonded to ^one ligand L ¹ by η ⁵ , and W binds to L ¹ and M ¹ each with a monovalent valence, thereby cooperating with L ¹ and M ^1. Represents a divalent substituent that forms a metallocycle, and each X ³ independently represents a monovalent anionic σ-bonded ligand, divalent anionic σ-bonded divalent to M ¹ A ligand, and an anionic σ-bonded ligand selected from the group consisting of a divalent anionic σ-bonded ligand that binds to each of L ¹ and M ¹ with a monovalent valence, X ⁴ represents a neutral Lewis base coordination compound, c is 1 or 2, provided that when c is 2 In some cases, two ligands L ¹ are bonded to each other via a divalent group, and the divalent group is a hydrocarbadiyl group having 1 to 20 carbon atoms, or a halohydro group having 1 to 12 carbon atoms. A carbadiyl group, a hydrocarbyleneoxy group having 1 to 12 carbon atoms, a hydrocarbyleneamino group having 1 to 12 carbon atoms, a silanediyl group, a halosilanediyl group, and a silyleneamino group, and d Is 0 or 1, e is 0, 1 or 2, provided that X ³ is a monovalent anionic σ-bonded ligand or a divalent anion bonded to L ¹ and M ¹ E is a natural number that is 1 or more smaller than the formal oxidation number of M ¹ , and X ³ is a divalent anionic σ bond ligand in which X ³ is bonded only to M ^1. If it is, e is the form oxidation number of M ¹ Ri (c + 1) or more less a natural number, f is 0, 1 or 2)
Examples of the ligand X ³ in the compound of the general formula (3) include a halide, a hydrocarbon group having 1 to 60 carbon atoms, a hydrocarbyloxy group having 1 to 60 carbon atoms, and 1 to 60 carbon atoms. A hydrocarbyl amide group having 1 to 60 carbon atoms, a hydrocarbyl sulfide group having 1 to 60 carbon atoms, a silyl group, and a composite group thereof.

Examples of the neutral Lewis base coordination compound X ^{4 in} the compound of the general formula (3) include phosphine, ether, amine, olefin having 2 to 40 carbon atoms, diene having 4 to 40 carbon atoms, these And a divalent group derived from the above compound.

  The transition metal compound [B] used in the present invention is preferably a compound represented by the following general formula (6).

(In the formula, R ⁶ and R ⁹ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 7 to 20 carbon atoms and having a hydrocarbon group on the aromatic ring. Each of the hydrocarbon groups, R ⁷ and R ⁸ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁷ and R ⁸ may be bonded to each other to form a ring; X ⁵ and X ⁶ each independently represent a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M ⁴ represents nickel or palladium.)

In the general formula (6), the aliphatic hydrocarbon group having 1 to 20 carbon atoms of R ⁶ and R ⁹ is a linear or branched alkyl group having 1 to 20 carbon atoms, or carbon A cycloalkyl group having a number of 3 or more and 20 or less is preferable. Specifically, methyl group, ethyl group, propyl group, 1-methylethyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, octyl group Decyl group, tetradecyl group, hexadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like. An appropriate substitution difference such as a lower alkyl group may be introduced on the ring of the cycloalkyl group.

Further, the aromatic hydrocarbon group having a total carbon number of 7 to 20 and having a hydrocarbon group on the aromatic ring includes, for example, an aromatic ring such as a phenyl group or a naphthyl group having a carbon number of 1 to 10 And a group in which one or more linear, branched, or cyclic hydrocarbon groups are introduced. R ⁶ and R ⁹ are preferably aromatic groups having a hydrocarbon group on the ring, and more preferably a 2,6-bis (1-methylethyl) phenyl group. R ⁶ and R ⁹ may be the same or different.

Examples of the hydrocarbon group having 1 to 20 carbon atoms in R ⁷ and R ⁸ include, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, and a cycloalkyl having 3 to 20 carbon atoms. Group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the like. Here, as a specific example of a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms, one or more carbon atoms of R ⁶ and R ⁹ above are used. The same thing as illustrated in description of 20 or less aliphatic hydrocarbon group can be mentioned. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, tolyl group, xylyl group, naphthyl group, and methylnaphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and Examples thereof include a phenethyl group. R ⁷ and R ⁸ may be the same or different. In addition, they may be bonded to each other to form a ring.

Examples of the halogen atom in X ⁵ and X ⁶ include a chlorine atom, a bromine atom, or an iodine atom, and the hydrocarbon group having 1 to 20 carbon atoms is the number of carbon atoms in R ⁷ and R ⁸ above. 1 to 20 hydrocarbon groups are as described above. X ⁵ and X ⁶ are particularly preferably a bromine atom or a methyl group. X ⁵ and X ⁶ may be the same or different.
In the present invention, the transition metal compound [B] is more preferably a compound represented by the following general formula (7).

(Wherein M ⁵ represents a transition metal selected from the group consisting of titanium, zirconium, and hafnium, and represents a transition metal having a formal oxidation number of +2, +3, or +4, and each R ¹⁰ independently represents: Represents a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a germyl group, a cyano group, a halogen atom, and a composite group thereof, provided that the substituent R ¹⁰ is When it is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group or a germyl group, in some cases, two adjacent substituents R ¹⁰ are bonded to each other to form a divalent group, whereby the two adjacent groups To form a ring by cooperating with a bond between two carbon atoms of the cyclopentadienyl ring each bonded to the substituent R ^10, and each X ⁷ independently represents a halogen atom, a carbon number of 1 or more and 20 below Hydrocarbyloxy group having 1 to 18 carbon atoms, hydrocarbylamino group having 1 to 18 carbon atoms, silyl group, hydrocarbylamide group having 1 to 18 carbon atoms, hydrocarbyl phosphide having 1 to 18 carbon atoms Represents a substituent selected from the group consisting of a group, a hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a composite group thereof. However, in some cases, two substituents X ⁷ cooperate to have 4 to 30 carbon atoms. The following neutral conjugated dienes or divalent groups are formed, and Y represents —O—, —S—, —NR ^* — or —PR ^* —, where R ^* is a hydrogen atom, carbon number 1 A hydrocarbon group having 12 or less carbon atoms, a hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, a halogenated alkyl group having 1 to 8 carbon atoms, a hydrocarbon group having 6 to 20 carbon atoms. Gen aryl group or represents these composite base,, Z is _{^{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * 2 CR * 2, CR * = CR *, CR * 2 SiR * 2 , or Represents GeR ^* ₂ , where R ^* is as defined above and r is 1, 2 or 3.

Specific examples of the transition metal compound [B] used in the present invention include the following compounds.
Bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl zirconium hydride, bis (cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) ) Neopentylzirconium hydride, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, (pentamethylcyclopentadienyl) (cyclopentadienyl) ) Zirconium dimethyl, bis (cyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis ( Clopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium dihydride, bis (fluorenyl) zirconium dimethyl, ethylene bis (indenyl) zirconium dimethyl, ethylene bis (indenyl) Zirconium diethyl, ethylenebis (indenyl) zirconium dihydride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dimethyl, ethylenebis (4-methyl-1-indenyl) zirconium dimethyl, ethylenebis (5 -Methyl-1-indenyl) zirconium dimethyl, ethylenebis (6-methyl-1-indenyl) zirconium dimethyl, ethylenebis (7-methyl-1-indenyl) zyl Nitrodimethyl, ethylenebis (5-methoxy-1-indenyl) zirconium dimethyl, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dimethyl, ethylenebis (4,7-dimethyl-1-indenyl) dimethylzirconium, ethylene Bis- (4,7-dimethoxy-1-indenyl) zirconium dimethyl, methylenebis (cyclopentadienyl) zirconium dihydride, methylenebis (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl) zirconium dihydride, isopropyl Liden (cyclopentadienyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dihydride, isopropylidene (cyclopentadienyl-fluorene) Nyl) zirconium dimethyl, silylene bis (cyclopentadienyl) zirconium dihydride, silylene bis (cyclopentadienyl) zirconium dimethyl, dimethylsilylene (cyclopentadienyl) zirconium dihydride, dimethylsilylene (cyclopentadienyl) zirconium dimethyl, (Nt-Butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(Nt-butyramide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethyl Silane] titanium dimethyl, [(N-methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-phenylamido) (tetramethyl-η ⁵ -cyclopentadie Nyl) dimethylsilane] titanium dimethyl, [(N-benzylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamide) (η ⁵ -cyclopentadienyl) -1,2-ethanediyl] titanium dimethyl, [(Nt-butylamide) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(N-methylamide) (η ⁵ -cyclopentadienyl) -1 , 2-ethanediyl] titanium dimethyl, [(N-methylamido) (η ⁵ -cyclopentadienyl) dimethylsilane] titanium dimethyl, [(Nt-butylamido) (η ⁵ -indenyl) dimethylsilane] titanium dimethyl, (N-benzylamide) (η ⁵ -indenyl) dimethylsilane ] Titanium dimethyl.

As specific examples of the transition metal compound [B] used in the present invention, the “dimethyl” part of the names of the zirconium and titanium compounds listed above as specific examples of the transition metal compound [B] The last part of the name of each compound, that is, the part appearing immediately after the part of “zirconium” or “titanium” and corresponding to the part of X ^{7 in} the general formula (6)) Also included are compounds having names that can be substituted for any of those listed above.
“Dibenzyl”, “2- (N, N-dimethylamino) benzyl”, “2-butene-1,4-diyl”, “s-trans-η ⁴ -1,4-diphenyl-1,3-butadiene” , “S-trans-η ⁴ -3-methyl-1,3-pentadiene”, “s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene”, “s-trans-η ⁴ -2” , 4-hexadiene, "" s- trans eta ⁴ -1,3-pentadiene "," s- trans eta ^{4-1,4-ditolyl-1,3-butadiene,} "" s- trans eta ⁴ - 1,4-bis (trimethylsilyl) -1,3-butadiene ”,“ s-cis-η ⁴ -1,4-diphenyl-1,3-butadiene ”,“ s-cis-η ⁴ -3-methyl-1 ” , 3-pentadiene ”,“ s-cis-η ⁴ -1,4-dibenzyl ”. -1,3-butadiene "," s-cis-η ⁴ -2,4-hexadiene "," s-cis-η ⁴ -1,3-pentadiene "," s-cis-η ⁴ -1,4- “Ditolyl-1,3-butadiene”, “s-cis-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene”.

The transition metal compound [B] used in the present invention can be synthesized by a generally known method. In the present invention, examples of the preferred synthesis method of the transition metal compound [B] include the method disclosed in US Pat. No. 5,491,246.
In the present invention, these transition metal compounds [B] may be used alone or as a mixture of plural kinds.

In the present invention, the transition metal compound [B] can be used for the transition metal compound (B-1) represented by the above general formula (3) and the nonpolar hydrocarbon solvent represented by the following general formula (4). It is preferable that it is a mixture with a soluble organomagnesium compound (B-2).
(M ² ) _g (Mg) _h (R ³ ) _i (R ⁴ ) _j (OR ⁵ ) _k (4)
{Wherein M ² is a metal atom belonging to the group consisting of Group 1, Group 2 and Group 3 of the Periodic Table, and R ³ , R ⁴ and R ⁵ each independently have 2 or more carbon atoms. It is a hydrocarbon group of 20 or less, and g, h, i, j and k are numbers satisfying the following relationship. 0 ≦ g, 0 <h, 0 ≦ i, 0 ≦ j, 0 ≦ k, i + j> 0, 0 ≦ k / (g + h) ≦ 2, m × g + 2h = i + j + k (where m is the valence of M ² ) }

The organomagnesium compound (B-2) is shown as a complex form of organomagnesium soluble in a nonpolar hydrocarbon solvent, but includes all of R ³ Mg and complexes of these with other metal compounds To do. The relationship m × g + 2h = i + j + k between the symbols g, h, i, j, k, and m indicates the stoichiometry between the valence of the metal atom and the substituent.

In the above general formula, the hydrocarbon groups represented by R ³ and R ⁴ are each independently an alkyl group, a cycloalkyl group or an aryl group, such as a methyl group, an ethyl group, a propyl group, or 1-methylethyl. Group, butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, pentyl group, hexyl group, octyl group, decyl group, phenyl group, tolyl group and the like, and R ³ R ⁴ and R ⁴ are preferably alkyl groups, and R ³ and R ⁴ are more preferably primary alkyl groups.
When g> 0, as the metal atom M ² , a metal element belonging to the group consisting of Group 1, Group 2 and Group 3 of the Periodic Table can be used. For example, lithium, sodium, potassium, beryllium, zinc, Boron, aluminum and the like can be mentioned, and aluminum, boron, beryllium and zinc are particularly preferable.

In the present invention, the molar ratio h / g of magnesium to metal atom M ² is not particularly limited, but is preferably 0.1 or more and 30 or less, and more preferably 0.5 or more and 10 or less. When an organomagnesium compound with g = 0 is used, for example, an organomagnesium compound in which R ³ is a 1-methylpropyl group is soluble in a nonpolar hydrocarbon solvent, and such a compound is also preferable in the present invention. Give the result.

In the above general formula (4), when g = 0, R ³ and R ⁴ are recommended to be any one of the following three groups (1), (2), and (3): .
(1) At least one of R ³ and R ⁴ is a secondary or tertiary alkyl group having 4 to 6 carbon atoms, preferably both R ³ and R ⁴ have 4 to 6 carbon atoms. Yes, and at least one is a secondary or tertiary alkyl group.
(2) R ³ and R ⁴ are alkyl groups different from each other, preferably R ³ is an alkyl group having 2 or 3 carbon atoms, and R ⁴ is an alkyl group having 4 or more carbon atoms. Be.
(3) At least one of R ³ and R ⁴ is a hydrocarbon group having 6 or more carbon atoms, preferably R ³ and R ⁴ are both alkyl groups having 6 or more carbon atoms.

These groups are specifically shown below.
In (1), examples of the secondary or tertiary alkyl group having 4 to 6 carbon atoms include 1-methylpropyl, 1,1-dimethylethyl, 1-methylbutyl, 1-ethylpropyl, and the like. 1-methylpropyl is particularly preferred.
In (2), examples of the alkyl group having 2 or 3 carbon atoms include an ethyl group, a propyl group, and a 1-methylethyl group, and an ethyl group is preferable. Examples of the alkyl group having 4 or more carbon atoms include a butyl group, an amyl group, a hexyl group, and an octyl group, and a butyl group and a hexyl group are preferable.
In (3), examples of the hydrocarbon group having 6 or more carbon atoms include a hexyl group, an octyl group, a decyl group, and a phenyl group. An alkyl group is preferable, and a hexyl group is more preferable.

  In general, increasing the number of carbon atoms in an alkyl group makes it easier to dissolve in a nonpolar hydrocarbon solvent, but the solution tends to increase in viscosity, and it is not preferable for handling to use a longer-chain alkyl group than necessary. In addition, although the said organomagnesium compound is used as a hydrocarbon solution, even if a trace amount of complexing agents, such as ether, ester, and amine, are contained or remain in the solution, it can be used without any problem.

Next, the alkoxy group (OR ⁵ ) will be described. The hydrocarbon group represented by R ⁵ is preferably an alkyl group or an aryl group having 3 to 10 carbon atoms.
Specifically, for example, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, hexyl, 2-methylpentyl, 2-ethylbutyl, 2-ethylpentyl , 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, octyl, decyl, phenyl group, etc., preferably butyl, 1-methylpropyl, 2- Methylpropyl, 2-methylpentyl and 2-ethylhexyl.

These organomagnesium compounds or organomagnesium complexes include an organomagnesium compound represented by the general formulas R ³ MgX and R ³ ₂ Mg (R ³ is as defined above, X is a halogen), and a general formula M ² R Reaction with an organometallic compound represented by ⁴ _r or M ² R ⁴ _r-1 H (M ² , R ⁴ , m are as defined above) in a nonpolar hydrocarbon solvent at 25 ° C. or higher and 150 ° C. or lower And, if necessary, a hydrocarbyloxymagnesium compound having a hydrocarbon group represented by R ⁵ that is soluble in an alcohol having a hydrocarbon group represented by R ⁵ or a nonpolar hydrocarbon solvent, and / or or central metal can be obtained by a method of reacting a hydrocarbyloxy metal compounds which are M ^2.

  Among these, when the organic magnesium component soluble in hydrocarbon and the alcohol are reacted, the order of the reaction is such that the alcohol is added to the organic magnesium component, the organic magnesium component is added to the alcohol, or Any method of adding both at the same time can be used. In the present invention, the reaction ratio between the organic magnesium component soluble in hydrocarbon and the alcohol is not particularly limited, but as a result of the reaction, the molar composition of the alkoxy group with respect to all the metal atoms in the resulting alkoxy group-containing organic magnesium component. The range of the ratio k / (g + h) is 0 ≦ k / (g + h) ≦ 2, and preferably 0 ≦ k / (g + h) <1.

In the present invention, the transition metal compound [B] can be obtained by mixing (B-1) and (B-2).
In the present invention, the method of mixing (B-1) and (B-2) is not particularly limited. For example, the method of adding (B-2) to (B-1), or Any method of adding (B-1) to the component (B-2) or adding both at the same time can be used.

In the present invention, the ratio of the number of moles of M ² contained in (B-2) to the number of moles of Mg contained in (B-2) relative to the number of moles of M ¹ contained in the transition metal compound (B-1) {(M ² + Mg ) / M ¹ } is preferably 0.005 or more and 5 or less, and more preferably 0.01 or more and 2 or less.
In the present invention, the amount of (B-1) used with respect to the carrier [A] is not particularly limited, but it is 5 × 10 ⁻⁶ mol / g or more and 10 with respect to 1 g of the carrier [A] of (B-1). It is preferably ⁻² mol / g or less, more preferably 10 ⁻⁵ mol / g or more and 10 ⁻³ mol / g or less.

  Next, the activated compound [C] containing a cation and a compatible non-coordinating anion and capable of reacting with the transition metal compound [B] to form a metal complex having catalytic activity will be described. To do.

  First, the compatible non-coordinating anion will be described. The compatibility in the present invention means that when the activating compound [C] is decomposed into an anion and a cation, the chemical structure of the anion will not be decomposed and become neutral, and the anion will react with the catalyst of the present invention. This means that the polymerization reaction of the olefin used is not adversely affected. The non-coordinating property in the present invention means that the anion cannot form a coordination bond with the transition metal compound [B], or the anion can form only a weak coordination bond with the transition metal compound [B]. It means that it is easily substituted with a neutral Lewis basic compound such as olefin. Furthermore, in the present invention, by using a compatible non-coordinating anion, when a coordination bond is not formed with the transition metal compound [B] (in such a case, the anion is a charge balancing anion in the catalyst of the present invention). Since the anion does not undergo decomposition, the neutralization of the transition metal compound [B] and the generation of neutral by-products in the aforementioned complex as the active species due to the decomposition of the anion Is avoided.

In the present invention, the activating compound [C] is preferably a compound represented by the following general formula (5).
[L ² −H] ^{n +} [M ³ _p Q ¹ _q ] ⁿ⁻ (5)
(Wherein [L ² —H] ^{n +} represents a proton-donating Bronsted acid, wherein L ² represents a neutral Lewis base, n is an integer of 1 to 7, and [M ³ _p Q ¹ _q ] ⁿ⁻ represents a compatible non-coordinating anion, provided that M ³ represents Group 5, Group 6, Group 7, Group 8, Group 9, Group 10 of the Periodic Table, Represents a metal element or metalloid belonging to any of Group 11, Group 12, Group 13, Group 14, Group 15, and Q ¹ is independently a hydrogen atom, a halogen atom, or 2 or more carbon atoms. Selected from the group consisting of a dihydrocarbyl amide group having 20 or less, a hydrocarbyloxy group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms, and a substituted hydrocarbon group having 1 to 40 carbon atoms. However, the number of Q which is a halide is 1 or less, and p is 1 or more and 7 or less. Q is an integer from 2 to 14, n is an integer from 1 to 7, and q−p = n.)

In the present invention, a more preferred example of the activating compound [C] is represented by the following general formula (8).
[L ² −H] ^{n +} [M ³ _p Q ¹ _s (G _t (T−H) _u ) _v ] ⁿ⁻ (8)
(Wherein [L ² −H] ^{n +} , L ² , M ³ , Q ¹ , n, and p are as defined in the general formula (5), and G is a u + 1 bond with M ³ and T. A polyvalent hydrocarbon group having a valence, wherein T is O, S, NR, or PR, wherein R is a hydrocarbyl, trihydrocarbylsilyl group, trihydrocarbylgermanium group, or hydrogen, and s is 0 or more. (It is an integer of 7 or less, t is 0 or 1, u is an integer of 0 or more and 3 or less, v is an integer of 1 or more and 8 or less, and s + v−p = n.)

In the present invention, the activating compound [C] is preferably a compound represented by the following general formula (9).
[L ² −H] ⁺ [BQ ² ₃ Q ³ ] ⁻ (9)
(Wherein L ² is as defined in formula (5). In the formula, [L ² —H] ⁺ represents a proton-donating Bronsted acid, and [BQ ² ₃ Q ³ ] ⁻ Is a compatible non-coordinating anion, Q ² is a pentafluorophenyl group, and the remaining one Q ³ is a substituted aryl group having 6 to 20 carbon atoms and having one OH group as a substituent. )

Specific examples of the compatible non-coordinating anion contained in the activated compound [C] of the present invention include, for example, tetrakisphenyl borate, tri (p-tolyl) (phenyl) borate, tris (pentafluorophenyl) ( Phenyl) borate, tris (2,4-dimethylphenyl) (hydrphenyl) borate, tris (3,5-dimethylphenyl) (phenyl) borate, tris (3,5-di-trifluoromethylphenyl) (phenyl) borate, Tris (pentafluorophenyl) (cyclohexyl) borate, tris (pentafluorophenyl) (naphthyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl ( 2,4- Hydroxyphenyl) borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5- Dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4 -Hydroxybutyl) borate, tris (pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4'-hydroxyphenyl) phenyl) borate, tris (pentaph Fluorophenyl) (6-hydroxy-2-naphthyl) borate and the like, and tris (pentafluorophenyl) (4-hydroxyphenyl) borate is preferable.
Examples of other preferred compatible non-coordinating anions include borates in which the hydroxy group of the borate exemplified above is substituted with an NHR group. Here, R is preferably a methyl group, an ethyl group or a t-butyl group.

Specific examples of the proton-providing Bronsted acid of the present invention include, for example, triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium and tri (n-octyl) ammonium. And trialkyl group-substituted ammonium cations. N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzyl Also suitable are N, N-dialkylanilinium cations such as anilinium.
Furthermore, dialkylammonium cations such as di- (i-propyl) ammonium and dicyclohexylammonium are also suitable, such as triphenylphosphonium, tri (methylphenyl) phosphonium, tri (dimethylphenyl) phosphonium and the like. Such triarylphosphonium cations, dimethylsulfonium, diethylfuronium, diphenylsulfonium and the like are also suitable.
In the present invention, these activating compounds [C] may be used alone or in combination.

In the present invention, it is preferable that the activation compound [C] is used in an amount sufficient for the component (B-1) to react. Specifically, the use amount of the activating compound [C] is 0.8 times or more and 5 times or less in a molar ratio ((B-1) / [C]) to (B-1), more preferably. 1 to 2 times.
In the present invention, when the activation compound [C] is added to the catalyst preparation reactor, the activation compound [C] is prepared through a sintered filter having a nominal filtration accuracy of 0.01 μm to 5 μm. Added to the liquid phase of the reactor.

  In the present invention, it is extremely important that the fine droplets of the activated compound [C] generated by passing through the sintered filter are added to the catalyst preparation reactor before re-aggregation. The activation compound [C] is added to the liquid phase of the catalyst preparation reactor through a sintered filter having a nominal filtration accuracy of 0.01 μm or more and 5 μm or less, whereby the activation compound [C] is used for catalyst preparation. By forming fine droplets in the liquid phase of the reactor and supporting these droplets on the carrier [A], it is possible to prepare a homogeneous catalyst with good dispersibility of the activated compound [C]. That is, in the present invention, fine droplets of the activating compound [C] are carried on the carrier [A], so that the activity is high and the polymer can be polymerized without causing adhesion to the reactor, etc. A catalyst capable of producing a polyolefin powder that is excellent in particle properties and does not float in a non-polar hydrocarbon solvent and can be easily separated from the solvent by centrifugation can be produced.

  The catalyst preparation reactor in the present invention is a reactor generally used when preparing an olefin polymerization catalyst such as a Ziegler catalyst and a metallocene catalyst. Although there is no restriction | limiting in particular about the shape of this reactor, The reactor with a vessel type and stirring equipment and temperature control equipment is preferable.

  In the present invention, the type of sintered filter is not particularly limited, and any sintered filter manufactured by sintering stainless metal powder, stainless metal fiber, polymer powder, or the like should be used. However, a sintered filter manufactured by sintering a stainless metal powder is preferable.

The nominal filtration accuracy of the sintered filter in the present invention is a contaminant particle size with a collection efficiency of 95% that passes through the sintered filter, and is a particle size measured by the method of JIS-B8356.
The nominal filtration accuracy of the sintered filter used in the present invention is from 0.01 μm to 5 μm, preferably from 0.03 μm to 4 μm, and more preferably from 0.05 μm to 3 μm. In the present invention, when the nominal filtration accuracy of the sintered filter is 0.01 μm or more, since the resistance when passing through the sintered filter is low, the activation compound [C] can be easily added to the reactor. In the following, since the dispersibility of the activation compound [C] is sufficient, a homogeneous catalyst can be produced. In the present invention, the nominal filtration accuracy of the sintered filter can be controlled by the diameter of the raw material before sintering. Specifically, for example, in the case of a sintered filter manufactured by sintering stainless steel metal powder, by reducing the diameter of the stainless steel metal particle, the nominal filtration accuracy of the sintered filter is reduced. Increasing the diameter increases the nominal filtration accuracy of the sintered filter.

In the present invention, the linear velocity of addition of the activation compound [C] through the sintered filter is not particularly limited, but is preferably 0.1 m / s or more and 100 m / s or less, preferably 1 m / s or more. It is more preferably 80 m / s or less, and further preferably 5 m / s or more and 60 m / s or less. The linear velocity of the addition is a velocity at which the fluid flows through the average pores of the sintered filter, and is a velocity calculated from the following mathematical formula.
F = H / (I × J × K)
F: Linear velocity of addition (m / s)
H: Rate of addition (m ³ / s)
I: Filtration area of the sintered filter (m ² )
J: Number of pores of sintered filter (pieces / m ² )
K: Average pore area of sintered filter (m ² / piece)

  In the present invention, when the linear velocity is 0.1 m / s or more, since the droplets are supported on the carrier [A] without agglomeration, a catalyst having good dispersibility of the activating compound [C] can be obtained. At 100 m / s or less, since the droplets of the activation compound [C] are sufficiently small, a catalyst having good dispersibility of the activation compound [C] can be obtained. In the present invention, since the linear velocity of this addition is calculated according to the above mathematical formula, it can be controlled by changing the balance of the filtration area, the number of pores and the average pore area of the sintered filter. That is, when the addition rate of the activation compound [C] is constant, the linear velocity of the addition is reduced when the filtration area, the number of pores and the multiplier of the average pore area of the sintered filter are increased, When the filtration area, the number of pores, and the multiplier of the average pore area of the sintered filter are reduced, the linear velocity of addition increases. In addition, when the same sintered filter is used, the linear velocity of addition can be controlled by the addition rate, that is, the linear velocity of addition increases by increasing the addition rate.

  In the present invention, the installation position of the sintered filter in the reactor for preparing the olefin polymerization catalyst is not particularly limited, but it is preferably located in the liquid phase of the reactor. By positioning the sintered filter in the nonpolar hydrocarbon solvent when the activating compound [C] is added, the activated compound [C] formed into fine droplets by the sintered filter is efficiently agglomerated without supporting the carrier [A ]. Further, in the present invention, solids such as catalyst preparation reactor walls, baffles, stirring blades and the like closest to the surface of the sintered filter (excluding piping and carrier [A] connected to the sintered filter) Is preferably not less than the distance that the activating compound [C] advances in 0.01 seconds (distance obtained by multiplying the addition linear velocity by 0.01 seconds), and more than the distance that advances in 0.05 seconds. More preferably. Since the activated compound [C] is adsorbed to the carrier [A] within 0.01 seconds, the wall of the reactor for catalyst preparation, baffles, and stirring are longer than the distance that the activated compound [C] travels in 0.01 seconds. If the distance from the solid such as a wing is long, almost the entire amount of the activating compound [C] is adsorbed on the carrier [A].

  In the present invention, it is important to stir the catalyst preparation reactor when preparing the catalyst, particularly when adding the activating compound [C]. In the present invention, since it is preferable that all raw materials including the activating compound [C] are uniformly supported on the carrier [A], the activating compound [C] is used as droplets, and the carrier [A] and It is preferable that the solid, which is an intermediate in each stage of catalyst preparation, is agitated with sufficient and sufficient strength to form a uniform slurry.

Next, the organoaluminum compound [D] used in the present invention will be described.
Examples of the organoaluminum compound [D] of the present invention include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and the like, or these alkylaluminum and methyl alcohol, ethyl alcohol, butyl alcohol, Reaction products with alcohols such as pentyl alcohol, hexyl alcohol, octyl alcohol and decyl alcohol, such as dimethylmethoxyaluminum, diethylethoxyaluminum, dibutylbutoxyaluminum and the like.

Furthermore, the range of the composition ratio of the alkylaluminum and the alcohols, that is, the molar ratio of Al / OH, when producing the reaction product is preferably 0.3 or more and 20 or less, more preferably 0.5 or more and 5 or less. Yes, more preferably 0.8 or more and 3 or less.
In the present invention, the amount of the organoaluminum compound [D] is preferably 0.01 or more and 1000 or less, and more preferably 0.1 or more and 100 or less, as a molar ratio to the transition metal compound [B]. More preferably, it is 1 or more and 10 or less.

Next, a method for producing a catalyst for olefin polymerization from the carrier [A], the transition metal compound [B], the activating compound [C], and the organoaluminum compound [D] will be described.
In the present invention, the conditions for producing the olefin polymerization catalyst from the support [A], the transition metal compound [B], the activation compound [C], and the organoaluminum compound [D] are not particularly limited. It is preferably carried out between 0 ° C. and 40 ° C. in a hydrogen solvent.

  The order of addition of the carrier [A], transition metal compound [B], activation compound [C], and organoaluminum compound [D] is not particularly limited, but the activation compound [C] and the organoaluminum compound [D] It is preferable to contact these in advance. For the sake of convenience, the contact product between the activation compound [C] and the organoaluminum compound [D] will be referred to as contact product [CD]. The method of combining the support [A], the transition metal compound [B], and the contact product [CD] is not particularly limited, but after the transition metal compound [B] and the contact product [CD] are contacted in advance, the support [ A method in which A] is contacted or a method in which the support [A] and the contact product [CD] are contacted in advance and then the transition metal compound [B] is contacted is preferable. When the transition metal compound [B] and the contact product [CD] are contacted in advance, the transition metal compound [B] is preferably contacted in a good solvent. Further, when the carrier [A] and the contact product [CD] are contacted in advance, it is preferable to contact them in a poor solvent for the transition metal compound [B]. Examples of the good solvent for the transition metal compound [B] include aromatic compounds such as benzene, toluene, and xylene. Examples of the poor solvent include isobutane, pentane, isopentane, hexane, heptane, octane, decane, Examples thereof include linear or branched hydrocarbon compounds such as dodecane and kerosene.

In the present invention, the amount of each component used and the ratio of the amounts used are not particularly limited, but it is preferable to use an amount of the activating compound [C] sufficient to activate the transition metal compound [B].
In the present invention, the transition metal compound [B] is used in an amount of 5 × 10 ⁻⁶ mol to 10 ⁻² mol, more preferably 10 ⁻⁵ mol to 10 ⁻³ mol, relative to 1 g of the carrier [A]. Is preferred.

In the present invention, the olefin polymerization catalyst may be prepolymerized with olefin. In the present invention, when prepolymerization is performed, the amount of the transition metal compound [B] used is 1 × 10 ⁻⁵ mol or more and 5 × 10 ⁻³ mol or less with respect to 1 g of the carrier [A]. Is preferably 5 × 10 ⁻⁵ mol or more and 10 ⁻³ mol or less. In the present invention, the prepolymerization temperature is not particularly limited, but is preferably -20 to 80 ° C, more preferably 0 to 50 ° C. In the present invention, the prepolymerization time varies depending on the prepolymerization temperature, but is preferably 0.5 hours or more and 100 hours or less, and more preferably 1 hour or more and 50 hours or less. In the present invention, the amount of the polymer produced by the prepolymerization is preferably from 0.1 g to 500 g, more preferably from 0.3 g to 300 g, further preferably from 1 g to 100 g, per 1 g of the olefin polymerization catalyst. The olefin used in the prepolymerization is preferably selected from olefins used in the polymerization described below, and ethylene is particularly preferable.
In the present invention, the activating compound [C] and the organoaluminum compound [D] are preferably contacted in advance.

Next, a specific embodiment in which olefin polymerization is performed in the presence of the catalyst of the present invention will be described. Ethylene is homopolymerized using the olefin polymerization catalyst of the present invention, or ethylene and preferably an α-olefin having 3 to 20 carbon atoms, a cyclic olefin having 3 to 20 carbon atoms, a general formula CH ₂ = CHR (provided that , R is an aryl group having 6 to 20 carbon atoms, and at least one olefin selected from the group consisting of linear, branched or cyclic dienes having 4 to 20 carbon atoms; Can be copolymerized.
In addition, the method for adding the catalyst for olefin polymerization of the present invention to a polymerization vessel as a slurry of aliphatic hydrocarbons and alicyclic hydrocarbons described later is preferable.

In the present invention, the α-olefin having 3 to 20 carbon atoms is, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-decene, The cyclic olefin having 3 to 20 carbon atoms selected from the group consisting of dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene is, for example, cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl- Selected from the group consisting of 2-norbornene, tetracyclododecene, and 2-methyl-1.4,5.8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; Examples of the compound represented by the general formula CH ₂ ═CHR (wherein R is an aryl group having 6 to 20 carbon atoms) include, for example, styrene and vinyl chloride. Examples of the linear, branched or cyclic diene having 4 to 20 carbon atoms such as chlorohexane include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, and 1,4-hexadiene. , And cyclohexadiene.

  By copolymerizing ethylene and the olefin (comonomer), the density and physical properties of the ethylene polymer can be controlled. The polymerization of olefins according to the present invention can be carried out either by suspension polymerization or gas phase polymerization. In the suspension polymerization method, a nonpolar hydrocarbon solvent can be used as a solvent for suspension polymerization, and olefin itself can also be used as a solvent.

  The amount of catalyst feed in the polymerization of ethylene using the olefin polymerization catalyst of the present invention is, for example, 1 wt% to 0.001 wt% of the catalyst with respect to the mass of the polymer obtained per hour. It is desirable to adjust the catalyst concentration in the polymerization system. The polymerization temperature is usually preferably 0 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 60 ° C. or higher, and 150 ° C. or lower, more preferably 110 ° C. or lower, more preferably 100 ° C. or lower. It is a range. The polymerization pressure is usually preferably from normal pressure to 10 MPa, more preferably from 0.2 to 5 MPa, and even more preferably from 0.5 to 3 MPa. The polymerization reaction may be batch, semi-continuous or continuous. Any method can be used. It is also possible to carry out the polymerization in two or more stages having different reaction conditions.

  Further, for example, as described in Patent Document 2, the molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

The polymerization method using the olefin polymerization catalyst of the present invention makes it possible to produce an olefin polymer having excellent powder properties. Specifically, since the polymer is obtained in the form of a powder not only having a narrow particle size distribution range but also having a high bulk density, the resulting polymer exhibits excellent fluidity. Furthermore, since the obtained powder does not float in the nonpolar hydrocarbon solvent, the solvent and the powder can be easily separated by centrifugation.
Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

  In the present invention, hydrogen, nitrogen, hexane, and Isopar E [trade names of body hydrocarbon mixtures manufactured by Exxon Chemical Company (USA)] used in Examples and Comparative Examples are MS-13X (manufactured by Showa Union). After dehydration, hexane was further used after deoxygenation by vacuum degassing using a vacuum pump. Ethylene, hexane, and 1-hexene used in Examples and Comparative Examples were dehydrated using MS-3A (manufactured by Showa Union), and hexane and 1-hexene were further degassed by vacuum degassing using a vacuum pump. Used after oxygen.

The physical properties of the samples in the examples were evaluated as follows.
(1) The molar amount of the surface hydroxyl group of the precursor of the carrier [A] The molar amount of the surface hydroxyl group of the precursor of the carrier [A] is obtained by reacting ethoxydiethylaluminum with the surface hydroxyl group of the precursor of the carrier [A]. Was calculated from the amount of generated ethane gas measured using a gas burette.
(2) Specific surface area of the precursor of the carrier [A] The specific surface area of the precursor of the carrier [A] was measured by the BET method using an autosorb 3MP device manufactured by Yuasa Ionics, using nitrogen as the adsorption gas. did.
(3) Average particle size of precursor of carrier [A] The average particle size of the precursor of carrier [A] was measured using SALD-2100 manufactured by Shimadzu Corporation.
(4) Polymerization activity of the catalyst The polymerization activity of the catalyst was expressed as the amount of polymer produced per hour (g) per 1 g of the olefin polymerization catalyst.
(5) Polymer melt flow rate (MFR)
The melt flow rate (MFR) of the polymer was measured at a temperature of 190 ° C. and a load of 2.16 kg according to JIS K7210.
(6) Density Density was measured according to the density gradient tube method of JIS K7112.
(7) Bulk density The bulk density was measured according to JIS K-6721 after the obtained powder was dried at 60 ° C for 1 hour.
(8) Adhesion of polymer to the polymerization vessel The evaluation of the adhesion of the polymer to the polymerization vessel is a measure of stable operation at the time of scale-up. When there was, it was set as x.
(9) Floating amount of powder in nonpolar hydrocarbon solvent Floating amount of powder in nonpolar hydrocarbon solvent is obtained by drying the obtained powder at 90 ° C for 1 hour, and then adding 5 g (weighed) of powder at room temperature. After stirring and mixing with 100 ml of hexane, the amount of powder suspended in hexane was measured.

[Example 1]
(Preparation of carrier [A])
Silica P-10 [manufactured by Fuji Silysia Ltd. (Japan)] was used as a precursor of the carrier [A]. Silica P-10 was calcined at 400 ° C. for 5 hours in a nitrogen atmosphere and dehydrated. The amount of the surface hydroxyl groups of the silica was 1.41mmol / g-SiO _2. The average particle diameter of silica was 23 μm, and the specific surface area was 300 m ² / g. 5 kg of this dehydrated silica was dispersed in 100 L of hexane in an autoclave having a capacity of 200 L sufficiently substituted with nitrogen to obtain a slurry. While maintaining the resulting slurry at 50 ° C. with stirring, 7.5 L of a hexane solution of triethylaluminum (concentration 1M) was added over 60 minutes, and then stirred for 2 hours to react triethylaluminum with the surface hydroxyl group of silica to obtain triethylaluminum. A support [A] containing silica treated with aluminum and a supernatant liquid, in which all surface hydroxyl groups of the silica treated with triethylaluminum were crushed was obtained. Thereafter, the supernatant liquid in the obtained reaction mixture was removed by decantation to remove unreacted triethylaluminum in the supernatant liquid. Thereafter, an appropriate amount of hexane was added to obtain 100 L of a hexane slurry of silica treated with triethylaluminum.

(Preparation of transition metal compound [B])
[(Nt-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) dimethylsilane] Titanium-1,3-pentadiene (hereinafter referred to as “titanium complex”) 0.5 mol was dissolved in 4 L of Isopar E. 50 ml of a 1M hexane solution of the general formula AlMg ₆ (C ₂ H ₅ ) ₃ (nC ₄ H ₉ ) ₁₂ previously synthesized from triethylaluminum and dibutylmagnesium was added, and further hexane was added to adjust the titanium complex concentration to 0.1M. To obtain a transition metal compound [B].

(Preparation of activating compound [C])
571 g of bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter abbreviated as “borate”) was added to 5 L of toluene and dissolved, and a 100 mM toluene solution of borate was dissolved. Obtained. To this borate toluene solution, 500 ml of a 1M hexane solution of ethoxydiethylaluminum was added at 25 ° C., and further hexane was added so that the borate concentration in the toluene solution was 70 mM. Then, the reaction mixture containing the borate which is an activation compound [C] was obtained by stirring at room temperature for 1 hour.

(Preparation of catalyst supported on silica)
5.7 L of this borate-containing reaction mixture was placed in a 200 L autoclave hexane liquid phase (approximately 20 cm below the interface, approximately 20 cm from the side (inner surface) of the autoclave, approximately 25 cm from the bottom (inner surface) of the autoclave, baffle. Was added to 100 L of the slurry of the carrier [A] obtained by the above operation with stirring at 15 ° C. through a sintered stainless steel filter (SMC Co., Ltd.) installed at a distance of about 15 cm from the center. In addition, the nominal filtration precision measured by the method of JIS-B8356 of this stainless steel sintered filter was 1 μm. The addition rate of this reaction mixture containing borate was 1.9 × 10 ⁻⁵ m ³ / s. The stainless steel metal filter had a filtration area of 0.00314 m ² , a pore number of 6.0 × 10 ⁸ / m ² , and an average pore area of 7.85 × 10 ⁻¹³ m ² / piece. Therefore, according to the following mathematical formula, the linear velocity of addition of the reaction mixture containing this borate was 12.8 m / s.
F = H / (I × J × K)
F: Linear velocity of addition (m / s)
H: Rate of addition (m ³ / s)
I: Filtration area of the sintered filter (m ² )
J: Number of pores of sintered filter (pieces / m ² )
K: Average pore area of sintered filter (m ² / piece)
Thus, a slurry of silica carrying borate was obtained. Further, 4 L of the transition metal compound [B] obtained above was added and stirred for 3 hours to react the titanium complex with borate. In this way, a catalyst was obtained which was a reaction mixture containing silica and a supernatant liquid and in which catalytically active species were formed on the silica.

(Copolymerization of ethylene and 1-butene)
800 ml of hexane was placed in an autoclave having a capacity of 1.8 L, and pressurized ethylene was placed in the autoclave to increase the internal pressure of the autoclave to 1 MPa. Further, 3 ml of 1-butene was placed in the autoclave. Next, the internal temperature of the autoclave was increased to 75 ° C., and the catalyst slurry obtained above was added to the autoclave in such an amount that the weight of the solid catalyst was 10 mg, and copolymerization of ethylene and 1-butene was started. . Copolymerization was carried out for 60 minutes while adding ethylene to the autoclave so that the internal pressure of the autoclave was maintained at 1 MPa. After completion of the copolymerization, the reaction mixture (copolymer slurry) was extracted from the autoclave, and the catalyst was deactivated with methanol. Thereafter, the reaction mixture was filtered, washed and dried to obtain 79 g of a dry powder of copolymer. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 7900 g-PE / g-catalyst / h. The obtained copolymer powder had an average particle size of 480 μm, a bulk density of 0.36 g / cm ³ , and exhibited extremely excellent fluidity. The amount of the copolymer powder suspended in hexane was 0 g. Therefore, it was found that the obtained copolymer powder exhibited extremely excellent powder characteristics. The copolymer had an MFR of 3.5 g / 10 min and a density of 941 kg / m ³ .

[Example 2]
(Preparation of catalyst supported on silica)
A catalyst was prepared in the same manner as in Example 1, except that the addition rate of this reaction mixture containing borate was 7.6 × 10 ⁻⁵ m ³ / s. According to the above mathematical formula, the linear velocity of addition of the reaction mixture containing this borate was 51.4 m / s.
(Copolymerization of ethylene and 1-butene)
Using this catalyst, ethylene and 1-butene were copolymerized in the same manner as in Example 1. 85 g of a dry powder of copolymer was obtained. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 8500 g-PE / g-catalyst / h. The obtained copolymer powder had an average particle size of 410 μm and a bulk density of 0.34 g / cm ³ , and exhibited extremely excellent fluidity. The amount of the copolymer powder suspended in hexane was 0 g. Therefore, it was found that the obtained copolymer powder exhibited extremely excellent powder characteristics. The copolymer had an MFR of 3.9 g / 10 min and a density of 940 kg / m ³ .

[Example 3]
(Preparation of catalyst supported on silica)
A catalyst was prepared in the same manner as in Example 1, except that a stainless steel sintered filter (manufactured by SMC Corporation) having a nominal filtration accuracy of 5 μm was used. The addition rate of this reaction mixture containing borate was 1.9 × 10 ⁻⁵ m ³ / s. The stainless steel metal filter had a filtration area of 0.00314 m ² , a pore number of 2.4 × 10 ⁷ pieces / m ² , and an average pore area of 1.96 × 10 ⁻¹¹ m ² / piece. Therefore, according to the above formula, the linear velocity of addition of the reaction mixture containing this borate was 12.9 m / s.
(Copolymerization of ethylene and 1-butene)
Using this catalyst, ethylene and 1-butene were copolymerized in the same manner as in Example 1. 65 g of dry powder of copolymer was obtained. When the inside of the autoclave was inspected, no polymer deposits were observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 6500 g-PE / g-catalyst / h. The obtained copolymer powder had an average particle size of 530 μm, a bulk density of 0.38 g / cm ³ , and exhibited extremely excellent fluidity. The amount of the copolymer powder suspended in hexane was 0 g. Therefore, it was found that the obtained copolymer powder exhibited extremely excellent powder characteristics. The copolymer had an MFR of 3.3 g / 10 min and a density of 942 kg / m ³ .

[Comparative Example 1]
(Preparation of catalyst supported on silica)
A catalyst was prepared in the same manner as in Example 1 except that the following method was adopted as a method for adding the reaction mixture containing borate.
Addition method: The reaction mixture containing borate was added in 15 minutes (addition linear velocity 0.11 m / s) from a pipe having an inner diameter of 8 mm provided in the gas phase part of the autoclave.
(Copolymerization of ethylene and 1-butene)
Polymerization evaluation was performed in the same manner as in Example 1. 31 g of dry powder of copolymer was obtained. When the inside of the autoclave was inspected, a slight amount of polymer was observed on the inner wall of the autoclave. The catalytic activity of the catalyst was 3100 g-PE / g-catalyst / h. The obtained copolymer powder had an average particle size of 320 μm and a bulk density of 0.25 g / cm ³ . The amount of the copolymer powder suspended in hexane was 0.19 g. The copolymer had an MFR of 4.1 g / 10 min and a density of 942 kg / m ³ .

[Comparative Example 2]
(Preparation of catalyst supported on silica)
A catalyst was prepared in the same manner as in Example 1 except that a sintered stainless steel filter (manufactured by SMC Corporation) having a nominal filtration accuracy of 10 μm was used. The addition rate of this reaction mixture containing borate was 1.9 × 10 ⁻⁵ m ³ / s. The stainless steel metal filter had a filtration area of 0.00314 m ² , a pore number of 6.0 × 10 ⁶ pieces / m ² , and an average pore area of 7.85 × 10 ⁻¹¹ m ² / piece. Therefore, according to the above formula, the linear velocity of addition of the reaction mixture containing this borate was 12.8 m / s.
(Copolymerization of ethylene and 1-butene)
Using this catalyst, ethylene and 1-butene were copolymerized in the same manner as in Example 1. 35 g of dry powder of copolymer was obtained. When the inside of the autoclave was inspected, a slight amount of polymer was observed on the inner wall of the autoclave. The polymerization activity of the catalyst was 3500 g-PE / g-catalyst / h. The obtained copolymer powder had an average particle size of 370 μm and a bulk density of 0.29 g / cm ³ . The amount of the copolymer powder suspended in hexane was 0.16 g. The copolymer had an MFR of 3.5 g / 10 min and a density of 942 kg / m ³ .

  The olefin polymerization catalyst and olefin polymerization method of the present invention are applicable to olefin suspension polymerization (slurry polymerization) and olefin polymerization in gas phase polymerization, especially ethylene homopolymerization or ethylene and α-olefin copolymerization. It is possible to produce a polymer having excellent powder properties with very high production efficiency.

Claims (6)

[A] A silica carrier and a hydroxyl group is substantially removed from the surface of the precursor of the carrier [A] by chemical treatment using an organoaluminum compound represented by the following general formula (1). Not carrier,
AlR ¹ _a X ¹ _3-a (1)
(In the formula, each R ¹ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 20 carbon atoms, and X ¹ is independently And represents a halide, hydride or an alkoxide group having 1 to 10 carbon atoms, and a is 1, 2 or 3.
[B] a transition metal compound represented by the following general formula ( 7 ),

( Wherein M ⁵ represents titanium having a formal oxidation number of +2, +3, or +4, and R ¹⁰ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, a gel mill, Represents a substituent selected from the group consisting of a group, a cyano group, a halogen atom, and a composite group thereof, provided that the substituent R ¹⁰ is a hydrocarbon group having 1 to 8 carbon atoms, a silyl group, or a germyl group. In some cases, two adjacent substituents R ¹⁰ are bonded to each other to form a divalent group, whereby two of the cyclopentadienyl rings that are respectively bonded to the two adjacent substituents R ¹⁰ In combination with a bond between carbon atoms to form a ring , each X ⁷ independently represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, carbon Number 1 to 18 Selected from the group consisting of a hydrocarbylamino group, a silyl group, a hydrocarbylamide group having 1 to 18 carbon atoms, a hydrocarbyl phosphide group having 1 to 18 carbon atoms, a hydrocarbyl sulfide group having 1 to 18 carbon atoms, and a composite group thereof. Provided that, in some cases, two substituents X ⁷ cooperate to form a neutral conjugated diene having 4 to 30 carbon atoms or a divalent group, and Y is —O—, -S-, -NR ^* -or -PR ^* - , wherein R ^* is a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbyloxy group having 1 to 8 carbon atoms, a silyl group, represents a number 1 to 8 of the halogenated alkyl group carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms or a composite group thereof,, Z is ^SiR _* 2, ^CR _* 2, _{^{iR * 2 SiR * 2, CR}} * 2 CR * 2, CR * = CR *, CR * 2 SiR * 2 , or represents ^GeR _{* 2,} where, ^{R *} is as defined above, r is 1, 2 or 3).
[C] A compound represented by the following general formula (9) which contains a cation and a compatible non-coordinating anion and can form a metal complex having catalytic activity by reacting with the transition metal compound [B]. activating compound,
[L ² −H] ⁺ [BQ ² ₃ Q ³ ] ⁻ (9)
(Wherein, ^{L 2} represents a neutral Lewis ^base, [L 2 ^{-H] +} represents a proton donating Bronsted _{^{acid, [BQ 2 3 Q 3]}} - is a non-coordinating anion compatible Q ² is a pentafluorophenyl group, and the remaining one Q ³ is a substituted aryl group having 6 to 20 carbon atoms and having one OH group as a substituent.
And [D] A method for producing an olefin polymerization catalyst in which an organoaluminum compound is reacted in a catalyst preparation reactor, comprising the following steps, wherein the addition of the compound produced in step 1 in step 2 below is performed: The method for producing an olefin polymerization catalyst, which is performed through a sintered filter having a nominal filtration accuracy of 0.01 μm or more and 5 μm or less.
Step 1: Step of bringing activated compound [C] into contact with organoaluminum compound [D] Step 2: Step of bringing carrier [A] into contact with the compound produced in Step 1 Step 3: With transition metal compound [B] The step of contacting the compound produced in step 2 The method for producing an olefin polymerization catalyst according to claim 1, wherein the organoaluminum compound represented by the general formula (1) is triethylaluminum. The transition metal compound [B] is converted to [(Nt-butylamide) (tetramethyl-η ⁵ The method for producing a catalyst for olefin polymerization according to claim 1 or 2, which is -cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene. The catalyst for olefin polymerization according to any one of claims 1 to 3, wherein the activating compound [C] is bis (hydrogenated tallow alkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate. Production method. An olefin polymerization catalyst produced by the production method according to any one of claims 1 to 4 . In the presence of an olefin polymerization catalyst produced by the production method according to any one of claims 1-4, the polymerization process of the polyolefin, wherein the polymerizing or copolymerizing olefins.