JP2006028326A - Method for producing catalyst for producing macromonomer, and method for producing macromonomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a particulate macromonomer having high polymerization activities, excellent processability and a long chain branch, and providing good morphology. <P>SOLUTION: The method for producing the macromonomer comprises polymerizing ethylene and optionally a ≥3C olefin in the presence of a catalyst comprising a component obtained by reacting (a) a specific transition metal compound with (b) a clay mineral treated with an organic compound at ≥50°C, and optionally (c) an organometal compound represented by the formula: M<SP>3</SP>R<SP>6</SP><SB>m</SB>(wherein, M<SP>3</SP>is an element selected from magnesium, zinc and aluminum; and R<SP>6</SP>is each independently a hydrogen atom, a halogen atom, a 1-20C hydrocarbon group or a 1-20C alkoxy group). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a macromonomer production catalyst and a method for producing a macromonomer.

  Low density polyethylene (LDPE) produced by the high pressure radical method is a branched polyolefin, and its side chain has a non-linear dendritic structure. Such a structure is excellent in molding processability such as melt fluidity and melt tension, and is advantageous when melt-processing a polymer, but on the other hand it reduces the mechanical strength of the solid polymer and the stretchability of the melt polymer. There are drawbacks.

  For this reason, linear high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) obtained with Ziegler catalysts or metallocene catalysts are used in applications that require the mechanical strength of solid polymers and the stretchability of molten polymers. Commonly used. However, these HDPE and LLDPE do not have good moldability, which is an advantage of LDPE.

  Examples of techniques for improving the molding processability of HDPE and LLDPE by a polyethylene production method include, for example, a) a method of broadening the molecular weight distribution by a multistage polymerization method using a conventional Ziegler catalyst (see, for example, Patent Documents 1 to 3), A) A method of producing polyethylene having long chain branches using a traditional Cr-based catalyst, c) A method of producing polyethylene having long chain branches by polymerizing ethylene using a specific metallocene catalyst (for example, patent documents) 4) has been proposed. However, the moldability of the polyethylene obtained by these methods is not yet sufficient, and the polyethylene obtained by the methods a) and b) has a problem that the mechanical strength is lowered due to the broad molecular weight distribution. there were.

  Therefore, a method of synthesizing a macromonomer using a specific metallocene catalyst and further copolymerizing the macromonomer and ethylene to produce polyethylene having a long chain branch (for example, see Patent Document 5) has been proposed. Yes. However, the macromonomer obtained by the production method disclosed herein has extremely low polymerization activity.

  A macromonomer that is copolymerized with ethylene to produce polyethylene having long chain branches must first have a vinyl end. Second, it needs to have an appropriate molecular weight. That is, if the molecular weight of the macromonomer is too short, moldability such as melt flowability and melt tension peculiar to polyethylene having a long chain branching is not expressed. Conversely, if the molecular weight is too long, the macromonomer is copolymerized with ethylene. Is not suitable as a macromonomer used to produce polyethylene having a long chain branch by copolymerizing with ethylene. Therefore, conventionally, in order to produce a macromonomer suitable for producing polyethylene having a long chain branch, a special catalyst system having a low polymerization activity was used, or polymerization was performed at an extremely low ethylene pressure. . For this reason, the conventional methods have problems such as extremely low catalytic activity, high catalyst costs, and coloring, gel generation, and physical property deterioration due to catalyst residues.

  Further, the conventional technique has a problem that the shape of the obtained macromonomer is bad. In industrial production, a macromonomer that is not only particulate but also has a high bulk density is desired. That is, if the bulk density is low, the concentration of the macromonomer particles in the polymerizer for producing the macromonomer and the various facilities accompanying it cannot be increased. Decreases. Further, when macromonomer particles having a low bulk density are used, even in the production of an ethylene-macromonomer copolymer, the copolymer morphology is deteriorated, the productivity is lowered, and the production becomes difficult.

  As described above, there has been a demand for a catalyst that is suitable for industrial production and can produce a particulate macromonomer having a high bulk density and good morphology with high polymerization activity.

JP-A-2-53811 JP-A-2-132109 JP-A-10-182742 US Pat. No. 5,272,236 Japanese translation of PCT publication No. 8-502303

  The present invention is suitable for industrial production, to produce a particulate macromonomer having a high bulk density and a good morphology.

In the present invention, by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms, (A) the number average molecular weight is 1000 or more and 50000 or less, and (B) the weight average molecular weight (Mw) and the number average molecular weight (Mn). The ratio (Mw / Mn) is 2 or more and 5 or less, and (C) Z represented by the relational expression Z = [X / (X + Y)] × 2 of the number of vinyl ends (X) and the number of saturated ends (Y). (A) a transition metal compound and (b) an organic compound used to produce a particulate macromonomer having a bulk density of 250 to 500 kg / m ^3. In preparing a treated clay mineral and, if necessary, a catalyst comprising (c) an organometallic compound, the clay mineral treated with (a) the transition metal compound and (b) the organic compound is heated at a temperature of 50 ° C. or higher. About how to react .

  Hereinafter, the present invention will be described in detail.

  The catalyst used in the present invention is a catalyst comprising (a) a transition metal compound, (b) a clay mineral treated with an organic compound, and optionally (c) an organometallic compound.

  First, (a) the transition metal compound will be described. (A) The transition metal compound is

式（２）中、Ｍ^１はチタン原子またはジルコニウム原子である。Ｘは各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０の炭化水素基置換シリル基、炭素数１〜２０の酸素原子含有炭化水素基、炭素数１〜２０の窒素原子含有炭化水素基または炭素数１〜２０のケイ素原子含有炭化水素基であり、具体的にはフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、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、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、２−メチルブチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、３−メチルペンチル基、４−メチルペンチル基、ネオヘキシル基、２，３−ジメチルブチル基、２，２−ジメチルブチル基、４−メチル−２−ペンチル基、３，３−ジメチル−２−ブチル基、１，１−ジメチルブチル基、２，３−ジメチル−２−ブチル基、シクロヘキシル基、ビニル基、プロペニル基、フェニル基、メチルフェニル基、ナフチル基等の炭素数１〜２０の炭化水素基、メトキシ基、エトキシ基等の炭素数１〜２０のアルコキシ基、ジメチルアミノ基、ジエチルアミノ基、ジ−ｎ−プロピルアミノ基等の炭素数１〜２０の炭化水素基置換アミノ基、トリメチルシリル基、トリエチルシリル基、フェニルジメチルシリル基、ジフェニルメチルシリル基等の炭素数１〜２０の炭化水素基置換シリル基、メトキシメチル基、２−メトキシエチル基等の炭素数１〜２０の酸素原子含有炭化水素基、ジメチルアミノエチル基、ジメチルアミノプロピル基、ジメチルアミノフェニル基等の炭素数１〜２０の窒素原子含有炭化水素基、トリメチルシリルメチル基、トリエチルシリルメチル基、３−トリメチルシリルプロピル基、３−トリエチルシリルプロピル基、８−トリメチルシリルオクチル基、８−トリエチルシリルオクチル基、４−トリメチルシリルフェニル基、４−トリエチルシリルフェニル基、（４−トリメチルシリルフェニル）メチル基、２−（４−トリメチルシリルフェニル）エチル基等の炭素数１〜２０のケイ素原子含有炭化水素基を例示することができる。Ｒ^１，Ｒ^２は一般式（３）、（４）または（５）で表されるＭ^１に配位する配位子である。

In formula (2), M ¹ is a titanium atom or a zirconium atom. X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. A hydrocarbon group-substituted silyl group, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms. Is a halogen atom such as fluorine atom, chlorine atom, bromine atom or iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, ne Hexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl group, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, 2,3 -A C1-C20 hydrocarbon group such as a dimethyl-2-butyl group, a cyclohexyl group, a vinyl group, a propenyl group, a phenyl group, a methylphenyl group, or a naphthyl group, or a C1-C20 group such as a methoxy group or an ethoxy group. A C1-C20 hydrocarbon group-substituted amino group such as alkoxy group, dimethylamino group, diethylamino group, di-n-propylamino group, trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group, diphenylmethylsilyl group, etc. C1-C20 hydrocarbon group substituted silyl group, methoxymethyl group, 2-methoxyethyl group, etc., C1-C20 oxygen atom-containing carbonization C1-C20 nitrogen-containing hydrocarbon group such as elementary group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminophenyl group, trimethylsilylmethyl group, triethylsilylmethyl group, 3-trimethylsilylpropyl group, 3-triethyl Silylpropyl group, 8-trimethylsilyloctyl group, 8-triethylsilyloctyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, (4-trimethylsilylphenyl) methyl group, 2- (4-trimethylsilylphenyl) ethyl group, etc. The C1-C20 silicon atom containing hydrocarbon group of these can be illustrated. R ¹ and R ² are ligands coordinated to M ¹ represented by the general formula (3), (4) or (5).

式中、Ｒ^４は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０の炭化水素基置換シリル基、炭素数１〜２０の酸素原子含有炭化水素基、炭素数１〜２０の窒素原子含有炭化水素基または炭素数１〜２０のケイ素原子含有炭化水素基であり、具体的にはフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、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、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、２−メチルブチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、３−メチルペンチル基、４−メチルペンチル基、ネオヘキシル基、２，３−ジメチルブチル基、２，２−ジメチルブチル基、４−メチル−２−ペンチル基、３，３−ジメチル−２−ブチル基、１，１−ジメチルブチル基、２，３−ジメチル−２−ブチル基、シクロヘキシル基、ビニル基、プロペニル基、フェニル基、メチルフェニル基、ナフチル基等の炭素数１〜２０の炭化水素基、メトキシ基、エトキシ基等の炭素数１〜２０のアルコキシ基、ジメチルアミノ基、ジエチルアミノ基、ジ−ｎ−プロピルアミノ基等の炭素数１〜２０の炭化水素基置換アミノ基、トリメチルシリル基、トリエチルシリル基、フェニルジメチルシリル基、ジフェニルメチルシリル基等の炭素数１〜２０の炭化水素基置換シリル基、メトキシメチル基、２−メトキシエチル基等の炭素数１〜２０の酸素原子含有炭化水素基、ジメチルアミノエチル基、ジメチルアミノプロピル基、ジメチルアミノフェニル基等の炭素数１〜２０の窒素原子含有炭化水素基、トリメチルシリルメチル基、トリエチルシリルメチル基、３−トリメチルシリルプロピル基、３−トリエチルシリルプロピル基、８−トリメチルシリルオクチル基、８−トリエチルシリルオクチル基、４−トリメチルシリルフェニル基、４−トリエチルシリルフェニル基、（４−トリメチルシリルフェニル）メチル基、２−（４−トリメチルシリルフェニル）エチル基等の炭素数１〜２０のケイ素原子含有炭化水素基を例示することができる。

In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or a carbon number. 1 to 20 hydrocarbon group-substituted silyl group, 1 to 20 oxygen atom-containing hydrocarbon group, 1 to 20 nitrogen atom-containing hydrocarbon group or 1 to 20 silicon atom-containing hydrocarbon group Yes, specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -Butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl Group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl group, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, Carbon numbers such as hydrocarbon groups having 1 to 20 carbon atoms such as 2,3-dimethyl-2-butyl group, cyclohexyl group, vinyl group, propenyl group, phenyl group, methylphenyl group and naphthyl group, methoxy group and ethoxy group C1-C20 hydrocarbon group-substituted amino group such as 1-20 alkoxy group, dimethylamino group, diethylamino group, di-n-propylamino group, trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group, diphenylmethyl C1-C20 hydrocarbon group such as silyl group Substituted silyl group, methoxymethyl group, 2-methoxyethyl group, etc., C1-C20 oxygen atom C 1-20 nitrogen-containing hydrocarbon group such as hydrocarbon group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminophenyl group, trimethylsilylmethyl group, triethylsilylmethyl group, 3-trimethylsilylpropyl group, 3 -Triethylsilylpropyl group, 8-trimethylsilyloctyl group, 8-triethylsilyloctyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, (4-trimethylsilylphenyl) methyl group, 2- (4-trimethylsilylphenyl) ethyl Examples thereof include silicon atom-containing hydrocarbon groups having 1 to 20 carbon atoms such as groups.

R ¹ and R ² form a sandwich structure with M ^1, and R ³ is represented by the general formula (6) or (7) and acts to bridge R ¹ and R ² .

式中、Ｒ^５は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０の炭化水素基置換シリル基、炭素数１〜２０の酸素原子含有炭化水素基、炭素数１〜２０の窒素原子含有炭化水素基または炭素数１〜２０のケイ素原子含有炭化水素基であり、具体的にはフッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、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、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、２−メチルブチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、３−メチルペンチル基、４−メチルペンチル基、ネオヘキシル基、２，３−ジメチルブチル基、２，２−ジメチルブチル基、４−メチル−２−ペンチル基、３，３−ジメチル−２−ブチル基、１，１−ジメチルブチル基、２，３−ジメチル−２−ブチル基、シクロヘキシル基、ビニル基、プロペニル基、フェニル基、メチルフェニル基、ナフチル基等の炭素数１〜２０の炭化水素基、メトキシ基、エトキシ基等の炭素数１〜２０のアルコキシ基、ジメチルアミノ基、ジエチルアミノ基、ジ−ｎ−プロピルアミノ基等の炭素数１〜２０の炭化水素基置換アミノ基、トリメチルシリル基、トリエチルシリル基、フェニルジメチルシリル基、ジフェニルメチルシリル基等の炭素数１〜２０の炭化水素基置換シリル基、メトキシメチル基、２−メトキシエチル基等の炭素数１〜２０の酸素原子含有炭化水素基、ジメチルアミノエチル基、ジメチルアミノプロピル基、ジメチルアミノフェニル基等の炭素数１〜２０の窒素原子含有炭化水素基、トリメチルシリルメチル基、トリエチルシリルメチル基、３−トリメチルシリルプロピル基、３−トリエチルシリルプロピル基、８−トリメチルシリルオクチル基、８−トリエチルシリルオクチル基、４−トリメチルシリルフェニル基、４−トリエチルシリルフェニル基、（４−トリメチルシリルフェニル）メチル基、２−（４−トリメチルシリルフェニル）エチル基等の炭素数１〜２０のケイ素原子含有炭化水素基を例示することができる。Ｍ^２はケイ素原子、ゲルマニウム原子または錫原子である。ｎは１〜５の整数である。

In the formula, each R ⁵ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or a carbon number. 1 to 20 hydrocarbon group-substituted silyl group, 1 to 20 oxygen atom-containing hydrocarbon group, 1 to 20 nitrogen atom-containing hydrocarbon group or 1 to 20 silicon atom-containing hydrocarbon group Yes, specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -Butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl Group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl group, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, Carbon numbers such as hydrocarbon groups having 1 to 20 carbon atoms such as 2,3-dimethyl-2-butyl group, cyclohexyl group, vinyl group, propenyl group, phenyl group, methylphenyl group and naphthyl group, methoxy group and ethoxy group C1-C20 hydrocarbon group-substituted amino group such as 1-20 alkoxy group, dimethylamino group, diethylamino group, di-n-propylamino group, trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group, diphenylmethyl C1-C20 hydrocarbon group such as silyl group Substituted silyl group, methoxymethyl group, 2-methoxyethyl group, etc., C1-C20 oxygen atom C 1-20 nitrogen-containing hydrocarbon group such as hydrocarbon group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminophenyl group, trimethylsilylmethyl group, triethylsilylmethyl group, 3-trimethylsilylpropyl group, 3 -Triethylsilylpropyl group, 8-trimethylsilyloctyl group, 8-triethylsilyloctyl group, 4-trimethylsilylphenyl group, 4-triethylsilylphenyl group, (4-trimethylsilylphenyl) methyl group, 2- (4-trimethylsilylphenyl) ethyl Examples thereof include silicon atom-containing hydrocarbon groups having 1 to 20 carbon atoms such as groups. M ² is a silicon atom, a germanium atom or a tin atom. n is an integer of 1-5.

Among them, in the general formula (2), the transition metal compound in which R ¹ is the general formula (3) and R ² is the general formula (3), (4) or (5) has a large number of vinyl ends, A macromonomer having a number average molecular weight of 1000 or more and 50000 or less is preferable because it can be produced with high polymerization activity.

(A) Transition metal compounds include methylene bis (cyclopentadienyl) titanium dichloride, isopropylidene bis (cyclopentadienyl) titanium dichloride, (methyl) (phenyl) methylene bis (cyclopentadienyl) titanium dichloride, diphenylmethylene bis (Cyclopentadienyl) titanium dichloride, ethylenebis (cyclopentadienyl) titanium dichloride, methylenebis (methylcyclopentadienyl) titanium dichloride, isopropylidenebis (methylcyclopentadienyl) titanium dichloride, (methyl) (phenyl) Methylenebis (methylcyclopentadienyl) titanium dichloride, diphenylmethylenebis (methylcyclopentadienyl) titanium dichloride Id, ethylenebis (methylcyclopentadienyl) titanium dichloride, methylene [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, isopropylidene [(cyclopentadienyl) (methylcyclopentadienyl)] Titanium dichloride, (methyl) (phenyl) methylene [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, diphenylmethylene [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, ethylene [ (Cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, methylenebis (2,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2, -Dimethylcyclopentadienyl) titanium dichloride, (methyl) (phenyl) methylenebis (2,4-dimethylcyclopentadienyl) titanium dichloride, diphenylmethylenebis (2,4-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) titanium dichloride, methylene [(cyclopentadienyl) (indenyl)] titanium dichloride, isopropylidene [(cyclopentadienyl) (indenyl)] titanium dichloride, (methyl) (phenyl) ) Methylene [(cyclopentadienyl) (indenyl)] titanium dichloride, diphenylmethylene [(cyclopentadienyl) (indenyl)] titanium dichloride, ethylene [ Clopentadienyl) (indenyl)] titanium dichloride, methylenebis (cyclopentadienyl) zirconium dichloride, isopropylidenebis (cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (cyclopentadienyl) zirconium dichloride, Diphenylmethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, (methyl) (Phenyl) methylenebis (methylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis Methylcyclopentadienyl) zirconium dichloride, ethylenebis (methylcyclopentadienyl) zirconium dichloride, methylene [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, isopropylidene [(cyclopentadienyl) ( Methylcyclopentadienyl)] zirconium dichloride, (methyl) (phenyl) methylene [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, diphenylmethylene [(cyclopentadienyl) (methylcyclopentadienyl) ] Zirconium dichloride, ethylene [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, methylenebis (2,4-dimethylcyclopenta) Enyl) zirconium dichloride, isopropylidenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis (2,4 -Dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, methylene [(cyclopentadienyl) (indenyl)] zirconium dichloride, isopropylidene [(cyclopentadienyl) (Indenyl)] zirconium dichloride, (methyl) (phenyl) methylene [(cyclopentadienyl) (indenyl)] zirconium dichloride, diphenylmethylene [( Cyclopentadienyl) (indenyl)] zirconium dichloride, ethylene [(cyclopentadienyl) (indenyl)] zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) titanium dichloride, diethylsilanediylbis (cyclopentadienyl) Titanium dichloride, di (n-propyl) silanediylbis (cyclopentadienyl) titanium dichloride, diisopropylsilanediylbis (cyclopentadienyl) titanium dichloride, dicyclohexylsilanediylbis (cyclopentadienyl) titanium dichloride, diphenylsilanediylbis ( Cyclopentadienyl) titanium dichloride, (ethyl) (methyl) silanediylbis (cyclopentadienyl) titanium Dichloride, (methyl) (n-propyl) silanediylbis (cyclopentadienyl) titanium dichloride, (methyl) (isopropyl) silanediylbis (cyclopentadienyl) titanium dichloride, (cyclohexyl) (methyl) bis (cyclopentadienyl) titanium Dichloride, (methyl) (phenyl) silanediylbis (cyclopentadienyl) titanium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (methylcyclopentadienyl) titanium dichloride, di (n- Propyl) silanediylbis (methylcyclopentadienyl) titanium dichloride, diisopropylsilanediylbis (methylcyclopentadienyl) Titanium dichloride, dicyclohexylsilanediylbis (methylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (methylcyclopentadienyl) titanium dichloride, (ethyl) (methyl) silanediylbis (methylcyclopentadienyl) titanium dichloride, ( Methyl) (n-propyl) silanediylbis (methylcyclopentadienyl) titanium dichloride, (methyl) (isopropyl) silanediylbis (methylcyclopentadienyl) titanium dichloride, (cyclohexyl) (methyl) bis (methylcyclopentadienyl) titanium Dichloride, (methyl) (phenyl) silanediylbis (methylcyclopentadienyl) titanium dichloride, dimethylsilanedi Ru [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, diethylsilanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, di (n-propyl) silanediyl [(cyclo Pentadienyl) (methylcyclopentadienyl)] titanium dichloride, diisopropylsilanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, dicyclohexylsilanediyl [(cyclopentadienyl) (methylcyclopenta Dienyl)] titanium dichloride, diphenylsilanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, (ethyl) (methyl) silanediyl [(cyclopenta Dienyl) (methylcyclopentadienyl)] titanium dichloride, (methyl) (n-propyl) silanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, (methyl) (isopropyl) silanediyl [(cyclo Pentadienyl) (methylcyclopentadienyl)] titanium dichloride, (cyclohexyl) (methyl) [(cyclopentadienyl) (methylcyclopentadienyl)] titanium dichloride, (methyl) (phenyl) silanediyl [(cyclopenta Dienyl) (methylcyclopentadienyl)] titanium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diethylsilanediylbis (2,4-dimethylsilane) Lopentadienyl) titanium dichloride, di (n-propyl) silanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, diisopropylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, dicyclohexylsilanediylbis (2 , 4-Dimethylcyclopentadienyl) titanium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, (ethyl) (methyl) silanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride (Methyl) (n-propyl) silanediylbis (2,4-dimethylcyclopentadienyl) titanium dichloride, (methyl) (isopropyl) silanediylbi (2,4-dimethylcyclopentadienyl) titanium dichloride, (cyclohexyl) (methyl) bis (2,4-dimethylcyclopentadienyl) titanium dichloride, (methyl) (phenyl) silanediylbis (2,4-dimethylcyclo) Pentadienyl) titanium dichloride, dimethylsilanediyl [(cyclopentadienyl) (indenyl)] titanium dichloride, diethylsilanediyl [(cyclopentadienyl) (indenyl)] titanium dichloride, di (n-propyl) silanediyl [( Cyclopentadienyl) (indenyl)] titanium dichloride, diisopropylsilanediyl [(cyclopentadienyl) (indenyl)] titanium dichloride, dicyclohexylsilanediyl [(cyclopenta Dienyl) (indenyl)] titanium dichloride, diphenylsilanediyl [(cyclopentadienyl) (indenyl)] titanium dichloride, (ethyl) (methyl) silanediyl [(cyclopentadienyl) (indenyl)] titanium dichloride, (methyl) (N-propyl) silanediyl [(cyclopentadienyl) (indenyl)] titanium dichloride, (methyl) (isopropyl) silanediyl [(cyclopentadienyl) (indenyl)] titanium dichloride, (cyclohexyl) (methyl) [(cyclo Pentadienyl) (indenyl)] titanium dichloride, (methyl) (phenyl) silanediyl [(cyclopentadienyl) (indenyl)] titanium dichloride, dimethylsilanediylbis ( Clopentadienyl) zirconium dichloride, diethylsilanediylbis (cyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (cyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (cyclopentadienyl) zirconium dichloride, Dicyclohexylsilanediylbis (cyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) Silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (Si Clopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) ) Zirconium dichloride, diethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dicyclohexyl Silanediylbis (methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis Methylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) ) Silanediylbis (methylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl [ (Cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, diethylsilanediyl [(cyclopenta Enyl) (methylcyclopentadienyl)] zirconium dichloride, di (n-propyl) silanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, diisopropylsilanediyl [(cyclopentadienyl) (methyl Cyclopentadienyl)] zirconium dichloride, dicyclohexylsilanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, diphenylsilanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride , (Ethyl) (methyl) silanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, (methyl) (n-propyl) silanediyl [( Cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, (methyl) (isopropyl) silanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, (cyclohexyl) (methyl) [(cyclo Pentadienyl) (methylcyclopentadienyl)] zirconium dichloride, (methyl) (phenyl) silanediyl [(cyclopentadienyl) (methylcyclopentadienyl)] zirconium dichloride, dimethylsilanediylbis (2,4-dimethyl) Cyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (2,4-dimethylsilane) Lopentadienyl) zirconium dichloride, diisopropylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4- Dimethylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,4-dimethylcyclopentadienyl) Zirconium dichloride, (methyl) (isopropyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (Methyl) bis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl [(cyclopentadienyl) ( Indenyl)] zirconium dichloride, diethylsilanediyl [(cyclopentadienyl) (indenyl)] zirconium dichloride, di (n-propyl) silanediyl [(cyclopentadienyl) (indenyl)] zirconium dichloride, diisopropylsilanediyl [(cyclo Pentadienyl) (indenyl)] zirconium dichloride, dicyclohexylsilanediyl [(cyclopentadienyl) (indenyl)] zirconium dichloride, diphenylsilanedi [(Cyclopentadienyl) (indenyl)] zirconium dichloride, (ethyl) (methyl) silanediyl [(cyclopentadienyl) (indenyl)] zirconium dichloride, (methyl) (n-propyl) silanediyl [(cyclopentadiyl) Enyl) (indenyl)] zirconium dichloride, (methyl) (isopropyl) silanediyl [(cyclopentadienyl) (indenyl)] zirconium dichloride, (cyclohexyl) (methyl) silanediyl [(cyclopentadienyl) (indenyl)] zirconium dichloride , (Methyl) (phenyl) silanediyl [(cyclopentadienyl) (indenyl)] zirconium dichloride and the like and dimethyl, diethyl and dihydro of the above transition metal compounds It may be exemplified diphenyl body, dibenzyl body.

  (B) The clay mineral processed with the organic compound is demonstrated. The clay mineral used is fine particles mainly composed of microcrystalline silicate. Most of the clay minerals have a layered structure as a structural feature, and it can be mentioned that the layers have negative charges of various sizes. In this respect, it is greatly different from a metal oxide having a three-dimensional structure such as silica or alumina. These clay minerals generally have a large layer charge, and the pyrophyllite, kaolinite, dickite and talc groups (negative charge per chemical formula is approximately 0), smectite groups (negative charge per chemical formula is approximately 0.25 to 0.25). 0.6), vermiculite group (negative charge per chemical formula is approximately 0.6 to 0.9), mica group (negative charge per chemical formula is approximately 1), brittle mica group (negative charge per chemical formula is approximately 2) It is classified. Each group shown here includes various clay minerals, and examples of the clay mineral belonging to the smectite group include montmorillonite, beidellite, saponite, hectorite and the like. Moreover, although these clay minerals exist naturally, a thing with few impurities can be obtained by artificial synthesis. In the present invention, all of the natural clay minerals shown here and clay minerals obtained by artificial synthesis can be used, and those not exemplified above but belonging to the definition of clay minerals can be used. it can. Furthermore, a mixture of a plurality of the above clay minerals can be used.

  The organic compound treatment in the component (b) of the present invention introduces organic ions between the clay mineral layers to form an ionic complex. Examples of the organic compound used in the organic compound treatment include a compound represented by the following general formula (9).

[R ⁷ R ⁸ _y-1 M ⁴ H] _a [A] _b (9)
In General Formula (9), [R ⁷ R ⁸ _y-1 M ⁴ H] is a cation, M ⁴ is an element selected from Group 15 or Group 16 of the periodic table, and R ⁷ has 1 carbon atom. a 30 hydrocarbon group, ^{R 8} are each independently hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, y is, ^{M 4} is a time y = 3 of the group 15 element, M ^{When 4} is a group 16 element, y = 2 and [A] is an anion, for example, fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, Oxalate ions, citrate ions, succinate ions, tetrafluoroborate ions or hexafluorophosphate ions can be used, but are not limited thereto. Further, a and b are integers selected so that charges are balanced.

M ⁴ in the formula (9) can be exemplified by a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms of R ⁷ and R ⁸ include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl. Group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl group, 3,3-dimethyl-2-butyl group, 1,1-dimethyl group Butyl group, 2,3-dimethyl-2-butyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, 2-methylcyclohexyl 3-methylcyclohexyl group, 4-methylcyclohexyl group, n-octyl group, isooctyl group, 1,5-dimethylhexyl group, 1-methylheptyl group, 2-ethylhexyl group, tert-octyl group, 2,3-dimethyl Cyclohexyl group, 2- (1-cyclohexenyl) ethyl group, n-nonyl group, n-decyl group, isodecyl group, geranyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, n-tridecyl group, n -Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, oleyl Group, behenyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylpheny group Group, 3-ethylphenyl group, 4-ethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-tert-butylphenyl group, 4-n-butylphenyl group, 4 -Sec-butylphenyl group, 4-tert-butylphenyl 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, 2,6-diethylphenyl group, 2-isopropyl-6-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl Group, 4-bromophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl 3-ethoxyphenyl group, 4-ethoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2,3-dihydroindene- Examples include 5-yl group, 2-biphenyl group, 4-biphenyl group, and p-trimethylsilylphenyl group. R ⁷ and R ⁸ may be bonded to each other.

Among the compounds represented by the formula (9), those in which M ³ is a nitrogen atom include methylamine hydrochloride, ethylamine hydrochloride, n-propylamine hydrochloride, isopropylamine hydrochloride, n-butylamine hydrochloride, Isobutylamine hydrochloride, tert-butylamine hydrochloride, n-pentylamine hydrochloride, isopentylamine hydrochloride, 2-methylbutylamine hydrochloride, neopentylamine hydrochloride, tert-pentylamine hydrochloride, n-hexylamine hydrochloride , Isohexylamine hydrochloride, n-heptylamine hydrochloride, n-octylamine hydrochloride, n-nonylamine hydrochloride, n-decylamine hydrochloride, n-undecylamine hydrochloride, n-dodecylamine hydrochloride, n- Tetradecylamine hydrochloride, n-hexadecylamine hydrochloride, n-octadecylamine salt Acid salt, allylamine hydrochloride, cyclopentylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, diallylamine hydrochloride, trimethylamine hydrochloride, tri-n-butylamine hydrochloride, triallylamine hydrochloride, hexylamine hydrochloride, 2-amino Heptane hydrochloride, 3-aminoheptane hydrochloride, n-heptylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-methylheptylamine hydrochloride, n-octylamine hydrochloride, tert-octylamine hydrochloride, Nonylamine hydrochloride, decylamine hydrochloride, undecylamine hydrochloride, dodecylamine hydrochloride, tridecylamine hydrochloride, tetradecylamine hydrochloride, pentadecylamine hydrochloride, hexadecylamine hydrochloride, heptadecylamine hydrochloride, octadecyl Amine hydrochloride, Nadecylamine hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 3-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexylamine hydrochloride, cyclohexane Dodecylamine hydrochloride, 2- (1-cyclohexenyl) ethylamine hydrochloride, geranylamine hydrochloride, N-methylhexylamine hydrochloride, dihexylamine hydrochloride, bis (2-ethylhexyl) amine hydrochloride, dioctylamine hydrochloride, Didecylamine hydrochloride, N-methylcyclohexylamine hydrochloride, N-ethylcyclohexylamine hydrochloride, N-isopropylcyclohexylamine hydrochloride, N-tert-butylcyclohexylamine hydrochloride, N-allylcyclohexyl Luamine hydrochloride, N, N-dimethyloctylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine hydrochloride, N, N-dimethyl-n-tetradecylamine hydrochloride, N , N-dimethyl-n-hexadecylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride, N, N-dimethyl-n-eicosylamine hydrochloride, N, N-dimethyl-n-docosylamine hydrochloride Salt, N, N-dimethyloleylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, tridodecylamine Hydrochloride, N-methyl-N-octadecyl-1-octadecylamine hydrochloride, N, N-dimethylcyclohexyl Luamine hydrochloride, N, N-dimethylcyclohexylmethylamine hydrochloride, N, N-diethylcyclohexylamine hydrochloride, pyrrolidine hydrochloride, piperidine hydrochloride, 2,5-dimethylpyrrolidine hydrochloride, 2-methylpiperidine hydrochloride, 3 -Methylpiperidine hydrochloride, 4-methylpiperidine hydrochloride, 2,6-dimethylpiperidine hydrochloride, 3,3-dimethylpiperidine hydrochloride, 3,5-dimethylpiperidine hydrochloride, 2-ethylpiperidine hydrochloride, 2,2 , 6,6-tetramethylpiperidine hydrochloride, 1-methylpyrrolidine hydrochloride, 1-methylpiperidine hydrochloride, 1-ethylpiperidine hydrochloride, 1-butylpyrrolidine hydrochloride, 1,2,2,6,6-penta Hydrochloric acid hydrochlorides such as methylpiperidine hydrochloride, aniline hydrochloride, N-methylaniline hydrochloride N-ethylaniline hydrochloride, N-allylaniline hydrochloride, o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, N, N-dimethylaniline hydrochloride, N-methyl-o-toluidine hydrochloride N-methyl-m-toluidine hydrochloride, N-methyl-p-toluidine hydrochloride, N-ethyl-o-toluidine hydrochloride, N-ethyl-m-toluidine hydrochloride, N-ethyl-p-toluidine hydrochloride N-allyl-o-toluidine hydrochloride, N-allyl-m-toluidine hydrochloride, N-allyl-p-toluidine hydrochloride, N-propyl-o-toluidine hydrochloride, N-propyl-m-toluidine hydrochloride N-propyl-p-toluidine hydrochloride, 2,3-dimethylaniline hydrochloride, 2,4-dimethylaniline hydrochloride, 2,5-dimethylaniline hydrochloride, 2, -Dimethylaniline hydrochloride, 3,4-dimethylaniline hydrochloride, 3,5-dimethylaniline hydrochloride, 2-ethylaniline hydrochloride, 3-ethylaniline hydrochloride, 4-ethylaniline hydrochloride, N, N-diethyl Aniline hydrochloride, 2-isopropylaniline hydrochloride, 4-isopropylaniline hydrochloride, 2-tert-butylaniline hydrochloride, 4-n-butylaniline hydrochloride, 4-sec-butylaniline hydrochloride, 4-tert-butyl Aniline hydrochloride, 2,6-diethylaniline hydrochloride, 2-isopropyl-6-methylaniline hydrochloride, 2-chloroaniline hydrochloride, 3-chloroaniline hydrochloride, 4-chloroaniline hydrochloride, 2-bromoaniline hydrochloride Salt, 3-bromoaniline hydrochloride, 4-bromoaniline hydrochloride, o-anisidine hydrochloride, m-anisidi Hydrochloride, p-anisidine hydrochloride, o-phenetidine hydrochloride, m-phenetidine hydrochloride, p-phenetidine hydrochloride, 1-aminonaphthalene hydrochloride, 2-aminonaphthalene hydrochloride, 1-aminofluorene hydrochloride, 2 -Aminofluorene hydrochloride, 3-aminofluorene hydrochloride, 4-aminofluorene hydrochloride, 5-aminoindane hydrochloride, 2-aminobiphenyl hydrochloride, 4-aminobiphenyl hydrochloride, N, 2,3-trimethylaniline hydrochloride Salt, N, 2,4-trimethylaniline hydrochloride, N, 2,5-trimethylaniline hydrochloride, N, 2,6-trimethylaniline hydrochloride, N, 3,4-trimethylaniline hydrochloride, N, 3 5-trimethylaniline hydrochloride, N-methyl-2-ethylaniline hydrochloride, N-methyl-3-ethylaniline hydrochloride, N-methyl -4-ethylaniline hydrochloride, N-methyl-6-ethyl-o-toluidine hydrochloride, N-methyl-2-isopropylaniline hydrochloride, N-methyl-4-isopropylaniline hydrochloride, N-methyl-2- tert-butylaniline hydrochloride, N-methyl-4-n-butylaniline hydrochloride, N-methyl-4-sec-butylaniline hydrochloride, N-methyl-4-tert-butylaniline hydrochloride, N-methyl- 2,6-diethylaniline hydrochloride, N-methyl-2-isopropyl-6-methylaniline hydrochloride, N-methyl-p-anisidine hydrochloride, N-ethyl-2,3-anisidine hydrochloride, N, N- Dimethyl-o-toluidine hydrochloride, N, N-dimethyl-m-toluidine hydrochloride, N, N-dimethyl-p-toluidine hydrochloride, N, N, 2,3-tetramethy Aniline hydrochloride, N, N, 2,4-tetramethylaniline hydrochloride, N, N, 2,5-tetramethylaniline hydrochloride, N, N, 2,6-tetramethylaniline hydrochloride, N, N, 3,4-tetramethylaniline hydrochloride, N, N, 3,5-tetramethylaniline hydrochloride, N, N-dimethyl-2-ethylaniline hydrochloride, N, N-dimethyl-3-ethylaniline hydrochloride, N, N-dimethyl-4-ethylaniline hydrochloride, N, N-dimethyl-6-ethyl-o-toluidine hydrochloride, N, N-dimethyl-2-isopropylaniline hydrochloride, N, N-dimethyl-4- Isopropylaniline hydrochloride, N, N-dimethyl-2-tert-butylaniline hydrochloride, N, N-dimethyl-4-n-butylaniline hydrochloride, N, N-dimethyl-4-sec-butylaniline Hydrochloride, N, N-dimethyl-4-tert-butylaniline hydrochloride, N, N-dimethyl-2,6-diethylaniline hydrochloride, N, N-dimethyl-2-isopropyl-6-methylaniline hydrochloride, N, N-dimethyl-2-chloroaniline hydrochloride, N, N-dimethyl-3-chloroaniline hydrochloride, N, N-dimethyl-4-chloroaniline hydrochloride, N, N-dimethyl-2-bromoaniline hydrochloride Salt, N, N-dimethyl-3-bromoaniline hydrochloride, N, N-dimethyl-4-bromoaniline hydrochloride, N, N-dimethyl-o-anisidine hydrochloride, N, N-dimethyl-m-anisidine hydrochloride Salt, N, N-dimethyl-p-anisidine hydrochloride, N, N-dimethyl-o-phenetidine hydrochloride, N, N-dimethyl-m-phenetidine hydrochloride, N, N-dimethyl-p-sulfate Netidin hydrochloride, N, N-dimethyl-1-aminonaphthalene hydrochloride, N, N-dimethyl-2-aminonaphthalene hydrochloride, N, N-dimethyl-1-aminofluorene hydrochloride, N, N-dimethyl-2 -Aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl-4-aminofluorene hydrochloride, N, N-dimethyl-5-aminoindan hydrochloride, N, N-dimethyl Fluorinated aromatic amine hydrochlorides such as 2-aminobiphenyl hydrochloride, N, N-dimethyl-4-aminobiphenyl hydrochloride, N, N-dimethyl-p-trimethylsilylaniline hydrochloride and hydrochlorides of the above compounds Examples include, but are not limited to, compounds replaced with hydrate, hydrobromide, hydroiodide or sulfate.

Among the compounds represented by formula (9), those in which M ⁴ is an oxygen atom include compounds such as methyl ether hydrochloride, ethyl ether hydrochloride, n-butyl ether hydrochloride, tetrahydrofuran hydrochloride, and phenyl ether hydrochloride Examples thereof include, but are not limited to, compounds in which the hydrochloride of the above compound is replaced with hydrofluoride, hydrobromide, hydroiodide, or sulfate.

Among the compounds represented by formula (9), those in which M ⁴ is a sulfur atom include diethylsulfonium fluoride, diethylsulfonium chloride, diethylsulfonium bromide, diethylsulfonium iodide, dimethylsulfonium fluoride, and dimethylsulfonium chloride. Examples thereof include dimethylsulfonium bromide and dimethylsulfonium iodide, but are not limited thereto.

Among the compounds represented by the formula (9), those in which M ⁴ is a phosphorus atom include triphenylphosphine hydrochloride, tri (o-tolyl) phosphine hydrochloride, tri (p-tolyl) phosphine hydrochloride, trimesi Examples thereof include compounds such as tilphosphine hydrochloride, and compounds obtained by replacing hydrochlorides of the above compounds with hydrofluoric acid salts, hydrobromide salts, hydroiodide salts or sulfate salts, but are not limited thereto. It is not something.

  In the organic compound treatment, it is preferable to carry out the treatment by selecting the conditions of a clay mineral concentration of 0.1 to 30% by weight and a treatment temperature of 0 to 150 ° C. Further, the organic compound may be prepared as a solid and dissolved in a solvent for use, or a solution of the organic compound may be prepared by a chemical reaction in the solvent and used as it is. Regarding the reaction amount ratio between the clay mineral and the organic compound, it is preferable to use an organic compound having an equivalent amount or more with respect to exchangeable cations of the clay mineral. As the treatment solvent, aliphatic hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as benzene or toluene, alcohols such as ethyl alcohol or methyl alcohol, ethers such as ethyl ether or n-butyl ether, Halogenated hydrocarbons such as methylene chloride or chloroform, acetone, 1,4-dioxane, tetrahydrofuran, water or the like can be used, but preferably alcohols or water is used alone or as a component of a solvent. .

In the present invention, component (c) can be added for the purpose of removing impurities in the olefin in addition to (a) the transition metal compound and (b) the clay mineral treated with the organic compound. This (c) organometallic compound has the following general formula (8)
M ³ R ⁶ _m (8)
(M ³ is an element selected from magnesium, zinc or aluminum, and each R ⁶ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms. M is 2 when M ³ is magnesium or zinc, and 3 when aluminum is aluminum.)
R ⁶ of component (c) is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl Group, 4-methyl-2-pentyl, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, 2,3-dimethyl-2-butyl group, n-pentyl group, isopentyl group, n- Octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, phenyl, cyclohex A xyl group can be exemplified.

  As the component (c), magnesium compounds such as diethyl magnesium, di-n-butyl magnesium and n-butyl ethyl magnesium, zinc compounds such as dimethyl zinc, diethyl zinc, diisopropyl zinc and di-n-butyl zinc, trimethylaluminum, Dimethyl aluminum hydride, triethyl aluminum, diethyl aluminum hydride, tri-n-propyl aluminum, di-n-propyl aluminum hydride, triisopropyl aluminum, diisopropyl aluminum hydride, tri-n-butyl aluminum, di-n-butyl aluminum hydride, tri Isobutylaluminum, diisobutylaluminum hydride, tri-tert-butylaluminum, di-tert-butylaluminum hydride, tri-n-he Aluminum such as silaluminum, di-n-hexyl aluminum hydride, triisohexyl aluminum, diisohexyl aluminum hydride, tri-n-octyl aluminum, di-n-octyl aluminum hydride, triisooctyl aluminum, diisooctyl aluminum hydride A compound can be illustrated. Among these, an aluminum compound is preferable because of high polymerization activity.

  The catalyst comprising component (a) and component (b) used in the present invention can be obtained by bringing component (a) and component (b) into contact in an organic solvent.

  As the contact solvent, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane or cyclohexane, aromatic hydrocarbons such as benzene, toluene or xylene, ethyl ether or n-butyl ether And ethers such as methylene chloride and chloroform, 1,4-dioxane, acetonitrile and tetrahydrofuran.

  The contact temperature between the component (a) and the component (b) is preferably 50 ° C. or higher and preferably selected from 50 to 200 ° C. By contacting the component (a) and the component (b) at such a contact temperature, the polymerization activity of the catalyst is improved and the bulk density of the macromonomer is also increased.

  As for the usage-amount of each component, the component (a) is 0.0001-100 mmol per 1g of component (b), Preferably it is 0.0005-10 mmol.

  The contact product of component (a) and component (b) prepared in this way may be used without washing, and is washed for the purpose of removing by-products generated during the reaction. It may be used after that. Moreover, the usage-amount of the component (c) in the case of using a component (c) is 0.001-10000 mmol, Preferably 0.01-1000 mmol of component (c) per 1 g of component (b). The molar ratio of component (a) to component (c) is 1: 0.1 to 10,000, preferably 1-1000.

  The method for adding component (c) to the catalyst comprising component (a) and component (b) is not particularly limited, but component (c) is added after contacting component (a) and component (b). The component (b) and the component (c) are contacted, and then the component (a) is added to the contact product of the component (b) and the component (c). The method of adding the contact product of) can be illustrated.

  Particulate macromonomer is obtained by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms in the presence of the catalyst for producing macromonomer produced by the method of the present invention as described above.

  Examples of the olefin having 3 or more carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, α-olefin such as vinylcycloalkane, norbornene, Examples include cyclic olefins such as norbornadiene, dienes such as butadiene or 1,4-hexadiene, and styrene. Two or more of these olefins can be mixed and used.

  The polymerization solvent may be any organic solvent that is generally used. Specifically, halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride, propane, n-butane, isobutane, n-pentane, n -C3-C20 aliphatic hydrocarbons such as hexane, n-heptane, n-octane, n-nonane, n-decane, aromatic hydrocarbons having 6-20 carbon atoms such as benzene, toluene, xylene, etc. The olefin itself can be used as a solvent. Gas phase polymerization without using a polymerization solvent is also possible.

  The polymerization temperature is preferably in the range of 0 to 120 ° C. When the polymerization temperature is within this range, a macromonomer having good polymerization activity and excellent particle shape can be easily obtained, which is preferable. The ethylene partial pressure is in the range of 0.001 to 300 MPa, preferably 0.005 to 50 MPa, more preferably 0.01 to 10 MPa. Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

  The macromonomer related to the present invention produced by the method as described above has a number average molecular weight of 1,000 to 50,000, preferably 5,000 to 30,000. The macromonomer having such a number average molecular weight is easy to incorporate the macromonomer in the copolymerization with ethylene, and the obtained ethylene-macromer copolymer has excellent moldability such as melt fluidity and melt tension. Are better. The ratio of the weight average molecular weight (Mw) to Mn (Mw / Mn) is 2 or more and 5 or less, preferably 2 or more and 4 or less, more preferably 2 or more and 3.5 or less.

The macromonomer obtained in the present invention has the general formula (1)
Z = [X / (X + Y)] × 2 (1)
(Where X is the number of vinyl ends per 1000 main chain methylene carbons of the macromonomer, Y is the number of saturated ends per 1000 main chain methylene carbons of the macromonomer)
Z represented by is 0.25 or more and 1 or less. It is well known to those skilled in the art that the number of vinyl terminals of an olefin polymer is determined by ¹ H-NMR, ¹³ C-NMR, FT-IR, or the like. For example, in ¹³ C-NMR, vinyl ends (CH═CH ₂ ) have peaks at 114 ppm and 139 ppm, and saturated ends (—CH ₂ CH ₂ CH ₃ ) have peaks at 32.3 ppm, 22.9 ppm, and 14.1 ppm. Its presence and amount can be confirmed. In the macromonomer of the present invention, Z, which is a relational expression of the number of vinyl ends per 1000 main chain methylene carbons and the number of saturated ends per 1000 main chain methylene carbons measured by ¹³ C-NMR, is 0.25 or more and 1 Hereinafter, it is preferably 0.50 or more and 1 or less.

Further, according to the production method of the present invention, a particulate macromer having a good morphology is obtained, and its bulk density is 250 kg / m ³ or more and 500 kg / m ³ or less, more preferably 300 kg / m ³ or more and 500 kg / m ^3. It is as follows. By using the method for producing a macromonomer of the present invention that achieves such a good morphology, the production of the macromonomer and the copolymerization of the macromonomer and ethylene can be carried out continuously and with high productivity. It is possible to produce an ethylene-macromonomer copolymer having industrial long chain branching in various processes in the technical field.

  According to the method for producing a macromonomer of the present invention, a macromonomer having excellent processability, physical properties suitable for the production of an ethylene-macromonomer copolymer having a long chain branch, and a good morphology is obtained. It can be produced with polymerization activity. Thereby, the ethylene-macromonomer copolymer having a long chain branch can be produced with high productivity.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  Preparation of the macromonomer synthesis catalyst, macromonomer synthesis and solvent purification were all carried out under an inert gas atmosphere. As the preparation of the macromonomer synthesis catalyst and the solvent used for the macromonomer synthesis, all the solvents that had been purified, dried, and deoxygenated by a known method in advance were used. Bis (cyclopentadienyl) zirconium dichloride was manufactured by Wako Pure Chemical Industries, Ltd. The other component (a) was synthesized and identified by a known method. The toluene solution (trade name: PMAO; Al: 2.4 mol / L) of methylalumoxane and the toluene solution (0.848M) of triisobutylaluminum were manufactured by Tosoh Finechem Corporation.

  Furthermore, various physical properties of the olefin polymers in Examples and Comparative Examples were measured by the following methods.

  The weight average molecular weight (Mw), the number average molecular weight (Mn) and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) were measured by gel permeation chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC apparatus, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 140 ° C., and 1 is used as the eluent. Measurement was performed using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 1.0 mg / mL, and 0.3 mL was injected and measured. The calibration curve of the molecular weight is calibrated using a polystyrene sample having a known molecular weight by the universal calibration method. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

The terminal structure of the polymer such as vinyl terminal and saturated terminal was measured by ¹³ C-NMR using a JNM-ECA400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. The solvent is tetrachloroethane-d2. The number of vinyl ends was determined from the average value of peaks at 114 ppm and 139 ppm as the number per 1000 main chain methylene carbons (chemical shift 30 ppm). Similarly, the number of saturated terminals (—CH ₂ CH ₂ CH ₃ ) was determined from the average values of peaks at 32.3 ppm, 22.9 ppm, and 14.1 ppm. Z (= [X / (X + Y)] × 2) was determined from the number of vinyl ends (X) and the number of saturated ends (Y).

Example 1
[Preparation of component (b)]
After adding 150 mL of ethanol and 8.3 mL of 37% concentrated hydrochloric acid to 350 mL of water, 29.7 g (0.1 mol) of N, N-dimethyloctadecylamine was added to the resulting solution and heated to 60 ° C. N, N-dimethyloctadecylamine hydrochloride solution was prepared. To this solution, 100 g of hectorite was added. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 1 L of 60 ° C. water. Then, it dried at 60 degreeC and 10 < ^-3 > torr for 24 hours, and the modified | denatured hectorite with an average particle diameter of 5.2 micrometers was obtained by grind | pulverizing with a jet mill. As a result of elemental analysis, the amount of N, N-dimethyloctadecyl ammonium ion per gram of modified hectorite was 0.848 mmol.

[Catalyst preparation]
2.0 g of the modified hectorite was dispersed in 5 mL of hexane. To this, 8.6 mL of a hexane solution (0.34M) of triisobutylaluminum was added and stirred at room temperature for 1 hour to obtain a contact product of component (b) and component (c). On the other hand, to 3.5 mg (10 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, 2.2 mL of n-hexane and 2.9 mL of a hexane solution (0.34 M) of triisobutylaluminum were added, and the mixture was stirred at room temperature. By stirring for a minute, a contact product of component (a) and component (c) was obtained. The total amount of the contact product of component (a) and component (c) is added to the total amount of the contact product of component (b) and component (c), and the mixture is stirred at 60 ° C. for 3 hours. A contact product of (b) and component (c) was obtained. The obtained contact product was washed twice with hexane and then diluted with 20 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Into a 2 L autoclave, 1200 mL of hexane and 2.1 mL of hexane solution of triisobutylaluminum (0.34 mol / L) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. Next, 2 mL (Zr: corresponding to 1 μmol) of the catalyst slurry was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 90 ° C. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 185 g of a macromonomer was obtained (polymerization activity: 123 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z, and the bulk density of the obtained macromonomer.

Comparative Example 1
[Catalyst preparation]
2.0 g of the modified hectorite prepared in [Preparation of component (b)] in Example 1 was dispersed in 5 mL of hexane. To this, 8.6 mL of a hexane solution (0.34M) of triisobutylaluminum was added and stirred at room temperature for 1 hour to obtain a contact product of component (b) and component (c). On the other hand, to 3.5 mg (10 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, 2.2 mL of n-hexane and 2.9 mL of a hexane solution (0.34 M) of triisobutylaluminum were added, and the mixture was stirred at room temperature. By stirring for a minute, a contact product of component (a) and component (c) was obtained. The total contact product of component (a) and component (c) is added to the total contact product of component (b) and component (c), and stirred at room temperature for 3 hours. A contact product of b) and component (c) was obtained. The obtained contact product was diluted with 20 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 ml of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 54 g of a macromonomer was obtained (polymerization activity: 36 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z, and the bulk density of the obtained macromonomer.

Comparative Example 2
[Manufacture of macromonomer]
To a 2 L autoclave, 1200 mL of toluene and 0.5 mL of a toluene solution of methylalumoxane (1.2 mmol in terms of Al) and 16 mg (55 μmol) of bis (cyclopentadienyl) zirconium dichloride were introduced, and the internal temperature of the autoclave was 90 ° C. The temperature was raised to. Next, ethylene was introduced until the partial pressure reached 0.27 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 0.27 MPa. The polymerization temperature was controlled at 90 ° C. 90 minutes after the start of polymerization, the internal pressure of the autoclave was released to 0 MPa. The macromonomer was dissolved in toluene. The polymer was precipitated with 2 L of industrial ethyl alcohol and the resulting macromonomer was dried for 12 hours. As a result, 140 g of a macromonomer was obtained (polymerization activity: 1.7 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z, and the bulk density of the obtained macromonomer.

Example 2
[Catalyst preparation]
A catalyst was prepared in the same manner as in Example 1 except that 7.0 mg (20 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride was used. The obtained contact product was washed twice with hexane and then diluted with 40 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 ml of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 168 g of macromonomer was obtained (polymerization activity: 112 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z, and the bulk density of the obtained macromonomer.

Example 3
[Catalyst preparation]
A catalyst was prepared in the same manner as in Example 1 except that 7.0 mg (20 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride was used. The obtained contact product was diluted with 40 ml of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 ml of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 155 g of macromonomer was obtained (polymerization activity: 103 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z and bulk density of the obtained macromonomer.

Comparative Example 3
[Catalyst preparation]
A catalyst was prepared in the same manner as in Comparative Example 1 except that 7.0 mg (20 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride was used. The obtained contact product was diluted with 40 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 ml of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 87 g of a macromonomer was obtained (polymerization activity: 58 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z, and the bulk density of the obtained macromonomer.

Example 4
[Catalyst preparation]
A catalyst was prepared in the same manner as in Example 1 except that 14 mg (40 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride was used. The obtained contact product was washed twice with hexane and then diluted with 80 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 mL of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 183 g of macromonomer was obtained (polymerization activity: 122 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z and bulk density of the obtained macromonomer.

Example 5
[Catalyst preparation]
A catalyst was prepared in the same manner as in Example 1 except that 15 mg (40 μmol) of diethylsilanediylbis (cyclopentadienyl) zirconium dichloride was used instead of 14 mg (40 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride. did. The obtained contact product was washed twice with hexane and then diluted with 80 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 mL of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 136 g of macromonomer was obtained (polymerization activity: 91 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z, and the bulk density of the obtained macromonomer.

Example 6
[Catalyst preparation]
A catalyst was prepared in the same manner as in Example 1 except that 28 mg (80 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride was used. The obtained contact product was washed twice with hexane and then diluted with 160 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 mL of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 183 g of macromonomer was obtained (polymerization activity: 122 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z, and the bulk density of the obtained macromonomer.

Comparative Example 4
[Catalyst preparation]
A catalyst was prepared in the same manner as in Comparative Example 1 except that 23 mg (80 μmol) of bis (cyclopentadienyl) zirconium dichloride was used instead of 3.5 mg (10 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride. . The obtained contact product was diluted with 160 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 mL of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 128 g of a macromonomer was obtained (polymerization activity: 85 kg macromonomer / mmol Zr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z, and the bulk density of the obtained macromonomer.

Example 7
[Catalyst preparation]
A catalyst was prepared in the same manner as in Example 1 except that 70 mg (200 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride was used. The obtained contact product was washed twice with hexane and then diluted with 400 mL of n-hexane to obtain a catalyst slurry (0.5 mmol Zr / L).

[Manufacture of macromonomer]
Polymerization was carried out in the same manner as in Example 1 except that 2 mL of the catalyst slurry prepared in the above [Catalyst preparation] (Zr: equivalent to 1 μmol) was used as the catalyst slurry. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released to 0 MPa, the contents of the autoclave were filtered, and the resulting macromonomer was dried for 12 hours. As a result, 161 g of macromonomer was obtained (polymerization activity: 108 kg macromonomer / mmolZr · hr). Table 1 shows Mn, Mw, Mw / Mn, the number of vinyl terminals, the number of saturated terminals, Z and bulk density of the obtained macromonomer.

Claims (4)

By polymerizing ethylene and optionally olefins having 3 or more carbon atoms,
(A) The number average molecular weight is 1000 or more and 50000 or less,
(B) Ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) is 2 or more and 5 or less (C) General formula (1)
Z = [X / (X + Y)] × 2 (1)
(Where X is the number of vinyl ends per 1000 main chain methylene carbons of the macromonomer, Y is the number of saturated ends per 1000 main chain methylene carbons of the macromonomer)
Z is 0.25 or more and 1 or less, and (D) the bulk density is 250 to 500 kg / m ^3.
(A) General formula (2) used to produce a particulate macromonomer

[Wherein, M ¹ is a titanium atom or a zirconium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 hydrocarbon group-substituted amino group, C1-C20 hydrocarbon group-substituted silyl group, C1-C20 oxygen atom-containing hydrocarbon group, C1-C20 nitrogen atom-containing hydrocarbon group, or carbon number 1 to 20 silicon atom-containing hydrocarbon groups, wherein R ¹ and R ² are each independently the general formula (3), (4) or (5)

(In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, carbon, A hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms .)
In a ligand coordinating to ^{M 1} represented, ^{R 1} and ^{R 2} form a sandwich structure together with ^{M 1, R 3} is the general formula (6) or (7)

(In the formula, each R ⁵ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted hydrocarbon group having 1 to 20 carbon atoms, carbon, A hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms And M ² is a silicon atom, a germanium atom or a tin atom.)
And R ¹ and R ² are cross-linked and n is an integer of 1 to 5. ]
A transition metal compound represented by
(B) a clay mineral treated with an organic compound, and optionally (c) general formula (8)
M ³ R ⁶ _m (8)
(M ³ is an element selected from magnesium, zinc or aluminum, and each R ⁶ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy having 1 to 20 carbon atoms. Is 2 when M ³ is magnesium or zinc and 3 when aluminum.)
In preparing a catalyst comprising an organometallic compound represented by
A method for producing a catalyst for producing a macromonomer, comprising reacting (a) a transition metal compound and (b) a clay mineral treated with an organic compound at a temperature of 50 ° C. or higher. (A) The transition metal compound has the general formula (2)

[Wherein, M ¹ is a titanium atom or a zirconium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 hydrocarbon group-substituted amino group, C1-C20 hydrocarbon group-substituted silyl group, C1-C20 oxygen atom-containing hydrocarbon group, C1-C20 nitrogen atom-containing hydrocarbon group, or carbon number 1 to 20 silicon atom-containing hydrocarbon group, and R ¹ is represented by the general formula (3)

(In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, carbon, A hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms .)
R ² is a ligand coordinated to M ¹ represented by the general formula (3), (4) or (5)

(In the formula, each R ⁴ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, carbon, A hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms .)
In a ligand coordinating to ^{M 1} represented, ^{R 1} and ^{R 2} form a sandwich structure together with ^{M 1, R 3} is the general formula (6) or (7)

(In the formula, each R ⁵ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted hydrocarbon group having 1 to 20 carbon atoms, carbon, A hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms And M ² is a silicon atom, a germanium atom or a tin atom.)
And R ¹ and R ² are cross-linked and n is an integer of 1 to 5. ]
The method for producing a macromonomer production catalyst according to claim 1, wherein the transition metal compound is represented by the formula: (B) A clay mineral treated with an organic compound is represented by the general formula (9)
[R ⁷ R ⁸ _y-1 M ⁴ H] _a [A] _b (9)
(Wherein [R ⁷ R ⁸ _y-1 M ⁴ H] is a cation, M ⁴ is an element selected from Group 15 or Group 16 of the periodic table, and R ⁷ has 1 to 30 carbon atoms. Each of R ⁸ is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, y is y = 3 when M ⁴ is a Group 15 element, and M ⁴ is (For group 16 elements, y = 2, [A] is an anion, and a and b are integers chosen to balance the charge.)
The method for producing a macromonomer production catalyst according to claim 1, wherein the mineral is a clay mineral treated with an organic compound represented by the formula: A method for producing a macromonomer, wherein ethylene and optionally an olefin having 3 or more carbon atoms are polymerized in the presence of the catalyst for producing a macromonomer produced by the method according to claim 1.