JP5895503B2 - Catalyst for producing ethylene polymer and method for producing ethylene polymer - Google Patents

Description

  The present invention relates to a catalyst for producing an ethylene polymer using an alumina-modified layered clay compound obtained by modifying a layered clay compound with alumina sol as a constituent, and a method for producing an ethylene polymer using the catalyst. Is.

  As a method for producing polyolefin by polymerization of olefin, it is already known to use a catalyst system containing a combination of a transition metal compound and an organometallic compound, and a metallocene catalyst using metallocene and methylaluminoxane is used as an olefin polymer. It has been disclosed to exhibit high activity during production (see, for example, Patent Document 1). However, although the catalyst system disclosed here is excellent in polymerization activity, since the catalyst system is soluble in a polymerization solvent that is usually used, a solution polymerization system is often adopted as a process, and the production process is limited. In addition, in order to produce a polymer exhibiting industrially useful physical properties, it is necessary to use a large amount of relatively expensive methylaluminoxane. For this reason, when these catalyst systems are used, there are problems such as a cost problem and a large amount of aluminum remaining in the polymer.

  On the other hand, a catalyst system in which the above catalyst system is supported on an inorganic oxide carrier such as silica is disclosed (for example, see Patent Document 2). However, the polymerization activity per methylaluminoxane was not sufficient even when the olefin was polymerized according to the methods described therein.

  As a method for improving these, it has been disclosed that when a gas phase polymerization is carried out using a catalyst system prepolymerized with a small amount of methylaluminoxane, a polymer having excellent polymerization activity and good particle properties can be obtained (for example, And Patent Documents 3 to 5). However, although the amount of methylaluminoxane used is small, the polymerization activity is still unsatisfactory and high activation of the catalyst system has been desired.

  Furthermore, it is disclosed that a special boron compound becomes an effective promoter as a new promoter without using an organoaluminum oxy compound such as methylaluminoxane (see, for example, Patent Documents 6 to 7). However, these boron compounds are very complicated compounds and have not yet solved the problem of cost.

  Further, as a co-catalyst replacing methylaluminoxane, a layered clay compound ion-exchanged with an organic cation is disclosed, and a polymer having high polymerization activity and good morphology in a slurry polymerization process has been produced (for example, patent document). 8-10). However, this catalyst system was not fully satisfactory in terms of polymerization activity.

  As a method for increasing the polymerization activity of a catalyst system using a layered clay compound ion-exchanged with the above-mentioned organic cation, the layered clay compound is reacted with a polynuclear metal oxide and then fired, and the reacted polynuclear metal oxide acts as a pillar. By doing so, there is a method in which the interlayer distance is expanded and the reaction field as a carrier of the layered clay compound is expanded.

  However, in the conventional method, when the polynuclear metal oxide is reacted with the layered clay compound, the exchangeable cation is consumed and the CEC (cation exchange capacity) is decreased. It has not been issued. Moreover, since the alumina reacted with the layered clay compound acts as a pillar and the interlayer distance is expanded, the function of the layered clay compound as a carrier is significantly different from that before the reaction.

  The present invention has been made in order to solve the above-described problems. In the gas phase polymerization and suspension polymerization, a polymer to the reactor wall is used without using an expensive organoaluminum oxy compound or boron compound in the polymerization of olefin. It is an object of the present invention to provide an inexpensive ethylene polymer production catalyst for producing an olefin polymer having an excellent polymerization activity and a good particle shape while suppressing adhesion of the polymer.

JP 58-19309 A JP-A-60-35006 Japanese Patent Laid-Open No. 4-8704 JP-A-4-11604 JP-A-4-213305 JP-T-1-501950 Japanese translation of PCT publication JP 7-224106 A Japanese Patent Laid-Open No. 10-324708 JP 11-335408 A

  Excellent polymerization activity and good particle shape while suppressing the adhesion of the polymer to the reactor wall in gas phase polymerization and suspension polymerization without using expensive organoaluminum oxy compound or boron compound in olefin polymerization The present invention provides an inexpensive catalyst for producing an ethylene polymer that produces an olefin polymer.

  An object of the present invention is to provide an ethylene-based polymer production catalyst using an alumina-modified layered clay compound obtained by modifying a layered clay compound with alumina sol as a constituent component, and an ethylene-based polymer production method using the catalyst.

  In the conventional method, when alumina is reacted with the layered clay compound, the exchangeable cation is consumed and the CEC (cation exchange capacity) is decreased, and thus the effect of sufficiently improving the activity has not been found. Moreover, since the alumina reacted with the layered clay compound acts as a pillar and the interlayer distance is expanded, the function of the layered clay compound as a carrier is significantly different from that before the reaction.

  In the present invention, the alumina-modified layered clay compound obtained by modifying the layered clay compound with alumina sol has an increased CEC (cation exchange capacity) value without increasing the interlayer distance compared to the layered clay compound as a raw material. To do. And it discovers that it will become an excellent catalyst for ethylene polymer manufacture by using the obtained alumina modified layered clay compound as a structural component, and will complete the present invention.

  That is, the present invention relates to an alumina-modified layered clay compound obtained by reacting the layered clay compound (A) with the alumina sol (B).

(In the formula, R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. A silyl group, a hydrocarbon group having 1 to 30 carbon atoms in which oxygen is introduced between carbon bonds, and a part of the hydrocarbon group having 1 to 30 carbon atoms is an alkylamino group having 1 to 30 carbon atoms. In which a part of carbon of the hydrocarbon group having 1 to 30 carbon atoms is substituted with silicon, M ¹ is an atom of Group 15 of the periodic table, and [A ⁻ ] is an anion. .)
Organically modified clay (C) modified with an organic compound represented by the general formula (2)
M ² Q ¹ aQ ² bQ ³ cQ ⁴ d (2)
(Wherein M ² is a titanium atom, a zirconium atom or a hafnium atom, and Q ¹ , Q ² , Q ³ and Q ⁴ are a cycloalkadienyl group, a substituted cycloalkadienyl group, a chelating ligand, Lewis base, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, the above One in which oxygen is introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms In the hydrocarbon group having 1 to 20 carbon atoms, a part of carbon is substituted with silicon, and these may be the same as or different from each other. Q ¹ , Q ² , Q ³ and Q ⁴ are And may be bonded via another atom or atomic group, and a, b, c and d each represent an integer of 0 to 4, and a + b + c + d ≦ 4.)
The catalyst for ethylene-type polymer manufacture containing the transition metal compound (D) represented by these, and the organoaluminum compound (E), and the manufacturing method of the ethylene-type polymer using this catalyst are provided.

  The present invention is described in detail below.

In the layered clay compound (A), the tetrahedron sheet in which the silica tetrahedron is continuous in two dimensions and the octahedron sheet in which the alumina octahedron, magnesia octahedron, etc. are continuous in two dimensions are 1: 1 or 2: 1. A layer called a silicate layer composed of a combination of layers is formed by overlapping several layers. Some silica tetrahedrons Si are Al, alumina octahedron Al is Mg, magnesia octahedrons. When Mg is replaced with Li or the like in the same type, the positive charge inside the layer is insufficient, and the entire layer is negatively charged. In order to compensate for this negative charge, Na ⁺ or Ca ²⁺ or the like is interposed between the layers. Are present. Kaolinite, talc, smectite, vermiculite, mica, brittle mica, curdstone, etc. exist as natural products or synthetic products. Or montmorillonite is more preferable.

  The alumina sol (B) is produced by various production methods, and various alumina sols are produced. The alumina particles in the produced alumina sol are composed of boehmite crystals, pseudoboehmite crystals, or amorphous alumina, and the shape thereof is as follows. As a granular shape, a rod shape, a fiber shape, a feather shape, and the like. In a stable alumina sol, an anion usually present around the colloidal particles of alumina prevents bonding between the colloidal particles of alumina, and thus the dispersed state of the colloidal particles of alumina in water is maintained.

  The alumina sol is produced by reacting an acid or alkali with a basic aluminum salt or by reacting an alkali gel with an acidic aluminum salt by peptization with an acid to have a boehmite structure. A method for producing an aqueous alumina sol containing plate-like colloidal particles of alumina hydrate, activated alumina powder showing incomplete crystal structure or amorphous structure in an aqueous medium having a pH of 9 or less at 120 to 225 ° C. A method for producing a suspension of alumina hydrate particles having a boehmite structure exhibiting various shapes such as plate, ribbon, and fiber, by reacting carbon dioxide with alkali aluminate The amorphous hydroxyaluminum carbonate gel obtained by mixing with an acid, base, salt or mixture thereof is mixed. The medium of the mixture has a pH of 11 or less, is heated at a temperature of 90 ° C. or less for at least 5 minutes, and is then treated at a temperature of 90 to 250 ° C. to show plate-like, ribbon-like, and fiber-like shapes. , A method for producing a suspension of pseudoboehmite and alumina hydrate particles having a boehmite structure, after hydrolyzing aluminum alkoxide with water at 75 ° C., the resulting slurry is hydrochloric acid, nitric acid, etc. at 80 ° C. or higher A method of producing a transparent aqueous alumina sol containing plate-like colloidal particles of alumina hydrate having a boehmite structure by peptization with acid, and by reacting an aqueous solution of organic acid with metallic aluminum powder under heating A method for producing an aqueous alumina sol containing fibrous colloidal particles of alumina hydrate, an aqueous solution of an acid such as hydrochloric acid and metallic aluminum When a colloidal particle of alumina hydrate is produced by reacting, an aqueous solution of secondary particles having a length of about 5 to 10 times the thickness by coexisting a small amount of silicate ion and a small amount of sulfate ion. A method for producing an alumina sol is known, but is not limited thereto.

  In consideration of the reactivity of the layered clay compound with the interlayer cation, an alumina sol that is feather-shaped colloidal alumina, has a stabilized structure with an acid, and has a cationic particle charge is preferable.

  The alumina-modified layered clay compound obtained by reacting the layered clay compound (A) with the alumina sol (B) has the following general formula (1):

(In the formula, R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. A silyl group, a hydrocarbon group having 1 to 30 carbon atoms in which oxygen is introduced between carbon bonds, and a part of the hydrocarbon group having 1 to 30 carbon atoms is an alkylamino group having 1 to 30 carbon atoms. In which a part of carbon of the hydrocarbon group having 1 to 30 carbon atoms is substituted with silicon, and at least one of R ^{1 to} R ³ has 21 or more carbon atoms, and M ¹ is (It is an atom of Group 15 of the periodic table, and [A ⁻ ] is an anion.)
As an organic modified clay (C) modified with an organic compound represented by formula (I), specific examples of the organic compound can be exemplified below.

In the general formula (1), the hydrocarbon group having 1 to 30 carbon atoms of R ¹ , R ² and R ³ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, an n-butyl group, Isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, neopentyl, tert-pentyl, cyclopentyl, 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, cyclohexyl group, n-heptyl group, cycloheptyl group Group, 2-methylcyclohexyl group, 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-dimethylcyclohexyl group, 2- (1-cyclohexenyl) ethyl group, n-nonyl group, n-decyl group, isodecyl group, geranyl group, n-undecyl group, n-dodecyl group, cyclododecyl group 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 Examples thereof include a group, n-tricosyl group, oleyl group, behenyl group, phenyl group and the like.

  Examples of the alkoxy group having 1 to 30 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, and a phenoxy group.

  A C1-C30 alkylamino group is an amino group which has the said C1-C30 hydrocarbon group as a substituent, and is a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diisopropylamino group. , Diphenylamino group, methylphenylamino group and the like.

  The alkylsilyl group having 1 to 30 carbon atoms is a silyl group having the hydrocarbon group having 1 to 30 carbon atoms as a substituent, and includes a trimethylsilyl group, a tri-tert-butylsilyl group, a ditert-butylmethylsilyl group, a tert- Examples thereof include a butyldimethylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a phenyldimethylsilyl group.

  As what introduce | transduced oxygen between carbon of carbon of the said C1-C30 hydrocarbon group, a methoxymethylene group, an ethoxymethylene group, etc. can be illustrated.

  As what substituted a part of said C1-C30 hydrocarbon group by the C1-C30 alkylamino group, a dimethylaminomethylene group, a diethylaminomethylene group, etc. can be illustrated.

  As what substituted a part of carbon of the said C1-C30 hydrocarbon group with silicon, a trimethylsilylmethylene group, a tert- butyldimethylsilylmethylene group, etc. can be illustrated.

[A ⁻ ] is an anion such as fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, oxalate ion, citrate ion, succinate ion, tetra Although fluoroborate ion or hexafluorophosphate ion can be used, it is not limited to these.

M ¹ is an atom of Group 15 of the periodic table, and can be exemplified by a nitrogen atom or a phosphorus atom. Specific examples of the organic compound represented by the general formula (1) when M ¹ 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-hexyl Amine 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-octadecy Ruamine hydrochloride, allylamine hydrochloride, cyclopentylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, diallylamine hydrochloride, trimethylamine hydrochloride, tri-n-butylamine hydrochloride, triallylamine hydrochloride, hexylamine hydrochloride, 2- Aminoheptane 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, Octadecylami Hydrochloride, nonadecylamine hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 3-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexylamine hydrochloride Salt, cyclododecylamine 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-allyl Chlorhexylamine 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, N, N-dimethyloleylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, triisodecylamine hydrochloride Dodecylamine hydrochloride, N-methyl-N-octadecyl-1-octadecylamine hydrochloride, N, N-dimethylsilane Chlorhexylamine hydrochloride, N, N-dimethylcyclohexylmethylamine hydrochloride, N, N-diethylcyclohexylamine hydrochloride, N, N-dimethyllaurylamine hydrochloride, N, N-dimethylmyristylamine hydrochloride, N, N -Dimethylpalmitylamine hydrochloride, N, N-dimethylstearylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, N, N-dimethylcocoalkylamine hydrochloride, N, N-dimethyl tallow alkylamine hydrochloride, N, N-dimethyl-cured tallow alkylamine hydrochloride, N, N-dimethyloleylamine hydrochloride, N-methyldidodecylamine hydrochloride, N-methyldicocoalkylamine hydrochloride, N-methyl-cured tallow alkylamine hydrochloride, N-methyldioleylamine hydrochloride, pyrrolidine hydrochloride, piperidine hydrochloride, , 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- Hydrochloric acid hydrochlorides such as butylpyrrolidine hydrochloride, 1,2,2,6,6-pentamethylpiperidine hydrochloride, aniline hydrochloride, N-methylaniline hydrochloride, N-ethylaniline hydrochloride, N-allyl Aniline hydrochloride, o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, N, N-dimethylaniline salt Salt, 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 Salt, 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 Salt, N-propyl-m-toluidine hydrochloride, N-propyl-p-toluidine hydrochloride, 2,3-dimethylaniline hydrochloride, 2,4-dimethylaniline hydrochloride, 2,5-dimethylaniline hydrochloride, 2 , 6-dimethylaniline hydrochloride, 3,4-dimethylaniline hydrochloride, 3,5-dimethylaniline hydrochloride, 2-ethylaniline hydrochloride, 3-ethylaniline hydrochloride, 4- Ethylaniline hydrochloride, N, N-diethylaniline hydrochloride, 2-isopropylaniline hydrochloride, 4-isopropylaniline hydrochloride, 2-tert-butylaniline hydrochloride, 4-n-butylaniline hydrochloride, 4-sec- Butylaniline hydrochloride, 4-tert-butylaniline hydrochloride, 2,6-diethylaniline hydrochloride, 2-isopropyl-6-methylaniline hydrochloride, 2-chloroaniline hydrochloride, 3-chloroaniline hydrochloride, 4- Chloroaniline hydrochloride, 2-bromoaniline hydrochloride, 3-bromoaniline hydrochloride, 4-bromoaniline hydrochloride, o-anisidine hydrochloride, m-anisidine hydrochloride, p-anisidine hydrochloride, o-phenetidine hydrochloride, m-phenetidine hydrochloride, p-phenetidine hydrochloride, 1-aminonaphthalene hydrochloride, 2-aminonaphth Len 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, 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 Salt, N-methyl-6-ethyl-o-toluidine hydrochloride, N-methyl-2-isopropylaniline hydrochloride, N-methyl-4-isopropyl Aniline 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- Tetramethylaniline 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, N, N-dimethyl-3-bromoaniline hydrochloride, N, N-dimethyl-4-bromoaniline hydrochloride, N, N-dimethyl-o-anisidine hydrochloride, N, N -Dimethyl-m-anisidine hydrochloride, N, N-dimethyl-p-anisidine hydrochloride, N, N-dimethyl-o-phenetidine hydrochloride, N, N-dimethyl-m-phenetidine hydrochloride, N, N-dimethyl -P-phenetidine hydrochloride, N, N-dimethyl-1-aminonaphthalene hydrochloride, N, N-dimethyl-2-aminonaphthalene hydrochloride, N, N-dimethyl-1-aminofluore Hydrochloride, N, N-dimethyl-2-aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl-4-aminofluorene hydrochloride, N, N-dimethyl-5 Hydrochloric acids of aromatic amines such as aminoindan hydrochloride, N, N-dimethyl-2-aminobiphenyl hydrochloride, N, N-dimethyl-4-aminobiphenyl hydrochloride, N, N-dimethyl-p-trimethylsilylaniline hydrochloride Examples of the salt and the compound in which the hydrochloride of the above compound is replaced with a hydrofluoric acid salt, a hydrobromide salt, a hydroiodide salt, or a sulfate salt are not limited thereto.

Among the compounds represented by formula (1), those in which M ¹ 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 the formula (1), those in which M ¹ 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 formula (1), those in which M ¹ 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.

  The organic modified clay (C) modified with the organic compound introduces organic ions between the layers of the alumina modified layered clay compound to form an ionic complex.

  In the organic compound modification treatment, it is preferable to perform the treatment by selecting the conditions where the concentration of the alumina-modified layered clay compound is 0.1 to 30% by weight and the treatment temperature is 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 alumina-modified layered clay compound and the organic compound, it is preferable to use an organic compound equivalent to or more than the exchangeable cation of the alumina-modified layered clay compound. 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. .

  Further, the particle size of the organically modified clay (C) used in the present invention is not particularly limited, but if it is too small, it will be difficult to settle and it will not be possible to efficiently prepare the catalyst. If it is too large, the catalyst will be transferred in a slurry. In order to clog the piping in the middle, it is preferably 1 to 100 μm. The method for adjusting the particle size is not particularly limited, and large particles may be pulverized to an appropriate particle size, small particles may be granulated to an appropriate particle size, or pulverization and granulation may be combined. Also good. The particle size may be adjusted for the alumina-modified layered clay compound before the organic compound modification or for the organic-modified clay (C) after the organic compound modification.

  The method of pulverization and granulation is not particularly limited. For pulverization, impact mill, rotary mill, cascade mill, cutter mill, cage mill, impact pulverizer, conical mill, colloid mill, compound mill, jet mill, vibration mill, stamp mill , Tube mill, disk mill, tower mill, medium stirring mill, hammer mill, pin mill, fret mill, pebble mill, ball mill, ball mill, planetary mill, ring ball mill, ring roll mill, rod mill, roller mill, roll crusher etc. as granulation May be any method such as rolling granulation, fluidized bed granulation, stirring granulation, compression granulation, extrusion granulation, crush granulation, melt granulation, spray granulation and the like.

The transition metal compound (D) is represented by the following general formula (2)
M ² Q ¹ aQ ² bQ ³ cQ ⁴ d (2)
(Wherein M ² is a titanium atom, a zirconium atom or a hafnium atom, and Q ¹ , Q ² , Q ³ and Q ⁴ are a cycloalkadienyl group, a substituted cycloalkadienyl group, a chelating ligand, Lewis base, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, the above One in which oxygen is introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms In the hydrocarbon group having 1 to 20 carbon atoms, a part of carbon is substituted with silicon, and these may be the same as or different from each other. Q ¹ , Q ² , Q ³ and Q ⁴ are And may be bonded via another atom or atomic group, and a, b, c and d each represent an integer of 0 to 4, and a + b + c + d ≦ 4.)
Preferably, the following general formula (3), general formula (4)

[Wherein, M ³ is a titanium atom, a zirconium atom or a hafnium 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, carbon An alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms in which oxygen is introduced between carbon-carbon bonds, and the above 1 to 20 carbon atoms A part of the hydrocarbon group is substituted with an alkylamino group having 1 to 20 carbon atoms, a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with silicon, and R ⁴ , R ⁵ Are each independently the general formula (5), (6), (7) or (8)

(In the formula, each R ⁷ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, or the above carbon number. What introduced oxygen between the carbon-carbon bond of 1-20 hydrocarbon group, What substituted a part of said C1-C20 hydrocarbon group by C1-C20 alkylamino group, The above (Some carbons of the hydrocarbon group having 1 to 20 carbon atoms are substituted with silicon.)
In a ligand coordinating to ^{M 3} represented, a sandwich structure is formed with ^{R 4} and ^{R 5 M 3, R 6} is the formula (9) or (10)

(In the formula, each R ⁸ 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, an alkylamino group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 alkylsilyl groups, those having oxygen introduced between the carbon-carbon bonds of the hydrocarbon group having 1 to 20 carbon atoms, and some of the hydrocarbon groups having 1 to 20 carbon atoms having 1 to 20 carbon atoms (Substituted by an alkylamino group, or by substituting part of carbon of the hydrocarbon group having 1 to 20 carbon atoms with silicon, and M ⁴ is a silicon atom, a germanium atom, or a tin atom.)
And R ⁴ and R ⁵ are cross-linked and n is an integer of 1 to 5. ]
The compound represented by these is used.

Examples of the cycloalkadienyl group and substituted cycloalkadienyl group of Q ¹ , Q ² , Q ³ and Q ⁴ include groups represented by the general formulas (5) to (8), specifically Cyclopentadienyl group, indenyl group, fluorenyl group, 2-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2-phenylindenyl group, 2 , 4-Diethylcyclopentadienyl group, 2-methoxycyclopentadienyl group, 2-dimethylaminocyclopentadienyl group, 2-trimethylsilylcyclopentadienyl group, 7-methylindenyl group, 7-ethylindenyl group Group, 7-phenylindenyl group, 2,7-dimethylindenyl group, 2-methoxy-7-methylindenyl group, 2-dimethylamino-7 Methyl indenyl group, 2-trimethylsilyl-7-methyl indenyl group, 4,7-dimethyl indenyl group, 4-methoxy-7-methyl indenyl group, tetrahydroindenyl group, 7-methyltetrahydroindenyl group, 7 -Ethyltetrahydroindenyl group, 7-phenyltetrahydroindenyl group, 2,7-dimethyltetrahydroindenyl group, 2-dimethylamino-7-methyltetrahydroindenyl group, 2-trimethylsilyl-7-tetrahydroindenyl group, 4 , 5,6,7-tetramethyltetrahydroindenyl group and the like. Examples of the chelating ligand include an ethylenediamine group, a bipyridine group, a phenanthroline group, and an acetylacetonate group. Examples of Lewis bases include amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine and pyridine, phosphines such as triethylphosphine and triphenylphosphine, thioethers such as tetrahydrothiophene, and benzoic acid. Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, n-butyl group, t-butyl group, and n-octyl group. Examples include a group, n-eicosyl group, phenyl group, benzyl group, o-toluyl group, m-toluyl group, p-toluyl group and the like. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, t-butoxy group, n-octoxy group and n-eoxy group. N-phenoxy group, 2-methylphenoxy group, 3-ethylphenoxy group, and the like. Examples of the alkylamino group having 1 to 20 carbon atoms include methylamino group, dimethylamino group, ethylamino group, methylethylamino group, n-propylamino group, di (n-propylamino group), iso-propylamino group, di (Iso-propylamino group), n-butylamino group, di (n-butylamino group), iso-butylamino group, di (iso-butylamino group), t-butylamino group, di (t-butylamino group) Group), phenylamino group, diphenylamino group, N, N-dimethylamino-N-methylene group and the like. Examples of the alkylsilyl group having 1 to 20 carbon atoms include methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, n-propylsilyl group, iso-propylsilyl group, and di (n-propylsilyl group). Group), di (iso-propylsilyl group), tri (n-propylsilyl group), tri (iso-propylsilyl group), n-butylsilyl group, iso-butylsilyl group, t-butylsilyl group, di (n-butylsilyl group) Group), di (iso-butylsilyl group), di (t-butylsilyl group), tri (n-butylsilyl group), tri (iso-propylsilyl group), tri (t-butylsilyl group), phenylsilyl group, diphenylsilyl Group, triphenylsilyl group, 0-toluylsilyl group, m-toluylsilyl group, p-toe It can be exemplified Irushiriru group. As what introduce | transduced oxygen between carbon of carbon of the said C1-C20 hydrocarbon group, a methoxymethylene group, an ethoxymethylene group, etc. can be illustrated. As what substituted a part of said C1-C20 hydrocarbon group by the C1-C20 alkylamino group, a dimethylaminomethylene group, a diethylaminomethylene group, etc. can be illustrated. As what substituted a part of carbon of the said C1-C20 hydrocarbon group with silicon, a trimethylsilylmethylene group, a tert- butyldimethylsilylmethylene group, etc. can be illustrated.

As specific examples of the transition metal compound (D), the following compounds can be exemplified. As specific examples of the transition metal compound (D), those corresponding to the general formula (3) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl). ) Zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, methylene bis (cyclopentadienyl) zirconium dichloride, those corresponding to general formula (4) include methylene bis (methylcyclopenta Dienyl) zirconium dichloride, methylenebis (butylcyclopentadienyl) zirconium dichloride, methylenebis (tetramethylcyclopentadienyl) zirconium dichloride, ethyl Bis (tetrahydroindenyl) zirconium dichloride, ethylenebis (2-methyl-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl (2,7 -Dimethyl-9-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium Dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2- Methyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, di Phenylmethylene (4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl)) zirconium dichloride, diphenylmethylene (2-methyl-4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene ( 2-methyl-4-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenyl-1-indenyl) (2,7-di-t- Butyl-9-fluoreni )) Zirconium dichloride, diphenylmethylene (4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, diphenylmethylene (4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl)) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzo-1- Indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl)) zirconium dichloride, diphenylmethylene (2-methyl-4) , 5-Benzo-1-yne Nyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl Bis (butylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethyl Silanediylbis (3-methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium Dichloride, dimethylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (1-indenyl) zirconium dichloride, dimethylsilanediylbis (2-methyl-1-indenyl) zirconium dichloride, dimethylsilanediylbis ( Tetrahydroindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclope Tadienyl) (1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4,7-dimethyl-1-indenyl) ) Zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride, Dimethylsilanediyl (cyclopentadienyl) (7-ethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-phenyl-1-indenyl) zirconium dichloride Dimethylsilanediyl (cyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methoxy-7-methyl-1-indenyl) zirconium dichloride, dimethyl Silanediyl (cyclopentadienyl) (2-trimethylsilyl-7-methyl1-indenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl ( Tetramethylcyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride, dimethyl Rusilanediyl (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-isopropyl-7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl ( Cyclopentadienyl) (4-phenyl-7-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-methoxy-7-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl ( Cyclopentadienyl) (4-trimethylsilyl-7-methyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (3,4-dimethylcyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zyl Nium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4-phenyl-7-methyl-1- Indenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7- Trimethyl-1-indenyl) zirconium dichloride, diethylsilanediylbis (cyclopentadienyl) zirconium dichloride, diethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diethyl Randiylbis (butylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diethyl Silanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (4-t-butyl-2-methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (tetramethylcyclopentadienyl) zirconium Dichloride, diethylsilanediylbis (1-indenyl) zirconium dichloride, diethylsilanediylbis (2-methyl-1-indenyl) zirconium dichloride , Diethylsilanediylbis (tetrahydro-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-dimethyl-9-fluorenyl) ) Zirconium dichloride, diethylsilanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (1-indenyl) zirconium dichloride, diethylsilanediyl (Cyclopentadienyl) (2-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (4,7-dimethyl-1-indenyl) di Conium dichloride, diethylsilanediyl (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride, Diethylsilanediyl (cyclopentadienyl) (7-ethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (7-phenyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) ) (2,7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (2-methoxy-7-methyl1-indenyl) zirconium dichloride, diethylsilanediyl Cyclopentadienyl) (2-trimethylsilyl-7-methyl 1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclo) Pentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (7-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (4 , 7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (4-isopropyl-7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl Clopentadienyl) (4-phenyl-7-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (4-methoxy-7-methyl-
1-indenyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (4-trimethylsilyl-7-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (3,4-dimethylcyclopentadienyl) (2,4 , 7-trimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (4 -Phenyl-7-methyl-1-indenyl) zirconium dichloride, diethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diethylsilanedi (Tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride, diphenimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride , Diphenylsilanediylbis (butylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (2,4-dimethylcyclopentadienyl) Zirconium dichloride, diphenylsilanediylbis (3-methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (4-t-butyl-2- Tilcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (tetramethylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (indenyl) zirconium dichloride, diphenylsilanediylbis (2-methyl-1-indenyl) zirconium dichloride, Diphenylsilanediylbis (tetrahydroindenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-9-fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl-2,7-dimethyl-9fluorenyl) zirconium dichloride, diphenyl Silanediyl (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium di Loride, diphenylsilanediyl (cyclopentadienyl) (1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) ( 4,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (7- Methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (7-ethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) ) (7-phenyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-methoxy-) 7-methyl 1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-trimethylsilyl-7-methyl 1-indenyl) zirconium dichloride, diphenylsilanediyl (tetramethylcyclopentadienyl) (7-methyl- 1-indenyl) zirconium dichloride, diphenylsilanediyl (tetramethylcyclopentadienyl) (2,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadi) Nyl) (7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-isopropyl) -7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-phenyl-7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-methoxy) -7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-trimethylsilyl-7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (3,4) -Dimethylcyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, diphenylsilane Diyl (tetramethylcyclopentadienyl) (4-phenyl-7-methyl-1-indenyl) zirconium dichloride, diphenylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium Dichloride, diphenylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, compounds in which zirconium atoms are changed to titanium atoms, hafnium atoms, Examples include compounds obtained by changing the loro form to a dimethyl form, a diethyl form, a dihydro form, a diphenyl form, and a dibenzyl form. Preferred transition metal compounds (D) include bis (cyclopentadienyl) zirconium dichloride, dimethyl form, and the like. Silanediylbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7 -Trimethyl-1-indenyl) zirconium dichloride and isopropylidene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and the like, but are not limited thereto. ,these Out it can be used in combination of two or more.

  The organoaluminum compound (E) is a constituent component of the catalyst for producing an ethylene polymer of the present invention, and is used together with the organically modified clay (C) and the transition metal compound (D).

  As the organoaluminum compound (E), for example, the following general formula (11)

(In the formula, R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁰ is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a chlorine atom.)
And a compound capable of alkylating a transition metal compound is preferable, and specific examples include alkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum.

Regarding the weight ratio when the layered clay compound (A) in the present invention is modified with the alumina sol (B), the effect of modification is clearly expressed, and when the amount of the alumina sol (B) is excessively increased, the CEC of the entire support is lowered. In view of the decrease in catalyst performance, it is preferable to react the alumina sol (B) in the range of 2.5 to 30 parts by weight with respect to 100 parts by weight of the layered clay compound (A).
There are no particular restrictions on reaction conditions such as reaction temperature and reaction time when the layered clay compound (A) is modified with the alumina sol (B), but the reaction temperature is 0 to 100 ° C., and the reaction time is several minutes to several tens of hours. It is preferable to carry out within a range. The reaction solvent is not particularly limited, but water or a commonly used organic solvent such as alcohol, acetone, THF, etc. can be used, but water or water as a main component is easy to handle. Is preferably used.
Alumina-modified layered clay compound and amount of organic compound in preparing organically modified clay (C) by modifying an alumina-modified layered clay compound obtained by modifying layered clay compound (A) with alumina sol (B) with an organic compound Although there is no restriction | limiting in ratio, It is preferable to use the organic compound more than CEC of an alumina modified layered clay compound.

  Since the alumina-modified layered clay compound obtained by modifying the layered clay compound (A) with the alumina sol (B) has many reaction fields effective for the construction of the polymerization activity field, CEC (cation exchange capacity per 100 g of the layered clay compound (A) ) Is 70.0 meq or more, and the action of the layered clay compound as a carrier is not significantly different from that before the reaction, so that the interlayer distance measured by XRD is 6.0 mm or more and 10.0 mm or less. preferable.

  The concentration of the alumina-modified layered clay compound with respect to the solvent in preparing the organic-modified clay (C) by modifying the alumina-modified layered clay compound obtained by modifying the layered clay compound (A) with the alumina sol (B) with an organic compound is 0. It is preferable to perform the treatment by selecting conditions of 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. 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. .

  The ratio of the organically modified clay (C), the transition metal compound (D) (component (D)) and the organoaluminum compound (E) (component (E)) in the present invention is not limited, but is the ratio shown below. It is desirable.

  The molar ratio of the component (D) to the component (E) per metal atom is in the range of (D component) :( E component) = 100: 1 to 1: 100000, and particularly in the range of 1: 1 to 1: 10000. It is preferable that the weight ratio of the component (D) to the component (C) is (D component) :( C component) = 10: 1 to 1: 10000, particularly 3: 1 to 1: 1000. It is preferable.

  The present invention provides an organic modified clay (C), a transition metal compound (D), and an organic compound obtained by modifying an alumina-modified layered clay compound obtained by reacting an alumina sol (B) with a layered clay compound (A). By using an ethylene polymer production catalyst containing an aluminum compound (E), it is possible to produce an ethylene polymer efficiently.

  There is no restriction on the method for preparing the catalyst for producing an ethylene-based polymer containing the components (C), (D) and (E) of the present invention. The method of mixing using the monomer which performs this as a solvent can be mentioned. Moreover, there is no restriction | limiting also about the order which makes these components react, and the temperature and processing time which perform this process also have no restriction | limiting. It is also possible to prepare an ethylene polymer production catalyst by using two or more types of component (D) and component (E).

The catalyst in the present invention can be used in any of usual polymerization processes, that is, slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization, and bulk polymerization.

  In the present invention, polymerization means not only homopolymerization of ethylene but also copolymerization with other olefins, and ethylene polymers obtained by these polymerizations are used to include not only homopolymers but also copolymers. .

  The ethylene polymerization in the present invention can be carried out either in the gas phase or in the liquid phase. Particularly when the polymerization is carried out in the gas phase, it is possible to efficiently and stably produce an ethylene polymer having a uniform particle shape. . Further, when the polymerization is performed in a liquid phase, the solvent used may be any organic solvent that is generally used, and specific examples include benzene, toluene, xylene, pentane, hexane, heptane, and the like. Olefins such as 1-butene, 1-octene and 1-hexene can also be used as a solvent.

  Other olefins used for copolymerization with ethylene of the present invention include α-olefins such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene, styrene and styrene derivatives, butadiene, 1 , 4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like conjugated and non-conjugated dienes, cyclobutene and other cyclic olefins, etc. Is mentioned. Further, three or more kinds of components can be mixed and polymerized, such as ethylene, propylene and styrene, ethylene, 1-hexene and styrene, ethylene, propylene, and ethylidene norbornene.

  There are no particular restrictions on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration in producing the ethylene-based polymer using the method of the present invention, but the polymerization temperature is −100 to 300 ° C. Is preferably 10 seconds to 20 hours, and the polymerization pressure is preferably from normal pressure to 3000 kg / cm 2 G. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The ethylene polymer obtained after the completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.

  The present invention has an excellent polymerization activity while suppressing the adhesion of the polymer to the reactor wall in gas phase polymerization and suspension polymerization without using an expensive organoaluminum oxy compound or boron compound in olefin polymerization. An ethylene polymer having a good particle shape can be produced. including

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise noted, the reagents used were commercially available products or those synthesized according to known methods.

  CEC (cation exchange capacity) was calculated by the following method.

  A sample dried in an oven at 105 ° C. for 2 hours was used as a measurement sample.

  1 g of the dried measurement sample is precisely weighed into a 300 mL flask.

  Add 50 mL of 1N aqueous ammonium acetate and soak overnight.

  No. Filtration is performed using 5A filter paper, and the inside of the flask is washed with an aqueous ammonium acetate solution, and then excess ammonium acetate is washed with 250 mL of methanol.

The sample on the filter paper is poured into a 300 mL flask with 50 m of 10% NaCl aqueous solution.
(Steam distillation)
Collect 50 mL of 1/10 NH ₂ SO _{4 in a} separate flask and place indicator (0.1% methyl orange) (for trap).

  Distilled water is boiled with a burner, and the generated water vapor is introduced into the sample flask.

  After putting 35 mL of 25% NaOH solution in the sample flask, boil with a burner.

  The gas generated from the sample flask is trapped in a flask containing sulfuric acid and an indicator.

The completion was determined with a distillation volume of about 100 mL in 30 minutes as a guide.
(Back titration)
Back-titration of the trap flask was performed with 1/10 N NaOH solution. (Discoloration: red → yellow)
CEC is calculated by the following equation.

Meq / 100 g = [(A × f) − (Bxf)] × 10 / sample amount (g)
A: 1/10 NH ₂ SO ₄ collected amount (mL)
B: 1 / 10N NaOH solution titration (mL)
f: Factors of A and B The interlayer distance was calculated by the following method.
[Measuring method]
Measuring equipment: Spectris X'pert PRO MPD
Tube: Cu
Tube voltage: 45kV
Tube current: 40 mA
Measurement speed: 0.1 deg / step, 15 sec / step
Irradiation width: 10mm
Detector: Proportional counter Filter: Ni
Anti-scattering slit: 1/4 deg
Receiving slit: 0.5mm
[Calculation of interlayer distance]
The interlayer distance was calculated from the peak top angle measured between 1.5 and 10 deg.

  A jet mill (trade name: CO-JET SYSTEM α MARK III, manufactured by Seishin Enterprise Co., Ltd.) was used for pulverization of the organically modified clay, and the particle size after pulverization was measured using a microtrack particle size distribution analyzer (trade name, manufactured by Nikkiso Co., Ltd.). MT3000) was used to measure ethanol as a dispersant.

  Preparation of the ethylene polymer production catalyst, production of the ethylene polymer and solvent purification were all carried out under an inert gas atmosphere.

  Trisodium aluminum hexane solution (20 wt%) and triisobutyl aluminum hexane solution (20 wt%) were manufactured by Tosoh Finechem Co., Ltd.

  Furthermore, various physical properties of the ethylene-based polymer in the examples were measured by the following methods.

  The density was measured by a density gradient tube method in accordance with JIS K6760 (1995).

  MFR (melt flow rate) was measured by a method according to ASTM D1238 Condition E.

Example 1
(1) Synthesis of Alumina-modified Hectorite In a 5 L vessel with a stirring blade, 2500 g of distilled water, 100 g of alumina sol (alumina content 10%, manufactured by Nissan Chemical Co., Ltd. (trade name) Alumina Sol-200), synthetic hectorite ( 100 g of Rockwood Additives (trade name: Laponite RDS) was dispersed and then stirred at room temperature for 6 hours.

As a result of measuring CEC of a sample obtained by partially collecting the obtained slurry and drying in an oven at 85 ° C., they were 80.2 (meq / 100 g solid) and 88.2 (meq / 100 g hectorite conversion). . The interlayer distance measured by XRD was 8.7 mm.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 6.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 25.5 g (48 mmol) manufactured by (trade name) Armin M2O) and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 65 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.6 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 61.8 mg (corresponding to a solid content of 7.14 mg) of the catalyst suspension obtained in (3) was added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 61 g of polymer (activity: 8,520 g / g catalyst). The MFR of this polymer was 0.082 g / 10 minutes.

Example 2
(1) Synthesis of alumina-modified hectorite In a 5 L vessel with a stirring blade, 2500 mL of distilled water, 75 g of alumina sol (alumina content 10%, manufactured by Nissan Chemical Co., Ltd. (trade name) Alumina Sol-200), synthetic hectorite ( 100 g of Rockwood Additives (trade name: Laponite RDS) was dispersed and then stirred at room temperature for 6 hours.

As a result of measuring CEC of a sample obtained by partially collecting the obtained slurry and drying in an oven at 85 ° C., they were 71.0 (meq / 100 g solid) and 76.3 (meq / 100 g hectorite conversion). . The interlayer distance measured by XRD was 8.2 mm.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 6.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 25.5 g (48 mmol) manufactured by (trade name) Armin M2O) and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 63 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 13.3 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 70.0 mg (corresponding to a solid content of 9.28 mg) of the catalyst suspension obtained in (3) was added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 75 g of polymer (activity: 8,060 g / g catalyst). The MFR of this polymer was 0.090 g / 10 minutes.

Example 3
(1) Synthesis of alumina-modified hectorite In a 5 L vessel with a stirring blade, 2500 g of distilled water, 50 g of alumina sol (alumina content 10%, manufactured by Nissan Chemical Co., Ltd. (trade name) Alumina Sol-200), synthetic hectorite ( 100 g of Rockwood Additives (trade name: Laponite RDS) was dispersed and then stirred at room temperature for 6 hours.

As a result of measuring CEC of a sample obtained by partially collecting the obtained slurry and drying in an oven at 85 ° C., they were 82.9 (meq / 100 g solid) and 87.0 (meq / 100 g hectorite conversion). . The interlayer distance measured by XRD was 7.9 mm.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 6.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 25.5 g (48 mmol) manufactured by (trade name) Armin M2O) and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 58 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.5 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 57.4 mg (corresponding to a solid content of 6.61 mg) of the catalyst suspension obtained in (3) was added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 59 g of polymer (activity: 8,900 g / g catalyst). The MFR of this polymer was 0.099 g / 10 min.

Example 4
(1) Synthesis of alumina-modified hectorite In a 5 L vessel with a stirring blade, 2500 g of distilled water, 25 g of alumina sol (alumina content: 10%, manufactured by Nissan Chemical Co., Ltd. (trade name) Alumina Sol-200), synthetic hectorite ( 100 g of Rockwood Additives (trade name: Laponite RDS) was dispersed and then stirred at room temperature for 6 hours.

As a result of measuring CEC of a sample obtained by partially collecting the obtained slurry and drying in an oven at 85 ° C., they were 71.6 (meq / 100 g solid) and 73.4 (meq / 100 g hectorite conversion). . The interlayer distance measured by XRD was 7.9 mm.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 6.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 25.5 g (48 mmol) manufactured by (trade name) Armin M2O) and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 61 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 15.0 g of the organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.7 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 58.7 mg (corresponding to a solid content of 6.87 mg) of the catalyst suspension obtained in (3) was added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 47 g of polymer (activity: 6,870 g / g catalyst). The MFR of this polymer was 0.039 g / 10 min.

Example 5
(1) Synthesis of alumina-modified hectorite In a 5 L vessel with stirring blades, 2500 g of distilled water, 200 g of alumina sol (alumina content 10%, (product name) Alumina Sol-200) manufactured by Nissan Chemical Co., Ltd., synthetic hectorite ( 100 g of Rockwood Additives (trade name: Laponite RDS) was dispersed and then stirred at room temperature for 6 hours.

As a result of measuring CEC of a sample obtained by partially collecting the obtained slurry and drying in an oven at 85 ° C., they were 64.5 (meq / 100 g solid) and 77.4 (meq / 100 g hectorite conversion). . The interlayer distance measured by XRD was 8.7 mm.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 6.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 25.5 g (48 mmol) manufactured by (trade name) Armin M2O) and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 69 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.4 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 58.7 mg (corresponding to a solid content of 6.87 mg) of the catalyst suspension obtained in (3) was added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 88 g of polymer (activity: 6,850 g / g catalyst). The MFR of this polymer was 0.087 g / 10 min.

Example 6
(1) Synthesis of alumina-modified hectorite In a 5 L vessel with a stirring blade, 2500 g of distilled water, 300 g of alumina sol (alumina content 10%, manufactured by Nissan Chemical Co., Ltd. (trade name) Alumina Sol-200), synthetic hectorite ( 100 g of Rockwood Additives (trade name: Laponite RDS) was dispersed and then stirred at room temperature for 6 hours.

As a result of measuring CEC of a sample obtained by partially collecting the obtained slurry and drying in an oven at 85 ° C., they were 57.3 (meq / 100 g solid) and 74.5 (meq / 100 g hectorite conversion). . The interlayer distance measured by XRD was 8.2 mm.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 6.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 25.5 g (48 mmol) manufactured by (trade name) Armin M2O) and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in a dryer at 85 ° C. for 12 hours to obtain 75 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 120 mL of hexane, and 120 ml of hexane was added to obtain a catalyst suspension (solid weight: 11.8 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 75.1 mg (corresponding to a solid content of 8.86 mg) of the catalyst suspension obtained in (3) was added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 37 g of polymer (activity: 5,690 g / g catalyst). The MFR of this polymer was 0.097 g / 10 min.

Example 7
(1) Synthesis of alumina-modified hectorite (2) Synthesis of organically modified clay (3) Preparation of catalyst suspension The same procedure as in Example 1 was performed.
(4) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 125 mg (corresponding to a solid content of 14.5 mg) of the catalyst suspension obtained in (3) were added. After the temperature rise, 25.1 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.80 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 1,070 ppm). . After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 71 g of polymer (activity: 4,880 g / g catalyst). The polymer had an MFR of 32.6 g / 10 min and a density of 928.2 kg / m ³ .

Example 8
(1) Synthesis of alumina-modified hectorite (2) Synthesis of organically modified clay (3) Preparation of catalyst suspension The same procedure as in Example 2 was performed.
(4) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 125 mg (corresponding to a solid content of 19.4 mg) of the catalyst suspension obtained in (3) were added to 70 ° C. After the temperature rise, 25.1 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.80 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 1,050 ppm). . After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 78 g of polymer (activity: 4,020 g / g catalyst). The polymer had an MFR of 18.5 g / 10 min and a density of 928.6 kg / m ³ .

Example 9
(1) Synthesis of alumina-modified hectorite (2) Synthesis of organically modified clay (3) Preparation of catalyst suspension The same procedure as in Example 3 was performed.
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 121 mg (corresponding to a solid content of 13.9 mg) of the catalyst suspension obtained in (3) were added, After the temperature rise, 25.1 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.80 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 1,050 ppm). . After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 56 g of polymer (activity: 4,020 g / g catalyst). The polymer had an MFR of 34.5 g / 10 min and a density of 928.4 kg / m ³ .

Example 10
(1) Synthesis of alumina-modified hectorite The same procedure as in Example 1 was performed.
(2) Synthesis of organically modified clay 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water were placed in a 300 mL flask, and 7.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 28.3 g (53 mmol) of (trade name) Armin M2O, manufactured by Co., Ltd., heating to 45 ° C. and adding 40 g of the slurry of the alumina / hectorite composite obtained in (1) per hectorite, The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 65 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.0 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, 73.6 mg (corresponding to a solid content of 8.10 mg) of the catalyst suspension obtained in (3) were added, and 85 After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 53 g of polymer (activity: 6,510 g / g catalyst). The MFR of this polymer was 0.108 g / 10 minutes.

Example 11
(1) Synthesis of alumina-modified hectorite The same procedure as in Example 1 was performed.
(2) Synthesis of organically modified clay 120 mL of industrial alcohol (Nippon Alcohol Sales Co., Ltd. (trade name) Echinen F-3) and 80 mL of distilled water were placed in a 300 mL flask, 5.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion) After adding 21.3 g (40 mmol) (trade name) Armin M2O) manufactured by Co., Ltd. and heating to 45 ° C., 40 g of the alumina / hectorite composite slurry obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 61 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.1 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 63.1 mg (corresponding to a solid content of 7.64 mg) of the catalyst suspension obtained in (3) was added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 70 g of polymer (activity: 9,100 g / g catalyst). The MFR of this polymer was 0.063 g / 10 min.

Example 12
(1) Synthesis of alumina-modified hectorite The same procedure as in Example 1 was performed.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 4.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion) After adding 17.0 g ( 32 mmol) (trade name: Armin M2O) manufactured by Co., Ltd. and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. This slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 57 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.7 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 72.3 mg (corresponding to a solid content of 9.18 mg) of the catalyst suspension obtained in (3) were added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 71 g of polymer (activity: 7760 g / g catalyst). The MFR of this polymer was 0.058 g / 10 min.

Comparative Example 1
(1) Synthesis of organically modified clay Into a 1 L flask, 120 mL of industrial alcohol (Japan Alcohol Sales Co., Ltd. (trade name) Echinen F-3) and 80 mL of distilled water were added, and 6.0 g of concentrated hydrochloric acid and methyl dioleylamine (Lion Corporation) After adding 25.5 g (48 mmol) of company-made (trade name) Armin M2O) and heating to 45 ° C. to disperse 40 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RD), then to 60 ° C. The mixture was heated up and stirred for 1 hour while maintaining the temperature.

  The slurry was separated by filtration, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 60 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.

As a result of measuring CEC of the synthetic hectorite, it was 65.7 (meq / 100 g hectorite conversion), and the interlayer distance measured by XRD was 7.9 mm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 15.0 g of the organically modified clay obtained in (1) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 13.0 wt%)
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 127 mg (corresponding to a solid content of 16.5 mg) of the catalyst suspension obtained in (2) were added to 85 ° C. After the temperature increase, ethylene was continuously supplied so that the partial pressure became 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 91 g of polymer (activity: 5,500 g / g catalyst). The MFR of this polymer was 0.16 g / 10 min.

Comparative Example 2
(1) Synthesis of alumina-modified hectorite (2) Synthesis of organically modified clay (3) Preparation of catalyst suspension The same procedure as in Comparative Example 1 was performed.
(4) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 131 mg of the catalyst suspension obtained in (3) (corresponding to a solid content of 17.1 mg) was added to 70 ° C. After the temperature increase, 25.1 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.80 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 1,030 ppm). . After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 58 g of polymer (activity: 3,360 g / g catalyst). The polymer had an MFR of 20.0 g / 10 min and a density of 928.2 kg / m ³ .

Comparative Example 3
(1) Synthesis of Alumina-modified Hectorite In a 5 L vessel with a stirring blade, 2500 g of distilled water, 500 g of alumina sol (alumina content 10%, manufactured by Nissan Chemical Co., Ltd. (trade name) Alumina Sol-200), synthetic hectorite ( 100 g of Rockwood Additives (trade name: Laponite RDS) was dispersed, and then stirred at room temperature for 6 hours.

As a result of measuring CEC of a sample obtained by partially collecting the obtained slurry and drying in an oven at 85 ° C., they were 38.7 (meq / 100 g solid) and 60.4 (meq / 100 g hectorite conversion). . The interlayer distance measured by XRD was 8.2 mm.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 6.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 25.5 g (48 mmol) manufactured by (trade name) Armin M2O) and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 79 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.6 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 81.1 mg (corresponding to a solid content of 10.22 mg) of the catalyst suspension obtained in (3) was added. After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 35 g of polymer (activity: 3,380 g / g catalyst). The MFR of this polymer was 0.037 g / 10 minutes.

Comparative Example 4
(1) Synthesis of alumina-modified hectorite In a 5 L vessel with a stirring blade, 2500 g of distilled water, 1000 g of alumina sol (alumina content 10%, manufactured by Nissan Chemical Co., Ltd. (trade name) Alumina Sol-200), synthetic hectorite ( 100 g of Rockwood Additives (trade name: Laponite RDS) was dispersed and then stirred at room temperature for 6 hours.

As a result of measuring CEC of a sample obtained by partially collecting the obtained slurry and drying in an oven at 85 ° C., it was 26.2 (meq / 100 g solid) and 51.6 (meq / 100 g hectorite conversion). . The interlayer distance measured by XRD was 8.2 mm.
(2) Synthesis of organically modified clay A 300 mL flask was charged with 120 mL of industrial alcohol (trade name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 80 mL of distilled water, and 6.0 g of concentrated hydrochloric acid and dioleylmethylamine (Lion After adding 25.5 g (48 mmol) manufactured by (trade name) Armin M2O) and heating to 45 ° C., 40 g of the slurry of the alumina / hectorite composite obtained in (1) was added per hectorite. The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 94 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After replacing 300 mL flask equipped with thermometer and reflux tube with nitrogen, 15.0 g of organically modified clay obtained in (2) and 67 mL of hexane were added, and then bis (indenyl) Add 0.224 g of zirconium dichloride, 0.016 g of dimethylmethylene (cyclopentadienyl-2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, and 84 mL of 20% triisobutylaluminum at 60 ° C. Stir for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 120 mL of hexane, and then 120 mL of hexane was added to obtain a catalyst suspension (solid weight: 14.1 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, 77.3 mg (corresponding to a solid content of 10.9 mg) of the catalyst suspension obtained in (3) were added, and 85 After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 11 g of polymer (activity: 990 g / g catalyst). The MFR of this polymer was less than 0.01 g / 10 minutes.

Example 13
(1) Synthesis of alumina-modified hectorite The same procedure as in Example 2 was performed.
(2) Synthesis of organically modified clay Into a 1 L flask was placed 300 mL of industrial alcohol (Japan Alcohol Sales Co., Ltd. (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation) After adding 42.4 g (120 mmol) of company (trade name) Armin DM22D) and heating to 45 ° C., 100 g of the alumina / hectorite composite slurry obtained in (1) was added per hectorite, The mixture was heated to 0 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 125 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(3) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (2) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4406 g of pentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.2 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 98 mg of the catalyst suspension obtained in (2) (corresponding to a solid content of 12.0 mg) was added to After the temperature increase, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 550 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 66.2 g of polymer (activity: 5,520 g / g catalyst). The MFR of this polymer was 0.30 g / 10 min.

Comparative Example 5
(1) Synthesis of organically modified clay Into a 1 L flask was placed 300 mL of industrial alcohol (Japan Alcohol Sales Co., Ltd. (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation) 42.4 g (120 mmol) made by company (trade name) Armin DM22D) was added, heated to 45 ° C., and 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RD) was added, and then heated to 60 ° C. The mixture was heated up and stirred for 1 hour while maintaining the temperature. The slurry was separated by filtration, washed twice with 200 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 130 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (2) and 108 mL of hexane were added, and then dimethylsilylene (cyclohexane) 0.4406 g of pentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.4 wt%).
(4) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 108 mg (corresponding to a solid content of 13.4 mg) of the catalyst suspension obtained in (2) was added at 65 ° C. After raising the temperature, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 550 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 54.9 g of polymer (activity: 4,090 g / g catalyst). The MFR of this polymer was 0.068 g / 10 min.

Claims (7)

An alumina-modified layered clay compound obtained by reacting alumina sol (B) in a range of 2.5 to 30 parts by weight with respect to 100 parts by weight of the layered clay compound (A) is represented by the general formula (1). ) Organically modified clay (C) modified with an organic compound represented by formula (2)

(In the formula, R ^{1 to} R ³ are each independently a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, and an alkyl having 1 to 30 carbon atoms. A silyl group, a hydrocarbon group having 1 to 30 carbon atoms in which oxygen is introduced between carbon bonds, and a part of the hydrocarbon group having 1 to 30 carbon atoms is an alkylamino group having 1 to 30 carbon atoms. In which a part of carbon of the hydrocarbon group having 1 to 30 carbon atoms is substituted with silicon, M ¹ is an atom of Group 15 of the periodic table, and [A ⁻ ] is an anion. .)
M ² Q ¹ aQ ² bQ ³ cQ ⁴ d (2)
(Wherein M ² is a titanium atom, a zirconium atom or a hafnium atom, and Q ¹ , Q ² , Q ³ and Q ⁴ are a cycloalkadienyl group, a substituted cycloalkadienyl group, a chelating ligand, Lewis base, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, alkylsilyl group having 1 to 20 carbon atoms, the above One in which oxygen is introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, and a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with an alkylamino group having 1 to 20 carbon atoms In the hydrocarbon group having 1 to 20 carbon atoms, a part of carbon is substituted with silicon, and these may be the same as or different from each other. Q ¹ , Q ² , Q ³ and Q ⁴ are And may be bonded via another atom or atomic group, and a, b, c and d each represent an integer of 0 to 4, and a + b + c + d ≦ 4.)
The catalyst for ethylene-type polymer manufacture containing the transition metal compound (D) represented by these, and an organoaluminum compound (E). The transition metal compound (D) is represented by the general formula (3) and the general formula (4).

[Wherein, M ³ is a titanium atom, a zirconium atom or a hafnium 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, carbon An alkylamino group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms in which oxygen is introduced between carbon-carbon bonds, and the above 1 to 20 carbon atoms A part of the hydrocarbon group is substituted with an alkylamino group having 1 to 20 carbon atoms, a part of the hydrocarbon group having 1 to 20 carbon atoms is substituted with silicon, and R ⁴ , R ⁵ Are each independently the general formula (5), (6), (7) or (8)

(In the formula, each R ⁷ 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, an alkylamino group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 alkylsilyl groups, those having oxygen introduced between the carbon-carbon bonds of the hydrocarbon group having 1 to 20 carbon atoms, and some of the hydrocarbon groups having 1 to 20 carbon atoms having 1 to 20 carbon atoms (Substituted with an alkylamino group, or part of the hydrocarbon group having 1 to 20 carbon atoms substituted with silicon.)
In a ligand coordinating to ^{M 3} represented, a sandwich structure is formed with ^{R 4} and ^{R 5 M 3, R 6} is the formula (9) or (10)

(In the formula, each R ⁸ 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, an alkylamino group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 alkylsilyl groups, those having oxygen introduced between the carbon-carbon bonds of the hydrocarbon group having 1 to 20 carbon atoms, and some of the hydrocarbon groups having 1 to 20 carbon atoms having 1 to 20 carbon atoms (Substituted by an alkylamino group, or by substituting part of carbon of the hydrocarbon group having 1 to 20 carbon atoms with silicon, and M ⁴ is a silicon atom, a germanium atom, or a tin atom.)
And R ⁴ and R ⁵ are cross-linked and n is an integer of 1 to 5. ]
The catalyst for producing an ethylene-based polymer according to claim 1, wherein The catalyst for producing an ethylene-based polymer according to claim 1 or 2, wherein the alumina sol (B) is an alumina sol having a cationic particle charge. The catalyst for producing an ethylene-based polymer according to any one of claims 1 to 3, wherein the layered clay compound (A) is a clay compound belonging to a smectite group hectorite. The alumina-modified layered clay compound obtained by modifying the layered clay compound (A) with the alumina sol (B) has a CEC (cation exchange capacity) per 100 g of the layered clay compound (A) of 70.0 meq or more, and was measured by XRD. The catalyst for producing an ethylene-based polymer according to any one of claims 1 to 4, wherein an interlayer distance is 6.0 to 10.0 mm. Organoaluminum compound (E) is represented by the general formula (11)

(In the formula, R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁰ is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a chlorine atom.)
The catalyst for producing an ethylene-based polymer according to any one of claims 1 to 5 , wherein A method for producing an ethylene polymer, wherein ethylene and optionally an olefin having 3 or more carbon atoms are polymerized in the presence of the catalyst for producing an ethylene polymer according to any one of claims 1 to 6 .