JP4528508B2 - NOVEL Olefin Polymerization Catalyst Component, Olefin Polymerization Catalyst, and Olefin Polymerization Method - Google Patents

Description

  The present invention relates to a novel olefin polymerization catalyst component, an olefin polymerization catalyst using the same, and an olefin polymerization method using the same, and in particular, an olefin polymerization catalyst for polymerizing olefins with high activity. The present invention relates to a novel cocatalyst for constituting, a catalyst for olefin polymerization using the same, and a method for polymerizing olefins using them.

It is known that a so-called single-site catalyst such as a metallocene complex is obtained by combining a transition metal compound having a specific structure and a specific cocatalyst to develop olefin polymerization ability.
Specific promoters include modified clays obtained by subjecting clay minerals such as mica and montmorillonite to acid treatment and / or salt treatment (for example, see Patent Document 1), or clays modified with ammonium salts (for example, patents). Reference 2).
In these modified clays, the interlayer cation is exchanged with another cation contained in the treatment agent to increase the interlayer distance (this property is called “swelling”), increase the surface area, etc. Or the device which raises the activity of clay by adjusting a chemical property is made | formed.
However, these cation exchanges are usually carried out in an aqueous solution, and there has been a problem that the residual moisture becomes a catalyst poison to reduce the activity. In order to solve this problem, a step of firing the modified clay at about 100 to 300 ° C. has been introduced. However, when firing at a higher temperature, there is a drawback that the activity is drastically lowered.

Moreover, as a technique of using a transition metal compound other than a metallocene complex and a clay mineral as a catalyst for olefin polymerization, the central metal is group 8-9, and the ligand contains an element of group 15-16, An olefin polymerization catalyst in which a complex having a structure coordinated to a central metal by the atom and a clay mineral is combined (see, for example, Patent Document 3) is disclosed.
Alternatively, for the olefin polymerization in which the central metal is a group 3 to 10 and a complex having a structure coordinated through three nitrogen atoms contained in the ligand skeleton and a specific ionic compound as essential components A catalyst (for example, see Patent Document 4) is disclosed. In Patent Document 4, a clay mineral is also disclosed, but it is considered to be an optional component for the purpose of a carrier function and does not disclose a promoter function.
However, these patent documents do not mention the problem at the time of high-temperature baking as described above.
JP-A-8-127613 (Claim 1) JP-A-7-224106 (Claims 1, (0010), (0011)) JP 2000-198812 A JP-A-11-315109 (Claim 17, (0241) to (0253))

  The object of the present invention is to modify the clay mineral used as a co-catalyst component of the olefin polymerization catalyst, and to further improve the activity of the resulting modified clay without reducing the activity even when calcination is performed at a high temperature. Another object of the present invention is to provide a co-catalyst component of the catalyst for use in the production, and further provide a catalyst for olefin polymerization using the same and a method for polymerizing olefins using them.

  As a result of intensive studies to solve the above problems, the present inventors can only prevent a decrease in activity by modifying with a specific basic compound after high-temperature firing of a clay mineral used as a co-catalyst for an olefin polymerization catalyst. In addition, the present inventors have found that further high activation can be achieved and completed the present invention.

That is, according to 1st invention of this invention, the manufacturing method of the catalyst component for olefin polymerization characterized by processing sequentially by following process [a-1]-[a-3] is provided.
[A-1]: A clay mineral or an ion-exchange layered compound is mixed with an ammonium cation, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , Step [a-2] of chemical treatment with a salt of a compound comprising an anion selected from the group consisting of OOCCH ₃ , CH ₃ COCHCOCH ₃ , OOCH and OOCCH ₂ CH ₃ : obtained in step [a-1] Step [a-3] of firing the solid material at a temperature of 200 ° C. or higher and lower than 700 ° C .: 1 g of the solid material obtained in step [a-2], ammonia, methylamine, ethylamine, 1-ethylbutylamine, A basic compound selected from the group consisting of cyclohexylamine, benzylamine, triethylamine, pyridine, 2-methylpyridine and N, N-dimethylphenylamine; Is contacted in a ratio of 0.001mmol / g~10mol / g, to obtain intercalation product of the basic compound

Further, according to the second aspect of the present invention, in the first invention, the step [a-2] calcination of the production of olefin polymerization catalyst component, characterized in that it is carried out at 300 ° C. or higher temperature A method is provided.

Moreover, according to the third invention of the present invention, in the first or second invention, after contacting the basic compound in the step [a-3], the unreacted basic compound is removed. A method for producing a catalyst component for olefin polymerization is provided.

  When the catalyst component for olefin polymerization of the present invention is used as a co-catalyst for a transition metal catalyst for olefin polymerization, the polymerization activity per solid component can be made extremely high.

  The novel olefin polymerization catalyst component of the present invention is a clay mineral-based modified clay used as a co-catalyst component of an olefin polymerization catalyst, and completely removes residual moisture by calcination at high temperature, Furthermore, it is a highly activated catalyst component, and its function is sufficiently exhibited when used with a transition metal compound. The present invention is described in detail below.

1. Clay mineral In the present invention, the modified clay used as a cocatalyst is obtained by modifying a clay mineral or an ion-exchange layered compound.
The clay mineral or ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with a weak binding force. For example, most clays Is mentioned. Clay is usually composed mainly of clay minerals. The ion exchange layered compound occupies most of the clay mineral, and is preferably an ion exchange layered silicate.

  The clay mineral or ion-exchangeable layered compound used in the present invention preferably has a pore volume of not less than 0.05 cc / g, particularly 0.1 to 5 cc / g, more preferably 0, as measured by mercury porosimetry. .3-5 cc / g is preferable.

The average particle size of the clay mineral or ion-exchangeable layered compound used in the present invention is 5 μm or more and 100 μm when used in a production process for obtaining a solid polymer in a polymerization system such as so-called gas phase polymerization or slurry polymerization. The following is preferred. If there are many fine particles of less than 5 μm, aggregation of the polymers, adhesion to the reactor, etc. are likely to occur, and depending on the polymerization process, it may cause a short pass or a long-term residence, which is not preferable. Coarse particles having a size of 100 μm or more are not preferable because problems such as clogging (for example, when the catalyst is fed) are likely to occur.
Moreover, when using for the manufacturing process which obtains a molten polymer in the state melt | dissolved in the solvent in polymerization system like what is called solution polymerization, or the temperature more than melting | fusing point, 20 micrometers or less, Furthermore, 10 micrometers or less are preferable.
As long as the particles satisfy these conditions, natural products or commercially available products may be used as raw materials, or the particle size may be controlled by classification, fractionation, granulation, pulverization, or the like.

  In the present invention, it is preferable to granulate a clay mineral or an ion-exchange layered compound from the viewpoint of improving the particle properties of the polyolefin produced. The shape of the granulated particles is preferably spherical. The granulation method is not particularly limited, but the spray granulation method is preferable. The particle strength can be controlled in the granulation process. In addition, particle size control such as classification, fractionation, granulation, and pulverization can be performed anywhere before, after, and after steps [a-1] to [a-3] described later.

An ion-exchange layered silicate (hereinafter, sometimes simply referred to as “silicate”) has a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other and have a binding force. Refers to a silicate compound in which the ions to be exchanged are exchangeable. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchangeable layered silicates. You may go out. Various known silicates can be used. Specific examples include the following layered silicates described in Haruo Shiramizu “Clay Mineralogy” Asakura Shoten (1995).
(I) 2: 1 type minerals Smectite group such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, etc .; vermiculite group such as vermiculite; mica such as mica, illite, sericite, marine Pylophilite-talc group such as pyrophyllite and talc; Chlorite group such as Mg chlorite.
(Ii) 2: 1 ribbon type minerals Sepiolite, palygorskite and the like.

  The silicate used as a raw material in the present invention may be a layered silicate in which the above mixed layer is formed. In the present invention, the main component silicate is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite.

  The clay mineral or ion-exchangeable layered compound used in the present invention contains exchangeable Group 1 metal cations (usually Na, K, for example). The content of the cation of the Group 1 metal is 0.1% by weight or more, preferably 0.5% by weight or more.

2. Modified clay In the present invention, the modified clay used as a co-catalyst can be obtained by sequentially treating the above clay mineral or ion-exchangeable layered compound in the following steps [a-1] to [a-3]. it can.
(1) Step [a-1]
In step [a-1], the above clay mineral or ion-exchange layered compound is chemically treated.
Examples of chemical treatment include acid treatment, alkali treatment, salt treatment, organic matter treatment and the like. These processes may be used in combination with each other. In the present invention, these treatment conditions are not particularly limited, and known conditions can be used.
In the acid treatment, impurities on the surface are removed and some or all of cations such as Al, Fe, and Mg having a crystal structure are eluted. The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid.
The salt treatment can form an ion complex, a molecular complex, an organic derivative, etc., and can change the surface area and interlayer distance. That is, by utilizing ion exchange properties and replacing exchangeable ions between layers with other large and bulky ions, a layered material with the layers expanded can be obtained.

  In the present invention, the exchangeable group 1 metal cation contained in at least one compound selected from the group consisting of an ion-exchange layered compound excluding silicate and an inorganic silicate before being treated with salts. It is necessary to exchange 40% or more, preferably 60% or more, with cations dissociated from the salts shown below.

The salt used in the salt treatment of the present invention for such ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of group 2 to 14 atoms, preferably, A compound comprising a cation containing at least one atom selected from the group consisting of 2 to 14 atoms and at least one anion selected from the group consisting of halogen atoms, inorganic acids and organic acids.
Solvents used for the salt treatment are usually polar solvents such as deionized pure water, alcohols such as ethanol, inorganic acids, organic acids, amines, and acetones.

The cation is a cation containing at least one atom selected from the group consisting of 2 to 16 group atoms, preferably a semi-metal atom such as boron or silicon, carbon, nitrogen, oxygen, phosphorus, sulfur. A molecular cation containing a nonmetallic atom such as carbon, nitrogen, oxygen, phosphorus, sulfur, and the like.
As anions, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ or C ₆ H ₅ O ₇ The anion which has can be illustrated.

Specific examples of the _{salts, CaCl 2, CaSO 4, CaC} 2 O 4, Ca (NO 3) 2, Ca 3 (C 6 H 5 O 7) 2, MgCl 2, MgSO 4, Mg (PO 4) 2 _{, Mg (ClO 4) 2,} Mg (OOCCH 3) 2, MgC 4 H 4 O 4, Sc (OOCCH 3) 2, Sc 2 (CO 3) 3, ScI 3, YCl 3, LaI 3, SmI 3, YbCl ₃ , Ti (SO ₄ ) ₂ , Zr (SO ₄ ) ₂ , Hf (SO ₄ ) ₂ , VOSO ₄ , VOCl ₃ , VCl ₃ , Nb (NO ₃ ) ₅ , TaCl ₅ , Cr (NO ₃ ) ₃ , CrCl _{3, MoOCl 4, MoCl 3,} WCl 4, MnCO 3, Fe (NO 3) 3, CoSO 4, Ni (ClO4) 2, NiSO 4, Pb (NO 3) 2, Pb _{O 4, CuCl 2, Cu (} NO 3) 2, ZnCl 2, Cd (NO 3) 2, AlCl 3, Al 2 (SO 4) 3, GeCl 4, Sn (SO 4) 2, Pb (NO 3) 2 , BCl ₃ , (CH ₃ ) ₂ BCl ₂ , SiCl ₄ , (CH ₃ ) ₂ SiCl ₂ , (C ₆ H ₅ ) ₃ C · SbF ₆ , NH ₄ Cl, (n-C ₄ H ₉ ) ₄ NCl, C ₆ H ₅ NH ₃ Cl, chloride (1-methylpyridinium), chloride (benzenediazonium), chloride (tetrahydrofuranium), chloride (1,4-dioxanium), chloride (tribenzylsulfonium), bromide (1 -Ethylthiazolium), phosphonium iodide, hydroxylated (benzyltriphenylphosphonium), and the like.

In addition, the above-mentioned chemically treated clay mineral or ion-exchange layered compound contains adsorbed water and interlaminar water, so moisture is removed by a known method such as heat dehydration under an inert gas flow. It is preferable to use it after that.
The method for removing moisture will be described in detail in the description of the step [a-2].

(2) Step [a-2]
Step [a-2] is a step of firing the solid material obtained in step [a-1] to remove moisture adsorbed on the clay mineral or ion-exchange layered compound, or moisture present between the layers. It is a baking operation process.
In Patent Document 1, such a moisture removal step is described as follows: “The temperature at the time of heating is 100 ° C. or higher, preferably 150 ° C. or higher so that the interlayer water does not remain. In addition, a heat dehydration method in which a crosslinked structure such as heating under air flow is formed is not preferable because the polymerization activity of the catalyst is lowered. Structural destruction means that a part of the elements constituting clay is volatilized by heat treatment and the crystal structure cannot be maintained, or a dehydration reaction occurs from the adjacent hydroxyl group on the silicate surface, and phase transition. This means that the crystal structure changes due to bonding, and adjacent layers are bonded to each other. For example, not only under air flow, but also under inert gas or vacuum, under high temperature firing exceeding 150 ° C. A dehydration reaction occurs from the adjacent hydroxyl group on the acid salt surface, and the layered structure is destroyed. As a result, it was considered that the high activity as an olefin polymerization catalyst could not be achieved due to the loss of the swelling property of the clay mineral and the inability to obtain a large surface area.
Surprisingly, however, in the present invention, the polymerization activity is improved by performing the step [a-3], which will be described later, after the high-temperature baking step exceeding 150 ° C.

The firing method is not particularly limited, but a method in which a solid is filled in a container in contact with a heating medium and heated and fired, a method in which heat is fired using a batch or continuous so-called rotary kiln, and fluidized drying using a heated gas. Although any method can be mentioned, any of these methods can be carried out under reduced pressure, normal pressure, or increased pressure, or under any gas flow. It is also possible to select a method of azeotropic dehydration with an organic solvent for the main purpose of removing water.
Preferably, the calcination is performed under vacuum exhaust or under an inert gas flow. In the case of evacuation, the degree of vacuum is 50 mmHg or less, preferably 10 mmHg or less.
Gas used as inert gas, there are _{N 2,} argon, helium, solid 1kg per 0.001~1000m ³ / hr, preferably 0.1 to 100 m ³ / hr, particularly preferably 1 to 50 m ³ / hr Is used.
The firing temperature is usually 200 ° C. or higher, preferably 300 ° C. or higher, more preferably 400 ° C. or higher, and the upper limit is less than 700 ° C., preferably less than 600 ° C.
The firing time varies depending on the type of solid, the moisture content before heating, or the firing temperature, but is usually 0.5 minutes or more, preferably 5 minutes or more, more preferably 10 minutes or more, and the upper limit is within 5 hours. , Preferably within 3 hours.

(3) Step [a-3]
Step [a-3] is a step of bringing the basic compound into contact with the solid obtained in step [a-2]. The compound calcined in the step [a-2] is preferably brought into contact with the basic compound after being allowed to cool to room temperature in vacuum, in an inert gas, or in the atmosphere. There is no denying that any temperature can be taken depending on the reactivity with the compound.

The basic compound used in the present invention is an organic compound or an inorganic compound having a lone electron pair (unshared electron pair) capable of forming a coordination bond in the molecule, preferably a group 15 atom or a group 16 atom. At least one atom selected from the group consisting of at least one lone electron pair (if there are a plurality of such atoms, at least one atom among the atoms). In which at least one pair of lone electrons exists).
When the basic compound used in the present invention is an organic compound, it preferably has 50 or less carbon atoms, more preferably 20 or less, and most preferably 12 or less.
As the group 15 atom, nitrogen and phosphorus are preferable, and nitrogen is particularly preferable. As the group 16 atom, oxygen and sulfur are preferable, and oxygen is particularly preferable.
Compounds containing atoms of group 15 include nitrogen-containing compounds such as aliphatic amines and aromatic amines (first to third amines), amides, imides, nitriles, isocyanides, hydroxylamines. Nitroso compounds, nitro compounds, azo compounds, azoxy compounds, hydrazines, amidines, amidooximes, amidrazones, hydrazidines, formazanes, urea derivatives, and the like.
Phosphine derivatives (including acetylphosphines, carbamoylphosphines, sulfonylphosphines, carbonylbisphosphines), phosphine oxides, phosphine imides, phosphoranes, various phosphoric acid derivatives (phosphates, thiophosphinates) , Phosphonates, halogenated phosphonates, amide phosphonates, phosphoric acid amides, acid anhydrides, etc.).
Examples of the arsenic compound, antimony compound, bismuth-containing compound such as arsine derivative, stibine derivative, bismachine derivative, and the like, and various derivatives of the same type as the phosphorus-containing compound are exemplified.

Specific examples of these compounds include (i) methylamine, ethylamine, 1-ethylbutylamine, cyclohexylamine, 2-naphthylamine, 2-benzofuranamine, aniline, anisidine, penetidine, toluidine, xylidine, benzylamine, 1,4 -Butanediamine, diphenylamine, triethylamine, pyridine, 2-methylpyridine, di-2-quinolylamine, bis (2-chloroethyl) amine, N, N-dimethylphenylamine, N-ethylidenemethylamine, hexaneamide, acetamide, benzenesulfone Amide, maleamide, oxyamide, alanine amide, N-methylbenzamide, acetanilide, diacetamide, triacetamide, succinimide, hexanenitrile, hexanedinitrile, cyclohex Ncarbonitrile, benzonitrile, ethyl cyanide, phenyl isocyanide, N-phenylhydroxylamine, phenoxylamine, cyclohexanone oxime, nitrosobenzene, nitromethane, azomethane, azobenzene, azoxybenzene, phenylhydrazine, N, N-dimethyl-N ′, N '-Dimethylhydrazine, 1-aminopiperazine, hexaneamidine, acetamidine, benzamide hydrazone, 1,3-diphenylformazan, dicyclohexylcarbodiimide, N, N-dimethylurea, thiourea,
(Ii) Ethylphosphine, cyclohexylarsine, 2-naphthylphosphine, triphenylphosphine, trivinylstibine, trimethylbismachine, phenylenebis (arsine), 2-phosphinoethylamine, 4-arsinoquinoline, acetyldiethylphosphine, carbonylbis (Phosphine), methoxydiphenylphosphine, chlorodiphenylphosphine, dichloro (phenyl) bismatine, triphenylphosphine oxide, methylenetriphenylphosphorane, S-methyldimethylthioarsinate, dimethylthiophosphine chloride, and the like.

Examples of compounds containing group 16 atoms include ethers, peroxides, aldehydes, ketones, ketenes, acetals, asylals, various carboxylic acid derivatives (esters, lactones, lactides) which are oxygen-containing compounds. , Lactams, acyl halides, acid anhydrides, etc.), amino acid derivatives, and the like.
Examples of the sulfur-containing compound include disulfides, sulfides, various sulfenic acid derivatives, various derivatives of the same kind as the oxygen-containing compound exemplified compounds such as thioaldehyde, thioketone, etc., and tetravalent sulfur, sulfoxides, Examples include sulfones, various sulfur acid derivatives, sultone, sultams, and the like.
Examples of the selenium-containing compound and the tellurium-containing compound include various derivatives of the same type as those exemplified for the sulfur-containing compound.

Specific examples of these compounds include (i) ethyl methyl ether, cyclopentyl phenyl ether, 1-isopropyl-n-propyl ether, ethyl vinyl ether, 1-chloro-2-ethoxyethane, oxirane, tetrahydrofuran, furan, anisole, ethyl phenyl. Peroxide, acetaldehyde, acrolein, benzaldehyde, 2-furaldehyde, maloaldehyde, phthalaldehyde, aminoacetaldehyde, acetone, ethyl methyl ketone, cyclohexyl acetone, acetophenone, di-2-furyl ketone, cyclohexanone, phenyl ketene, cyclohexanone dimethyl acetal, 1 , 3-dioxolane, ethylidene dipropionate, acetoin, ethyl acetate, diethyl malonate, hydroacrylolacto , .Gamma.-butyrolactone, 4-butane lactam, acetyl chloride, acetic anhydride, phthalic anhydride,
(Ii) diethyl sulfide, diphenyl sulfide, thiacyclooctane, thiophene, cyclohexanecarbothialdehyde, 4-heptanethione, cyclohexanethione, thioacetone, 1-ethoxy-1- (ethylthio) butane, S-ethylhexanethioate, hexanethioamide, Thioacetyl chloride, bis (thiobenzoic acid) anhydride, diphenyl sulfoxide, p-bis (ethylsulfinyl) benzene, diethylsulfone, thiophene 1,1-dioxide, diphenyldisulfone, thiobenzaldehyde oxide, ethylethanesulfinate, phenylmethanesulfonate , Ethanesulfenamide, benzenesulfonohydrazine, dimethyl sulfate, N-sulfinylaniline, selenourea, diethyl selenide, serena Kuropentan, diethyl telluride, and the like.

  Among the basic compounds used in the present invention, the inorganic compounds include ammonia, hydroxylamine, hydrazine, triazane, triazene, tetrazane, tetrazene, tetrazadiene, pentazane, phosphine, arsine, stibine, bismatine, phosphinas acid, arsinas acid, phosphonas. Acid, arsonasic acid, phosphoric acid, arsenas acid, phosphinic acid, arsic acid, phosphonic acid, arsonic acid, diphosphonic acid, poly (dichlorinated phosphonitriles), phosphorane, arsolane, disulfane, trisulfane, tetrasulfuric acid And sulfane.

In the contact method of step [a-3], when the above basic compound is brought into contact with the solid substance obtained in step [a-2], if the basic compound is a gas or a liquid under the contact reaction conditions, The catalytic reaction may be carried out without using a solvent, and the catalytic reaction can also be carried out using an inert solvent such as butane, hexane, pentane and toluene or an inert gas such as nitrogen, argon and helium. . When the basic compound is solid under catalytic reaction conditions, the catalytic reaction can be carried out using a good solvent for the compound.
The contact reaction can be carried out under any conditions, but the contact temperature is usually between −50 ° C. and 200 ° C., preferably between 0 ° C. and 100 ° C., and the contact time is usually between 0.1 min and It is carried out for 200 hours, preferably 1 minute to 100 hours, and the contact concentration is usually 1 to 1000 g / L for a solid substance, preferably 10 to 800 g / L, and 0.0001 g / L for a basic compound. 800 g / L, preferably between 0.001 g / L and 500 g / L, in a ratio of basic compound to 1 g of solid matter, 0.001 mmol / g to 10 mol / g, preferably 0.1 mmol / g to 1 mol / g More preferably, it is 1 mmol / g to 100 mmol / g.

The product obtained by the step [a-3] is preferably an intercalation product of a basic compound. In general, an intercalation product is also called an intercalation compound, and is a compound formed by inserting various compounds, molecules, metals, various ions, etc. between crystal layers of layered compounds such as clay minerals or ion-exchangeable layered compounds. In other words, the formation of an intercalation product is said to affect the catalytic action by changing the interlayer distance of the mother crystal layer, the charge density of the layer, and the like.
In the present invention, there is an effect even when the contact with the basic compound is merely a reaction on the outer surface of the clay mineral or the ion-exchangeable layered compound, but the interlayer distance is increased by the insertion of the basic compound, the so-called interlayer In order to improve the co-catalyst function for olefin polymerization, it is preferable that the reaction proceeds on the inner surface of the crystal and the acid-base characteristics of the layer change. The generation of the intercalation product can be confirmed by the change before and after the intercalation of the distance between the bottom surfaces measured by the powder X-ray diffraction method.

When used as a catalyst for olefin polymerization, the solid product obtained by performing the treatment of step [a-3] is usually used after removing unreacted basic compounds. The removal method is appropriately selected from conventionally known methods depending on the properties of the basic compound used.
That is, when the basic compound is a gas, it can be removed by evacuation, and is carried out by heating to an appropriate temperature between room temperature and the firing temperature of step [a-2] as necessary. Instead of this, it can also be carried out by circulation of an inert gas such as nitrogen. When the basic compound is in a liquid or solution state, a method of repeating decantation by standing or removal of the supernatant by filtration and stirring and washing performed by adding an inert solvent can be employed.

3. Olefin Polymerization Catalyst In the present invention, the transition as described below is performed using the modified clay mineral or the ion-exchange layered compound obtained by sequentially performing the steps [a-1] to [a-3] described above as the promoter component [A]. An olefin polymerization catalyst is obtained in combination with the metal compound component [B]. In this case, the organoaluminum compound component [C] is preferably used as a catalyst constituent.
The transition metal compound used in the present invention is a known complex, and is a complex constituting an olefin polymerization catalyst capable of producing a polymer having a narrow molecular weight distribution or copolymer composition distribution as a so-called single site catalyst.
A specific structure will be shown and described below. The atomic periodicity in the present invention is based on the group 18 system recommended by IUPAC in 1989.

(1) Transition metal compound (component [B])
Examples of the transition metal complex compound used for olefin polymerization in combination with the cocatalyst component [A] include all transition metal compounds of Groups 3 to 10 of the periodic table having a property that is activated cationically. Specifically, Group 3 transition metal complex compounds, Group 4-6 metallocene compounds, Group 4 metal bisamides, Group 8-10 metal biimino compounds, Group 4-10 metal salicylaldiminato compounds, or 8 to Bisimino compounds of group 9 metals (derivatives of so-called Brookhart complexes and Gibson complexes) can be mentioned.
When these transition metal compounds are not dialkyl compounds, it is necessary that organometallic compounds such as Na, Li, Ag, Hg, Zn, Al, and Ga that can convert them into dialkyl compounds are present in advance or at the same time. It is.

Examples of transition metal compounds in groups 4 to 6 of the periodic table having at least one conjugated 5-membered ring ligand, that is, metallocene compounds, include those represented by the following general formulas (1) to (4). Can do.
^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY ··· (1)
^{_{Q (C 5 H 4-c}} R 1 c) (C 5 H 4-d R 2 d) MXY ··· (2)
^{_{Q (C 5 H 4-e}} R 3 e) ZMXY ··· (3)
^{_{(C 5 H 5-f R}} 4 f) MXYW ··· (4)
Here, Q represents two conjugated 5-membered ring ligands, conjugated 5-membered ring ligand and Z group, or rings formed by bonding alkyl groups added adjacent to two conjugated 5-membered rings. A hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 40 carbon atoms, such as silicon, germanium, oxygen, nitrogen or phosphorus, M is a periodic table of 4 to 6 Group transition metals X, Y, and W are σ-covalent auxiliary ligands that react with component (A) to become active species having olefin polymerization ability.
Specifically, each independently represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen, nitrogen, silicon, or phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, wherein Z is oxygen, sulfur, Or a silicon, oxygen, nitrogen or phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms.
M is particularly preferably Ti, Zr, or Hf.
R ¹ , R ² , R ³ and R ⁴ are each independently a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing oxygen, silicon, phosphorus, nitrogen or boron-containing hydrocarbon having 1 to 20 carbon atoms. Indicates. Examples of the oxygen-containing hydrocarbon group include an alkoxy group, an alkoxyalkyl group, an aryloxy group, and an alkoxyaryl group.
Two adjacent R ¹ , R ² , R ³ and R ⁴ may be bonded to each other to form a 4-membered ring to a 10-membered ring. a, b, c, d, e, and f are integers that satisfy 0 ≦ a, b, f ≦ 5, and 0 ≦ c, d, and e ≦ 4, respectively.

Among the above-mentioned ^{_{ligands, (C 5 H 5-a}} R 1 a), (C 5 H 5-b R 2 b), (C 5 H 4-c R 1 c), (C 5 H 4 _{-d R} 2 _^d) indenyl group, a fluorenyl group, preferably an azulenyl group or moiety hydrogenated azulenyl group, particularly these ligands have a substituent at the 2-position and 4-7 position are preferred.
Examples of the crosslinkable group Q include an alkylene group, an alkylidene group, a silylene group, and a germylene group. Specifically, a methylene group, an ethylene group, a dimethylsilylene group, a diphenylsilylene group, a dimethylgermylene group, and the like are preferable.

  Specific examples of zirconium complexes represented by the above general formulas (1) to (4) are exemplified below, but compounds in which zirconium is replaced with hafnium or titanium can be used in the same manner.

  Zirconium complex represented by the general formula (1): biscyclopentazinylzirconium dimethyl, bis (2-methylcyclopentazinyl) zirconium dimethyl, bis (2-methyl-4,5-benzoindenyl) zirconium dimethyl, bisfluore Nilzirconium dimethyl, biscyclopentazinylzirconium dichloride, bis (2-methyl-4-phenylazurenyl) zirconium dichloride, and the like.

  Zirconium complex represented by the general formula (2): dimethylsilylene bis (1,1′-cyclopentadienyl) zirconium dimethyl, dimethylsilylene bis (1,1′-2-methylindenyl) zirconium dimethyl, dimethylsilylene bis ( 1,1′-2-methyl-4,5-benzoindenyl) zirconium dimethyl, dimethylsilylene bis (1,1′-cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (1,1′-2-methyl-) 4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (1,1′-2-methyl-4-phenylazurenyl) zirconium dichloride, dimethylgermylenebis (1,1′-2-methyl-4-phenyl) Azulenyl) zirconium dichloride, dimethylsilylene bis [7 7 '- {1-isopropyl-3- (4-chlorophenyl) indenyl)} zirconium dichloride and the like.

  Zirconium complex represented by the general formula (3): (t-butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dimethyl, (t-butylamide) (tetramethylcyclopentadienyl) silanediylzirconium Dimethyl, (phenylphosphido) dimethyl (tetradimethylcyclopentadienyl) silanediylzirconium dimethyl, (t-butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (t-butylamide) ( Tetramethylcyclopentadienyl) silanediylzirconium dichloride and the like.

  Zirconium complex represented by the general formula (4): (cyclopentadienyl) (phenoxy) zirconium dimethyl, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dimethyl, (pentamethylcyclopentadienyl) (phenoxy ) Zirconium dimethyl, (cyclopentadienyl) (phenoxy) zirconium dichloride, (2,3-dimethylcyclopentadienyl) (phenoxy) zirconium dichloride, (pentamethylcyclopentadienyl) (phenoxy) zirconium dichloride, (pentamethyl) Cyclopentadienyl) (2,6-di-i-propylphenoxy) zirconium dichloride, (cyclopentadienyl) zirconium chlorodimethyl, (pentamethylcyclopentadienyl) zirconium chloro Methyl, (pentamethylcyclopentadienyl) zirconium isopropoxydimethyl, (cyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) zirconium triisopropoxide, ( Pentamethylcyclopentadienyl) zirconium triisopropoxide and the like.

  Further, as a special example of a metallocene compound, a ligand containing one or more elements other than carbon in a 5-membered ring or 6-membered ring disclosed in JP-A-7-188335 and JACS, 1996, 118, p2291 is used. The transition metal compound which has can also be used.

  Next, as a nonmetallocene compound in which the central metal is a group 4 or group 8-10 element, an N atom or an O atom as shown in the following general structural formula is directly coordinated to the central metal, Examples thereof include a bridged transition metal compound having a bulky substituent on a nitrogen atom or an oxygen atom.

Examples of Group 4 metal compounds in the periodic table include:
(I) Bisamide compounds having an NN type ligand as shown in the following general formula (5) can be mentioned.

Here, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, a halogen, oxygen or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, U is a bonding group that bridges two N atoms, 1 to 20 hydrocarbon group or a silicon, nitrogen, oxygen or sulfur-containing hydrocarbon group having 1 to 40 carbon atoms, M ′ is a group 4 transition metal in the periodic table, X and Y are hydrogen atoms, halogens, A hydrocarbon group having 1 to 20 carbon atoms or an oxygen, nitrogen, silicon or phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms is shown.

Specifically, R ⁵ is preferably t-butyl, trimethylsilyl, 2,6-diisopropylphenyl, or 2,4,6-trimethylphenyl group.
U is preferably a propenyl, 2-phenylpropenyl, or 2,2-diphenylpropenyl group. M ′ is any one of Ti, Zr, and Hf, and X and Y are preferably any of Cl, methyl, benzyl, and dimethylamide.
More specifically, (R ⁵ , U, M ′, X, Y) = (t-butyl, propenyl, Ti, Cl, Cl), (trimethylsilyl, propenyl, Ti, Cl, Cl), (2, 6 Combinations that are -diisopropenylphenyl, propenyl, Ti, Cl, Cl) or (trimethylsilyl, 2-phenylpropenyl, Ti, Cl, Cl) are preferred. Examples of these compounds are disclosed in Macromolecules, 1996, p5241; JACS, 1997, 119, p3830; JACS, 1999, 121, p5798.

(Ii) Bisamidinato compounds having an NN type ligand as shown in the following general formula (6) can be mentioned.

Here, R ⁶ and R ⁷ are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing oxygen or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, M ′ is a group 4 transition metal in the periodic table, X , Y represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen, nitrogen, silicon or phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms.
Specifically, R ⁶ is preferably any of t-butyl, cyclohexyl, trimethylsilyl, 2,6-diisopropylphenyl, 2,4,6-trimethylphenyl, and R ⁷ is methyl, isopropyl, phenyl And any of paratolyl is preferable. Further, it is preferable that M ′ is any one of Ti, Zr, and Hf, and X and Y are any one of Cl, methyl, benzyl, and dimethylamide.
More specifically, (R ⁶ , R ⁷ , M ′, X, Y) = (t-butyl, phenyl, Zr, Cl, Cl), (trimethylsilyl, phenyl, Zr, Cl, Cl), (2, 6-diisopropenylphenyl, propenyl, Ti, Cl, Cl) or (trimethylsilyl, tolyl, Zr, Cl, Cl) is preferred. Examples of these compounds are disclosed in Organometallics, 1998, p3155.

(Iii) Salicylaldiminato compounds having an N—O type ligand as shown in the following general formula (7) can be mentioned.

Here, R ⁸ and R ⁹ are each a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms, such as a halogen, oxygen, nitrogen, silicon or sulfur-containing hydrocarbon, and R ¹⁰ is a hydrogen atom having 1 carbon atom. A hydrocarbon group having ˜20 or a halogen-containing oxygen, nitrogen, or silicon-containing hydrocarbon having 1 to 20 carbon atoms, M ′ is a group 4 transition metal in the periodic table, X and Y are hydrogen atoms, halogens, carbon number 1 -20 hydrocarbon group or a C1-C20 oxygen, nitrogen, silicon, or phosphorus containing hydrocarbon group is shown.

Specifically, R ⁸ is preferably one of hexyl, cyclohexyl, phenyl, tolyl, pentafluorophenyl, paramethoxyphenyl, and 2,4-dimethylpyrrolyl, and R ⁹ is t-butyl or It is an adamantyl group, and R ¹⁰ is preferably a hydrogen atom, methyl, ethyl, or methoxy group. M is preferably any one of Ti, Zr, and Hf, and X and Y are preferably any one of Cl, methyl, benzyl, and dimethylamide.
More specifically, (R ⁸ , R ⁹ , R ¹⁰ , M ′, X, Y) = (cyclohexyl, t-butyl, hydrogen atom, Zr, Cl, Cl), (phenyl, t-butyl, hydrogen atom) , Zr, Cl, Cl), (tolyl, t-butyl, hydrogen atom, Zr, Cl, Cl), (pentafluorophenyl, t-butyl, hydrogen atom, Zr, Cl, Cl), (pentafluorophenyl, t -Butyl, hydrogen atom, Ti, Cl, Cl), (2,5-dimethylpyrrolyl, t-butyl, hydrogen atom, Zr, Cl, Cl) is preferred. Examples of these compounds are disclosed in JP-A-11-315109.

As an example of a compound of a periodic table group 8-10 metal,
(I) The biimino compound which has a NN type ligand as shown to the following general formula (8) or (9) can be mentioned.

Here, R ¹¹ and R ¹³ are each a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing oxygen, nitrogen, silicon, or sulfur-containing hydrocarbon having 1 to 20 carbon atoms, R ¹² and R ¹⁴ are hydrogen atoms, A hydrocarbon group having 1 to 20 carbon atoms, or a halogen, oxygen, nitrogen or silicon-containing hydrocarbon having 1 to 20 carbon atoms, and R ¹⁴ may be bonded to each other. M ′ represents Ni or Pd, and X and Y represent a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, or an oxygen, nitrogen, silicon or phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms.

Specifically, R ¹¹ is paratolyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, or 2,4,6-trimethylphenyl, and R ¹² is a hydrogen atom, methyl, ethyl, or propyl. And R ¹³ is 2,6-dimethylphenyl, 2-t-butylphenyl, or 2,6-diisopropylphenyl. R ¹⁴ is a hydrogen atom, methyl, 1,8-naphthyl, —SCH ₂ CH ₂ S—, or —OCH ₂ CH ₂ O— as examples of those bonded to each other. M ″ is Ni or Pd, and X and Y are Cl, Br, methyl, or benzyl groups.
More specifically, (R ¹¹ , R ¹² , X, Y) = (2,6-dimethylphenyl, hydrogen atom, Cl, Cl), (2,4,6-trimethylphenyl, hydrogen atom, Cl, Cl) ), (2,6-diisopropylphenyl, hydrogen atom, Cl, Cl), (p-tolyl, methyl, Cl, Cl), (2,6-dimethylphenyl, methyl, Cl, Cl), or (2,6 A combination which is -dimethylpyrrolyl, hydrogen atom, Cl, Cl) is preferred.
Alternatively, (R ¹³ , R ¹⁴ , M ′, X, Y) = (2,6-dimethylphenyl, hydrogen atom, Ni, Br, Br), (2-t-butylphenyl, hydrogen atom, Ni, Br, Br), (2,6-diisopropylphenyl, hydrogen atom, Ni, Br, Br), (2,6-diisopropylphenyl, 1,8-naphthyl, Ni, Br, Br), (2,5-dimethylpyrrolyl) , Hydrogen atom, Ni, Br, Br) or (2,6-diisopropylphenyl, hydrogen atom, Pd, Br, Br).
These compounds are disclosed in JACS, 1995, 117, p6414, WO96 / 23010, Chemical Communication, 1998, p849, JACS, 1998, 120, p4049, WO98 / 27124.

  (Ii) Salicylaldiminato compounds having an NO type ligand as shown in the following general formula (10) can be mentioned.

Here, R ⁸ and R ⁹ are hydrocarbon groups having 1 to 20 carbon atoms or hydrocarbons having 1 to 20 carbon atoms, such as halogen, oxygen, nitrogen, silicon or sulfur, and R ¹⁰ is a hydrogen atom and having 1 carbon atom. A hydrocarbon group having ˜20 or a halogen, oxygen, nitrogen or silicon-containing hydrocarbon having 1 to 20 carbon atoms, M ′ is Ni or Pd, X and Y are hydrogen atoms, halogens, carbon atoms having 1 to 20 carbon atoms A hydrogen group or an oxygen, nitrogen, silicon or phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms is shown.

Specifically, R ⁸ is hexyl, cyclohexyl, phenyl, tolyl, pentafluorophenyl, paramethoxyphenyl, or pyrrole group, R ⁹ is t-butyl or adamantyl group, and R ¹⁰ is a hydrogen atom. , Methyl, ethyl, or methoxy group, M ′ is Ni, and X and Y are preferably Cl, methyl, benzyl, or dimethylamide.
More specifically, (R ⁸ , R ⁹ , R ¹⁰ , M ′, X, Y) = (phenyl, t-butyl, hydrogen atom, Ni, Br, Br), (p-tolyl, t-butyl, (Hydrogen atom, Ni, Br, Br), (phenyl, t-butyl, hydrogen atom, Ni, Br, Br) or (2,5-dimethylpyrrolyl, t-butyl, hydrogen atom, Ni, Br, Br) A combination is preferred. Examples of these compounds are disclosed in JP-A-11-315109.

(2) Organoaluminum compound (component [C])
The single site catalyst described above can be expected to improve the polymerization activity when the organoaluminum compound component [C] is further combined.
For example, the general formula AlR _3-i X _i
(In the formula, R is a C1-20 hydrocarbon group, X is hydrogen, an alkoxy group, halogen, and i is a number of 0 ≦ i <3. However, when X is hydrogen, i is 0 <i <. 3)
The compound shown by is used.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and trioctylaluminum, or alkoxy such as dimethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, and diisobutylaluminum ethoxide. A halogen-containing alkylaluminum such as diethylaluminum chloride, or a halide-containing alkylaluminum such as diethylaluminum halide.
Of these, trialkylaluminum is particularly preferred. More preferred are triisobutylaluminum and trioctylaluminum.
An aluminoxane can be illustrated as an organoaluminum compound other than this.

(3) Preparation of catalyst The usage-amount of component [A] and component [B] is used by the optimal quantity ratio in each combination.
When a clay mineral or an ion-exchange layered silicate is used as the component [A], the transition metal complex is in the range of 0.0001 to 10 mmol, preferably 0.001 to 1 mmol, per 1 g of the component [A].
These use ratios are examples of normal ratios, and the present invention is not limited by the range of use ratios described above as long as the catalyst is purposeful. It is natural.

  Before using a catalyst for polyolefin production comprising a transition metal complex and a co-catalyst as a catalyst for olefin polymerization (main polymerization), it is supported on a carrier, if necessary, and then ethylene, propylene, 1-butene, 1-hexene. , 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and other olefins may be preliminarily polymerized in a small amount. A known method can be used as the prepolymerization method.

4). Polymerization of Olefin The olefin can be polymerized or copolymerized using the component [A] and the component [B] described above and, if necessary, an olefin polymerization catalyst comprising the component [C].
Examples of the olefin that can be polymerized by the olefin polymerization catalyst of the present invention include olefins having 2 to 12 carbon atoms, such as ethylene, propylene, 1-butene, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene- Examples thereof include 1,1-hexene and 1-octene. In particular, ethylene and propylene are preferably used. The polymerization can be suitably applied to random copolymerization and block copolymerization in addition to homopolymerization. As a comonomer in the copolymerization, in addition to the above-mentioned olefin, conjugated dienes such as hexene vinylcycloalkane and butadiene, non-conjugated dienes such as 1,5-hexadiene, styrene or derivatives thereof, oxygen atoms, So-called polar monomers such as acrylic acid derivatives and acrylamide derivatives containing nitrogen atoms can also be used.

The polymerization reaction is carried out in the presence of an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene, cyclohexane, or a solvent such as liquefied α-olefin, or substantially no liquid phase of solvent or monomer. It is preferable to carry out by vapor phase polymerization. The gas phase polymerization can be performed using a reaction apparatus such as a fluidized bed, a stirred bed, and a stirred fluidized bed equipped with a stirrer / mixer. Conditions such as polymerization temperature and polymerization pressure are not particularly limited, but the polymerization temperature is generally −50 to 350 ° C., preferably 0 to 300 ° C., and the polymerization pressure is usually normal pressure to about 2000 kgf / cm ² , The pressure is preferably from normal pressure to 1500 kgf / cm ² , more preferably from normal pressure to 1300 kgf / cm ² . Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention will not be restrict | limited by these Examples, unless it deviates from the summary.
The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere, and the solvent was dehydrated with MS-13X and then deaerated by bubbling with purified nitrogen.
The distance (d) between the bottom surfaces of the clay is determined by Bragg using the diffraction angle (θ) of the diffraction peak on the (001) plane and the wavelength (λ) of the X-ray from the diffraction pattern obtained by the powder X-ray diffraction method. This was calculated from the formula 2dsin θ = nλ. The RAD-B system manufactured by Rigaku Denki Co., Ltd. was used to measure the diffraction pattern, the source was CuKα ray (Ni filter), the scan speed was 1 ° / min, and the sampling interval was 0.01 °.

Example 1
[A-1] Step of preparing NH ₄ ⁺ exchanged montmorillonite An aqueous solution containing 5.0 g of NH ₄ Cl (2.40 g) corresponding to a 10-fold equivalent is obtained by weighing 5.0 g of a commercially available granulated product of swellable montmorillonite into a 200 ml Erlenmeyer flask. 125 ml was added. Ion exchange was performed in a constant temperature bath at 30 ° C. The ion exchange was once taken out after 24 hours, filtered, and then dispersed again in an NH ₄ Cl aqueous solution having the same concentration for 24 hours.
After solid-liquid separation by filtration, 200 ml of ethanol was washed from the filter paper into a 200 ml beaker, stirred lightly, and then filtered again. This ethanol washing operation was performed 5 times. The washed NH ₄ ⁺ montmorillonite was dried in air at approximately 30 ° C. overnight. When the NH ₄ ⁺ exchange rate was measured by SEM-EDX for the obtained dried sample, Na ⁺ ions were not observed, and the exchange rate was almost 100%.
[A-2] _NH ^{4 +} put _NH ^{4 +} montmorillonite approximately 1g after firing step drying of montmorillonite porcelain evaporating quite common, was set in a muffle furnace. The temperature was raised to 400 ° C. at a rate of 3.3 ° C./min, and further calcined at that temperature for 4 hours.
[A-3] Preparation process of pyridine-treated montmorillonite Approximately 1.0 g of NH ₄ ⁺ montmorillonite baked under predetermined conditions was weighed into a 20 ml eggplant flask. After adding 10 ml of pyridine, a condenser tube was attached, and the tube was set in an oil bath maintained at 70 ° C. and heat-treated for 72 hours. After the treatment, pyridine was removed by filtration. The obtained sample was washed with 50 ml of ethanol and separated by filtration five times to sufficiently wash away residual pyridine. The obtained pyridine-treated montmorillonite was dried in a glass ampoule at room temperature for 4 hours under reduced pressure, and stored in a glove box under a nitrogen atmosphere while blocking the air.
[A-4] Catalyst synthesis step 100 mg of pyridine-treated montmorillonite dried at room temperature was precisely weighed into a 20 ml Schlenk tube in a glove box. The Schlenk tube taken out from the glove box was connected to a nitrogen line, and 6.0 ml of toluene dehydrated by MS-13X and 4.0 ml of triisobutylaluminum (TIBA: 0.25 mmol / L) were added, followed by treatment for 1.5 hours. did. After the treatment, 5 ml of the supernatant was extracted by decantation, and 15 ml of dehydrated toluene was added. After stirring for about 1 minute, 15 ml of the supernatant was extracted by decantation. This washing operation was further performed twice. A toluene solution of bis (cyclopentadienyl) zirconium dichloride (Cp ₂ ZrCl ₂ ) (equivalent to ₂₀ μmol, Cp ₂ ZrCl ₂ / montmorillonite = 200 μmol / g) was added, and the total liquid volume was adjusted to 10.0 ml with dehydrated toluene. Thereafter, a catalyst slurry was prepared by contact treatment for 30 minutes.
[A-5] Polymerization of ethylene First, the autoclave was sufficiently dried in a dryer at 130 ° C., and then quickly assembled and purged with N ₂ . When the autoclave cooled to room temperature, 50 ml of dehydrated hexane was injected with a syringe under N ₂ , and then the slurry of Cp ₂ ZrCl ₂ / pyridine-treated montmorillonite prepared in (a-4) was withdrawn with a needled pipette (14 mg). (Equivalent to montmorillonite) It was injected into an autoclave. Finally, TIBA (0.25 mmol / L) and 3.37 ml were added (Al / Zr = 300), and the system was quickly replaced with ethylene three times. Thereafter, an autoclave was set in a water bath previously maintained at 60 ° C., and polymerization was carried out at 0.7 MPa and 60 ° C. for 1.5 hours.
After completion of the polymerization time, the autoclave was quenched with a water bath and the remaining ethylene in the system was quickly purged. Finally, the autoclave was opened, the polyethylene slurry was taken out, and the polyethylene was recovered by suction filtration. The polyethylene was dried at 40 ° C. for about 1 day and weighed. The catalyst activity was expressed as a polyethylene yield per hour / montmorillonite weight (g-PE / g-clay / h) from the polyethylene yield and the injected montmorillonite weight. The results are shown in Table 1.

(Comparative Example 1)
Except that the preparation step of the pyridine-treated montmorillonite of [a-3] was not carried out, the catalyst was prepared in the same manner as in Example 1, and ethylene was polymerized. The results are shown in Table 1.

  From the comparison between Example 1 and Comparative Example 1 in Table 1, it can be seen that when the basic compound treatment in the step [a-3] is performed with pyridine, the activity is improved. Intercalation of pyridine between the clay layers is confirmed by the increased distance between the bottom surfaces.

(Example 2)
In the firing step of [a-2] NH ₄ ⁺ montmorillonite of Example 1, a catalyst was prepared in the same manner as in Example 1 except that the firing temperature was changed to 500 ° C., and ethylene was polymerized. The results are shown in Table 2.

(Example 3)
In the preparation process of [a-3] pyridine-treated montmorillonite of Example 2, the catalyst was prepared in the same manner as in Example 2 except that the drying after pyridine treatment was changed from vacuum drying at room temperature to vacuum drying at 200 ° C. Ethylene was polymerized. The results are shown in Table 2.

Example 4
In the preparation step of [a-3] pyridine-treated montmorillonite of Example 2, the catalyst was prepared in the same manner as in Example 2 except that the drying after pyridine treatment was changed from vacuum drying at room temperature to vacuum drying at 400 ° C. Ethylene was polymerized. The results are shown in Table 2.

(Comparative Example 2)
[A-3] A catalyst was prepared in the same manner as in Example 2 except that the preparation step of pyridine-treated montmorillonite was not performed, and ethylene was polymerized. The results are shown in Table 2.

(Comparative Example 3)
[A-3] In the preparation process of pyridine-treated montmorillonite, a catalyst was prepared in the same manner as in Example 2 except that ion-exchanged water was used instead of pyridine, and ethylene was polymerized. The results are shown in Table 2.

(Example 5)
A catalyst was prepared in the same manner as in Example 1 except that the calcination temperature was changed to 300 ° C. in the calcination process of [a-2] NH ₄ ⁺ montmorillonite in Example 1, and ethylene was polymerized. The results are shown in Table 2.

Similarly to Table 1, it can be seen from the comparison between Example 2 and Comparative Example 2 in Table 2 that the activity is improved when the basic compound treatment in Step [a-3] is performed with pyridine. Intercalation of pyridine between the clay layers is confirmed by the increased distance between the bottom surfaces. Examples 2 to 4 are examples comparing ethylene polymerization activities when the temperature when removing the unreacted basic compound in step [a-3] was changed, but removal at a temperature higher than room temperature was performed. Although it was preferable for improving the activity, the results showed almost the same activity at 200 ° C and 400 ° C.
Further, Comparative Example 3 is an example in which water, which is a general substance that intercalates between clay layers instead of the basic compound, is contacted in Step [a-3]. There was no difference in distance and polymerization activity, indicating that there was no activity improvement effect. Example 5, Example 1 and Example 2 are examples for comparing the difference in the firing temperature of the step [a-2], but tend to be highly active at slightly higher temperatures at 300 ° C, 400 ° C and 500 ° C. The result was shown.

(Example 6)
In the firing step of [a-2] NH ₄ ⁺ montmorillonite of Example 1, the firing temperature was changed to 300 ° C., and in the preparation step of [a-3] pyridine-treated montmorillonite, 28% ammonia water was used instead of pyridine treatment. The catalyst was the same as in Example 1 except that the treatment was performed at 30 ° C. for 24 hours (the filtration and washing operations were the same as the pyridine treatment), and the subsequent drying was changed from vacuum drying at room temperature to vacuum drying at 300 ° C. Preparation was performed and ethylene was polymerized. The results are shown in Table 3.

(Comparative Example 4)
In the same manner as in Example 6 except that the baking temperature was changed to 50 ° C. in the baking process of [a-2] NH ₄ ⁺ montmorillonite in Example 6 and further the preparation process of [a-3] ammonia water treatment was not performed. A catalyst was prepared and ethylene was polymerized. The results are shown in Table 3.

(Comparative Example 5)
In the same manner as in Example 6, except that the firing temperature was changed to 200 ° C. in the firing step of [a-2] NH ₄ ⁺ montmorillonite in Example 6 and further the preparation step of [a-3] ammonia water treatment was not performed. A catalyst was prepared and ethylene was polymerized. The results are shown in Table 3.

(Comparative Example 6)
In the same manner as in Example 6, except that the baking temperature was changed to 300 ° C. in the baking step of [a-2] NH ₄ ⁺ montmorillonite in Example 6 and further the preparation step of [a-3] ammonia water treatment was not performed. A catalyst was prepared and ethylene was polymerized. The results are shown in Table 3.

  Example 6 and Comparative Example 4 to Comparative Example 6 in Table 3 are examples in which ammonia is used as the basic compound in the step [a-3], but in the same manner as in the case of pyridine, the step [a-3 ] Indicates that an activity improvement effect can be obtained.

(Example 7)
A catalyst was prepared in the same manner as in Example 6 except that the firing temperature was changed to 400 ° C. in the firing step of [a-2] NH ₄ ⁺ montmorillonite in Example 6, and polymerization of ethylene was performed. The results are shown in Table 4.

(Comparative Example 7)
[A-3] A catalyst was prepared in the same manner as in Example 7 except that the preparation step of the ammonia water-treated montmorillonite was not performed, and ethylene was polymerized. The results are shown in Table 4.

  Table 4 is an example when ammonia is used as the basic compound in the step [a-3], and Table 3 shows a case where the firing temperature in the step [a-2] is different. Again, the activity improvement effect is obtained by the step [a-3].

(Example 8)
Pyridine-treated montmorillonite was prepared in the same manner as [a-1] to [a-3] in Example 1.
[A-4] Catalyst Preparation 100 mg of the pyridine-treated montmorillonite obtained in [a-3] above was slurried with 9.6 ml of n-heptane, and 59.6 mg of TIBA (0.30 mmol, 0.36 ml of heptane solution) was stirred here at room temperature. ) Was added. After stirring for 10 minutes, 4.2 mg of Fe complex-1 (Fe-1) (8.0 μmol, 8.0 ml of toluene solution) was added. Stirring was further continued for 10 minutes to obtain a catalyst slurry. Complex Fe-1 was synthesized according to the method described in the literature (Journal of American Chemical Society, Volume 120, page 4049, Supporting Information).
The structural formula of Fe-1 is shown below.

[A-5] Ethylene-1-hexene copolymerization Slurry polymerization was performed using the catalyst obtained in [a-4]. That is, 1.5 L of n-heptane, 2.5 mmol of TIBA, and 180 ml of 1-hexene were added to a 3 L autoclave, the temperature was raised to 80 ° C., ethylene gas was introduced, and the total pressure was increased to 20 kg / cm ² -G. Next, the entire amount of the catalyst slurry was introduced together with ethylene, and polymerization was carried out at 80 ° C. while maintaining the total pressure at 22 kg / cm ² -G. After 1 hour, ethanol was added to stop the polymerization. The obtained polymer was separated by filtration and dried under hot air. The results are shown in Table 5.

(Comparative Example 8)
[A-3] A catalyst was prepared in the same manner as in Example 8 except that the preparation step of pyridine-treated montmorillonite was not performed, and ethylene-1-hexene copolymerization was performed. The results are shown in Table 5.

  Table 5 shows an example of using the same component [A] as in Table 1 and using a biimino compound having Fe as the central metal instead of the metallocene complex as the transition metal compound of component [B]. This shows that when the basic compound treatment of [a-3] is performed with pyridine, an activity improving effect is obtained.

  When the catalyst component for olefin polymerization of the present invention is used as a co-catalyst for a transition metal catalyst for olefin polymerization, the polymerization activity per solid component can be extremely increased, and the catalyst residue needs to be removed from the obtained polymer. This is industrially useful.

Claims (3)

The manufacturing method of the catalyst component for olefin polymerization characterized by processing sequentially by following process [a-1]-[a-3].
[A-1]: A clay mineral or an ion-exchange layered compound is mixed with an ammonium cation, Cl, Br, I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ , ClO ₄ , Step [a-2] of chemical treatment with a salt of a compound comprising an anion selected from the group consisting of OOCCH ₃ , CH ₃ COCHCOCH ₃ , OOCH and OOCCH ₂ CH ₃ : obtained in step [a-1] Step [a-3] of firing the solid material at a temperature of 200 ° C. or higher and lower than 700 ° C .: 1 g of the solid material obtained in step [a-2], ammonia, methylamine, ethylamine, 1-ethylbutylamine, A basic compound selected from the group consisting of cyclohexylamine, benzylamine, triethylamine, pyridine, 2-methylpyridine and N, N-dimethylphenylamine; Is contacted in a ratio of 0.001mmol / g~10mol / g, to obtain intercalation product of the basic compound   The method for producing a catalyst component for olefin polymerization according to claim 1, wherein the calcination in step [a-2] is performed at a temperature of 300 ° C or higher.   The method for producing a catalyst component for olefin polymerization according to claim 1 or 2, wherein unreacted basic compound is removed after contacting the basic compound in step [a-3].