JP2013166876A - Olefin polymerization catalyst, sheet-form olefinic polymer and production method thereof, and molded body including the sheet-form olefinic polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an olefin polymerization catalyst carried on a sheet-form fabric material achieving high olefin polymerization activity; an olefinic polymer using the catalyst and production method thereof; and a molded body using the olefinic polymer.SOLUTION: With an olefin polymerization catalyst obtained by carrying a specific aluminoxane preparation and a transition metal compound on a carrier comprising a sheet-form fabric material, high polymerization activity and a sheet-form olefinic polymer having excellent physical properties are obtained. The efficiency in production of a molded body is good because the polymer is obtained in a sheet form concurrently with polymerization.

Description

  The present invention relates to a catalyst for olefin polymerization comprising an aluminoxane preparation containing a gel-like aluminoxane obtained under specific conditions and a transition metal complex supported on a sheet, and a sheet obtained by the catalyst. The present invention relates to an olefin polymer and a method for producing the same. Moreover, it is related with the molded object manufactured using the said olefin polymer.

  Olefin polymerization catalysts consisting of metallocene compounds and other transition metal compounds, so-called single-site catalysts, are highly active and provide a polymer with a narrow molecular weight distribution and a uniform introduction of comonomers. Its importance has increased in recent years because it gives olefin polymers that have not been obtained. These transition metal compounds need to be reacted with another compound that functions as a cocatalyst. Examples of the most commonly used cocatalyst include aluminoxane (for example, methylaluminoxane). Since aluminoxane is usually used as a supported catalyst that is industrially easy to handle, it is supported on a carrier material. In particular, inorganic porous materials such as silica gel are practically used industrially because they can support aluminoxane with high efficiency because of their features such as high porosity, high specific area, and reaction points capable of binding to aluminoxane.

  On the other hand, if an organic substance such as a resin is used as a carrier instead of an inorganic carrier, the product physical properties can be prevented from being deteriorated due to inorganic residues, and a composite material of a resin carrier and an olefin polymer can be produced. It is possible to provide a product with high added value, and recently, a supported olefin polymerization catalyst using an organic carrier has attracted attention. In particular, when a carrier preliminarily shaped with an organic substance is used, a product can be obtained by being used as a molded product as it is after polymerization, or only by some molding.

  In Patent Document 1, a non-woven fabric-supported olefin polymerization catalyst is prepared by supporting a methylaluminoxane and then a metallocene compound on a polyvinyl alcohol nanofiber nonwoven fabric prepared by an electrospinning method, and then ethylene is polymerized. A method for obtaining a sheet-like ethylene polymer is disclosed. However, in this method, in order to support methylaluminoxane that exhibits sufficient polymerization activity, it is a nanofiber nonwoven fabric having a high specific surface area, and a hydroxyl group is included in the basic skeleton of the polymer such as polyvinyl alcohol. It is limited to the nonwoven fabric which has a functional group which reacts and bonds with aluminoxane. Therefore, for example, a nonwoven fabric with a large fiber diameter manufactured by the spunbond method or the melt blown method, or a polyolefin nonwoven fabric that does not have a functional group that reacts with and binds to an aluminoxane in the first place cannot carry sufficient aluminoxane. A sufficient ethylene polymerization activity cannot be achieved. That is, it was difficult to provide a nonwoven fabric-olefin polymer composite sheet containing a sufficient amount of an olefin polymer as required.

JP 2010-534749 gazette

  The problem to be solved by the present invention in view of the background art is to provide a fiber-sheet-supported olefin polymerization catalyst that achieves high ethylene polymerization activity, and to provide a sheet-shaped olefin-based catalyst using the catalyst. The object is to provide a coalescence and a production method thereof, and to provide a molded body using the sheet-like olefin polymer.

  As a result of investigations to solve the above-mentioned problems, the present inventors have obtained an aluminoxane preparation containing a gel-like aluminoxane obtained under specific conditions and a transition metal compound supported on a fiber sheet. It has been found that the above-mentioned problems can be solved by the fiber sheet-supported olefin polymerization catalyst, and the present invention has been completed.

That is, the catalyst for olefin polymerization according to the present invention is
(A) an aluminoxane preparation containing a toluene insoluble component in a molar ratio of aluminum atom to oxygen atom in the range of 1.00 to 1.40 and 40 mol% or more in terms of aluminum atom, and (B) transition (C) a fiber sheet,
To be obtained.

  The (A) aluminoxane preparation is preferably a preparation obtained by allowing an oxygen-containing compound to act on an organoaluminum compound.

  The organoaluminum compound is preferably trialkylaluminum, and the oxygen-containing compound is preferably water.

  Moreover, it is preferable that the said transition metal compound has a structure of the following general formula (IV).

(In the formula (IV), M represents a transition metal atom of Groups 4 and 5 of the periodic table,
m represents an integer of 1 to 4,
R ^{1 to} R ⁵ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring,
R ⁶ represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting of only primary or secondary carbon, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, monocyclic or dicyclic Selected from a cyclic alicyclic hydrocarbon group, an aromatic hydrocarbon group and a halogen atom,
n is a number that satisfies the valence of M;
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other. To form a ring. )
In the present invention, the sheet-like olefin polymer is obtained by polymerizing one or more olefins selected from olefins having 2 to 20 carbon atoms in the presence of the above-described olefin polymerization catalyst.

  In the present invention, the molded body comprises the above sheet-like olefin polymer.

  The catalyst for olefin polymerization according to the present invention includes an aluminoxane preparation containing a gel-like aluminoxane obtained under specific conditions as an essential component, thereby efficiently supporting the aluminoxane component on the fiber sheet. Therefore, high olefin polymerization activity can be achieved. Furthermore, a sheet-like olefin polymer obtained by using the olefin polymerization catalyst and a molded article using the polymer have practically excellent characteristics.

Hereinafter, the olefin polymerization catalyst according to the present invention, a sheet-like ethylene polymer obtained using the olefin polymerization catalyst, and a molded article obtained using the polymer will be described.
<Olefin polymerization catalyst>
The olefin polymerization catalyst of the present invention comprises:
(A) an aluminoxane preparation containing a toluene insoluble component in a molar ratio of aluminum atoms to oxygen atoms in the range of 1.00 to 1.40 and 40 mol% or more in terms of aluminum atoms, and
(B) a transition metal compound, (C) a fiber sheet,
It is characterized in that it is obtained by being supported on.

Hereinafter, each component of (A)-(C) and the manufacturing method of the catalyst for olefin polymerization are explained in full detail.
[(A) Aluminoxane Preparation]
In the present invention, the (A) aluminoxane preparation is a reaction product of an organoaluminum compound and an oxygen-containing compound, and is a preparation comprising an aluminoxane compound and an unreacted organoaluminum compound. Furthermore, in the present invention, (A) the aluminoxane preparation has a molar ratio of aluminum atoms to oxygen atoms in the whole aluminoxane preparation in the range of 1.00 to 1.40, and is converted to aluminum atoms in the entire aluminoxane preparation. And contains 40 mol% or more of toluene insoluble components.

A conventionally well-known aluminoxane compound can be obtained, for example by the preparation method like following (1)-(4), and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or water of crystallization with an organoaluminum compound by adding an organoaluminum compound to the suspension of the hydrocarbon medium.
(2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound in a medium such as decane, benzene, or toluene.
(4) A method of reacting an organoaluminum compound with a carbonyl compound such as benzoic acid in a medium such as decane, benzene, and toluene.

  In general, conventionally known aluminoxane preparations have a molar ratio of aluminum atoms to oxygen atoms set to a value exceeding 1.40. This means that a significant amount of unreacted organoaluminum compound is contained in the aluminoxane preparation. By coordinating the unreacted organoaluminum compound to the oxygen atom of the aluminoxane compound, the aluminoxane compound can be obtained as a solution uniformly dissolved in a solvent such as toluene.

  On the other hand, when the molar ratio of the aluminum atom to the oxygen atom is 1.40 or less, that is, when the amount of the oxygen-containing compound added is large in the above preparation method, the unreacted organoaluminum compound reacts with the oxygen-containing compound. Increases the molecular weight of the aluminoxane compound and reduces the amount of the organoaluminum compound coordinated to the oxygen atom of the aluminoxane, so that a strong interaction works between the aluminoxane compound molecules or between the molecules of the aluminoxane compounds that are approaching. Therefore, it is known that the aluminoxane compound becomes a gel.

  In the prior art, there is a uniform aluminoxane solution in which the molar ratio of aluminum atoms to oxygen atoms is set to a value exceeding 1.40 so that the aluminoxane preparation is supported on a catalyst carrier for easy handling. It is used, and there is no intention to actively use the gelled aluminoxane preparation.

  On the other hand, in the (A) aluminoxane preparation used in the present invention, the molar ratio of aluminum atom to oxygen atom is set to 1.00 in order to intentionally produce the above-described high molecular weight aluminoxane compound and an aggregate of the aluminoxane compound. It is set in the range of 1.40 or less.

The aluminoxane compound and the aggregate of the aluminoxane compound, which are thus increased in molecular weight, are included in the aluminoxane preparation, and thus advantageously work when supported on the (C) fiber sheet material to be described later for the following reason. It is considered a thing.
(I) When the aluminoxane compound in the aluminoxane preparation has a high molecular weight or an aggregate is formed, a part of the preparation (the aluminoxane compound) gels, so that the aluminoxane compound is physically made of a fiber sheet. It adheres to the object and becomes difficult to come off easily.
(Ii) When the fiber sheet and the aluminoxane compound are supported via chemical bonds by partial reaction, the aluminoxane compound is increased in molecular weight or associated with the fiber sheet reaction point. Since the amount of the supported aluminoxane compound increases, the aluminoxane compound can be efficiently supported on the fiber sheet.

  In the present invention, the upper limit of the molar ratio of the aluminum atom to the oxygen atom in the (A) aluminoxane preparation is 1.40 as described above, preferably 1.35, and more preferably 1.30. When the upper limit of the molar ratio becomes a small value, the amount of the unreacted organoaluminum compound in the aluminoxane preparation is not small and the amount of the aluminoxane compound increases. That is, since the high molecular weight aluminoxane compound and the aggregate of the aluminoxane compound in the aluminoxane preparation are further increased, and (C) the fiber sheet-like material described later is more efficiently supported. preferable.

  On the other hand, the lower limit of the molar ratio indicates a state in which all of the unreacted organoaluminum compound is consumed at 1.00, and when it is less than the numerical value, the aluminoxane compound in the (A) aluminoxane preparation in the present invention is From gel to solid state, it is considered that not only is it difficult to carry on a (C) fiber sheet, which will be described later, but the function as a co-catalyst is impaired. Therefore, the lower limit of the molar ratio is preferably 1.10, more preferably 1.20.

  The molar ratio of the aluminum atom to the oxygen atom in the (A) aluminoxane preparation described above is determined by the amount of the organoaluminum compound and the oxygen-containing compound used in preparing the aluminoxane preparation. More specifically, it depends on the ratio between the number of moles of aluminum atoms contained in the organoaluminum compound and the number of moles of oxygen atoms contained in the oxygen-containing compound.

  Alternatively, the molar ratio of aluminum atoms to oxygen atoms in the (A) aluminoxane preparation may be determined by directly analyzing the resulting aluminoxane preparation.

  In the present invention, the (A) aluminoxane preparation is characterized in that it contains 40 mol% or more of a toluene-insoluble component in terms of aluminum atoms in the entire aluminoxane preparation.

  The toluene-insoluble component is derived from the above-described high molecular weight aluminoxane compound and an aggregate of the aluminoxane compound.

  The ratio of the toluene insoluble component is the mol of aluminum atoms contained in the filtrate obtained by filtering a dispersion of the aluminoxane preparation (Al mole number: A mol) in toluene at 20 ° C. with a glass filter. From the recovery rate of the number (the number of Al moles: B mol), it can be obtained by the formula represented by ((A−B) / A) × 100.

  The lower limit of the proportion of the toluene insoluble component is 40 mol%, preferably 45 mol%, more preferably 50 mol%.

  The fact that the lower limit of the ratio of the toluene-insoluble component is a large value means that there are many high-molecular weight aluminoxane compounds and aggregates of aluminoxane compounds in the aluminoxane preparation, and will be described later (C ) This is a more preferable embodiment because it is more efficiently carried on the fiber sheet.

  On the other hand, the upper limit of the proportion of the toluene insoluble component is not particularly provided, but is usually 100 mol%. When the upper limit is 100 mol%, all of the aluminoxane compounds in the aluminoxane preparation are high molecular weight or form an aggregate, so that (C) loading onto the fiber sheet-like material described later is more efficient. It is thought to be done.

  (A) The aluminoxane compound contained in the aluminoxane preparation has a structure represented by the following general formula (I) or general formula (II), or a repeating unit represented by the following general formula (IIIa) and the following general formula (IIIb ).

(In the formulas (I), (II) and (IIIa), R is a hydrocarbon group having 1 to 10 carbon atoms, and in the formulas (I) and (II), m represents an integer of 2 to 500. In the formulas (IIIa) and (IIIb), n and p each represents an integer of 1 or more.)
The (A) aluminoxane preparation may contain an unreacted organoaluminum compound in addition to the aluminoxane compounds represented by the above general formulas.
[(A) Method for producing aluminoxane preparation]
In this invention, (A) aluminoxane preparation is obtained by reaction of an organoaluminum compound and an oxygen containing compound as above-mentioned.

  In the present invention, (A) a method for obtaining an aluminoxane preparation may be a conventionally known method shown in the above (1) to (4), but the molar ratio of aluminum atoms to oxygen atoms in the entire aluminoxane preparation. Is in the range of 1.00 or more and 1.40 or less, and the organoaluminum compound and the oxygen-containing compound are reacted at a ratio such that the composition is in the above range.

  In the present invention, the (A) aluminoxane preparation is prepared by adding an oxygen-containing compound to a solution-like aluminoxane preparation in which the molar ratio of aluminum atoms to oxygen atoms is generally 1.40. The molar ratio of aluminum atoms to oxygen atoms may be adjusted to be in the range of 1.00 to 1.40. The production method also conceptually includes a method obtained by the reaction of the organoaluminum compound and the oxygen-containing compound described above.

As the method for adding the oxygen-containing compound, the same method as the method for obtaining the aluminoxane preparation by reacting the oxygen-containing compound directly with the organoaluminum compound can be employed. For example, the following methods are mentioned.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. Of adding the aluminoxane preparation to a hydrocarbon medium suspension of
(2) A method in which water, ice or water vapor is directly applied to an aluminoxane preparation in a medium such as benzene or toluene.
(3) A method in which an organotin oxide, carbonyl compound, alcohol compound or the like is allowed to act on an aluminoxane preparation in a medium such as benzene or toluene.

In the present invention, (A) the organoaluminum compound used for the preparation of the aluminoxane preparation is represented by the following general formula (a): R ^a _m Al (OR ^b ) _n H _p X _q (a)
(In the formula (a), R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which may be the same or different from each other, X represents a halogen atom, m Is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3)
Examples of the organoaluminum compound belonging to the general formula (a) include the following compounds.

General formula R ^a _m Al (OR ^b ) _3-m (wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other). M is preferably a number of 1.5 ≦ m ≦ 3.), An organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein R ^a is 1 to 1 carbon atoms) 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m is preferably 0 <m <3.), An organoaluminum compound represented by the general formula R ^a _m AlH _{3 − m} (wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3), a general formula during _{^{R a m Al (oR b)}} n X q ( wherein, ^{R a} and ^{R b} are identical to each other May represent different hydrocarbon groups having 1 to 15, preferably 1 to 4, carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, q Is a number of 0 ≦ q <3 and m + n + q = 3).

More specifically, as the organoaluminum compound belonging to the general formula (a), trimethylaluminum, triethylaluminum, tripropylaluminum, tri (n-butyl) aluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecyl Aluminum, triisopropylaluminum, triisobutylaluminum, tri (sec-butyl) aluminum, tri (tert-butyl) aluminum, tri (2-methylbutyl) aluminum, tri (3-methylbutyl) aluminum, tri (2-methylpentyl) aluminum , Tri (3-methylpentyl) aluminum, tri (4-methylpentyl) aluminum, tri (2-methylhexyl) aluminum, tri (3-methylhexyl) Trialkylaluminum such as aluminum and tri (2-ethylhexyl) aluminum; Tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; Triarylaluminum such as triphenylaluminum and tritylaluminum; Diethylaluminum hydride, Diisobutylaluminum hydride dialkylaluminum hydride such _{as; (iC 4 H 9) x} Al y (C 5 H 10) z ( wherein, x, y, z are each a positive _number, .iC 4 _{H 9} is a z ≧ 2x isobutyl Alkenylaluminum such as isoprenylaluminum represented by the following: isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum Alkylaluminum alkoxides such as um isopropoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide dialkylaluminum alkoxides such as Sid; R a ^2; ethylaluminum sesquichloride ethoxide, butyl aluminum sesqui butoxide alkyl sesquichloride alkoxide _{such. 5} Al (OR ^b ) _0.5 (wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15 carbon atoms, which may be the same as or different from each other, preferably 1 to 4). A partially alkoxylated alkylaluminum having an average composition represented by: diethylaluminum phenoxide, diethylaluminum (2,6-di-tert-butyl 4-methylphenoxide), ethyla Minium bis (2,6-di-tert-butyl 4-methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl 4-methylphenoxide), isobutylaluminum bis (2,6-di-tert-butyl 4- Dialkylaluminum aryloxides such as methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide Alkyl aluminum sesquihalides such as ethyl aluminum dichloride, propyl aluminum dichloride Partially halogenated alkylaluminums such as alkylaluminum dihalides such as butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride Other partially hydrogenated alkylaluminums, and the like include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclyl, ethylaluminum ethoxybromide, and the like.

  Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Moreover, you may use an organoaluminum compound individually by 1 type or in combination of 2 or more types as needed.

  Examples of the oxygen-containing compound used for the preparation of the (A) aluminoxane preparation in the present invention include water, organotin oxide, carboxyl compound, carbonyl compound, alcohol compound, ether compound and the like. Here, water includes not only what is directly added to the reaction system but also water contained in a compound containing adsorbed water or a salt containing crystal water.

  Of these, oxygen-containing compounds promote the association of compounds containing oxygen atoms that react with organoaluminum compounds to give aluminoxane compounds and aluminoxane atoms through interactions such as reaction or coordination, thereby reducing solubility. It can be roughly classified into compounds containing oxygen atoms that contribute to.

  Examples of the former include water, dimethyltin oxide, and benzoic acid, and examples of the latter include alcohols and ethers. In addition, among the latter, in addition to the oxygen-containing compound, compounds having a hetero atom such as a sulfur atom or a nitrogen atom, specifically thiols, sulfides, amines, etc. can be exemplified. Specifically, an oxygen-containing compound is used.

  Of the above-mentioned oxygen-containing compounds, water is particularly preferable because it provides an aluminoxane compound efficiently, further promotes association of the aluminoxane compound, and lowers solubility.

In the present invention, the preparation of the (A) aluminoxane preparation is usually performed in a solvent capable of dissolving the organoaluminum compound. Solvents used for the preparation include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane, Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons, especially chlorinated products And hydrocarbon solvents such as bromide. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable, and toluene is more preferable.
[(B) Transition metal compound]
In the present invention, as the (B) transition metal compound, a compound used for a known catalyst for olefin polymerization can be used without any particular limitation. Specifically, a metallocene compound or a transition metal complex having a ligand containing a hetero atom (various post-metallocene compounds) can be used.

  Among these, preferred metallocene compounds include those described in International Publication No. 01/53369, International Publication No. 01/27124, Japanese Patent Application Laid-Open No. 3-193396, Japanese Patent Application Laid-Open No. 02-41303, or International. The thing as described in the publication 06/025540 pamphlet is mentioned.

  Among the postmetallocene compounds, particularly preferred are transition metal complexes having a so-called phenoxyimine ligand represented by the following general formula (IV).

  In the above general formula (IV), M represents a transition metal atom in Groups 4 and 5 of the periodic table, preferably a Group 4 transition metal atom. Specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum, and the like are preferable, titanium, zirconium, and hafnium are more preferable, and titanium or zirconium is particularly preferable.

  In general formula (IV), a dotted line connecting N and M generally indicates that N is coordinated to M, but may or may not be coordinated in the present invention. .

  In the general formula (IV), m represents an integer of 1 to 4, preferably an integer of 2 to 4, and more preferably 2.

In the general formula (IV), R ^{1 to} R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, or boron. A containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Examples of the hydrocarbon group include a linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms, a cyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic group having 6 to 30 carbon atoms. A hydrocarbon group is mentioned. Specifically, the number of carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, n-hexyl group, etc. 1-30, preferably 1-20, more preferably 1-10 linear or branched alkyl groups; 2-30 carbon atoms such as vinyl, allyl and isopropenyl groups, preferably 2 20 linear or branched alkenyl groups;
A linear or branched alkynyl group having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms such as an ethynyl group or a propargyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, A cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20, more preferably 3 to 10 carbon atoms such as a cycloheptyl group and an adamantyl group; a carbon atom such as a cyclopentadienyl group, an indenyl group and a fluorenyl group A cyclic unsaturated hydrocarbon group having a number of 5 to 30; a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, an anthracenyl group, etc., having 6 to 30, preferably 6 to 20, more preferably 6 carbon atoms. To 10 aryl groups; tolyl group, iso-propylphenyl group, t-butylphenyl group, di- Examples thereof include alkyl-substituted aryl groups such as methylphenyl group and di-t-butylphenyl group.

  The hydrocarbon group may have a hydrogen atom substituted with a halogen, and examples of the hydrocarbon group in which such a hydrogen atom is substituted with a halogen include a trifluoromethyl group, a pentafluorophenyl group, and a chlorophenyl group. Examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

  The hydrocarbon group may be substituted with other hydrocarbon groups, and examples of the hydrocarbon group substituted with such a hydrocarbon group include aryl group-substituted alkyl groups such as a benzyl group and a cumyl group. Etc.

  Furthermore, the hydrocarbon group is a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, a carboxylic anhydride group, etc. Oxygen-containing group; amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group is ammonium salt Nitrogen-containing groups such as those; boron-containing groups such as boranediyl group, boranetriyl group, diboranyl group; mercapto group, thioester group, dithioester group, alkylthio group, arylthio group, thioacyl group, thioether group, thiocyanate group , Isothiocyanate ester group, sulfone ester Groups, sulfonamido groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups and other sulfur-containing groups; phosphide groups, phosphoryl groups, thiophosphoryl groups, phosphato groups and other phosphorus-containing groups; It may have a silicon-containing group; a germanium-containing group; or a tin-containing group.

  Examples of the heterocyclic compound residue include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, and sulfur-containing compounds such as thiophene, and heterocycles thereof. Examples include a group further substituted with a substituent such as an alkyl group or alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms in the formula compound residue.

  Examples of the silicon-containing group include silyl group, siloxy group, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, and more specifically, methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group. Group, triethylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, dimethyl-t-butylsilyl group, dimethyl (pentafluorophenyl) silyl group and the like. Among these, a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group and the like are preferable, and in particular, a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group Group, dimethylphenylsilyl group is preferred. Specific examples of the hydrocarbon-substituted siloxy group include a trimethylsiloxy group.

  Examples of the germanium-containing group or the tin-containing group include groups in which silicon of the silicon-containing group is replaced with germanium or tin.

  Among the groups listed as groups that the hydrocarbon group may have, specifically as an alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, t-butoxy group; specific examples of aryloxy group include phenoxy group, 2,6-dimethylphenoxy group, 2,4,6-trimethylphenoxy group; specific examples of ester group include acetyloxy group, benzoyloxy group, Methoxycarbonyl group, phenoxycarbonyl group, p-chlorophenoxycarbonyl group; Specifically as acyl group, formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybenzoyl group; specifically as amino group Is a dimethylamino group, an ethylmethylamino group, a diphenylamino group; an imino group Specifically, methylimino group, ethylimino group, propylimino group, butylimino group, phenylimino group; as amide group, specifically as acetamido group, N-methylacetamido group, N-methylbenzamide group; as imido group Specifically, acetoimide group, benzimide group; thioester group specifically includes acetylthio group, benzoylthio group, methylthiocarbonyl group, phenylthiocarbonyl group; alkylthio group specifically includes methylthio group, ethylthio group; arylthio group Specifically, a phenylthio group, a methylphenylthio group, a naphthylthio group; Specifically, as a sulfone ester group, a methyl sulfonate group, an ethyl sulfonate group, a phenyl sulfonate group; Phenyl Ruhon'amido group, N- methyl sulfonamide group, N- methyl -p- toluenesulfonamide group, and a structural unit having, respectively.

Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, neopentyl group, and n-hexyl group. A linear or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms; 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group; Preferably 6-20 aryl groups;
These aryl groups have substituents such as halogen atoms, alkyl groups or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, aryl groups or aryloxy groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. A substituted aryl group substituted with 1 to 5 is preferred.

R ^{1 to} R ⁵ may be a heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, or tin-containing group as described above. These examples may be the same as those exemplified in the description of the hydrocarbon group.

For R ¹ of R ¹ to R ⁵ in formula (IV), from the viewpoint of giving olefin polymers aspects and high molecular weight olefin polymerization catalytic activity, linear having 1 to 20 carbon atoms or It is preferably a group selected from a branched hydrocarbon group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms.

In the general formula (IV), R ⁶ represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting of only primary or secondary carbon, an aliphatic hydrocarbon group having 4 or more carbon atoms, or aryl group substitution. It is selected from alkyl groups, monocyclic or bicyclic alicyclic hydrocarbon groups, aromatic hydrocarbon groups and halogen atoms. Among these, from the viewpoint of olefin polymerization catalyst activity, from the viewpoint of providing a high molecular weight olefin polymer and from the viewpoint of hydrogen resistance during polymerization, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, It is preferably a group selected from a monocyclic or bicyclic alicyclic hydrocarbon group and an aromatic hydrocarbon group, more preferably a branched hydrocarbon group such as a t-butyl group; a benzyl group, 1- Aryl-substituted alkyl groups such as methyl-1-phenylethyl group (cumyl group), 1-methyl-1,1-diphenylethyl group, 1,1,1-triphenylmethyl group (trityl group); hydrocarbon at the 1-position An alicyclic carbon having 6 to 15 carbon atoms such as a cyclohexyl group, an adamantyl group, a norbornyl group, a tetracyclododecyl group having a group, or a double ring structure Originally, and the like.

In the general formula (IV), n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, aluminum A containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X are A plurality of groups represented by X may be bonded to each other to form a ring. In X, the halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group, phosphorus-containing group, silicon-containing group, germanium-containing group, tin-containing group Are the same as those exemplified in the description of R ^{1 to} R ⁵ above. Of these, a halogen atom and a hydrocarbon group are preferable.

In the present invention, the transition metal compound represented by the general formula (I) can be produced without limitation by, for example, the production method described in JP-A-11-315109.
[(C) Fiber sheet]
In the present invention, the (C) fiber sheet-like product serves as a carrier for supporting the above-mentioned (A) aluminoxane preparation and (B) transition metal compound.

  In the present invention, the (C) fiber sheet-like product is a name for convenience, and the “sheet” is a general term for a molded product on a plane. It is a concept including a membrane) and a tape.

  The (C) fiber sheet material used in the present invention is selected according to the use of the sheet-shaped olefin polymer according to the present invention, and can be used without any limitation as long as the fiber is formed into a sheet shape. it can.

  (C) Specifically, the fiber sheet-like material is not particularly limited as long as it is a sheet-like material made of fibers, such as non-woven fabric, felt, paper, woven fabric, and knitted fabric. Among them, a nonwoven fabric that is low in cost and can be selected from a wide range of materials and physical properties is suitable in the present invention.

  The material for the nonwoven fabric can be selected from natural polymers such as cellulose, and synthetic resins such as polyolefin, polyester, polyamide, and polyvinyl alcohol. Among these, polyolefin nonwoven fabrics are preferably used because they are versatile and can be manufactured at low cost, and the effects of the present invention are remarkably exhibited.

  The polyolefin nonwoven fabric is not particularly limited as long as it is produced by a known method, and examples thereof include a dry method, a wet method, a melt blown method, a spun bond method, a flash spinning method, and a tow opening method.

  The polyolefin used as the material for the non-woven fabric made of polyolefin is not particularly limited as long as it is used in the known method for producing a non-woven fabric, and is one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms. Mention may be made of polyolefins obtained by polymerizing olefins. Specifically, polyethylene, polypropylene, polybutene, poly (4-methyl-1-pentene), ethylene-propylene copolymer, propylene-butene copolymer, ethylene-propylene-butene terpolymer, and other α- Examples include olefin copolymers. Also, copolymers of the above-mentioned olefins with 50% or less of other reactive monomers, such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-maleic anhydride copolymer, ethylene-ethyl. Examples thereof include acrylate-maleic anhydride terpolymers.

The catalyst for olefin polymerization according to the present invention can carry (A) an aluminoxane preparation containing a gel-like insoluble component formed by high molecular weight and formation of an aggregate on (C) a fiber sheet. It is a feature. At this time, it is not an essential requirement that the (C) fiber sheet has a reaction point for forming a chemical bond with the (A) aluminoxane preparation, but more efficiently (A ) So that the aluminoxane preparation is supported on the (C) fiber sheet, (A) a solution containing the aluminoxane preparation and (C) the wettability of the fiber sheet; In order to intentionally generate a reaction site with the (A) aluminoxane preparation on the sheet-like product, (C) a modification treatment of the surface of the fiber-made sheet product may be performed. Examples of the modification treatment include UV-O ₃ treatment, plasma treatment, corona discharge treatment, flame treatment, and graft polymerization.

About the manufacturing method and raw material of the (C) fiber sheet used for this invention, and the presence or absence of a modification | denaturation process, it comprises the sheet-like olefin polymer to be obtained by this invention, and this sheet-like olefin polymer. Although it is selected according to the required performance of the molded product, an example of the remarkable effect of the present invention is a polyolefin nonwoven fabric having a fiber diameter of about 0.5 μm to 100 μm. A polyethylene non-woven fabric or a polypropylene non-woven fabric produced by the above method is a preferred example.
[Method for producing olefin polymerization catalyst]
The catalyst for olefin polymerization according to the present invention is obtained by supporting the above-mentioned (A) aluminoxane preparation and (B) transition metal compound on (C) a fiber sheet.

  In the present invention, “supporting” means (C) a fiber sheet-like material serving as a carrier, and (A) an aluminoxane preparation and (B) a transition metal compound are chemically bonded (covalent bond, ionic bond, etc.). And a state of being attached through an interaction, a state of being physically held, or a state of both.

  Hereinafter, a method for supporting (A) the aluminoxane preparation and (B) the transition metal compound on the (C) fiber sheet will be described in detail.

  In the present invention, the supporting can be carried out by impregnating the (C) fiber sheet into a solvent containing (A) an aluminoxane preparation and (B) a transition metal compound.

  As the impregnation method, (A) a method of impregnating a fiber sheet into a solvent in which an aluminoxane preparation and (B) a transition metal compound are mixed (premix method), (A) an aluminoxane preparation (C) A method of impregnating (C) a fiber sheet-like material carried by (A) an aluminoxane preparation in a solvent containing (B) a transition metal compound, after impregnating the (C) fiber sheet-like material in the solvent containing ( Any of the sequential methods can be carried out, but the premix method is preferred in that (C) the catalyst component is efficiently supported on the fiber sheet.

  Hereinafter, the premix method which is a preferred embodiment will be further described.

  (A) A method comprising impregnating a fiber sheet-like product with a solvent containing both an aluminoxane preparation and (B) a transition metal compound, and (C) The solvent containing the catalyst component is infiltrated. At that time, when (C) the fiber surface of the fiber sheet and the aluminoxane compound are chemically bonded, it is possible to wash away components that are not held in the (C) fiber sheet by performing a washing operation. It is.

  The solvent used for the above loading and washing is a solvent that is soluble in the (B) transition metal compound and has an affinity for the gelled aluminoxane compound in the (A) aluminoxane preparation, and does not deactivate the catalyst. Things are desirable. Preferably, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; common hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as ethylene chloride and chlorobenzene Or a mixture thereof.

  The concentration of (A) aluminoxane preparation and (B) transition metal compound in the solvent containing (A) aluminoxane preparation and (B) transition metal compound used for impregnation is supported on (C) fiber sheet. The concentration of the (A) aluminoxane preparation is 0.001 to 10 mol / L, preferably 0.01 to 1 mol / L, more preferably 0.05 to 0.5 g / L / mol. Moreover, the density | concentration of (B) transition metal compound is 0.001-50 mmol / L, Preferably, it is 0.01-5 mmol / L, More preferably, it is 0.05-1 mmol / L.

As for the temperature and time for impregnation, the concentrations of (A) aluminoxane preparation and (B) transition metal compound are the same as the above concentrations, and (C) the amount supported on the fiber sheet and the desired polymer production amount. Generally, the temperature is -50 to 100 ° C, preferably -30 to 100 ° C, more preferably 0 to 30 ° C. In addition, the time cannot be set unconditionally because there is a balance with the concentration, but it is generally 1 to 60 minutes, preferably 2 to 30 minutes.
<Sheet-like olefin polymer, method for producing the polymer>
The sheet-like olefin polymer of the present invention is obtained by polymerizing one or more olefins selected from olefins having 2 to 20 carbon atoms in the presence of the olefin polymerization catalyst.

  In the present invention, “polymerization” may include the meaning of copolymerization such as random copolymerization and block copolymerization in addition to homopolymerization.

  Examples of the olefin having 2 to 20 carbon atoms include ethylene and α-olefins having 3 to 20 carbon atoms. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1 Linear olefins such as butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 4-methyl- Examples thereof include branched olefins such as 1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene.

Other olefins include aromatic vinyl compounds such as styrene and allylbenzene;
Alicyclic vinyl compounds such as vinylcyclohexane and vinylcycloheptane can also be used.

  These olefins may be used alone or in combination.

  In the method for producing a sheet-like olefin polymer according to the present invention, in addition to the above-mentioned olefin polymerization catalyst, the olefin polymerization reaction is carried out with high activity and the properties of the resulting olefin polymer are adjusted. Other components can also be used in addition.

The other components can be used without particular limitation as long as the performance of the olefin polymerization catalyst containing (A) an aluminoxane preparation and (B) a transition metal compound is not impaired. Among them, compounds that can be used typically and react with the components (D) :( B) to form ion pairs will be described below.
[(D): Compound that reacts with component (B) to form an ion pair]
In the present invention, compounds that can be used during the olefin polymerization reaction to form an ion pair by reacting with the component (B) include organoaluminum compounds, boron halide compounds, phosphorus halide compounds, sulfur halide compounds, Examples include a halogenated titanium compound, a halogenated silane compound, a halogenated germanium compound, and a tin halide compound.

  Among these, examples of the organoaluminum compound include compounds represented by the following formula (D-1), (D-2), or (D-3).

R ^a _n AlX _3-n (D-1)
(In Formula (D-1), ^Ra is a C1-C12 hydrocarbon group, X is a halogen atom or a hydrogen atom, and n is 1-3.)
The hydrocarbon group having 1 to 12 carbon atoms is, for example, an alkyl group, a cycloalkyl group, or an aryl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, Hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

  Specific examples of such organoaluminum compounds include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Le aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

  Moreover, the organoaluminum compound represented by a following formula can also be used.

R ^a _n AlY _3-n (D-2)
(In the formula (D-2), Ra is the same as in the above formula (D-1), Y is -OR ^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -SiR. ^f ₃ group or —N (R ^g ) AlR ^h ₂ group, n is 1 to 2, and R ^b , R ^c , R ^d and R ^h are methyl group, ethyl group, isopropyl group, isobutyl group, cyclohexyl And R ^e is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R ^f and R ^g are methyl group, ethyl group, etc.)
As the organoaluminum compound represented by the formula (D-2), specifically, the following compounds are used.
(I) R ^a _n Al (OR ^b ) A compound represented by _3-n , for example, an alkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, diethylaluminum-2-ethylhexoxide, etc. .
_{^{(Ii) R a n Al (}} OSiR c 3) a compound represented by _3-n, e.g., _{Et 2 Al (OSiMe 3),} (iso-Bu) 2 Al (OSiMe 3), (iso-Bu) 2 Al ( OSiEt ₃ ) and the like.
_{^{(Iii) R a n Al (}} OAlR d 2) a compound represented by _3-n, e.g., Et ₂ AlOAlEt _2, such as _{(iso-Bu) 2 AlOAl (} iso-Bu) 2.
_{^{(Iv) R a n Al (}} NR e 2) a compound represented by _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHEt, Et 2 AlN (Me 3 Si) 2, (iso-Bu) ₂ AlN (Me ₃ Si) ₂ etc.
_{^{(V) R a n Al (}} SiR f 3) a compound represented by _3-n, such as _{(iso-Bu) 2 AlSiMe 3} .
^(Vi) _{R a} n Al ^[N (R g) -AlR ^h _2] A compound represented by _3-n, e.g., _{Et 2 AlN (Me) -AlEt 2} , (iso-Bu) 2 AlN (Et) Al ( iso-Bu) _{2 and the} like.

  Further, as the organoaluminum compound, a compound represented by the following formula (D-3) which is a complex alkylated product of a Group I metal and aluminum can be used.

M ¹ AlR ^j ₄ (D-3)
(In Formula (D-3), M ¹ is Li, Na, K, and R ^j is a hydrocarbon group having 1 to 15 carbon atoms)
_{Specifically, LiAl (C 2 H 5)} 4, LiAl (C 7 H 15) 4 and the like.

  Among the organoaluminum compounds described above, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and diisobutylaluminum hydride are particularly preferable.

  Specific examples of boron halide compounds, phosphorus halide compounds, sulfur halide compounds, titanium halide compounds, halogenated silane compounds, halogenated germanium compounds, and tin halide compounds include the following compounds. .

Boron halide compounds such as boron trifluoride, boron trichloride, boron tribromide;
Phosphorus trichloride, phosphorous tribromide, phosphorous triiodide, phosphorous pentachloride, phosphorous pentabromide, phosphorous oxychloride, phosphorous oxybromide, methyldichlorophosphine, ethyldichlorophosphine, propyldichlorophosphine, butyldichlorophosphine, cyclohexyldichloro Phosphine, phenyldichlorophosphine, methyldichlorophosphine oxide, ethyldichlorophosphine oxide, butyldichlorophosphine oxide, cyclohexyldichlorophosphine oxide, phenyldichlorophosphine oxide, methylphenylchlorophosphine oxide, dibromotriphenylphosphorane, tetraethylphosphonium chloride, dimethyldiphenylphosphonium Iodide, ethyltriphenylphosphonium chloride, allyltriphenylphosphonium chloride Benzyl triphenyl phosphonium chloride, allyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, phosphorus halide compound such as benzyl bromide;
Sulfur halide compounds such as sulfur dichloride, thionyl chloride, sulfuryl chloride, thionyl bromide;
Titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxytrichlorotitanium, ethoxytrichlorotitanium, butoxytrichlorotitanium, ethoxytribromotitanium, butoxytribromotitanium, dimethoxydichlorotitanium, diethoxydichlorotitanium, Titanium halide compounds such as dibutoxydichlorotitanium, diethoxydibromotitanium, trimethoxychlorotitanium, triethoxychlorotitanium, tributoxychlorotitanium, triethoxybromotitanium;
Silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, methoxytrichlorosilane, ethoxytrichlorosilane, butoxytrichlorosilane, ethoxytribromosilane, butoxytribromosilane, dimethoxydichlorosilane, diethoxydichlorosilane, dibutoxydichlorosilane, Diethoxydibromosilane, trimethoxychlorosilane, triethoxychlorosilane, tributoxychlorosilane, triethoxybromosilane, methyltrichlorosilane, ethyltrichlorosilane, butyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dibutyldichlorosilane, Diphenyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, tributylchlorosilane, triphenylchlorosilane Halogenated silane compounds such as silane;
Germanium tetrafluoride, germanium tetrachloride, germanium tetraiodide, methoxytrichlorogermanium, ethoxytrichlorogermanium, butoxytrichlorogermanium, ethoxytribromogermanium, butoxytribromogermanium, dimethoxydichlorogermanium, diethoxydichlorogermanium, dibutoxydichlorogermanium, Halogenated germanium compounds such as diethoxydibromogermanium, trimethoxychlorogermanium, triethoxychlorogermanium, tributoxychlorogermanium, triethoxybromogermanium;
Tin tetrafluoride, tin tetrachloride, tin tetrabromide, tin tetraiodide, methoxytrichlorotin, ethoxytrichlorotin, butoxytrichlorotin, ethoxytribromotin, butoxytribromotin, dimethoxydichlorotin, diethoxydichlorotin, Dibutoxydichlorotin, diethoxydibromotin, trimethoxychlorotin, triethoxychlorotin, tributoxychlorotin, triethoxybromotin, methyltrichlorotin, ethyltrichlorotin, butyltrichlorotin, phenyltrichlorotin, dimethyldichlorotin, Tin halide compounds such as diethyldichlorotin, dibutyldichlorotin, diphenyldichlorotin, trimethylchlorotin, triethylchlorotin, tributylchlorotin and triphenylchlorotin.

  These compounds may be used independently and may combine 2 or more types. Further, it may be diluted with a hydrocarbon or a halogenated hydrocarbon.

Among the specific examples of the compounds exemplified as the component (D), preferably, trialkylaluminum, alkenylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, alkylaluminum alkoxide, (Iso-Bu) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) ₂ , LiAl (C ₂ H ₅ ) ₄ , halogenated silane compounds and halogenated titanium compounds, more preferably trialkylaluminum, alkenylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, Examples include alkylaluminum dihalide, alkylaluminum hydride, and alkylaluminum alkoxide, more preferably trialkylaluminum and alkylaluminum halide, and further preferably triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethyl Aluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride.

  In the method for producing a sheet-like olefin polymer according to the present invention, a prepolymerization catalyst obtained by prepolymerizing an α-olefin in the presence of the olefin polymerization catalyst and, if necessary, the component (D). It is also possible to carry out the polymerization in the presence of. This prepolymerization is performed, for example, by prepolymerizing the α-olefin in an amount of 0.01 to 1000 g, preferably 0.03 to 500 g, particularly preferably 0.1 to 100 g, per 1 g of the olefin polymerization catalyst. For the prepolymerization, a known method can be used without limitation.

  Next, the main polymerization (polymerization) performed after passing through the pre-polymerization or without going through the pre-polymerization will be described.

  In the main polymerization, the olefin having 2 to 20 carbon atoms is polymerized in the presence of the olefin polymerization catalyst.

  In the present invention, the prepolymerization and the main polymerization can be carried out by either liquid phase polymerization or gas phase polymerization. In addition, a known method can be adopted as a polymerization method, and a batch method can be simply adopted. However, a continuous roll-to-roll method is utilized by taking advantage of the characteristics of a sheet-like supported olefin polymerization catalyst. Polymerization can also be carried out.

  In the case of liquid phase polymerization, the reaction medium is preferably an inert hydrocarbon medium. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; cycloheptane, methylcycloheptane, cyclohexane, methylcyclohexane, methylcyclopentane, cyclooctane, methylcyclo Examples thereof include alicyclic hydrocarbons such as octane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; or a mixture thereof.

  Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Besides these, olefin which is liquid at the reaction temperature can be used as the reaction medium.

  The molecular weight of the resulting olefin polymer can be adjusted by the polymerization conditions, and in particular by adjusting the presence of hydrogen in the polymerization system.

  In the main polymerization in the method for producing a sheet-like olefin polymer of the present invention, the transition metal compound (B) is usually 0.000001 mmol to 0.5 mmol in terms of transition metal atoms per liter of polymerization volume. , Preferably in an amount of 0.00005 mmol to 0.1 mmol. In addition, the (A) aluminoxane preparation is converted into aluminum atoms in the aluminoxane preparation, and the transition metal atom in the (B) transition metal compound (in the prepolymerization catalyst component when prepolymerization) is 1 mol. Is usually used in an amount of 1 mol to 200000 mol, preferably 5 mol to 50000 mol (in the present invention, as described above, (A) the aluminoxane preparation and (B) the transition metal compound are (C) Since it is used by being supported on a fiber sheet, it is appropriately adjusted in the above-mentioned range in the supporting process.

  When the above component (D) is used, the molar ratio [(D) / M] of the component (D) and the total transition metal atom (M) in the transition metal compound (B) is usually 0.01. ˜100,000, preferably 0.05 to 50,000.

  In the polymerization in the present invention, the polymerization temperature of the olefin is usually 0 ° C to 200 ° C, preferably 20 ° C to 100 ° C, more preferably 30 ° C to 90 ° C, and particularly preferably 40 ° C to 80 ° C. The pressure is usually set to normal pressure to 10 MPa, preferably normal pressure to 5 MPa. In the polymerization in the present invention, the polymerization time of the olefin is usually 10 minutes or more, preferably 30 minutes or more in the case of a batch system.

  The sheet-like olefin polymer produced by the above polymerization method has a shape in which the polymer is uniformly attached on the sheet-like material while maintaining the shape of the (C) fiber sheet-like material used as the catalyst carrier. Become. That is, the shape of the (C) fiber sheet is a replica, and the polymer is formed in a state resulting from the (C) fiber sheet.

  Furthermore, the obtained sheet-like olefin polymer tends to be formed with good morphology along the fibers of the (C) fiber sheet-like product. For this reason, it is easy to obtain a molded article having a uniform quality, which will be described later.

  The sheet-like olefin polymer according to the present invention has an intrinsic viscosity [η] in the range of 1 dl / g to 50 dl / g. A preferred lower limit is 5 dl / g, more preferably 10 dl / g. On the other hand, the preferable upper limit is 45 dl / g, more preferably 40 dl / g, and particularly preferably 30 dl / g.

Further, the sheet-like olefin polymer according to the present invention has a basis weight (gram weight of the olefin polymer per square meter) of 1 to 10000 g / m ² , preferably 5 to 1000 g / m ² , more preferably 10 ˜500 g / m ² . In the present invention, the sheet-like olefin polymer is produced using an olefin polymerization catalyst in which (A) an aluminoxane preparation having the above-mentioned specific properties is supported on (C) a fiber sheet. From this, since there are many olefin polymerization active sites on the (C) fiber sheet-like material, the olefin polymer can adhere to the (C) fiber sheet-like material more. .
<Molded body made of olefin polymer>
The molded body of the present invention is characterized in that it is obtained by further processing and molding the sheet-like olefin polymer, and the (C) fiber sheet-like product and the olefin polymer contained in the olefin polymerization catalyst are This is a composite sheet-like molded body.

  In the present invention, the molded body is preferably in a form utilizing the shape of the sheet-like olefin polymer, for example, a sheet or a film, and further, a separator or a filter further processed from these primary molded bodies. Can be mentioned.

  The molding method of the molded body is not particularly limited as long as it is a known method for molding a polymer. Specific examples include press molding, calendar molding, uniaxial stretching molding, and biaxial stretching molding.

  Although the molded body of the present invention is obtained by the molding method of the molded body, since the sheet-shaped olefin polymer is used as the initial molded material, the molding process can be simplified. That is, in the olefin polymer produced in the presence of an olefin polymerization catalyst using a general particulate carrier, it is necessary to melt the resin and mold the initial molding material at the initial stage of the molding process. In the present invention, since a sheet-like catalyst for olefin polymerization is used, the molding of the initial molding material obtained in this step has already been completed at the production stage of the olefin polymer.

The present invention will be described below based on examples, but it goes without saying that the present invention is not limited to the following examples without departing from the gist thereof.
The materials and reagents used in the examples are as follows.
(Fiber sheet)
Melt blown nonwoven fabric made of polypropylene (Mitsui Chemicals: “Syntex nano3”, average fiber diameter 1.0 μm, basis weight 15 g / m ² )
-Polypropylene spun pond non-woven fabric (Mitsui Chemicals: “Syntex PB-0220”, average fiber diameter 20 μm, basis weight 20 g / m ² )
(Reagent used)
-Toluene used what was refine | purified using the organic solvent refinement | purification apparatus by GlassContor.
As the toluene solution of aluminoxane, a 20 wt% methylaluminoxane / toluene solution (atom ratio of aluminum and oxygen: Al / O = 1.47, 3.06 mol / L in terms of aluminum atoms) manufactured by Nippon Alkyl Aluminum Co. was used.
-Triisobutylaluminum was manufactured by Tosoh Finechem Corporation diluted with toluene (1.0 M).
(Preparation of hydrated toluene)
Water toluene prepared as follows was used.

A 100 ml glass container sufficiently purged with nitrogen was inserted with 100 mL of dehydrated toluene and 34.7 μL of distilled water, and irradiated with ultrasonic waves for 5 minutes to obtain a uniform transparent solution (water content 400 ppm).
(Quantification of toluene insoluble components)
A reaction solution of a toluene solution of methylaluminoxane described later and a hydrated toluene was filtered through a G4 glass filter at room temperature of 20 ° C., and the residue on the filter was washed with 20 mL of dehydrated toluene.

  The proportion of the toluene insoluble component is calculated from the number of moles of aluminum converted from the amount of methylaluminoxane (A mol) and the number of moles of aluminum atoms (B mol) contained in the obtained filtrate and the recovered cleaning liquid ((A -B) / A) It calculated | required in conversion of the aluminum atom by the formula represented by x100.

The aluminum content contained in the obtained filtrate and the recovered cleaning solution was quantified by high frequency plasma emission analysis (ICP).
[Example 1]
(Preparation of catalyst component solution)
1 ml of a toluene solution of methylaluminoxane (3.06 mmol in terms of aluminum atom) was inserted into a fully substituted 30 ml glass container, and the liquid temperature was maintained at 0 ° C. while stirring. Thereto, 20.0 ml of the hydrated toluene was added dropwise over 10 minutes, and after the liquid temperature was returned to room temperature, stirring was continued for 30 minutes. Next, 5.3 mL of a toluene solution (1.16 mol / L) of a transition metal compound represented by the following general formula (1) was charged, and stirring was continued for 5 minutes to prepare a catalyst component solution.

(Supporting catalyst components)
Simultaneously with the preparation of the catalyst component solution, a fiber sheet used as a carrier is prepared. A non-woven fabric “Syntex nano3” (50 mm × 75 mm) is wound around a Teflon (registered trademark) core (diameter 10 mm, length 60 mm) and fixed with Teflon (registered trademark) yarn. The nonwoven fabric fixed to the core is inserted into a sufficiently dried 30 ml glass container and left in a nitrogen atmosphere for 30 minutes or more. Thereto, 25 ml of the catalyst component solution is inserted, and the nonwoven fabric is immersed in the catalyst component solution. After performing ultrasonic irradiation for 2 minutes for deaeration, about 24 mL of catalyst component solution is extracted, and then a washing operation is performed. For washing, the operation of charging 25 mL of toluene and extracting 25 mL again was repeated twice.
(polymerization)
Charge 500 mL of dehydrated heptane into a 500 mL glass polymerization vessel sufficiently purged with nitrogen, and perform nitrogen bubbling for 30 minutes. The nonwoven fabric carrying the catalyst component adjusted as described above is introduced from the inlet of the polymerization vessel. Thereafter, ethylene was charged at 10 L / min, and polymerization was performed at 60 ° C. for 30 minutes in an atmospheric pressure ethylene gas atmosphere. The polymerization was stopped by adding a small amount of isobutanol. Thereafter, the fixed core material is removed, and only the outer peripheral portion where the ethylene polymer is generated is cut out. The obtained ethylene polymer sheet was immersed overnight in a mixed solvent of acetone and methanol (each having the same volume) containing a small amount of hydrochloric acid. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene polymer sheet was weighed and the basis weight (gram weight per square meter) was calculated. Table 1 shows the measurement results of catalyst activity and basis weight.
[Example 2]
(Preparation of catalyst component solution)
In a fully substituted 30 ml glass container, 11.8 ml of dehydrated toluene and 1 ml of toluene solution of methylaluminoxane (3.06 mmol in terms of aluminum atom) were inserted, and the liquid temperature was maintained at 0 ° C. while stirring. 7.9 ml of water-containing toluene was added dropwise over 10 minutes, the temperature of the solution was returned to room temperature, and stirring was continued for 30 minutes. Next, 5.3 mL of a toluene solution (1.16 mol / L) of the transition metal compound represented by the above general formula (1) was charged and stirring was continued for 5 minutes to prepare a catalyst component solution.
(Supporting catalyst components)
Simultaneously with the preparation of the catalyst component solution, a fiber sheet used as a carrier is prepared. The top and bottom of a nonwoven fabric “Syntex nano3” (75 mm long × 50 mm wide), which has been subjected to UV-ozone treatment for 15 minutes on each side, are fixed to a hanging shaft using Teflon (registered trademark) yarn and a Teflon (registered trademark) jig. . The nonwoven fabric fixed with the jig is wound up and charged into a 30 mL glass container, and after nitrogen replacement for 30 minutes or more, the catalyst component solution is immersed in the nonwoven fabric by charging 25 mL of the catalyst component solution. After performing ultrasonic irradiation for 2 minutes for deaeration, about 24 mL of catalyst component solution is extracted, and then a washing operation is performed. For washing, the operation of charging 25 mL of toluene and extracting 25 mL again was repeated twice.
(polymerization)
Charge 500 mL of dehydrated heptane into a 500 mL glass polymerization vessel sufficiently purged with nitrogen, and perform nitrogen bubbling for 30 minutes. Charge 0.5 ml of triisobutylaluminum decane solution (0.1 mmol / L). The nonwoven fabric carrying the catalyst component adjusted as described above is introduced from the inlet of the polymerization vessel so that the nonwoven fabric spreads inside the polymerization vessel. Ethylene was charged at 100 L / min, polymerization was performed at 60 ° C. for 30 minutes in an atmospheric pressure ethylene gas atmosphere, and then the polymerization was stopped by adding a small amount of isobutanol. The fixed jig was removed and immersed in methanol containing a small amount of hydrochloric acid overnight. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours. The obtained ethylene polymer sheet was weighed and the basis weight (gram weight per square meter) was calculated. Table 1 shows the measurement results of catalyst activity and basis weight.
[Example 3]
The same operation as in Example 1 was carried out except that the nonwoven fabric “Syntex PB-0220” was used as the fiber sheet used as the carrier to obtain an ethylene polymer sheet. The obtained ethylene polymer sheet was weighed and the basis weight (gram weight per square meter) was calculated. Table 1 shows the measurement results of catalyst activity and basis weight.
[Comparative Example 1]
The same procedure as in Example 1 was performed except that the same amount of dehydrated toluene was used instead of hydrolyzed toluene. Table 1 shows the molar ratio of aluminum atoms to oxygen atoms in the aluminoxane preparation, the ratio of the toluene insoluble component in the aluminoxane preparation, and the polymerization results.
[Comparative Example 2]
The same procedure as in Example 2 was performed except that dehydrated toluene was used instead of hydrolyzed toluene. Table 1 shows the molar ratio of aluminum atoms to oxygen atoms in the aluminoxane preparation, the ratio of the toluene insoluble component in the aluminoxane preparation, and the polymerization results.
[Comparative Example 3]
The same procedure as in Example 3 was performed except that dehydrated toluene was used instead of hydrolyzed toluene. Table 1 shows the molar ratio of aluminum atoms to oxygen atoms in the aluminoxane preparation, the ratio of the toluene insoluble component in the aluminoxane preparation, and the polymerization results.

  Since the sheet-like olefin polymer obtained using the olefin polymerization catalyst according to the present invention can obtain a sheet and a film by a simple production process, it has high energy efficiency at the time of product production. The possibility is high.

Claims (8)

(A) an aluminoxane preparation containing a toluene insoluble component in a molar ratio of aluminum atom to oxygen atom in the range of 1.00 to 1.40 and 40 mol% or more in terms of aluminum atom, and (B) transition (C) a fiber sheet,
A catalyst for olefin polymerization obtained by being supported on a catalyst. The olefin polymerization catalyst according to claim 1, wherein the (A) aluminoxane preparation is a preparation obtained by allowing an oxygen-containing compound to act on an organoaluminum compound. The olefin polymerization catalyst according to claim 2, wherein the organoaluminum compound is trialkylaluminum. The olefin polymerization catalyst according to claim 2 or 3, wherein the oxygen-containing compound is water. The catalyst for olefin polymerization according to any one of claims 1 to 4, wherein the transition metal compound has a structure represented by the following general formula (IV).

(In the formula (IV), M represents a transition metal atom of Groups 4 and 5 of the periodic table,
m represents an integer of 1 to 4,
R ^{1 to} R ⁵ may be the same or different and are each a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, phosphorus A containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be linked to each other to form a ring,
R ⁶ represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms consisting of only primary or secondary carbon, an aliphatic hydrocarbon group having 4 or more carbon atoms, an aryl group-substituted alkyl group, monocyclic or dicyclic Selected from a cyclic alicyclic hydrocarbon group, an aromatic hydrocarbon group and a halogen atom,
n is a number that satisfies the valence of M;
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing A group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other. To form a ring. ) A sheet-like olefin polymer obtained by polymerizing one or more olefins selected from olefins having 2 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to claim 1. The manufacturing method of the sheet-like olefin type polymer obtained by superposing | polymerizing 1 or more types of olefins chosen from a C2-C20 olefin in presence of the olefin polymerization catalyst of Claims 1-5. A molded article comprising the sheet-shaped olefin polymer according to claim 6.