JP5318366B2 - Olefin polymerization catalyst and process for producing the catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low-cost catalyst for olefin polymerization that has high catalytic activity and can produce an olefin polymer excellent in melt fluidity, moldability and particle performance by improving a non-metallocene olefin polymerization catalyst technically as a post metallocene catalyst. <P>SOLUTION: This catalyst for olefin polymerization comprises a component (A) and a component (B). The component (A) is a homogeneous polymerization catalyst component having a transition metal. The component (B) is a catalyst component prepared by bringing a component (B-1) into contact with a component (B-2). The component (B-1) is an ion-exchanging layered compound intercalated with a transition metal ion of group third to eleventh of the periodic table or the transition metal complex ion. The component (B-2) is an organic compound of molecular weight of &le;1,000 that has at least two elements of group fifteenth or sixteenth having a non-covalent electron pair in the molecule, in which the elements of group fifteenth or sixteenth are connected via 1-6 elements of group 14th. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a novel catalyst for olefin polymerization, a method for producing the catalyst, and a method for producing an olefin polymer using the catalyst for polymerization, and more particularly, a heavy catalyst having high catalytic activity and excellent melt fluidity and particle properties. It can be produced by contacting a specific transition metal compound, an ion-exchange layered compound ion-exchanged with a transition metal, and a specific organic compound. The present invention relates to a binary olefin polymerization catalyst using an intercalate containing at least a compound and a process for producing the same, and further using the polymerization catalyst, the melt flowability is excellent while suppressing an increase in low molecular weight components. The present invention relates to a method for producing an olefin polymer, which can stably and economically produce an olefin polymer having a wide molecular weight distribution.

Polyolefins, which are main polymers in resin materials that are heavily used as industrial materials, are industrially produced mainly by Ziegler catalysts and metallocene catalysts using transition metal compounds.
As a transition metal compound in such a catalyst, a compound of a group 4 element in the periodic table (long-period type) having a cyclopentadienyl group or its analog as a ligand is most widely used. A metallocene group compound of a Group 3 element that uses a rare earth metal that is a MAO type (see Patent Document 1), a transition metal compound of a Group 5 to 7 element, and olefin polymerization using them are also reported (patent) References 2 to 4), development and application in such a catalyst field are widely deployed.

Furthermore, as a central metal, a periodic transition such as iron as a Group 8 element in the periodic table, cobalt as a Group 9 element, nickel or palladium as a Group 10 element, and copper as a Group 11 element The component of the olefin polymerization catalyst which has a metal element is also found (refer nonpatent literature 1 and patent documents 5-7).
Among these, as a non-metallocene catalyst called a post metallocene catalyst, for example, a so-called Brooke in which nickel or palladium is coordinated to a special ligand having a bidentate nitrogen atom double-bonded to a carbon atom. The Hart catalyst (PTL 5) has attracted attention, but generally the polymerization activity is not sufficiently high.
In a catalyst system combined with methylaluminoxane (MAO) using a compound having a coordination site such as a bidentate or more nitrogen atom as a ligand of nitrogen atom, ethylene is polymerized with high activity. Inhibition of the growth reaction of the polymer chain is remarkable, and it is difficult to obtain a polymer having a high molecular weight. Further, the particle properties of the resulting polymer are poor.

Improvements in particle properties in such non-metallocene complex catalyst systems have also been studied. For example, polydentate nitrogen ligand complexes of Group 8 to 10 elements and phenoxyimine ligand complexes of Group 3 to 11 elements can be converted to silica. Attempts have been made to support the catalyst with a cocatalyst, or in combination with a clay mineral as a cocatalyst and carrier (see Patent Documents 8 and 9).
This catalyst system combining clay minerals and non-metallocene complexes is highly active and can improve particle properties and molecular weight to some extent, but it is an expensive non-metallocene complex obtained through complicated synthesis and purification separation processes. Is used as a catalyst raw material, the cost of the catalyst is increased, which is economically disadvantageous, and the loading of the complex is insufficient, so that the particle properties are not always good.

Therefore, attempts have been made to obtain a catalyst system that does not require the use of an expensive nonmetallocene complex.For example, a pyridine derivative having an aminomethyl group as a substituent on the carbon adjacent to the nitrogen of the pyridine ring, and a periodic table. Although a polymerization catalyst comprising a group 8-10 transition metal-containing compound has also been proposed (see Patent Document 10), sufficient results have not been obtained in terms of polymerization activity and powder properties.
In addition, two types of olefin polymers with different molecular weights are produced in order to improve the molding processability and product characteristics such as melt flowability by appropriately lowering the molecular weight of the olefin polymer and appropriately widening the molecular weight distribution. Although attempts have been made to use different metallocene complexes and nonmetallocene complexes in the same polymerization system (see Patent Documents 11 and 12), sufficient results have been obtained in terms of polymerization activity and powder properties. Absent.

Japanese Patent Laid-Open No. 9-95514 (refer to claim 1 of claims) Japanese translation of PCT publication No. 2002-503733 (see abstract) Japanese translation of PCT publication No. 2002-541152 (refer to claim 3 of claims) Japanese translation of PCT publication No. 2003-527403 (refer to claim 5 of claims) International publication of WO 96/23010 (see middle of page 1) International publication of WO 98/27124 (see the top of page 1) Japanese Patent Laid-Open No. 11-171915 (see summary) Japanese Patent Laid-Open No. 9-278821 (see summary) Japanese Patent Laid-Open No. 2000-313712 (refer to claim 1 of claims) JP 2000-344821 A (see abstract) JP 2000-198812 A (see abstract) JP-A-9-278823 (see abstract)

Journal of American Chemical Society Vol. 117, p. 6414 Catalyst 44 3 194 (2002)

In view of the background and direction of research and development of the olefin polymerization catalyst described above in the background art, the development and improvement of non-metallocene olefin polymerization catalysts as post-metallocene catalysts have led to improvements in catalyst performance and polymer properties. In view of improvements in various physical properties, polymerization processes, and industrial economics, it is considered important and strongly demanded in the field of olefin-based resin materials as main industrial materials. Therefore, the present invention develops such a polymerization catalyst. It is aimed at.
Specifically, using a wide variety of transition metals in the periodic table, selecting specific ligands to which the transition metals coordinate, and improving the technology of nonmetallocene olefin polymerization catalysts. Developed an economically inexpensive catalyst for olefin polymerization, which can solve the conventional problems in such polymerization catalyst, and can produce a polymer having high catalytic activity and excellent melt fluidity and particle properties. A method for producing an olefin polymer, which can stably and economically produce an olefin polymer having a broad molecular weight distribution and excellent fluidity while suppressing an increase in low molecular weight components using the catalyst. It is a problem to be solved by the invention in the present invention.

By the way, the present inventors, in the same way as in the present invention, in view of the problems in the prior art of olefin polymerization catalyst and the intention to improve the technology of nonmetallocene olefin polymerization catalyst, Research on olefin polymerization catalysts using specific transition metal complex compounds in which transition metal atoms are coordinated by intercalation to ligands having two or more group 15 or group 16 atoms such as oxygen and oxygen. Prior to the invention.
“(A) component: an ion-exchange layered compound in which transition metal ions of Group 3 to 11 of the periodic table or the transition metal complex ions are intercalated; and (B) component: Periodic table 15th. ˜Catalyst component for olefin polymerization obtained by contacting an organic compound having at least two group 16 elements and having a molecular weight of 1,000 or less ”as a constitution, can produce a polymer having high catalytic activity and excellent particle properties An economically inexpensive catalyst for olefin polymerization is realized, and a stable and economically advantageous method for producing an olefin polymer can be carried out using the polymerization catalyst. (Japanese Patent Application No. 2006-244865).

In order to solve the above-described problems of the present invention, the present inventors use a variety of transition metals in the periodic table, select a specific ligand to which the transition metal coordinates, and select a non-metallocene system. In order to improve the technology of the olefin polymerization catalyst of the present invention, the invention of the prior application relating to the above-mentioned olefin polymerization catalyst, which is common to the present invention and the subject of the invention, was developed.
In addition, when using a catalyst component in which an organic compound ligand is further intercalated to an ion-exchangeable layered compound in which transition metal ions and the like are intercalated, selection of other catalyst components to be used and The function, the production conditions of the catalyst, the role of the cocatalyst, etc. were examined and tested from various viewpoints. As a result of such thought and demonstration process, the catalyst component in which the transition metal ion and the organic compound ligand are intercalated is brought into contact with various homogeneous polymerization catalyst components having a transition metal. It can be found that the polymerization catalyst can solve the above-mentioned problems of the present invention, and results such as improvement of catalyst performance, improvement of various physical properties of the polymer, stabilization of the polymerization process, and improvement of industrial economics, etc. As a result, the present invention has been created.

Thus, the present invention uses a specific transition metal compound belonging to Groups 3 to 11 of the periodic table as one component and coordinates an organic compound having a coordination site such as a bidentate nitrogen atom or oxygen atom. In particular, an ion-exchange layered compound is employed as a co-catalyst / support using a ligand having a bidentate nitrogen atom double-bonded to a carbon atom.
The co-catalyst ion-exchange layered compound is then intercalated with a transition metal atom and further contacted with an organic compound having a specific coordination site to synthesize an ion-exchange layered compound, which is then transitioned. It is used as a co-catalyst for a metal compound, and in combination with a homogeneous polymerization catalyst component having a transition metal, a binary olefin polymerization catalyst having two or more different polymerization active sites is obtained.

That is, the basic gist of the present invention resides in an olefin polymerization catalyst characterized by containing at least the following components (A) and (B).
(A) component: homogeneous polymerization catalyst component having a transition metal (B) component: a compound obtained by contacting the component (B-1) and the component (B-2).
Component (B-1): an ion-exchange layered compound in which transition metal ions of Group 3 to 11 of the periodic table or the transition metal complex ions are intercalated.
Component (B-2): a compound having a molecular weight of 1,000 or less, having at least two group 15 or group 16 elements having an unshared electron pair in the molecule, and group 15 or group 16 These organic compounds are linked through 1 to 6 Group 14 elements.

In the present invention, more specifically, the component (A) is preferably a metallocene compound of a transition metal of Groups 3-6 of the periodic table, and preferably of Groups 8-10 of the periodic table. A transition metal bisimide compound, a transition metal halide of group 3 to 10 of the periodic table, a bisamide compound or bisalkoxide compound of a transition metal of groups 4 to 6 of the periodic table, periodic table 3 to 3. Any one of the group 11 transition metal phenoxyimine compounds.
As the component (B-1), at least one transition metal ion or the transition metal complex ion of Ti, Zr, Hf, V, Nb, Cr, Mn, Fe, Co, Ni, and Pd is intercalated. The ion exchange layered compound is an organic compound represented by the following general formula (B-2a).
AQA '(B-2a)
(In the formula, A and A ′ are hydrocarbon compound-bonding groups having 1 to 30 carbon atoms and having at least one element selected from Group 15 or Group 16 of the Periodic Table (in the same compound, A and A ′ May be the same or different), Q is a divalent cyclic compound having a pyridine skeleton, a pyrazine skeleton, a bipyridine skeleton, a morpholine skeleton, a pyrrole skeleton, a furyl skeleton, a thiofuryl skeleton, an amine skeleton, A phosphine skeleton, an ether skeleton, a thioether skeleton, a hexenylene skeleton, a hexynylene skeleton, a heptadienylene skeleton, an ethenylpropane skeleton, a diethylbenzene skeleton, and at least one pair of unshared electron pairs or π bonds, and A and A ′ Indicates a binding group linked at a position.)

  Furthermore, the catalyst for olefin polymerization of the present invention comprises an ion-exchange layered compound (so-called host compound) in which transition metal ions and the like are intercalated as component (B-1), and component (B-2) as component (B-2). By contacting with an organic compound (so-called guest compound), the organic compound is further intercalated into an ion-exchangeable layered compound to form component (B) of the catalyst component, and then transition as component (A) It can manufacture by contacting the homogeneous polymerization catalyst component which has a metal, and (B) component.

  As described above in paragraphs 0011 and 0012, the present invention synthesizes an ion-exchange layered compound in which a transition metal atom is intercalated with an organic compound having a specific coordination site in an ion-exchange layered compound. However, this compound is used as a co-catalyst for a transition metal compound and combined with a homogeneous polymerization catalyst component having a transition metal, and has a novel and unique structure, which improves catalyst performance and various polymers. It is characterized by many outstanding results such as improvement of physical properties and stabilization of polymerization process and improvement of industrial economy.

  In the above, since the background to the creation of the present invention and the configuration and characteristics of the invention have been described in general, the present invention will be clarified from the overview of the present invention. It consists of The inventions described in [1] and [11] are basic inventions, and other inventions constitute embodiments of the basic invention.

[1] An olefin polymerization catalyst comprising at least the following components (A) and (B):
(A) Component: A homogeneous polymerization catalyst component having a transition metal.
(B) Component: A catalyst component obtained by contacting the component (B-1) and the component (B-2).
Component (B-1): an ion-exchange layered compound in which the transition metal ions of Group 3 to 11 of the periodic table or the transition metal complex ions are intercalated.
Component (B-2): a compound having a molecular weight of 1,000 or less, and having an unshared electron pair in the molecule
An organic compound having at least two Group 15 or Group 16 elements, wherein the Group 15 or Group 16 elements are linked via 1 to 6 Group 14 elements.
[2] The catalyst for olefin polymerization according to [1], wherein the component (A) is a metallocene compound of a transition metal of Groups 3 to 6 of the periodic table.
[3] The olefin polymerization catalyst according to [2], wherein the metallocene compound is any one of Ti, Zr, Hf, V, and Cr.
[4] The olefin polymerization catalyst according to [1], wherein the component (A) is a bisimide compound of a transition metal of Groups 8 to 10 of the periodic table.
[5] The olefin polymerization catalyst according to [4], wherein the bisimide compound is any one of Fe, Co, Ni, and Pd.
[6] The component (A) is a halide of a transition metal of Groups 3 to 10 of the periodic table, a bisamide compound or a bisalkoxide compound of a transition metal of Groups 4 to 6 of the periodic table, or Periodic Tables 3 to 11 The catalyst for olefin polymerization according to [1], which is a compound selected from the group consisting of phenoxyimine compounds of transition metals.
[7] As the component (B-1), at least one transition metal ion or transition metal complex ion of Ti, Zr, Hf, V, Nb, Cr, Mn, Fe, Co, Ni, and Pd is present. The catalyst for olefin polymerization according to any one of [1] to [6], which is an intercalated ion-exchange layered compound.
[8] The olefin polymerization catalyst according to any one of [1] to [7], wherein the component (B-2) is an organic compound represented by the following general formula (B-2a).
AQA '(B-2a)
(In the formula, A and A ′ are hydrocarbon compound-bonding groups having 1 to 30 carbon atoms and having at least one element selected from Group 15 or Group 16 of the Periodic Table (in the same compound, A and A ′ May be the same or different), Q is a divalent cyclic compound having a pyridine skeleton, a pyrazine skeleton, a bipyridine skeleton, a morpholine skeleton, a pyrrole skeleton, a furyl skeleton, a thiofuryl skeleton, an amine skeleton, A phosphine skeleton, an ether skeleton, a thioether skeleton, a hexenylene skeleton, a hexynylene skeleton, a heptadienylene skeleton, an ethenylpropane skeleton, a diethylbenzene skeleton, and at least one pair of unshared electron pairs or π bonds, and A and A ′ Indicates a binding group linked at a position.)
[9] The olefin polymerization catalyst according to [8], wherein the group 15 or group 16 element of the component (B-2) is nitrogen, phosphorus, oxygen or sulfur.
[10] The olefin polymerization catalyst as described in any one of [1] to [9], which contains an organoaluminum compound as the optional component (C).
[11] An ion-exchange layered compound in which a transition metal ion or a transition metal complex ion of Group 3 to 11 of the periodic table as component (B-1) is intercalated, and component (B-2) A compound having a molecular weight of 1,000 or less and having at least two Group 15 or Group 16 elements having an unshared electron pair in the molecule, and the Group 15 or Group 16 element is By contacting an organic compound connected through 1 to 6 group 14 elements, the organic compound is further intercalated into an ion-exchangeable layered compound to form component (B) of the catalyst component Then, the homogeneous polymerization catalyst component having a transition metal as the component (A) and the component (B) are contacted, and the binary containing at least the component (A) and the component (B) For producing a catalyst for olefin polymerization.
[12] A method for producing an olefin polymer, wherein the olefin is polymerized or copolymerized using the olefin polymerization catalyst according to any one of [1] to [10].

  In the present invention, an economically inexpensive catalyst for olefin polymerization that can produce a polymer having high catalytic activity and excellent melt flowability, molding processability, and particle properties is realized. In polymerization and copolymerization of α-olefins mainly composed of propylene, an olefin polymer having excellent fluidity while suppressing a significant increase in low molecular weight components can be produced stably and economically advantageously. Further, since the polymer is generated at the polymerization active point between the clay layers, the clay fine particles can be highly dispersed.

  The outline of the skeleton of the present invention and the features thereof have been outlined above, and the present invention will be described in detail below by describing embodiments of the invention in detail.

1. About Olefin Polymerization Catalyst (1) (A) Component In the olefin polymerization catalyst of the present invention, a homogeneous polymerization catalyst component having a transition metal is used as the (A) component which is a catalyst component. That is, the component (A) is a known homogeneous catalyst component, specifically, at least one transition metal compound selected from the following (A-1) to (A-5).
(A-1): Group 3-10 transition metal halides in the periodic table (A-2): Group 3-6 transition metal metallocene compounds in the periodic table (A-3): Periodic table Bisamide or bisalkoxide compounds of Group 4-6 transition metals (A-4): Bisimide compounds of Group 8-10 transition metals (A-5): Periodic table of Group 3-11 transition metals Phenoxyimine compounds Here, the transition metal compounds (A-1) to (A-5) are more specifically as follows.

[I] Explanation of (A-1) The component (A-1) is a transition metal halide of Groups 3 to 10 of the periodic table, preferably Ti, Zr, Hf, V, Nb, Cr, Mo , Mn, Fe, Co, Ni, Pd halides, and more preferably Ti, Zr, Hf, V, Cr, Ni halides.

Specifically, preferably, TiF ₃ , TiCl ₃ , TiBr ₃ , TiI ₃ , TiFCl ₂ , TiClBr ₂ , TiCl ₂ Br, TiBrI ₂ , TiBr ₂ I, TiCl ₂ I, TiFI ₂ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , TiFCl ₃ , TiF ₂ Cl ₂ , TiCl ₂ Br ₂ , TiCl ₃ Br, TiBrI ₃ , TiBr ₂ I ₂ , TiBr ₃ I, TiCl ₃ I, TiCl ₂ I ₂ , TiFI ₃ , TiF ₂ I _{2 , TiOCl 2, ZrF 3, ZrCl} 3, ZrBr 3, ZrI 3, ZrFCl 2, ZrF 4, ZrCl 4, ZrBr 4, ZrI 4, ZrFCl 3, ZrCl 2 Br 2, ZrOCl 2, HfF 3, HfCl 3, HfBr 3 , HfI ₃ , HfFCl ₂ , HfF _{4, HfCl 4, HfBr 4,} HfI 4, HfFCl 3, HfCl 2 Br 2, HfOCl 2, VCl 2, VF 3, VCl 3, VBr 3, VI 3, VFCl 2, VOF 3, VOCl 3, VF 4, NbF _{5, NbCl 5, NbBr 5,} NbI 5, CrF 2, CrF 3, CrCl 2, CrCl 3, CrBr 3, MoF 6, MoCl 3, MoCl 5, MoOCl 4, MnF 2, MnF 3, MnBr 2, MnCl 2, _{MnI 2, Mn (CO) 5} Br, FeF 2, FeF 3, FeBr 2, FeBr 3, FeCl 2, FeCl 3, FeI 2, CoF 2, CoF 3, CoCl 2, CoBr 2, CoI 2, NiF 2, NiCl _{2, NiBr 2, NiI 2,} PdCl 2, PdBr 2, dI _2, and the like.

More preferably, TiF ₃ , TiCl ₃ , TiBr ₃ , TiI ₃ , TiFCl ₂ , TiClBr ₂ , TiCl ₂ Br, TiBrI ₂ , TiBr ₂ I, TiCl ₂ I, TiFI ₂ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , TiFCl ₃ , TiF ₂ Cl ₂ , TiCl ₂ Br ₂ , TiCl ₃ Br, TiBrI ₃ , TiBr ₂ I ₂ , TiBr ₃ I, TiCl ₃ I, TiCl ₂ I ₂ , TiFI ₃ , TiF ₂ I ₂ , TiOCl _{2 , ZrF 3, ZrCl 3, ZrBr} 3, ZrI 3, ZrFCl 2, ZrF 4, ZrCl 4, ZrBr 4, ZrI 4, ZrFCl 3, ZrCl 2 Br 2, ZrOCl 2, HfF 3, HfCl 3, HfBr 3, HfI 3 , HfFCl _{2, HfF} 4, _{fCl 4, HfBr 4, HfI 4} , HfFCl 3, HfCl 2 Br 2, HfOCl 2, VCl 2, VF 3, VCl 3, VBr 3, VI 3, VFCl 2, VOF 3, VOCl 3, VF 4, CrF 2, CrF ₃ , CrCl ₂ , CrCl ₃ , CrBr ₃ , NiF ₂ , NiCl ₂ , NiBr ₂ , NiI ₂ .

Incidentally, particularly _{preferred, TiCl 3, TiBr 3, TiCl} 4, TiBr 4, ZrCl 3, ZrBr 3, ZrCl 4, ZrBr 4, HfCl 3, HfBr 3, HfI 3, HfCl 4, HfBr 4, VCl 3, VBr 3 , CrCl ₃ , CrBr ₃ , NiCl ₂ , NiBr ₂ .

[Ii] Explanation of (A-2) The component (A-2) is a metallocene compound of a transition metal of Group 3-6 of the Periodic Table, specifically, a periodic rule having at least one conjugated five-membered ring ligand. Table 3 to 6 transition metal compounds, preferably compounds represented by the following general formula [a1], [a2], [a3] or [a4].

（式の[ａ１]〜[ａ４]中、Ｅ及びＥ´は、共役五員環構造を有する配位子（同一化合物内においてＥ及びＥ´は同一でも異なっていてもよい）を表し、Ｑ´は、２つの共役五員環配位子を任意の位置で架橋する結合性基を表し、Ｚは、Ｍ´と結合している窒素原子、酸素原子、リン原子又はイオウ原子を含む１価又は２価の基を表し、Ｑ″は、共役五員環配位子の任意の位置とＺを架橋する結合性基を表し、Ｍ´は、周期律表３〜６族から選ばれる金属原子を表し、また、Ｘ´及びＹ´は、Ｍ´と結合した水素原子、ハロゲン原子、炭化水素基、アルコキシ基、アミノ基、リン含有炭化水素基又はケイ素含有炭化水素基を表す。）

(In the formulas [a1] to [a4], E and E ′ represent a ligand having a conjugated five-membered ring structure (E and E ′ may be the same or different in the same compound), and Q 'Represents a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and Z is a monovalent group including a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom bonded to M'. Or Q ″ represents a binding group that bridges Z with an arbitrary position of the conjugated five-membered ring ligand, and M ′ represents a metal atom selected from Groups 3 to 6 in the periodic table X ′ and Y ′ represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group bonded to M ′.

E and E ′ are conjugated five-membered ring ligands, and these may be the same or different in the same compound as described above. Typical examples of the conjugated five-membered ring ligand (E and E ′) include a cyclopentadienyl group and an indenyl group, a fluorenyl group, and an azulenyl group having a cyclopentadienyl moiety as a part of the structure. be able to.
As a substituent on these conjugated five-membered ring ligands, a halogen group or an alkoxy group (for example, a group having 1 to 12 carbon atoms) in addition to a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. A silicon-containing hydrocarbon group (for example, a group having about 1 to 24 carbon atoms containing a silicon atom in the form of —Si (R ¹ ) (R ² ) (R ³ )), a phosphorus-containing hydrocarbon group (for example, a phosphorus atom A group having about 1 to 18 carbon atoms in the form of -P (R ¹ ) (R ² ), a nitrogen-containing hydrocarbon group (for example, a nitrogen atom in the form of -N (R ¹ ) (R ² )) A group having about 1 to 18 carbon atoms) or a boron-containing hydrocarbon group (for example, a group having about 1 to 18 carbon atoms containing a boron atom in the form of -B (R ¹ ) (R ² )). When there are a plurality of these substituents, each substituent may be the same or different.

Q ′ is a binding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and Q ″ is a binding group that bridges an arbitrary position of the conjugated five-membered ring ligand with a Z group. Represents.
Specifically, Q ′ and Q ″ are (i) an alkylene group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, and a cyclohexylene group; ) Silylene group such as silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group, tetramethyldisylylene group, (c) hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum, Specifically, (CH ₃ ) ₂ Ge group, (C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆ H ₅ ) P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ ) B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group, (C ₆ H ₅ ) Al group, (CH ₃ O) Al group, etc. There is a preferred one It is an alkylene group and a silylene group.

  M ′ is a metal atom selected from Groups 3 to 6 of the periodic table, preferably a Group 4 atom of the periodic table, more preferably titanium, zirconium or hafnium.

Z represents a monovalent or divalent substituent containing a nitrogen atom, oxygen atom, phosphorus atom or sulfur atom bonded to M ′. Specific examples of preferable examples of Z include oxygen (—O—), sulfur (—S—), an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. A thioalkoxy group, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, and a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms.
In the compound represented by [a4] in the above general formula, it may be coordinated to M ′ by a lone pair of a nitrogen atom, oxygen atom, phosphorus atom or sulfur atom in Z.

X ′ and Y ′ are each hydrogen, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and 1 carbon atom. -20, preferably 1-12 phosphorus-containing hydrocarbon groups (specifically, for example, diphenylphosphine groups), or silicon-containing hydrocarbon groups having 1-20 carbon atoms, preferably 1-12 (specifically, Is, for example, a trimethylsilyl group or a bis (trimethylsilyl) methyl group).
X ′ and Y ′ may be the same or different. Of these, a halogen group, a hydrocarbon group (particularly a group having 1 to 8 carbon atoms) and an amino group are preferred.

  Accordingly, among the compounds represented by the general formula [a1], [a2], [a3] or [a4] which are preferable as the component (A-2), particularly preferable ones have the following respective substituents. is there. In the following, when a substituent position is not shown, it is an arbitrary position.

E and E ′: cyclopentadienyl, n-butyl-cyclopentadienyl, dimethyl-cyclopentadienyl, diethyl-cyclopentadienyl, ethyl-n-butyl-cyclopentadienyl, ethyl-methyl-cyclopenta Dienyl, n-butyl-methyl-cyclopentadienyl, indenyl, 2-methyl-indenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-methyl-benzoindene Nyl, 4-hydroazurenyl, 2,4-dimethylhexahydroazurenyl, 2-methyl-4-phenyl-4H-azurenyl, 2-methyl-4-phenyl-hexahydroazurenyl Q ′ and Q ″: ethylene, dimethylsilylene Isopropylidene Z: t-butylamide, phenylamide, Black hexylamide M': a transition metal of Group 4 X'and Y': chlorine, methyl, diethylamino, benzyl

A specific example of this transition metal compound when M ′ is zirconium is as follows.
(A) A compound represented by the general formula [a1], that is, a transition metal compound having no linking group Q ′ and having two conjugated five-membered ring ligands (1) Bis (cyclopentadienyl) zirconium dichloride (2) bis (methylcyclopentadienyl) zirconium dichloride, (3) bis (dimethylcyclopentadienyl) zirconium dichloride, (4) bis (pentamethylcyclopentadienyl) zirconium dichloride, (5) bis (i -Propylcyclopentadienyl) zirconium dichloride, (6) bis (n-butylcyclopentadienyl) zirconium dichloride, (7) bis (t-butylcyclopentadienyl) zirconium dichloride, (8) bis (ethyl-n) -Butyl-cyclopentadienyl) zirconium dichloride, (9) bis (ethyl- Til-cyclopentadienyl) zirconium dichloride, (10) (cyclopentadienyl) (n-butyl-cyclopentadienyl) zirconium dichloride, (11) bis (indenyl) zirconium dichloride, (12) bis (tetrahydroindenyl) ) Zirconium dichloride, (13) bis (2-methylindenyl) zirconium dichloride, (14) bis (fluorenyl) zirconium dichloride, (15) bis (cyclopentadienyl) zirconium monochloride monohydride, (16) bis (cyclo Pentadienyl) methylzirconium monochloride, (17) bis (cyclopentadienyl) zirconium dimethyl, (18) (cyclopentadienyl) (indenyl) zirconium dichloride, (19) (cyclopenta Enyl) (fluorenyl) zirconium dichloride, (20) tris (indenyl) zirconium hydride

(B-1) A compound represented by the general formula [a2], wherein the bonding group Q ′ is an alkylene group (1) Methylenebis (indenyl) zirconium dichloride, (2) Ethylenebis (indenyl) Zirconium dichloride, (3) ethylene bis (indenyl) methyl zirconium monochloride, (4) ethylene bis (indenyl) zirconium diethoxide, (5) ethylene bis (indenyl) zirconium dimethyl, (6) ethylene bis (4,5, 6,7-tetrahydroindenyl) zirconium dichloride, (7) ethylenebis (2-methylindenyl) zirconium dichloride, (8) ethylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclo Pentadienyl) zirconium dichloride, (9) ethylene 1,2-bis (4-indenyl) zirconium dichloride, (10) ethylene-1,2-bis [4- (2,7-dimethylindenyl)] zirconium dichloride, (11) isopropylidenebis (indenyl) Zirconium dichloride, (12) isopropylidene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylpentadienyl) zirconium dichloride, (13) dichloro {1,1′-dimethylmethylenebis [2- Methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium, (14) dichloro {1,1′-ethylenebis [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium, ( 15) Dichloro {1,1′-trimethylenebis [2-methyl-4- (4-biphenylyl) -4H-a Zrenyl]} zirconium, (16) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (17) isopropylidene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) ) Zirconium dichloride, (18) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, (19) isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (20) isopropylidene (2, 5-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride (21) ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (22) ethylene (2,5-dimethyl) (Lucyclopentadienyl) (fluorenyl) zirconium dichloride, (23) diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, (24) cyclohexylidene (cyclopentadienyl) ( Fluorenyl) zirconium dichloride, (25) cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride

(B-2) A compound represented by the general formula [a2], wherein the bonding group Q ′ is a silylene group transition metal compound (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis ( 4,5,6,7-tetrahydroindenyl) zirconium dichloride, (3) dimethylsilylenebis (2-methylindenyl) zirconium dichloride, (4) dimethylsilylenebis (2-methyl-4,5,6,7- Tetrahydroindenyl) zirconium dichloride, (5) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, (6) dimethylsilylene bis (2-methyl-) 4,5-benzoindenyl) zirconium dichloride, (7) dimethylsilylenebi (2-methyl-4-phenylindenyl) zirconium dichloride, (8) dimethylsilylene bis (2-methyl-4,4-dimethyl-4,5,6,7-tetrahydro-4-silenyldenyl) zirconium dichloride, (9 ) Dimethylsilylene bis [4- (2-phenylindenyl)] zirconium dichloride, (10) dimethylsilylene bis [1- (2-methyl-4-phenyl-4H-azurenyl)] zirconium dichloride, (11) dichloro {1 , 1′-dimethylsilylenebis [2-i-propyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium, (12) dichloro {1,1′-dimethylsilylenebis [2-methyl-4- ( 2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium, (13) dichloro { Methylsilylene-1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl] -1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium, (14) phenylmethylsilylenebis ( Indenyl) zirconium dichloride, (15) phenylmethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, (16) phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5 '-Dimethylcyclopentadienyl) zirconium dichloride, (17) phenylmethylsilylene bis (tetramethylcyclopentadienyl) zirconium dichloride, (18) diphenylsilylene bis (indenyl) zirconium dichloride, (19) tetramethyldisilylene bis ( Indeni ) Zirconium dichloride, (20) dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, (21) dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (22) diethyl Silylene (2-methylcyclopentadienyl) (2 ', 7'-di-t-butylfluorenyl) zirconium dichloride, (23) Dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride

(B-3) Transition metal compound represented by the general formula [a2], wherein the bonding group Q ′ is a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum. (1) Dimethylgermanium bis (Indenyl) zirconium dichloride, (2) dimethylgermanium (cyclopentadienyl) (fluorenyl) zirconium dichloride, (3) methylaluminum bis (indenyl) zirconium dichloride, (4) phenylaluminum bis (indenyl) zirconium dichloride, (5) Phenylphosphinobis (indenyl) zirconium dichloride, (6) ethyl foranobis (indenyl) zirconium dichloride, (7) phenylaminobis (indenyl) zirconium dichloride, (8) phenylamino (cyclopentadi) Yl) (fluorenyl) zirconium dichloride, (9) Dichloro {1,1'-dimethyl-gel Mi alkylene bis [2-methyl-4- (4-biphenylyl) -4H- azulenyl]} zirconium

(C) A compound represented by the general formula [a3], that is, a transition metal compound having no conjugated group Q ′ and one conjugated five-membered ring ligand (1) pentamethylcyclopentadienyl-bis ( Phenyl) aminozirconium dichloride, (2) indenyl-bis (phenyl) amidozirconium dichloride, (3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride, (4) pentamethylcyclopentadienylphenoxyzirconium dichloride, (5) cyclopentadienyl zirconium trichloride, (6) pentamethylcyclopentadienyl zirconium trichloride, (7) cyclopentadienyl zirconium benzyl dichloride, (8) cyclopentadienyl zirconium dichlorohydride, (9) cyclo Emissions Taj enyl zirconium triethoxide

(D) A compound represented by the general formula [a4], that is, a transition metal compound having one conjugated five-membered ring ligand bridged by a binding group Q ″. Amidozirconium dichloride, (2) dimethylsilylene (tetramethylcyclopentadienyl) t-butylamidozirconium dichloride, (3) dimethylsilylene (indenyl) cyclohexylamidezirconium dichloride, (4) dimethylsilylene (tetrahydroindenyl) decylamidozirconium Dichloride, (5) Dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl) amino) zirconium dichloride, (6) Dimethylgermane (tetramethylcyclopentadienyl) (phenyl) aminozirconium dichloride

Moreover, the compound which substituted the chlorine atom of the compound of said (i)-(d) by the bromine atom, the iodine atom, the hydrogen atom, the methyl group, phenyl, etc. is illustrated as a specific compound.
Furthermore, in the present invention, a compound in which the central metal of the zirconium compound exemplified in the above (a) to (d) is replaced with zirconium, titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, scandium, yttrium, or the like. Further, a compound in which the chlorine atom is replaced with a bromine atom, an iodine atom, a hydrogen atom, a methyl group, phenyl or the like is also exemplified as a specific compound.
In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including.

  Furthermore, as a special example of a metallocene compound, a ligand containing one or more elements other than carbon in a 5-membered ring or a 6-membered ring disclosed in JP-A-7-188335 or JACS, 1996, 118, p2291 Transition metal compounds having can also be used.

  Of the transition metal compounds exemplified above, preferred are a zirconium compound, a hafnium compound, a titanium compound, a vanadium compound and a chromium compound, and more preferred are a zirconium compound, a hafnium compound and a titanium compound.

[Iii] Explanation of (A-3) The component (A-3) is a bisamide or bisalkoxide compound of a transition metal of Groups 4 to 6 of the periodic table. It is a compound represented by this.
(R ¹ R ² N) _m ML _nm [a5]
(R ³ O) _m ML _nm [a6]
(In the formulas [a5] and [a6], M is a group 4-6 transition metal in the periodic table, and R ¹ , R ² , and R ³ are each independently a monovalent hydrocarbon group, A monovalent hydrocarbon group having an optional substituent, a divalent hydrocarbon group, and a divalent hydrocarbon group having an optional substituent, wherein R ¹ and R ² that substitute the same nitrogen atom are nitrogen atoms Rings containing atoms may be formed, each R ¹ , R ² , R ³ on different nitrogen or oxygen atoms may be linked together, n is the valence of M, and m is L is an integer of 1 to n, L is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, amino A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (specifically, for example, a diphenylphosphine group), or Is a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbons (specifically, for example, a trimethylsilyl group or a bis (trimethylsilyl) methyl group). Of these, a halogen group, a hydrocarbon group (particularly a group having 1 to 8 carbon atoms) and an amino group are preferable.

Among the components (A-3), preferred examples of the group 4 metal compound of the periodic table include bisamide compounds having an NN type ligand as shown in the following general formula [a7]. .

（式の[ａ７]中、Ｒ^５は、炭素数１〜２０の炭化水素基、炭素数１〜２０の、ハロゲン原子、酸素含有炭化水素基、又はケイ素含有炭化水素基を表し、Ｕは、２つのＮ原子を架橋する結合性基であって、炭素数１〜２０の炭化水素基、又は炭素数１〜４０の、ケイ素、窒素、酸素若しくはイオウ含有炭化水素基を表し、Ｍ´は周期律表第４族遷移金属を表し、Ｘ及びＹは、水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、又は炭素数１〜２０の、酸素、窒素、ケイ素若しくはリン含有炭化水素基を表す。）

(In the formula [a7], R ⁵ represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an oxygen-containing hydrocarbon group, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and U is A bonding group that bridges two N atoms, and represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 40 carbon atoms, silicon, nitrogen, oxygen, or sulfur, and M ′ represents a period Represents a Group 4 transition metal in the table, and X and Y are a hydrogen atom, a halogen atom, 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. Represents.)

Of these, R ⁵ is preferably t-butyl, trimethylsilyl, 2,6-diisopropylphenyl, or 2,4,6-trimethylphenyl.
U is preferably a propenyl, 2-phenylpropenyl, or 2,2-diphenylpropenyl group.
M ′ is preferably any one of Ti, Zr, and Hf.
X and Y are preferably any one of a chlorine atom, a methyl group, a benzyl group, and a dimethylamide group.
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.

  Among the components (A-3), another preferable example of the Group 4 metal compound of the periodic table is a bisamidinate compound having an NN type ligand as shown in the following general formula [a8]. Can do.

(In the formula [a8], R ⁶ and R ⁷ represent a hydrocarbon group having 1 to 20 carbon atoms, a halogen, oxygen or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, and M ′ represents a periodic rule. Table 4 represents a transition metal, and X and Y represent a hydrogen atom, a halogen atom, 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. .)

Of these, R ⁶ is preferably t-butyl, cyclohexyl, trimethylsilyl, 2,6-diisopropylphenyl, or 2,4,6-trimethylphenyl. R ⁷ is preferably any one of methyl, isopropyl, phenyl and paratolyl. M ′ is preferably any one of Ti, Zr, and Hf. X and Y are preferably a chlorine atom, a methyl group, a benzyl group, or a dimethylamide group.

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) are preferred.
Examples of these compounds are disclosed in Organometallics, 1998, p3155.

  Among the components (A-3), another preferred example of the Group 4 metal compound of the periodic table has an OO-type ligand as shown in the following general formulas [a9] and [a10]. Bisphenoxy compounds can be mentioned.

（式の［ａ９］及び［ａ１０］中、Ｍは、周期表第４族遷移金属を表し、Ｘはメチレン基、エチリデン、プロピリデンなどのアルキリデン基又は硫黄原子を表し、Ｒ¹ 及びＲ² は、同一又は異なっていてもよい水素、ハロゲン、トリメチルシリル、トリエチルシリル、トリフェニルシリル基などの珪素含有基、メチル、エチル、プロピル、ブチル、イソブチル、ペンチル、イソペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、フェニル、トリル、クロロメチル、クロロエチルなどのハロゲン置換基を有していてもよい炭素数が１〜２０の炭化水素基、メトキシ、エトキシ、プロポキシ、ブトキシ基などのアルコキシ基、フェノキシ、メチルフェノキシ、ペンタメチルフェノキシ基などのアリールオキシ基、アミド、ジメチルアミド、ビス（トリメチルシリル）アミド基などのアミド基、メチルチオアルコキシ、フェニルチオアルコキシ基などのチオアルコキシ基を表し、Ｒ³ はＭに配位する中性の配位子であり、Ｒ^4-は、上記一般式［２］中の金属カチオンを安定化させることのできる対アニオンを示す。）

(In the formulas [a9] and [a10], M represents a Group 4 transition metal in the periodic table, X represents an alkylidene group such as a methylene group, ethylidene, or propylidene, or a sulfur atom, and R ¹ and R ² are May be the same or different hydrogen, halogen, trimethylsilyl, triethylsilyl, silicon-containing group such as triphenylsilyl group, methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, C1-C20 hydrocarbon group optionally having halogen substituents such as phenyl, tolyl, chloromethyl, chloroethyl, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy groups, phenoxy, methylphenoxy, penta Aryloxy group such as methylphenoxy group, amide, dimethylamide Represents an amide group such as bis (trimethylsilyl) amide group, a thioalkoxy group such as methylthioalkoxy and phenylthioalkoxy group, R ³ is a neutral ligand coordinated to M, and R ⁴⁻ represents the above-mentioned A counter anion capable of stabilizing the metal cation in the general formula [2] is shown.)

R ¹ may be bonded to each other to form a ring. Specific examples include alkylene groups such as methylene groups and ethylene groups, ethylidene groups, propylidene groups, isopropylidene groups, phenylmethylidene groups, diphenylmethylidene groups, and the like, dimethylsilylene groups, diethylsilylene groups, and dipropylene. Silicon-containing groups such as silylene group, diisopropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methylisopropylsilylene group, methyl-t-butylsilylene group, dimethylgermylene group, diethylgermylene group, etc. Examples include germanium-containing groups, amines, and phosphines.

Furthermore, in the formula [a9], R ² may be bonded to each other to form a bidentate ligand. Specific examples of such R ² include —OCH ₂ O—. , -O CH ₂ CH ₂ O- , -O (O- C ₆ H ₄₎ O- Etc. R ³ is a neutral coordination coordinated to M, such as ethers such as tetrahydrofuran and diethyl ether, nitriles such as acetonitrile, amides such as dimethylformamide, phosphines such as trimethylphosphine, and amines such as trimethylamine. And R ⁴⁻ stabilizes a metal cation in the above general formula [a10] such as tetraphenylborate, tetra (p-tolyl) borate, carbadodecaborate, dicarboundeborate, hexafluorophosphate, etc. A counter anion capable of forming

  Specific examples of the compound represented by the formula [a9] include 2,2′-methylene-4,4 ′, 6,6′-tetra-t-butyldiphenoxytitanium dichloride, 2,2′-methylene- 4,4'-dimethyl-6,6'-di-t-butyldiphenoxytitanium dichloride, 2,2'-isobutylidene-4,4 ', 6,6'-tetramethyldiphenoxytitanium dichloride, 2,2' -Thio-4,4'-dimethyl-6,6'-di-t-butyldiphenoxytitanium dichloride, 2,2'-thio-4,4'-dimethyl-6,6'-di-t-butyldi Phenoxytitanium dichloride, 2,2'-isobutylidene-4,4 ', 6,6'-tetramethyldiphenoxytitanium dichloride, 2,2'-methylene-4,4', 6,6'-tetra t-butyldiphenoxytitanium dimethyl, 2,2'-methylene-4,4 ', 6,6'-tetra-t-butyldiphenoxytitanium dimethoxide, 2,2'-methylene-4,4', 6 , 6'-tetra-t-butyldiphenoxytitanium bis (dimethylamide), 2,2'-methylene-4,4 ', 6,6'-tetra-t-butyldiphenoxytitanium bis (methylthiolate), 2 2,2'-methylene-4,4 ', 6,6'-tetra-t-butyldiphenoxytitanium-1,2-benzenedioxide and the like.

Specific examples of the compound represented by the formula [a10] include 2,2′-methylene-4,4 ′, 6,6′-tetra-t-butyldiphenoxytitanium chloride tetraphenylborate, 2,2 '-Methylene-4,4'-dimethyl-6,6'-di-t-butyldiphenoxytitanium chloride tetraphenylborate, 2,2'-isobutylidene-4,4', 6,6'-tetramethyldiphenoxy Titanium chloride tetraphenylborate, 2,2'-thio-4,4'-dimethyl-6,6'-di-t-butyldiphenoxytitanium chloride tetraphenylborate, 2,2'-thio-4,4'- Dimethyl-6,6'-di-t-butyldiphenoxytitanium chloride tetraphenylborate, 2,2'-isobutylidene-4,4 '6,6'-tetramethyldiphenoxytitanium chloride tetraphenylborate, 2,2'-methylene-4,4 ', 6,6'-tetra-t-butyldiphenoxytitaniummethyltetraphenylborate, 2,2'- Methylene-4,4 ', 6,6'-tetra-t-butyldiphenoxytitanium methoxide tetraphenylborate, 2,2'-methylene-4,4', 6,6'-tetra-t-butyldiphenoxy Examples thereof include titanium dimethylamide tetraphenylborate, 2,2′-methylene-4,4 ′, 6,6′-tetra-t-butylbushenoxytitanium methylthiolate tetraphenylborate, and tetrahydrofuran complexes of these compounds. It is done.
In addition, the same compound as the above is mentioned also about a zirconium compound and a hafnium compound. Further, a mixture of these compounds may be used.

[Iv] Explanation of (A-4) Examples of bisimide compounds of Group 8-10 transition metals of the periodic table include NN type coordination as shown in the following general formula [a11] or [a12] A bisimino compound having a child can be mentioned.

（式の[ａ１１]、[ａ１２]中、Ｒ^１１及びＲ^１３は、炭素数１〜２０の炭化水素基、又は炭素数１〜２０の、ハロゲン、酸素、窒素、ケイ素若しくはイオウ含有炭化水素を表し、Ｒ^１２及びＲ^１４は、水素原子、炭素数１〜２０の炭化水素基、又は炭素数１〜２０のハロゲン、酸素、窒素若しくはケイ素含有炭化水素を表す。また、２つのＲ^１４は互いに結合し環状構造を形成していてもよい。Ｍ´は、８〜１０の遷移金属を表す。、Ｘ及びＹは、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、又は炭素数１〜２０の、酸素、窒素、ケイ素若しくはリン含有炭化水素基を表す。）

(In the formulas [a11] and [a12], R ¹¹ and R ¹³ represent a hydrocarbon group having 1 to 20 carbon atoms, or a halogen, oxygen, nitrogen, silicon or sulfur-containing hydrocarbon having 1 to 20 carbon atoms. R ¹² and R ¹⁴ represent a hydrogen atom, 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 two R ¹⁴ are M ′ represents a transition metal having 8 to 10. X and Y are a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. Represents an oxygen, nitrogen, silicon or phosphorus-containing hydrocarbon group of ˜20.)

Of these, R ¹¹ is preferably a paratolyl group, a 2,6-dimethylphenyl group, a 2,6-diisopropylphenyl group, or a 2,4,6-trimethylphenyl group. R ¹² is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group. R ¹³ is preferably a 2,6-dimethylphenyl group, a 2-t-butylphenyl group, or a 2,6-diisopropylphenyl group. R ¹⁴ is preferably a hydrogen atom or a methyl group. Further, examples of those two ^{R 14} are bonded to each other _{1,8-naphthalene-diyl,} it is preferable -SCH 2 _CH 2 S-, or -OCH ₂ CH ₂ O-in which. M ′ is preferably Fe, Co, Ni, or Pd. X and Y are preferably a chlorine atom, a bromine atom, a methyl group, or a benzyl group.

More specifically, (R ¹¹ , R ¹² , M ′, X, Y) = (2,6-dimethylphenyl, hydrogen atom, Fe, Cl, Cl), (2,6-dimethylphenyl, hydrogen atom, Co, Cl, Cl), (2,4,6-trimethylphenyl, hydrogen atom, Fe, Cl, Cl), (2,6-diisopropylphenyl, hydrogen atom, Fe, Cl, Cl), (p-tolyl, A combination of (methyl, Fe, Cl, Cl), (2,6-dimethylphenyl, methyl, Fe, Cl, Cl), or (2,6-dimethylpyrrolyl, hydrogen atom, Fe, Cl, Cl) is preferable. .
Further, (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 atoms, Ni, Br, Br) or (2,6-diisopropylphenyl, hydrogen atoms, Pd, Br, Br).
These compounds are disclosed in JACS, 1995, 117, p6414, WO 96/23010, Chemical Communication, 1998, p849, JACS, 1998, 120, p4049, WO 98/27124.

[V] Explanation of (A-5) Examples of phenoxyimine compounds of Group 3-11 transition metals of the periodic table have an N—O type ligand represented by the following general formula [a13]. Mention may be made of salicylaldiminato compounds.

（式の[ａ１３]中、Ｒ^８及びＲ^９は、炭素数１〜２０の炭化水素基、又は炭素数１〜２０の、ハロゲン、酸素、窒素、ケイ素若しくはイオウ含有炭化水素を表し、Ｒ^１０は、水素原子、炭素数１〜２０の炭化水素基、又は炭素数１〜２０のハロゲン、酸素、窒素若しくはケイ素含有炭化水素を表す。Ｍ´は、周期律表３〜１１族遷移金属を表し、Ｘ及びＹは、水素原子、ハロゲン、炭素数１〜２０の炭化水素基、又は炭素数１〜２０の、酸素、窒素、ケイ素若しくはリン含有炭化水素基を表す。ｐは１又は２を表す。）

(In the formula [a13], R ⁸ and R ⁹ represent 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, and R ¹⁰ Represents a hydrogen atom, 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 M ′ represents a transition metal of group 3 to 11 in the periodic table. , 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, and p represents 1 or 2. .)

Of these, R ⁸ is preferably a hexyl group, a cyclohexyl group, a phenyl group, a tolyl group, a pentafluorophenyl group, a paramethoxyphenyl group, or a 2,4-dimethylpyrrolyl group. R ⁹ is preferably a t-butyl or adamantyl group. R ¹⁰ is preferably a hydrogen atom, a methyl group, an ethyl group, or a methoxy group. M ′ is preferably Ti, Zr, Hf, V, Cr, Fe, Co, Ni, or Pd, more preferably Ti, Zr, Hf, or V, and particularly preferably Ti, Zr, or Hf. X and Y are preferably a chlorine atom, a methyl group, a benzyl group, or a dimethylamide group.

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.
A plurality of (A-1) to (A-5) can be used at the same time if necessary.

(2) Component (B) The olefin polymerization catalyst of the present invention uses a compound obtained by contacting the following component (B-1) and component (B-2) as the component (B) of the catalyst component. .
Component (B-1): an ion-exchange layered compound in which transition metal ions of Group 3 to 11 of the periodic table or the transition metal complex ions are intercalated.
Component (B-2): a compound having a molecular weight of 1,000 or less, having at least two Group 15 or Group 16 elements having an unshared electron pair in the molecule, A group element is an organic compound linked via 1 to 6 group 14 elements.

[I] Explanation of the component (B-1) The component (B-1) is a transition metal ion of Group 3 to 11 or a transition metal complex ion of the periodic table, preferably Ti, Zr, Hf, V, Nb. , Cr, Fe, Co, Ni, Pd at least one transition metal ion or the transition metal complex ion, more preferably at least one transition of Ti, Zr, V, Cr, Fe, Co, Ni An ion-exchangeable layered compound in which they are intercalated with a metal ion or a transition metal complex ion is used.

  In general, an ion-exchange layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force, and examples thereof include most clays. Clay is usually composed of a clay mineral as a main component. These clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and may be artificial synthetic products. For more information on clay and clay minerals, see Haruo Shiramizu's “Clay Mineralogy-Basics of Clay Science” (published in Asakura Shoten in 1988) and “The Clay Handbook Second Edition” (published by Gihodo Publishing in 1987) edited by the Japan Clay Society. There is a description.

Specific examples of clay and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, serpentine such as chrysotile, lizardite and antigolite. Tribes, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and other smectites, vermiculite minerals such as vermiculite, illite, sericite, mica minerals such as sea green stone, attapulgite, sepiolite, palygorskite, bentonite, xylem Examples include clay, gyrome clay, hysingelite, pyrophyllite, and chlorite. These may form a mixed layer.
Of the specific examples of the ion-exchangeable layered compound, preferably, kaolin groups such as dickite, nacrite, kaolinite, anorcite, halloysite groups such as metahalloysite, halloysite, serpentine groups such as chrysotile, lizardite, and antigolite, Examples thereof include smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, and hectorite, vermiculite minerals such as vermiculite, and mica minerals such as illite, sericite, and sea chlorite. Particularly preferred are montmorillonite, sauconite, and beidellite. , Smectites such as nontronite, saponite and hectorite. Moreover, synthetic hectorite, synthetic mica (mica), synthetic saponite, etc. are preferably mentioned as artificial synthetic compounds.

Examples of other ion-exchangeable layered compounds include ionic crystalline compounds having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl ₂ type, and a CdI ₂ type.
Specific examples thereof include α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) _2. , Α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ ) ₂ · H ₂ O, crystalline acidic salts of polyvalent metals such as niobates (see “Akashi Yamanaka Catalyst 32, 1 (1990), page 9”).

  These ion-exchangeable layered compounds may be used as they are without any special treatment, or chemicals such as ball mill or jet mill grinding, sieving or classification by cyclone, classification, acid treatment, alkali treatment, salt treatment, etc. You may use after performing a process, a granulation process, drying, etc. Moreover, you may use individually or in mixture of 2 or more types.

The ion-exchangeable layered compound of the present invention includes the above-mentioned general ion-exchangeable layered compound, a Group 3-11 transition metal, preferably Ti, Zr, Hf, V, Nb, Cr, Fe, Co. , Ni, Pd at least one transition metal ion or the transition metal complex ion, more preferably at least one of Ti, Zr, V, Cr, Fe, Co, Ni, or the transition metal ion Intercalated complex ions are used.
A well-known intercalating method is a salt treatment, which is carried out by substituting an exchangeable cation between layers with a transition metal ion or a transition metal complex ion using ion exchange.
In the present invention, 1% or more, preferably 10% or more, more preferably 30% or more, most preferably 50% or more of the exchangeable ions contained in the ion-exchangeable layered compound before being treated with salts. It is necessary to perform ion exchange with the transition metal ion or the transition metal complex ion.

For the purpose of such ion exchange, the salts used in the salt treatment containing the transition metal ion or the transition metal complex ion of the present invention are Ti, Zr, Hf, V, Nb, Cr, Fe, Co, At least one of Ni and Pd, more preferably, at least one of Ti, Zr, V, Cr, Fe, Co, and Ni, particularly preferably Ti, Zr, Cr, and Fe. It is a compound containing ions.
Preferably, it is selected from the group consisting of a cation containing at least one element of Ti, Zr, Hf, V, Nb, Cr, Fe, Co, Ni, and Pd, a halogen atom, an inorganic acid, and an organic acid. A compound comprising at least one anion, and more preferably, a cation containing at least one element of Ti, Zr, V, Cr, Fe, Co, and Ni, and Cl, Br, I, F, S, O, 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, the group consisting of _{OOCCH 2 CH 3, OOCH (C} 2 H 5) C 4 H 9, C 2 H 4 O 4 and C ₆ H ₅ O ₇ Consisting of at least one anion selected from A compound.

More specifically, the salts include Ti (OOCCH ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO ₄ ) ₂ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , TiCl ₃ · AlCl ₃ , Zr (OOCCH ₃ ) ₄ , Zr (CH ₃ COCHCOCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ , Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrBr ₄ , ZrI ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (ClO ₄ ) ₂ , ZrO (SO ₄ ), Hf (OOCCH ₃ ) ₄ , Hf (CO ₃ ) ₂ , Hf (NO ₃ ) ₄ , Hf ( SO ₄ ) ₂ , HfOCl ₂ , HfF ₄ , HfCl ₄ , HfBr ₄ , HfI ₄ , V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl ₃ , VCl ₃ , VCl ₄ , VBr ₃ , Nb (OOCCH (C ₂ H _{5) C 4 9) 4, NbF 5, NbI} 5, NbCl 5, NbBr 5, Cr (CH 3 COCHCOCH 3) 3, Cr (OOCH) 2 OH, Cr (NO 3) 3, Cr (ClO 4) 3, CrPO 4, Cr ₂ (SO ₄ ) ₃ , CrO ₂ Cl ₂ , CrF ₃ , CrCl ₃ , CrBr ₃ , CrI ₃ , Fe (OOCCH ₃ ) ₂ , Fe (CH ₃ COCHCOCH ₃ ) ₃ , FeCO ₃ , Fe (NO ₃ ) ₃ , Fe (ClO ₄ ) ₃ , FePO ₄ , FeSO ₄ , Fe ₂ (SO ₄ ) ₃ , FeF ₃ , FeCl ₃ , FeBr ₃ , FeI ₂ , FeC ₆ H ₅ O ₇ , Co (OOCCH ₃ ) ₂ , Co (CH ₃ COCHCOCH ₃ ) ₃ , CoCO ₃ , Co (NO ₃ ) ₂ , CoC ₂ O ₄ , Co (ClO ₄ ) ₂ , Co ₃ (PO ₄ ) ₂ , CoSO ₄ , CoF ₂ , CoCl ₂ , CoBr ₂ , CoI ₂ , NiCO ₃ , Ni (NO ₃ ) ₂ , NiC ₂ O ₄ , Ni (ClO ₄ ) ₂ , NiSO ₄ , NiCl ₂ , NiBr ₂ , Pd (C ₅ H ₇ O ₂ ) ₂ , PdCl ₂ , PdBr ₂ , PdI ₂ , Pd (CN) ₂ , Pd (NO ₃ ) ₂ , PdSO ₄ , Pd (O ₂ CCF ₃ ) _{2 and the} like.

As salts used in the salt treatment of the transition metal ion or the transition metal complex ion of the present invention for the purpose of ion exchange, further, Ti, Zr, Hf, V, Nb, Cr, Fe, Co, Ni, Pd Contains at least one element, NH ₃ , NO ₂ , CN And so-called complex salt compounds containing CO, H ₂ O, OH, halogen atoms, ether compounds and the like.
Specifically, TiCl ₄ (NH ₃ ) ₂ , ZrCl ₄ · 2C ₄ H ₈ O, ZrO (OH) _0.8 (SO ₄ ) _0.6 · XH ₂ O, Hf (OC ₃ H ₇ ) ₄ · _{C 3 H 7 OH, VCl 3} (C 4 H 8 O) 2-3, Cr 3 (OH) 2 (OOCCH 3) 7, [Co (NH 3) 6] Cl 3, CoCr 2 O 4, CoMoO 4, CoWO ₄ , Co (CO) ₃ (NO), [Co (NH ₃ ) ₆ ] Cl ₃ , [(C ₆ H ₅ ) ₃ P] ₂ NiBr ₂ , [(C ₆ H ₅ ) ₃ P] ₂ NiCl ₂ , [Ni (NH ₃ ) ₆ ] Cl ₂ , [Ni (NH ₃ ) ₆ ] I ₂ , NiCO ₃ .2Ni (OH) ₂ , Pd (NH ₃ ) ₂ (NO ₂ ) ₂ , Pd (NH ₃ ) ₄ (NO ₃ ) ₂ , PdCl ₂ (CH ₃ CN) ₂ , PdCl ₂ (C ₆ H ₅ CN) ₂ , Pd (NH ₃ ) ₂ Cl _{2 and the} like.
In addition, as a transition metal ion used by salt processing or the salt containing the said transition metal complex ion, a transition metal salt is preferable among a transition metal salt and a transition metal complex salt.

At least one of Ti, Zr, Hf, V, Nb, Cr, Fe, Co, Ni, and Pd is applied to the ion-exchangeable layered compound by the above-described salt treatment containing the transition metal ion or the transition metal complex ion. Confirmation that the transition metal ion or the transition metal complex ion is intercalated can be usually carried out by observing changes in the elemental composition and the X-ray diffraction peak before and after the salt treatment.
Elemental analysis, in particular, observes a decrease in the content of interlayer ionic elements in the raw material and an increase in the content of transition metals after salt treatment. Further, among the X-ray diffraction peaks, in particular, it is performed by observing whether or not the X-ray diffraction peak indicating the bottom surface interval (see FIG. 1) of the layered compound is changed before and after the salt treatment.

In addition to the salt treatment containing the transition metal ion or the transition metal complex ion, the acid treatment can be performed sequentially or in combination. Such acid treatment not only removes impurities on the surface, but also elutes part or all of cations such as Al, Fe, Mg, etc. in the crystal structure, and promotes intercalation of transition metal ions or transition metal complex ions. be able to. The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid.
Two or more kinds of salts and acids containing the transition metal ion or the transition metal complex ion used in the treatment may be used. When combining salt treatment and acid treatment, there are a method of performing salt treatment after acid treatment, a method of performing weak acid treatment after salt treatment, and a method of simultaneously performing salt treatment and acid treatment. is there.

  The treatment conditions with salts and acids are not particularly limited, but usually the salt and acid concentrations are selected from 0.1 to 30% by weight, the treatment temperature is from room temperature to boiling point, and the treatment time is from 5 minutes to 24 hours. Thus, it is preferable to carry out the reaction under the condition that at least a part of the substance (cation or the like) constituting the ion-exchangeable layered compound is eluted. The salts and acids can be used in a mixture with an organic solvent such as toluene, n-heptane or ethanol, or can be used without a solvent if the salts are liquid at the treatment temperature, but are preferably used as an aqueous solution. It is done. Some types of salt show similar effects to acid treatment.

In the present invention, the salt treatment and acid treatment as necessary are performed, but shape control may be performed by pulverization or granulation before treatment, between treatments, and after treatment. Further, other chemical treatments such as alkali treatment and organic matter treatment may be used in combination.
As the component (B-1) thus obtained, those having a pore volume with a radius of 20 mm or more measured by a mercury intrusion method are 0.1 cc / g or more, particularly 0.3 to 5 cc / g. . The average particle size of the component (B-1) is preferably 5 μm or more and 100 μm or less. When there are many fine particles of less than 5 μm, aggregation of the polymers and adhesion to the reactor 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 exceeding 100 μm are not preferable because problems such as clogging (for example, during catalyst feeding) easily occur. As long as the particles satisfy these conditions, natural products or commercially available products may be used as they are, or the particle size may be controlled by classification or classification.

The granulation method is not particularly limited as long as it satisfies the above particle size and shape, but the spray granulation method is preferable. The particle strength can be controlled in the granulation process. In order to obtain a preferred range of crushing strength, it is preferable that the ion-exchangeable layered compound particles of the present invention are refined and then re-particulated. The ion-exchangeable layered compound may be refined by any method. As a method for miniaturization, either dry pulverization or wet pulverization is possible, but wet pulverization is preferable. Wet pulverization refers to a pulverization method using water as a dispersion medium and utilizing the swellability of an ion-exchangeable layered compound. For example, a forced stirring method using polytron or the like, a dyno mill, a pearl mill or the like can be exemplified. The particle size before granulation and the volume fraction of particles less than 1 μm are 0.01 to 5 μm in average particle size and 10% or more of the particle fraction in less than 1 μm, preferably the average particle size is 0.1 to 0.1 μm. The particle fraction of 3 μm and less than 1 μm is 40% or more. As a dispersion for spray granulation, water is usually used.
The shape of the granulated particles is preferably spherical. The concentration of the ion-exchangeable layered compound in the spray granulation raw material slurry liquid from which spherical particles are obtained depends on the slurry viscosity, but is 0.1 to 50%, preferably 1 to 30%, particularly preferably 2 to 20%. It is. The temperature at the inlet of the hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C when water is taken as an example. In order to produce the ion-exchangeable layered compound having a specific pore distribution of the present invention, it is preferable to perform granulation before chemical treatment.

[Ii] Explanation of Component (B-2) Component (B-2) is a compound having a molecular weight of 1,000 or less, and at least a Group 15 or Group 16 element having an unshared electron pair in the molecule. 2 elements, and the Group 15 or Group 16 elements are linked via 1 to 6 Group 14 elements.
Examples of the component (B-2) include organic compounds having a molecular weight of 1,000 or less represented by the following general formula [b2].
Y- (X) n-Y ′ [b2]
(In the formula [b2], X represents an element belonging to Group 14 of the Periodic Table, and when there are a plurality of elements, X may be the same or different, and is further composed of hydrogen or any element of Groups 13-17. Y and Y ′ are elements of Group 15 or Group 16 of the Periodic Table, which may be the same or different, each having one or more pairs of unshared electrons. Furthermore, it can have an arbitrary substituent composed of hydrogen or any element of Groups 13 to 17. n is an integer of 1 to 6.
Formula [b2] is an example of a compound having two Group 15 and Group 16 elements in the molecule, but three or more Group 15 and Group 16 elements may be present in the molecule. Good. In addition, (B-2) component needs to have the ability to coordinate to the transition metal atom in (B-1) component, therefore, (B-2) non-covalent in the molecule | numerator of component Among the electron pairs, at least two unshared electron pairs can take a three-dimensional structure capable of coordinating with the transition metal at the same time.

  A preferred example of the component (B-2) is a coordination compound having multidentate coordination ability as shown in the following general formulas (B-2a) to (B-2g). Hereinafter, the compounds (B-2a) to (B-2g) will be specifically described.

(I) (B-2a)
It is an organic compound having a molecular weight of 1,000 or less, represented by the following general formula [b-2a] and having two or more Group 15-16 elements of the Periodic Table.
AQA '[b-2a]
(In the formula [b-2a], A and A ′ are each a hydrocarbon compound-binding group having 1 to 30 carbon atoms having at least one element selected from Groups 15 to 16 of the periodic table (in the same compound). A and A ′ may be the same or different), Q is a divalent cyclic compound having a pyridine skeleton, a pyrazine skeleton, a bipyridine skeleton, a morpholine skeleton, a pyrrole skeleton, a furyl skeleton, a thiofuryl skeleton, An amine skeleton, a phosphine skeleton, an ether skeleton, a thioether skeleton, a hexenylene skeleton, a hexynylene skeleton, a heptadienylene skeleton, an ethenylpropane skeleton, a diethylbenzene skeleton, and at least one pair of unshared electron pairs or π bonds, and A and A ′ Is a binding group that links at any position.)
More specifically, the organic compound used as the component (B-2a) includes at least one group 15-16 element in the periodic table in which A and A ′ each independently have a skeleton represented by the following structural formula. It is an organic compound containing a single component.

  (B-2a) is a skeleton in which Q is represented by the following structural formula, wherein X is an independent hydrogen, an alkyl group having 1 to 20 carbon atoms, a halogen or silicon containing 1 to 20 carbon atoms. An alkyl group, an alkenyl group having 1 to 20 carbon atoms, a halogen or silicon containing alkenyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms containing halogen or silicon. It is a coordinating compound characterized by these.

  More specifically, A and A ′ are each composed of a binding group represented by the following structure.

  Further, it is a coordinating compound characterized in that Q is an organic compound composed of any of the bonding groups represented by the following structures.

  Furthermore, (B-2a) is preferably a coordinating compound characterized by being one of the following organic compounds.

(B) (B-2b)
It is an organic compound having a molecular weight of 1,000 or less having two nitrogen elements, selected from the following general formulas [I] to [IV].

［式中、Ｒ¹、Ｒ⁴、Ｒ¹⁰及びＲ¹⁵は、それぞれ独立に炭素数３〜２０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基、又は炭素数８〜２０のアラルキル基を示し、これらの基において、イミノ基の窒素原子に結合する炭素原子は少なくとも２個の炭素原子と結合している。Ｒ²、Ｒ³、Ｒ⁵〜Ｒ⁹、Ｒ¹¹〜Ｒ¹⁴、及びＲ¹⁶〜Ｒ²⁵は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、置換されていてもよい炭素数６〜２０のアリール基、又は炭素数７〜２０のアラルキル基を示す。］

[Wherein R ¹ , R ⁴ , R ¹⁰ and R ¹⁵ are each independently an alkyl group having 3 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, or 8 to 20 carbon atoms. In these groups, the carbon atom bonded to the nitrogen atom of the imino group is bonded to at least two carbon atoms. R ² , R ³ , R ^{5 to} R ⁹ , R ^{11 to} R ¹⁴ , and R ^{16 to} R ²⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number 6 -20 aryl group or C7-20 aralkyl group is shown. ]

Specifically, examples of the alkyl group having 3 to 20 carbon atoms of R ¹ , R ⁴ , R ¹⁰ and R ¹⁵ include isopropyl group, isopropenyl group, n-butyl group, s-butyl group and t-butyl. Group, 1-methylbutyl group, t-pentyl group, 1-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, cyclohexyl group, cyclohexenyl group, 1 -Methylhexyl group, 1-ethylpentyl group, cycloheptyl group, methylcyclohexyl group, ethylcyclohexyl group, dimethylcyclohexyl group, propylcyclohexyl group, methylethylcyclohexyl group, 1-methylheptyl group, etc. are preferable, They are i-propyl group, s-butyl group, t-butyl group, and cyclohexyl group.

  Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, o-propylphenyl group, and m-propyl. Phenyl group, p-propylphenyl group, butylphenyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 2,4,6-trimethylphenyl group 2,3-diisopropylphenyl group, 2,4-diisopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, α-naphthyl group, β-naphthyl group, diphenylmethyl group, anthryl group, Examples thereof include a phenanthryl group, a 5,6,7,8-tetrahydronaphthyl group, a biphenyl group, and the like, preferably a phenyl group, an o-tolyl group, o -Propylphenyl group, 2,4-xylyl group, 2,6-xylyl group, 2,4,6-trimethylphenyl group, 2,4-diisopropylphenyl group, 2,6-diisopropylphenyl group.

  Examples of the aryl group of the aralkyl group having 8 to 20 carbon atoms include a phenyl group and a naphthyl group. Examples of the group to which the aryl group is bonded include an alkyl group and an alkenyl group. For example, 1-phenyl-ethyl Group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group , (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2-ethylphenyl) ) Methyl group, (2-propylphenyl) methyl group, (2-butylphenyl) methyl group, (2,6-dipropylphenyl) methyl group, naphthylmethyl Group, 1-methyl-1-phenyl-ethyl group, 1- (2-methyl-phenyl) -isopropyl group, etc., preferably 1-phenyl-ethyl group, (2-methylphenyl) methyl group, ( 2,4-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (2,6-dipropylphenyl) methyl group, 1-phenyl-isopropyl group It is.

R ² , R ³ , R ^{5 to} R ⁹ , R ^{11 to} R ¹⁴ and R ^{16 to} R ²⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 6 to 6 carbon atoms. A 20 aryl group or a C7-20 aralkyl group is shown.
Specifically, examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, isopropyl group, isopropenyl group, n-butyl group, s-butyl group, t-butyl group, and 1-methylbutyl group. T-pentyl group, 1-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, cyclohexyl group, cyclohexenyl group, 1-methylhexyl group, 1 -Ethylpentyl group, cycloheptyl group, methylcyclohexyl group, ethylcyclohexyl group, dimethylcyclohexyl group, propylcyclohexyl group, methylethylcyclohexyl group, 1-methylheptyl group and the like, preferably methyl group, ethyl group, An isopropyl group, a s-butyl group, a t-butyl group, and a cyclohexyl group.

  Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, ethylphenyl group, o-propylphenyl group, and m-propyl. Phenyl group, p-propylphenyl group, butylphenyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 2,4,6-trimethylphenyl group 2,3-diisopropylphenyl group, 2,4-diisopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, α-naphthyl group, β-naphthyl group, diphenylmethyl group, anthryl group, Examples thereof include a phenanthryl group, a 5,6,7,8-tetrahydronaphthyl group, a biphenyl group, and the like, preferably a phenyl group, an o-tolyl group, o -Propylphenyl group, 2,4-xylyl group, 2,6-xylyl group, 2,4,6-trimethylphenyl group, 2,4-diisopropylphenyl group, 2,6-diisopropylphenyl group.

Examples of the aryl group of the aralkyl group having 7 to 20 carbon atoms include a phenyl group and a naphthyl group, and examples of the group to which the aryl group is bonded include an alkyl group and an alkenyl group. Phenyl-ethyl group, (2-methylphenyl) methyl group, (3-methylphenyl) methyl group, (4-methylphenyl) methyl group, (2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) ) Methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (4,6-dimethylphenyl) methyl group, (2 -Ethylphenyl) methyl group, (2-propylphenyl) methyl group, (2-butylphenyl) methyl group, (2,6-dipropylphenyl) methyl group, Examples include butylmethyl group, 1-phenyl-isopropyl group, 1- (2-methyl-phenyl) -isopropyl group, 1-phenyl-isopropyl group, and preferably benzyl group, 1-phenyl-ethyl group, (2- Methylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethylphenyl) methyl group, (2,6-dipropylphenyl) methyl group , 1-phenyl-isopropyl group.
In addition, in the substituents exemplified in paragraphs 0095 to 0100, when a plurality of structural isomers are present, they are arbitrary structural isomers.

R ¹ and R ² , R ³ and R ⁴ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , R ¹⁰ and R ¹¹ , R ¹⁴ and R ¹⁵ may form a ring containing a nitrogen atom. n is an integer of 1 or more, when n is 2 or more, and if adjacent R ⁷ may form a ring. R ² and R ³ , R ⁵ and R ⁶ , R ⁸ and R ⁹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ And R ¹⁹ , R ²⁰ and R ²¹ , R ²² and R ²³ , R ²³ and R ²⁴ , and R ²⁴ and R ²⁵ may form a ring containing a carbon atom.

  Specific examples of the compound used as (B-2b) include the following compounds.

  As specific examples of (B-2b), preferred compounds are as follows.

  As specific examples of (B-2b), more preferable compounds are as follows.

(C) (B-2c)
It is an organic compound having a molecular weight of 1,000 or less having two nitrogen elements selected from the following general formulas [V] to [X].

[Wherein R ²⁶ , R ²⁷ , R ^{29 to} R ³² , R ^{34 to} R ³⁷ , R ³⁹ , R ⁴⁰ , R ⁴² , R ⁴³ , R ⁴⁵ , R ⁴⁶ , R ⁴⁸ and R ⁴⁹ are independent of each other. A hydrogen atom, a hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, and a hydrocarbylene group having an arbitrary substituent. R ²⁶ and R ²⁷ , R ²⁹ and R ³⁰ , R ³¹ and R ³² , R ³⁶ and R ³⁷ , and R ⁴² and R ⁴³ which substitute the same nitrogen atom may form a ring containing a nitrogen atom. R ³⁴ and R ³⁵ , R ⁴⁵ and R ⁴⁶ which substitute the same carbon-nitrogen double bond may form a ring containing a carbon-nitrogen double bond with each other. R ³⁹ and R ⁴⁰ , R ⁴⁸ and R ⁴⁹ substituting the same carbon atom may form a ring containing a carbon atom. R ²⁸ , R ³³ , R ³⁸ , R ⁴¹ , R ⁴⁴ and R ⁴⁷ are each an independent hydrocarbyl group, a hydrocarbyl group having an optional substituent, a hydrocarbylene group, and a hydrocarbylene group having an optional substituent. Yes, and adjacent R ²⁸ , R ³³ , R ³⁸ , R ⁴¹ , R ⁴⁴ , and R ⁴⁷ may form a ring. n is an integer of 1 or more. ]
Specifically, this is the same as paragraphs 0095 to 0100 in (B-2b).

n is an integer of 1 or more. When n is 2 or more, adjacent R ²⁸ , R ³³ , R ³⁸ , R ⁴¹ , R ⁴⁴ , and R ⁴⁷ may form a ring, and form a ring. A double bond may be formed between two adjacent atoms.

Specific examples of (B-2c) include the compounds shown below.

(D) (B-2d)
An organic compound having a molecular weight of 1,000 or less and having one nitrogen element and one oxygen element selected from the following general formulas [XI] to [XVIII].

R ^{50 to} R ⁷⁸ (other than the bridging moiety) are an independent hydrogen atom, hydrocarbyl group, hydrocarbyl group having an arbitrary substituent, hydrocarbylene group, and hydrocarbylene group having an optional substituent. R ⁵² and R ⁵³ , or R ⁵⁷ and R ⁵⁸ that substitute the same nitrogen atom may form a ring. R ⁵⁶ , R ⁵⁷ and R ⁵⁸ which substitute the same carbon-nitrogen single bond may form a ring by the two or three substituents. R ⁶¹ and R ⁶² , and R ⁶⁹ and R ⁷⁰ that substitute the same carbon-nitrogen double bond may form a ring containing a carbon-nitrogen double bond. R ⁶⁵ and R ⁶⁶ , and R ⁷³ and R ⁷⁴ that substitute the same carbon atom may form a ring containing a carbon-nitrogen double bond.
R (bridging moiety) is an independent hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, a hydrocarbylene group having an arbitrary substituent, and adjacent R (crosslinking moieties) are: A ring may be formed. n is an integer of 1 or more.
Specifically, this is the same as paragraphs 0095 to 0100 in (B-2b).

R ⁵² and R ⁵³ , R ⁵⁷ and R ⁵⁸ substituting for the same nitrogen atom may form a ring containing a nitrogen atom. R ⁵¹ and R ⁵² or R ⁵³ , R ⁵⁶ and R ⁵⁷ or R ⁵⁸ , R ⁶¹ and R ⁶² , R ⁶⁹ and R ⁷⁰ , which substitute the same carbon-nitrogen bond, form a ring containing a carbon-nitrogen bond with each other. May be. R ⁵⁴ and R ⁵⁵ , R ⁵⁵ and R ⁵⁶ , R ⁶⁰ and R ⁶¹ , R ⁶⁵ and R ⁶⁶ , R ⁶⁷ and R ⁶⁸ , R ⁶⁸ and R ⁶⁹ , R ⁷¹ and R ⁷² , R ⁷³ and R ⁷⁴ , R ⁵¹ , R ⁵⁵ , R ⁶⁰ , R ⁶⁴ , R ⁶⁸ , R ⁷² , R ⁷⁵ , and R ⁷⁷ may form a ring containing a carbon atom.

In the formula, R ⁵⁵ , R ⁶⁰ , R ⁶⁴ , R ⁶⁸ , R ⁷² , R ⁷⁵ and R ⁷⁷ represent an alkylene group having 1 to 20 carbon atoms. Specifically, examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an i-propylidene group, a 1-methylethylene group, an n-butylene group, a 1-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, 1-methylbutylene group, 1,3-dimethyltrimethylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 1,3 -A dimethylbutylene group etc. are mentioned, Preferably, they are a methylene group, ethylene group, trimethylene group, and i-propylidene group.

n is an integer of 1 or more, and when n is 2 or more, adjacent R ⁵¹ , R ⁵⁵ , R ⁶⁰ , R ⁶⁴ , R ⁶⁸ , R ⁷² , R ⁷⁵ , and R ⁷⁷ may form a ring. In addition, a double bond may be formed between two adjacent atoms forming a ring, or an aromatic ring may be formed.

  Specific examples of (B-2d) include the compounds shown below.

(E) (B-2e)
An organic compound having a molecular weight of 1,000 or less and having one phosphorus atom and one oxygen atom or nitrogen atom selected from the following general formulas [XIX] to [XXII].

R ^{79 to} R ⁹⁶ (other than the bridging moiety) are an independent hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, and a hydrocarbylene group having an arbitrary substituent. R ⁷⁹ and R ⁸⁰ , R ⁸³ and R ⁸⁴ , R ⁸⁷ and R ⁸⁸ , and R ⁹² and R ⁹³ that substitute the same phosphorus atom may form a ring containing a phosphorus atom. R ⁹⁰ and R ⁹¹ which substitute the same carbon atom may form a ring containing a carbon atom.
R (bridging moiety) is an independent hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, or a hydrocarbylene group having an arbitrary substituent. May be formed. n is an integer of 1 or more.
Specifically, this is the same as paragraphs 0095 to 0100 in (B-2b).

R ⁷⁹ and R ⁸⁰ , R ⁸³ and R ⁸⁴ , R ⁸⁷ and R ⁸⁸ , and R ⁹² and R ⁹³ that substitute the same phosphorus atom may form a ring containing a phosphorus atom. R ⁸¹ and R ⁷⁹ or R ⁸⁰ , R ⁸⁵ and R ⁸³ or R ⁸⁴ , R ⁸⁹ and R ⁸⁷ or R ⁸⁸ , R ⁹⁴ and R ⁹² or R ⁹³ , which substitute the same carbon-phosphorus bond, are carbon-phosphorus A ring containing a bond may be formed. R ⁸⁹ and R ⁹⁰ or R ⁹¹ , R ⁹⁴ and R ⁹⁵ or R ⁹⁶ which substitute the same carbon-nitrogen bond may form a ring containing a carbon-nitrogen bond with each other. R ⁸⁵ and R ⁸⁶ , R ⁹⁰ and R ⁹¹ , R ⁹⁴ and R ⁹⁵ , R ⁸¹ , R ⁸⁵ , R ⁸⁹ , and R ⁹⁴ , which replace the same carbon atom, form a ring containing carbon atoms. May be. R ⁸¹ and R ⁸² substituting the same oxygen atom may form a ring containing an oxygen atom.

In the formula, R ⁸¹ , R ⁸⁵ , R ⁸⁹ and R ⁹⁴ represent an alkylene group having 1 to 20 carbon atoms. Specifically, examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an i-propylidene group, a 1-methylethylene group, an n-butylene group, a 1-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, 1-methylbutylene group, 1,3-dimethyltrimethylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 1,3 -A dimethylbutylene group etc. are mentioned, Preferably, they are a methylene group, ethylene group, trimethylene group, and i-propylidene group.

n is an integer of 1 or more, and when n is 2 or more, adjacent R ⁸¹ , R ⁸⁵ , R ⁸⁹ , and R ⁹⁴ may form a ring, and between adjacent two atoms forming the ring is It may be a double bond or may form an aromatic ring.

  Specific examples of (B-2e) include the compounds shown below.

(F) (B-2f)
It is an organic compound having a molecular weight of 1,000 or less having two oxygen elements selected from the following general formulas [XXIII] and [XXIV].

In Formula XXIII, Y ¹ and Y ² are an oxygen atom or a sulfur atom and are independent of each other. R ¹⁰² and R ¹⁰⁴ are an independent hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, and a hydrocarbylene group having an arbitrary substituent. R ¹⁰³ is an independent hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, or a hydrocarbylene group having an arbitrary substituent, and adjacent R ¹⁰³ may form a ring. Good. R ¹⁰³ and R ¹⁰⁴ replacing R ¹⁰² and R ^{103, Y 2} substituting Y ¹ may form a ring containing ^{Y 1} and ^{Y 2,} respectively. n is an integer of 1 or more.
In formula XXIV, Y ³ and Y ⁴ are an oxygen atom or a sulfur atom and are independent of each other. R ¹⁰⁵ and R ¹⁰⁷ are each an independent hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, and a hydrocarbylene group having an arbitrary substituent. R ¹⁰⁶ is an independent hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, or a hydrocarbylene group having an arbitrary substituent, and adjacent R ¹⁰⁶ may form a ring. Good. R ¹⁰⁵ and R ¹⁰⁶ substituting Y ³ may each form a ring containing Y ³ . n is an integer of 1 or more.
Specifically, this is the same as paragraphs 0095 to 0100 in (B-2b). n is an integer of 1 or more, and when n is 2 or more, the adjacent R ¹⁰³ and R ¹⁰⁶ may form a ring, and the two adjacent atoms forming the ring are double bonds. Or an aromatic ring may be formed.

Specific examples of (B-2f) include the following compounds.

(G) (B-2g)
An organic compound having a molecular weight of 1,000 or less and having one phosphorus element and one nitrogen element selected from the following general formulas [XXV] to [XXVII].

R ^{97 to} R ¹⁰³ , R ^{105 to} R ¹⁰⁸ , R ¹¹⁰ and R ¹¹¹ are each an independent hydrocarbyl group, a hydrocarbyl group having an optional substituent, a hydrocarbylene group, and a hydrocarbylene group having an optional substituent. is there.
R ¹⁰⁴ and R ¹⁰⁹ are each an independent hydrocarbyl group, a hydrocarbyl group having an arbitrary substituent, a hydrocarbylene group, and a hydrocarbylene group having an arbitrary substituent. Adjacent R ¹⁰⁴ and R ¹⁰⁹ are A ring may be formed. n is an integer of 1 or more.
Specifically, this is the same as paragraphs 0095 to 0100 in (B-2b).

R ⁹⁷ and R ⁹⁸ , R ¹⁰² and R ¹⁰³ , R ¹⁰⁷ and R ¹⁰⁸ which substitute the same phosphorus atom may form a ring containing a phosphorus atom. R ⁹⁹ and R ⁹⁷ or R ⁹⁸ , R ¹⁰⁴ and R ¹⁰² or R ¹⁰³ , R ¹⁰⁹ and R ¹⁰⁷ or R ¹⁰⁸ which substitute the same carbon-phosphorus bond may form a ring containing a carbon-phosphorus bond with each other. Good. R ¹⁰⁰ and R ¹⁰¹ which substitute the same nitrogen atom may form a ring containing a nitrogen atom. R ⁹⁹ and R ¹⁰⁰ or R ¹⁰¹ , R ¹⁰⁵ and R ¹⁰⁶ , R ¹⁰⁹ and R ¹¹⁰ or R ¹¹¹ , which substitute the same carbon-nitrogen bond, may form a ring containing a carbon-nitrogen bond with each other. R ⁹⁹ , R ¹⁰⁴ and R ¹⁰⁵ , R ¹¹⁰ and R ¹¹¹ , R ¹⁰⁴ , and R ¹⁰⁹ that substitute the same carbon atom may form a ring containing a carbon atom.

Examples of the alkylene group having 1 to 20 carbon atoms of R ¹⁰⁴ and R ¹⁰⁹ include a methylene group, an ethylene group, a trimethylene group, an i-propylidene group, a 1-methylethylene group, an n-butylene group, and a 1-methyltrimethylene group. 1,1-dimethylethylene group, 1,2-dimethylethylene group, 1-methylbutylene group, 1,3-dimethyltrimethylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 1, A 3-dimethylbutylene group is exemplified, and a methylene group, an ethylene group, a trimethylene group, and an isopropylidene group are preferable.

n is an integer of 1 or more, and when n is 2 or more, R ⁹⁹ , R ¹⁰⁴ , and R ¹⁰⁹ on adjacent carbon atoms may form a ring or are adjacent to each other to form a ring. The double atom may be a double bond or an aromatic ring may be formed.

  Specific examples of (B-2g) include the compounds shown below.

[Iii] Component (B) derived from (B-1) and (B-2) Component (B-2) is a compound selected from (B-2a) to (B-2g) described in detail above However, two or more of these may be used.
In the present invention, the component (B-1) and the component (B-2) are contacted to obtain the component (B). As a preferred specific example, a guest compound ((B-2) component) is intercalated with respect to a metal ion such as iron ion-exchanged with a cation between layers of a host compound ((B-1) component). Are complexed between the layers to form a novel polymerization catalyst component. This state and processing steps (processing flow) are shown in FIG.

In the present invention, the component (B-1) is intercalated with at least one transition metal ion or the transition metal complex ion of Ti, Zr, Hf, V, Nb, Cr, Fe, Co, Ni, and Pd. A catalyst component for olefin polymerization, characterized by being an ion-exchanged layered silicate, obtained by contacting the component (B-1) and the component (B-2), and further intercalated The ion-exchange layered compound (component (B)) is an olefin polymerization catalyst component characterized by having an interlayer distance of 10 to 30 angstroms by X-ray diffraction measurement.
That is, the component (B) includes the above-mentioned organic compound (the so-called host compound) which is ion-exchanged with any of transition metal ions of Ti, Zr, V, Cr, Fe, Co, and Ni. It is a catalyst component for olefin polymerization, characterized by intercalating a so-called guest compound) between layers.

As this guest compound, 2,6- [2,4,6- (CH ₃ ) ₃ Ph—N═C (CH ₃ ) —)] ₂ C ₅ H ₃ N (abbreviation PBI: known compound) is preferably used. Used and intercalated to metal ions such as iron ion-exchanged with cations between the host compound layers and complexed between the layers to form a novel polymerization catalyst component. This state and processing steps (processing flow) are posted as FIG. 1 to clarify the features of the present invention.

  Specifically, a host compound having a cation such as sodium (ion-exchangeable layered compound, ie, (B-1) component precursor) is ion-exchanged in an aqueous solution of a transition metal salt, filtered, washed, calcined, Drying by vacuum evacuation is performed to obtain an ion-exchanged host compound (component (B-1)). Next, contact treatment is performed with a solution of the guest compound (component (B-2)) in an organic solvent (such as n-butanol), washing, and removal of the solvent by vacuum exhaust drying to obtain a polymerization catalyst component (component (B)). it can.

The contact can be carried out by any method, but the general form is described below.
Usually, the concentration of the component (B-1) at the time of contact is 0.1 to 60% by weight, preferably 1 to 30% by weight, more preferably 5 to 20% by weight. The concentration is 10 ^{−3 to 1} mol / L, preferably 10 ^{−2 to} 0.3 mol / L, more preferably 0.05 to 0.1 mol / L, and the component (B-1) and (B-2) The ratio of the components is 0.001 to 10 mmol / g, preferably 0.01 to 2 mmol / g, and more preferably 0.1 to 1 mmol / g.
The contact is preferably carried out in a liquid, in a hydrocarbon solvent such as toluene, n-heptane, ethanol, diethyl ether, acetone, various organic solvents including alcohols, ethers, aldehydes, or in an aqueous solution. However, if the component (B-2) is liquid at the treatment temperature, it can be used without solvent, and preferably the component (B-2) is solubilized in alcohol or ether. And in a solvent that can swell the layered compound of component (B-1). The treatment temperature is not particularly limited as long as it is a temperature at which a liquid exists in the system, but is preferably 0 ° C to 100 ° C, more preferably room temperature to 80 ° C. The treatment time is generally selected from 5 minutes to 720 hours, but at least part of the component (B-2) is intercalated between the layers of the ion-exchange layered compound (B-1). It is preferable to carry out under the conditions to be adjusted.

(B-1) Confirmation that the component (B-2) was intercalated between the layers of the component (B-1) Intercalation of the transition metal ion or the transition metal complex ion between the layers of the component (B-1) Similar to the confirmation, the distance between the bottom surfaces measured by elemental analysis and X-ray diffraction measurement is used.
Generally, in powder method X-ray diffraction measurement of a layered compound, a diffraction peak peculiar to a layered structure appears on the low angle side. This diffraction peak is called a bottom reflection peak, and is a diffraction line derived from repetition in the direction in which the layers are stacked. If the d value is calculated using the Bragg equation from the diffraction angle of the diffraction peak and the X-ray wavelength used, the distance between the bottom surfaces can be obtained. The distance between the bottom surfaces includes the thickness of the layer itself. In the present invention, the bottom surface distance of the component (B-1) after the component (B-2) is intercalated between the layers is preferably 10.0 to 30.0 mm, more preferably in the case of smectite. Is 12.0 to 20.0 cm, and particularly preferably 13.0 to 18.0 cm. Further, the amount of increase in the bottom surface separation distance of the ion-exchange layered compound before and after the intercalation treatment is usually greater than 0% and 20.0% or less, preferably 1.0-15.0%, more preferably It is 3.0-10.0 ?, and particularly preferably 4.0-7.0 ?. The distance between the bottom surfaces of the layered compound can be calculated from the shift of 2θ around 5 to 10 degrees by X-ray diffraction measurement.

  After removing the excess component (B-2) after the catalytic reaction, usually by washing with water or an organic solvent, an organic solvent that does not poison a general olefin polymerization catalyst, for example, dehydrated toluene, What is washed with non-polar hydrocarbon solvent such as hexane, heptane, etc., and treated with organoaluminum compound, organomagnesium compound, organozinc compound, organoalkali compound, etc. as necessary is the catalyst component for olefin polymerization The olefin polymerization catalyst of the present invention is used together with the component (A), and is used for the production of an olefin polymer as a bare catalyst or as a prepolymerization catalyst.

(3) Arbitrary component The components (A) and (B) of the catalyst component are used as essential catalyst components for olefin polymerization. An aluminum compound or the like is used as necessary. A compound represented by the following general formula is preferably used.
AlR _p X _3-p
(In this formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, hydrogen, an alkoxy group, or an amino group. P is in the range of 1 to 3). The compounds shown are suitable. R is preferably an alkyl group, and X is a chlorine atom when it is halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 to 8 carbon atoms when it is an amino group. The amino group of is preferable. In the present invention, it goes without saying that the compounds represented by this formula can be used alone, in combination of two or more, or in combination. Moreover, this use is possible not only at the time of catalyst preparation but also at the time of preliminary polymerization or polymerization.

Specific examples of preferable compounds as the component (C) include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum. Examples include chloride, diethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, and diisobutylaluminum chloride.
Of these, trialkylaluminum with p = 3 or dialkylaluminum hydride in which p = 2 and X is hydrogen is preferable. More preferably, R is a trialkylaluminum having 1 to 8 carbon atoms, particularly preferably triethylaluminum or triisobutylaluminum.

2. Preparation of Olefin Polymerization Catalyst (1) Contact The catalyst according to the present invention is formed by bringing the above-mentioned components into contact with each other outside or inside the polymerization tank, simultaneously or continuously, or once or multiple times. Can be made.
The contacting of each component is usually performed in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although contact temperature is not specifically limited, It is preferable to carry out between -20-150 degreeC. Arbitrary combinations are possible as the contact order, but particularly preferable ones for each component are as follows. Usually, the component (B) and the component (C) are first contacted. The component (C) can be added to the component (B) before, simultaneously with, or after the component (A). Preferably, the component (C) is added before the component (A).
After contacting each component, it can be washed with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

(2) Use amount of each component The use amount of the components (A), (B) and (C) used in the present invention is arbitrary. For example, the amount of component (A) used relative to component (B) is preferably in the range of 0.1 to 1,000 μmol, particularly preferably 0.5 to 500 μmol, relative to 1 g of component (B). The amount of component (C) used relative to component (B) is preferably in the range of 0.001 to 100 mmol, particularly preferably 0.05 to 10 mmol, relative to 1 g of component (B).

3. Polymerization of Olefin As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer are in efficient contact. Specifically, a slurry method using an inert solvent, a solution polymerization method, a bulk method using a monomer such as propylene as a solvent substantially without using an inert solvent, or each monomer substantially using no liquid solvent. A gas phase method for keeping the gas in a gaseous state can be employed. The polymerization method is applied to continuous polymerization and batch polymerization.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene or the like is used alone or as a mixture as a polymerization solvent. Furthermore, halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene can also be used.
The polymerization temperature is −50 to 200 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure can be carried out in the range of 0 to 2,000 kg / cm ² G.
The polymerization catalyst of the present invention is used for polymerization and copolymerization of α-olefins mainly composed of ethylene and propylene.

  In order to describe the present invention more specifically, preferred examples and corresponding comparative examples are described below. The contrast between each example and the comparative example demonstrates the rationality and significance of the requirements of the configuration of the present invention, and further demonstrates the superiority of the present invention over the prior art. In addition, the measuring method used for an Example and a comparative example is as follows.

(1) Measurement of distance between bottom surfaces of ion-exchangeable layered compound In the present invention, by measuring the powder X-ray diffraction pattern of the ion-exchangeable layered compound which is component (B), diffraction by the (001) plane of the layered compound The progress of intercalation between layers was confirmed from the d value of the peak.
For the measurement, RAD-B system (X-ray: CuKα (wavelength: 0.3 mm) manufactured by Rigaku Corporation.
15406 nm) with a counter monochromator was used. Measurement conditions are tube voltage: 40 kV, tube current: 30 mA, scan axis: 2θ / θ, measurement range = 2 ° to 15 °, scan speed = 1 ° / min, divergence slit: 1 °, scattering slit: 1 °, Light receiving slit: 0.30 mm.
Here, the diffraction peak at the (001) plane is called a bottom reflection peak, and the d value calculated from the diffraction angle using the Bragg equation corresponds to the sum of the thickness of the layer itself and the interlayer distance, that is, the bottom surface separation distance. To do. Therefore, if the d value of the (B-1) component subjected to the intercalation processing increases compared to before the processing, this indicates that the layer has spread, and it can be determined that the (B-2) component has been intercalated between the layers. (See FIG. 1). The component (B-1) treated with the component (B-2) is intercalated between the layers competitively with the component (B-2) by evacuating at 110 ° C. for 1 hour before measurement. The removed solvent was selectively removed before use in the measurement.

(2) Measurement of polymer molecular weight by GPC In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are those measured by gel permeation chromatography (GPC).
Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene. Standard polystyrenes used are the following brands manufactured by Tosoh Corporation. F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method. The viscosity equation [η] = K × M ^α used for conversion to molecular weight uses the following numerical values.
PS: K = 1.38 × 10 ⁻⁴ α = 0.70
PE: K = 3.92 × 10 ⁻⁴ α = 0.733
PP: K = 1.03 × 10 ⁻⁴ α = 0.78
The measurement conditions for GPC are as follows.
Apparatus: Waters GPC (ALC / GPC 150C) Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm) Column: Showa Denko AD806M / S (3) Mobile phase solvent: o- Dichlorobenzene Measurement temperature: 140 ° C. Flow rate: 1.0 ml / min Injection volume: 0.2 ml Sample preparation: Prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT). And dissolve at 140 ° C. for about 1 hour.
The baseline and section of the obtained chromatogram are performed as illustrated in FIG.

(3) Measurement of melting point (Tm) of polymer by DSC It was measured according to JIS K7121. 5 mg of sample was melted at 170 ° C. for 5 minutes, cooled to 20 ° C. at a rate of 10 ° C./minute, held for 1 minute, and then a melting curve was measured at a temperature increase rate of 10 ° C./minute up to 170 ° C. (° C.) was defined as the melting point (Tm-DSC).

(4) Measurement of MI MI was measured with a load of 190 ° C. and 2.16 kg in accordance with JIS K6760.

[Example 1]
(1) Synthesis of Fe ³⁺ ion-exchanged montmorillonite 24.2 g of iron nitrate nonahydrate was placed in a 1 L flask containing 500 mL of ion-exchanged water, and dissolved by stirring. 20.0 g of a commercially available montmorillonite (Benley SL, manufactured by Mizusawa Chemical Co., Ltd.) whose interlayer cation is Na ⁺ was added and stirred well. After stirring, the mixture was allowed to stand at room temperature for 24 hours for ion exchange, and then montmorillonite was collected by filtration. Next, the collected montmorillonite was put into 500 mL of an aqueous solution containing 24.2 g of newly prepared iron nitrate nonahydrate, and further ion exchanged for 24 hours. Montmorillonite was collected by filtration, dispersed in about 500 mL of ethanol, washed, and then filtered. This washing operation was further performed 4 times. The obtained exchanger was dried at about 40 ° C. until the ethanol odor disappeared, and then dried under reduced pressure at 200 ° C. for 2 hours.

(2) Catalyst component preparation (Montmorillonite-diiminopyridine ligand complex preparation)
0.50 g of the dried Fe ³⁺ ion-exchanged montmorillonite obtained in (1) above was weighed into a 30 mL flask under a nitrogen atmosphere, and 0.50 mmol of 2,6- [2,4,6- (CH ₃ ) was added thereto. ₃ Ph—N═C (CH ₃ ) —)] 5.0 mL of a solution obtained by dissolving ₂ C ₅ H ₃ N ligand in 16.8 mL of dehydrated n-butanol was added, and the mixture was stirred for 5 minutes and then kept at 70 ° C. The reaction was allowed to proceed for 24 hours in an oil bath. After the completion of the reaction time, the reaction solution was cooled to room temperature, and the supernatant was extracted as much as possible. Further, 10 mL of dehydrated n-butanol was added and stirred for 1 minute for washing. After standing, when the catalyst component settled, the supernatant liquid was extracted as much as possible. This washing operation with n-butanol was performed three times. Next, 10 mL of dehydrated n-heptane was added for washing. After sedimentation of the catalyst component, the supernatant was extracted as much as possible. This washing operation was performed three times. Finally, the solvent was evacuated at room temperature, and after no solvent was visually confirmed, drying was performed under reduced pressure for 30 minutes to obtain a catalyst component. The distance between the bottom surfaces (d value) of the catalyst component thus obtained increased from 9.8 mm before treatment with the diiminopyridine ligand to 14.1 mm.

(3) Ethylene / 1-hexene copolymerization Using the montmorillonite-diiminopyridine ligand complex obtained in (2) above and biscyclopentadienylzirconium dichloride, slurry copolymerization of ethylene / 1-hexene is performed. went. That is, 0.50 L of n-heptane, 20 ml of 1-hexene and 2.5 mmol of triethylaluminum were added to a 1 L autoclave, the temperature was raised to 70 ° C., and ethylene was further introduced until the partial pressure became 2.0 MPa. Next, 2.0 μmol of biscyclopentadienylzirconium dichloride (component of 2.0 ml of toluene solution) as component (A) and 20 mg of the complex (component of 20 ml of heptane slurry) as component (B) are pre-contacted at room temperature for 10 minutes. Then, polymerization was started by press-fitting with argon, the polymerization was continued for 23 minutes at 70 ° C. while maintaining the ethylene partial pressure at 2.0 MPa, and then the polymerization was stopped by adding ethanol. The obtained ethylene / 1-hexene copolymer was 63 g. The results are shown in Table 1.

[Comparative Example 1]
Polymerization was carried out in the same manner as in Example 1 (3) except that the component (A), biscyclopentadienylzirconium dichloride, was not used. The ethylene / 1-hexene copolymer obtained by polymerization for 25 minutes was 67 g. The results are shown in Table 1.

[Example 2]
In place of biscyclopentadienylzirconium dichloride as component (A), 2.4 μmol of Ni bisimide complex (compound (Ia) below) (2.4 ml of toluene solution) was used, and 1-hexene was not used. Except for the above, polymerization was carried out in the same manner as in Example 1 (3). The ethylene polymer obtained by performing the polymerization for 21 minutes was 78 g. The results are shown in Table 1.

[Comparative Example 2]
Polymerization was carried out in the same manner as in Example 2 except that the Ni bisimide complex (Ia) as the component (A) was not used. The ethylene polymer obtained by carrying out the polymerization for 25 minutes was 74 g. The results are shown in Table 1.

[Example 3]
Using the montmorillonite-diiminopyridine ligand complex obtained in Example 1 (2) and biscyclopentadienylzirconium dichloride, slurry copolymerization of ethylene / 1-hexene was performed. That is, 1.50 L of n-heptane, 180 ml of 1-hexene and 1.0 mmol of triethylaluminum were added to a 3 L autoclave, the temperature was raised to 80 ° C., and 19 Nml of hydrogen and ethylene were introduced until the partial pressure became 2.0 MPa. Next, 10.0 μmol of biscyclopentadienylzirconium dichloride (component for 10.0 ml of toluene solution) as component (A) and 100 mg of the complex (component of 20 ml of heptane slurry) as component (B) are pre-contacted at room temperature for 10 minutes. After that, polymerization was started by press-fitting with argon, and the polymerization was continued at 80 ° C. for 60 minutes while maintaining the ethylene partial pressure at 2.0 MPa, and then ethanol was added to stop the polymerization. The obtained ethylene / 1-hexene copolymer was 107 g. The results are shown in Table 2.

[Comparative Example 3]
Polymerization was carried out in the same manner as in Example 3 except that the component (A), biscyclopentadienylzirconium dichloride, was not used. The amount of ethylene / 1-hexene copolymer obtained by polymerization for 45 minutes was 199 g. The results are shown in Table 2.

[Example 4]
(1) Synthesis of Mg ²⁺ ion-exchanged montmorillonite 20 Kg of commercially available swellable montmorillonite (Benley SL, manufactured by Mizusawa Chemical Co., Ltd.) 187 kg of magnesium sulfate aqueous solution (magnesium sulfate concentration 6.9 wt%, sulfuric acid concentration 11.2 wt%) It was dispersed in and stirred at 90 ° C. for 7 hours. After filtering and washing this with demineralized water, the obtained solid cake was dried at 110 ° C. for 10 hours. Lumps in the obtained dried montmorillonite were removed with a sieve having an opening of 75 μm, and 10 kg of Mg ²⁺ ion-exchanged montmorillonite particles that passed through the sieve were obtained.
(2) Synthesis of Ti ⁴⁺ ion-exchanged montmorillonite 150 g of Mg ²⁺ ion-exchanged montmorillonite particles obtained in the above (1) were contained in commercially available titanyl sulfate (manufactured by Sakai Chemical Industry Co., Ltd., containing 7.5% as TiO ₂ ). It was dispersed in a mixed solution of 958 g of SO ₄ solution and 51.2 g of sulfuric acid and stirred at 90 ° C. for 3 hours. After this was filtered and washed with demineralized water to pH 3.5, the obtained water-containing solid cake was preliminarily dried at 110 ° C. for 10 hours and further dried under reduced pressure at 200 ° C. for 2 hours to obtain Ti ⁴⁺ ion-exchanged montmorillonite. Obtained.
(3) Catalyst component preparation (Montmorillonite-diiminopyridine ligand complex preparation)
Next, 0.50 g of Ti ⁴⁺ ion-exchanged montmorillonite obtained in (2) was weighed into a 30 mL flask under a nitrogen atmosphere, and 0.50 mmol of 2,6- [2,4,6- (CH ₃ ) ₃ was added thereto. Ph—N═C (CH ₃ ) —)] 5.0 mL of a solution obtained by dissolving ₂ C ₅ H ₃ N ligand in 16.8 mL of dehydrated n-butanol was added, and the oil was kept at 70 ° C. after stirring for 5 minutes. The reaction was allowed to proceed for 24 hours in the bath. After the completion of the reaction time, the reaction solution was cooled to room temperature, and the supernatant was extracted as much as possible. Further, 10 mL of dehydrated n-butanol was added and stirred for 1 minute for washing. After standing, when the catalyst component settled, the supernatant liquid was extracted as much as possible. This washing operation with n-butanol was performed three times. Next, 10 mL of dehydrated n-heptane was added for washing. After sedimentation of the catalyst component, the supernatant was extracted as much as possible. This washing operation was performed three times. Finally, the solvent was evacuated at room temperature, and after no solvent was visually confirmed, drying was performed under reduced pressure for 30 minutes to obtain a catalyst component.
(4) Ethylene / 1-hexene copolymerization Except for using the montmorillonite-diiminopyridine ligand complex, the Ti ⁴⁺ ion-exchanged montmorillonite-diiminopyridine ligand complex obtained in (3) above was used. Polymerization was carried out in the same manner as in Example 3. The ethylene / 1-hexene copolymer obtained by polymerization for 60 minutes was 36 g. The results are shown in Table 2.

[Comparative Example 4]
Polymerization was conducted in the same manner as in Example 4 except that the component (A), biscyclopentadienylzirconium dichloride, was not used. The ethylene / 1-hexene copolymer obtained by polymerization for 60 minutes was 16 g. The results are shown in Table 2.

[Example 5]
(1) Synthesis of Zr ⁴⁺ ion-exchanged montmorillonite 200 g of Mg ²⁺ ion-exchanged montmorillonite particles obtained in Example 4 (1) were mixed with 900 g of pure water, commercially available zirconium (IV) sulfate tetrahydrate (Mitsuwa Chemical Co., Ltd. )) It was dispersed in a mixed solution of 427 g and 125 g of sulfuric acid and stirred at 90 ° C. for 3 hours. After this was filtered and washed with demineralized water to pH 3.5, the obtained water-containing solid cake was preliminarily dried at 110 ° C. for 10 hours, and further dried under reduced pressure at 200 ° C. for 2 hours to obtain Zr ⁴⁺ ion-exchanged montmorillonite. Obtained.
(2) Catalyst component preparation (Montmorillonite-diiminopyridine ligand complex preparation)
A catalyst component was obtained in the same manner as in Example 4 (3) except that instead of Ti ⁴⁺ ion exchange montmorillonite, Zr ⁴⁺ ion exchange montmorillonite obtained in (1) was used.
(3) Ethylene / 1-hexene copolymerization Except for using the Zr ⁴⁺ ion-exchanged montmorillonite-diiminopyridine ligand complex obtained in (2) above as the montmorillonite-diiminopyridine ligand complex. Polymerization was carried out in the same manner as in Example 4. The ethylene / 1-hexene copolymer obtained by polymerization for 60 minutes was 45 g. The results are shown in Table 2.

[Comparative Example 5]
Polymerization was carried out in the same manner as in Example 5 except that the component (A), biscyclopentadienylzirconium dichloride, was not used. The ethylene / 1-hexene copolymer obtained by polymerization for 60 minutes was 39 g. The results are shown in Table 2.

[Example 6]
(1) Synthesis of Cr ³⁺ ion-exchanged montmorillonite 200 g of Mg ²⁺ ion-exchanged montmorillonite particles obtained in Example 4 (1) were mixed with 1,000 g of pure water and 240 g of commercially available chromium (III) nitrate nonahydrate. It was dispersed in and stirred at 90 ° C. for 3 hours. This was filtered and washed with demineralized water to pH 3.5, and the resulting water-containing solid cake was preliminarily dried at 110 ° C. for 10 hours and further dried under reduced pressure at 200 ° C. for 2 hours to obtain Cr ³⁺ ion-exchanged montmorillonite. Obtained.
(2) Catalyst component preparation (Montmorillonite-diiminopyridine ligand complex preparation)
A catalyst component was obtained in the same manner as in Example 4 (3) except that instead of Ti ⁴⁺ ion-exchanged montmorillonite, Cr ³⁺ ion-exchanged montmorillonite obtained in (1) was used.
(3) Ethylene / 1-hexene copolymerization Except that the Cr ³⁺ ion exchange montmorillonite-diiminopyridine ligand complex obtained in (2) above was used as the montmorillonite-diiminopyridine ligand complex. Polymerization was carried out in the same manner as in Example 4. The ethylene / 1-hexene copolymer obtained by polymerization for 60 minutes was 23 g. The results are shown in Table 2.

[Comparative Example 6]
Polymerization was carried out in the same manner as in Example 6 except that the component (A) biscyclopentadienylzirconium dichloride was not used, hydrogen was not added, and 60 ml of 1-hexene was added. The ethylene / 1-hexene copolymer obtained by polymerization for 60 minutes was 16 g. The results are shown in Table 2.

[Comparative Example 7]
(1) Synthesis of Zn ²⁺ ion-exchanged montmorillonite
40 kg of commercially available montmorillonite (Benley SL, manufactured by Mizusawa Chemical Co., Ltd.) was dispersed in 160 kg of 25% sulfuric acid and stirred at 90 ° C. for 2 hours. This was filtered and washed with demineralized water to pH 3.5, and then the obtained water-containing solid cake was preliminarily dried at 110 ° C. for 10 hours to obtain acid-treated montmorillonite. Among the pre-dried montmorillonite, particles that passed through a sieve having an opening of 150 mesh were further subjected to ³ kg / hr using a rotary kiln at a temperature of 200 ° C. under a countercurrent nitrogen stream (nitrogen flow rate 49 Nm ³ / hr). Continuous drying at a speed (retention time 10 minutes) was collected under dry nitrogen. 200 g of the obtained acid-treated montmorillonite was dispersed in an aqueous solution in which 115 g of zinc sulfate heptahydrate (ZnSO ₄ .7H ₂ O), 10 g of sulfuric acid and 675 g of demineralized water were dissolved in a ₂ L flask at 30 ° C. Stir for 2 hours. After the treatment, this solid component was washed with demineralized water and pre-dried to obtain a treated montmorillonite. This pre-dried Zn ²⁺ ion-exchanged montmorillonite was placed in a 1 L flask and subjected to heat dehydration treatment at 200 ° C. for 2 hours under a reduced pressure of 1 mmHg.
(2) Treatment of montmorillonite with organoaluminum To a 100 mL flask, 1 g of dry Zn ²⁺ ion-exchanged montmorillonite obtained in (1) above and 25 mL of heptane were added, and then 3.2 mL (2.0 mmol) of a heptane solution of triethylaluminum with stirring at room temperature Min) and reacted for 1 hour, followed by washing with heptane.
(3) Ethylene / 1-hexene copolymer (A) As a component, biscyclopentadienylzirconium dichloride was obtained at 8.0 μmol (8.0 ml as a toluene solution), and (B) as a component obtained in (2) above. Ethylene / 1-hexene copolymerization was carried out in the same manner as in Example 3 except that 100 mg of organoaluminum-treated Zn ²⁺ ion-exchanged montmorillonite (20 ml as a heptane slurry) was used and 2.4 mmol of triethylaluminum was used. The ethylene / 1-hexene copolymer obtained by polymerization for 60 minutes was 42 g. The results are shown in Table 2.

[Consideration by contrast between Example and Comparative Example]
Considering the above examples and comparative examples in contrast, the catalyst for olefin polymerization of the present invention is a homogeneous polymerization catalyst component having a transition metal of component (A) and a specific component of component (B). Since it is a catalyst containing an ion-exchange layered compound in which an organic compound is intercalated, it is possible to produce an olefin polymer having high catalytic activity, a narrow molecular weight distribution, excellent melt flowability, and excellent moldability. It can be said that has been revealed.
If Examples 1-6 and Comparative Examples 1-6 are contrasted, each Example will not use (A) component, and compared with each Comparative Example which consists only of (B) component, generally polymerization activity is high, The MI value, which is an index of melt fluidity and molding processability, is increased. Compared to Comparative Example 3 corresponding to Example 3 only, the catalytic activity is low, but the MI value is very high.
Since Comparative Example 7 is a catalyst that uses a Group 12 metal different from the present invention in the component (B-1) and does not use the component (B-2), the catalytic activity and MI value are not substantially inferior. However, it can be said that it is not a catalyst that highlights the characteristics of the catalyst of the present invention.
Thus, the rationality and significance of the requirements of the construction of the present invention have been demonstrated, and the superiority of the present invention over the prior art has also been clarified.

It is a schematic diagram which illustrates the state by which the intercalation cation was intercalated by the ion-exchange layered compound, and the process flow figure which illustrates an intercalation process process. It is a graph which illustrates the base line and section of a chromatograph in GPC measurement.

Claims (7)

An olefin polymerization catalyst comprising at least the following component (A) and component (B):
Component (A): a metallocene compound of a transition metal of Groups 3-6 of the periodic table or a bisimide compound of a transition metal of Groups 8-10 of the periodic table.
(B) Component: A catalyst component obtained by contacting the component (B-1) and the component (B-2).
Component (B-1): an ion-exchange layered compound in which transition metal ions of Group 3 to 11 of the periodic table or the transition metal complex ions are intercalated.
(B-2) Component: Any of the following organic compounds.

The olefin polymerization catalyst according to claim 1, wherein the metallocene compound is any one of Ti, Zr, Hf, V, and Cr. 2. The olefin polymerization catalyst according to claim 1, wherein the bisimide compound is any one of Fe, Co, Ni, and Pd. 3. As the component (B-1), at least one transition metal ion or the transition metal complex ion of Ti, Zr, Hf, V, Nb, Cr, Mn, Fe, Co, Ni, and Pd is intercalated. The olefin polymerization catalyst according to any one of claims 1 to 3 , wherein the catalyst is an ion-exchanged layered compound. The olefin polymerization catalyst according to any one of claims 1 to 4 , which contains an organoaluminum compound as the optional component (C). As the component (B-1), an ion-exchange layered compound in which a transition metal ion of Group 3 to 11 of the periodic table or the transition metal complex ion is intercalated, and (B-2) as a component , by contacting the organic compounds described 請 Motomeko 1, those organic compounds further intercalated ion-exchangeable layered compound to form a (B) component of the catalyst components, then to claim 1 The binary system containing at least the component (A) and the component (B), wherein the homogeneous polymerization catalyst component having a transition metal as the component (A) described above is contacted with the component (B) A method for producing an olefin polymerization catalyst. A method for producing an olefin polymer, wherein the olefin is polymerized or copolymerized using the olefin polymerization catalyst according to any one of claims 1 to 5 .

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