JP2002080515A - Method for manufacturing polar olefin copolymer and polar olefin copolymer obtained by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a polar olefin copolymer having excellent properties in a mild polymerization condition. SOLUTION: This method is to copolymerized a non polar olefin and a polar olefin in the presence of a catalyst comprising a transition metal compound of a metal selected from the 4th, 5th, 6th and 11th groups of the periodic table, expressed by formula IV, (M' is a transition metal atom of the fourth, fifth, sixth and eleventh groups of the periodic table, (m) is 1-6, A is O, Si, Se and N(R6), (n) is an integer satisfying the number of valence of the M', R1 to R4, R6 are each H, a halogen atom, a hydrocarbon group, or the like, X is a halogen atom, O, a hydrocarbon group, or the like), and (B) one or more kinds of compounds selected from the group consisting of (B-1) an organometallic compound, (B-2) an organo-aluminoxy compound and (B-3) an ionized ionic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polar olefin copolymer and a polar olefin copolymer obtained by the method, and more particularly, to a method for producing a non-polar olefin and a polar olefin in the presence of a specific catalyst. The present invention relates to a method for producing a polar olefin copolymer to be copolymerized and a polar olefin copolymer obtained by the method.

[0002]

BACKGROUND OF THE INVENTION Olefin polymers are generally used in various fields such as for various molded articles because of their excellent mechanical properties. However, in recent years, the requirements for physical properties of olefin polymers have been diversified, and olefin polymers having various properties have been desired. As an olefin polymer satisfying such a requirement, for example, a polar olefin copolymer obtained by copolymerizing a non-polar olefin and a polar olefin and imparting properties which are not provided by a non-polar olefin-only polymer is known. As a method for producing a polar olefin copolymer obtained by copolymerizing a non-polar olefin and a polar olefin, a radical polymerization method is well known in the art. For example, an ethylene-vinyl acetate copolymer or an ethylene-acrylate copolymer is known. Coalescence and the like are manufactured by this method.

When a polar olefin copolymer is produced by a radical polymerization method, reaction conditions of high temperature and high pressure are often required, and a method of obtaining a polar olefin copolymer under milder conditions has been desired. . As a method for obtaining a polar olefin copolymer under such mild conditions, a method of copolymerizing a non-polar olefin and a polar olefin using a transition metal complex catalyst has recently been reported. For example, Brookhar
t et al. reported a method for obtaining a copolymer of a nonpolar olefin such as ethylene and methyl acrylate under mild conditions using a diimine complex of palladium (J. Am. Chem. Soc.
1998,120,888). However, there are still few examples in which a non-polar olefin and a polar olefin are copolymerized with a transition metal complex catalyst, and the types of polar olefins that can be copolymerized are also limited.

[0004] Under such circumstances, it has been desired to develop a method for producing a polar olefin copolymer which has excellent copolymerizability of a polar olefin and can produce a polar olefin copolymer having excellent properties. ing.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is intended to obtain a polar olefin copolymer having excellent properties under mild polymerization conditions. And a polar olefin copolymer obtained by the method.

[0006]

SUMMARY OF THE INVENTION The method for producing a polar olefin copolymer according to the present invention comprises: (A0) a catalyst comprising a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the following general formula (1). L _m MX _n (1) (wherein M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, and m Is an integer of 1 to 6, n is a number satisfying the valence of M, L is a ligand coordinating to M, and in the following chemical formulas (2) and (3), The values obtained by subtracting the sum of the total energies of the compounds on the left-hand side from the total energies of the compounds on the right-hand side obtained as described above are defined as the coordination energy E _{1 of} ethylene and the coordination energy E _{2 of} methyl acrylate. energy E ₁ and a Coordinating the energy E ₂ of the acrylic acid methyl
Is a ligand having a difference ΔE (ΔE = E ₁ −E ₂ ) of 50 kJ / mol or less,

[0007]

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(Wherein M represents a transition metal atom selected from Groups 3 to 11 of the periodic table which is the same as M in the formula (1), a represents an integer of 1 to 3, and b represents Represents 0 or +1 and represents a methyl group. Me represents a methyl group.) X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, and n Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. The method for producing a polar olefin copolymer according to another embodiment of the present invention includes: (A0) a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the general formula (1); ) (B
At least one compound selected from the group consisting of -1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which reacts with a transition metal compound (A0) to form an ion pair. And a non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst consisting of

In the present invention, the transition metal compound represented by the general formula (1) is preferably a transition metal compound selected from Groups 4, 5, 6, and 11 of the periodic table. The method for producing a polar olefin copolymer according to another embodiment of the present invention is selected from (A1), (C), Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (c). A compound of a transition metal, and M′X _k (c) (wherein, M ′ represents a transition metal atom selected from Groups 4, 5, 6, and 11 of the periodic table, and k satisfies the valence of M ′) X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, and a heterocyclic group. Represents a compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and when k is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other; A plurality of groups may be bonded to each other to form a ring.) (A i) Compound represented by the following general formula (I)

[0010]

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(Wherein A represents an oxygen atom, a sulfur atom or a selenium atom, or a nitrogen atom having a substituent R ⁶ , wherein R ¹ to R ⁶ may be the same or different and each represent a hydrogen atom, a halogen atom Represents a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, Two or more of these groups may be connected to each other to form a ring); and (B) (B-1)
From at least one compound selected from the group consisting of an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that forms an ion pair by reacting with the reaction product (A1). A non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst.

Further, a method for producing a polar olefin copolymer according to another aspect of the present invention comprises the steps of (A2) (C) Periodic Table Nos. 4, 5, 6
And a compound of a transition metal selected from Group 11 and (Ai
i) Compound represented by the following general formula (II)

[0013]

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(Wherein D represents a nitrogen atom or a phosphorus atom, Q represents a nitrogen atom or a phosphorus atom, or a substituent R ¹³
S represents a nitrogen atom or a phosphorus atom, or a carbon atom substituted with a substituent R ¹⁴ , and T represents a nitrogen atom or a phosphorus atom, or a substituent R ¹⁵
And R ¹¹ to R ¹⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, Aluminum-containing groups, phosphorus-containing groups,
It represents a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and two or more of these groups may be connected to each other to form a ring. Reacts with (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) the above reaction product (A2) to form an ion pair. A nonpolar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising at least one compound selected from the group consisting of:

The method for producing a polar olefin copolymer according to another embodiment of the present invention is selected from (A3) (C ′), groups 3 to 11 of the periodic table represented by the following general formula (c ′). A compound of a transition metal; MX _k (c ′) (wherein M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, k is a number satisfying the valence of M, and X is hydrogen) Atom, halogen atom, oxygen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group , A germanium-containing group or a tin-containing group, and when k is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other (A-iii) the following general Compounds represented by formula (III)

[0016]

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(In the formula, A represents an oxygen atom, a sulfur atom or a selenium atom, or a nitrogen atom having a substituent R ²⁶ , R ²¹ to R ²⁸ may be the same or different, and may be a hydrogen atom, a halogen atom Represents a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, And a non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst consisting of a reaction product of (a) and (b). I have.

Further, a method for producing a polar olefin copolymer according to another embodiment of the present invention comprises the steps of: (A3) (C ′), a periodic table represented by the above general formula (c ′);
A reaction product of a compound of a transition metal selected from the group consisting of (A-iii) and a compound represented by the general formula (III), and (B)
At least one selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which reacts with the above reaction product (A3) to form an ion pair. It is characterized in that a non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst composed of various compounds.

In the present invention, the compounds of the transition metal represented by the above general formula (c ') are represented by the following formulas 4, 5, 6, and 11:
It is preferably a compound of a transition metal selected from the group. Further, the method for producing a polar olefin copolymer according to another aspect of the present invention includes: (A4) a compound of a transition metal selected from Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (IV). When,

[0020]

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(Wherein M ′ has the same meaning as M ′ in the general formula (c), m is an integer of 1 to 6, and A, R ¹ to R ⁴ and R ⁶ each represent M in (I),
A has the same meaning as R ¹ to R ⁴ and R ⁶ , n is a number satisfying the valence of M ′, X is the same as X in the above general formula (1), and n is 2 or more In the formula, a plurality of atoms or groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring. (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) the transition metal compound (A4)
Is characterized in that a nonpolar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising at least one compound selected from the group consisting of compounds that form an ion pair by reacting with the compound.

Further, a method for producing a polar olefin copolymer according to another embodiment of the present invention comprises: (A5) a transition selected from Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (V). Metal compounds,

[0023]

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(Wherein M ′ has the same meaning as M ′ in the general formula (c), m is an integer of 1 to 6, and D, Q, S, T
And R ¹¹ to R ¹⁵ have the same meanings as D, Q, S, T and R ¹¹ to R ^{15 in the} general formula (II), respectively.
Is a number that satisfies the valence of M ′, and X is the general formula (1)
In the case where n is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X are bonded to each other to form a ring It may be formed. (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) the transition metal compound (A5)
Is characterized in that a nonpolar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising at least one compound selected from the group consisting of compounds forming an ion pair by reacting with the compound.

Further, a method for producing a polar olefin copolymer according to another embodiment of the present invention comprises: (A6) a method of preparing a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the following general formula (VI). Copolymerizing a nonpolar olefin and a polar olefin in the presence of a catalyst comprising:

[0026]

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(Wherein M has the same meaning as M in the general formula (c ′), m is an integer of 1 to 6, A and R ²¹ to
R ²⁷ represents A and R ²¹ to A in the general formula (III), respectively.
Synonymous with R ²⁷ , n is a number satisfying the valence of M,
Has the same meaning as X in the general formula (1), and when n is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X May combine with each other to form a ring. Further, the method for producing a polar olefin copolymer according to another embodiment of the present invention includes: (A6) a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the general formula (VI);
(B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) the transition metal compound (A6)
Is characterized in that a nonpolar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising at least one compound selected from the group consisting of compounds that form an ion pair by reacting with the compound.

In the present invention, the transition metal compound represented by the general formula (VI) is preferably a transition metal compound selected from Groups 4, 5, 6, and 11 of the periodic table.
A polar olefin copolymer according to the present invention is characterized by being obtained by any one of the above-described methods for producing a polar olefin copolymer. Hereinafter, the reaction product (A1)
And a reaction product (A)
2) a compound that forms an ion pair by reacting with 2), a compound that forms an ion pair by reacting with the reaction product (A3), a compound that forms an ion pair by reacting with a transition metal compound (A4), and a transition metal compound A compound that forms an ion pair by reacting with (A5) and a compound that forms an ion pair by reacting with the transition metal compound (A6) may be referred to as an “ionized ionic compound”.

[0029]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a polar olefin copolymer according to the present invention will be specifically described below. The method for producing a polar olefin copolymer according to the present invention is a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the following general formula (1), and represented by chemical formulas (2) and (3).
, The values obtained by subtracting the sum of the total energies of the compounds on the left side from the total energies of the compounds on the right side obtained by the density functional theory were defined as the coordination energy E _{1 of} ethylene and the coordination energy E _{2 of} methyl acrylate, respectively. At this time, a transition metal compound (A0) having at least one ligand L having a difference ΔE in coordination energy between ethylene and methyl acrylate of 50 kJ / mol or less, and an organometallic compound (B-1) if necessary , Organic aluminum oxy compounds
(B-2) and a non-polar olefin and a polar olefin in the presence of a catalyst comprising at least one compound (B) selected from the group consisting of the ionized ionic compound (B-3); Alternatively, a compound (C) of a transition metal selected from Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (c) and a compound represented by the following general formula (I) or (II): And at least one selected from the group consisting of organometallic compounds (B-1), organoaluminum oxy compounds (B-2) and ionized ionic compounds (B-3)
A non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising the compound (B), or a transition metal selected from groups 3 to 11 of the periodic table represented by the following general formula (c ′) Reaction product of the compound (C ′) of formula (I) with a compound represented by the following general formula (III), and if necessary, an organometallic compound (B-1), an organoaluminumoxy compound (B-2) and an ionized ion A nonpolar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising at least one compound (B) selected from the group consisting of the hydrophilic compounds (B-3), or a compound represented by the following general formula (IV) or ( V) a transition metal compound selected from Groups 4, 5, 6 and 11 of the periodic table, an organometallic compound (B-1), an organoaluminumoxy compound (B-2), and an ionized ionic compound (B At least one selected from the group consisting of -3) A non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst consisting of the compound (B), or a transition metal compound selected from Groups 3 to 11 of the periodic table represented by the following general formula (VI): If necessary, a catalyst comprising at least one compound (B) selected from the group consisting of an organometallic compound (B-1), an organoaluminum oxy compound (B-2), and an ionized ionic compound (B-3) A nonpolar olefin and a polar olefin are copolymerized in the presence of

Transition metal compound (A0) The transition metal compound (A0) is represented by the following formula (1). L _m MX _n (1) In the formula (1), M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably a transition metal selected from Groups 4, 5, 6, and 11 of the periodic table. Is an atom. In particular,
Scandium, yttrium, lanthanoid, titanium,
Zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese,
Rhenium, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, etc., preferably titanium, zirconium, hafnium, vanadium,
A transition metal atom selected from Groups 4, 5, 6, and 11 of the periodic table such as niobium, tantalum, chromium, molybdenum, tungsten, copper, and silver, and more preferably titanium;
Vanadium and chromium.

In the formula (1), m is an integer of 1 to 6,
It is preferably an integer of 1 to 4. In the formula (1), n is M
And more specifically, an integer of 0 to 5, preferably 1 to 4, and more preferably 1 to 3. In the formula (1), L is a ligand coordinated to M, and in formulas (2) and (3), the total energy of the compound on the left side is calculated from the total energy of the compound on the right side obtained by the density functional theory method. difference in the value obtained by subtracting the sum and coordination energy E ₂ of each coordinate energy E ₁ and methyl acrylate ethylene when defining a coordination energy E ₂ coordinating energy E ₁ and methyl acrylate ethylene ΔE (ΔE
= E ₁ -E ₂ ) is 50 kJ / mol or less.

[0032]

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In the chemical formulas (2) and (3), M represents a transition metal atom selected from the same Group 3 to 11 of the periodic table as M in the above formula (1). This ligand L may take any coordination form with respect to the metal M as long as the difference ΔE of coordination energy is 50 kJ / mol or less. Examples include a coordination bond, an ionic bond, and a hydrogen bond. Further, the ligand L may be monodentate or bidentate or more polydentate with respect to the transition metal atom M, and any atom of the ligand L is coordinated to the metal. You may.

In the chemical formulas (2) and (3), a represents the number of ligands L, and b represents the charge of the compound in []. b is 0 or +1; a is determined by the valence of the ligand L and the transition metal atom M; and an integer of 1 to 3 such that the charge of the compound [L _a -M-Me] is 0 or +1. Selected from inside. Me in the chemical formulas (2) and (3) represents a methyl group.

In the present invention, the value obtained by subtracting the sum of the total energies of the compounds on the left-hand side from the total energy of the compounds on the right-hand side obtained by the density functional theory in the chemical formulas (2) and (3) is the coordination energy E of ethylene, respectively. ₁ and the coordination energy E _{2 of} methyl acrylate. Here, the density functional theory referred to in the present invention refers to the program ADF2
It means the calculation using the BLYP method using 000.01.

As a calculation procedure, first, the structure of each compound in chemical formulas (2) and (3) is optimized, and the total energy of each compound in the structure is calculated. Then pull the total energy sum of the left side of the compound from the total energy of the right-hand side of a compound of formula (2) and (3), the coordination energy E ₂ coordinating energy E ₁ and methyl acrylate ethylenically their values respectively I do.

At the time of structural optimization, the base metal is a triple zata type, a methyl group coordinated to the center metal, all atoms in ethylene and methyl acrylate, and an atom in the ligand L as basis functions. Among them, the double zata type is used for the atom bonded to the metal atom, and the single zata type is used for the other atoms. In the chemical formula (3), as the coordination structure of methyl acrylate, one in which carbonyl oxygen is coordinated to the central metal M of the complex is shown. The coordination structure is determined by the result of the structure optimization calculation. Result If the olefin carbon of the methyl acrylate has an interaction with the central metal M, its structure is used to determine the total energy of the compound.

Next, the total energy is calculated for the obtained optimum structure. As a basis function at this time, a triple zata type is used for the central metal, and a double zata type added with a polarization function is used for other atoms. It also corrects Pauli's relativistic potential. Based on the obtained total energies of the compounds, the sum of the total energies of the compounds on the left side is subtracted from the total energies of the compounds on the right side of chemical formulas (2) and (3), and this value is assigned to the distribution of ethylene and methyl acrylate, respectively. position as an energy E ₁ and E _2. Next, the difference Δ in the coordination energy between ethylene and methyl acrylate
E is calculated by ΔE = E ₁ −E ₂ .

In the present invention, the difference ΔE between the coordination energy of ethylene and the coordination energy of methyl acrylate is 50
a nonpolar olefin and a polar olefin in the presence of a catalyst comprising a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the general formula (1) having a ligand L of not more than kJ / mol. Copolymerize. The coordination energy E _{1 of} ethylene and the coordination energy E ₂ of methyl acrylate indicate the degree of stabilization due to the coordination of each monomer to the transition metal, and the difference ΔE is a measure indicating the difference in the degree of stabilization. Becomes In the present invention, ΔE is 50 kJ / mo.
1 or less, preferably 30 kJ / mol or less, more preferably 20 kJ / mol or less.

In the formula (1), X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group,
Phosphorus-containing group, halogen-containing group, heterocyclic compound residue,
Shows a silicon-containing group, a germanium-containing group or a tin-containing group. When X is an oxygen atom, M and X are bonded by a double bond.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cyclopentyl, cyclohexyl, norbornyl,
Cycloalkyl groups having 3 to 30 carbon atoms such as adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl,
And aryl groups such as dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 30 carbon atoms has been substituted with halogen. Among them, those having 1 to 20 carbon atoms are preferable.

Specific examples of the oxygen-containing group include an oxy group;
Peroxy group; hydroxy group; hydroperoxy group; alkoxy group such as methoxy, ethoxy, propoxy, butoxy; aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, naphthoxy; arylalkoxy group such as phenylmethoxy, phenylethoxy; acetoxy group; Carbonyl group; acetylacetonate group (acac); oxo group and the like.

Specific examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, and triisobutylbenzene sulfonate. Sulfonate groups such as phonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, A sulfinate group such as pentafluorobenzene sulfinate; an alkylthio group; an arylthio group; a sulfate group; a sulfide group; a polysulfide group;

Specific examples of the nitrogen-containing group include an amino group;
Alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; arylamino groups and alkylarylamino groups such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenylamino; trimethylamine And alkyl or arylamine groups such as triethylamine, triphenylamine, N, N, N ', N'-tetramethylethylenediamine (tmeda), and N, N, N', N'-tetraphenylpropylenediamine (tppda). Can be

Specific examples of the boron-containing group include BR
₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). As the aluminum-containing group, specifically, AlR ₄ (R is hydrogen,
Alkyl group, an aryl group which may have a substituent, a halogen atom, etc.). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methylphosphite, ethylphosphite, and phenylphosphite. Phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups, and the like.

Specific examples of the halogen-containing group include P
F₆, BF_FourFluorine-containing groups such as ClO _Four, SbCl₆What
Which chlorine-containing groups, IO_FourAnd iodine-containing groups such as
You. Specifically, as a heterocyclic compound residue, a pillow
Pyridine, pyrimidine, quinoline, triazine, etc.
Nitrogen-containing compounds, furan, oxygen-containing compounds such as pyran,
Residues such as sulfur-containing compounds such as thiophene, and
These heterocyclic compound residues preferably have 1 to 30 carbon atoms.
Preferably, 1 to 20 alkyl groups, alkoxy groups, etc.
And a group further substituted by a substituent.

Specific examples of the silicon-containing group include hydrocarbons such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl. A substituted silyl group; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include groups in which silicon of the silicon-containing group is replaced with germanium. Specific examples of the tin-containing group include a group in which silicon of the silicon-containing group is substituted with tin.
When k is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.

The bonding mode between X and transition metal atom M is not particularly limited, and examples of the bonding mode between X and transition metal atom M include a covalent bond, a coordinate bond, an ionic bond, and a hydrogen bond. The ligand L and the transition metal M in the general formula (1) and the chemical formulas (2) and (3) are completely the same, including the valence of the metal, but the numbers a and n of the ligands in the respective formulas Need not be identical.

Reaction Product (A1) The reaction product (A1) comprises a compound (C) of a transition metal selected from Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (c): It is a reaction product with the compound represented by the general formula (I). (Transition metal compound (C)) M′X _k (c) In the formula, M ′ represents a transition metal atom selected from Groups 4, 5, 6, and 11 of the periodic table, and specifically, titanium, zirconium, Group 4 metal atoms of hafnium, vanadium, niobium, group 5 metal atoms of tantalum, chromium, molybdenum,
It is a Group 6 metal atom of tungsten and a Group 11 metal atom of copper, silver, and gold. Of these, titanium, vanadium and chromium are preferred.

X has the same meaning as X in the above formula (1). When k is 2 or more, a plurality of atoms or groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.
The bonding mode between X and the transition metal atom M ′ is not particularly limited,
Examples of the bonding mode between X and the transition metal atom M ′ include a covalent bond, a coordinate bond, an ionic bond, and a hydrogen bond.

K is a number that satisfies the valence of M ′, is determined by the valence of the transition metal atom M ′ and the valence of X, and is a number such that these positive and negative valences are neutralized. Here, assuming that the absolute value of the valence of the transition metal atom M ′ is a and the absolute value of the valence of X is b, a relationship of a = b × k is established. More specifically, for example, if M ′ is Ti
A ^3+, X is Cl ^- if k is 3, and the transition metal compound represented by the general formula (c) is a TiCl _3. If M ′ is Zr ⁴⁺ and X is SO ₄ ²⁻ , k is 2 and the transition metal compound represented by the general formula (c) is Zr (SO ₄ ) ₂ .

When X is composed of two or more kinds of groups, k is divided into two or more numbers so that the positive and negative valences are neutralized. For example, when X is two kinds of groups, The absolute value of the valence of one X is b ₁ , the number is k ₁ , and the other X is
Assuming that the absolute value of the valence is b ₂ and the number is k ₂ , the relationship a = b ₁ × k ₁ + b ₂ × k ₂ holds. Specifically, for example, when M ′ is V ⁵⁺ and X is O ²⁻ and Cl ⁻ , the transition metal compound represented by the general formula (c) is VOCl ₃ or VO ₂ Cl, and When M ′ is V ⁴⁺ and X is O ²⁻ and SO ₄ ²⁻ , the transition metal compound represented by the general formula (c) is [VO] [SO ₄ ].

As the transition metal compound represented by the general formula (c), specifically, for example, TiCl ₃ , TiCl ₄ , T
iBr ₃ , TiBr ₄ , ZrCl ₄ , ZrBr ₄ , HfBr
₄ , HfCl ₄ , VCl ₄ , VCl ₅ , VBr ₄ , VBr ₅ ,
NbCl ₅ , NbBr ₅ , TaCl ₅ , TaBr ₄ , CrC
l ₃ , CrCl ₂ , MoCl ₅ , MoCl ₃ , WCl ₆ , W
Cl ₅ , CuCl ₂ , CuBr ₂ , AgCl ₂ , AuCl ₂
Halides of transition metals such as TiCl ₄ .2 (TH
F), a transition metal halide, such as _{ZrCl 4 · 2 (Et 2 O} ), tetrahydrofuran (THF), acetonitrile, complex compound with the electron donor compound such as diethyl _{ether; ZrOCl 2, HfOCl 2, VOCl} 2, V
OBr, VOCl ₃ , NbOBr ₃ , CrO ₂ Cl ₂ , Mo
OBr, MoOCl ₃ , MoO ₂ Cl ₂ , WOCl ₄ , WO
₂ Br ₂ , CuCl ₂ .2CuO.4H ₂ O, CuBr _{2.
Cu (OH) 2, CuBr 2} · 3Cu (OH) 2 and transition metal compound having a halogen atom such as oxyhalides of a transition metal, a transition metal compound having a hydrocarbon group such as _{Ti (CH 2 Ph) 4,} Ti (O-iPr) ₄ , Zr
(O-iPr) ₄ , Cu (acac) ₂ , MoO (aca)
c) ₂ , W (OPh) ₅ , Cr (acac) ₃ , VO (a
cac) ₂ , V (acac) ₃ , Mo (CO) ₆ , W (C
O) ₆ , a transition metal compound having an oxygen-containing group such as [VO] [SO ₄ ] .5H ₂ O, Ti (N (Me) ₂ ) ₄ , Zr
Transition metal compounds having a nitrogen-containing group such as (N (Me) ₂ ) ₄ are exemplified.

In the transition metal compound (C), M ′ is titanium, vanadium, chromium or copper, and X is a halogen atom, an alkyl group, an oxygen-containing group or a nitrogen-containing group, particularly a chlorine atom, a bromine atom or a methyl group. It is preferred that The reaction product (A1) is a reaction product of the transition metal compound (C) represented by the general formula (c) as described above and the compound (Ai) represented by the following general formula (I). .

[0056]

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In the general formula (I), A represents an oxygen atom (—O—);
A sulfur atom (—S—) or a selenium atom (—Se—), or a nitrogen atom having a substituent R ⁶ (—N (R ⁶ ) —) is shown.
R ¹ to R ⁶ may be the same or different from each other and include a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, It represents a cyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group.

The halogen atom includes fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-
Butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-pentyl, n-hexyl and the like, a linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms; vinyl, allyl ( allyl), a linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms such as isopropenyl; a linear alkenyl group having 2 to 30 carbon atoms, preferably 2 to 20 such as ethynyl and propargyl; Or a branched alkynyl group; having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl.
A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl, and fluorenyl; and a carbon atom having a carbon atom number such as phenyl, benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl and anthryl. 6-30, preferably 6-20, aryl groups; tolyl, iso-propylphenyl,
Examples thereof include alkyl-substituted aryl groups such as t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

The above-mentioned hydrocarbon group may have a hydrogen atom substituted by a halogen atom, for example, a halogenated hydrocarbon having 1 to 30, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. Groups. The hydrocarbon group may have a hydrogen atom substituted by another hydrocarbon group, and examples thereof include an aryl-substituted alkyl group such as benzyl and cumyl.

Further, the hydrocarbon group may be a heterocyclic compound residue; an alkoxy group, an aryloxy group, an ester group,
Oxygen-containing groups such as ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, carboxylic anhydride groups; amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, Nitrogen groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, nitrogen-containing groups such as those in which amino groups are ammonium salts; mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups A thioacyl group, a thioether group, a thiocyanate group, an isothiocyanate group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group,
A sulfur-containing group such as a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group; a phosphorus-containing group such as a phosphide group, a phosphoryl group, a thiophosphoryl group, a phosphato group, a silicon-containing group, a germanium-containing group, or tin It may have a contained group.

Among the hydrocarbon groups, among them,
Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, etc. having 1 to 30 carbon atoms, preferably 1 to 20 linear or branched An alkyl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms such as phenyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, and anthryl; a halogen atom and 1 to 30 carbon atoms, preferably 1-20
An alkyl or alkoxy group having 6 to 3 carbon atoms
A substituted aryl group in which 1 to 5 substituents such as 0, preferably 6 to 20 aryl groups or aryloxy groups are substituted is preferred.

The heterocyclic compound residue is a cyclic group containing 1 to 5 heteroatoms in the group, and examples of the heteroatom include O, N, S, P and B. Examples of the ring include a 4- to 7-membered monocyclic and polycyclic ring, preferably a 5- to 6-membered monocyclic and polycyclic ring. Specifically, for example, pyrrole, pyridine, pyrimidine, quinoline, residues of nitrogen-containing compounds such as triazine, furan, residues of oxygen-containing compounds such as pyran, residues of sulfur-containing compounds such as thiophene, and the like. The residue has 1 to 30 carbon atoms,
Preferably, the alkyl group has 1 to 20 carbon atoms, and has 1 to 3 carbon atoms.
A group further substituted with 0, preferably 1 to 20 substituents such as an alkoxy group is exemplified.

The oxygen-containing group is a group containing 1 to 5 oxygen atoms in the group, and does not include the above-mentioned heterocyclic compound residue. Further, a group containing a nitrogen atom, a sulfur atom, a phosphorus atom, a halogen atom, or a silicon atom and in which these atoms are directly bonded to an oxygen atom is not included in the oxygen-containing group. Specific examples of the oxygen-containing group include, for example, an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group,
Examples include a peroxy group and a carboxylic anhydride group, and an alkoxy group, an aryloxy group, an acetoxy group, a carbonyl group, and a hydroxy group are preferable. When the oxygen-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

The nitrogen-containing group is a group containing 1 to 5 nitrogen atoms in the group, and does not include the above-mentioned heterocyclic compound residue. Specific examples of the nitrogen-containing group include, for example, an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, and a diazo group. And those in which an amino group is an ammonium salt, and an amino group, an imino group, an amide group, an imide group, a nitro group, and a cyano group are preferable. When the nitrogen-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

The sulfur-containing group has a sulfur atom in the group of 1 to 1.
It is a group containing 5 heterocyclic compound residues. Specific examples of the sulfur-containing group include, for example, a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, Examples thereof include a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group, a sulfonate group, and a sulfinate group. A sulfonate group, a sulfinate group, an alkylthio group, and an arylthio group are preferable. When the sulfur-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

The silicon-containing group is a group containing 1 to 5 silicon atoms in the group, for example, a silyl group, a siloxy group,
Examples thereof include a hydrocarbon-substituted silyl group and a hydrocarbon-substituted siloxy group. Among them, specific examples of the hydrocarbon-substituted silyl group include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluoro Phenyl) silyl and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy. When the silicon-containing group contains a carbon atom, the number of carbon atoms is desirably in the range of 1 to 30, preferably 1 to 20.

The phosphorus-containing group is a group containing 1 to 5 phosphorus atoms in the group, and does not include the above-mentioned heterocyclic compound residue. Specific examples of the phosphorus-containing group include a phosphino group, a phosphoryl group, a phosphothioyl group, and a phosphono group. The boron-containing group is a group containing 1 to 5 boron atoms in the group, and does not include the above-mentioned heterocyclic compound residue. Specific examples of the boron-containing group include groups such as an alkyl-substituted boron, an aryl-substituted boron, a boron halide, and an alkyl-substituted boron halide. As the alkyl group-substituted boron, (Et) ₂ B
−, (IPr) ₂ B−, (iBu) ₂ B−, (nC ₅ H ₁₁ ) ₂
B-, C ₈ H ₁₄ B- (9-borabicyclononyl group); (C ₆ H ₅ ) ₂ B- as an aryl-substituted boron; BCl _2- as a boron halide; an alkyl-substituted halogen (Et) BCl-, (iBu)
BCl- and the like. Here, Et is an ethyl group,
iPr represents an isopropyl group, and iBu represents an isobutyl group.

Specific examples of the aluminum-containing group include A
lR ₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Examples of the germanium-containing group and the tin-containing group include those in which silicon of the silicon-containing group is replaced with germanium and tin. Incidentally, the heterocyclic compound residue,
Oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, boron-containing groups, germanium-containing groups, tin-containing groups, silicon-containing groups and phosphorus-containing groups are represented by the following formula: Alternatively, the group is preferably a group which directly bonds to the carbon atom in A.

Next, the examples of R ^{1 to} R ⁵ described above will be described more specifically. Among the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy,
Isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, aryloxy groups include phenoxy,
2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like, acyl groups include formyl, acetyl, benzoyl, p-chlorobenzoyl, p-methoxybensoyl and the like, and ester groups include acetyloxy and Benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like are preferably exemplified.

Of the nitrogen-containing groups, amide groups include acetamido, N-methylacetamido, N-methylbenzamide, and amino groups include methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino. An alkylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, an arylamino group such as methylphenylamino or an alkylarylamino group, an imide group such as acetoimide and benzimide; and an imino group such as Methylimino, ethylimino, propylimino, butylimino, phenylimino and the like are preferably exemplified.

Among the sulfur-containing groups, alkylthio groups include methylthio, ethylthio and the like, arylthio groups include phenylthio, methylphenylthio, and nartylthio, and thioester groups include acetylthio, benzoylthio, methylthiocarbonyl and phenylthio. Carbonyl and the like, and sulfonate groups such as methyl sulfonate, ethyl sulfonate, and phenyl sulfonate; and sulfonamide groups such as phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide. Are preferred.

Examples of the sulfonate group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p -Chlorobenzenesulfonate, pentafluorobenzenesulfonate, etc. include sulfinate groups such as methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, pentafluoro Benzene sulfinate and the like can be mentioned.

Among the phosphorus-containing groups, examples of the phosphino group include dimethylphosphino and diphenylphosphino, and examples of the phosphoryl group include methylphosphoryl, isopropylphosphoryl, and phenylphosphoryl. Examples include phosphothioyl, isopropyl phosphothioyl, and phenyl phosphothioyl. Examples of the phosphono group include a phosphate group such as dimethyl phosphate, diisopropyl phosphate, and diphenyl phosphate, and a phosphate group.

R ^{1 to} R ⁶ represent an aliphatic ring, an aromatic ring or a hydrocarbon ring containing a hetero atom (for example, a nitrogen atom or the like) by linking two or more of these groups, preferably adjacent groups, to each other. May be formed, and these rings may further have a substituent. Among the compounds represented by the general formula (I), the compound represented by the following general formula (Ia) includes a compound in which R ³ and R ⁴ are linked to form an aromatic ring.

[0075]

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Wherein A, R ¹ , R ² , R ⁵ to R ¹⁰ are
Each has the same meaning as A and R ¹ to R ^{6 in the} general formula (I). R ¹ , R ² , and R ^{5 to} R ¹⁰ may be the same or different from each other, and two or more of them may be connected to each other to form a ring. Among the compounds represented by the general formula (I) or (Ia), a compound in which R ⁵ is a hydrogen atom is particularly preferable.

The compounds represented by the general formula (I) include the following compounds. Among the compounds represented by the general formula (I), compounds in which R ³ , R ⁴ and R ⁵ are linked to form an aromatic ring, and A is a nitrogen atom having a substituent R ⁶ include: The following general formula (Ib)
There is a compound represented by

[0078]

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In the formula, R ¹ , R ² , R ⁶ , R ¹¹ to R
¹⁵ has the same meaning as R ¹ to R ⁶ in the general formula (I), respectively. R ¹ , R ² , R ⁶ , and R ^{11 to} R ¹⁵ may be the same or different, and two or more of them may be connected to each other to form a ring. The above general formula (I-
Among the compounds represented by b), a compound in which R ⁶ is a hydrogen atom is particularly preferable.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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The reaction between the transition metal compound (C) and the compound represented by the general formula (I) (compound (I)) is as follows.
For example, it is performed as follows. That is, the transition metal compound (C) and the compound (I) are mixed at a low temperature in the presence of a solvent, and are mixed at -78 ° C to room temperature or under reflux conditions for about 1 hour.
Stir for ~ 48 hours. As the solvent, a solvent usually used for such a reaction can be used, and among them, a polar solvent such as ether and tetrahydrofuran (THF), and a hydrocarbon solvent such as toluene are preferably used.

[0098] The R ⁵ in the compound (I) is the general formula (I)
Is a hydrogen atom and has an active hydrogen group, the compound (I) is brought into contact with a base to prepare a salt, or the compound (I) is brought into contact with a silicon compound to form a silicon compound, It can also be reacted with a metal compound (C). Examples of the base used in this case include basic alkali metal compounds such as n-butyllithium and sodium hydride; basic alkaline earth metal compounds such as ethylmagnesium bromide; and organic bases such as triethylamine and pyridine. Is done. Examples of the silicon compound include alkylsilyl chlorides such as trimethylsilyl chloride and triethylsilyl chloride.

By reacting the transition metal compound (C) with the compound (I), at least a part of X in the general formula (c) is substituted with a ligand derived from the compound (I). The number of the ligands can be adjusted by changing the charge ratio of the transition metal compound (C) to the compound (I). The molar ratio of the reaction between the transition metal compound (C) and the compound (I) is usually 1 to 6 mol, preferably 1 to 4 mol per 1 mol of the transition metal compound (C).
Is a mole.

In the reaction, two or more kinds of compounds (I) may be used, or different kinds of compounds (I) may be added sequentially during the reaction. In this manner, a compound in which a plurality of kinds of ligands coordinate with the transition metal can be synthesized. The ratio of the ligand coordinated to the transition metal compound can be adjusted by changing the charging ratio of two or more types of compounds (I).

When any of R ^{1 to} R ⁴ and R ^{6 in} the compound (I) is a hydrogen atom, a substituent other than a hydrogen atom can be introduced at any stage of the reaction. The composition and structure of the reaction product (A1) were determined by elemental analysis, X-ray crystal structure analysis, mass spectrum, NMR, I
It can be confirmed by analyzing with R or the like.

The reaction product (A) thus obtained
1) includes a transition metal compound (IV) described later, and a compound (compound (A1) in which a part of X in the above general formula (c) is substituted by a ligand derived from compound (I). -a)), unreacted transition metal compound (C), compound (I) and the like. This reaction product (A1) can be used as a mixture without performing a purification operation after the reaction, or can be used after being purified by a purification operation such as distillation or recrystallization.

It is also possible to exchange the metal in the compound contained in the obtained reaction product (A1) with another transition metal selected from Groups 4, 5, 6, and 11 of the periodic table by a conventional method. is there. Further, the compound (A1) in the reaction product (A1)
-a) further converting substituents other than the ligand derived from compound (I), such as converting a remaining halogen group into a hydrocarbon group or converting an amide group into a halogen group. It is also possible.

Reaction product (A2) The catalyst component (A2) is a reaction product of the transition metal compound (C) represented by the general formula (c) and a compound represented by the following general formula (II). .

[0105]

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In the general formula (II), D represents a nitrogen atom or a phosphorus atom. Q nitrogen atom (= N-) or phosphorus atoms (= P-), or substituted with a substituent R ¹³ carbon atom ^{(= C (R 13) -} ) indicates a. S represents a nitrogen atom (-N =) or a phosphorus atom (-P =), or substituted with a substituent R ¹⁴ carbon atom ^{(-C (R 14) =)} .

[0107] T is a nitrogen atom (= N-) or phosphorus atoms (= P-), or substituted with a substituent R ¹⁵ carbon atom ^{(= C (R 15) -} ) shows a. R ^{11 to} R ¹⁶ may be the same or different from each other, and R ^{1 to} R ⁶ in the above general formula (I)
Is synonymous with In these R ^{11 to} R ¹⁶ , a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group,
In the boron-containing group, the germanium-containing group, the tin-containing group, the silicon-containing group, and the phosphorus-containing group, the atomic group characterizing the group is represented by N of the formula (II), a carbon atom, a carbon atom in Q, S, or T. Or a group which directly bonds to D.

R ^{11 to} R ¹⁶ represent an aliphatic ring, an aromatic ring or a hydrocarbon ring containing a hetero atom (for example, a nitrogen atom or the like) by linking two or more of these groups, preferably adjacent groups, to each other. These rings may be formed, and these rings may further have a substituent. Among the compounds represented by the general formula (II), a compound in which R ¹⁶ is a hydrogen atom is particularly preferable.

The compounds represented by the general formula (II) include the following compounds.

[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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The reaction between the transition metal compound (C) and the compound represented by the general formula (II) is performed, for example, as follows. That is, the transition metal compound (C) and the compound (II) are mixed at a low temperature in the presence of a solvent,
At room temperature or under reflux conditions for about 1 to 48 hours. As the solvent, those similar to the solvent used for preparing the above reaction product (A1) are used.

[0117] The compound (II) is in the general formula (II) R ¹⁶
Is a hydrogen atom and has an active hydrogen group, the compound (II) is contacted with a base to prepare a salt, or the compound (II) is contacted with a silicon compound to form a silicon compound, It can also be reacted with a metal compound (C). Examples of the base and the silicon compound used in this case are the same as those used for preparing the above reaction product (A1).

By reacting the transition metal compound (C) with the compound (II), at least a part of X in the general formula (c) is substituted with a ligand derived from the compound (II). The number of the ligands can be adjusted by changing the charging ratio of the transition metal compound (C) to the compound (II). The molar ratio when reacting the transition metal compound (C) with the compound (II) is such that the compound (II) is usually 1 to 6 mol, preferably 1 to 4 mol per mol of the transition metal compound (C).
Is a mole.

In the reaction, two or more compounds (II) may be used, or different compounds (II) may be added sequentially during the reaction. In this manner, a compound in which a plurality of kinds of ligands coordinate with the transition metal can be synthesized. The ratio of the ligand coordinated to the transition metal compound can be adjusted by changing the charging ratio of two or more kinds of compounds (II).

Further, when any of R ^{11 to} R ¹⁵ in the compound (II) is a hydrogen atom, a substituent other than a hydrogen atom can be introduced at any stage of the reaction. The composition and structure of the reaction product (A2) were determined by elemental analysis, X
It can be confirmed by analyzing by line crystal structure analysis, mass spectrum, NMR, IR and the like. The reaction product (A2) thus obtained contains a transition metal compound (V) described later, and a part of X in the general formula (c) is a derivative derived from the compound (II). A compound substituted with a ligand (compound (A2-a)), an unreacted transition metal compound (C), a compound (II), and the like may be included.

After the reaction, the reaction product (A2) can be used as a mixture without performing purification,
It can also be used after purification by a purification operation such as distillation or recrystallization. In addition, metals in the compound contained in the obtained reaction product (A2) were identified as Periodic Tables 4, 5, 6, and 11
It is also possible to exchange with another transition metal selected from the group by a conventional method.

Further, the compound (A2) in the reaction product (A2)
-a) to further convert a substituent other than the ligand derived from compound (II), such as converting a remaining halogen group into a hydrocarbon group, or converting an amide group into a halogen group. It is also possible. Reaction Product (A3) The catalyst component (A3) is a reaction product of a transition metal compound (C ′) represented by the following general formula (c ′) and a compound represented by the following general formula (III). (Transition metal compound (C ′)) MX _k (c ′) wherein M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, preferably selected from Groups 4, 5, 6, and 11. It is a transition metal atom. Specifically, scandium,
Yttrium, lanthanoid, titanium, zirconium,
Hafnium, vanadium, niobium, tantalum, chromium,
Molybdenum, tungsten, manganese, rhenium, iron,
Ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, etc., preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper, silver, etc. It is a transition metal atom selected from Groups 5, 6, and 11, more preferably titanium, vanadium, and chromium.

X and k have the same meanings as X and k in the general formula (c). When k is 2 or more, a plurality of groups represented by X may be the same or different from each other;
May be bonded to each other to form a ring.

[0124]

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In the general formula (III), A represents an oxygen atom (—O
-), Sulfur atom (-S-) or selenium atom (-Se
-) Or a nitrogen atom having a substituent R ²⁶ (-N (R ²⁶ )
-). R ^{21 to} R ²⁸ may be the same or different from each other, and have the same meaning as R ^{1 to} R ⁶ in formula (I).

In these R ^{21 to} R ²⁸ , the hetero-containing group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing group, germanium-containing group, tin-containing group, silicon-containing group and phosphorus-containing group are It is preferred that the atomic group characterizing the group is such a group that is directly bonded to N, carbon atom or A in the formula (III). R ^{21 to} R ²⁸ are two of these
Two or more groups, preferably adjacent groups, may be linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom (such as a nitrogen atom), and these rings may further have a substituent. You may have.

Among the compounds represented by the above general formula (III), a compound in which R ²⁸ is a hydrogen atom is particularly preferred. Examples of the compound represented by the general formula (III) include the following compounds.

[0128]

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[0129]

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[0130]

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The reaction between the transition metal compound (C ′) and the compound represented by the general formula (III) is performed, for example, as follows. That is, the transition metal compound (C ′) and the compound (III) are mixed at a low temperature in the presence of a solvent,
The mixture is stirred at 78 ° C. to room temperature or under reflux conditions for about 1 to 48 hours. As the solvent, those similar to the solvent used for preparing the above reaction product (A1) are used.

Compound (III) is a compound represented by the general formula (III)
^{When 28} is a hydrogen atom and has an active hydrogen group, the compound (III) is contacted with a base to prepare a salt, or the compound (III) is contacted with a silicon compound to form a silicon compound, It can also be made to react with a transition metal compound (C '). Examples of the base and the silicon compound used in this case are the same as those used for preparing the above reaction product (A1).

By reacting the transition metal compound (C ′) with the compound (III), at least a part of X in the general formula (c ′) is substituted with a ligand derived from the compound (III). However, the number of the ligands depends on the transition metal compound (C ′).
It can be adjusted by changing the charging ratio of the compound and the compound (III). Transition metal compound (C ′) and compound (I
When the compound (III) is reacted with 1 mol of the transition metal compound (C ′) in an amount of usually 1 to 6 mol,
Preferably it is 1-4 mol.

In the reaction, two or more types of compounds (III) may be used, or different types of compounds (III) may be added sequentially during the reaction. In this manner, a compound in which a plurality of kinds of ligands coordinate with the transition metal can be synthesized. The ratio of the ligand coordinated to the transition metal compound can be adjusted by changing the charging ratio of two or more kinds of compounds (III).

Further, in the compound (III), R ^{21 to} R ²⁷
When either is a hydrogen atom, a substituent other than a hydrogen atom can be introduced at any stage of the reaction. The composition and structure of the reaction product (A3) were determined by elemental analysis, X
It can be confirmed by analyzing by line crystal structure analysis, mass spectrum, NMR, IR and the like. The reaction product (A3) thus obtained contains a transition metal compound (VI) described later, and a part of X in the general formula (c ′) is derived from the compound (III). A compound substituted with a ligand (compound (A3-a)), an unreacted transition metal compound (C ′), a compound (III), or the like may be included.

After the reaction, the reaction product (A3) can be used as a mixture without performing purification,
It can also be used after purification by a purification operation such as distillation or recrystallization. In addition, metals in the compound contained in the obtained reaction product (A3) were identified as Periodic Tables 4, 5, 6, and 11
It is also possible to exchange with another transition metal selected from the group by a conventional method.

Further, the compound (A3) in the reaction product (A3)
-a) to further convert a substituent other than the ligand derived from compound (III), such as converting a remaining halogen group into a hydrocarbon group, or converting an amide group into a halogen group. It is also possible. Transition metal compound (A4) The transition metal compound (A4) is a compound of a genus transition metal selected from Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (IV).

[0138]

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(In the formula,... Between atoms in N... M ′ indicates a coordinate bond, but in the present invention, those not coordinated are also included.) In the above general formula (IV), M ′ has the same meaning as M ′ in the general formula (c), and is particularly preferably an atom of titanium, vanadium, chromium, or copper. m is an integer of 1 to 6, preferably 1 to 4.

A has the same meaning as A in the general formula (I). R ^{1 to} R ⁴ and R ⁶ represent R ¹ to R in the general formula (I).
It is synonymous with R ⁶ . R ^{1 to} R ⁴ and R ⁶ represent an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom by connecting two or more groups, preferably adjacent groups, to each other. These rings may be formed, and these rings may further have a substituent. Further, when m is plural, R ¹ to R ⁴ and R ⁶ contained and one of the radicals R ¹ to R ⁴ and R ⁶ contained in one ligand and other ligands And one of the groups may be bonded to R ¹
Together, R ² together, R ³ together, R ⁴ together, R ⁶ to each other may be the same or different from each other.

N is a number that satisfies the valence of M ′, and is specifically 0 to 5, preferably 1 to 4, more preferably 1 to 4.
It is an integer of 3. X has the same meaning as X in the above general formula (c). When n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.

Among the transition metal compounds represented by the general formula (IV), a compound in which R ³ and R ⁴ are linked to form an aromatic ring is represented by the following general formula (IV-a).

[0143]

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In the general formula (IV-a), A, M ', X, m
And n are A, M ′, and
It is synonymous with X, m and n. R ¹ , R ² , and R ^{6 to} R ¹⁰ may be the same or different from each other, and are represented by the general formula (I)
It has the same meaning as R ^{1 to} R ⁶ in. Also, R ¹ , R ² , R ^{6 to} R ¹⁰
And two or more of these may be connected to each other to form a ring.

In the transition metal compound represented by the general formula (IV), m is 2 and one of R ^{1 to} R ⁴ and R ⁶ contained in any one of the ligands; Examples of the compound in which one of R ^{1 to} R ⁴ and R ⁶ contained in the other ligand is linked include, for example, a compound represented by the following general formula (IV-
There is a compound represented by b).

[0146]

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In the formula (IV-b), A, M ', X and n have the same meanings as A, M', X and n in the formula (IV). R ¹ to R ⁴ and R ⁶ may be the same or different, R ¹ to R ⁶ in the general formula (I)
Is synonymous with Further, two or more of R ^{1 to} R ⁴ and R ⁶ may be connected to each other to form a ring.

A ′ may be the same as or different from A,
Oxygen atom (-O-), sulfur atom (-S-) or selenium atom (-Se-), or linking group 'nitrogen atom with ^{(-N (R 6' R 6} ) -) shows a. R ¹ ′ to R ⁴ ′ and R ⁶ ′ may be the same or different, and have the same meaning as R ^{1 to} R ⁶ in the general formula (I). Two or more of R ¹ ′ to R ⁴ ′ and R ⁶ ′ may be linked to each other to form a ring. R ¹ to R ⁴ and R ⁶ and R ¹ ′ to R ⁴ ′ and R ⁶ ′ may be the same or different from each other.

[0149] Y is at least the one group, R ¹ '~R ^4' least linking group joining the single group or a single bond selected from selected from R ¹ to R ^4. The bonding group is not particularly limited, but preferably has a structure in which the main chain is composed of 3 or more atoms, more preferably 4 or more and 20 or less, and particularly preferably 4 or more and 10 or less. In addition, this bonding group may have a substituent.

Specific examples of the bonding group represented by Y include groups containing at least one atom selected from oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium, tin, boron and the like. Specifically, -O-, -S-, -S
e- and other chalcogen atom-containing groups; -NH-, -N (C
_{H 3) 2 -, - PH} -, - P (CH 3) 2 - a nitrogen or phosphorus atom-containing groups such _{as; -CH 2 -, - CH 2} -CH 2 -,
A hydrocarbon group having 1 to 20 carbon atoms such as —C (CH ₃ ) ₂ —; a cyclic unsaturated hydrocarbon residue having 6 to 20 carbon atoms such as benzene, naphthalene and anthracene;
A heterocyclic compound residue having 3 to 20 carbon atoms including a heteroatom such as quinoline, thiophene and furan;
A silicon atom-containing group such as H ₂ —, —Si (CH ₃ ) ₂ —,
Tin atom-containing groups such as SnH ₂ — and —Sn (CH ₃ ) ₂ —;
_{-BH -, - B (CH 3} ) -, - BF- like boron atom-containing groups such as.

Among the compounds represented by the above general formula (IV-b), those in which R ³ and R ⁴ and R ³ ′ and R ⁴ ′ are linked to form an aromatic ring are represented by the following general formula (IV-c) expressed.

[0152]

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In the formula (IV-c), A, M ', X and n have the same meanings as A, M', X and n in the formula (IV). R ¹ , R ² , and R ^{6 to} R ¹⁰ may be the same or different from each other, and R ¹ to R in the above general formula (I)
It is synonymous with R ⁶ . Further, two or more of R ¹ , R ² , and R ^{6 to} R ¹⁰ may be connected to each other to form a ring.

A ′ may be the same or different from A,
Oxygen atom (-O-), sulfur atom (-S-) or selenium atom (-Se-), or linking group 'nitrogen atom with ^{(-N (R 6' R 6} ) -) shows a. R ¹ ′, R ² ′ and R ⁶ ′ to R ¹⁰ ′ may be the same or different from each other,
It has the same meaning as R ^{1 to} R ⁶ in. R ¹ ', R ² ', R ⁶ 'to R ¹⁰ '
And two or more of these may be connected to each other to form a ring. Further the ^{R 1, R 2, R 6} ~R 1 0, R 1 ',
R ² ′ and R ⁶ ′ to R ¹⁰ ′ may be the same or different from each other.

Y is a bond between at least one group selected from R ¹ , R ² and R ^{6 to} R ¹⁰ and at least one group selected from R ¹ ′, R ² ′ and R ⁶ ′ to R ¹⁰ ′. Or a single bond. The bonding group is not particularly limited,
It preferably has a structure in which the main chain is composed of 3 or more atoms, more preferably 4 or more and 20 or less, particularly preferably 4 or more and 10 or less. In addition, this bonding group may have a substituent. Specific examples of the bonding group represented by Y include the same groups as Y in the above general formula (IV-b).

Among the transition metal compounds represented by the above general formula (IV), compounds in which R ³ , R ⁴ and R ⁵ are linked to form an aromatic ring are represented by the following general formula (IV-d) Compound.

[0157]

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In the above general formula (IV-d), M ′, X, m and n have the same meanings as M ′, X, m and n in the above general formula (IV). R ¹ , R ² and R ^{11 to} R ¹⁵ may be the same or different from each other, and R ¹ in the above general formula (I)
~R ⁶ as synonymous. Further, two or more of R ¹ , R ² , and R ^{11 to} R ¹⁵ may be connected to each other to form a ring.

The following formulas (IV), (IV-a) and (IV
-b), (IV-c) and (IV-d).

[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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[0181]

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[0182]

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In the above examples, when the compound is a compound of a Group 4 metal, a compound in which the Group 4 metal of the compound is replaced with another Group 4 metal can be exemplified. For example, when the exemplified compound is a Ti compound, Can also be exemplified. In the above examples, when the compound is a Group 5 metal compound, a compound in which the Group 5 metal of the compound is replaced with another Group 5 metal can also be exemplified. For example, when the exemplified compound is a V compound, V is represented by Nb Alternatively, a compound in which Ta is substituted is also exemplified.

In the above examples, when the compound is a compound of a Group 6 metal, a compound in which the Group 6 metal of the compound is replaced with another Group 6 metal can also be exemplified.
When it is an r compound, a compound in which Cr is replaced with Mo or W can also be exemplified. In the above examples, the compound is 1
When the compound is a Group 1 metal compound, a compound in which the Group 11 metal of the compound is replaced with another Group 11 metal can also be exemplified. For example, when the exemplified compound is a Cu compound, a compound in which Cu is replaced with Ag or Au is also exemplified. it can.

Transition Metal Compound (A5) The transition metal compound (A5) is a compound of a transition metal selected from Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (V).

[0186]

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(In the above formula,... Between atoms in N... M ′ indicate a coordinate bond, but in the present invention, those not coordinated are also included.) In the above general formula (V), M ′ is M ′ in the above general formula (c).
It is synonymous with, and titanium, vanadium, chromium, and copper atoms are particularly preferred. D, Q, S and T have the same meanings as D, Q, S and T in the general formula (II), respectively.

M is an integer of 1 to 6, preferably 1
-4. R ^{11 to} R ¹⁵ may be the same or different from each other, and have the same meaning as R ^{11 to} R ¹⁶ in formula (II). R ^{11 to} R ¹⁵ are two or more of these groups,
Preferably, adjacent groups may be connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom, and these rings may further have a substituent. Good. Furthermore, one of R ¹¹ to R ¹⁵ m is a plurality of time, where the one group of R ¹¹ to R ¹⁵ contained in any one of the ligands, contained in other ligands may be a number of groups are bonded, R ¹¹ together, R ¹² together, R ¹³
, R ¹⁴ and R ¹⁵ may be the same or different.

N is a number that satisfies the valency of M ′, and is specifically 0 to 5, preferably 1 to 4, more preferably 1 to 4.
It is an integer of 3. X has the same meaning as X in the above general formula (c). When n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.

In the transition metal compound represented by the above general formula (V), m is 2 and one of R ^{11 to} R ¹⁵ contained in any one of the ligands and another coordination compound Examples of the compound to which one of R ^{11 to} R ¹⁵ contained in the compound is linked include a compound represented by the following general formula (Va).

[0191]

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In the general formula (Va), M ′, X, n, D,
Q, S and T have the same meanings as M ′, X, n, D, Q, S and T in the general formula (V), respectively. R ¹¹
To R ¹⁵ may be the same or different from each other the same meanings as R ¹¹ to R ¹⁶ in the general formula (II). R ^{11 to} R ¹⁵ are
Two or more of these may be connected to each other to form a ring.

D ′ may be the same as or different from D,
Indicates a nitrogen atom or a phosphorus atom. Q ′ may be the same or different from Q, and may be a nitrogen atom (= N−) or a phosphorus atom (= P−), or a carbon atom substituted with a substituent R ¹³ ′ (= C (R ¹³ ′) — ). S ′ may be the same as or different from S, and may be a nitrogen atom (-N =) or a phosphorus atom (-
P =) or a carbon atom substituted with a substituent R ¹⁴ ′ (—C
(R ¹⁴ ′) =).

T ′ may be the same or different from T,
A nitrogen atom (= N-) or a phosphorus atom (= P-), or
Substituent R^Fifteen'Substituted carbon atom (= C (R^Fifteen')-)
Is shown. R¹¹'~ R^Fifteen'May be the same or different
Often, R in the above general formula (I) ¹~ R⁶Is synonymous with R
¹¹'~ R^Fifteen'Means that two or more of these
To form a ring. Also R¹¹Or R^FifteenAnd R
¹¹'Or R^Fifteen'Is the same or different
May be.

[0195] Y is at least the one group, at least one coupling the group bonding group or a single bond selected from R ¹¹ '~R ^15' is selected from R ¹¹ to R ^15. The linking group is not particularly limited, but preferably has a main chain of atom 3
It has a structure composed of not less than 4, more preferably not less than 4 and not more than 20, particularly preferably not less than 4 and not more than 10.
In addition, this bonding group may have a substituent. Specific examples of the bonding group represented by Y include Y in the general formula (IV-b).
And the same groups as mentioned above.

Examples of the transition metal compound represented by the above general formula (V) or (Va) are shown below.

[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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In the above examples, when the compound is a compound of a Group 4 metal, a compound in which the Group 4 metal of the compound is replaced with another Group 4 metal can also be exemplified. For example, when the exemplified compound is a Ti compound, Can also be exemplified. In the above examples, when the compound is a Group 5 metal compound, a compound in which the Group 5 metal of the compound is replaced with another Group 5 metal can also be exemplified. For example, when the exemplified compound is a V compound, V is represented by Nb Alternatively, a compound in which Ta is substituted is also exemplified.

In the above examples, when the compound is a compound of a Group 6 metal, a compound in which the Group 6 metal of the compound is replaced with another Group 6 metal can also be exemplified.
When it is an r compound, a compound in which Cr is replaced with Mo or W can also be exemplified. In the above examples, the compound is 1
When the compound is a Group 1 metal compound, a compound in which the Group 11 metal of the compound is replaced with another Group 11 metal can also be exemplified. For example, when the exemplified compound is a Cu compound, a compound in which Cu is replaced with Ag or Au is also exemplified. it can.

Transition metal compound (A6) The transition metal compound (A6) is a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the following general formula (VI).

[0208]

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(In the formulas,... Between atoms in N... M indicate a coordinate bond, but in the present invention, those not coordinated are also included.) In the above general formula (VI), M Has the same meaning as M in the above general formula (c ′), and is preferably the fourth or fifth periodic table of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper, silver, etc.
A transition metal atom selected from Groups 6 and 11, more preferably titanium, vanadium, and chromium.

M is an integer of 1 to 6, preferably 1
-4. A is the same as A in the general formula (III).
It is synonymous. R^{twenty one}~ R²⁷Are the same but different
R in the general formula (III)^{Two 1}~ R²⁸Synonymous with
You. R^{twenty one}~ R²⁷Represents two or more of these groups,
Or adjacent groups are connected to each other to form an aliphatic ring, an aromatic ring or
Represents a hydrocarbon ring containing a heteroatom such as a nitrogen atom.
These rings may further have a substituent
May be. Furthermore, when m is plural, one of
R contained in the ligand of ^{twenty one}~ R²⁷One of the groups and the other
R contained in the ligand of^{twenty one}~ R²⁷Is linked to one of the groups
R^{twenty one}Each other, R^{twenty two}Each other, R^{twenty three}Each other,
R^{twenty four}Each other, R^{twenty five}Each other, R²⁶Each other, R²⁷Are identical to each other
But they may be different.

N is a number that satisfies the valence of M, and is specifically 0 to 5, preferably 1 to 4, more preferably 1 to 3.
Is an integer. X has the same meaning as X in the general formula (c ′). When n is 2 or more, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring.

In the transition metal compound represented by the general formula (VI), m is 2, and one of R ^{21 to} R ²⁷ contained in any one of the ligands is different from the other ligands. Examples of the compound to which one of R ^{21 to} R ²⁷ included in the ligand is linked include a compound represented by the following general formula (VI-a).

[0213]

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In the above formula (VI-a), A, M, X and n have the same meanings as A, M, X and n in the above formula (VI), respectively. R ²¹ to R ²⁷ may be the same or different, have the same meanings as R ^{2 1} to R ²⁸ in the general formula (III). R ²¹ to R ²⁷ is two or more of them may be bonded to each other to form a ring.

A ′ may be the same or different from A,
Oxygen atom (-O-), sulfur atom (-S-) or selenium
Atom (-Se-) or bonding group R²⁶'With a nitrogen atom
(-N (R²⁶') Indicates-). R^{twenty one}'~ R²⁷'Are identical to each other
And may be different from each other. ¹~
R⁶Is synonymous with R^{twenty one}'~ R²⁷'Is two of these
More than one may be connected to each other to form a ring. Also
R^{twenty one}~ R²⁷And R^{twenty one}'~ R²⁷'Is the same as each other
But they may be different.

Y is a bonding group or a single bond bonding at least one group selected from R ^{21 to} R ²⁷ and at least one group selected from R ²¹ ′ to R ²⁷ ′. The linking group is not particularly limited, but preferably has a main chain of atom 3
It has a structure composed of not less than 4, more preferably not less than 4 and not more than 20, particularly preferably not less than 4 and not more than 10.
In addition, this bonding group may have a substituent. Specific examples of the bonding group represented by Y include Y in the general formula (IV-b).
And the same groups as mentioned above.

The following are examples of the transition metal compound represented by the general formula (VI) or (VI-a).

[0218]

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[0219]

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[0220]

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[0221]

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[0222]

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[0223]

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[0224]

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[0225]

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In the above examples, compounds in which the transition metal of the compound is replaced by another transition metal in the same group can also be exemplified. For example, when the exemplified compound is a Ti compound, a compound in which Ti is replaced by Zr or Hf can also be exemplified. . Next, each compound of the component (B) will be described. In the method of the present invention, the transition metal compound (A1), (A1)
In (2), (A4) or (A5), these transition metal compounds and (B-1) an organometallic compound, (B-2) an organic aluminum oxy compound, and (B-3) an ionized ionic compound A nonpolar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising the component (B), which is at least one selected compound.

In the method of the present invention, in the transition metal compound (A0), (A3) or (A6),
One preferred embodiment is to copolymerize a nonpolar olefin and a polar olefin in the presence of a catalyst comprising the transition metal compound and the component (B). (B-1) Organometallic Compound Specific examples of the organometallic compound (B-1) include organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table as described below.

[0228] (B-1a) In the formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m
≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <
The number is 3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0229] (B-1b) Formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is from 1 to 15 carbon atoms, preferably 1-4 hydrocarbon group A complex alkylated product of a Group 1 metal and aluminum represented by the following formula: (B-1c) Formula R ^a R ^b M ³ (where R ^a and R ^b may be the same or different from each other, and have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Wherein M ³ is Mg, Zn or Cd.) A dialkyl compound of a Group 2 or Group 12 metal represented by the formula:

As the organoaluminum compound belonging to (B-1a), the following compounds can be exemplified. In formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, from 1 to 15 carbon atoms, preferably 1-4 hydrocarbon group indicates, m is preferably a number of 1.5 ≦ m ≦ 3. the organic aluminum compound represented by), the general formula R ^a _m AlX _3-m (wherein, R ^a is from 1 to 15 carbon atoms , Preferably 1-4
X is a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by), the general formula R ^a _m AlH _3-m (wherein, R ^a is from 1 to 15 carbon atoms, preferably 1 to 4
And m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <m
≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3, and m + n + q = 3. The organoaluminum compound represented by).

As the organoaluminum compound belonging to (B-1a), more specifically, trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum,
Tri-n-alkylaluminums such as tridecylaluminum; triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-te
rt-butyl aluminum, tri-2-methylbutyl aluminum, tri-3-methylbutyl aluminum, tri-2-methylpentyl aluminum, tri-3-methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-
Tri-branched alkyl aluminum such as 2-methylhexyl aluminum, tri-3-methylhexyl aluminum and tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triphenyl aluminum and tolyl aluminum triaryl aluminum such as diethyl aluminum hydride, diisobutyl aluminum dialkyl hydride such as _{hydride; (i-C 4 H 9} ) x Al y (C 5 H 10) z ( wherein, x, y, z are positive numbers And z ≧ 2x.) Trialkenyl aluminum such as triisoprenyl aluminum; isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum Alkyl aluminum alkoxides such as minium isopropoxide;
Represented by like ^{_{R a 2.5 Al (OR b)}} 0.5; alkyl sesquichloride alkoxides such as ethyl aluminum sesqui ethoxide, butyl aluminum sesqui butoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide Partially alkoxylated alkylaluminum having an average composition; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide),
Ethyl aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutyl aluminum (2,6-di-t-
Dialkyl aluminum aryloxides such as butyl-4-methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide Dialkylaluminum halides such as diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Partially halogenated alkyl aluminum; of diethyl aluminum Dialkylaluminum hydrides such as hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride and alkylaluminum dihydride such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethyl Partially alkoxylated and halogenated alkyl aluminums such as aluminum ethoxy bromide and the like.

Also, a compound similar to (B-1a) may be used.
For example, two or more aluminum atoms through a nitrogen atom
Organoaluminum compounds to which compound
You. As such a compound, specifically, (C_TwoH_Five)_Two
AlN (C_TwoH_Five) Al (C_TwoH_Five)_TwoAnd the like. Said
Compounds belonging to (B-1b) include LiAl (C_TwoH_Five)_Four,
LiAl (C₇H_Fifteen) _FourAnd the like.

In addition, as the organometallic compound (B-1), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide , Propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, compounds capable of forming the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium or a combination of aluminum halide and alkylmagnesium can be used. Among the organometallic compounds (B-1), an organoaluminum compound is preferred. The above-mentioned organometallic compounds (B-1) are used alone or in combination of two or more.

(B-2) Organoaluminum oxy compound The organoaluminum oxy compound (B-2) may be a conventionally known aluminoxane.
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-7. A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, and adsorbed water or water of crystallization is added to the organic aluminum. A method of reacting with a compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane. Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Solvents used for preparing aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. An alicyclic hydrocarbon such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, a petroleum fraction such as gasoline, kerosene or light oil, or a halide of the above aromatic hydrocarbon, aliphatic hydrocarbon or alicyclic hydrocarbon; (For example, chlorinated products, brominated products, etc.). Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organic aluminum oxy compound, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less in terms of Al atom.
Particularly preferably, the content is 2% or less, that is, those which are insoluble or hardly soluble in benzene. Examples of the organic aluminum oxy compound include an organic aluminum oxy compound containing boron represented by the following general formula (i).

[0239]

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In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. The organoaluminum oxy compound containing boron represented by the general formula (i) includes an alkylboronic acid represented by the following general formula (ii) and R ²⁰ -B- (OH) ₂ ... (Ii) In the formula, R ²⁰ represents the same group as described above.) It can be produced by reacting an organoaluminum compound in an inert solvent in an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours. .

Specific examples of the alkylboronic acid represented by the general formula (ii) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n-butylboronic acid. Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid, and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include those described in (B-1a) above.
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above. Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The above-mentioned (B-2) organoaluminum oxy compounds are used alone or in combination of two or more. (B-3) Ionized ionic compound The ionized ionic compound (B-3) is obtained by reacting the above reaction product (A
A compound that reacts with 1) to form an ion pair, a compound that reacts with the above reaction product (A2) to form an ion pair, a compound that reacts with the above reaction product (A3) to form an ion pair, A compound that forms an ion pair by reacting with the transition metal compound (A4), a compound that forms an ion pair by reacting with the transition metal compound (A5), and an ion pair that forms a reaction with the above transition metal compound (A6) Compound.
Therefore, at least one of the above reaction product and the above transition metal compound that forms an ion pair upon contact with the transition metal compound is included in this compound.

Examples of such compounds include those described in JP-A No. 1-5
01950, JP-A-1-50203, JP-A-3-179005, JP-A-3-179006
JP, JP-A-3-207703, JP-A-3-2703
And Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP 07704, USP-5321106 and the like. Furthermore, a heteropoly compound and an isopoly compound can also be mentioned.

Specifically, examples of the Lewis acid include BR
₃ (R is a phenyl group which may have a substituent such as fluorine, a methyl group, and a trifluoromethyl group or fluorine.), For example, trifluoroboron, triphenylboron , Tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o -Tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include a compound represented by the following general formula (iii).

[0247]

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In the formula, R ²² includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{23 to} R ²⁶ may be the same or different, and represent an organic group, preferably an aryl group or a substituted aryl group.

Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation. Specifically, as the ammonium cation, a trimethylammonium cation,
Trialkylammonium cations such as triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N- 2,4,
N, N-dialkylanilinium cations such as 6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation;

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation. The R ^22, are preferred, such as carbonium cation, ammonium cation, particularly triphenyl carbonium cation, N, N- dimethylanilinium cation, N, is N- diethylanilinium cation.

As the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt,
Dialkylammonium salts, triarylphosphonium salts and the like are also included. Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammoniumtetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) ammonium Such as tetra (o- tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like. Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
An N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a boron compound represented by the following formula (iv) or (v), and the like are also included.

[0254]

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(In the formula, Et represents an ethyl group.)

[0256]

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Specific examples of the borane compound include, for example, decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecarate Salts of anions such as borate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (II
I) and salts of metal borane anions such as bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-
Dicarbadecaborane, dodecahydride-1-phenyl-
1,3-dicarbanona borane, dodeca hydride-1-methyl-1,3-dicarbanona borane, undeca hydride-1,
3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane, 2,7-dicarboundecaborane, undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, Dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate , Tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carboundecaborate, tri (n-butyl) ammonium 7,8-dicarbaun Decaborate, tri (n-butyl) ammonium 2,9-dicarboundecaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundeca Hydride-8-ethyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride -8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride- 8-allyl-7,9
-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-
Salts of anions such as dicarboundecaborate and tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3- Dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis ( Undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), (N-butyl) ammonium bis (undecahydride)
-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride
-7,8-dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8
-Dimethyl-7,8-dicarboundecaborate) ferrate (II
I), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride) -7,8-dicarboundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-
Carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7) -Carbaundecaborate) nickel carboxane (IV) salts and the like.

The heteropoly compound is composed of atoms consisting of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more kinds of atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostovanadate acid, phosphomolybdatovantovanadate acid, germanomolybdatovantovanadate acid, phosphomolybdine Tungstic acid, phosphomolybdniobic acid, salts of these acids, for example metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, With barium etc. And organic salts such as triphenylethyl salt, and isopoly compounds, and the like.

The heteropoly compound and the isopoly compound are not limited to one kind of the above compounds, and two or more kinds can be used. The ionized ionic compound (B-3) as described above is used alone or in combination of two or more. (C) Carrier In the present invention, one kind of component selected from the above reaction products (A1) to (A3), transition metal compounds (A0) and (A4) to (A6) (hereinafter referred to as “component (A)”) And / or organometallic compound (B-1),
At least one compound selected from the organic aluminum oxy compound (B-2) and the ionized ionic compound (B-3) (hereinafter sometimes referred to as “component (B)”) may be used as a carrier (C). ). When used, the carrier (C) is an inorganic or organic compound, and is a granular or fine solid. Among them, the inorganic compound is preferably a porous oxide, an inorganic chloride, a clay, a clay mineral or an ion-exchange layered compound.

As the porous oxide, specifically, Si
O ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , C
aO-, ZnO, BaO, etc. ThO _2, or using a composite or mixture containing them, for example, natural or synthetic _{zeolites, SiO 2 -MgO, SiO 2 -Al} 2 O 3, Si
O ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , S
such as iO ₂ -TiO ₂ -MgO can be used. Among them, those containing SiO ₂ and / or Al ₂ O ₃ as a main component are preferable.

The above-mentioned inorganic oxide is prepared by adding a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ )
₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained. The properties of such a porous oxide vary depending on the kind and the production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 300 μm.
200 μm and a specific surface area of 50 to 1000 m ² /
g, preferably in the range of 100 to 700 m ² / g,
It is desirable that the pore volume is in the range of 0.3 to 3.0 cm ³ / g. Such a carrier may be 100-
It is used after firing at 1000C, preferably 150-700C.

As inorganic chlorides, MgCl ₂ , MgB
r ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, after dissolving an inorganic chloride in a solvent such as alcohol, a material obtained by precipitating into fine particles with a precipitant can also be used. The clay used as a carrier is usually composed mainly of a clay mineral. The ion-exchangeable layered compound used as a carrier is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and the contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. In addition, as these clays, clay minerals and ion-exchangeable layered compounds, not only natural ones but also artificially synthesized ones can be used. In addition, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral,
Hexagonal fine packing type, antimony type, CdCl ₂ type,
Examples thereof include ionic crystalline compounds having a layered crystal structure such as CdI ₂ type.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gairome clay, allophane, hysingelite, pyrophyllite, pumice group, montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, Nacrite, dickite, halloysite, and the like. As the ion-exchangeable layered compound, α-Zr (HAsO ₄ ) ₂ .H
_{2 O, α-Zr (HPO} 4) 2, α-Zr (KPO 4) 2 · 3
H 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 (HP
O ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ , γ-Ti (NH ₄ PO ₄ )
Such polyvalent metal crystalline acid salts of such ₂ · H ₂ O and the like.

The clay, clay mineral or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more with a radius of 20 Å or more measured by a mercury intrusion method, and 0.3 to 5 cc / g. g are particularly preferred. Here, the pore volume is measured by a mercury intrusion method using a mercury porosimeter in a range of pore radius of 20 to 3 × 10 ⁴ Å. When a carrier having a radius of 20 Å or more and a pore volume of less than 0.1 cc / g is used as a carrier, a high polymerization activity tends to be hardly obtained.

It is also preferable to apply a chemical treatment to clay and clay minerals. As the chemical treatment, any of a surface treatment for removing impurities adhering to the surface, a treatment for affecting the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment increases the surface area by removing impurities on the surface and eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative, and the like are formed, and the surface area and the interlayer distance can be changed.

The ion-exchange layered compound has an ion-exchange property.
To convert the exchangeable ions between layers into another large bulky ion.
Layered by exchanging with
It may be a compound. Such bulky ions are layered
It plays a pillar role to support the structure, usually a pillar
Called. In addition, another layer is formed between the layers of the layered compound.
Introducing a substance is called intercalation. I
The guest compound to be intercalated is TiC
l_Four, ZrCl_FourCationic inorganic compounds such as Ti (O
R)_Four, Zr (OR)_Four, PO (OR)_Three, B (OR)_ThreeWhat
Which metal alkoxide (R is a hydrocarbon group, etc.), [Al
₁₃O_Four(OH)_{twenty four}]⁷⁺, [Zr_Four(OH) ₁₄]²⁺, [Fe
_ThreeO (OCOCH_Three)₆]⁺Such as metal hydroxide ions
Is mentioned. These compounds may be used alone or in combination of two or more.
Used in combination.

Further, when intercalating these compounds, Si (OR) ₄ , Al (OR) ₃ , Ge
A polymer obtained by hydrolyzing a metal alkoxide (R is a hydrocarbon group or the like) such as (OR) _4, a colloidal inorganic compound such as SiO _2, or the like can also be present. Examples of the pillars include oxides formed by intercalating the metal hydroxide ions between layers and then heating and dehydrating the layers.

The clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after performing a treatment such as ball milling or sieving. Further, it may be used after water is newly added and adsorbed or subjected to heat dehydration treatment. Further, they may be used alone or in combination of two or more. Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, teniolite and synthetic mica.

The organic compound has a particle size of 10 to 300.
Granular or particulate solids in the range of μm can be mentioned. Specifically, ethylene, propylene, 1-
Butene, 4-methyl-1-pentene, etc. having 2 to 2 carbon atoms
Examples thereof include (co) polymers formed mainly from 14α-olefin or vinylcyclohexane, (co) polymers formed mainly from styrene, and modified products thereof.

(D) Organic Compound Component In the present invention, at the time of polymerization, a specific organic compound component (D), which will be further described later, can be used if necessary. The organic compound component (D) is used, if necessary, for the purpose of improving the polymerization performance and the physical properties of the produced polymer. Such organic compounds include alcohols, phenolic compounds, carboxylic acids, carboxylic esters,
Phosphorus compounds, sulfonates, halogenated hydrocarbons and the like.

With alcohols and phenolic compounds
In general, R³¹-OH is used
(Where R³¹Is a hydrocarbon group having 1 to 50 carbon atoms or
Represents a halogenated hydrocarbon group having 1 to 50 carbon atoms.
You. ), Alcohols such as R ³¹Is halogenated carbonized
Hydrogen is preferred. Also, as a phenolic compound
A hydrocarbon having 1 to 20 carbon atoms at the α, α'-position of the hydroxyl group
Are preferably substituted.

As the carboxylic acid, R is usually³²-COO
The one represented by H is used. R ³²Represents 1 to 1 carbon atoms
50 hydrocarbon groups or halogens having 1 to 50 carbon atoms
A halogenated group having 1 to 50 carbon atoms.
Hydrogenated hydrocarbon groups are preferred. As carboxylate
Is the above R³²-Alkyl of carboxylic acid represented by -COOH
Or aryl esters, for example,
-N-butyl chlorocrotonate or ethyl trichloroacetate
Of carboxylic acids containing halogenated hydrocarbon groups such as
Is desirable for enhancing the polymerization activity.

As the phosphorus compound, phosphoric acids having a P—O—H bond, P-OR, phosphates having a P ＝ O bond, and phosphine oxide compounds are preferably used. As the sulfonate, those represented by the following general formula are used.

[0275]

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In the formula, M is an element belonging to groups 1 to 14 of the periodic table. R ³³ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. m is an integer of 1 to 7, and n is 1 ≦ n ≦ 7
It is.

Examples of the halogenated hydrocarbon include, for example, chloroform and carbon tetrachloride. Other Transition Metal Compounds In the present invention, during the polymerization, a transition metal compound other than the above transition metal compounds (A0) and (A4) to (A6) can be used in combination.

Specific examples of such transition metal compounds include the following transition metal compounds. (a-1) a transition metal imide compound represented by the following general formula:

[0279]

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In the formula, M represents a transition metal atom selected from Groups 8 to 10 of the periodic table, and is preferably nickel, palladium or platinum. R ^{31 to} R ³⁴ may be the same or different from each other, and may be a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or nitrogen, oxygen. And a hydrocarbon group substituted with a substituent containing at least one element selected from phosphorus, sulfur and silicon.

In the groups represented by R ^{31 to} R ³⁴ , two or more of these groups, preferably adjacent groups, may be connected to each other to form a ring. q shows the integer of 0-4. X
Represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group, When q is 2 or more, a plurality of groups represented by X may be the same or different.

(A-2) Transition metal amide compound represented by the following general formula:

[0283]

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In the formula, M represents a transition metal atom selected from Groups 3 to 6 of the periodic table, and is preferably titanium, zirconium or hafnium. R ′ and R ″ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group having 1 to 50 carbon atoms, a halogenated hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, or ,nitrogen,
It represents a substituent having at least one element selected from oxygen, phosphorus, sulfur and silicon.

M is an integer of 0 to 2. n is 1 to 5
Is an integer. A represents an atom selected from Groups 13 to 16 of the periodic table, and specific examples include boron, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, germanium, selenium, and tin. Preferably, there is. When n is 2 or more, a plurality of A may be the same or different from each other.

E is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. When m is 2, two Es may be the same or different from each other;
Alternatively, they may be connected to each other to form a ring. p
Is an integer of 0 to 4.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. Represents a group, and when p is 2 or more,
A plurality of groups represented by X may be the same or different. Of these, X represents a halogen atom and 1 carbon atom.
It is preferably from 20 to 20 hydrocarbon groups or sulfonate groups.

(A-3) Transition metal diphenoxy compound represented by the following general formula:

[0289]

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In the formula, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, l and m are each an integer of 0 or 1, and A and A ′ are carbon atoms having 1 to 50 carbon atoms. A hydrogen group, a halogenated hydrocarbon having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms having a substituent containing oxygen, sulfur or silicon, or halogenation having 1 to 50 carbon atoms It is a hydrocarbon group, and A and A 'may be the same or different.

B is a hydrocarbon group having 1 to 50 carbon atoms,
A halogenated hydrocarbon group having 1 to 50 carbon atoms, R ¹ R ² Z
A group represented by the formula: oxygen or sulfur, wherein R ¹
And R ² is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms containing at least one hetero atom, and Z represents carbon, nitrogen, sulfur, phosphorus or silicon.

P is a number satisfying the valence of M. X is
A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group; In the case of two or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.

(A-4) At least one of the following general formulas
Metal compound containing a ligand having a cyclopentadienyl skeleton containing two heteroatoms

[0294]

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In the formula, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table. X represents an atom selected from Groups 13, 14 and 15 of the periodic table, and at least one of Xs is an element other than carbon. a is 0 or 1. R may be the same or different from each other, and represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a hydrocarbon-substituted silyl group, or selected from nitrogen, oxygen, phosphorus, sulfur and silicon. A hydrocarbon group having a substituent containing at least one element,
Two or more Rs may be connected to each other to form a ring.

B is an integer of 1 to 4, and when b is 2 or more, each [((R) a) ₅ -X ₅ ] group may be the same or different, and furthermore, Rs are crosslinked. May be. c is M
Is a number that satisfies the valence of Y is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
20 halogenated hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, silicon-containing groups or nitrogen-containing groups. When c is 2 or more, a plurality of groups represented by Y may be the same or different, and a plurality of groups represented by Y may be bonded to each other to form a ring.

[0297] In (a-5) formula RB (Pz) ₃ transition metal compound represented by MX _n Formula, M represents a transition metal selected from periodic table 3 to 11 group. R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Pz represents a pyrazolyl group or a substituted pyrazolyl group.

N is a number satisfying the valence of M. X is
A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group; In the case of two or more, a plurality of groups represented by X may be the same or different from each other, or may be bonded to each other to form a ring.

(A-6) Transition metal compound represented by the following general formula

[0300]

Embedded image

In the formula, Y ¹ and Y ³ may be the same or different from each other and are elements selected from Group 15 of the periodic table, and Y ² is an element selected from Group 16 of the periodic table. is there. R ^{41 to} R ⁴⁸ may be the same or different from each other, and include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, It represents a sulfur-containing group or a silicon-containing group, and two or more of these may be linked to each other to form a ring.

(A-7) Compound of a compound represented by the following general formula and a transition metal atom belonging to Groups 8 to 10 of the periodic table

[0303]

Embedded image

In the formula, R ^{51 to} R ⁵⁴ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon having 1 to 20 carbon atoms. And two or more of these may be connected to each other to form a ring. (a-8) Transition metal compound represented by the following general formula

[0305]

Embedded image

In the formula, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and m is an integer of 0 to 3. n is an integer of 0 or 1. p is an integer of 1 to 3. q
Is a number that satisfies the valence of M.

R ^{61 to} R ⁶⁸ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a carbon atom having 1 to 2 carbon atoms.
A hydrocarbon group of 0, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. May be formed. X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group or a nitrogen-containing group. , Q
Is two or more, the groups represented by X may be the same or different from each other, or the groups represented by X may be bonded to each other to form a ring.

Y is a group for bridging the borata benzene ring, and represents carbon, silicon or germanium. A is
Shows an element selected from Group 14, 15, or 16 of the periodic table. (a-9) A transition metal compound containing a ligand having a cyclopentadienyl skeleton other than the above (a-4) (a-10) A compound containing magnesium, titanium and halogen as essential components.

In the method for producing a polar olefin copolymer according to the present invention,
A non-polar olefin and a polar olefin are copolymerized in the presence of the catalyst composed of the component (A) and the component (B) as described above. FIG. 1 shows an example of a process for preparing the olefin polymerization catalyst used in the present invention.

The non-polar olefin is an unsaturated hydrocarbon consisting of only carbon atoms and hydrogen atoms. Specifically, for example, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1- Butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1
Α having 2 to 20 carbon atoms such as -dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene
-Olefins; cycloolefins having 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene and tetracyclododecene; butadiene, isoprene, 4-methyl-1,3-pentadiene,
1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1, 6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylnorbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-
Cyclic or linear diene or polyene having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds, such as nonadiene and 5,9-dimethyl-1,4,8-decatriene; styrene, o-methylstyrene, m-methylstyrene,
aromatic vinyl compounds such as p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene; vinylcyclohexane and the like. As the non-polar olefin, α-olefin is preferable, and ethylene is particularly preferable.

In the present invention, the polar olefin is
An unsaturated hydrocarbon having a polar group, specifically, for example, acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodesenic acid, 12-tridecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 15-
Hexadecenoic acid, 16-heptadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid, 20-henicosenoic acid, 21-docosenoic acid, 22-tricosenoic acid, methacrylic acid, 2-methylpentenoic acid, 2,2 -Dimethyl-3-butenoic acid,
2,2-dimethyl-4-pentenoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, 2,6-heptadienoic acid, 2- (4-isopropylbenzylidene) -4-pentenoic acid, allylmalonic acid, 2- ( 1
0-undecenyl) malonic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] -5-heptene-2-carboxylic acid, bicyclo [2.
2.1] Unsaturated carboxylic acids such as 5-heptene-2,3-dicarboxylic acid and metal salts such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt and calcium salt thereof, and unsaturated carboxylic acids thereof Unsaturated carboxylic esters such as methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester and (5-norbornen-2-yl) ester of an acid (where the unsaturated carboxylic acid is a dicarboxylic acid) When it is an acid, it may be a monoester or a diester), and amides of these unsaturated carboxylic acids, unsaturated carboxylic acid amides such as N, N-dimethylamide (where the unsaturated carboxylic acid is When it is a dicarboxylic acid, it may be a monoamide or a diamide); for example, maleic anhydride, Conic acid, allylsuccinic anhydride, isobutenylsuccinic anhydride, (2,7-octadien-1-yl) succinic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] -5-heptene-2 Unsaturated carboxylic anhydrides such as 1,3-dicarboxylic anhydride; for example, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate,
Vinyl esters such as vinyl trifluoroacetate; halogenated olefins such as vinyl chloride, vinyl fluoride, allyl bromide, allyl chloride, allyl fluoride, allyl bromide; allyl trimethylsilane, diallyldimethylsilane, 3- Silylated olefins such as butenyltrimethylsilane, allyltriisopropylsilane and allyltriphenylsilane; for example, acrylonitrile, 2-cyanobicyclo [2.2.1] -5-heptene, 2,3-dicyanobicyclo [2.2.1]- Unsaturated nitriles such as 5-heptene; for example, allyl alcohol, 3-butenol, 4-pentenol, 5-hexenol, 6-butenol, 7-octenol, 8-nonenol, 9-decenol, 10-undecenol, 11- Unsaturated alcohol compounds such as dodecenol and 12-tridecenol, and their acetates and benzoates Acid ester,
Unsaturated esters such as propionate, caproate, caprate, laurate and stearate; substituted phenols such as vinylphenol and allylphenol; for example, methylvinylether, ethylvinylether, allylmethylether, allyl Unsaturated ethers such as propyl ether, allyl butyl ether, allyl methallyl ether, methoxystyrene and ethoxystyrene; for example, butadiene monoxide, 1,2-epoxy-7-octene, 3-vinyl 7-
Unsaturated epoxides such as oxabicyclo [4.1.0] heptane; unsaturated aldehydes such as acrolein and undecenal, and unsaturated acetal such as dimethyl acetal and diethyl acetal; methyl vinyl ketone, ethyl vinyl ketone; Unsaturated ketones such as allyl methyl ketone, allyl ethyl ketone, allyl propyl ketone, allyl butyl ketone, allyl benzyl ketone, and unsaturated acetals such as dimethyl acetal and diethyl acetal; for example, allyl methyl sulfide, allyl phenyl sulfide, Allyl isopropyl sulfide, allyl n-propyl sulfide,
Unsaturated thioethers such as 4-pentenylphenyl sulfide; unsaturated sulfoxides such as allyl phenyl sulfoxide; unsaturated sulfones such as allyl phenyl sulfone; unsaturated phosphines such as allyl diphenyl phosphine; and allyl diphenyl phosphine oxide And unsaturated phosphine oxides such as Further, unsaturated hydrocarbons having a combination of the above-mentioned polar groups, such as vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, methyl 4- (3-butenyloxy) benzoate, allyl trifluoroacetate, o-chlorostyrene, p-chlorostyrene, divinylbenzene, glycidyl acrylate, allyl glycidyl ether, (2H-perfluoropropyl) -2-propenyl ether, linalool oxide, 3-allyloxy
-1,2-propanediol, 2- (allyloxy) ethanol, N
-Allylmorpholine, allylglycine, N-vinylpyrrolidone, allyltrichlorosilane, acryltrimethylsilane, allyldimethyl (diisopropylamino) silane, 7-octenyltrimethoxysilane, allyloxytrimethylsilane, allyloxytriphenylsilane, etc. . The polar olefin is preferably any of unsaturated carboxylic acid derivatives (particularly acid anhydrides, esters, amides), halogenated olefins and vinyl esters.

At the time of polymerization, the method of adding the component (A) to the polymerization vessel, the method of using each component, the method of addition, and the order of addition are arbitrarily selected, but the following methods are exemplified. (1) A method in which the component (A) and the component (B) are added to a polymerization vessel in an arbitrary order. (2) A method in which the catalyst in which the component (A) and the component (B) are brought into contact in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (4) A method in which the catalyst component in which the component (A) is supported on the carrier (C) and the component (B) are added to the polymerization reactor in any order. (5) A method in which a catalyst in which the component (A) and the component (B) are supported on a carrier (C) is added to a polymerization reactor. (6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the carrier (C) and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (7) A method in which the catalyst component in which the component (B) is supported on the carrier (C) and the component (A) are added to the polymerization reactor in any order. (8) A method in which the catalyst component in which the component (B) is supported on the carrier (C), the component (A), and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (9) A method in which a component in which the component (A) is supported on the carrier (C) and a component in which the component (B) is supported on the carrier (C) are added to the polymerization vessel in an arbitrary order. (10) Component (A) supported on carrier (C), component (B) supported on carrier (C), and component (B)
To the polymerization vessel in any order. In this case, the components (B) may be the same or different. (11) A method in which the component (A), the component (B), and the organic compound component (D) are added to a polymerization vessel in any order. (12) A method in which the component (B) and the component (D) are brought into contact in advance, and the component (A) is added to the polymerization reactor in any order. (13) A method in which the component (B) and the component (D) supported on the carrier (C) and the component (A) are added to the polymerization vessel in any order. (14) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (D) are added to the polymerization reactor in an arbitrary order. (15) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance, and the component (B) and the component (D) are added to the polymerization reactor in an arbitrary order. (16) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component in which the component (B) and the component (D) are brought into contact in advance are added to the polymerization reactor in any order. (17) A method in which the component (A) supported on the carrier (C), the component (B), and the component (D) are added to the polymerization vessel in any order. (18) A method in which a component in which the component (A) is supported on the carrier (C) and a component in which the component (B) and the component (D) are brought into contact in advance are added to the polymerization reactor in an arbitrary order. (19) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are brought into contact in an arbitrary order in advance is added to a polymerization reactor. (20) A method in which the catalyst component in which the component (A), the component (B) and the component (D) are brought into contact in advance, and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (21) Component (A), component (B), and component (D) as carrier (C)
A method in which a catalyst supported on a polymer is added to a polymerization reactor. (22) Component (A), component (B), and component (D) as carrier (C)
A method in which the catalyst component supported on the polymer and the component (B) are added to the polymerization reactor in any order. In this case, the components (B) may be the same or different.

The solid catalyst component in which the component (A) and, if necessary, the component (B) are supported on the carrier (C) may be prepolymerized with an olefin. The polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof; The polar olefin itself can be used as a solvent.

In the copolymerization of a non-polar olefin and a polar olefin using the above catalyst, the component (A) is used in an amount of usually 10 ^-12 to 1 per liter of reaction volume.
It is used in an amount of 0 ^-2 mol, preferably 10 ^-10 to 10 ^-3 mol. Even when the component (A) is used at a relatively low concentration, the olefin can be polymerized with high polymerization activity.

The component (B-1) has a molar ratio of the component (B-1) to the transition metal atom (M or M ') in the component (A) [(B-1) / M
Or M ′] is used in an amount such that it is usually 0.01 to 100,000, preferably 0.05 to 50,000. Component (B-2) is an aluminum atom in component (B-2),
The molar ratio with the transition metal atom (M or M ') in the component (A) [(B-2) / M or M'] is usually from 10 to 50,000.
It is used in an amount such that it becomes 0, preferably 20 to 100,000.

The component (B-3) has a molar ratio of the component (B-3) to the transition metal atom (M or M ') in the component (A) [(B-3) / M
Or M ′] is used in an amount such that it is usually 1 to 10, preferably 1 to 5. When component (D) is used, when component (B) is component (B-1), the molar ratio [(D)
/ (B-1)] is usually 0.01 to 10, preferably 0.1 to
In the case of component (B-2) in such an amount as to be 5, the molar ratio of component (D) to the aluminum atom in component (B-2) [(D) / (B-2)] Is usually 0.001-2, preferably 0.005-1, and when the component (B-3) is used, the molar ratio [(D) / (B-3)] is usually 0. .01-1
It is used in an amount such that it becomes 0, preferably 0.1 to 5.

The amounts of the non-polar olefin and the polar olefin to be subjected to the polymerization are not particularly limited, and are appropriately selected depending on the kind of the olefin used, the copolymerization ratio of the copolymer to be obtained, and the like. The polymerization temperature using such a polymerization catalyst is usually -50 to 200C, preferably 0 to 170C.
Range. The polymerization pressure is usually from normal pressure to 100 kg /
cm ² , preferably normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained polar olefin copolymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. further,
It can also be adjusted by the difference of the component (B) used. The polar olefin copolymer of the present invention has superior adhesiveness, paintability, compatibility, hydrophilicity, oil resistance, etc. as compared with conventional olefin polymers, and can be used in application fields utilizing these properties. it can. Further, the polar olefin copolymer of the present invention can be used as a modifier or the like by mixing with another polymer such as polyethylene or polypropylene.

[0319]

According to the present invention, a polar olefin copolymer can be produced by copolymerizing a non-polar olefin and a polar olefin with high polymerization activity.

[0320]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. The structure of the compound obtained in the synthesis example is 270 MHz
¹ H-NMR (JEOL GSH-270 type), FT-IR (SHIMA
DZU FTIR-8200D type), FD-Mass spectrometry (JEOL SX-
102A type), metal content analysis (dry ashing, diluted nitric acid dissolution, analysis by ICP method, instrument: SHIMADZU ICPS-8000)
Type), carbon, hydrogen, nitrogen content analysis (Heraus CHNO
Type) and the like.

The intrinsic viscosity ([η]) was measured at 135 ° C. in decalin.

[0322]

Synthesis Example 1 Synthesis of Ligand Precursor (L1) Ethanol was placed in a 100 ml reactor which was sufficiently purged with nitrogen.
0 ml, aniline 0.71 g (7.62 mmol) and 3-t-butylsalicylaldehyde 1.35 g (7.58
mmol) and stirring was continued at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, and purified by a silica gel column to obtain 1.83 g (7.2) of an orange oily compound (ligand precursor (L1)) represented by the following formula L1.
3 mmol, yield 95%).

[0323]

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¹ H-NMR (CDCl ₃ ): 1.47 (s, 9H), 6.88 (dd, 1H),
7.24-7.31 (m, 4H), 7.38-7.46 (m, 3H), 8.64 (s, 1H), 13.95
(s, 1H) IR (neat): 1575, 1590, 1610 cm ^-1 FD ^- mass spectrometry: 253 (M ⁺ )

[0325]

Synthesis Example 2 Synthesis of Ligand Precursor (L2) 0.95 g (7.58 mmol) of salicylaldehyde instead of 3-t-butylsalicylaldehyde in Synthesis Example 1
The reaction and purification were carried out in the same manner as in Synthesis Example 1 except that was used. As a result, 1.39 g (7.05) of an orange solid solution of a compound represented by the following formula L2 (ligand precursor (L2)) was obtained.
mmol, 93% yield).

[0326]

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FD-mass spectrometry: 197 (M ⁺ )

[0328]

Synthesis Example 3 Synthesis of Ligand Precursor (L3) Ethanol 1 was placed in a 100 ml reactor sufficiently purged with nitrogen.
50 ml, aniline 5.0 g (53 mmol) and pyrrole 2-carboxaldehyde 5.1 g (53 mmo)
After l) was added and 1 ml of formic acid was added, stirring was continued at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure to remove the solvent, and the residue was purified by a silica gel column to give 6.0 g of a white solid of a compound represented by the following formula L3 (ligand precursor (L3)) (3
4.9 mmol, yield 66%).

[0329]

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¹ H-NMR (CDCl ₃ ): 6.3 (d, 1H), 6.69 (dd, 1H),
6.89 (d, 1H), 7.1-7.5 (m, 4H), 8.29 (s, 1H), 9.85 (brs, 1H) FD
-Mass spec: 170

[0331]

Synthesis Example 4 Synthesis of Ligand Precursor (L4) 2,4-Di-t-butylphenol was placed in a 200 mL reactor purged with nitrogen.
0 g and 50 ml of acetic acid were added, and 3.0 ml of concentrated nitric acid was added under ice cooling.
Was quickly dropped. After completion of the dropwise addition, the mixture was stirred at the same temperature for 1 minute, and the reaction solution was poured into 200 ml of water. The organic layer extracted with diethyl ether was washed with water, concentrated, separated and purified by column chromatography to obtain yellow crystals.
1 g was obtained (yield 84%).

¹ H-NMR (CDCl ₃ , δ): 11.41 (s, 1H), 7.94 (d, 1
H, 2 Hz), 7.63 (d, 1 H, 2 Hz), 1.43 (s, 9 H), 1.29 (s, 9 H) Subsequently, the total amount of the above-obtained compounds, 50 mg of 5% palladium on carbon and 100 ml of ethanol were placed in a 200 ml reactor. , And stirred for 48 hours under one atmosphere of hydrogen. After filtering the reaction solution through celite, the solvent was distilled off to obtain 4.1 g of white crystals (89% yield).

¹ H-NMR (CDCl ₃ , δ): 6.92 (d, 1H, 2 Hz), 6.82
(d, 1H, 2Hz), 5.70 (s, 1H), 3.19 (br1H), 141 (s, 9H), 1.28 (s,
9H) Subsequently, 2.83 g of the obtained compound and 50 ml of ethanol were added to a 100 ml reactor purged with nitrogen, and 1.63 g of benzaldehyde and 1.80 g of acetic acid were further added.
0 ml was added, and the mixture was stirred at room temperature for 24 hours. After concentrating the reaction solution, it was separated and purified by column chromatography,
Compound represented by the following formula L4 (ligand precursor (L4))
3.2 g of yellow crystals were obtained (80%).

[0334]

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¹ H-NMR (CDCl ₃ , δ): 8.70 (s, 1H), 7.96 to 7.92
(m, 2H), 7.73 (s, 1H), 7.48-7.43 (m, 3H), 7.25 (d, 1H, 2Hz),
7.17 (d, 1H, 2Hz), 1.46 (s, 9H), 1.35 (s, 9H)

[0336]

Synthesis Example 5 Synthesis of Ligand Precursor (L5) 1.40 g (12.8 mmol) of o-aminophenol and 50 ml of ethanol were added to a 100 ml reactor purged with nitrogen, and 1.63 g (1.
5.4 mmol) and 1.0 ml of acetic acid, and the mixture was stirred at room temperature for 24 hours. After concentrating the reaction solution, it was separated and purified by column chromatography, and a yellow crystal 1.7 of a compound represented by the following structural formula L5 (ligand precursor (L5)) was obtained.
4 g (8.83 mmol, yield 69%) were obtained.

¹ H-NMR (CDCl ₃ , δ): 8.71 (s, 1H), 7.95 to 7.88
(m, 2H), 7.52-7.43 (m, 3H), 7.32-7.16 (m, 3H), 7.04-6.86
(m, 2H) FD-Mass Spec: 197

[0338]

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[0339]

Synthesis Example 6 Synthesis of Ligand Precursor (L6) In a 300 ml reactor equipped with a Dean-Stark tube.
18.2 g of p-nitrobenzaldehyde (0.12 mo
l), n-butanol 50 ml, p-toluenesulfonic acid 1
500 mg of hydrate and 150 ml of toluene were charged, and the mixture was stirred under reflux conditions for 2.5 hours. After cooling the reaction solution to room temperature, twice with 100 ml of a saturated aqueous solution of sodium hydrogen carbonate,
It was washed once with pure water. After the organic phase was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was dried with a vacuum pump to obtain 30.9 g (yield: 92%) of a compound (a) represented by the following structural formula as a yellow oil.

[0340]

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In a 2-liter reactor sufficiently purged with nitrogen, 28.2 g (0.10 g) of the compound (a) obtained above was added.
mol) and 500 ml of dry THF, and cooled to -65 ° C. Subsequently, 330 ml (0.33 m) of vinylmagnesium bromide (1M, THF solution) was added using a dropping funnel.
ol) was added dropwise over 25 minutes, and the mixture was stirred at -40 ° C for 1 hour. The reaction solution was poured into 1 L of a saturated aqueous solution of ammonium chloride, and 300 ml of diethyl ether was added, and the extraction operation was repeated twice. The organic phase was concentrated, THF 200 ml, 0.
After adding 10 ml of a 5M aqueous hydrochloric acid solution and stirring at room temperature for 20 minutes, 200 ml of a saturated aqueous sodium carbonate solution was added, and pH
After confirming 8, the extraction operation was repeated twice with 100 ml of ethyl acetate. The compound (b) represented by the following structural formula was purified as a pale yellow solid by column chromatography.
0.6 g (yield 73%) was obtained. ¹ H-NMR (CDCl ₃ ): 6.62 to 6.65 (t, 1H), 7.25 to 7.30 (m, 2H), 7.3
4-7.37 (t, 1H), 7.65-7.68 (d, 1H), 7.93-7.97 (d, 1H), 10.13
(s, 1H) FD-Mass Spectroscopy: 145 Elemental Analysis: Found (wt%) C; 74.4 H; 4.7 N; 9.6 Theoretical (wt%) C; 74.5 H; 4.9 N; 9.7

[0342]

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In a 100 ml reactor sufficiently purged with nitrogen, 1.20 g (8.27 g) of the compound (b) obtained above.
mmol), dehydrated ethanol 40 ml, aniline 0.7
7 g (8.27 mmol) and acetic acid (catalytic amount) were charged, and the mixture was stirred at room temperature for 3 hours. After concentrating the reaction solution, the reaction solution was purified by column chromatography, and the compound represented by the following formula L6 (ligand precursor (L6)) was converted into a pale yellow oil in 1.5 parts.
3 g (yield 85%) was obtained. ¹ H-NMR (CDCl ₃ ): 6.50-6.60 (t, 1H), 7.10-7.40 (m, 8H), 8.6
3 (s, 1H), 10.76 (bs, 1H) FD-Mass Spec: 220

[0344]

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[0345]

Synthesis Example 7 Synthesis of Ligand Precursor (L7) In Synthesis Example 1, 0.76 g (7.62 mmol) of cyclohexylamine was used instead of aniline, and 0.1 g of salicylaldehyde was used instead of 3-t-butylsalicylaldehyde. 95
The reaction was carried out in the same manner as in Synthesis Example 1 except that g (7.58 mmol) was used. By distilling off the solvent, a compound represented by the following formula (L7) (ligand precursor (L7))
Was obtained as a yellow oil (1.51 g, 7.43 mmol, 98% yield).

FD-mass spectrometry: 203

[0347]

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[0348]

Synthesis Example 8 Synthesis of ligand precursor (L8) In Synthesis Example 1, 2-hydroxy-5-methoxybenzaldehyde 1.1 was used in place of 3-t-butylsalicylaldehyde.
Synthesis Example 1 except that 5 g (7.58 mmol) was used.
The reaction was carried out in the same manner as described above. By distilling off the solvent, the compound represented by the following formula (L8) (the ligand precursor (L
8)) as orange oil 1.69 g (7.43 mmol)
1, yield 98%).

FD-mass spectrometry: 227

[0350]

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[0351]

Synthesis Example 9 Synthesis of Ligand Precursor (L9) In Synthesis Example 1, 2.05 g (7.62 mmol) of n-octadecylamine was used instead of aniline, and salicyl was used instead of 3-t-butylsalicylaldehyde. Aldehyde 0.
The reaction was carried out in the same manner as in Synthesis Example 1 except that 95 g (7.58 mmol) was used and 120 ml of a toluene / methanol mixed solvent (5/1 volume ratio) was used instead of ethanol as the solvent. By distilling off the solvent, 2.75 g (7.35 mmol, 97% yield) of a compound represented by the following structural formula (L9) (ligand precursor (L9)) was obtained as a yellow oil.

FD-mass spectrometry: 373

[0353]

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[0354]

Synthesis Example 10 Synthesis of Ligand Precursor (L10) In Synthesis Example 1, 0.34 g (3.81 mmol) of 1,4-tetramethylenediamine was used in place of aniline.
The reaction was carried out in the same manner as in Synthesis Example 1 except that 0.95 g (7.58 mmol) of salicylaldehyde was used in place of t-butyl salicylaldehyde and the reaction was carried out while dehydrating with a Dean-Stark tube under reflux. After evaporating the solvent, 0.56 g (1.90 mmol, 50% yield) of a compound represented by the following formula (L10) (ligand precursor (L10)) as yellow crystals was obtained by recrystallization from hot MeOH. Obtained.

FD-mass spectrometry: 296

[0356]

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[0357]

Synthesis Example 11 Synthesis of Ligand Precursor (L11) In Synthesis Example 1, 0.44 g (3.81 mmol) of 1,6-hexamethylenediamine was used in place of aniline.
The reaction was carried out in the same manner as in Synthesis Example 1 except that 0.95 g (7.58 mmol) of salicylaldehyde was used in place of t-butyl salicylaldehyde and the reaction was carried out while dehydrating with a Dean-Stark tube under reflux. After evaporating the solvent, recrystallization from hot MeOH gave 1.13 g (3.49 mmol, 92% yield) of a compound represented by the following formula (L11) (ligand precursor (L11)) as yellow crystals. Obtained.

FD-mass spectrometry: 324

[0359]

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[0360]

Synthesis Example 12 Synthesis of ligand precursor (L12) Same as Synthesis Example 1 except that 0.82 g (7.62 mmol) of 2- (aminomethyl) pyridine was used in place of aniline in Synthesis Example 1. The reaction and purification were carried out.
A compound represented by the following formula (L12) (a ligand precursor (L
12)) as yellow oil (1.83 g, 6.82 mm)
ol, yield 90%).

FD-mass spectrometry: 268

[0362]

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[0363]

Synthesis Example 13 Synthesis of Ti-L1 Complex In a 300 ml reactor which was sufficiently dried and purged with argon,
1.785 g (7.05 mmo) of ligand precursor (L1)
l) and 100 ml of diethyl ether, and charged at −78 ° C.
And stirred. Thereto 4.78 n-butyllithium
ml (1.55 mmol / ml n-hexane solution, 7.
40 mmol) was added dropwise over 5 minutes, then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. with 7.05 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 3.53 mmol) and diethyl ether 40
The mixture was gradually added dropwise to the mixed solution (ml). After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered with a glass filter, and the obtained solid was dissolved and washed with 50 ml of methylene chloride to remove insolubles. The filtrate was concentrated under reduced pressure, the precipitated solid was dissolved in methylene chloride in 10 ml, and 70 ml of pentane was slowly added with stirring. The mixture was allowed to stand at room temperature to precipitate reddish brown crystals. The crystals were separated by filtration with a glass filter, washed with pentane, and dried under reduced pressure to obtain 1.34 g (2.15 mmol, yield 61%) of a red-brown crystal complex (1) represented by the following formula (1). .

[0364]

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¹ H-NMR (CDCl ₃ ): 1.35 (s, 18H), 6.82-7.43 (m,
16H), 8.07 (s, 2H) IR (KBr): 1550, 1590, 1600 cm ^-1 FD-mass spectrometry: 622 (M ⁺ ) Elemental analysis: Ti; 7.7% (7.7) C; 65.8% (65.5) H ; 6.0% (5.8) N; 4.5% (4.5) () is calculated value

[0366]

[Synthesis Example 14] Synthesis of Ti-L3 complex In a 100 ml reactor sufficiently dried and purged with argon,
Ligand precursor (L3) (1.04 g; 6.08 mmol)
A solution of l) in 16 ml of diethyl ether was cooled to -78 ° C, and a 1.45 N n-BuLi / hexane solution was added to (4.2).
ml; 6.08 mmol) was slowly added dropwise, followed by heating to room temperature. This solution was slowly dropped into a mixed solution of 6.08 ml of a titanium tetrachloride solution (0.5 mmol / ml heptane solution, 3.04 mmol) and 16 ml of diethyl ether cooled to −78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 8 hours, the reaction solution was filtered with a glass filter, the filtrate was concentrated under reduced pressure, the precipitated solid was dissolved in 5 ml of methylene chloride, and 10 ml of hexane was slowly added with stirring. The mixture was allowed to stand at room temperature to precipitate a black-brown solid. This solid was separated by filtration with a glass filter, washed with pentane, and dried under reduced pressure to give a black-brown solid complex (2) represented by the following formula (2) as 1.10.
g (2.40 mmol, 79% yield).

[0367]

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¹ H-NMR (CDCl ₃ ): 6.0-7.9 (m, 16H), 7.80 (s, 2
H) FD-mass spectrometry: 456 (M +) Elemental analysis: Ti; 10.4% (10.5)

[0369]

Synthesis Example 15 Synthesis of Ti-L4 Complex 618 mg of the ligand precursor (L4) obtained in Synthesis Example 4 was dissolved in 10 ml of toluene, and the obtained solution was dissolved in 0.1 m
The solution was dropped into 10 ml of a toluene solution of titanium chloride at room temperature while stirring at room temperature. After stirring at the same temperature for 24 hours, the reaction mixture was filtered with a glass filter.
10 ml of n-hexane was added to the obtained filtrate, and -4 was added.
The mixture was allowed to stand at 0 ° C. for 5 hours, and the obtained solid was filtered, and 241 mg of reddish brown crystals of complex (3) corresponding to the following structural formula (3)
Was obtained (33% yield).

[0370]

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FD-MS: 734 (M ⁺ ), 307 (ligand fragment)

[0372]

Synthesis Example 16 Synthesis of VL2 Complex (1) In a 300 ml reactor which was sufficiently dried and purged with argon,
0.99 g (5.0 ml) of ligand precursor (L2) and TH
F100ml, cooled to -78 ° C and stirred. 3.23 ml of n-butyl lithium (1.55 m
mol / ml n-hexane solution, 5.0 mmol)
Then, the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was cooled to −78 ° C. with VCl _3. (THF) _3.
It was gradually dropped into a mixed solution of 0.62 g (1.67 mmol) and 40 ml of THF. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. The mixture was further stirred at room temperature for 5 hours. After distilling THF under reduced pressure, the solid was dissolved in methylene chloride, and the insoluble matter was removed by filtration. After concentrating the obtained filtrate, pentane was added slowly with stirring, whereby a reddish brown solid precipitated. The reddish-brown solid was separated by filtration with a glass filter, washed with pentane, and dried under reduced pressure to obtain 0.44 g (0.69 g) of the complex (4) represented by the following formula.
mmol, yield; 41%).

[0373]

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FD-MS: 639 (M ⁺ )

[0375]

Synthesis Example 17 Synthesis of VL2 Complex (2) [VO] [SO ₄ ] .5H ₂ O 3.30 g (13 mmol)
l) was dissolved in 100 ml of pure water, and this aqueous solution was combined with 5.13 g (26 mmol) of the ligand precursor (L2) and 95%
% Ethanol was added dropwise to the solution. Further, after adding a 50 ml aqueous solution of 4.6 g (56 mmol) of sodium acetate, the reaction solution was stirred under reflux for 20 minutes. After leaving the obtained reaction solution at room temperature for 2 hours, the precipitated deep green powder was separated by filtration with a glass filter, washed with water, ethanol and ether, and dried under reduced pressure, thereby obtaining a complex (5) represented by the following formula: 4.48 g (9.75 mmol, yield;
75%).

[0376]

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FD-MS: 459 (M ⁺ )

[0378]

[Synthesis Example 18] Synthesis of Cr-L1 complex In a 300 ml reactor which was sufficiently dried and purged with argon,
1.785 g (7.05 mmo) of ligand precursor (L1)
l) and 100 ml of THF, and cooled to -78 ° C.
Stirred. 4.78 ml of n-butyllithium (1.
55 mmol / ml, n-hexane solution, 7.40 mmol
1) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution. This solution was gradually dropped into a mixed solution of 0.558 g (3.53 mmol) of chromium trichloride and 40 ml of THF cooled to -78 ° C. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. After further stirring at room temperature for 5 hours, the reaction solution was filtered through a glass filter,
Further, the obtained solid was dissolved and washed with 50 ml of methylene chloride to remove insolubles. The filtrate was evaporated to dryness under reduced pressure, and ether /
Green powder was precipitated by reprecipitation with hexane. The powder was filtered off with a glass filter, washed with hexane, and dried under reduced pressure to obtain 1.04 g (1.76 mmol, yield 50) of a complex (6) represented by the following formula.
%)Obtained.

[0379]

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FD-mass spectrometry: 592 (M +) Elemental analysis: Cr; 8.9% (8.8) C; 69.3% (69.0) H; 6.4% (6.1) N; 5.0% (4.7) (): calculated value

[0381]

Synthesis Example 19 Synthesis of Cu-L1 Complex Ligand precursor (L1) 500 in a 100 ml eggplant flask
mg (1.97 mmol) and 30 ml of methanol
And heated to 50 ° C. In another 50 ml eggplant flask, 200 mg (1.10 mmol) of copper acetate (II) was added, 15 ml of methanol was added, and the mixture was stirred while being heated to 50 ° C. This copper acetate-methanol solution was added to the methanol solution of the ligand precursor (L1) with a pipette while stirring. At this time, a brown solid precipitated, and was cooled to room temperature and filtered with a glass filter. The solid was washed twice with 20 ml of methanol and dried under reduced pressure.
510 mg of complex (7) was obtained as a shiny brown solid (yield: 82%).

[0382]

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FD-Mass Spec: 568 (M ⁺ )

[0384]

Synthesis Example 20 Synthesis of V-L7 Complex [VO] [SO ₄ ] · 5H ₂ O 1.10 g (4.86 m)
mol) was dissolved in 25 ml of MeOH, and 1.96 g (9.64 mmol) of ligand precursor (L7) in MeOH was added thereto.
A 25 ml solution of H was added dropwise at room temperature. Further pyridine 1
After adding ml, the reaction solution was stirred under reflux for 2 hours. After leaving the obtained reaction solution at room temperature for 2 hours, the precipitated green powder was separated by filtration with a glass filter, and washed with methanol.
The complex (8) represented by the following formula by drying under reduced pressure
Was obtained as a green powder (1.25 g, 2.65 mmol, yield: 55%).

FD-mass spectrometry: 471 (M ⁺ )

[0386]

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[0387]

Synthesis Example 21 Synthesis of V-L8 Complex In Synthesis Example 20, 2.19 g (9.64 mmol) of ligand precursor (L8) was used instead of ligand precursor (L7), and the reaction time was 4 hours. Synthesis Example 20 except that the time was changed
Reaction and purification treatments were carried out in the same manner as described above. 0.39 g of a complex (9) represented by the following structural formula as blue-green powder (0.
74 mmol, yield; 15%).

FD-mass spectrometry: 419 (M ⁺ )

[0389]

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[0390]

Synthesis Example 22 Synthesis of VL9 Complex In Synthesis Example 20, 3.60 g (9.64 mmol) of the ligand precursor (L9) was used instead of the ligand precursor (L7), and the reaction solvent was toluene. / Methanol mixed solvent (1 /
The reaction was carried out in the same manner as in Synthesis Example 20, except that the ratio was 1 volume ratio). After evaporating the solvent, the residue was extracted with hexane, and the solvent was evaporated to dryness to obtain 2.39 g (2.94 mmol, yield; 61%) of a complex (10) represented by the following structural formula as a light brown powder.

FD-mass spectrometry: 811 (M ⁺ )

[0392]

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[0393]

Synthesis Example 23 Synthesis of V-L10 Complex In Synthesis Example 20, 1.44 g (4.86 mmol) of the ligand precursor (L10) was used instead of the ligand precursor (L7), and the solvent amount was 100 ml. And the amount of pyridine is 2 ml
The reaction and purification were carried out in the same manner as in Synthesis Example 20, except that 1.13 g (3.12 mmol, yield; 64) of the complex (11) represented by the following structural formula as a yellow-green powder
%)Obtained.

FD-mass spectrometry: 361 (M ⁺ )

[0395]

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[0396]

Synthesis Example 24 Synthesis of V-L11 Complex In Synthesis Example 20, 1.58 g (4.86 mmol) of the ligand precursor (L11) was used instead of the ligand precursor (L7), and the solvent amount was 100 ml. And the amount of pyridine is 2 ml
The reaction and purification were carried out in the same manner as in Synthesis Example 20, except that 1.02 g (2.61 mmol, yield; 54) of a complex (12) represented by the following structural formula as a yellow-green powder
%)Obtained.

FD-mass spectrometry: 389 (M ⁺ )

[0398]

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[0399]

Synthesis Example 25 Synthesis of V-L12 Complex In a 100 ml reactor which was sufficiently dried and purged with argon,
0.43 g (1.61 mmol) of the ligand precursor (L12)
l) and 15 ml of diethyl ether were charged, cooled to -78 ° C, and stirred. 1.00m of n-butyl lithium
l (1.59 mmol / ml n-hexane solution, 1.5
9 mmol) was added dropwise over 10 minutes, and then the temperature was slowly raised to room temperature, and stirring was continued at room temperature for 4 hours to prepare a lithium salt solution.

This solution was cooled to 0 ° C. with VCl ₃ (t
hf) 30.59 g (1.57 mmol) of diethyl ether in 15 ml was slowly added dropwise. After completion of the dropwise addition, stirring was continued while slowly raising the temperature to room temperature. The mixture was further stirred at room temperature for 3 hours. After completion of the stirring, the solvent was distilled off under reduced pressure, and the remaining tan solid was extracted with 30 ml of methylene chloride. The extract was filtered through a glass filter, concentrated to about 10 ml, and 15 ml of hexane was added. The precipitated solid was collected by filtration with a glass filter, washed with pentane, and dried under reduced pressure to obtain 0.37 g of a complex (13) represented by the following formula (13) as a tan powder (0.10 mmol, yield 60).
%)Obtained.

FD-Mass Spec: 388

[0402]

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[0403]

Synthesis Example 26 Synthesis of Ti-L6 Complex 0.85 g (3.9 mmol) of ligand precursor (L6) was placed in a 50-mL Schlenk flask sufficiently purged with argon.
l) was dissolved in 15 ml of diethyl ether, cooled to -78 ° C, and then slowly stirred with butyllithium (1.
2.48 ml (3.9 mmol) of a 6M hexane solution was added, and the temperature was gradually returned to room temperature to prepare a lithium salt solution of the ligand. On the other hand, 3.86 ml (1.93 mmol) of titanium tetrachloride (0.5 M heptane solution) was charged into another Schlenk flask purged with argon and degassed by -78.
At 6 ° C., 6 ml of diethyl ether was added, and the mixture was returned to room temperature with slow stirring. The solution was returned to −78 ° C. again, and the lithium salt solution of the ligand prepared above was added dropwise, followed by stirring at room temperature overnight. After evaporating the solvent with a vacuum pump, 30 ml of dichloromethane was added and insolubles were removed by filtration, and the filtrate was concentrated.
The complex (14) represented by the following structural formula was obtained as a dark purple solid by recrystallization from a hexane-dichloromethane solvent.
94 g (87% yield) was obtained. FD-Mass Spec: 556

[0404]

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[0405]

Synthesis Example 27 Synthesis of V-L4 Complex 2.50 g (8.1 mmol) of a ligand precursor (L4) was dissolved in 50 ml of hexane, and 4.0 ml (6 M) of an n-butyllithium hexane solution (1.6 M) was dissolved. .4 mmol) was added dropwise with stirring at room temperature. After stirring at the same temperature for 1 hour, the generated yellow precipitate was filtered through a glass filter,
After washing with 15 ml of n-hexane, the residue was dried under vacuum to obtain 1.79 g of a lithium phenoxide derivative as a raw material compound. This was dissolved in 50 ml of THF at room temperature.
Vanadium trichloride THF solution (0.02
3M) was added dropwise with stirring to 125 ml (2.86 mmol). After completion of the dropwise addition, the temperature of the reaction solution was raised to room temperature.
After stirring for hours, the solvent was removed under vacuum, and 50 ml of toluene was added and dissolved at room temperature. After the inorganic salts in the obtained solution were removed by glass filter filtration, the entire solution was concentrated to about 10 ml. To this solution, 80 ml of n-hexane was added, and the mixture was stirred for 1 hour. The resulting precipitate was filtered with a glass filter to obtain 20 ml of n-hexane.
and dried under vacuum to obtain 1.23 g of a complex (15) represented by the following structural formula (brown powder, yield 4).
6%). FD-MS (m / z): 703 (100% intensity, M ⁺ ), 309 (58% intensity, ligand fragment)

[0406]

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[0407]

Synthesis Example 28 Synthesis of V-L5 Complex The reaction and purification were carried out in the same manner as in Synthesis Example 27 except that the ligand precursor (L5) was used instead of the ligand precursor (L4). Complex (16) represented by the structural formula
23 g was obtained (brown powder, 48% yield). FD-MS (m / z): 478 (intensity 100%, M ⁺ ), 197 (intensity 52%, ligand fragment)

[0408]

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[0409]

Example 1 Ethylene-norbornene with complex (1)
Dicarboxylic anhydride copolymer Into a 500 ml glass autoclave sufficiently purged with nitrogen was charged 250 ml of toluene, and norbornene was added.
0.5 mmol of -2,3-dicarboxylic anhydride (hereinafter abbreviated as "NDCA"), 100 l of ethylene / hr
And the liquid and gas phases were saturated with ethylene. Then, methylaluminoxane was converted to aluminum atom by 2.50.
mmol, followed by the complex (1) obtained in Synthesis Example 13.
Was added to initiate polymerization. After reacting at 25 ° C. for 10 minutes in an atmosphere of ethylene gas at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After sufficiently washing the polymer with methanol and drying under reduced pressure at 80 ° C. for 10 hours, 1.15 g of a polymer was obtained. IR and ¹³ C-NM of this polymer
When R was measured, the obtained polymer was an ethylene-NDCA copolymer containing NDCA at 0.02 mol%.

In the chemical formulas (2) and (3), the ligand L in the complex (1), the number a of the ligands is 2, and the central metal M is Ti (IV). When the energy difference ΔE was calculated, it was 20.3 kJ / mol.

[0411]

Example 2 Ethylene-maleic anhydride with complex (2)
Acid anhydride copolymerization Same as Example 1 except that complex (2) obtained in Synthesis Example 14 was used instead of complex (1) in Example 1 and 0.5 mmol of maleic anhydride was used instead of NDCA. And subjected to post-treatment to obtain 0.06 g of a polymer. When IR and ¹³ C-NMR of this polymer were measured,
The obtained polymer was an ethylene-maleic anhydride copolymer containing 0.01 mol% of maleic anhydride.

In the above chemical formulas (2) and (3), the ligand L in the complex (2), the number a of the ligands are 2, and the central metal M is Ti (IV). When the energy difference ΔE was calculated, it was 43.6 kJ / mol.

[0413]

Example 3 Ethylene-norbornene with complex (3)
Dicarboxylic anhydride copolymer 250 ml of toluene is charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and the liquid phase and the gas phase are saturated with 100 l / hr of ethylene. Thereafter, 0.5 mmol of NDCA, 0.25 mmol of triisobutylaluminum, 0.005 mmol of the complex (3) obtained in Synthesis Example 15, and 0.006 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate were added, followed by polymerization. Started. After reacting at 75 ° C. for 30 minutes in an atmosphere of ethylene gas at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. The polymer was sufficiently washed with methanol and dried under reduced pressure at 80 ° C. for 10 hours.
3 g were obtained. The polymer was measured for IR and ¹³ C-NMR.
It was an ethylene-NDCA copolymer contained in mol%.

In the chemical formulas (2) and (3), the ligand L in the complex (3), the number a of the ligands are 2, and the central metal M is Ti (IV). The calculated energy difference ΔE was 24.2 kJ / mol.

[0415]

Example 4 Ethylene-norbornene with complex (4)
Dicarboxylic anhydride copolymer 250 ml of toluene is charged into a 500 ml-volume glass autoclave sufficiently purged with nitrogen, and the liquid phase and the gas phase are saturated with 100 l / hr of ethylene. Thereafter, 0.5 mmol of NDCA, 0.1 mmol of diethylaluminum chloride, 0.5 mmol of ethyltrichloroacetate, and 0.005 mmol of the complex (4) obtained in Synthesis Example 16 were added to initiate polymerization.
After reacting at 25 ° C. for 10 minutes in an atmosphere of ethylene gas at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the entire amount of the polymer, and hydrochloric acid was added, followed by filtration through a glass filter. After sufficiently washing the polymer with methanol and drying under reduced pressure at 80 ° C. for 10 hours, 0.38 g of a polymer was obtained. IR and ¹³ CN of this polymer
When the MR was measured, the obtained polymer was an ethylene-NDCA copolymer containing NDCA of 0.03 mol%.

In the chemical formulas (2) and (3), the ligand having the ligand L in the complex (4), the number a of the ligands is 2, and the central metal M is V (III). When the energy difference ΔE was calculated, it was −26.9 kJ / mol.
Met.

[0417]

Example 5 Ethylene-norbornene with complex (5)
By performing the same polymerization and post Example 4 except for using complex obtained in Synthesis Example 17 in place of the complex (4) in the dicarboxylic acid anhydride copolymer Example 4 (5) 0.5 mmol The polymer was added to 0.
24 g were obtained. When the IR and ¹³ C-NMR of this polymer were measured, the obtained polymer had an NDCA of 0.0
The ethylene-NDCA copolymer contained in an amount of 2 mol%, which is represented by the above formula (2) or (3),
Ligands of complex (5) having ligand L, number of ligands a
Was 2, and the difference ΔE in coordination energy was calculated with the central metal M as V (IV), and it was 9.1 kJ / mol.

[0418]

Example 6 Ethylene-norbornene with complex (6)
Dicarboxylic anhydride copolymerization Example 1 was repeated except that the complex (6) obtained in Synthesis Example 18 was used instead of the complex (1).
Post-processing was performed. 0.05 g of polymer was obtained. When the IR and ¹³ C-NMR of this polymer were measured, the obtained polymer was an ethylene-NDCA copolymer containing 0.02 mol% of NDCA.

[0419]

Example 7 Ethylene-methyl methoxide by complex (7)
250 ml of toluene was placed in a 500 ml glass polymerization vessel (with a stirring spring) which had been replaced with nitrogen in a copolymer of nitrogen, and ethylene was blown in the toluene from the tube for 10 minutes while stirring slowly. Then, 3.39 ml (5 mmo) of a toluene solution of methylaluminoxane having an Al concentration of 1.475 M was used.
l), 2.5 ml of a 0.01 M toluene solution of complex (7)
(0.025 mmol), methyl methacrylate 2m
The mixture was stirred at 20 ° C. for 6 hours while flowing ethylene at 50 liter / hr (600 rpm).
The reaction was quenched by adding 25 ml of isobutanol and 5 ml of hydrochloric acid to the reaction solution, stirred at room temperature for 30 minutes, and added with 1.5 liter of methanol, and the resulting slurry was filtered with a glass filter. 958 mg of polymer were obtained. When the obtained polymer was subjected to IR measurement, an ethylene-methyl methacrylate copolymer containing a carbonyl group derived from methyl methacrylate was obtained.

[0420]

Example 8 Ethylene-maleic anhydride with complex (1)
Acid copolymerization Polymerization was carried out in the same manner as in Example 1 except that maleic anhydride was used in place of NDCA, and post-treatment was carried out to obtain 0.30 g of a polymer. When the IR and ¹³ C-NMR of this polymer were measured, the obtained polymer was an ethylene-maleic anhydride copolymer containing 0.02 mol% of maleic anhydride.

[0421]

Example 9 Ethylene-norbornene with complex (14)
And dicarboxylic anhydride copolymer. In Example 1, the complex (14) obtained in Synthesis Example 26 was used in place of the complex (1), and the amount of NDCA was 2.0 mmol.
The polymerization was carried out in the same manner as in Example 1 except that the polymerization time was changed to 60 minutes, and post-treatment was carried out to obtain 0.03 g of a polymer. When the IR and ¹³ C-NMR of the obtained polymer were measured, the obtained polymer was an ethylene-NDCA copolymer containing NDCA of 0.02 mol per 100 mol of ethylene units.

[0422]

Comparative Example 1 In Example 1, dicyclopentadienyl titanium dichloride (Cp ₂ Ti) was used in place of complex (1).
Polymerization was carried out in the same manner as in Example 1 except that Cl ₂ was used. No polymer was obtained. In the above chemical formulas (2) and (3), the ligand energy L was calculated as a cyclopentadienyl group, the number of ligands a was 2, and the central metal M was Ti (IV). However, it was 93.1 kJ / mol. "

[0423]

Comparative Example 2 Polymerization was carried out in the same manner as in Example 5 except that dicyclopentadienyltitanium dichloride was used instead of complex (5). No polymer was obtained.

[0424]

Examples 10 to 17 Complex (5) and Complex (15)
Ethylene-Polar Olefin Copolymer Into a 500 ml glass autoclave sufficiently purged with nitrogen, 250 ml of hexane was charged, and the liquid phase and the gas phase were saturated with ethylene at the flow rates shown in Table 1. Thereafter, a polar olefin shown in Table 1, diethylaluminum chloride or ethylaluminum dichloride as a co-catalyst, and then a complex (5) or a complex (15) as a catalyst were added in the amounts shown in Table 1, respectively, to initiate polymerization. Polymerization was carried out at 25 ° C. for the time shown in Table 1 while ethylene blowing was continued, and the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of hydrochloric acid-methanol to precipitate the entire amount of the polymer, and then filtered through a glass filter. After sufficiently washing the polymer with methanol, the polymer was dried under reduced pressure at 80 ° C. for 10 hours. The yield of the obtained polymer, [η] and ¹³ C-NM
Table 1 summarizes the polar olefin content determined by R measurement. The polar olefin was contained in all the polymers, and an ethylene-polar olefin copolymer was obtained.

[0425]

[Table 1]

[0426]

Examples 18 to 21 Complexes (8), (9), (10) and
And (13) ethylene by - in methyl acrylate copolymer Example 10, except that the complex used as the catalyst instead of the complexes shown in Table 2 was carried out by following the procedure of polymerization and post treatment as in Example 10. The yield of the obtained polymer, [η]
Table 2 summarizes the content of methyl acrylate determined by ¹³ C-NMR measurement together with the results of Example 10 in which polymerization was carried out under the same conditions. All the polymers contained methyl acrylate, and an ethylene-methyl acrylate copolymer was obtained.

[0427]

Examples 22 and 23 According to the complexes (11) and (12)
Ethylene-methyl acrylate copolymerization Example 10 was the same as Example 10 except that 4 mmol of ethyl trichloroacetate was added before the addition of the catalyst at the start of the polymerization, and the complex used as the catalyst was replaced with the complex shown in Table 2. Was subjected to polymerization and post-treatment. The yield of the obtained polymer, [η] and the content of methyl acrylate determined by ¹³ C-NMR measurement are shown in Table 2 together with the results of Example 10. All the polymers contained methyl acrylate, and an ethylene-methyl acrylate copolymer was obtained.

[0428]

[Table 2]

[0429]

Examples 24 to 28 Complexes (5) and (15)
Ethylene-propylene-methyl acrylate copolymer Into a 500 ml glass autoclave sufficiently purged with nitrogen, 250 ml of hexane was charged, and the liquid phase and the gas phase were saturated with an ethylene / propylene mixed gas at the flow rates shown in Table 3. I let it. Then, 6 mmol of methyl acrylate,
8 mmol of diethylaluminum chloride or ethylaluminum dichloride as cocatalyst, followed by 0.04 mmol of complex (5) or complex (15) as catalyst
1 was added to initiate polymerization. The polymerization was carried out at 25 ° C. for the time shown in Table 3 while continuously blowing the ethylene / propylene mixed gas, and then the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction product was poured into a large amount of hydrochloric acid-methanol to precipitate the entire amount of the polymer, and then filtered through a glass filter. After sufficiently washing the polymer with methanol, the operation of dissolving in hot toluene and then throwing it into a large amount of methanol to precipitate the polymer was repeated twice to purify the polymer. Then at 130 ° C for 10
It dried under reduced pressure for hours. Table 3 summarizes the yield, [η] and the contents of propylene and methyl acrylate obtained by ¹³ C-NMR measurement of the obtained polymer. All the polymers contained methyl acrylate, and an ethylene-propylene-methyl acrylate copolymer was obtained.

The distribution of monomer-monomer chains in the copolymer obtained in Example 26 was determined by ¹³ C-NMR. As a result, this copolymer had 65.75 ethylene-ethylene chains.
4 mol%, ethylene-propylene chain 32.0 mol%, ethylene-methyl acrylate chain 0.2 mol%,
The polymer had 1.6 mol% of propylene-propylene chains, 0.7 mol% of propylene-methyl acrylate chains, and 0.1 mol% of methyl acrylate-methyl acrylate chains.

[0431]

[Table 3]

[0432]

Example 29 Copolymerization of ethylene-propylene-methyl acrylate with complex (5) (in the presence of ethyl trichloroacetate) Same as Example 26 except that ethylaluminum dichloride was added and then 4 mmol of ethyltrichloroacetate was added. Was subjected to polymerization and post-treatment. 2.76 g of polymer were obtained. When ¹³ C-NMR of this polymer was measured, the obtained polymer was an ethylene-propylene-methyl acrylate copolymer containing 1.6 mol% of methyl acrylate. The propylene content is 11.6 mol% and [η] is 1.75 dl
/ G.

[0433]

Example 30 Ethylene propylene with complex (15)
Down - in methyl acrylate copolymer (hydrogenated coexistence) Example 26 similarly polymerized and post Example 26 except for using the ethylene / further hydrogen in propylene mixed gas 20 l / hr a mixed gas obtained by adding Was done. 2.37 g of polymer were obtained. Further, when ¹³ C-NMR of this polymer was measured, the obtained polymer was ethylene-containing containing 0.6 mol% of methyl acrylate.
It was a propylene-methyl acrylate copolymer. The propylene content is 19.4 mol% and [η] is 2.31 d
1 / g.

[0434]

EXAMPLE 31 Ethylene-propylene-methacrylate
Measurement of heat seal strength of aluminum copolymer against aluminum sheet of copolymer obtained in Example 30 (thickness of 100 μm)
m) to make a 25 mm wide strip. Then, the upper and lower sides were sandwiched between aluminum foils (thickness: 50 μm) of the same width, and heat sealing was performed at 200 ° C. for 5 seconds with a heat sealer. A strip having a width of 15 mm was cut out from the seal portion, and the peel strength was measured. Peeling condition is 180 ° peeling, peeling speed 200mm
/ Min. Peel strength is 0.90kg / 15min
Met.

On the other hand, an ethylene / propylene copolymer containing no methyl acrylate (propylene content: 18.4)
Mol%, [η]: 2.29 dl / g) was measured by the same method and found to be 0.08 kg / 15 min. It was revealed that the ethylene-propylene-methyl acrylate copolymer obtained in Example 30 had higher peel strength and higher adhesiveness to aluminum.

[0436]

Example 32 Methyl ethylene-propylene-acrylate
Measurement of Contact Angle of Copolymer A film of the copolymer obtained in Example 30 was prepared from a hot toluene solution. Using this film, the advancing and receding contact angles of the copolymer with respect to water were measured by a droplet method and found to be advancing contact angle of 60 ° and receding contact angle of 93 °.

On the other hand, an ethylene / propylene copolymer containing no methyl acrylate (propylene content: 18.4)
When the contact angle (mol%, [η]: 2.29 dl / g) was measured by the same method, the forward contact angle was 88 ° and the receding contact angle was 105 °. It was found that the ethylene-propylene-methyl acrylate copolymer obtained in Example 30 had a smaller contact angle and a higher wettability to water.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of a process for preparing an olefin polymerization catalyst used in the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yasuhiko Suzuki 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Yukihiro Takagi 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals Corporation (72) Inventor Terunori Fujita 580-32 Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals Corporation ( 72) Inventor Tomoaki Matsuki 580-32 Nagaura, Sodegaura-shi, Chiba Prefecture Mitsui Chemicals, Inc. (72) Inventor Takashi Nakano 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals F-term (reference) 4J028 AA01A AB01A AC08A AC26A AC37A AC42A AC44A AC46A AC47A AC48A AC49A AC50A BA00A BA01B BB00A BB01B BC01B BC05B BC06B BC12B BC13B BC15B BC16B BC19B BC24B BC25B BC27B BC29B CA26C CA27C CAEBC 07 EB08 EB09 EB10 EB12 EB13 EB14 EB21 EB24 EB25 EC02 FA02 FA03 FA04 GA04 4J128 AA01 AB01 AC08 AC26 AC37 AC42 AC44 AC46 AC47 AC48 AC49 AC50 AE00 BA00A BA01B BB00A BB01B BC01B BC05B27 BC13 BC12 BC13 BC13 BC13 BCBC EB04 EB05 EB07 EB08 EB09 EB10 EB12 EB13 EB14 EB21 EB24 EB25 EC02 FA02 FA03 FA04 GA04

Claims (14)

[Claims] (A0) Copolymerizing a non-polar olefin and a polar olefin in the presence of a catalyst comprising a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the following general formula (1) L _m MX _n (1) (wherein M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, and m is an integer of 1 to 6) N is a number that satisfies the valence of M; L is a ligand that coordinates to M, and in the following chemical formulas (2) and (3), the compound on the right-hand side obtained by the density functional method total energy of a value obtained by subtracting the sum when defining a coordinated energy E ₁ and coordination energy E ₂ methyl acrylate ethylene respectively coordinated energy E ₁ and acrylic acid ethylene compounds of the left side from the total energy of the Coordination of methyl The difference between the energy _{E 2 ΔE (ΔE = E 1} -
E ₂ ) is a ligand having a value of 50 kJ / mol or less; (In the formula, M is the same as M in the formula (1).
Represents a transition metal atom selected from the group, a represents an integer of 1 to 3, b represents the charge of the compound in [], is 0 or +1 and Me represents a methyl group. X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, and n Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. ). (A0) A compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the general formula (1) according to claim 1, and (B) (B-1) an organometallic compound The presence of a catalyst comprising at least one compound selected from the group consisting of (B-2) an organoaluminum oxy compound and (B-3) a compound which reacts with the transition metal compound (A0) to form an ion pair. A method for producing a polar olefin copolymer, wherein a non-polar olefin and a polar olefin are copolymerized below. 3. The transition metal compound represented by the general formula (1) according to claim 1 is a transition metal compound selected from Groups 4, 5, 6, and 11 of the periodic table. 3. The method for producing a polar olefin copolymer according to item 1. (A1) (C) Periodic Tables 4, 5, and 6 represented by the following general formula (c):
And a compound of a transition metal selected from Group 11 and M′X _k ... (C) (wherein M ′ represents a transition metal atom selected from Groups 4, 5, 6, and 11 of the periodic table; X is a number that satisfies the valence of X, X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
Represents an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. (Ai) a compound represented by the following general formula (I): (In the formula, A represents an oxygen atom, a sulfur atom or a selenium atom, or a nitrogen atom having a substituent R ⁶ , wherein R ¹ to R ⁶ may be the same or different from each other and may be a hydrogen atom, a halogen atom, a hydrocarbon, Groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, boron-containing groups, aluminum-containing groups, phosphorus-containing groups, residues of heterocyclic compounds, silicon-containing groups, germanium-containing groups or tin-containing groups, of which (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B) an organoaluminum oxy compound. (B-3) A non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising at least one compound selected from the group consisting of compounds forming an ion pair by reacting with the above reaction product (A1). To polymerize Method for producing a polar olefin copolymer, wherein. (A2) (C) Periodic tables Nos. 4, 5, and 6 represented by the following general formula (c):
And a compound of a transition metal selected from Group 11 and M′X _k ... (C) (wherein M ′ represents a transition metal atom selected from Groups 4, 5, 6, and 11 of the periodic table; X is a number that satisfies the valence of X, X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
Represents an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. (A-ii) a compound represented by the following general formula (II): (Wherein D represents a nitrogen atom or a phosphorus atom, Q represents a nitrogen atom or a phosphorus atom, or a carbon atom substituted with a substituent R ¹³ , S represents a nitrogen atom or a phosphorus atom, or a substituent R ¹⁴ T represents a nitrogen atom or a phosphorus atom, or a carbon atom substituted by a substituent R ¹⁵ ; R ¹¹ to R ¹⁶ may be the same or different from each other;
Hydrogen atom, halogen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, phosphorus containing group, heterocyclic compound residue, silicon containing group, germanium containing group or tin It shows a contained group, and two or more of these groups may be connected to each other to form a ring. Reacts with (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) the above reaction product (A2) to form an ion pair. A method for producing a polar olefin copolymer, comprising copolymerizing a nonpolar olefin and a polar olefin in the presence of a catalyst comprising at least one compound selected from the group consisting of: 6. (A3) (C ′) Periodic tables 3 to 11 represented by the following general formula (c ′):
And a transition metal compound selected from the group: MX _k ... (c ') (wherein M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, and k is a number satisfying the valence of M) X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
Represents an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. (A-iii) a compound represented by the following general formula (III): (In the formula, A represents an oxygen atom, a sulfur atom or a selenium atom, or a nitrogen atom having a substituent R ²⁶ , and R ²¹ to R ²⁸ may be the same or different from each other;
Hydrogen atom, halogen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, phosphorus containing group, heterocyclic compound residue, silicon containing group, germanium containing group or tin It shows a contained group, and two or more of these groups may be connected to each other to form a ring. ), Wherein a non-polar olefin and a polar olefin are copolymerized in the presence of a catalyst comprising the reaction product of the above. 7. (A3) (C ′) Periodic Tables 3 to 11 represented by the following general formula (c ′):
And a transition metal compound selected from the group: MX _k ... (c ') (wherein M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, and k is a number satisfying the valence of M) X represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
Represents an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group; Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. (A-iii) a compound represented by the following general formula (III): (In the formula, A represents an oxygen atom, a sulfur atom or a selenium atom, or a nitrogen atom having a substituent R ²⁶ , and R ²¹ to R ²⁸ may be the same or different from each other;
Hydrogen atom, halogen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, phosphorus containing group, heterocyclic compound residue, silicon containing group, germanium containing group or tin It shows a contained group, and two or more of these groups may be connected to each other to form a ring. Reacts with (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) the reaction product (A3) to form an ion pair. A method for producing a polar olefin copolymer, comprising copolymerizing a non-polar olefin and a polar olefin in the presence of a catalyst comprising at least one compound selected from the group consisting of: 8. The general formula (c ′) according to claim 6 or 7
7. The compound of a transition metal represented by the formula: is a compound of a transition metal selected from Groups 4, 5, 6, and 11 of the periodic table.
Or the method for producing a polar olefin copolymer according to item 7. (A4) a compound of a transition metal selected from Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (IV): (Wherein, M ′ represents a transition metal atom selected from Groups 4, 5, 6, or 11 of the periodic table, m is an integer of 1 to 6, A is an oxygen atom, a sulfur atom or a selenium atom, or a substituted A nitrogen atom having a group R ⁶ , wherein R ¹ to R ⁴ and R ⁶ may be the same or different from each other and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, Containing group, boron containing group, aluminum containing group, sulfur containing group, phosphorus containing group,
A silicon-containing group, a germanium-containing group, or a tin-containing group, of which two or more groups may be linked to each other to form a ring, and when m is 2 or more, any one of ^{One of} R ¹ to R ⁴ and R ⁶ contained in the ligand is bonded to one of R ¹ to R ⁴ and R ⁶ contained in the other ligand. May be
R ^{1 s} , R ^{2 s} , R ^{3 s} , R ^{4 s} , and R ^{6 s} may be the same or different from each other, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, oxygen Atoms, hydrocarbon groups,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, and n Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. From the group consisting of (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which reacts with the transition metal compound (A4) to form an ion pair. A method for producing a polar olefin copolymer, comprising copolymerizing a non-polar olefin and a polar olefin in the presence of a catalyst comprising at least one selected compound. (A5) A compound of a transition metal selected from Groups 4, 5, 6, and 11 of the periodic table represented by the following general formula (V): (Wherein, M ′ represents a transition metal atom selected from Groups 4, 5, 6, and 11 of the periodic table, m is an integer of 1 to 6, D represents a nitrogen atom or a phosphorus atom, and Q represents nitrogen. An atom or a phosphorus atom, or a carbon atom substituted with a substituent R ¹³ , S represents a nitrogen atom or a phosphorus atom, or a carbon atom substituted with a substituent R ¹⁴ , T is a nitrogen atom or a phosphorus atom, or A carbon atom substituted by a substituent R ¹⁵ , wherein R ¹¹ to R ¹⁵ may be the same or different from each other,
Hydrogen atom, halogen atom, hydrocarbon group, oxygen containing group, sulfur containing group, nitrogen containing group, boron containing group, aluminum containing group, phosphorus containing group, heterocyclic compound residue, silicon containing group, germanium containing group or tin Two or more of these may be linked to each other to form a ring, and when m is 2 or more, R ¹¹ to R ¹⁵ contained in any one of the ligands One of the groups may be bonded to one of R ¹¹ to R ¹⁵ contained in another ligand, and R ^{11 s} , R ^{12 s} , and R ^{13 s} may be bonded to each other.
R, R ¹⁴ and R ¹⁵ may be the same or different from each other, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, and n Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. From the group consisting of (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which forms an ion pair by reacting with the transition metal compound (A5). A method for producing a polar olefin copolymer, comprising copolymerizing a nonpolar olefin and a polar olefin in the presence of a catalyst comprising at least one selected compound. (A6) Nonpolar olefin and polar olefin are copolymerized in the presence of a catalyst comprising a compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the following general formula (VI). A method for producing a polar olefin copolymer, characterized by comprising: (Wherein, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, m is an integer of 1 to 6, and A has an oxygen atom, a sulfur atom or a selenium atom, or a substituent R ²⁶ . R ^{21 to} R ²⁷ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, A phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring; In the case of 2 or more, one group of R ²¹ to R ²⁷ contained in any one ligand and one group of R ²¹ to R ²⁷ contained in another ligand And R ²¹ and R ²² and R ²² and R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, an oxygen atom , Hydrocarbon groups,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, and n Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. ). (A6) A compound of a transition metal selected from Groups 3 to 11 of the periodic table represented by the following general formula (VI): (Wherein, M represents a transition metal atom selected from Groups 3 to 11 of the periodic table, m is an integer of 1 to 6, and A has an oxygen atom, a sulfur atom or a selenium atom, or a substituent R ²⁶ . R ^{21 to} R ²⁷ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, A phosphorus-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring; In the case of 2 or more, one group of R ²¹ to R ²⁷ contained in any one ligand and one group of R ²¹ to R ²⁷ contained in another ligand And R ²¹ and R ²² and R ²² and R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ may be the same or different, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, an oxygen atom , Hydrocarbon groups,
Oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group or tin-containing group, and n Is 2 or more, the plurality of atoms or groups represented by X may be the same or different from each other, and the plurality of groups represented by X may be bonded to each other to form a ring. From the group consisting of (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound that reacts with the transition metal compound (A6) to form an ion pair. A method for producing a polar olefin copolymer, comprising copolymerizing a non-polar olefin and a polar olefin in the presence of a catalyst comprising at least one selected compound. 13. The transition metal compound represented by the general formula (VI) according to claim 11 or 12,
The method for producing a polar olefin copolymer according to claim 11 or 12, which is a compound of a transition metal selected from Groups 6 and 11. 14. A polar olefin copolymer obtained by the method for producing a polar olefin copolymer according to any one of claims 1 to 13.