JP2018104405A - Complex and process for preparing complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel complex having at least one carbon-carbon double bond and / or carbon-carbon triple bond. The complex of the present invention is represented by the formula (1). ((RCOO) 8M5 (OH) 2) n (1) [In formula (1), M is a metal atom, R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or It is an alkynyl group having 2 to 18 carbon atoms. A plurality of R's may be the same or different from each other. However, at least one of R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer of 1 or more. ] [Selection diagram] None

Description

  The present invention relates to a complex, and more particularly to a complex having a reactive functional group. The present invention also relates to a method for producing a complex.

  Patent Document 1 discloses a macroporous ion-selective exchange resin obtained by cross-linking polymerization of a well-defined polymerizable metal complex, wherein at least 2 metal complexes represented by the general formula: MaLbBcXd (1) are present. A macroporous ion-selective exchange resin, wherein M is a main group metal and / or subgroup, characterized by reacting with monomers and / or oligomer crosslinkers having two polymerizable carbon-carbon multiple bonds Metal, L is a polymerizable ligand, B is a non-polymerizable ligand, X is a non-polymerizable anion, a is an integer of 1-6, b is an integer of 1-8, c is an integer of 0-4 , D represents an integer of 0-6).

  Non-Patent Document 1 discloses a method of preparing zinc zinc acetate monooxide by heating zinc acetate (II) in a vacuum.

Non-Patent Document 2 discloses a method for producing Zn ₄ O carboxylate in carboxylic acid and zinc oxide in carbon tetrachloride.

  Non-Patent Document 3 discloses a method of producing basic zinc 2-ethylhexanoate by reacting zinc oxide and zinc 2-ethylhexanoate in toluene.

JP-A-1-245859 New Experimental Chemistry Course 1st Edition, Volume 8 p. 986 Inorganic Chem. 201,49,4620-4625 Can. J. Chem. 1983, 61, 1218

  An object of the present invention is to provide a novel complex having at least one carbon-carbon double bond and / or carbon-carbon triple bond. Further, when a complex having at least one carbon-carbon double bond and / or carbon-carbon triple bond is produced by a conventional production method, the carbon-carbon double bond and / or the carbon-carbon triple bond is There is a problem that the target complex cannot be obtained due to self-polymerization. This invention is made | formed in view of the said situation, and makes it a subject to provide the novel manufacturing method which manufactures a complex.

The present invention relates to a complex represented by the formula (1).
((RCOO) ₈ M ₅ (OH) ₂ ) _n (1)
[In Formula (1), M is a metal atom, R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. A plurality of R may be the same or different. However, at least one of R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer greater than or equal to 1]

［構造式（２）において、Ｍ¹〜Ｍ^５は同一または異なって金属原子であり、Ｒ¹〜Ｒ^８は、それぞれ同一または異なって、水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基を表す。Ｒ¹〜Ｒ^８のうち少なくとも１個は炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基である。ｎは、１以上の整数である。］ The complex represented by the formula (1) is preferably a complex having a structure represented by the structural formula (2).

[In Structural Formula (2), M ^{1 to} M ⁵ are the same or different and are metal atoms, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer of 1 or more. ]

［構造式（３）において、Ｍ¹〜Ｍ^５は同一または異なって金属原子であり、Ｒ¹〜Ｒ^８は、それぞれ同一または異なって、水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基を表す。Ｒ¹〜Ｒ^８のうち少なくとも１個は炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基である。］ The complex represented by the structural formula (2) (n = 1 or more) is preferably a complex having the structure (n = 1) represented by the structural formula (3).

[In Structural Formula (3), M ^{1 to} M ⁵ are the same or different and are metal atoms, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. ]

The method for producing a complex of the present invention is characterized in that a compound represented by formula (4) and a metal oxide represented by formula (5) are reacted in a solvent in the presence of water.
[M ⁶ (RCOO) _x ] · yH ₂ O (4)
M ⁷ _a O _b (5)
Wherein (4), ^{M 6} is a metal atom, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group or an alkynyl group having 2 to 18 carbon atoms having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M ⁶ and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R may be the same or different. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ]

The method for producing a complex of the present invention includes a step of obtaining a first complex by reacting a compound represented by formula (4) and a metal oxide represented by formula (5) in a solvent, and
Reacting the first complex with water to obtain a second complex.
[M ⁶ (RCOO) _x ] · yH ₂ O (4)
M ⁷ _a O _b (5)
Wherein (4), ^{M 6} is a metal atom, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group or an alkynyl group having 2 to 18 carbon atoms having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M ⁶ and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R may be the same or different. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ]

The method for producing a complex of the present invention is characterized in that a carboxylic acid represented by formula (6) and a metal oxide represented by formula (5) are reacted in a solvent.
RCOOH (6)
M ⁷ _a O _b (5)
[In Formula (6), R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ]

  According to the present invention, a novel complex having at least one carbon-carbon double bond and / or carbon-carbon triple bond is obtained. Moreover, the novel manufacturing method which manufactures a complex can be provided.

Figure 2 is an IR spectrum of a preferred complex of the present invention. It is IR spectrum of zinc diacrylate. 2 is an X-ray diffraction spectrum of a preferred complex of the present invention. It is an X-ray diffraction spectrum of zinc diacrylate. Figure 2 is an IR spectrum of a preferred complex of the present invention. It is an ASAP-MS spectrum of the intermediate complex of the production method of the present invention. It is an ASAP-MS spectrum of the intermediate complex of the production method of the present invention. It is IR spectrum of the intermediate complex of the manufacturing method of this invention. It is an X-ray diffraction spectrum of the intermediate complex of the production method of the present invention. Figure 2 is an IR spectrum of a preferred complex of the present invention.

The present invention relates to a complex represented by the formula (1).
((RCOO) ₈ M ₅ (OH) ₂ ) _n (1)
[In formula (1), M is a metal atom, OH is a hydroxy group, RCOO is a carboxylate group, R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or the number of carbon atoms. 2 to 18 alkynyl groups. A plurality of R may be the same or different. However, at least one of R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer of 1 or more. ]
A complex is a molecular compound in which an atom or atomic group called a ligand is bonded to a metal atom or metal ion, and is also called a coordination compound.

  Examples of the metal atom (M) include alkali metals such as lithium, sodium, potassium, rubidium and cesium; alkaline earth metals such as calcium, strontium and barium; scandium, titanium, vanadium, chromium, manganese, iron and cobalt Transition metals such as nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold; beryllium, magnesium, aluminum, zinc , Base metals such as gallium, cadmium, indium, tin, thallium, lead, bismuth, and polonium. The said metal atom may be individual or 2 or more types. Among these, as the metal atom, those having an oxidation number of +2 are preferable, and beryllium, magnesium, calcium, zinc, barium, nickel, cadmium, and lead are more preferable. In the formula (1), a plurality of metal atoms (M) may be the same or different, but are preferably all the same.

  Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl. Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear.

  Examples of the alkenyl group having 2 to 18 carbon atoms include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, isopropenyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, 6 -Heptenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group, 10-undecenyl group, 11-dodecenyl group, 8-tridecenyl group, 12-tridecenyl group, 13-tetradecenyl group, 8-pentadecenyl group, 14 -Pentadecenyl group, 15-hexadecenyl group, 8-heptadecenyl group, 10-heptadecenyl group, 16-heptadecenyl group, 17-octadecenyl group are mentioned. The alkenyl group having 2 to 18 carbon atoms may be either linear or branched, but is preferably linear. As said C2-C18 alkenyl group, what has one carbon-carbon double bond is preferable. As the position of the double bond, those having a carbon-carbon double bond at the α, β position or at the terminal of the alkenyl group are preferable. The alkenyl group has preferably 8 or less carbon atoms, more preferably 6 or less, and still more preferably 4 or less. As the alkenyl group having 2 to 18 carbon atoms, a vinyl group, an isopropenyl group, a 1-propenyl group, or a 2-propenyl group is preferable.

  Examples of the alkynyl group having 2 to 18 carbon atoms include ethynyl group, 1-propynyl group, 2-propenyl group, 3-butynyl group, 4-pentynyl group, 5-hexynyl group, 6-heptynyl group, and 7-octynyl group. 8-noninyl group, 9-decynyl group, 10-undecynyl group, 11-dodecynyl group, 8-tridecynyl group, 12-tridecynyl group, 13-tetradecynyl group, 8-pentadecynyl group, 14-pentadecynyl group, 15-hexadecynyl group 8-heptadecynyl group, 10-heptadecynyl group, 16-heptadecynyl group and 17-octadecynyl group. The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, but is preferably linear. As said C2-C18 alkynyl group, what has one carbon-carbon triple bond is preferable. As the position of the triple bond, those having a carbon-carbon triple bond at the α, β position or at the terminal of the alkynyl group are preferable. The number of carbon atoms of the alkynyl group is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less. The alkynyl group having 2 to 18 carbon atoms is preferably an ethynyl group, a 1-propynyl group, or a 2-propynyl group.

  In the formula (1), at least one of R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. That is, the complex represented by the formula (1) has one or more carbon-carbon unsaturated bonds. The number of alkenyl groups having 2 to 18 carbon atoms or alkynyl groups having 2 to 18 carbon atoms in R is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and most preferably Eight.

  In the formula (1), at least one of R is an alkenyl group having 2 to 18 carbon atoms having a carbon-carbon double bond at the terminal, or a C2 to C18 having a carbon-carbon triple bond at the terminal. An alkynyl group is preferred. The number of the alkenyl group having 2 to 18 carbon atoms having a carbon-carbon double bond at the terminal in R or the number of alkynyl groups having 2 to 18 carbon atoms having a carbon-carbon triple bond at the terminal is 3 or more. More preferably, it is 4 or more, more preferably 5 or more, and most preferably 8.

  In the formula (1), a plurality of Rs may be the same or different, but are preferably all the same.

  In formula (1), the complex of n = 1 is a basic structural unit of the complex. Complexes in which these basic structural units are integrated (n is an integer of 2 or more) are also included in the present invention. The n is an integer of 1 or more, and is preferably an integer of 2 or more. In the integrated complex (n is an integer of 2 or more), the upper limit of n is not particularly limited, but is preferably 100 million, more preferably 1 million, and even more preferably 10,000.

  As the complex represented by the formula (1), for example, a complex in which R is all a vinyl group and a metal atom (M) is zinc; R is an isopropenyl group, and a metal atom (M) is zinc. Some complexes are mentioned.

［構造式（２）において、Ｍ¹〜Ｍ^５は同一または異なって金属原子、Ｏは酸素原子、Ｈは水素原子であり、Ｒ¹〜Ｒ^８は、それぞれ同一または異なって、水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基を表す。Ｒ¹〜Ｒ^８のうち少なくとも１個は炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基である。ｎは、１以上の整数である。］ The complex represented by the formula (1) is preferably a complex having a structure represented by the structural formula (2).

[In the structural formula (2), M ^{1 to} M ⁵ are the same or different and are metal atoms, O is an oxygen atom, H is a hydrogen atom, and R ^{1 to} R ⁸ are the same or different and are each a hydrogen atom, carbon A C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer of 1 or more. ]

  In the structural formula (2), the atomic groups of adjacent structural units are described outside the parentheses. In the structural formula (2), a bond indicated by a broken line on a solid line indicates a hybrid bond of a carboxylate group. In the structural formula (2), both the covalent bond and the coordinate bond are shown by solid lines.

  In the structural formula (2), the complex with n = 1 is a basic structural unit of the complex. Complexes in which these basic structural units are integrated (n is an integer of 2 or more) are also included in the present invention. The n is an integer of 1 or more, and is preferably an integer of 2 or more. In the integrated complex (n is an integer of 2 or more), the upper limit of n is not particularly limited, but is preferably 100 million, more preferably 1 million, and still more preferably 10,000.

The integrated complex of the structural formula (2) has a three-dimensional structure represented by the following formulas (2-1) and (2-2). Formula (2-2) shows an ORTEP diagram (Oak Ridge Thermal-Ellipsoid Plot Program) of the crystal structure of the integrated complex. From these structural formulas, it can be seen that the integrated complex of the structural formula (2) has a three-dimensional structure in which four structural units are bonded to one structural unit.

［構造式（３）において、Ｍ¹〜Ｍ^５は同一または異なって金属原子、Ｏは酸素原子、Ｈは水素原子であり、Ｒ¹〜Ｒ^８は、それぞれ同一または異なって、水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基を表す。Ｒ¹〜Ｒ^８のうち少なくとも１個は炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基である。］
The complex represented by the structural formula (2) (n = 1 or more) is preferably a complex having the structure (n = 1) represented by the structural formula (3).

[In Structural Formula (3), M ^{1 to} M ⁵ are the same or different and are metal atoms, O is an oxygen atom, H is a hydrogen atom, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, carbon A C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. ]

  In the structural formula (3), a bond indicated by a broken line on a solid line indicates a hybrid bond of a carboxylate group. In Structural Formula (3), both the covalent bond and the coordinate bond are shown by solid lines.

  The complex represented by the structural formula (3) is a basic structural unit. The integrated complex (n = 2 or more) in Formula (1) and Structural Formula (2) and the complex (n = 1) represented by Structural Formula (3) exist in an equilibrium state in a solvent. The abundance ratio varies depending on the solvent, temperature, and concentration. The complex (n = 1) represented by the structural formula (3) changes to an integrated complex (an integer of n = 2 or more) in a more stable state. For example, in the solid state, a more stable integrated complex (an integer of n = 2 or more) can be obtained. Moreover, in a low concentration solution, since it is stabilized by a solvent, the ratio of the complex of Structural formula (3) becomes high.

In the structural formula (2) or (3), examples of the metal atom represented by M ^{1 to} M ⁵ include the same as M in the formula (1). Among these, as the metal atom, those having an oxidation number of +2 are preferable, and beryllium, magnesium, nickel, calcium, zinc, barium, cadmium, and lead are more preferable. The metal atoms represented by M ^{1 to} M ⁵ may be different from each other, but all are preferably the same metal atom.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ^{1 to} R ⁸ in the structural formula (2) or (3) include those similar to R in the formula (1). The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear.

Examples of the alkenyl group having 2 to 18 carbon atoms represented by R ^{1 to} R ⁸ in the structural formula (2) or (3) include those similar to R in the formula (1). The alkenyl group having 2 to 18 carbon atoms may be either linear or branched, but is preferably linear. As the alkenyl group having 2 to 18 carbon atoms, those having a carbon-carbon double bond at the α-, β-position or terminal are preferable. The alkenyl group has preferably 8 or less carbon atoms, more preferably 6 or less, and still more preferably 4 or less. As the alkenyl group having 2 to 18 carbon atoms, a vinyl group, an isopropenyl group, a 1-propenyl group, or a 2-propenyl group is preferable.

Examples of the alkynyl group having 2 to 18 carbon atoms represented by R ^{1 to} R ⁸ in the structural formula (2) or (3) include those similar to R in the formula (1). The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, but is preferably linear. As said C2-C18 alkynyl group, what has a carbon-carbon triple bond in the (alpha) and (beta) position or the terminal is preferable. The number of carbon atoms of the alkynyl group is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less. The alkynyl group having 2 to 18 carbon atoms is preferably an ethynyl group, a 1-propynyl group, or a 2-propynyl group.

In Structural Formula (2) or (3), at least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. The number of alkenyl groups having 2 to 18 carbon atoms or alkynyl groups having 2 to 18 carbon atoms in R ^{1 to} R ⁸ is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. The most preferred is 8.

In Structural Formula (2) or (3), at least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms having a carbon-carbon double bond at the end, or a carbon-carbon triple at the end. An alkynyl group having 2 to 18 carbon atoms having a bond is preferable. The number of the C2-C18 alkenyl group having a carbon-carbon double bond at the terminal in R ^{1 to} R ⁸ or the number of the C2-C18 alkynyl group having a carbon-carbon triple bond at the terminal is as follows: The number is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, and most preferably 8.

In the structural formula (2) or (3), R ^{1 to} R ⁸ may be the same or different, but are preferably the same.

As the complex having the structural formula (2) or (3), R ^{1 to} R ⁸ are all vinyl groups, and metal atoms M ^{1 to} M ⁵ are zinc (zinc acrylate hydroxocluster), and R ^A complex (zinc methacrylate hydroxocluster) in which ^{1 to} R ⁸ are all isopropenyl groups and the metal atoms M ^{1 to} M ⁵ are zinc is exemplified.

The method for producing a complex of the present invention is characterized in that a compound represented by the formula (4) and a metal oxide represented by the formula (5) are reacted in a solvent in the presence of water ( First production method).
[M ⁶ (RCOO) _x ] · yH ₂ O (4)
M ⁷ _a O _b (5)
Moreover, the method for producing the complex of the present invention comprises a step of obtaining a first complex by reacting a compound represented by the formula (4) and a metal oxide represented by the formula (5) in a solvent, and A step of reacting the first complex with water to obtain a second complex (second production method).
Wherein (4), ^{M 6} is a metal atom, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group or an alkynyl group having 2 to 18 carbon atoms having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M ⁶ and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R may be the same or different. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ]

The present invention also provides a method for producing a complex (third production), which comprises reacting a carboxylic acid represented by formula (6) with a metal oxide represented by formula (5) in a solvent. Method).
RCOOH (6)
M ⁷ _a O _b (5)
[In Formula (6), R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ]

  In the description of the present invention, the compound represented by the formula (4) may be simply referred to as “compound (4)”. The metal oxide represented by the formula (5) may be simply referred to as “metal oxide (5)”. The carboxylic acid represented by the formula (6) may be simply referred to as “carboxylic acid (6)”. In addition, the step of obtaining the first complex by reacting the compound represented by the formula (4) and the metal oxide represented by the formula (5) in a solvent may be simply referred to as “first step”. The process of obtaining the second complex by reacting the first complex with water may be simply referred to as “second process”.

  First, the raw material used with the manufacturing method of the complex of this invention is demonstrated. R in the compound (4) is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms.

  Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl. Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear.

  Examples of the alkenyl group having 2 to 18 carbon atoms include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group. Group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, and octadecenyl group. The alkenyl group having 2 to 18 carbon atoms may be either linear or branched, but is preferably linear. As said C2-C18 alkenyl group, what has one carbon-carbon double bond is preferable. As the position of the double bond, those having a carbon-carbon double bond at the α, β position or at the terminal of the alkenyl group are preferable. The alkenyl group has preferably 8 or less carbon atoms, more preferably 6 or less, and still more preferably 4 or less. As the alkenyl group having 2 to 18 carbon atoms, a vinyl group, an isopropenyl group, a 1-propenyl group, or a 2-propenyl group is preferable.

  Examples of the alkynyl group having 2 to 18 carbon atoms include ethynyl group, 1-propynyl group, 2-propenyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, A dodecynyl group, a tridecynyl group, a tetradecynyl group, a pentadecynyl group, a hexadecynyl group, a heptadecinyl group, a heptadecynyl group, and an octadecynyl group are exemplified. The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, but is preferably linear. As said C2-C18 alkynyl group, what has one carbon-carbon triple bond is preferable. The position of the carbon-carbon triple bond is preferably α, β-position or one having a carbon-carbon triple bond at the terminal of the alkynyl group. The number of carbon atoms of the alkynyl group is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less. The alkynyl group having 2 to 18 carbon atoms is preferably an ethynyl group, a 1-propynyl group, or a 2-propynyl group.

In the compound (4), examples of the metal atom (M ⁶ ) include alkaline earth metals such as calcium, strontium and barium; scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium and zirconium. , Niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold and other transition metals; beryllium, magnesium, aluminum, zinc, gallium, cadmium, indium, tin , Base metals such as thallium, lead, bismuth and polonium. Among these, the metal atom is preferably a metal atom capable of forming a divalent or higher valent metal ion, and more preferably a metal atom capable of forming a divalent metal ion. The metal atom is preferably at least one metal selected from the group consisting of beryllium, magnesium, calcium, zinc, barium, cadmium, and lead. A metal atom can also be used individually or in mixture of 2 or more types.

x represents the number of carboxylate groups (RCOO) in the compound (4). x is a number corresponding to the oxidation number of the metal atom M ⁶ and is an integer of 2 or more. As x, for example, 2 to 5 is preferable, and 2 is more preferable. y is an integer of 0 or more. As y, for example, 0 to 5 is preferable, and 0 is more preferable. This is because when y is 1 or more, the yield of the target complex may decrease.

  As a specific example of the compound (4), a fatty acid metal salt is preferable. Examples of the fatty acid constituting the fatty acid metal salt include saturated fatty acids having 1 to 19 carbon atoms and unsaturated fatty acids having 3 to 20 carbon atoms.

  Examples of the saturated fatty acid include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, Examples include pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and nonadecanoic acid. Examples of the unsaturated fatty acid include propenoic acid (acrylic acid), 2-methylprop-2-enoic acid (methacrylic acid), 2-butenoic 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-dodecenoic acid, 12-tridecenoic acid, 9-tetradecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 9 Unsaturated fatty acids having a carbon-carbon double bond such as hexadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 9-octadecenoic acid, 11-octadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid; 3-butynoic acid, 4-pentynoic acid, 5-hexynoic acid, 6-heptynoic acid, 7-octynic acid, 8-noninic acid, 9-decynoic acid, 10-c Decynoic acid, 11-dodecynoic acid, 12-tridecynoic acid, 9-tetradecynoic acid, 13-tetradecynoic acid, 14-pentadesinic acid, 9-hexadesinic acid, 15-hexadesinic acid, 16-heptadesinic acid, 9-octadesinic acid, 11- Examples include unsaturated fatty acids having a carbon-carbon triple bond such as octadecynoic acid, 17-octadesinic acid, and 18-nonadesinic acid.

  The unsaturated fatty acid having a carbon-carbon double bond is preferably one having one carbon-carbon double bond. The position of the carbon-carbon double bond is preferably α, β position or the terminal of unsaturated fatty acid. The unsaturated fatty acid having a carbon-carbon triple bond is preferably one having one carbon-carbon triple bond. The position of the carbon-carbon triple bond is preferably α, β position or the terminal of unsaturated fatty acid.

Examples of the metal atom (M ⁶ ) of the fatty acid metal salt include alkaline earth metals such as calcium, strontium and barium; scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, Transition metals such as niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold; beryllium, magnesium, aluminum, zinc, gallium, cadmium, indium, tin, Examples include base metals such as thallium, lead, bismuth, and polonium. Among these, as the metal atom, a metal atom capable of forming a divalent metal ion is preferable, and beryllium, magnesium, calcium, zinc, barium, cadmium, and lead are more preferable. A metal atom can also be used individually or in mixture of 2 or more types.

  The fatty acid metal salt is preferably a metal salt of a divalent metal ion of a fatty acid, more preferably a metal salt of a divalent metal ion of an unsaturated fatty acid, more preferably a divalent metal ion of acrylic acid or methacrylic acid. The metal salt is preferred.

  In the production method of the present invention, it is preferable to use zinc acrylate and / or zinc methacrylate as the compound (4).

  When using 2 or more types of the said fatty acid metal salt together as a compound (4), what is necessary is just to adjust suitably content of each fatty acid metal salt according to the desired complex. In addition, 33 mol% or more is preferable, as for the content rate of the unsaturated fatty acid in the fatty acid which comprises a compound (4), 50 mol% or more is more preferable, More preferably, it is 66 mol% or more. It is also preferred that all fatty acids constituting the compound (4) are unsaturated fatty acids. Moreover, 33 mol% or more is preferable, as for the content rate of the unsaturated fatty acid which has the carbon-carbon double bond in the fatty acid which comprises a compound (4), 50 mol% or more is more preferable, More preferably, it is 66 mol% or more. It is also preferred that the fatty acids constituting the compound (4) are all unsaturated fatty acids having a carbon-carbon double bond. Although the fatty acid which comprises a compound (4) may use multiple types together, it is also preferable that it is 1 type.

  As an aspect of the fatty acid metal salt used as the compound (4), an aspect containing one kind of fatty acid and one kind of metal ion; an aspect containing a plurality of kinds of fatty acid and one kind of metal ion; An embodiment containing a plurality of types of metal ions; an embodiment containing a plurality of types of fatty acids and a plurality of types of metal ions. Among these, an embodiment containing one kind of fatty acid and one kind of metal ion is preferable. The said fatty acid metal salt may be used independently and may use 2 or more types together.

In the manufacturing method of this invention, the metal oxide represented by Formula (5) is used.
M ⁷ _a O _b (5)
Examples of the metal atom (M ⁷ ) include alkali metals such as lithium, sodium, potassium, rubidium and cesium; alkaline earth metals such as calcium, strontium and barium; scandium, titanium, vanadium, chromium, manganese, iron and cobalt Transition metals such as nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold; beryllium, magnesium, aluminum, zinc , Base metals such as gallium, cadmium, indium, tin, thallium, lead, bismuth, and polonium. Among these, the metal atom M ⁷ is preferably a metal atom capable of forming a divalent metal ion, more preferably beryllium, magnesium, calcium, zinc, barium, cadmium, or lead. A metal atom can also be used individually or in mixture of 2 or more types.

In the first manufacturing method and the second production method of the present invention, metal atom M ⁷ of the compound (4) of the metal atom M ⁶ and the metal oxide (5) may be the same or different, with the same Preferably there is.

  In the metal oxide (5), a is preferably an integer of 1 to 5, preferably 1 to 3, and most preferably 1. b is preferably an integer of 1 or more and 7 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or more and 3 or less, and particularly preferably 1. The metal oxide (5) is preferably a divalent metal oxide having a = 1 and b = 1.

  Specific examples of the metal oxide (5) include oxides of alkali metals such as lithium oxide, sodium oxide, potassium oxide, rubidium oxide and cesium oxide; oxidation of alkaline earth metals such as calcium oxide, strontium oxide and barium oxide. Scandium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, yttrium oxide, zirconium oxide, niobium oxide, molybdenum oxide, technetium oxide, ruthenium oxide, rhodium oxide, Palladium oxide, silver oxide, hafnium oxide, tantalum oxide, tungsten oxide, rhenium, osmium oxide, iridium oxide, platinum oxide, gold oxide and other transition metal oxides, beryllium oxide, magnesium oxide, aluminum oxide, zinc oxide, gallium oxide Arm, cadmium oxide, indium oxide, tin oxide, thallium oxide, lead oxide, bismuth oxide, oxides of base metals, such as oxidation polonium and the like. The said metal oxide can also be used individually or in mixture of 2 or more types. Among these, the metal oxide is preferably a divalent metal oxide, more preferably beryllium oxide, magnesium oxide, calcium oxide, zinc oxide, barium oxide, cadmium oxide, or lead oxide. In the present invention, it is particularly preferable to use zinc oxide as the metal oxide (5).

  The solvent used in the reaction of the production method of the present invention (hereinafter sometimes referred to as “first solvent”) is not particularly limited, but is dichloromethane, 1,2-dichloroethane, chloroform, chlorobenzene, dichlorobenzene, benzene, toluene, Examples include xylene, tetrahydrofuran, 1,4-dioxane, ethyl acetate, propyl acetate, isopropyl acetate, and acetonitrile. For the second production method, alcohols such as methanol, ethanol, propanol, and isopropanol are also included. From the viewpoint of increasing the yield of the complex, it is preferable to use dichloromethane as the solvent.

  In the first production method of the present invention, the compound represented by the above formula (4) and the metal oxide represented by the formula (5) are reacted in a solvent in the presence of water. In the second production method of the present invention, the compound represented by the formula (4) and the metal oxide represented by the formula (5) are reacted in a solvent (preferably in a solvent not containing water). And obtaining the first complex, and reacting the first complex with water to obtain the second complex.

  The reaction between the compound (4) and the metal oxide (5) is performed, for example, by dissolving or dispersing the compound (4) and the metal oxide (5) in the first solvent and stirring the reaction solution. .

  Specifically, first, the metal oxide (5) is dissolved or dispersed in a solvent in a reaction vessel. While stirring the liquid in which the metal oxide (5) is dissolved or dispersed in the solvent, the liquid in which the compound (4) is dissolved or dispersed in the solvent is added. A liquid in which the compound (4) is dissolved or dispersed in a solvent may be added dropwise. In this case, the dropping time is not particularly limited, but it is preferably dropped over 0.5 to 3 hours. After completion of the dropwise addition, it is preferable to carry out the reaction while further stirring.

  In the 1st manufacturing method of this invention, when reacting in a solvent in presence of water, the quantity of the water which exists in a reaction system is with respect to a total of 100 mass parts of a compound (4) and a metal oxide (5). 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, preferably 1000 parts by mass or less, more preferably 900 parts by mass or less, and still more preferably 800 parts by mass or less. This is because if the amount of water is within the above range, the complex can be obtained in high yield and the operation is not complicated. In addition, what is necessary is just to add water to reaction container similarly to a compound (4) or a metal oxide (5).

  In the 2nd manufacturing method of this invention, when making a compound (4) and a metal oxide (5) react, it is preferable to perform reaction on the conditions in which water does not exist substantially in a reaction system. Therefore, the reaction is preferably performed in an inert gas atmosphere such as argon or nitrogen.

  In the reaction between the compound (4) and the metal oxide (5), the charged molar ratio of the compound (4) to the metal oxide (5) ((4) / (5)) is preferably 3/2 or more. / 1 or more is more preferable, 5/1 or less is preferable, and 4/1 or less is more preferable. It is because the yield of the obtained complex will become high if the molar ratio ((4) / (5)) of the compound (4) with respect to a metal oxide (5) is in the said range.

  Further, the amount of the solvent used in the reaction is preferably 1000 parts by mass or more, more preferably 2000 parts by mass or more, and still more preferably 3000 with respect to 100 parts by mass in total of the compound (4) and the metal oxide (5). It is not less than 10000 parts by mass, preferably not more than 8000 parts by mass, and more preferably not more than 6000 parts by mass. If the amount of the solvent used exceeds 10000 parts by mass, the amount of work during synthesis increases, and if it is less than 1000 parts by mass, the yield of the complex may decrease.

  The reaction temperature (liquid temperature of the reaction solution) is preferably −20 ° C. or higher, more preferably 0 ° C. or higher, further preferably 10 ° C. or higher, particularly preferably 20 ° C. or higher, preferably 100 ° C. or lower, more preferably 90 ° C. or lower. Preferably, 80 ° C. or lower is more preferable, and 50 ° C. or lower is particularly preferable. When the reaction temperature is −20 ° C. or higher, the reaction rate between the compound (4) and the metal oxide (5) can be increased. Further, when the reaction temperature is 100 ° C. or lower, self-polymerization of the compound (4) can be prevented.

The reaction time is preferably 1 hour or longer, more preferably 2 hours or longer, and further preferably 3 hours or longer. This is because if the reaction time is too short, the yield of the complex decreases. From the viewpoint of increasing productivity, the reaction time is preferably 300 hours or less, more preferably 200 hours or less, and even more preferably 100 hours or less.
The completion of the reaction can be confirmed by, for example, collecting a part of the reaction solution and measuring infrared absorption, or measuring the weight change of a component dissolved in the reaction solution. .

  In the 1st manufacturing method of this invention, the target complex is obtained by making a compound (4) and a metal oxide (5) react in presence of water. In the second production method of the present invention, an intermediate first complex is obtained by reacting compound (4) with metal oxide (5). And a 2nd complex (target complex) is obtained by making this 1st complex and water react.

In the second production method of the present invention, the first complex obtained as an intermediate is a complex represented by the following formula (7), more preferably a complex represented by the structural formula (8). is there.
[M ₄ O (RCOO) ₆ ] _n (7)
[In Formula (7), M is a metal atom, R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. In the formula (7), a plurality of R may be the same or different. However, at least one of R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer greater than or equal to 1, Preferably it is an integer of 1-8. ]

  In the formula (7), specific examples of the metal atoms M and R can be the same as those exemplified in the formula (1).

  As the first complex represented by the formula (7), for example, a complex in which R is all a vinyl group and a metal atom (M) is zinc; R is an isopropenyl group, and a metal atom (M) is The complex which is zinc is mentioned.

［構造式（８）において、Ｍ¹〜Ｍ⁴は同一または異なって金属原子であり、Ｒ¹〜Ｒ⁶は、それぞれ同一または異なって、水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基を表す。Ｒ¹〜Ｒ⁶のうち少なくとも１個は炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基である。］ The complex represented by the formula (7) is preferably a complex represented by the structural formula (8).

[In Structural Formula (8), M ^{1 to} M ⁴ are the same or different and are metal atoms, and R ^{1 to} R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁶ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. ]

  In the structural formula (8), a bond indicated by a broken line on a solid line indicates a hybrid bond of a carboxylate group. In Structural Formula (8), both the covalent bond and the coordinate bond are shown by solid lines.

In the structural formula (8), specific examples of the metal atoms M ^{1 to} M ⁴ and R ^{1 to} R ⁶ can be the same as those exemplified in the structural formula (2).

In the structural formula (8), the first complex is a complex (zinc acrylate oxocluster) in which M ^{1 to} M ⁴ are zinc and R ^{1 to} R ⁶ = —CH═CH ₂ , and —C ( it is preferable CH ₃₎ = it is CH ₂ and is complex (methacrylic acid zinc oxo clusters).

  It is preferable that the 1st manufacturing method of this invention has an insoluble matter removal process, a precipitation process, a collection | recovery process, or a refinement | purification process after completion | finish of reaction with a compound (4) and a metal oxide (5). The insoluble matter removal step, the precipitation step, the recovery step, and the purification step can be appropriately combined as necessary.

(Insoluble matter removal process)
After completion of the reaction, insoluble matters are removed from the reaction solution. Examples of the insoluble material include unreacted raw materials or polymers obtained by self-polymerization of the compound (4). The method for removing insoluble matters is not particularly limited, and examples thereof include a method for filtering the reaction solution.

(Precipitation process)
In the precipitation step, the target complex dissolved in the first solvent (the solvent used in the reaction) is precipitated by introducing the second solvent into the reaction solution from which insolubles have been removed. The reaction solution contains a target complex and, for example, an unreacted compound (4). If the solubility of the target complex in the second solvent is lower than the solubility of the compound (4) in the second solvent, the target complex can be selectively precipitated. The second solvent is not particularly limited as long as it can selectively precipitate the target complex in the reaction solution. Examples of the second solvent include hydrocarbons such as hexane, pentane, cyclohexane, and heptane.

  The input amount of the second solvent may be appropriately adjusted so that the target complex can be precipitated. The input amount of the second solvent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, with respect to 100 parts by mass of the first solvent. Part or less, more preferably 150 parts by weight or less, still more preferably 100 parts by weight or less.

  In addition, the target complex may be precipitated by removing a part of the first solvent and the second solvent after adding the second solvent. As a method for removing a part of the first solvent and the second solvent, vacuum concentration is preferable. The reaction liquid may be heated during concentration under reduced pressure. The temperature of the reaction solution during concentration is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.

  The precipitated target complex can be obtained by filtering and drying.

(Recovery process)
In the recovery step, the solvent is removed from the reaction solution from which insolubles have been removed. By removing the solvent, the target complex present in the reaction solution can be recovered.

  Examples of the method for removing the solvent include vacuum drying and heat drying, and vacuum drying is preferred. The reaction liquid may be heated when drying under reduced pressure. The temperature of the reaction solution during drying is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.

(Purification process)
In the purification step, the purity of the target complex can be increased by performing reprecipitation for the target complex obtained in the precipitation step or the recovery step. Specifically, after the obtained target complex is dissolved in the first solvent, the second solvent is added to the solution to precipitate and recover the target complex.

  As the first solvent and the second solvent used in the purification step, those exemplified in the reaction step and the precipitation step can be used. Moreover, the usage-amount of a 2nd solvent is the same as that of the said precipitation process. The purification step may be performed a plurality of times depending on the desired purity of the target complex.

  In the 2nd manufacturing method of this invention, it is preferable to have an insoluble matter removal process, a collection | recovery process, a precipitation process, or a refinement | purification process after completion | finish of reaction with a compound (4) and a metal oxide (5). The insoluble matter removal step, the recovery step, the precipitation step, and the purification step can be appropriately combined as necessary.

(Insoluble matter removal process)
After completion of the reaction step, insoluble matters are removed from the reaction solution. Examples of the insoluble material include unreacted raw materials or polymers obtained by self-polymerization of the compound (4). The method for removing insoluble matters is not particularly limited, and examples thereof include a method for filtering the reaction solution.

(Recovery process)
In the recovery step, the solvent is removed from the reaction solution from which insolubles have been removed. By removing the solvent, a mixture of the compound (4) and the generated first complex is obtained.

  Examples of the method for removing the solvent include vacuum drying and heat drying, and vacuum drying is preferred. The reaction liquid may be heated when drying under reduced pressure. The temperature of the reaction solution during drying is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.

In the second production method of the present invention, the following precipitation step may be performed prior to the recovery step.
By performing the precipitation step, the purity of the first complex contained in the reaction solution can be increased.
(Precipitation process)
In the precipitation step, the second solvent is added to the reaction solution from which insolubles have been removed in the reaction step, and the precipitate is removed. By introducing the second solvent into the reaction solution, raw materials, by-products and the like dissolved in the first solvent are precipitated. By removing this precipitate, the purity of the first complex contained in the reaction solution can be increased.

  The second solvent is not particularly limited as long as it can selectively precipitate the compound (4) in the reaction solution. That is, the solubility of the first complex in the second solvent is higher than the solubility of the compound (4) in the second solvent. Examples of the second solvent include hydrocarbons such as hexane, pentane, cyclohexane, and heptane.

  The input amount of the second solvent may be appropriately adjusted so that the compound (4) can be precipitated. The input amount of the second solvent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, with respect to 100 parts by mass of the first solvent. Part or less, more preferably 150 parts by weight or less, still more preferably 100 parts by weight or less.

  In addition, after adding the second solvent, the compound (4) may be precipitated by removing a part of the first solvent and the second solvent. As a method for removing a part of the first solvent and the second solvent, vacuum concentration is preferable. The reaction liquid may be heated during concentration under reduced pressure. The temperature of the reaction solution during concentration is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.

  Examples of the method for removing the precipitate include a method of filtering the reaction solution. The target first complex is obtained by removing the first solvent and the second solvent from the filtrate from which the precipitate has been removed.

(Purification process)
In the purification step, reprecipitation is performed on the mixture of the first complex and compound (4) obtained by the recovery step and / or the precipitation step. Specifically, after the obtained mixture of the first complex and the compound (4) is dissolved in the first solvent, the second solvent is added to the solution to precipitate the compound (4). Remove.

  As the first solvent and the second solvent used in the purification step, those exemplified in the reaction step and the precipitation step can be used. Moreover, the usage-amount of a 2nd solvent and the suitable aspect of the removal method of a precipitate are the same as that of the said precipitation process. After removing the precipitate, the target first complex is obtained by removing the solvent from the filtrate. The preferred embodiment of the method for removing the solvent is the same as in the recovery step. The purification step may be performed a plurality of times depending on the desired purity of the first complex.

  The 2nd manufacturing method of this invention includes the process (reaction 2nd process) which makes the obtained 1st complex and water react, and obtains a 2nd complex. Examples of the method of reacting the first complex with water in the second reaction step include a method of exposing the first complex to a high humidity atmosphere. The humidity of the high humidity atmosphere is preferably 50% RH or more, more preferably 60% RH or more, and still more preferably 70% RH or more. Further, the temperature (air temperature) of the high humidity atmosphere is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, Preferably, it is 100 degrees C or less.

  Although the addition amount of water with respect to the first complex is not particularly limited, it is preferably 3 parts by mass or more, preferably 5 parts by mass or more with respect to 100 parts by mass of the first complex, and 10 parts by mass or more. More preferably it is. If it is 3 mass parts or more, the reaction efficiency of a 1st complex and water will become high. The upper limit of the amount of water added is not particularly limited, and is preferably 100 parts by mass and more preferably 50 parts by mass with respect to 100 parts by mass of the first complex.

  The reaction product of the first complex and water is also preferably purified. This is because the purity of the second complex is increased.

The present invention includes a method for producing a complex, which comprises reacting a carboxylic acid represented by formula (6) and a metal oxide represented by formula (5) in a solvent (third). Production method).
RCOOH (6)
M ⁷ _a O _b (5)
[In Formula (6), R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ]
In the third production method, water is generated by the reaction of the carboxylic acid (6) and the metal oxide (5). Therefore, it is not necessary to add water to the reaction system unlike the first production method and the second production method.

  R in the carboxylic acid (6) is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms.

  Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl. Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, but is preferably linear.

  Examples of the alkenyl group having 2 to 18 carbon atoms include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group. Group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, and octadecenyl group. The alkenyl group having 2 to 18 carbon atoms may be either linear or branched, but is preferably linear. As said C2-C18 alkenyl group, what has one carbon-carbon double bond is preferable. As the position of the double bond, those having a carbon-carbon double bond at the α, β position or at the terminal of the alkenyl group are preferable. The alkenyl group has preferably 8 or less carbon atoms, more preferably 6 or less, and still more preferably 4 or less. As a C2-C18 alkenyl group, a vinyl group, an isopropenyl group, 1-propenyl group, and 2-propenyl group are preferable.

  Examples of the alkynyl group having 2 to 18 carbon atoms include ethynyl group, 1-propynyl group, 2-propenyl group, isopropynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, noninyl group, decynyl group , An undecynyl group, a dodecynyl group, a tridecynyl group, a tetradecynyl group, a pentadecynyl group, a hexadecynyl group, a heptadecinyl group, a heptadecinyl group, and an octadecynyl group. The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, but is preferably linear. As said C2-C18 alkynyl group, what has one carbon-carbon triple bond is preferable. The position of the carbon-carbon triple bond is preferably α, β-position or one having a carbon-carbon triple bond at the terminal of the alkynyl group. The number of carbon atoms of the alkynyl group is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less. The alkynyl group having 2 to 18 carbon atoms is preferably an ethynyl group, an isopropynyl group, a 1-propynyl group, or a 2-propynyl group.

  Specific examples of the carboxylic acid (6) include saturated fatty acids having 1 to 19 carbon atoms and unsaturated fatty acids having 3 to 20 carbon atoms.

  Examples of the saturated fatty acid include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, Examples include pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and nonadecanoic acid. Examples of the unsaturated fatty acid include propenoic acid (acrylic acid), 2-methylprop-2-enoic acid (methacrylic acid), 2-butenoic 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-dodecenoic acid, 12-tridecenoic acid, 9-tetradecenoic acid, 13-tetradecenoic acid, 14-pentadecenoic acid, 9 Unsaturated fatty acids having a carbon-carbon double bond such as hexadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 9-octadecenoic acid, 11-octadecenoic acid, 17-octadecenoic acid, 18-nonadecenoic acid; 3-butynoic acid, 4-pentynoic acid, 5-hexynoic acid, 6-heptynoic acid, 7-octynic acid, 8-noninic acid, 9-decynoic acid, 10-c Decynoic acid, 11-dodecynoic acid, 12-tridecynoic acid, 9-tetradecynoic acid, 13-tetradecynoic acid, 14-pentadesinic acid, 9-hexadesinic acid, 15-hexadesinic acid, 16-heptadesinic acid, 9-octadesinic acid, 11- Examples include unsaturated fatty acids having a carbon-carbon triple bond such as octadecynoic acid, 17-octadesinic acid, and 18-nonadesinic acid.

  The unsaturated fatty acid having a carbon-carbon double bond is preferably one having one carbon-carbon double bond. The position of the carbon-carbon double bond is preferably α, β position or the terminal of unsaturated fatty acid. The unsaturated fatty acid having a carbon-carbon triple bond is preferably one having one carbon-carbon triple bond. The position of the carbon-carbon triple bond is preferably α, β position or the terminal of unsaturated fatty acid.

  When using 2 or more types of the said fatty acid together as carboxylic acid (6), what is necessary is just to adjust suitably content of each fatty acid according to the desired complex. In addition, 33 mol% or more is preferable, as for the content rate of the unsaturated fatty acid in the fatty acid which comprises carboxylic acid (6), 50 mol% or more is more preferable, More preferably, it is 66 mol% or more. It is also preferred that all the fatty acids constituting the carboxylic acid (6) are unsaturated fatty acids. Further, the content of unsaturated fatty acid having a carbon-carbon double bond in the fatty acid constituting the carboxylic acid (6) is preferably 33 mol% or more, more preferably 50 mol% or more, and further preferably 66 mol% or more. . It is also preferred that the fatty acids constituting the carboxylic acid (6) are all unsaturated fatty acids having a carbon-carbon double bond. Although the fatty acid which comprises carboxylic acid (6) may use multiple types together, it is also preferable that it is 1 type.

  As the carboxylic acid (6), acrylic acid and / or methacrylic acid are preferable.

The metal oxide represented by Formula (5) is demonstrated.
M ⁷ _a O _b (5)
Examples of the metal atom (M ⁷ ) include lithium, sodium, potassium, rubidium, cesium and other alkali metals; calcium, strontium, barium and other alkaline earth metals; scandium, titanium, vanadium, chromium, manganese, iron, cobalt Transition metals such as nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold; beryllium, magnesium, aluminum, zinc , Base metals such as gallium, cadmium, indium, tin, thallium, lead, bismuth, and polonium. Among these, the metal atom M ⁷ is preferably a metal atom capable of forming a divalent metal ion, more preferably beryllium, magnesium, calcium, zinc, barium, cadmium, or lead. A metal atom can also be used individually or in mixture of 2 or more types.

  In the metal oxide (5), a is preferably an integer of 1 to 5, preferably 1 to 3, and most preferably 1. b is preferably an integer of 1 or more and 7 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or more and 3 or less, and particularly preferably 1. The metal oxide (5) is preferably a divalent metal oxide having a = 1 and b = 1.

  Specific examples of the metal oxide (5) include oxides of alkali metals such as lithium oxide, sodium oxide, potassium oxide, rubidium oxide and cesium oxide; oxidation of alkaline earth metals such as calcium oxide, strontium oxide and barium oxide. Scandium oxide, titanium oxide, vanadium oxide, chromium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, yttrium oxide, zirconium oxide, niobium oxide, molybdenum oxide, technetium oxide, ruthenium oxide, rhodium oxide, Palladium oxide, silver oxide, hafnium oxide, tantalum oxide, tungsten oxide, rhenium, osmium oxide, iridium oxide, platinum oxide, gold oxide and other transition metal oxides, beryllium oxide, magnesium oxide, aluminum oxide, zinc oxide, gallium oxide Arm, cadmium oxide, indium oxide, tin oxide, thallium oxide, lead oxide, bismuth oxide, oxides of base metals, such as oxidation polonium and the like. The said metal oxide can also be used individually or in mixture of 2 or more types. Among these, the metal oxide is preferably a divalent metal oxide, more preferably beryllium oxide, magnesium oxide, calcium oxide, zinc oxide, barium oxide, cadmium oxide, or lead oxide. In the present invention, it is particularly preferable to use zinc oxide as the metal oxide (5).

  The first solvent used in the reaction step of the third production method is not particularly limited, but dichloromethane, 1,2-dichloroethane, chloroform, chlorobenzene, dichlorobenzene, benzene, toluene, xylene, tetrahydrofuran, 1,4-dioxane, acetic acid. Examples thereof include ethyl, propyl acetate, isopropyl acetate, acetonitrile, methanol, ethanol, propanol and isopropanol. From the viewpoint of increasing the yield of the complex, it is preferable to use dichloromethane as the solvent.

  A specific method for producing a complex in which the carboxylic acid (6) and the metal oxide (5) are reacted is, for example, by dissolving or dispersing the carboxylic acid (6) and the metal oxide (5) in a first solvent, The reaction solution is preferably stirred (reaction step); the insoluble matter is removed from the reaction solution (insoluble matter removal step); and the target complex is precipitated from the reaction solution (precipitation step).

(Reaction process)
In the reaction step, the carboxylic acid (6) and the metal oxide (5) are dissolved or dispersed in the first solvent, and the reaction solution is stirred. In this step, the carboxylic acid (6) and the metal oxide (5) are contacted in a solvent to form a complex.

  Specifically, first, the metal oxide (5) is dissolved or dispersed in a solvent in a reaction vessel. While stirring the liquid in which the metal oxide (5) is dissolved or dispersed in the solvent, the liquid in which the carboxylic acid (6) is dissolved or dispersed in the solvent is added dropwise. The dropping of the liquid obtained by dissolving or dispersing the carboxylic acid (6) in a solvent is not particularly limited, but it is preferably performed over 0.5 to 3 hours. After completion of the dropwise addition, it is preferable to carry out the reaction while further stirring.

  The reaction is preferably performed in an inert gas atmosphere such as argon or nitrogen.

  In the reaction of carboxylic acid (6) with metal oxide (5), the charged molar ratio of carboxylic acid (6) to metal oxide (5) ((6) / (5)) is preferably more than 1/2. 1/1 or more is more preferable, 2/1 or less is preferable, and 7/4 or less is more preferable. It is because the yield of the obtained complex will become high if the molar ratio ((6) / (5)) of carboxylic acid (6) with respect to metal oxide (5) is in the said range.

  The amount of the first solvent used in the reaction step is preferably 1000 parts by mass or more, more preferably 2000 parts by mass or more, with respect to 100 parts by mass in total of the carboxylic acid (6) and the metal oxide (5). More preferably, it is 3000 parts by mass or more, preferably 10,000 parts by mass or less, more preferably 8000 parts by mass or less, and still more preferably 6000 parts by mass or less. If the amount of the first solvent used exceeds 10,000 parts by mass, the amount of work during synthesis increases, and if it is less than 1000 parts by mass, the yield of the complex may decrease.

  The reaction temperature in the reaction step (liquid temperature of the reaction solution) is preferably −20 ° C. or higher, more preferably 0 ° C. or higher, further preferably 10 ° C. or higher, particularly preferably 20 ° C. or higher, preferably 100 ° C. or lower, 90 ° C. The following is more preferable, 80 ° C. or lower is further preferable, and 50 ° C. or lower is particularly preferable. When the reaction temperature is −20 ° C. or higher, the reaction rate between the carboxylic acid (6) and the metal oxide (5) can be increased. Moreover, self-polymerization of carboxylic acid (6) can be prevented as reaction temperature is 100 degrees C or less.

  The reaction time in the reaction step is preferably 1 hour or longer, more preferably 2 hours or longer, and further preferably 3 hours or longer. This is because if the reaction time is too short, the yield of the complex decreases. From the viewpoint of increasing productivity, the reaction time is preferably 300 hours or less, more preferably 200 hours or less, and even more preferably 100 hours or less. The completion of the reaction can be confirmed by, for example, collecting a part of the reaction solution and measuring infrared absorption, or measuring the weight change of a component dissolved in the reaction solution. .

  In the 3rd manufacturing method of this invention, it is preferable to have an insoluble matter removal process, a precipitation process, a collection | recovery process, and a refinement | purification process after completion | finish of reaction with carboxylic acid (6) and a metal oxide (5).

(Insoluble matter removal process)
After completion of the reaction, insoluble matters are removed from the reaction solution. Examples of the insoluble material include unreacted raw materials or polymers obtained by self-polymerization of carboxylic acid (6). The method for removing insoluble matters is not particularly limited, and examples thereof include a method for filtering the reaction solution.

(Precipitation process)
In the precipitation step, the target complex dissolved in the first solvent is precipitated by introducing the second solvent into the reaction solution from which insolubles have been removed. The reaction solution contains, for example, the target complex and unreacted carboxylic acid (6). If the solubility of the target complex in the second solvent is lower than the solubility of the carboxylic acid (6) in the second solvent, the target complex can be selectively precipitated. The second solvent is not particularly limited as long as it can selectively precipitate the target complex in the reaction solution. Examples of the second solvent include hydrocarbons such as hexane, pentane, cyclohexane, and heptane.

  The input amount of the second solvent may be appropriately adjusted so that the target complex can be precipitated. The input amount of the second solvent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, with respect to 100 parts by mass of the first solvent. Part or less, more preferably 150 parts by weight or less, still more preferably 100 parts by weight or less.

  In addition, the target complex may be precipitated by removing a part of the first solvent and the second solvent after adding the second solvent. As a method for removing a part of the first solvent and the second solvent, vacuum concentration is preferable. The reaction liquid may be heated during concentration under reduced pressure. The temperature of the reaction solution during concentration is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.

  The precipitated target complex is preferably filtered and dried.

(Recovery process)
In the recovery step, the solvent is removed from the reaction solution from which insolubles have been removed. By removing the solvent, the target complex present in the reaction solution can be recovered.

  Examples of the method for removing the solvent include vacuum drying and heat drying, and vacuum drying is preferred. The reaction liquid may be heated when drying under reduced pressure. The temperature of the reaction solution during drying is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 60 ° C. or lower.

(Purification process)
In the purification step, the purity of the target complex can be increased by performing reprecipitation for the target complex obtained in the precipitation step or the recovery step. Specifically, after the obtained target complex is dissolved in the first solvent, the second solvent is added to the solution to precipitate and recover the target complex.

  As the first solvent and the second solvent used in the purification step, those exemplified in the reaction step and the precipitation step can be used. Moreover, the usage-amount of a 2nd solvent is the same as that of the said precipitation process. The purification step may be performed a plurality of times depending on the desired purity of the target complex.

The method for producing the complex of the present invention is suitable as a method for producing the complex represented by the formula (1) and the complex represented by the structural formula (2) or (3). Although the detail of the complex represented by Formula (1) is as having mentioned above, the summary is as follows.
((RCOO) ₈ M ₅ (OH) ₂ ) _n (1)
[In Formula (1), M is a metal atom, R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. A plurality of R may be the same or different. However, at least one of R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer greater than or equal to 1]

［構造式（２）において、Ｍ¹〜Ｍ^５は同一または異なって金属原子であり、Ｒ¹〜Ｒ^８は、それぞれ同一または異なって、水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基を表す。Ｒ¹〜Ｒ^８のうち少なくとも１個は炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基である。ｎは、１以上の整数である。］ The details of the complex having the structure represented by the structural formula (2) are as described above, and the gist thereof is as follows.

[In Structural Formula (2), M ^{1 to} M ⁵ are the same or different and are metal atoms, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer of 1 or more. ]

［構造式（３）において、Ｍ¹〜Ｍ^５は同一または異なって金属原子であり、Ｒ¹〜Ｒ^８は、それぞれ同一または異なって、水素原子、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基を表す。Ｒ¹〜Ｒ^８のうち少なくとも１個は炭素数２〜１８のアルケニル基または炭素数２〜１８のアルキニル基である。］ The details of the complex represented by the structural formula (3) are as described above, but the gist is as follows.

[In Structural Formula (3), M ^{1 to} M ⁵ are the same or different and are metal atoms, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. ]

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to the following examples, and all modifications and embodiments without departing from the gist of the present invention are not limited thereto. Included in range.

[Evaluation method]
(1) Direct introduction-mass spectrometry (DI-MS)
A mass spectrometer (manufactured by Waters, SynaptG2-S type) was used for mass spectrometry.
Ionization method: Atmospheric pressure solid sample probe (ASAP)
Measurement mode: Pos., Neg.
Measurement range: m / z = 50-1500

(2) CHN elemental analysis Elemental analysis was performed using an organic trace element analyzer (manufactured by J-Science Laboratories, Microcoder JM10 type).

(3) Measurement of zinc content The complex (0.1057 g) was weighed into a 100 ml beaker and dissolved by adding 50 ml of distilled water. 10 ml of acetic acid-sodium acetate (pH 5) buffer solution was added to this, and several drops of XO indicator (Wako Pure Chemical Industries, Ltd., 0.1 w / v% xylenol orange solution / 0.1 g / 100 ml = 0.39696M for titration) Was added. Finally, it prepared to 100 ml with distilled water. This prepared solution was titrated with a 0.05 mol / l EDTA standard solution (manufactured by Dojindo).

(4) Infrared spectroscopic analysis Infrared spectroscopic analysis is performed by a total reflection absorption measurement method (ATR method) using diamond as a prism for total reflection absorption measurement, and Fourier transform infrared spectrophotometer, Perkin Elmer Co., Ltd. Manufactured, “Measuring device: Spectrum One”).

(5) Powder X-ray diffraction X-ray diffraction measurement was performed using a wide-angle X-ray diffractometer (manufactured by Rigaku Corporation, “RINT-TTR type III”). The measurement sample was pulverized using an agate mortar. The measurement conditions are as follows.
X-ray source; CuKα tube voltage-tube current; 50kV-300mA
Step width: 0.02deg.
Measurement speed: 5deg./min
Slit system: Divergence-Light reception-Scattering: 0.5deg.-Open-0.5deg.
Monochromator: Diffraction line curved crystal monochromator

(6) Single crystal X-ray structure analysis (X-ray diffraction measurement)
Device: XtaLAB PRO MM007
Data measurement and processing software: CrysAlisPro
Structural analysis program package: CrystalStructure
X-ray source: Cu Kα (λ = 1.54184 angstrom)
Tube voltage and tube current: 40 kV-30 mA
Measurement temperature: -173 ℃ (using spraying cryogenic equipment)
Collimator diameter: Φ0.5mm
Camera length: 39.25 mm
Vibration angle: 0.20 °

The sample for measurement was produced as follows.
The complex (5 mg) and ethyl acetate (833 uL) were placed in a 4 mL vial and heated to 60 ° C. to dissolve the complex (concentration 6 mg / mL). The solution was allowed to stand at 20 ° C. for 1 month to obtain a hexagonal plate-shaped 0.1 mm complex single crystal.
Crystals were collected from the sample bottle and injected into Paratone-N (Hampton Research) on a whole glass slide. Each Paratone-N was scooped with MicroLoopLD100 · mφ (MiTeGen), rapidly frozen in a gas flow of a cryogenic device, and X-ray diffraction was measured. X-ray diffraction data measurement and processing were performed using the software CrysAlisPro and the structural analysis program package CrystalStructure.

[Production example]
(Example Production Example 1)
A reaction vessel was charged with zinc oxide (10 g, 123 mmol) and 250 ml of dichloromethane and stirred in an ice bath at 0 ° C. A solution obtained by dissolving acrylic acid (12.6 g, 174 mmol) in 125 ml of dichloromethane was dropped at a dropping speed of 2 mL / min. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred at room temperature (rt) for 12 hours. The obtained reaction solution was filtered to remove a precipitate insoluble in the solvent. 300 mL of hexane was added to the filtrate, and the mixture was concentrated under reduced pressure until the liquid volume became about 1/4 to obtain a precipitate. The precipitate was taken out by filtration and dried to obtain Complex 1 (yield 7.18 g, yield 35%). In Example Production Example 1, the following raw materials were used.
Zinc oxide: manufactured by Kishida Chemical Co., Ltd. acrylic acid: manufactured by Sigma Aldrich, Inc. dichloromethane: manufactured by Kishida Chemical Co., Ltd.

  The complex 1 obtained in Example 1 was subjected to infrared spectroscopic analysis, elemental analysis, zinc content measurement, and X-ray diffraction measurement. The test results are shown below.

IR spectrum peaks: 413 cm ⁻¹ , 469 cm ⁻¹ , 688 cm ⁻¹ , 829 cm ⁻¹ , 972 cm ⁻¹ , 1068 cm ⁻¹ , 1274 cm ⁻¹ , 1372 cm ⁻¹ , 1435 cm ⁻¹ , 1522 cm ⁻¹ , 1568 cm ⁻¹ _, 1644 cm ^{− 1}

Anal. Calcd for C ₂₄ H ₂₆ O ₁₈ Zn ₅ : C, 31.02; H, 2.82. Found: C, 30.36; H, 2.77.

FIG. 1 shows the IR spectrum of Complex 1 of Example 1 and FIG. 2 shows the IR spectrum of zinc diacrylate. From the IR spectrum, the absorption derived from the vinyl group of acrylate and the absorption derived from the vibration of (HO) Zn ₃ were confirmed. Two types of absorption derived from the vibration of carboxylate groups having different coordination states were confirmed.

Moreover, the zinc content measurement was performed by the following method. That is, Complex 1 (0.1057 g) obtained in Example 1 was weighed into a 100 ml beaker and dissolved by adding 50 ml of distilled water. 10 ml of acetic acid-sodium acetate (pH 5) buffer solution was added to this, and several drops of XO indicator (Wako Pure Chemical Industries, Ltd., 0.1 w / v% xylenol orange solution / 0.1 g / 100 ml = 0.39696M for titration) Was added. Finally, it prepared to 100 ml with distilled water. This adjustment solution was titrated with a 0.05 mol / l EDTA standard solution (manufactured by Dojindo). The zinc content was determined from the titration amount of 11.53 ml from reddish purple to yellow, which was the discoloration at the end point. The measured value of the zinc content was 35.7% by mass, which was very close to the theoretical value of 35.2% by mass. From these results, it was confirmed that the complex 1 produced above was a compound represented by Zn ₅ (OCOCHCH ₂ ) ₈ (OH) ₂ .

As a result of elemental analysis, the carbon content of Complex 1 of Example 1 was 30.36% by mass, and the hydrogen content was 2.77% by mass. The difference between the analysis result and the estimated value was that the carbon content was 0.66% by mass and the hydrogen content was 0.05% by mass. Since the atomic composition was very close to the estimated value, it was confirmed that the purity of the complex 1 (Zn ₅ (OCOCHCH ₂ ) ₈ (OH) ₂ ) was high.

  FIG. 3 shows an X-ray diffraction spectrum of Complex 1 of Example 1 and FIG. 4 shows an X-ray diffraction spectrum of zinc diacrylate. From the X-ray diffraction spectrum, it was confirmed that the complex 1 of Example Production Example 1 had a crystal structure different from that of zinc diacrylate.

(Example Production Example 2)
A reaction vessel was charged with zinc oxide (2.5 g, 31 mmol), zinc acrylate (19.1 g, 92 mmol), 375 ml of dichloromethane and water (0.75 mL, 41 mmol) and stirred at 40 ° C. for 3 hours. The solvent was refluxed. The obtained reaction solution was filtered to remove a precipitate insoluble in the solvent. 300 mL of hexane was added to the filtrate, and the mixture was concentrated under reduced pressure until the liquid volume became about 1/4 to obtain a precipitate. The precipitate was taken out by filtration and dried to obtain Complex 2 (6.72 g, yield 31%).

  FIG. 5 shows the IR spectrum of Complex 2 of Production Example 2.

IR spectrum peaks: 405 cm ⁻¹ , 469 cm ⁻¹ , 688 cm ⁻¹ , 829 cm ⁻¹ , 972 cm ⁻¹ , 1066 cm ⁻¹ , 1273 cm ⁻¹ , 1366 cm ⁻¹ , 1431 cm ⁻¹ , 1522 cm ⁻¹ , 1564 cm ⁻¹ _, 1642 cm ^{− 1}

From the IR spectrum, for the complex 2 obtained in Example Production Example 2, the absorption derived from the vinyl group of acrylate and the absorption derived from the vibration of (HO) Zn ₃ were confirmed. Two types of absorption derived from the vibration of carboxylate groups having different coordination states were confirmed.

  The production conditions and results of Examples 1 to 2 are summarized in Table 1.

収率（％）＝１００×（各収量をクラスターの分子量で割った値）／（原料から得られるクラスターの理論値（モル））

Yield (%) = 100 × (value obtained by dividing each yield by the molecular weight of the cluster) / (theoretical value (mole) of the cluster obtained from the raw material)

(Example Production Example 3)
Under an argon atmosphere, zinc oxide (125 g, 1540 mmol), zinc acrylate (955 g, 4600 mmol) and 18.7 L of dichloromethane were charged in a reaction vessel, and the mixture was stirred at 40 ° C. for 3 hours. The solvent was refluxed. The obtained reaction solution was filtered to remove a precipitate insoluble in the solvent. 14.3 L of hexane was added to the filtrate, and the mixture was concentrated under reduced pressure until the liquid volume became about 1/4 to obtain a precipitate. The precipitate was taken out by filtration, and the filtrate was concentrated and dried to obtain the first complex 3. The obtained first complex 3 is gradually reacted with water (moisture) in an environment of 20 ° C. to 30 ° C. and a humidity of 50% or more to thereby obtain the second complex 3 (target complex, 116 g, yield 12%). Got.

(Example Production Example 4)
12 hours after the reaction solution reached 40 ° C., the reaction was terminated to obtain the first complex 4, and the reaction was performed in the same manner as in Example Production Example 3 to obtain the second complex 4 (target complex). Yield 79 g, yield 8%).

(Example Production Example 5)
24 hours after the reaction solution reached 40 ° C., the reaction was terminated to obtain the first complex 5, and the reaction was carried out in the same manner as in Example Production Example 3 to obtain the second complex 5 (target complex). Yield 25 g, yield 3%).

(Example manufacturing example 6)
48 hours after the reaction solution reached 40 ° C., the reaction was terminated to obtain the first complex 6, and the reaction was carried out in the same manner as in Production Example 3 to obtain the second complex 6 (target complex). Yield 70 g, yield 8%). The production conditions and results of Example Production Examples 3 to 6 are summarized in Table 2.

収率（％）＝１００×（各収量をクラスターの分子量で割った値）／（原料から得られるクラスターの理論値（モル））

Yield (%) = 100 × (value obtained by dividing each yield by the molecular weight of the cluster) / (theoretical value (mole) of the cluster obtained from the raw material)

  About the 1st complex 3 of the implementation manufacture example 3, mass spectrometry, elemental analysis, zinc content measurement, X-ray diffraction measurement, and infrared spectroscopic analysis were performed. The test results are shown below.

High-resolution ASAP-MS (positive) spectrum measurement result
Positive ion HR-ASAP-MS m / z: 632.7715
[M-CH ₂ CHCOO] ⁺ (calcd. For C ₁₅ H ₁₅ O ₁₁ Zn ₄ 632.7707 Δ1.2ppm
High-resolution ASAP-MS (negative) spectrum measurement result
Negative ion HR-ASAP-MS m / z: 735.7762
[M + O ₂ ] ^- (calcd. For C ₁₈ H ₁₈ O ₁₅ Zn ₄ 735.7740 Δ2.9ppm

Anal. Calcd for C ₁₈ H ₁₈ O ₁₃ Zn ₄ : C, 30.71; H, 2.58. Found: C, 30.72; H, 2.50.

IR spectrum ^{peaks: 520cm -1, 600cm -1, 675cm} -1, 828cm -1, 968cm -1, 1067cm -1, 1276cm -1, 1370cm -1, 1436cm -1, 1572cm -1, 1643cm -1

The ASAP-MS spectrum of the first complex 3 obtained in Example 3 is shown in FIGS. In addition, anions [Zn ₄ O (OCOCHCH ₃ ) ₆ O ₂ ] ⁽⁻⁾ estimated from Zn ₄ O (OCOCHCH ₂ ) ₆ and cations [Zn ₄ O (OCOCHCH ₃ ) ₅ ] ⁽⁺⁾ The ASAP-MS spectrum simulation pattern is shown in FIGS.

As shown in FIGS. 6 and 7, the ASAP-MS spectrum showed a pattern similar to the simulation pattern. In addition, the obtained experimental values 632.7715 and 735.7762 are cations [Zn ₄ O (OCOCHCH ₃ ) ₅ ] ⁽⁺⁾ : C ₁₅ H ₁₅ O ₁₁ Zn ₄ estimated value 632.7707, anions [Zn ₄ O (OCOCHCH ₃ ) ₆ O ₂ ] ⁽⁻⁾ : C ₁₈ H ₁₈ O ₁₅ Zn _{4 It} was a value very close to the estimated value of 75.7740. The measured value of the zinc content was 36.8% by mass, which was very close to the theoretical value of 37.2% by mass. From these results, it was confirmed that the first complex 3 produced above was a compound represented by Zn ₄ O (OCOCHCH ₂ ) ₆ .

From the results of elemental analysis, the carbon content of the first complex 3 was 30.72% by mass, and the hydrogen content was 2.50% by mass. The difference between the analysis result and the estimated value was 0.01% by mass for carbon content and 0.08% by mass for hydrogen content. Since the atomic composition was very close to the estimated value, it was confirmed that the purity of the first complex (Zn ₄ O (OCOCHCH ₂ ) ₆ ) was very high.

FIG. 8 shows the IR spectrum of the first complex 3, and FIG. 9 shows the X-ray diffraction spectrum of the first complex 3. From the IR spectrum, absorption derived from the vinyl group of acrylate and absorption derived from the vibration of Zn ₄ O were confirmed. It was also confirmed that the coordination state of the carboxylate group was different from that of zinc diacrylate. From the X-ray diffraction spectrum, it was confirmed that the first complex 3 (zinc acrylate oxocluster) had a crystal structure different from that of zinc diacrylate.

  FIG. 10 shows the IR spectrum of the second complex 3 obtained in Example Production Example 3.

IR spectrum peaks: 413 cm ⁻¹ , 469 cm ⁻¹ , 688 cm ⁻¹ , 829 cm ⁻¹ , 972 cm ⁻¹ , 1068 cm ⁻¹ , 1274 cm ⁻¹ , 1372 cm ⁻¹ , 1435 cm ⁻¹ , 1522 cm ⁻¹ , 1568 cm ⁻¹ _, 1644 cm ^{− 1}

From the IR spectrum, the second complex 3 obtained in Example Production Example 3 was confirmed to have absorption derived from the vinyl group of acrylate and absorption derived from vibration of (HO) Zn ₃ . Two types of absorption derived from the vibration of carboxylate groups having different coordination states were confirmed.

  Example The structure of the second complex 3 obtained in Production Example 3 was determined by single crystal X-ray structural analysis. As a result, it was found to have the following structure. The arrow indicates the symmetry center of this structure, and the part surrounded by a line is a part of the adjacent molecule that interacts.

The atomic composition ratio and zinc content corresponding to Zn ₅ (OCOCHCH ₂ ) ₈ (OH) ₂ were confirmed by EDTA titration and mass spectrometry, and the metal cluster of the present invention was confirmed. Furthermore, XRD has a crystal structure different from that of zinc acrylate (FIG. 2). From FT-IR, the presence of vinyl group, absorption derived from vibration of (HO) Zn ₃ and two different types From the time when absorption derived from vibration of acrylate was confirmed, it was confirmed that Zn ₅ (OCOCHCH ₂ ) ₈ (OH) ₂ could be synthesized with high purity.

(Comparative Production Example 1)
A reaction vessel was charged with zinc acrylate (2.0 g, 9.6 mmol) and 140 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. To this reaction solution, 3 mL of water and 20 mg of 4-methoxyphenol as a polymerization inhibitor were further added as additives. The reaction solution was stirred for 12 hours while refluxing toluene at 110 ° C. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The filtration residue was 1.77 g (88.5%). The obtained filtrate was concentrated to obtain a concentrate (0.21 g, 10.5%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 2)
The reaction was carried out in the same manner as in Comparative Production Example 1 except that chloroform was used as a solvent and the reaction solution was stirred while refluxing chloroform at 60 ° C. The filtration residue was 0.24 g (12%). The resulting filtrate was concentrated to give a concentrate (1.44 g, 72%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 3)
The reaction was conducted in the same manner as in Comparative Production Example 1 except that 140 mL of 1,2-dichlorobenzene was used as a solvent and the reaction solution was stirred at 110 ° C. while refluxing 1,2-dichlorobenzene. There was no insoluble matter in the reaction solution. The obtained filtrate could not be concentrated, and the target product could not be obtained.

(Comparative Production Example 4)
The reaction was conducted in the same manner as in Comparative Production Example 1 except that 140 mL of propyl acetate was used as a solvent and the reaction solution was stirred at 100 ° C. while refluxing propyl acetate. The filtration residue was 1.71 g (85.5%). The desired product could not be obtained.

(Comparative Production Example 5)
The reaction was performed in the same manner as Comparative Production Example 1 except that 140 mL of acetone was used as a solvent and the reaction solution was stirred while refluxing acetone at 56 ° C. The filtration residue was 0.26 g (13%). The resulting filtrate was concentrated to give a concentrate (1.54 g, 77%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 6)
The reaction was performed in the same manner as in Comparative Production Example 1 except that 140 mL of N, N-dimethylformamide (DMF) was used as a solvent and the reaction solution was stirred at 100 ° C. There was no insoluble matter in the reaction solution. The obtained filtrate could not be concentrated, and the target product could not be obtained.

(Comparative Production Example 7)
The reaction was performed in the same manner as in Comparative Production Example 1 except that 140 mL of acetonitrile was used as a solvent and the reaction solution was stirred at 82 ° C. while refluxing acetonitrile. There was no insoluble matter in the reaction solution. The resulting filtrate was concentrated to give a concentrate (1.8 g, 90%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 8)
The reaction was performed in the same manner as in Comparative Production Example 1 except that 140 mL of dimethyl sulfoxide (DMSO) was used as a solvent and the reaction solution was stirred at 100 ° C. There was no insoluble matter in the reaction solution. The obtained filtrate could not be concentrated, and the target product could not be obtained.

  The production conditions and results of Comparative Production Examples 1 to 8 are summarized in Table 3.

収率（％）＝１００×（各収量をクラスターの分子量で割った値）／（原料から得られるクラスターの理論値（モル））

Yield (%) = 100 × (value obtained by dividing each yield by the molecular weight of the cluster) / (theoretical value (mole) of the cluster obtained from the raw material)

(Comparative Production Example 9)
A reaction vessel was charged with zinc acrylate (5.02 g, 24 mmol) and 200 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. To this reaction solution, 3 mL of water was further added as an additive. The reaction solution was stirred for 2 hours while refluxing toluene at 110 ° C. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (0.38 g, 7.6%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 10)
A reaction vessel was charged with zinc acrylate (2.00 g, 9.6 mmol) and 200 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. To this reaction solution, 2 mL of water was further added as an additive. The reaction solution was stirred for 2 hours while refluxing toluene at 110 ° C. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (0.37 g, 18.6%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 11)
A reaction vessel was charged with zinc acrylate (2.01 g, 9.7 mmol) and 200 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. To this reaction solution, 2 mL of water was further added as an additive. The reaction was stirred at 90 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (1.07 g, 53.2%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 12)
A reaction vessel was charged with zinc acrylate (2.04 g, 9.8 mmol) and 200 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. To this reaction solution, 0.5 mL of water was further added as an additive. The reaction solution was stirred at 110 ° C. for 1 hour while refluxing toluene. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (1.67 g, 81.7%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 13)
A reaction vessel was charged with zinc acrylate (2.01 g, 9.7 mmol) and 200 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. The reaction solution was stirred at 110 ° C. for 1 hour while refluxing toluene. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (0.30 g, 14.8%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 14)
A reaction vessel was charged with zinc acrylate (2.08 g, 10 mmol) and 200 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. To the reaction solution, 1 mL of water was further added as an additive. The reaction solution was stirred for 2 hours while refluxing toluene at 110 ° C. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (0.85 g, 41%). When the concentrate was analyzed, the target product was not confirmed.

(Comparative Production Example 15)
A reaction vessel was charged with zinc acrylate (10 g, 4.8 mmol) and 49 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. The reaction solution was stirred at 110 ° C. for 5 hours while refluxing toluene. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (0.26 g, 2.6%). When the concentrate was analyzed, a polymer of zinc acrylate was confirmed.

(Comparative Production Example 16)
A reaction vessel was charged with zinc acrylate (10 g, 4.8 mmol) and 49 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. The reaction solution was stirred at 110 ° C. for 24 hours while refluxing toluene. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (0.08 g, 0.8%). When the concentrate was analyzed, a polymer of zinc acrylate was confirmed.

(Comparative Production Example 17)
A reaction vessel was charged with zinc acrylate (10 g, 4.8 mmol) and 97 mL of toluene as a solvent, and the zinc acrylate was dissolved or dispersed in toluene. The reaction solution was stirred at 110 ° C. for 24 hours while refluxing toluene. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (0.03 g, 0.3%). When the concentrate was analyzed, a polymer of zinc acrylate was confirmed.

(Comparative Production Example 18)
A reaction vessel was charged with zinc acrylate (10 g, 4.8 mmol) and 97 mL of xylene as a solvent, and the zinc acrylate was dissolved or dispersed in xylene. The reaction solution was stirred at 110 ° C. for 5 hours while refluxing xylene. After completion of the reaction, the reaction solution was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (0.19 g, 1.9%). When the concentrate was analyzed, a polymer of zinc acrylate was confirmed.

  The reaction conditions and results of Comparative Production Examples 9 to 18 are summarized in Table 4.

収率（％）＝１００×（各収量をクラスターの分子量で割った値）／（原料から得られるクラスターの理論値（モル））

Yield (%) = 100 × (value obtained by dividing each yield by the molecular weight of the cluster) / (theoretical value (mole) of the cluster obtained from the raw material)

(Comparative Production Example 19)
A reaction vessel was charged with zinc oxide (30 g, 369 mmol) and 250 ml of dichloromethane and stirred at 0 ° C. A solution obtained by dissolving acrylic acid (13.3 g, 184 mmol) in 125 ml of dichloromethane was dropped at a dropping speed of 2.5 mL / min. After completion of dropping, the temperature was raised to 40 ° C. and stirred for 3 hours to complete the reaction. The obtained reaction solution was filtered to remove a precipitate insoluble in the solvent. 300 mL of hexane was added to the filtrate, and the mixture was concentrated under reduced pressure until the liquid volume became about 1/4 to obtain a concentrate. Analysis of the concentrate did not identify the desired product.

(Comparative Production Example 20)
A solution in which zinc oxide (2.5 g, 31 mmol) and zinc acrylate (19.1 g, 92 mmol) were dissolved or dispersed in 375 ml of dichloromethane was stirred in a reaction vessel at 40 ° C. for 3 hours. The solvent was refluxed. The obtained reaction solution was filtered to remove a precipitate insoluble in the solvent. 300 mL of hexane was added to the filtrate, and the mixture was concentrated under reduced pressure until the liquid volume became about 1/4 to obtain a precipitate. The precipitate was removed by filtration, and the filtrate was dried to obtain a concentrate (1.82 g). The concentrate was an oxo acrylate cluster, and no hydroxo cluster acrylate was identified.

  The reaction conditions and results of Comparative Production Examples 19 to 20 are summarized in Table 5.

収率（％）＝１００×（各収量をクラスターの分子量で割った値）／（原料から得られるクラスターの理論値（モル））

Yield (%) = 100 × (value obtained by dividing each yield by the molecular weight of the cluster) / (theoretical value (mole) of the cluster obtained from the raw material)

[Preparation of rubber composition]
Each raw material was kneaded with the formulation shown in Table 6 to prepare a rubber composition.

The materials used in Table 6 are as follows.
BR730: manufactured by JSR, high cis polybutadiene (cis-1,4-bond content = 96 mass%, 1,2-vinyl bond content = 1.3 mass%, Mooney viscosity (ML _{1 + 4} (100 ° C.) ) = 55, molecular weight distribution (Mw / Mn) = 3)
Zinc acrylate hydroxocluster: second complex 3 obtained in Example 3
ZN-DA90S: Zinc acrylate (10% by weight zinc stearate coated product) manufactured by Nippon Touch Techno Fine Chemical Co., Ltd.
Zinc oxide: Toho Zinc Co., Ltd.
Dicumyl peroxide: NOF Corporation, “Park Mill (registered trademark) D”

  Table 6 shows the hardness and rebound resilience of slabs made from the rubber composition. As a result, all the crosslinked rubber molded bodies (slabs) using the complex of the present invention have high resilience performance, and their usefulness as a crosslinking agent was confirmed.

  If the rubber composition of the present invention is used, a crosslinked rubber molded article having excellent resilience performance can be obtained. Therefore, the rubber composition of the present invention can be used for sports equipment such as golf balls and tennis balls.

Claims (23)

Complex represented by Formula (1).
((RCOO) ₈ M ₅ (OH) ₂ ) _n (1)
[In Formula (1), M is a metal atom, R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. A plurality of R may be the same or different. However, at least one of R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer of 1 or more. ]   In the formula (1), at least one of R is an alkynyl group having 2 to 8 carbon atoms having a carbon-carbon double bond at a terminal or a alkynyl having 2 to 8 carbon atoms having a carbon-carbon triple bond at a terminal. The complex according to claim 1, which is a group.   The complex according to claim 1 or 2, wherein the metal atom M is at least one metal atom selected from the group consisting of zinc, beryllium, lead, magnesium, nickel, and copper. Metal atom M is zinc, R = -CH = CH ₂ or -C _(CH 3) = complex according to any one of claims 1 to 3 is CH _2. n = 1 or more, The complex in any one of Claims 1-4 which has a structure represented by Structural formula (2).

[In Structural Formula (2), M ^{1 to} M ⁵ are the same or different and are metal atoms, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. ] The complex according to claim 5, wherein n = 1 and has a structure represented by the structural formula (3).

[In Structural Formula (3), M ^{1 to} M ⁵ are the same or different and are metal atoms, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. ] The complex according to claim 5 or 6, wherein M ^{1 to} M ⁵ are at least one metal atom selected from the group consisting of zinc, beryllium, lead, magnesium, nickel, and copper. R < ¹ > -R < ⁸ > is the complex as described in any one of Claims 5-7 which is the same or different and represents a C2-C18 alkenyl group or a C2-C18 alkynyl group. M ¹ ~M ⁵ is ^{zinc, R 1 ~R 8 = -CH =} CH 2 or -C _(CH 3) = complex according to any one of claims 5-8 is CH _2. A method for producing a complex, comprising reacting a compound represented by the formula (4) and a metal oxide represented by the formula (5) in a solvent in the presence of water.
[M ⁶ (RCOO) _x ] · yH ₂ O (4)
M ⁷ _a O _b (5)
Wherein (4), ^{M 6} is a metal atom, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group or an alkynyl group having 2 to 18 carbon atoms having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M ⁶ and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R may be the same or different. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ] A step of reacting a compound represented by the formula (4) with a metal oxide represented by the formula (5) in a solvent to obtain a first complex; and
A step of reacting the first complex with water to obtain a second complex.
[M ⁶ (RCOO) _x ] · yH ₂ O (4)
M ⁷ _a O _b (5)
Wherein (4), ^{M 6} is a metal atom, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group or an alkynyl group having 2 to 18 carbon atoms having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M ⁶ and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R may be the same or different. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ]   The method for producing a complex according to claim 11, wherein the reaction between the first complex and water is performed by exposing the first complex to an atmosphere having a relative humidity of 50% or more.   The molar ratio ((4) / (5)) of the compound represented by the formula (4) and the metal oxide represented by the formula (5) is 3/2 to 5/1. The manufacturing method of the complex as described in any one of these. The manufacturing method of the complex characterized by making the carboxylic acid represented by Formula (6), and the metal oxide represented by Formula (5) react in a solvent.
RCOOH (6)
M ⁷ _a O _b (5)
[In Formula (6), R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. In formula (5), M ⁷ is a metal atom. a is an integer of 1-5. b is an integer of 1-7. ]   The molar ratio ((6) / (5)) of the carboxylic acid represented by the formula (6) and the metal oxide represented by the formula (5) is more than 1/2 and 7/4 or less. 14. A method for producing the complex according to 14.   The method for producing a complex according to any one of claims 10 to 15, wherein dichloromethane is used as the solvent.   The manufacturing method of the complex as described in any one of Claims 10-16 made to react at the temperature of the range of -20 degreeC-100 degreeC. The manufacturing method of the complex as described in any one of Claims 10-17 which manufactures the complex represented by Formula (1).
((RCOO) ₈ M ₅ (OH) ₂ ) _n (1)
[In Formula (1), M is a metal atom, R is a hydrogen atom, a C1-C18 alkyl group, a C2-C18 alkenyl group, or a C2-C18 alkynyl group. A plurality of R may be the same or different. However, at least one of R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. n is an integer greater than or equal to 1] The complex represented by formula (1) (n = 1 or more) is a method for producing a complex according to claim 18, having a structure represented by structural formula (2).

[In Structural Formula (2), M ^{1 to} M ⁵ are the same or different and are metal atoms, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. ] The complex production method according to claim 19, wherein the complex (n = 1 or more) represented by the structural formula (2) has a structure (n = 1) represented by the structural formula (3).

[In Structural Formula (3), M ^{1 to} M ⁵ are the same or different and are metal atoms, and R ^{1 to} R ⁸ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, An alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms is represented. At least one of R ^{1 to} R ⁸ is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. ] In the structural formula (2) or (3), M ^{1 to} M ⁵ are at least one metal atom selected from the group consisting of zinc, beryllium, lead, magnesium, nickel, and copper. A method for producing the described complex. In Structural Formula (2) or (3), R ^{1 to} R ⁸ are the same or different and each represents an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. A method for producing the complex according to claim 1. In Structural Formula (2) or (3), M ^{1 to} M ⁵ are zinc, and R ^{1 to} R ⁸ = —CH═CH ₂ or —C (CH ₃ ) ═CH _2. The manufacturing method of the complex as described in any one of these.

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