Method for producing complex

Abstract

To provide a method for producing a novel complex having an identical molecular framework but differing in crystal packings (crystal structures).SOLUTION: There is provided a method for producing a novel complex that causes a compound represented by a formula (1) to be reacted in an organic solvent in presence of water. [M(RCOO)x] yH2O (1). [In the formula (1), M is a metal atom, R is H, a C1-18 alkyl group, or a C2-18 alkenyl or alkynyl group. x is a number corresponding to an oxidation number of a metal atom M and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R groups may be the same or different].SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a complex. [Background technology]

[0002] The present inventors have filed patent applications relating to novel complexes and methods for producing the same. Patent Document 1 discloses a complex having a structure represented by structural formula (2), where n is 1 or more. [ka] [In structural formula (2), M 1 ~M 5 are the same or different metal atoms, and R 1 ~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. R 1 ~R 8 At least one of these is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms.]

[0003] Patent Document 1 also describes a method for producing a complex having a structure represented by structural formula (2): A method for producing a complex is disclosed, which comprises reacting a compound represented by formula (4) with a metal oxide represented by formula (5) in a solvent in the presence of water (Production Method 1). Also disclosed is a method for producing a complex having a structure represented by structural formula (2), which comprises a step of reacting a compound represented by formula (4) with a metal oxide represented by 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 (Production Method 2). [M 6 (RCOO) x ]·yH2O···(4) M 7 a O b (5) [In formula (4), M 6is 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 an alkynyl group having 2 to 18 carbon atoms. x is a metal atom M 6 and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R's may be the same or different. In formula (5), M 7 is a metal atom; a is an integer from 1 to 5; and b is an integer from 1 to 7.]

[0004] Patent Document 1 discloses a method for producing a complex having a structure represented by structural formula (2), which is characterized by reacting a carboxylic acid represented by formula (6) with a metal oxide represented by formula (5) in a solvent (Production Method 3). RCOOH ···(6) M 7 a O b (5) [In formula (6), R 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. In formula (5), M 7 is a metal atom; a is an integer from 1 to 5; and b is an integer from 1 to 7.] [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-104405 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a method for producing a novel complex that has the same molecular structure as the complex described in Patent Document 1 but has a different packing (crystal structure). [Means for solving the problem]

[0007] The present invention is a method for producing a complex having a structure represented by structural formula (2), which comprises reacting a compound represented by formula (1) in an organic solvent in the presence of water. [M(RCOO) x ]·yH2O···(1) In formula (1), M is a metal atom, and R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R's may be the same or different. In structural formula (2), M 1 ~M 5 are the same or different metal atoms, and R 1 ~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. R 1 ~R 8 At least one of these 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 2 or more.]

[0008] [ka] Effect of the Invention

[0009] According to the present invention, a novel and useful method for producing a complex having the structure of structural formula (2) can be provided. [Brief description of the drawings]

[0010] [Figure 1] 1 is an ESI-MS spectrum of the complex of Example 1 of the present invention. [Diagram 2] 1 is a 1H-NMR chart of the complex of Example 1 of the present invention. [Diagram 3] 1 shows the crystal structure of the complex of Example 1 of the present invention, determined by single crystal X-ray diffraction. [Figure 4] 1 is a powder X-ray diffraction spectrum of the complex of Example 1 of the present invention. [Diagram 5] 1 is a powder X-ray diffraction spectrum of the complex of Example 2 of the present invention. [Figure 6] 1 is an IR spectrum of the complex of Example 2 of the present invention. [Figure 7] 1 is a powder X-ray diffraction spectrum of the complex disclosed in JP 2018-104405 A. [Figure 8] This is the crystal structure obtained by single crystal X-ray diffraction of the complex disclosed in JP 2018-104405 A. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention is a method for producing a complex having a structure represented by structural formula (2), which comprises reacting a compound represented by formula (1) in an organic solvent in the presence of water. [M(RCOO) x ]·yH2O···(1) [In formula (1), M is a metal atom, and R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R's may be the same or different. In structural formula (2), M 1 ~M 5 are the same or different metal atoms, and R 1 ~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. R 1 ~R 8 At least one of these 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 2 or more.]

[0012] In the production method of the present invention, a compound represented by formula (1) is reacted in an organic solvent in the presence of water. The "reaction" in the production method of the present invention is a reaction in which a compound represented by formula (1) reacts with water molecules in an organic solvent in the presence of water and crystallizes to form a complex having a structure represented by structural formula (2). Note that in the production method of the complex of the present invention, a metal oxide such as that disclosed in JP 2018-104405 A is not used in the reaction.

[0013] First, the compound represented by formula (1) (hereinafter sometimes simply referred to as "compound (1)") will be described. [M(RCOO) x ]·yH2O···(1)

[0014] R in the compound (1) 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.

[0015] Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, but is preferably linear.

[0016] 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, 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 linear is preferred. The alkenyl group having 2 to 18 carbon atoms preferably has one carbon-carbon double bond. The position of the double bond is preferably the α, β position, or the carbon-carbon double bond is preferably at the terminal of the alkenyl group. The number of carbon atoms in the alkenyl group is preferably not more than 8, more preferably not more than 6, and even more preferably not more than 4. The alkenyl group having 2 to 18 carbon atoms is preferably a vinyl group, an isopropenyl group, a 1-propenyl group, or a 2-propenyl group.

[0017] Examples of the alkynyl group having 2 to 18 carbon atoms include ethynyl, 1-propynyl, 2-propenyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, and octadecynyl. The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, but linear is preferred. The alkynyl group having 2 to 18 carbon atoms preferably has one carbon-carbon triple bond. The carbon-carbon triple bond is preferably at the α or β position, or at the terminal of the alkynyl group. The number of carbon atoms in the alkynyl group is preferably 8 or less, more preferably 6 or less, and even 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.

[0018] In the compound (1), examples of the metal atom (M) include alkaline earth metals such as calcium, strontium, and barium; transition metals such as scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, and gold; and base metals such as beryllium, magnesium, aluminum, zinc, gallium, cadmium, indium, tin, thallium, lead, bismuth, and polonium. Among these, the metal atom is preferably a metal atom capable of forming a divalent or higher 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. The metal atom can be used alone or as a mixture of two or more kinds.

[0019] x represents the number of carboxylate groups (RCOO) in compound (1). x is a number corresponding to the oxidation number of the metal atom M and is an integer of 2 or more. x is, for example, preferably 2 to 5, and more preferably 2. y is an integer of 0 or more. y is, for example, preferably 0 to 5, and more preferably 0.

[0020] A specific example of the compound (1) is a fatty acid metal salt. 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 19 carbon atoms.

[0021] 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, 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-hexadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid, 9-octadecenoic acid, 11-octadecenoic acid, 17-octadecenoic acid, and 18-nonadecenoic acid. unsaturated fatty acids having a carbon-carbon double bond such as propynoic acid, 3-butynoic acid, 4-pentynoic acid, 5-hexynoic acid, 6-heptynoic acid, 7-octynoic acid, 8-nonynoic acid, 9-decynoic acid, 10-undecynoic acid, 11-dodecynoic acid, 12-tridecynoic acid, 9-tetradecynoic acid, 13-tetradecynoic acid, 14-pentadecynoic acid, 9-hexadecynoic acid, 15-hexadecynoic acid, 16-heptadecynoic acid, 9-octadecynoic acid, 11-octadecynoic acid, 17-octadecynoic acid, and 18-nonadecynoic acid.

[0022] 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 the α- or β-position, or the terminal of the 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 the α- or β-position, or the terminal of the unsaturated fatty acid.

[0023] The metal atom (M) of the fatty acid metal salt may be, for example, an alkaline earth metal such as calcium, strontium, or barium; a transition metal such as scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, or gold; or a base metal such as beryllium, magnesium, aluminum, zinc, gallium, cadmium, indium, tin, thallium, lead, bismuth, or polonium. Among these, the metal atom is preferably a metal atom capable of forming a divalent metal ion, more preferably beryllium, magnesium, calcium, zinc, barium, cadmium, or lead. The metal atom may be used alone or as a mixture of two or more kinds.

[0024] 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, and even more preferably a metal salt of a divalent metal ion of acrylic acid or methacrylic acid.

[0025] In the production method of the present invention, it is preferable to use zinc diacrylate and / or zinc dimethacrylate as compound (1).

[0026] When two or more kinds of the fatty acid metal salts are used in combination as compound (1), the content of each fatty acid metal salt may be appropriately adjusted according to the desired complex. The content of unsaturated fatty acid in the fatty acid constituting compound (1) is preferably 33 mol% or more, more preferably 50 mol% or more, and even more preferably 66 mol% or more. It is also preferable that all the fatty acids constituting compound (1) are unsaturated fatty acids. The content of unsaturated fatty acid having carbon-carbon double bond in the fatty acid constituting compound (1) is preferably 33 mol% or more, more preferably 50 mol% or more, and even more preferably 66 mol% or more. It is also preferable that all the fatty acids constituting compound (1) are unsaturated fatty acids having carbon-carbon double bonds. Although multiple kinds of fatty acids constituting compound (1) may be used in combination, it is also preferable that only one kind is used.

[0027] The fatty acid metal salt used as compound (1) may be in the form of one fatty acid and one metal ion; one fatty acid and one metal ion; one fatty acid and one metal ion; or one fatty acid and one metal ion. Among these, the form of one fatty acid and one metal ion is preferred. The fatty acid metal salt may be used alone or in combination of two or more.

[0028] In the production method of the present invention, an organic solvent is used. The organic solvent is preferably one capable of dissolving compound (1). Examples of the organic solvent include tetrahydrofuran (THF), ethanol, isopropyl alcohol, propyl acetate, and isopropyl ether.

[0029] In the production method of the present invention, the compound represented by formula (1) is reacted in an organic solvent in the presence of water. It is preferable that water is mixed with the organic solvent.

[0030] The ratio (volume ratio) of the organic solvent to water is preferably 1 / 10 or more, more preferably 1 / 1 or more, and even more preferably 10 / 1 or more, and is preferably 5000 / 1 or less, more preferably 1000 / 1 or less, and even more preferably 500 / 1 or less. By setting the ratio (volume ratio) of the organic solvent to water within the above range, the production ratio of the complex of formula (2) is high and the yield is also good.

[0031] The amount of the mixture of the organic solvent and water added is preferably 3 mL or more, more preferably 5 mL or more, and even more preferably 7 mL or more, and is preferably 1000 mL or less, more preferably 500 mL or less, and even more preferably 100 mL or less, per 1 g of compound (1). By setting the amount of the mixture of the organic solvent and water added within the above range, compound (1) is sufficiently dissolved, and the amount of crystals of the complex of formula (2) produced is increased, resulting in a good yield.

[0032] The temperature of the reaction is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher, and is preferably 100°C or lower, more preferably 90°C or lower, and even more preferably 80°C or lower.

[0033] The reaction time is preferably 1 minute or more, more preferably 30 minutes or more, and even more preferably 60 minutes or more, and is preferably 300 minutes or less, more preferably 180 minutes or less, and even more preferably 120 minutes or less.

[0034] (Insoluble matter removal process) After the reaction step is completed, insoluble matters are removed from the reaction solution. Examples of insoluble matters include unreacted raw materials and polymerized products of compound (1) that are self-polymerized. The method for removing insoluble matters is not particularly limited, and includes filtering the reaction solution.

[0035] (Precipitation process) In the precipitation step, the reaction solution from which the insoluble matter has been removed is concentrated by removing the solvent. By concentrating the reaction solution, a complex having a structure represented by structural formula (2) is precipitated.

[0036] Methods for removing the solvent include drying under reduced pressure and drying by heating, with drying under reduced pressure being preferred. The reaction liquid may be heated during drying under reduced pressure. The temperature of the reaction liquid during drying is preferably 100° C. or lower, more preferably 80° C. or lower, and even more preferably 60° C. or lower.

[0037] (Recovery process) The concentrated liquid containing the precipitate is filtered, and the precipitate is dried to recover the complex having the structure represented by structural formula (2).

[0038] (purification process) In the purification step, the purity of the target complex can be increased by reprecipitation of the target complex obtained in the precipitation step or the recovery step. The purification step may be performed multiple times depending on the desired purity of the target complex.

[0039] The present invention produces a complex having a structure represented by formula (2).

[0040] A complex is a molecular compound in which a metal atom or metal ion is bound to an atom or atomic group called a ligand, and is also called a coordination compound.

[0041] [ka] [In structural formula (2), M 1 ~M 5 are the same or different metal atoms, O is an oxygen atom, H is a hydrogen atom, and R 1 ~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. R 1 ~R 8At least one of these 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 2 or more.]

[0042] The complex of structural formula (2) is a complex formed by bonding the basic structural units in parentheses. In structural formula (2), the bond with a dashed line on a solid line indicates a hybrid bond of the carboxylate group. In structural formula (2), both covalent bonds and coordinate bonds are shown with solid lines.

[0043] In structural formula (2), n is an integer of 2 or greater. There is no particular upper limit to n, but it is preferably 100 million, more preferably 1 million, and even more preferably 10,000.

[0044] More specifically, the complex of structural formula (2) has a three-dimensional structure represented by the following formulas (2-1) and (2-2). Formula (2-1) shows a part of the three-dimensional structure of the complex of structural formula (2). As shown in formula (2-1), the complex of structural formula (2) has a three-dimensional structure in which two structural units are bonded to one structural unit. One carboxylate group (R 2 Of the oxygen atoms in the COO), one oxygen atom is connected to a metal atom M present in the same structural unit. 2 The other oxygen atom is coordinated to a metal atom M 4 The carboxylate group (R 6 Of the oxygen atoms in the COO), one oxygen atom is connected to a metal atom M present in the same structural unit. 5 The other oxygen atom is coordinated to a metal atom M 1 Coordinate to.

[0045] Formula (2-2) shows a part of the molecular structure of the complex of structural formula (2), but the complex of structural formula (2) has an infinitely long structure formed by bonding basic structural units.

[0046] [ka]

[0047] [ka]

[0048] In structural formula (2), M 1 ~M 5 Examples of the metal atom represented by the formula (1) include the same as M in formula (1). Among these, the metal atom is preferably one having an oxidation number of +2, and more preferably beryllium, magnesium, nickel, calcium, zinc, barium, cadmium, and lead. M 1 ~M 5 The metal atoms represented by the formula (I) may be different from one another, but it is preferable that they are all the same metal atom.

[0049] In structural formula (2), R 1 ~R 8 Examples of the alkyl group having 1 to 18 carbon atoms represented by the formula (1) include the same as those for R in formula (1). The alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, with linear being preferred.

[0050] In structural formula (2), R 1 ~R 8 Examples of the alkenyl group having 2 to 18 carbon atoms represented by the formula include the same as R in formula (1). The alkenyl group having 2 to 18 carbon atoms may be either linear or branched, but linear is preferred. The alkenyl group having 2 to 18 carbon atoms is preferably one having a carbon-carbon double bond at the α, β position or at the terminal. The number of carbon atoms in the alkenyl group is preferably 8 or less, more preferably 6 or less, and even more preferably 4 or less. The alkenyl group having 2 to 18 carbon atoms is preferably a vinyl group, an isopropenyl group, a 1-propenyl group, or a 2-propenyl group.

[0051] In structural formula (2), R 1 ~R 8Examples of the alkynyl group having 2 to 18 carbon atoms represented by the formula include the same as R in formula (1). The alkynyl group having 2 to 18 carbon atoms may be either linear or branched, but linear is preferred. The alkynyl group having 2 to 18 carbon atoms is preferably one having a carbon-carbon triple bond at the α, β positions or at the terminal. The number of carbon atoms in the alkynyl group is preferably 8 or less, more preferably 6 or less, and even 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.

[0052] In structural formula (2), R 1 ~R 8 At least one of the R is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms. 1 ~R 8 The number of alkenyl groups having 2 to 18 carbon atoms or alkynyl groups having 2 to 18 carbon atoms in the alkyl group is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, and most preferably 8.

[0053] In structural formula (2), R 1 ~R 8 At least one of the R is preferably an alkenyl group having 2 to 18 carbon atoms and a carbon-carbon double bond at its terminal, or an alkynyl group having 2 to 18 carbon atoms and a carbon-carbon triple bond at its terminal. 1 ~R 8 The number of alkenyl groups having 2 to 18 carbon atoms and having a carbon-carbon double bond at a terminal, or alkynyl groups having 2 to 18 carbon atoms and having a carbon-carbon triple bond at a terminal, is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and most preferably 8.

[0054] In structural formula (2), R 1 ~R 8 may be the same or different, but are preferably all the same.

[0055] The complexes having the structural formula (2) include R 1 ~R8 are all vinyl groups, and the metal atom M 1 ~M 5 Complexes in which R is zinc (zinc acrylate hydroxoclusters), and 1 ~R 8 are all isopropenyl groups, and the metal atom M 1 ~M 5 is a zinc complex (zinc methacrylate hydroxocluster).

[0056] The complex having the structure represented by structural formula (2) obtained by the production method of the present invention preferably has peaks in its powder X-ray diffraction spectrum (XRD) at 2θ=9.0, 9.2, 12.9, and 13.1. EXAMPLES

[0057] The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the following examples, and all modifications and embodiments that do not deviate from the spirit of the present invention are included within the scope of the present invention.

[0058] [Evaluation method] (1) ESI-MS spectrum The ESI-MS spectrum was measured using the following equipment. Equipment: JEOL JMS-T100LP AccuTOF LC-plus

[0059] (2)1H-NMR spectrum 1H-NMR spectra were measured using the following equipment. Equipment: Bruker Ascend 500

[0060] (3) Infrared spectroscopy The infrared spectroscopic analysis was performed by the attenuated total reflection method (ATR method) using diamond as a prism for the attenuated total reflection measurement, using a Fourier transform infrared spectrophotometer (PerkinElmer Co., Ltd., "Measurement device: Spectrum One")

[0061] (4) Powder X-ray diffraction spectrum The powder X-ray diffraction spectrum was measured using a wide-angle X-ray diffractometer (Rigaku Corporation, "RINT-TTR III type"). The measurement sample was pulverized using an agate mortar. The measurement conditions were as follows: X-ray source; CuKα ray Tube voltage-tube current: 50kV-300mA Measurement temperature: room temperature (20℃~30℃) Step width; 0.02deg. Measurement speed; 5deg. / min Slit system; divergence-reception-scattering: 0.5deg.-open-0.5deg. Monochromator; Diffraction curved crystal monochromator

[0062] (5) Single crystal X-ray structure analysis (X-ray diffraction measurement) Equipment: XtaLAB PRO MM007 Data acquisition and processing software: CrysAlisPro Structural analysis program package: CrystalStructure X-ray source: Cu Kα (λ = 1.54184 angstroms) Tube voltage / current: 40 kV-30 mA Measurement temperature: -173℃ (using a spray low-temperature device) Collimator diameter: Φ0.5mm Camera length: 39.25 mm Vibration angle: 0.20°

[0063] The measurement samples were prepared 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 left to stand at 20°C for one month to obtain a single crystal of the complex in the shape of a hexagonal plate with a size of 0.1 mm. A crystal was taken from the sample bottle and poured into Paratone-N (Hampton Research) on a hole slide. The crystal was picked up together with the Paratone-N using a MicroLoopLD 100 mφ (MiTeGen), and was rapidly frozen using a gas flow from a cryogenic device, after which X-ray diffraction measurements were performed. X-ray diffraction data were collected and processed using the software CrysAlisPro and the structure analysis program package CrystalStructure.

[0064] [Production Example] (Manufacturing Example 1) Zinc diacrylate (4.198 g, 20 mmol) was added to a reaction vessel and THF / H2O (volume ratio 100 / 1, 30 mL) and reacted at 25°C for 1 hour. The resulting reaction liquid (white suspension) was centrifuged to separate into a colorless solution and a white precipitate. The separated colorless solution was concentrated under air to about 5 mL, resulting in a precipitate (colorless crystals). The filtrate solution was removed by filtration, and the precipitate was dried to obtain a white solid (yield 1.614 g, 38%).

[0065] The ESI-MS of the white solid obtained in Example 1 is shown in FIG. 1 H-NMR is shown in Figure 2. From these results, it was confirmed that the white solid obtained in Example 1 has the same molecular structure as the complex in JP 2018-104405 A.

[0066] The crystal structure of the complex obtained in Example 1, obtained by single crystal X-ray structure analysis, is shown in Figure 3, and the powder X-ray diffraction spectrum is shown in Figure 4. The complex obtained in Example 1 has powder XRD peaks at 2θ = 9.0, 9.2, 12.9, and 13.1.

[0067] (Manufacturing Example 2) Zinc diacrylate (420g, 2mol) was added to THF / H2O (volume ratio 100 / 1, 3.0L) in a reaction vessel, heated to 40℃ to dissolve the zinc diacrylate, and reacted for 1 hour. Insoluble matter in the resulting reaction solution was removed by filtration. The filtrate was concentrated to about 1 / 10 of its volume to obtain a precipitate. The precipitate was filtered, collected, and dried (yield 298g, 71%).

[0068] The powder X-ray diffraction spectrum of the precipitate obtained in Example 2 is shown in Figure 5, and the FT-IR measurement results are shown in Figure 6. From the FT-IR measurement results, it was confirmed that the precipitate obtained in Example 2 has the same molecular structure as the complex in JP 2018-104405 A.

[0069] In addition, the results of the powder X-ray diffraction spectrum were consistent with the pattern of the complex obtained in Example 1, indicating that the complex obtained in Example 2 had the same crystal structure as the complex obtained in Example 1.

[0070] (Complex of JP 2018-104405 A) The powder X-ray diffraction spectrum of the complex prepared by the manufacturing method of Example 1 of JP 2018-104405 A is shown in Figure 7, and the crystal structure obtained by single crystal X-ray structure analysis is shown in Figure 8. The complex of JP 2018-104405 A has powder XRD peaks at 2θ = 8.8, 9.8, and 10.3.

[0071] When comparing the crystal structure of the complex obtained by the manufacturing method of the present invention (see FIG. 3) with the crystal structure of the complex obtained by the manufacturing method of JP 2018-104405 A (see FIG. 8), it is clear that the two crystal structures are different.

[0072] (Comparative Manufacturing Example 1) Zinc diacrylate (20 g) and 500 mL of ethanol as an organic solvent were added to a reaction vessel, and the mixture was stirred at room temperature for 60 minutes to dissolve. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (17 g). When the concentrate was analyzed, it was found to be a mixture of zinc diacrylate and a complex having a structure represented by structural formula (2). The obtained complex represented by structural formula (2) had powder XRD peaks at 2θ = 8.8, 9.8, and 10.3, which corresponded to the complex in JP 2018-104405 A.

[0073] (Comparative Manufacturing Example 2) Zinc diacrylate (20 g) and 500 mL of isopropyl alcohol as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (3 g). When the concentrate was analyzed, it was found to be a mixture of zinc diacrylate and a complex having a structure represented by structural formula (2). The obtained complex represented by structural formula (2) had powder XRD peaks at 2θ = 8.8, 9.8, and 10.3, and corresponded to the complex in JP 2018-104405 A.

[0074] (Comparative Manufacturing Example 3) Zinc diacrylate (20 g) and 500 mL of acetone as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (5 g). Analysis of the concentrate revealed that it was zinc diacrylate.

[0075] (Comparative Manufacturing Example 4) Zinc diacrylate (20 g) and 500 mL of methyl ethyl ketone as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (1 g). When the concentrate was analyzed, it was found to be zinc diacrylate.

[0076] (Comparative Manufacturing Example 5) Zinc diacrylate (20 g) and 500 mL of propyl acetate as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (2 g). When the concentrate was analyzed, it was found to be a mixture of zinc diacrylate and a complex having a structure represented by structural formula (2). The obtained complex represented by structural formula (2) had powder XRD peaks at 2θ = 8.8, 9.8, and 10.3, corresponding to the complex in JP 2018-104405 A.

[0077] (Comparative Manufacturing Example 6) Zinc diacrylate (20 g) and 500 mL of ethyl acetate as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (2 g). When the concentrate was analyzed, it was found to be zinc diacrylate.

[0078] (Comparative Manufacturing Example 7) Zinc diacrylate (20 g) and 500 mL of methyl propionate as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (3 g). Analysis of the concentrate revealed that it was zinc diacrylate.

[0079] (Comparative Manufacturing Example 8) Zinc diacrylate (20 g) and 500 mL of isopropyl ether as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (1 g). When the concentrate was analyzed, it was found to be a mixture of zinc diacrylate and a complex having a structure represented by structural formula (2). The obtained complex represented by structural formula (2) had powder XRD peaks at 2θ = 8.8, 9.8, and 10.3, corresponding to the complex in JP 2018-104405 A.

[0080] (Comparative Manufacturing Example 9) Zinc diacrylate (20 g) and 500 mL of dioxane as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (3 g). Analysis of the concentrate revealed that the concentrate was zinc diacrylate.

[0081] (Comparative Manufacturing Example 10) Zinc diacrylate (20 g) and 500 mL of acetonitrile as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated to obtain a concentrate (1 g). When the concentrate was analyzed, it was found to be a mixture of zinc diacrylate and a complex having a structure represented by structural formula (2). The obtained complex represented by structural formula (2) had powder XRD peaks at 2θ = 8.8, 9.8, and 10.3, which corresponds to the complex of JP 2018-104405.

[0082] (Comparative Manufacturing Example 11) Zinc diacrylate (20 g) and 500 mL of toluene as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated, but zinc diacrylate was not dissolved in the filtrate and no crystals were precipitated. In addition, 19.3 g of insoluble matter was recovered.

[0083] (Comparative Manufacturing Example 12) Zinc diacrylate (20 g) and 500 mL of cyclohexane as an organic solvent were added to a reaction vessel and dissolved at room temperature. The insoluble matter was filtered to obtain a filtrate. The obtained filtrate was concentrated, but zinc diacrylate was not dissolved in the filtrate and no crystals were precipitated. In addition, 20.2 g of insoluble matter was recovered. [Industrial Applicability]

[0084] The present invention provides a novel and useful method for producing a complex having the structure of structural formula (2). The complex having the structure of structural formula (2) is useful as a co-crosslinking agent that utilizes the reaction of carbon-carbon unsaturated bonds. It is particularly suitable as a co-crosslinking agent for rubber compositions.

[0085] A preferred embodiment (1) of the present invention is a method for producing a complex having a structure represented by structural formula (2), which comprises reacting a compound represented by formula (1) in an organic solvent in the presence of water. [M(RCOO) x ]·yH2O···(1) [In formula (1), M is a metal atom, and R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R's may be the same or different. In structural formula (2), M 1 ~M 5 are the same or different metal atoms, and R 1 ~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. R 1 ~R 8 At least one of the groups 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 2 or more.]

[0086] [ka]

[0087] A preferred embodiment (2) of the present invention is a method for producing the complex of embodiment (1), wherein the compound represented by formula (1) is zinc diacrylate or zinc dimethacrylate.

[0088] A preferred embodiment (3) of the present invention is the method for producing a complex according to embodiment (1) or (2), in which tetrahydrofuran is used as the organic solvent.

[0089] A preferred embodiment (4) of the present invention is the method for producing a complex according to any one of the embodiments (1) to (3), wherein the volume ratio of the organic solvent to water is 1 / 10 to 5000 / 1.

[0090] A preferred embodiment (5) of the present invention is a compound represented by the formula (2): 1 ~M 5 The above is a method for producing a complex according to any one of aspects (1) to (4), in which the metal atom is at least one kind selected from the group consisting of zinc, beryllium, lead, magnesium, nickel, and copper.

[0091] A preferred embodiment (6) of the present invention is a compound represented by the formula (2): 1 ~R 8 represents the same or different alkenyl groups having 2 to 18 carbon atoms or alkynyl groups having 2 to 18 carbon atoms, which is a method for producing a complex according to any one of the embodiments (1) to (5).

[0092] A preferred embodiment (7) of the present invention is a compound represented by the formula (2): 1 ~M 5 is zinc, R 1 ~R 8 The present invention relates to a method for producing a complex according to any one of embodiments (1) to (6), wherein the complex is -CH=CH2 or -C(CH3)=CH2.

Claims

1. A method for producing a complex having a structure represented by structural formula (2), comprising reacting a compound represented by formula (1) in an organic solvent in the presence of water. [M(RCOO) ｘ ]・yH ２ O・・・(1) [In formula (1), M is a metal atom, and R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkenyl group having 2 to 18 carbon atoms, or an alkynyl group having 2 to 18 carbon atoms. x is a number corresponding to the oxidation number of the metal atom M and is an integer of 2 or more. y is an integer of 0 or more. A plurality of R's may be the same or different. In structural formula (2), M 1 ~M ５ are the same or different metal atoms, R 1 ~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. 1 ~R ８ At least one of the groups 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 2 or more.] 【Chemistry 1】

2. 2. The method for producing a complex according to claim 1, wherein the compound represented by formula (1) is zinc diacrylate or zinc dimethacrylate.

3. The method for producing a complex according to claim 1, wherein tetrahydrofuran is used as the organic solvent.

4. 2. The method for producing a complex according to claim 1, wherein a volume ratio of the organic solvent to water is 1 / 10 to 5000 / 1.

5. In structural formula (2), M １ ~M ５ The method for producing a complex according to claim 1, wherein is at least one metal atom selected from the group consisting of zinc, beryllium, lead, magnesium, nickel and copper.

6. In structural formula (2), R １ ~R ８ The method for producing a complex according to claim 1, wherein each of the groups represented by the formula (I) is an alkenyl group having 2 to 18 carbon atoms or an alkynyl group having 2 to 18 carbon atoms, which may be the same or different.

7. In structural formula (2), M １ ~M ５ is zinc, R １ ~R ８ =-CH=CH ２ or -C(CH ３ ) = CH ２ The method for producing the complex according to claim 1,

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