JP6040977B2 - Ether chelate and polyether chelate ferromagnetic organic ferrofluids - Google Patents

Description

    The present invention relates to a novel ferromagnetic organic magnetic fluid. More specifically, the present invention relates to a novel ferromagnetic organic magnetic fluid, a method for producing the same, and an evaluation test for confirming ferromagnetism.

A salt composed of a cation such as imidazolium ion and an anion such as BF ₄ ⁻ is called an ionic liquid and is a relatively low viscosity liquid. This ionic liquid can be used as a reaction solvent in the field of synthetic organic chemistry due to its characteristics, and as an electrolyte for secondary batteries and dye-sensitized solar cells because it is highly conductive, non-volatile, and non-flammable. It is being considered. On the other hand, Hamaguchi et al. Recently reported 1-butyl-3-methylimidazolium tetrachloroferrate as a new ionic liquid (Non-patent Document 1). This ionic liquid has magnetism and is attracted to the magnet. Conventionally known ferrofluids are fluids in which ultrafine particles of ferromagnetic material such as magnetite are dispersed in a liquid. In general, liquids, ferromagnetic ultrafine particles, and ferromagnetic ultrafine particles that serve as a medium are stable. It is a composite material composed of a surfactant for dispersion. Magnetic fluid has a unique property that it is attracted to a magnet while being a liquid, and the characteristics of this property are utilized in various fields. For example, rotary shaft seals, vibration dampers, tilt sensors, angle sensors, and the like are being used, and their fields of use are expanding. However, it is known that the ultrafine particles of the ferromagnetic material dispersed in the magnetic fluid are attracted to the magnet, and therefore segregate based on the magnetic field. In addition, there are problems such as evaporation of the solvent. 1-Butyl-3-methylimidazolium tetrachloroferrate developed by Hamaguchi et al. Is expected to be applied in various fields as a new magnetic fluid that overcomes these problems.

  Japanese Patent Laid-Open No. 2007-131608

  S. Hayashi, H .; Hamaguchi, Chem. Lett. , 33, 1590 (2004)

  Conventional magnetic fluid and 1-butyl-3-methylimidazolium tetrachloroferrate (dark brown) developed by Hamaguchi et al. Cannot transmit light, so it is a transparent magnetic fluid with excellent visible light permeability Is required. Further, 1-butyl-3-methylimidazolium tetrachloroferrate and a colorless and transparent dysprosium derivative (Patent Document 1) excellent in visible light transmittance made of an organic onium cation and a tetrahalogenodisprosate are used in a magnet. Although it has enough magnetism to be attracted, it does not have magnetism to reach the magnet until it is against gravity, and the magnetism still remains small. When considering practicality, it is required to strengthen the magnetism itself.

  As a result of diligent research, the present inventor has completed the present invention shown below.

  In order to achieve such an object, the present invention provides an ether chelate-type ferromagnetic organic magnetic fluid and a polyether chelate-type ferromagnetic organic magnetic fluid represented by the structural formulas [I] and [II] in a high yield with a simple operation. Can be offered at.

In order to achieve the above object, the present invention reacts a magnetic metal salt represented by the following structural formula [X] with an ether represented by the following structural formula [Ia] to form the structural formula [I]. There is an advantage that the ether chelate type ferromagnetic organic magnetic fluid represented by the following formula can be produced simply, efficiently, in large quantities and at low cost. Also, a polyether chelate type ferromagnetic compound represented by the structural formula [II] is prepared by reacting a magnetic metal salt represented by the following structural formula [X] with a polyether represented by the following structural formula [IIa]. There is an advantage that the organic magnetic fluid can be manufactured easily, efficiently, in large quantities, and inexpensively.
Further, in the present invention, when the metal in the magnetic metal salt represented by the structural formula [X] is divalent Fe, divalent Mn, or trivalent Dy, the metal is represented by the structural formulas [I] and [II]. The ferromagnetic organic ferrofluids are all transparent ferrofluids with excellent visible light transmittance and are ferrofluids that reach the magnets even against gravity. When the metal in the magnetic metal salt uses trivalent Fe or divalent Co, the ferromagnetic organic magnetic fluid represented by the structural formulas [I] and [II] is colored, Magnetism is extremely strong, and it is a ferromagnetic ferrofluid that easily reaches the magnet against gravity. Further, when the metal in the magnetic metal salt is trivalent Nd or trivalent Sm, the magnetism is smaller than that when the metal is used, but the organic magnetic fluid represented by the structural formulas [I] and [II] Are all transparent magnetic fluids with excellent visible light transmittance.

In the present invention, various diamagnetic organic compounds are bonded to a metal salt having magnetism through a coordinate bond, and thereby it is possible to exhibit a significantly stronger magnetism than the original metal salt having magnetism.
Compared with conventional ionic magnetic fluids, it can provide much stronger magnetism. That is, the conventional ionic magnetic fluid is attracted to the magnet, but does not have a magnetism strong enough to reach the magnet itself even against gravity. The magnetic strength of the ferromagnetic organic ferrofluid of the present invention is proved by the experimental results of self-attaching to the magnet against gravity. In addition, among the ferromagnetic organic magnetic fluids [I] and [II] of the present invention, those using FeCl ₂ , MnCl ₂ , DyCl ₃ , NdCl ₃ and SmCl ₃ as magnetic metal salts have been more recently required. It is a transparent ferrofluid with high visible light transparency. Since the ferromagnetic organic ferrofluids [I] and [II] of the present invention have more types of metal salts having magnetism than before, the useful ferromagnetic organic ferrofluids are produced according to the purpose. Can do. Moreover, even if it soaks into a base material such as filter paper, it easily attaches to the magnet, so that it can be applied to the base material.
The ether chelate type ferromagnetic organic magnetic fluid [I] and the polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention are widely used in electronic materials, medicine (especially drug delivery systems), pharmaceuticals, and organic synthesis. be able to.

  Evaluation test of magnetism of ether chelate type ferromagnetic organic magnetic fluid [I] and polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention (1)   Evaluation test of magnetism of ether chelate type ferromagnetic organic magnetic fluid [I] and polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention (2)   Evaluation test of magnetism of ether chelate type ferromagnetic organic magnetic fluid [I] and polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention (3)   Evaluation test of magnetism of ether chelate type ferromagnetic organic magnetic fluid [I] and polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention (4)

  The ether chelate type ferromagnetic organic magnetic fluid [I] and the polyether chelate type ferromagnetic organic magnetic fluid [II] according to the present invention will be described.

（式中、Ｒｃ、Ｒｄは炭素原子数が１ないし６のアルキル基を意味し、ＲｃとＲｄが一体となって環状エーテル構造を有しても良い。Ｍは、３価Ｆｅ、２価Ｆｅ、２価Ｃｏ、２価Ｍｎ、３価Ｄｙ、３価Ｎｄ、３価Ｓｍを意味し、Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子を意味し、ｎは、２又は３の整数を意味し、ｎ´は、３又は４の整数を意味する。）で表される。The ether chelate type ferromagnetic organic magnetic fluid [I] has the structural formula [I]:

(In the formula, Rc and Rd represent an alkyl group having 1 to 6 carbon atoms, and Rc and Rd may be integrated to have a cyclic ether structure. M represents trivalent Fe, divalent Fe. Divalent Co, divalent Mn, trivalent Dy, trivalent Nd, and trivalent Sm are meant, X is a halogen atom such as fluorine atom, chlorine atom, bromine atom, and iodine atom, and n is 2 Or an integer of 3 and n ′ means an integer of 3 or 4.

  In the structural formula [I], the alkyl group having 1 to 6 carbon atoms represented by Rc and Rd is a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2-pentyl, 3-pentyl, 3-methyl-2-butyl, 2-methyl-2- Butyl, 2-methyl-1-butyl, 2,2-dimethyl-1-propyl group, n-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 2-methyl-2-pentyl, 2 -Methyl-3-pentyl, 4-methyl-2-pentyl, 4-methyl-1-pentyl, 3-methyl-1-pentyl, 3-methyl-2-pentyl, 3-methyl-3-pentyl 2-ethyl-1-butyl, 2,3-diethyl-1-butyl, 2,3-dimethyl-2-butyl group, 2,2-dimethyl-1-butyl group, 3,3-dimethyl-2-butyl group 3,3-dimethyl-1-butyl group and the like. Moreover, the alkyl group represented by Rc and Rd may have a cyclic ether structure as a unit, and examples thereof include ethylene oxide, oxetane, tetrahydrofuran, and pyran.

（式中、Ｒｉ、Ｒｊ、ＲｋおよびＲｌは水素原子あるいは炭素原子数が１ないし２のアルキル基を意味し、ＲｉとＲｋは一体となって環状構造を有しても良いことを意味するポリエーテルであり、Ｍは３価Ｆｅ、２価Ｆｅ、２価Ｃｏ、２価Ｍｎ、３価Ｄｙ、３価Ｎｄ、３価Ｓｍを意味し、Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子などのハロゲン原子を意味する。ｎは、２又は３の整数を意味し、ｍは、４〜２０の整数を意味する。）で表される。The polyether chelate type ferroorganic magnetic fluid [II] has the structural formula [II]:

(In the formula, Ri, Rj, Rk and Rl represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and Ri and Rk together represent a poly structure which may have a cyclic structure. Ether, M means trivalent Fe, divalent Fe, divalent Co, divalent Mn, trivalent Dy, trivalent Nd, trivalent Sm, X is fluorine atom, chlorine atom, bromine atom, iodine This means a halogen atom such as an atom, n means an integer of 2 or 3, and m means an integer of 4 to 20.

  In the structural formula [II], the alkyl group having 1 or 2 carbon atoms represented by Ri, Rj, Rk and Rl means methyl or ethyl, and Ri and Rk are integrated to form a cyclic structure. Examples thereof include cyclopropane, cyclobutane, cyclopentane, and cyclohexane.

  In the present specification, n represents normal, sec represents secondary, tert represents tertiary, Me represents methyl, Et represents ethyl, Pr represents propyl, Bu represents butyl, and Ph represents a phenyl group.

  Next, production methods of the ether chelate type ferromagnetic organic magnetic fluid [I] and the polyether chelate type ferromagnetic organic magnetic fluid [II] will be described.

（式中、Ｒｃ、Ｒｄ、Ｍ、Ｘ、ｎおよびｎ´は前記と同じ意味を有する）。First, the ether chelate type ferromagnetic organic magnetic fluid [I] can be obtained by the reaction of the ether represented by the structural formula [Ia] and the magnetic metal salt [X] according to the following chemical reaction formula.

(Wherein Rc, Rd, M, X, n and n ′ have the same meaning as described above).

The ether chelate-type ferroorganic fluid represented by the structural formula [I] is an ether represented by the structural formula [Ia] (for example, dimethyl ether, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n- Butyl ether, diisobutyl ether, di n-pentyl ether, diisopentyl ether, di n-hexyl ether, diisohexyl ether, ethyl methyl ether, methyl n-propyl ether, methyl isopropyl ether, n-butyl methyl ether, isobutyl methyl ether Methyl n-pentyl ether, methyl isopentyl ether, n-hexyl methyl ether, isohexyl methyl ether, ethyl n-propyl ether, ethyl isopropyl ether, n-butyl ethyl ether, isobutyl ether Ether, ethyl n-pentyl ether, ethyl isopentyl ether, ethyl n-hexyl ether, ethyl isohexyl ether, n-butyl n-propyl ether, n-butyl isopropyl ether, n-butyl isobutyl ether, n-butyl n-pentyl Ether, n-butyl isopentyl ether, n-butyl n-hexyl ether, n-butyl isohexyl ether, diisobutyl ether, isobutyl n-pentyl ether, isobutyl isopentyl ether, isobutyl n-hexyl ether, isobutyl isohexyl ether, n -Pentyl isopentyl ether, n-pentyl n-hexyl ether, n-pentyl isohexyl ether, diisopentyl ether, isopentyl n-hexyl ether, isopent Ruisohexyl ether, n-hexyl isohexyl ether, diisohexyl ether, ethylene oxide, oxetane, tetrahydrofuran, pyran) and a magnetic metal salt represented by the structural formula [X] (for example, iron (III) chloride, iron chloride ( II), cobalt chloride (II), manganese chloride (II), dysprosium chloride (III), neodymium chloride (III), samarium chloride (III) or iron fluoride (III), iron fluoride (II), fluoride Cobalt (II), manganese fluoride (II), dysprosium fluoride (III), neodymium (III) fluoride, samarium fluoride (III) or iron bromide (III), iron bromide (II), bromide Cobalt (II), manganese (II) bromide, dysprosium (III) bromide, neodymium (III) bromide, Marium (III) or iron (III) iodide, iron (II) iodide, cobalt (II) iodide, manganese (II) iodide, dysprosium (III) iodide, neodymium (III) iodide, iodide It can be produced by the reaction of samarium (III)).
This reaction is usually carried out in a reaction solvent, and as the solvent used, a polar solvent such as water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, acetone or the like can be used, preferably water, Methanol and acetone are preferably used, and water is more preferably used. Moreover, the reaction temperature of this reaction can be performed in the range from -30 ° C to 80 ° C, preferably in the range from -10 ° C to 40 ° C, and more preferably from 0 ° C to 30 ° C. It is good to carry out in the range of ° C.

（式中、Ｒｉ、Ｒｊ、Ｒｋ、Ｒｌ、Ｍ、Ｘ、ｎおよびｍは前記と同じ意味を有する）。Next, the polyether chelate type ferromagnetic organic magnetic fluid [II] is obtained by reacting the polyether represented by the structural formula [IIa] with the magnetic metal salt [X] according to the following chemical reaction formula. Can do.

(Wherein Ri, Rj, Rk, Rl, M, X, n and m have the same meaning as described above).

The polyether chelate type ferroorganic fluid represented by the structural formula [II] is a polyether represented by the structural formula [IIa] (for example, polyethylene glycol, poly 1-methyl ethylene glycol, poly 2-methyl ethylene). Glycol, poly 1,1-dimethylethylene glycol, poly 1,2-dimethyl ethylene glycol, poly 2,2-dimethyl ethylene glycol, poly 1-ethyl ethylene glycol, poly 2-ethyl ethylene glycol, poly 1,1-diethyl ethylene Glycol, poly 1,2-diethyl ethylene glycol, poly 2,2-diethyl ethylene glycol, poly 1,1,2,2-tetramethyl ethylene glycol, poly 1,1,2,2-tetraethyl ethylene glycol, polycyclopropoxy Rate, polycyclobutoxy Rate, polycyclopentoxylate, polycyclohexoxylate) and a magnetic metal salt represented by the general formula [X] (for example, iron (III) chloride, iron (II) chloride, cobalt (II) chloride, manganese chloride ( II), dysprosium chloride (III), neodymium chloride (III), samarium chloride (III) or iron fluoride (III), iron fluoride (II), cobalt fluoride (II), manganese fluoride (II), Dysprosium (III) fluoride, neodymium (III) fluoride, samarium fluoride (III) or iron (III) bromide, iron (II) bromide, cobalt (II) bromide, manganese (II) bromide, Dysprosium (III) bromide, neodymium (III) bromide, samarium (III) bromide, iron (III) iodide, iron (II) iodide, cobalt iodide (II), Manganese (II) iodide (II), dysprosium iodide (III), iodide neodymium (III), can be prepared by the reaction of samarium iodide (III)).
This reaction is usually carried out in a reaction solvent, and as the solvent to be used, a polar solvent such as water, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, acetone or the like can be used, preferably water, Methanol and acetone are preferably used, and water is more preferably used. Moreover, the reaction temperature of this reaction can be performed in the range of -30 ° C to 80 ° C, preferably in the range of -10 ° C to 60 ° C, and more preferably 0 ° C to 40 ° C. It is good to carry out in the range of ° C.

  The present invention will be described in more detail with reference to examples.

Iron chloride (III) tetrahydrofuran complex [Iα], iron chloride (II) tetrahydrofuran complex [Iβ], cobalt chloride (II) tetrahydrofuran complex [Iγ], manganese chloride (II) tetrahydrofuran complex [Iδ], dysprosium chloride (III) tetrahydrofuran Synthesis of complex [Iε], neodymium chloride (III) tetrahydrofuran complex [Iζ] and samarium (III) chloride tetrahydrofuran complex [Iη]

559 mg (2.59 mmol × 3) of tetrahydrofuran was added to 1 ml of an aqueous solution of iron (III) chloride (containing 2.59 mmol of iron (III) chloride in 1 ml of water) or 1 ml of an aqueous solution of dysprosium (III) chloride (dysprosium in 1 ml of water). 1 ml (containing 2.59 mmol of (III)) or 1 ml of aqueous solution of neodymium chloride (III) containing 2.59 mmol of neodymium (III) chloride or 1 ml of aqueous solution of samarium (III) chloride (samarium chloride in 1 ml of water) Each (III) was dissolved in 2.59 mmol), stirred for 5 minutes and allowed to stand.
On the other hand, 746 mg (2.59 mmol × 4) of tetrahydrofuran was added to 1 ml of an aqueous iron (II) chloride solution (containing 2.59 mmol of iron (II) chloride in 1 ml of water) or cobalt (II) chloride (chlorinated in 1 ml of water). Each was dissolved in cobalt (II) (containing 2.59 mmol) or manganese chloride (II) (containing 2.59 mmol of manganese (II) chloride in 1 ml of water), stirred for 5 minutes and allowed to stand.
Next, the magnetization of each solution was confirmed using a neodymium magnet (neodymium magnet was a cylindrical shape [diameter 10 mm, length 20 mm, surface magnetic flux density: 5600 gauss, attractive force (kg) reference value: 4 .4). As a result, it was confirmed that each solution was strongly attracted to the neodymium magnet.
Here, of the two layers, a magnetized layer was separated.
Next, 10 ml of acetone was added to each solution for dilution, and anhydrous magnesium sulfate was added, followed by drying for 30 minutes (moisture removal can be performed by lyophilization). After the anhydrous magnesium sulfate was removed by filtration, the filtrate was distilled off under reduced pressure, and almost quantitatively, iron chloride (III) tetrahydrofuran complex [Iα], iron chloride (II) tetrahydrofuran complex [Iβ], cobalt chloride (II) tetrahydrofuran was obtained. Complex [Iγ], manganese chloride (II) tetrahydrofuran complex [Iδ], dysprosium chloride (III) tetrahydrofuran complex [Iε], neodymium chloride (III) tetrahydrofuran complex [Iζ] and samarium chloride (III) tetrahydrofuran complex [Iη] are obtained. I was able to. The properties of these magnetic fluids are shown below.
Iron (III) chloride tetrahydrofuran complex [Iα]: Brown, extremely low viscosity / Iron chloride (II) tetrahydrofuran complex [Iβ]: Transparent yellow, low viscosity / Cobalt chloride (II) tetrahydrofuran complex [Iγ]: Dark blue, low viscosity / Manganese chloride (II) tetrahydrofuran complex [Iδ]: light pink transparent, low viscosity / dysprosium chloride (III) tetrahydrofuran complex [Iε]: colorless transparent, low viscosity / neodymium chloride (III) tetrahydrofuran complex [Iζ]: light green blue Transparent, low viscosity / samarium (III) chloride complex [Iη]: light yellow transparent, low viscosity

Iron chloride (III) polyethylene glycol complex [IIα], iron chloride (II) polyethylene glycol complex [IIβ], cobalt chloride (II) polyethylene glycol complex [IIγ], manganese chloride (II) polyethylene glycol complex [IIδ], dysprosium chloride Synthesis of (III) polyethylene glycol complex [IIε], neodymium chloride (III) polyethylene glycol complex [IIζ] and samarium chloride (III) polyethylene glycol complex [IIη]

1399 mg of polyethylene glycol (12.28 times of 2.59 mmol in terms of —CH ₂ CH ₂ O-ethyleneoxy group) and 1 ml of an aqueous solution of iron (III) chloride (2. 59 mmol) or 1 ml of iron (II) chloride aqueous solution (containing 2.59 mmol of iron (II) chloride in 1 ml of water) or cobalt chloride (II) (containing 2.59 mmol of cobalt (II) chloride in 1 ml of water) ) Or manganese (II) chloride (containing 2.59 mmol of manganese (II) chloride in 1 ml of water) or 1 ml of aqueous dysprosium (III) chloride (containing 2.59 mmol of dysprosium (III) in 1 ml of water), or 1 ml of neodymium (III) chloride aqueous solution (2.59 mmol of neodymium (III) chloride in 1 ml of water) Each) or 1 ml of an aqueous samarium (III) chloride solution (containing 2.59 mmol of samarium (III) chloride in 1 ml of water), respectively, and stirred for 5 minutes and allowed to stand.
Next, the magnetization of each solution was confirmed using a neodymium magnet (neodymium magnet was a cylindrical shape [diameter 10 mm, length 20 mm, surface magnetic flux density: 5600 gauss, attractive force (kg) reference value: 4 .4). As a result, it was confirmed that each solution was strongly attracted to the neodymium magnet.
Here, of the two layers, a magnetized layer was separated.
Next, 10 ml of acetone was added to each solution for dilution, and anhydrous magnesium sulfate was added, followed by drying for 30 minutes (moisture removal can be performed by lyophilization). After the anhydrous magnesium sulfate was removed by filtration, the filtrate was distilled off under reduced pressure, and almost quantitatively, iron chloride (III) polyethylene glycol complex [IIα], iron chloride (II) polyethylene glycol complex [IIβ], cobalt chloride (II ) Polyethylene glycol complex [IIγ], manganese chloride (II) polyethylene glycol complex [IIδ], dysprosium chloride (III) polyethylene glycol complex [IIε], neodymium chloride (III) polyethylene glycol complex [IIζ] and samarium (III) chloride polyethylene A glycol complex [IIη] could be obtained.
The properties of these magnetic fluids are shown below.
Iron chloride (III) polyethylene glycol complex [IIα]: brown, large viscosity / iron chloride (II) polyethylene glycol complex [IIβ]: light green, large viscosity / cobalt chloride (II) polyethylene glycol complex [IIγ]: reddish purple, Viscosity / Manganese (II) chloride polyethylene glycol complex [IIδ]: light pink, viscosity / dysprosium chloride (III) polyethylene glycol complex [IIε]: Colorless and transparent, viscosity / neodymium chloride (III) polyethylene glycol complex [IIζ] : Light green blue transparent, large viscosity / Samarium chloride (III) polyethylene glycol complex [IIη]: Light yellow transparent, large viscosity

Evaluation test of magnetism of ether chelate type ferromagnetic organic magnetic fluid [I] and polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention (1)
The ether chelate type ferromagnetic organic magnetic fluid [I] and the polyether chelate type ferromagnetic organic magnetic fluid [II] were subjected to the following magnetic strength evaluation test.
1 ml of specimen (magnetic fluid) is put in a glass sample tube (10 ml), and a neodymium magnet (neodymium magnet is cylindrical [diameter 10 mm, length 20 mm, surface magnetic flux density: 5600 gauss, adsorption force (kg) reference value: 4 .4) was applied from the side of the sample tube, and the states of being pulled to the magnet were compared. Samples of iron (III) chloride aqueous solution (iron chloride (III) 2.59 mmol of 1 ml aqueous solution), iron chloride (II) aqueous solution (iron (II) chloride 2.59 mmol of 1 ml aqueous solution), cobalt chloride (II) aqueous solution ( 1 ml of cobalt (II) chloride 2.59 mmol, 1 ml of manganese (II) chloride (1 ml of 2.95 mmol of manganese (II) chloride), dysprosium (III) chloride (2.59 mmol of dysprosium (III) chloride) Aqueous solution), neodymium chloride (III) aqueous solution (1 ml aqueous solution of 2.59 mmol of neodymium chloride (III)), and samarium (III) chloride (1 ml aqueous solution of 2.59 mmol of samarium (III) chloride). went.
The ether chelate type ferromagnetic organic magnetic fluid [I] and the polyether chelate type ferromagnetic organic magnetic fluid [II] were both attracted to the magnet much more strongly than the standard products. III) Complexes, iron chloride (II) complexes, cobalt chloride (II) complexes, manganese chloride (II) complexes, and dysprosium chloride (III) complexes tended to be attracted very strongly to the magnet. In addition, the neodymium chloride (III) complex was attracted less to the magnet than these. Furthermore, the samarium (III) chloride complex was attracted less to the magnet than the neodymium chloride (III) complex. These results are shown in FIG.
The 1-butyl-3-methylimidazolium tetrachloroferrate (2.59 mmol) and 1-butyl-3-methylimidazolium tetrachlorodisprosate (2.59 mmol) already reported are Compared with the aqueous solution of iron (III) chloride (1 ml aqueous solution of 2.59 mmol of iron (III) chloride) and the aqueous solution of dysprosium chloride (III) (1 ml aqueous solution of 2.59 mmol of dysprosium (III) chloride) It was.

Evaluation test of magnetism of ether chelate type ferromagnetic organic magnetic fluid [I] and polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention (2)
1 ml of specimen (magnetic fluid) is put in a glass sample tube (10 ml), and a neodymium magnet (neodymium magnet is cylindrical [diameter 10 mm, length 20 mm, surface magnetic flux density: 5600 gauss, adsorption force (kg) reference value: 4 .4) was applied from the side surface of the sample tube, and fixed in a state inclined by 60 degrees. Here, it was confirmed that it was attracted to the magnet against gravity, and the state of the specimen (magnetic fluid) at that time was summarized in [FIG. 2]. (The experiment was conducted in consideration of the results shown in FIG. 1).
On the other hand, standard iron (III) chloride aqueous solution (iron chloride (III) 2.59 mmol in 1 ml aqueous solution), iron chloride (II) aqueous solution (iron chloride (II) 2.59 mmol in 1 ml aqueous solution), cobalt (II) chloride Aqueous solution (1 ml aqueous solution of cobalt (II) chloride 2.59 mmol), aqueous manganese chloride (II) solution (1 ml aqueous solution of manganese (II) chloride 2.59 mmol), aqueous dysprosium (III) chloride (2.59 mmol dysprosium (III) chloride) 1 ml aqueous solution), neodymium chloride (III) aqueous solution (neodymium (III) chloride 2.59 mmol 1 ml aqueous solution), samarium (III) chloride (samarium (III) 2.59 mmol 1 ml aqueous solution) However, all these specimens are magnets against gravity. They were not attracted.

Evaluation test of magnetism of ether chelate type ferromagnetic organic magnetic fluid [I] and polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention (3)
As shown in the operation outline, put 5 ml of a specimen (magnetic fluid) into a wide-mouth plastic container (20 ml), and add a neodymium magnet (neodymium magnet is cylindrical [diameter 10 mm, length 20 mm, surface magnetic flux density: 5600 gauss, adsorption power (kg ) Reference value: 4.4) was fixed at a position 2 mm from the liquid level, and it was confirmed that the specimen (magnetic fluid) was attracted to the magnet by itself and arrived at the magnet against gravity. At this time, the amount of the specimen (magnetic fluid) attached to the magnet was measured, and the amount was summarized in [FIG. 3]. In order to prevent simple adhesion to the magnet, we made sure that it was not in direct contact with the liquid surface from the beginning. The specimen (magnetic fluid) used in this test was selected in consideration of the results shown in FIG.
In addition, an iron (III) chloride aqueous solution (iron (III) 2.59 mmol / ml aqueous solution 5 ml), an iron (II) chloride aqueous solution (iron (II) 2.59 mmol / ml aqueous solution 5 ml), cobalt chloride ( II) aqueous solution (cobalt (II) chloride 2.59 mmol / ml aqueous solution 5 ml), manganese (II) chloride aqueous solution (manganese (II) 2.59 mmol / ml aqueous solution 5 ml), dysprosium (III) chloride aqueous solution (dysprosium chloride (III) ) 2.59 mmol / ml aqueous solution 5 ml), neodymium chloride (III) aqueous solution (neodymium chloride (III) 2.59 mmol / ml aqueous solution 5 ml), samarium (III) chloride (samarium (III) chloride 2.59 mmol / ml aqueous solution 5 ml) The same experiment was carried out for these samples. Re also, I was not attracted to the magnet against the force of gravity.

Evaluation test of magnetism of ether chelate type ferromagnetic organic magnetic fluid [I] and polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention (4)
Various magnetic fluids were soaked in filter paper (5 mm × 20 mm), excess magnetic fluid was removed, and the samples were left to stand at room temperature for 24 hours to prepare specimens.
For this specimen (filter paper soaked with magnetic fluid), magnetism using a neodymium magnet (cylindrical shape [diameter 10 mm, length 20 mm], surface magnetic flux density: 5600 gauss, adsorption force (kg) reference value: 4.4). An evaluation test was conducted.
As shown in FIG. 4, all the specimens were attracted to the magnet and arrived at the magnet themselves. This fact suggests a new application of the ether chelate and polyether chelate ferroorganic fluids of the present invention. In particular, the magnetic force of the specimen prepared using [Iα] was strong and jumped to the magnet from a distance of 4 mm. In addition, in the case of a sample prepared using [Iδ], the location (position) of the sample was not selected, and the sample was firmly attached to the magnet at the center and at the end. In other cases, the magnet was firmly attached at the center, but at the end, only a part of the magnet was attached to the magnet and sagged down.

  Finally, FT-IR spectra were measured for representative [Iα] and [IIα] in the ferromagnetic organic magnetic fluid of the present invention.

Strong absorption was observed in FT-IR spectral data 2975 cm ⁻¹ (C—H stretching vibration) and 1070 cm ⁻¹ (C—O stretching vibration) of [Iα].
Measuring device: PerkinElmer Spectrum100 FT-IR
Sample preparation: Liquid film method (using KBr plate)
Measurement range: 400 to 4000 cm ⁻¹

[IIα] FT-IR spectrum data 3300-3500 cm ⁻¹ (OH stretching vibration) weak absorption, but 2980 cm ⁻¹ (CH stretching vibration) and 1080 cm ⁻¹ (CO stretching vibration) strong absorption Was observed.
Measuring device: PerkinElmer Spectrum100 FT-IR
Sample preparation: Liquid film method (using KBr plate)
Measurement range: 400 to 4000 cm ⁻¹

Industrial applicability

In the present invention, various diamagnetic organic compounds are bonded to a metal salt having magnetism through a coordinate bond, and thereby it is possible to exhibit a significantly stronger magnetism than the original metal salt having magnetism.
Compared with conventional ionic magnetic fluids, it can provide much stronger magnetism. In other words, the conventional ionic ferrofluid is attracted to the magnet, but it does not have strong magnetism enough to reach the magnet itself against the force of gravity. Can be increased. The ferromagnetic organic magnetic fluid of the present invention has proved its magnetic strength by an experimental result of self-attaching to a magnet against gravity. Further, among the ferromagnetic organic magnetic fluids [I] and [II] of the present invention, those using FeCl ₂ , MnCl ₂ , DyCl ₃ , NdCl ₃ and SmCl ₃ as magnetic metal salts are more highly needed in recent years. It is a transparent ferrofluid that excels in visible light transmission. Since the ferromagnetic organic ferrofluids [I] and [II] of the present invention have more types of metal salts having magnetism than before, the useful ferromagnetic organic ferrofluids are produced according to the purpose. Can do. Moreover, even if it soaks into a base material such as filter paper, it easily attaches to the magnet, so that it can be used for manufacturing various magnetic base materials.
The ether chelate type ferromagnetic organic magnetic fluid [I] and the polyether chelate type ferromagnetic organic magnetic fluid [II] of the present invention are electronic materials, medical (especially drug delivery systems), pharmaceuticals, organic synthesis, functional reagents, etc. Can be widely used.

Claims (3)

Structural formula [I]:

(In the formula, Rc and Rd represent an alkyl group having 1 to 6 carbon atoms, and Rc and Rd may be integrated to have a cyclic ether structure. M represents trivalent Fe, divalent Fe. Divalent Co, divalent Mn, trivalent Dy, trivalent Nd, and trivalent Sm are meant, X is a halogen atom such as fluorine atom, chlorine atom, bromine atom, and iodine atom, and n is 2 Or an integer of 3 and n ′ means an integer of 3 or 4.) An ether chelate-type ferroorganic magnetic fluid characterized by Structural formula [II]:

(In the formula, Ri, Rj, Rk and Rl represent a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and Ri and Rk together represent a poly structure which may have a cyclic structure. Ether, M means trivalent Fe, divalent Fe, divalent Co, divalent Mn, trivalent Dy, trivalent Nd, trivalent Sm, X is fluorine atom, chlorine atom, bromine atom, iodine Means a halogen atom such as an atom, n means an integer of 2 or 3, and m means an integer of 4 to 20.) Magnetic fluid. Magnetic metal salt MXn (M means trivalent Fe, divalent Fe, divalent Co, divalent Mn, trivalent Dy, trivalent Nd, trivalent Sm, X is fluorine atom, chlorine atom, bromine atom, iodine A halogen atom such as an atom, and n represents an integer of 2 or 3.) and an ether or a polyether, respectively, to thereby react the structural formulas [I] and [II] shown in claim 1 and 2. A method for producing a ferromagnetic organic magnetic fluid selected from:

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