JP2006169384A - Substance selectively bondable to boric acid and method for removing or recovering boric acid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently remove or recover boric acid from a boric acid-containing solution. <P>SOLUTION: Boric acid can be removed and recovered from a boric acid-containing solution by passing the solution containing boric acid through a carrier such as a polymer, resin or gelled substance in which siro-inositol is introduced as a functional group, or by bringing the solution containing boric acid into contact with such a carrier batchwise to make boric acid bond selectively to the carrier, and then liberating the bonded boric acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a derivative for immobilization of inositol having boric acid binding ability, and a carrier such as a polymer, a resin, or a gel-like substance, which is produced from the derivative as a raw material and introduced with scyllo-inositol as a functional group. .
The present invention also relates to a method for treating a boric acid-containing solution using the polymer, resin, or gel substance. Moreover, since boron can be combined as boric acid from seawater, the present invention relates to a method for recovering boric acid from seawater.

で表される既知の化合物である。 Scyllo-inositol has the following three-dimensional structural formula (A)

It is a known compound represented by.

Scyllo-inositol is one of myo-inositol's steric heterogeneous substances and is widely found in animals and plants. Further, it is known that scyllo-inositol itself has the ability to bind boric acid to form a scyllo-inositol boric acid complex (see Non-Patent Document 1).
This scyllo-inositol boric acid complex (showing Na salt as an example) is a substance represented by the following three-dimensional structural formula (B).

On the other hand, boron naturally exists as boric acid and is a substance present in seawater in an amount of 4 to 5 ppm in terms of boron. Boric acid is a substance that exhibits biocidal activity at a high concentration (several tens to several hundreds of mM), and the standards for drainage into the environment are severely restricted.
However, in the chemical industry, the plating industry, and the glass and enamel industry, wastewater containing boric acid is generated, so that the treatment of boric acid is a serious issue in these industries.
As an old treatment method, a method of removing it as an insoluble precipitate with slaked lime and aluminum sulfate is known, but there is a problem that the amount of sludge generated increases.

Further, a boric acid selective binding resin has been developed, and a resin having a functional group of N-methylglucamine, a rare metal sintered immobilization support, and the like are used. However, when other anions are mixed, the selectivity of boric acid is lowered, the target capacity cannot be exhibited, the amount of wastewater generated during regeneration is increased, and the adsorption capacity of boric acid is low. There is a problem that the number of processes increases.
“Journal of Organic Chemistry”, USA, Vol. 23, p.329-330 (1958) (full text: NaBH4 reduction of scyllo-inosose and determination of structure of scyllo-inositol borate complex)

Under such circumstances, the present inventors paid attention to the formation of a selective complex of scyllo-inositol and boric acid, and the polymer introduced with scyllo-inositol as a functional group is boric acid. I thought it could be combined. Therefore, an object of the present invention is to provide a carrier such as a polymer having such ability.
Furthermore, an object of the present invention is to establish a method for recovering boric acid from seawater using the carrier.

The present inventors examined the production of a derivative for immobilizing scyllo-inositol, which is necessary for producing a polymer introduced with scyllo-inositol as a functional group, and using scyllo-inosose as a raw material, Protecting the five hydroxyl groups of inosose, introducing a substituent as a linker molecule into the ketone moiety, removing the protecting group, and succeeding in producing the desired derivative for immobilizing scyllo-inositol. And it succeeded in making the derivative | guide_bodies for scyllo-inositol immobilization by polymerizing by a polymerization reaction.
Moreover, it confirmed that the said polymer | macromolecule has a boric-acid binding ability and a release ability with respect to boric-acid containing water, and confirmed that this ability could be exhibited also with respect to seawater.
Thus, the present invention has been completed.

（４）（２）または（３）のシロ−イノシトール誘導体を、担体となる物質に共有結合させるか、あるいは該誘導体を高分子重合用モノマー分子と重合させることによって得られる、シロ−イノシトール基を有する、ホウ酸選択的結合担体。
（５）担体が高分子、樹脂、またはゲル状物質である、（４）のホウ酸選択的結合担体。
（６）（４）または（５）のシロ−イノシトール基を有するホウ酸選択的結合担体に、ホウ酸含有溶液を通過させるか、または、バッチ式で接触させることにより、ホウ酸を選択的に結合させて除去する工程を含む、ホウ酸含有溶液の処理方法。
（７）（４）または（５）のシロ−イノシトール基を有するホウ酸選択的結合担体に、ホウ酸含有溶液を通過させるか、または、バッチ式で接触させることにより、ホウ酸を選択的に結合させ、結合したホウ酸を回収する工程を含む、ホウ酸の回収方法。
（８）ホウ酸含有溶液が海水であることを特徴とする、（７）のホウ酸の回収方法。
（９）（４）または（５）のシロ−イノシトール基を有するホウ酸選択的結合担体に、ホウ酸含有溶液を通過させるか、または、バッチ式で接触させることにより、ホウ酸を選択的に結合させ、結合したホウ酸を回収する工程を含む、ホウ酸の製造方法。 That is, the present invention is as follows.
(1) A polymer, resin, or gel substance in which scyllo-inositol having boric acid binding ability is introduced as a functional group.
(2) A scyllo-inositol derivative in which at least one hydrogen bonded to the carbon skeleton of scyllo-inositol is substituted with a linker molecule for binding scyllo-inositol to a carrier for immobilization.
(3) The scyllo-inositol derivative of (2) represented by the following general formula (I).

(4) A scyllo-inositol group obtained by covalently bonding the scyllo-inositol derivative of (2) or (3) to a substance serving as a carrier or polymerizing the derivative with a monomer molecule for polymer polymerization. A boric acid selective binding carrier.
(5) The boric acid selective binding carrier according to (4), wherein the carrier is a polymer, resin, or gel substance.
(6) A boric acid-selective binding carrier having a scyllo-inositol group of (4) or (5) is passed through a boric acid-containing solution or contacted in a batch mode to selectively react boric acid. A method for treating a boric acid-containing solution, comprising the step of bonding and removing.
(7) A boric acid-selective binding carrier having a scyllo-inositol group of (4) or (5) is passed through a boric acid-containing solution or contacted in a batch mode to selectively react boric acid. A method for recovering boric acid, comprising a step of binding and recovering the bound boric acid.
(8) The boric acid recovery method according to (7), wherein the boric acid-containing solution is seawater.
(9) The boric acid-selective binding carrier having a scyllo-inositol group of (4) or (5) is passed through a boric acid-containing solution or contacted in a batch mode, thereby selectively treating boric acid. A method for producing boric acid, comprising a step of binding and recovering the bound boric acid.

A carrier such as a polymer, a resin, or a gel-like substance into which scyllo-inositol having boric acid binding ability of the present invention is introduced as a functional group has the ability to selectively remove boric acid from a solution containing boric acid. Therefore, it is useful as a new boric acid wastewater treatment substrate.
It can also be used to produce boric acid from seawater, an inexhaustible resource.

Details of the present invention will be described below.
The scyllo-inositol derivative of the present invention is a scyllo-inositol derivative for immobilizing scyllo-inositol on a carrier (also referred to as “derivative for scyllo-inositol immobilization”), preferably on the carbon skeleton of scyllo-inositol. At least one hydrogen bonded is a scyllo-inositol derivative substituted with a linker molecule for binding scyllo-inositol to an immobilization carrier.

  The type of the derivative of the present invention is not particularly limited as long as a linker molecule is introduced into scyllo-inositol, but preferably a linker molecule having an alkenyl or alkynyl group is introduced, and the following general formula ( The scyllo-inositol derivative represented by I) is particularly preferred.

式（I）中、ｎは0〜20の整数を示し、R₁はC₂〜C₁₀アルケニル基、C₂〜C₁₀アルキニル基、あるいは、下記一般式（II）で表されるフェニル基を示し、R₂は水素、トリアルキルシリル基を示す。

In the formula (I), n represents an integer of 0 to 20, and R ₁ represents a C _{2 to} C ₁₀ alkenyl group, a C _{2 to} C ₁₀ alkynyl group, or a phenyl group represented by the following general formula (II). R ₂ represents hydrogen or a trialkylsilyl group.

式（II）中R₃、R₄、R₅は水素、C₁〜C₁₀アルキル基を示し、これらの基が同一または、異なってもよい。R₆は水素、C₁〜C₁₀アルキル基、アルコキシ基を示す。

In the formula (II), R ₃ , R ₄ and R ₅ represent hydrogen and a C _{1 to} C ₁₀ alkyl group, and these groups may be the same or different. R ₆ represents hydrogen, a C ₁ -C ₁₀ alkyl group, or an alkoxy group.

  The scyllo-inositol of the present invention is particularly preferably 1-C-allyl-siro-inositol (formula III), 1-Cp-vinylbenzyl-siro-inositol (formula V), 1-Cp-vinylphenyl. -Scyllo-inositol (formula VI) and the like.

Examples of the method for producing a derivative having such a structure include the following examples using scyllo-inosose as a raw material. In general, when scyllo-inosose is used as a raw material, a scyllo-inosose pentatrialkylsilyl compound synthesized by protecting five hydroxyl groups with a trialkylsilyl group corresponding to R _{2 represented} by the general formula (I) This is used as a raw material, and a linker molecule corresponding to — (CH ₂ ) _n —R ₁ represented by the general formula (I) is coupled by a Grineer reaction, and a trialkyl which is a protective group for a hydroxyl group by an acid. The silyl group can be removed and purified to produce a derivative for immobilizing scyllo-inositol.

  The scyllo-inosose used as a raw material can be scyllo-inosose produced by microbial fermentation from myo-inositol (Japanese Patent Laid-Open No. 2003-102492, etc.), or scyllo-oxidized myo-inositol with platinum oxide. Can be innosauce. For the reaction for the purpose of protecting the hydroxyl group, a dried product of scyllo-inosose is required, but it is preferable that it is dried by a treatment such as spray drying or freeze drying.

  The protection of the hydroxyl group requires 5 molar equivalents or more in order to protect the five hydroxyl groups of scyllo-inosose. For the protection reaction, trialkylsilyl chloride is used, and a reagent having an alkyl moiety of methyl, ethyl, propyl, or isopropyl is preferably used. As the reaction solvent, tertiary amine or pyridine may be added in an amount of 5 molar equivalents or more, and ethyl acetate or THF can be added as an additional solvent. The reaction temperature is 50 to 80 ° C., preferably 70 ° C., and the reaction time is 1 to 5 hours, preferably 2 hours. Stirring is necessary because the initial scyllo-inosose does not dissolve. For purification, after adding a small amount of water to stop the reaction, a nonpolar solvent such as hexane or toluene is added to precipitate the resulting pyridine hydrochloride, which is filtered, and the organic solvent in the filtrate is water or sodium bicarbonate water. To remove salt and pyridine. After the organic solvent layer is dehydrated with anhydrous sodium sulfate or the like, the solvent is distilled off and concentrated to isolate a scyllo-inosose pentatrialkylsilyl compound in which the hydroxyl group is protected. A method for producing a substance having an alkyl alkyl group (syllo-inosose pentatrimethylsilyl: Resistry No. 676655-71-3) is also described in Japanese Patent Application Laid-Open No. 2004-107287 (manufacturing method of scyllo-inositol). A manufacturing method similar to that described above is shown.

Next, the scyllo-inosose pentatrialkylsilyl compound is dissolved in dehydrated THF and, under stirring, the linker molecule corresponding to — (CH ₂ ) _n —R _{1 represented} by the general formula (I) 1 mole equivalent or more of the reagent is added dropwise. Examples of Grignard reagents, the alkenyl magnesium chloride, alkynyl magnesium chloride or,, C ₂ -C ₁₀ alkenyl or C ₂ -C ₁₀ phenyl magnesium chloride substituted with an alkynyl group, an alkenyl magnesium bromide, alkynyl magnesium bromide, Alternatively, C ₂ -C ₁₀ alkenyl or C ₂ -C ₁₀ phenyl magnesium bromide was substituted with an alkynyl group, and more specifically, vinyl magnesium chloride, vinyl magnesium bromide, allyl magnesium chloride, allyl magnesium bromide, p- Vinylbenzylmagnesium chloride, p-vinylbenzylmagnesium bromide, p-vinylphenylmagnesium chloride, p-vinylphenylmagnesium bromide De is illustrated. The reaction temperature is −5 to 40 ° C., preferably 20 ° C., and the reaction time is 30 minutes to 5 hours, preferably 1 hour. Stirring is necessary to make the reaction solution uniform.

For purification, after adding a small amount of water to stop the reaction, add a nonpolar solvent such as hexane or toluene to precipitate the produced magnesium halide salt, filter this, and wash the organic solvent in the filtrate with water. The remaining salt is removed. It can also be concentrated at this stage and isolated with a protecting group, and is used in organic solvent-based polymerization reactions. When used for a water-based or polar solvent-based polymerization reaction, 5 moles of a small amount of acid and water or a lower alcohol such as methanol or ethanol are added to the scyllo-inosose pentatrialkylsilyl compound in the organic solvent layer. When an equivalent amount or more is added and stirred, the protecting group is removed and the derivative for fixing scyllo-inositol begins to precipitate.
The reaction temperature of the deprotecting group is −5 to 40 ° C., preferably 20 ° C., and the reaction time is 30 minutes to 5 hours, preferably 1 hour. Stirring is necessary to make the reaction solution uniform. In the purification, the precipitated substance is filtered and dried, and then a derivative powder for fixing scyllo-inositol can be obtained.

By introducing the derivative for immobilizing scyllo-inositol of the present invention into a carrier such as a polymer, a resin or a gel substance, a carrier that selectively binds boric acid (boric acid selective binding carrier) can be obtained. it can.
Hereinafter, a method for obtaining a boric acid selective binding carrier by covalently bonding a derivative for scyllo-inositol immobilization to a substance serving as a carrier or polymerizing with a monomer molecule for polymer polymerization will be described.
The substance to be a carrier is not particularly limited as long as a functional group capable of covalently bonding a derivative for immobilization of scyllo-inositol is introduced onto the surface of a carrier that has already been shaped, for example, polystyrene, silica gel, or silicon. Examples of the functional group to which the derivative for immobilizing scyllo-inositol can be covalently bonded include an amino group, a glycidyl group, and a carbonyl group.

  Copolymerization monomer molecules for copolymerization with scyllo-inositol immobilization derivatives include ethylene, propylene, acrylamide, styrene, methacrylamide, acrylic acid, methacrylic acid, acrylonitrile, terephthalic acid, propylene oxide , Phenylenediamine, formaldehyde and the like. Copolymerization monomer molecules for polymerization can be incorporated into the polymer by coexisting a derivative for immobilizing scyllo-inositol under the polymerization conditions of the monomer molecule alone or as a mixture. polymerization). If necessary, a crosslinking agent such as N, N-methylene-bisacrylamide, divinylbenzene or the like can be added to the polymer by adding it. As a combination in this case, it is preferable to react the silo-inositol-immobilized derivative with a protecting group with an organic solvent-based monomer molecule and the scyllo-inositol-immobilized derivative with the protecting group removed with an aqueous monomer molecule. . As the polymerization reaction, an existing polymerization reaction such as radical polymerization or cationic polymerization can be used, but radical polymerization is preferable. The polymerization initiators and polymerization accelerators used at that time are AIBN (2,2'-azobis (2,4-dimethylvaleronitrile)), TEMED (N, N, N ', N'-tetramethylethylenediamine) Or persulfate. Furthermore, the solvent is only required to dissolve the above solute, and examples include water, alcohols, glycols, esters such as acetonitrile and ethyl acetate, ethers such as THF, and nonpolar organic solvents such as toluene and hexane. . Further, when all the solutes are mixed, a solvent is not required as long as a uniform liquid state is obtained without a solvent.

In addition, after the polymerization reaction with the scyllo-inositol-immobilized derivative with a protecting group, the protecting group can be removed by washing with a small amount of an acid catalyst in water or a lower alcohol such as methanol or ethanol. . In addition, during polymerization, oil in water or water in
By selecting an oil suspension polymerization reaction system, shaping of a polymer, resin, or gel-like substance can be performed.

  By using the boric acid selective binding polymer, the boric acid selective binding resin, or the boric acid selective binding gel material thus prepared, boric acid containing solution, preferably boric acid containing water boric acid. Removal treatment or boric acid recovery can be performed. Such a boric acid-containing solution treatment method and boric acid recovery method can be performed as shown in the following figures.

First, the boric acid bonding principle will be described. In the normal state of the immobilized scyllo-inositol group, all six hydroxyl groups are coordinated in the equatorial direction. When a solution containing boric acid adjusted to pH 5.5 or more, preferably pH 8 to 10, with hydroxylated light metal such as NaOH or KOH is allowed to act on this, six hydroxyl groups are coordinated in the axial direction. And binds to two molecules of boric acid. The combined scyllo-inositol group becomes a divalent anion derived from boric acid, has a strong acidity, and can bind a cation. Further, this reaction is an endothermic reaction, and it is better that the temperature at the time of boric acid bonding is high. Furthermore, it becomes easier to bind by including a counter cation such as Na ⁺ . The counter cation source used at that time is preferably NaCl, KCl, MgCl ₂ , CaCl ₂ or the like, but is not particularly limited to a combination of salts containing these metal ions. The concentration is 0.01 to 2000 mM, preferably 10 to 600 mM.

  Next, the release principle will be described. Liberation releases boric acid quickly by acidifying the pH of the solution with an acid. The acid used is preferably a mineral acid such as hydrochloric acid or sulfuric acid. At this time, the six hydroxyl groups (coordinated in the axial direction) bonded to two molecules of boric acid are coordinated in the equatorial direction.

From the above, it is necessary to adjust at least pH 5.5 or more, preferably pH 8 to 10, as pretreatment of boric acid-containing water.
There are two types of methods for binding and releasing boric acid from the boric acid-containing water prepared as described above using the polymer, resin, or gel-like substance.

  The batch method is a method in which boric acid-containing water and the polymer, resin, or gel substance are mixed, heated if necessary, boric acid is combined, and water from which boric acid has been removed is obtained by filtration. is there. Furthermore, the method of releasing is by mixing the polymer, resin, or gel substance bound with boric acid obtained by filtration with an acidic solution, releasing and dissolving boric acid in the solution, and filtering. Made. Thereby, the polymer, resin, or gel-like substance from which boric acid is liberated can be obtained. This method is effective for treating high-concentration boric acid because the addition of alkali is easy to adjust in order to prevent the pH of the solution at the time of binding from increasing with acidity.

  The column method is a method of obtaining water from which boric acid eluted by passage is removed by passing heated boric acid-containing water, if necessary, into the polymer, resin, or gel substance. Further, the liberation method is performed by passing an acidic solution through a column packed with the polymer, resin, or gel substance to which boric acid is bound, releasing boric acid into the solution, and elution through the column. . Thereby, the polymer, resin, or gel particles from which boric acid is liberated can be obtained. This method is effective for treating low-concentration boric acid having a low pH change at the time of binding because it is only a method for allowing the solution to pass.

Further, when seawater is used as a solution containing boric acid, boric acid can be produced from seawater using the polymer, resin, or gel substance. The boric acid concentration in seawater
0.4-0.5 mM, pH 7.5-8.5, NaCl concentration is about 580 mM, satisfying the conditions for boric acid-containing water described above, and can be used as boric acid-containing water without pretreatment. There are two types of methods for binding and releasing boric acid from seawater using the polymer, resin, or gel-like substance, the batch method and the column method described above, and both methods are effective for recovering boric acid. However, the column type is superior in resin regeneration and handling.

  The seawater from which the fine particles have been removed is heated to 20 to 120 ° C., preferably 50 to 70 ° C., and this is passed through a column of the same temperature packed with the polymer, resin, or gel substance, and boric acid is added. Combine. After the binding, boric acid is eluted by passing it through an acidic solution, preferably an aqueous hydrochloric acid or mineral acid such as sulfuric acid. The eluate can be concentrated and boric acid can be isolated in crystalline form.

[Example]
Hereinafter, the present invention will be specifically described with reference to examples.

Method for producing 1-C-allyl-syllo-inositol, a derivative for immobilization of scyllo-inositol. 20 g (0.112 mol) of scyllo-inosose dried by spray drying is placed in a 1000 ml three-necked flask, 63 ml of pyridine, acetic acid A mixed solvent consisting of 70 ml of ethyl was added, stirred and suspended, and heated to 70 ° C. To this solution, 86 ml of trimethylsilyl chloride was added dropwise. After completion of dropping, the mixture was allowed to react at 70 ° C. for 2 hours with stirring. After completion of the reaction, 300 ml of hexane was added and stirred, and the precipitated salt was filtered. The filtrate was put into a separatory funnel, and the hexane layer was washed with 200 ml of 5% sodium bicarbonate water and then with 200 ml of water. The hexane layer was taken out, dehydrated by adding anhydrous sodium sulfate, and concentrated to obtain 55.0 g (0.102 mol) of crude scyllo-inosose pentatrimethylsilyl (yield 91%).

30 g (55.5 mmol) of the crude scyllo-inosose pentatrimethylsilyl thus obtained was placed in a 1000 ml three-necked flask and dissolved by adding 180 ml of dehydrated THF. To this solution, 57 ml of 2M allylmagnesium chloride / THF solution was added dropwise. After completion of the dropwise addition, the mixture was reacted at room temperature with stirring for 2 hours. After completion of the reaction, 12 ml of water was added dropwise to decompose excess allylmagnesium chloride. After the reaction solution was concentrated, 300 ml of hexane was added and stirred, and the precipitated salt was filtered. The filtrate was put into a separatory funnel, and the hexane layer was washed with 100 ml of 5% sodium bicarbonate water and then with 100 ml of water. The hexane layer is taken out, placed in a 1000 ml eggplant flask, 1 ml of concentrated hydrochloric acid and 15 ml of methanol are added, and the mixture is stirred at room temperature to obtain white 1-C-allyl-siro-inositol and 2-C-allyl-myo-inositol. A mixture precipitated. This suspension was filtered, and the solid was washed with ethanol and dried to obtain 10.2 g (46.4 mmol) of a mixture of 1-C-allyl-siro-inositol and 2-C-allyl-myo-inositol ( (Yield 83% based on scyllo-inosose pentatrimethylsilyl).
From the HPLC analysis, it was found that the mixing ratio of the obtained 1-C-allyl-siro-inositol and 2-C-allyl-myo-inositol was 52:48.
HPLC analysis conditions were as follows: column: Wakosil NH2 column φ4.6 × 250 mm, column temperature: 20 ° C., moving bed: 80% acetonitrile, flow rate: 2 ml / min, detection: RI detector. Under these conditions, 2-C-allyl-myo-inositol is detected at 10.2 min and 1-C-allyl-siro-inositol is detected at 10.6 min.

  Next, 9 g (40.9 mmol) of the mixture was placed in a 300 ml eggplant flask, dissolved by adding 100 ml of water, and 5.6 g (90.3 mmol) of boric acid was dissolved in 5N NaOH while adjusting to pH 9.5. . This solution was heated at 70 ° C. for 30 minutes, cooled to room temperature, and then passed through a strongly basic ion exchange resin 200 ml column. This passing liquid contains 2-C-allyl-myo-inositol. Next, 250 ml of 1N hydrochloric acid solution was passed through the column to elute the 1-C-allyl-siro-inositol boric acid complex. The elution solution was concentrated, methanol was added to the concentrate, and the mixture was further concentrated three times to remove acidic and free boric acid by azeotropy with methanol. Finally, 100 ml of water was added to the concentrate to dissolve it, and this solution was passed through a strongly acidic ion exchange resin 200 ml column and a strongly basic ion exchange resin 400 ml column to remove NaCl. The passing liquid was concentrated to 20 ml, and 100 ml of ethanol was added thereto to crystallize 1-C-allyl-siro-inositol. The obtained 1-C-allyl-siro-inositol was 4.01 g (18.2 mmol) (yield 37% from scyllo-inosose pentatrimethylsilyl). Similarly, 2-C-allyl-myo-inositol is passed through a strongly acidic ion exchange resin column and a strongly basic ion exchange resin column to remove boric acid and sodium ions, and then concentrated and crystallized from ethanol. Then, 4.2 g (19.1 mmol) of 2-C-allyl-myo-inositol was obtained (39% yield based on scyllo-inosose pentatrimethylsilyl).

1-C-allyl-siro-inositol (formula III)
Appearance: White powder Solubility: Soluble in water Molecular weight: EI-MS m / z 220 (M ⁺ )
¹ H-NMR (D ₂ O): δ 5.99 ppm (1H), 5.01 ppm (2H), 3.37 ppm (2H), 3.31 ppm (2H), 3.22 ppm (1H), 2.29 ppm (2H)

2-C-allyl-myo-inositol (formula IV)
Appearance: White powder Solubility: Soluble in water Molecular weight: EI-MS m / z 220 (M ⁺ )
¹ H-NMR (D ₂ O): δ 5.69 ppm (1H), 5.09 ppm (2H), 3.43 ppm (2H), 3.18 ppm (2H), 3.07 ppm (1H), 2.39 ppm (2H)

Method for producing boric acid selective binding gel particles using 1-C-allyl-siro-inositol In a plastic container, 1-C-allyl-siro-inositol 4 g (18.2 mmol), acrylamide 4 g (56.3 mmol), N , N-methylene-bisacrylamide 240 mg (1.6 mmol) and ammonium persulfate 400 mg were dissolved in water, and a solution prepared to a solution volume of 18 ml was added to TEMED (N, N,
When 40 μl of (N ′, N′-tetramethylethylenediamine) was added and mixed quickly, heat was generated immediately and polymerized into a gel. This gel-like substance was taken out and extruded on a 0.5 mm stainless mesh to obtain gel particles of about 0.2 to 0.5 mm. The gel particles were washed with water and dialyzed to prepare gel particles introduced with scyllo-inositol as a functional group.
From the HPLC analysis, 1-C-allyl-siro-inositol contained in the washing and dialysis solution is 2.72 g. Therefore, 1.28 g of 1-C-allyl-siro-inositol is contained in 18 ml of the gel particles. I found out that it was taken in. HPLC conditions are the same as in Example 1.

Method for producing 1-Cp-vinylbenzyl-siro-inositol which is a derivative for immobilizing scyllo-inositol 1000 ml of crude scyllo-inosose pentatrimethylsilyl 30 g (55.5 mmol) obtained in the same manner as in Example 1 The solution was placed in a three-necked flask and dissolved by adding 180 ml of dehydrated THF. To this solution, 62 ml of 1.3 M p-vinylbenzylmagnesium chloride / diethyl ether solution was added dropwise. After completion of the dropwise addition, the mixture was reacted at room temperature with stirring for 2 hours. After completion of the reaction, 12 ml of water was added dropwise to decompose excess p-vinylbenzylmagnesium chloride. After the reaction solution was concentrated, 300 ml of hexane was added and stirred, and the precipitated salt was filtered. The filtrate was put into a separatory funnel, and the hexane layer was washed with 100 ml of 5% sodium bicarbonate water and then with 100 ml of water. The hexane layer was taken out, dehydrated by adding anhydrous sodium sulfate, concentrated, and 39.0 g of a liquid 1-Cp-vinylbenzyl-siro-inositol pentatrimethylsilyl crude product was obtained.
The obtained 1-C-p-vinylbenzyl-siro-inositol pentatrimethylsilyl crude product was obtained as 1-Cp-vinylbenzyl-siro-inositol pentatrimethylsilyl, 2-Cp-vinylbenzyl- It is considered that a myo-inositol pentatrimethylsilyl product is produced, but as a result of NMR analysis, a 1-Cp-vinylbenzyl-siro-inositol pentatrimethylsilyl product was produced stereoselectively.
Dissolve 39.0 g of liquid 1-C-p-vinylbenzyl-siro-inositol pentatrimethylsilyl crude product in 300 ml of hexane, place in a 1000 ml eggplant flask, add 1 ml of concentrated hydrochloric acid and 15 ml of ethanol, and stir at room temperature. Then, white 1-Cp-vinylbenzyl-siro-inositol was precipitated. The suspension was filtered, and the solid was washed with a mixed solution of ethanol and hexane (1: 1) and dried to obtain 13.1 g (44.2 mmol) of 1-Cp-vinylbenzyl-siro-inositol (white). -Yield 79.4% from inosource pentatrimethylsilyl).

1-Cp-vinylbenzyl-siro-inositol (formula V)
Appearance: White powder Solubility: Insoluble in water, soluble in DMSO, ethylene glycol Molecular weight: EI-MS m / z 296 (M ⁺ )
¹ H-NMR (D ₂ O): δ 7.29 ppm (4H), 6.64 ppm (1H), 5.70 ppm (1H), 5.15 ppm (1H), 3.44 ppm (2H), 3.30 ppm (2H), 3.22 ppm ( 1H), 2.94ppm (2H)

Method for producing boric acid selective binding gel particles using 1-Cp-vinylbenzyl-siro-inositol In a plastic container, 5.4 g (18.2 mmol) of 1-Cp-vinylbenzyl-siro-inositol, acrylamide Ethylene glycol was added to 4 g (56.3 mmol), N, N-methylene-bisacrylamide 240 mg (1.6 mmol) so that the liquid volume was 16 ml, and dissolved at 50 ° C., and AIBN ( 2 ml of ethylene glycol in which 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved was mixed, and immediately the solution was heated to 90 ° C. to polymerize into a gel. This gel-like substance was taken out and extruded on a 0.5 mm stainless mesh to obtain gel particles of about 0.2 to 0.5 mm. The gel particles were washed with water and dialyzed to prepare gel particles introduced with scyllo-inositol as a functional group.
From the results of TLC analysis of the washing solution, 1-Cp-vinylbenzyl-siro-inositol contained in the washing solution was quantitatively determined in 1 ml of gel particles. I found out that it was taken in.
TLC analysis was performed using a silica gel TLC plate (containing a fluorescent agent), developed with a developing solvent of chloroform: methanol: water = 5: 5: 1, dried, and then irradiated with ultraviolet light (254 nm), and the spot size with an Rf value of 0.72 Compared.

Method for producing 1-C-p-vinylphenyl-siro-inositol, a derivative for immobilizing scyllo-inositol 1000 ml of crude scyllo-inosose pentatrimethylsilyl compound 30 g (55.5 mmol) obtained in the same manner as in Example 1 The solution was placed in a three-necked flask and dissolved by adding 180 ml of dehydrated THF. To this solution, 48 ml of a 1.5 M mixed solution of p-vinylphenylmagnesium chloride / THF / toluene (1: 1) was added dropwise. After completion of the dropwise addition, the mixture was reacted at room temperature with stirring for 2 hours. After completion of the reaction, 12 ml of water was added dropwise to decompose excess p-vinylphenylmagnesium chloride. After the reaction solution was concentrated, 300 ml of hexane was added and stirred, and the precipitated salt was filtered. The filtrate was put into a separatory funnel, and the hexane layer was washed with 100 ml of 5% sodium bicarbonate water and then with 100 ml of water. The hexane layer was taken out, anhydrous sodium sulfate was added for dehydration, and after concentration, 37.5 g of a liquid 1-Cp-vinylphenyl-siro-inositol pentatrimethylsilyl crude product was obtained.
The obtained crude product of 1-Cp-vinylphenyl-siro-inositol pentatrimethylsilyl was obtained as 1-Cp-vinylphenyl-siro-inositol pentatrimethylsilyl, 2-Cp-vinylphenyl- It is considered that a myo-inositol pentatrimethylsilyl product is produced. As a result of NMR analysis, a 1-Cp-vinylphenyl-siro-inositol pentatrimethylsilyl product was produced stereoselectively.
37.5 g of liquid 1-C-p-vinylphenyl-siro-inositol pentatrimethylsilyl crude product is dissolved in 300 ml of hexane, placed in a 1000 ml eggplant flask, 1 ml of concentrated hydrochloric acid and 15 ml of ethanol are added, and the mixture is stirred at room temperature. Then, white 1-Cp-vinylphenyl-siro-inositol precipitated. The suspension was filtered, and the solid was washed with a mixed solution of ethanol and hexane (1: 1) and then dried to obtain 12.5 g (44.3 mmol) of 1-Cp-vinylphenyl-siro-inositol (white). -Yield 79.5% from inosource pentatrimethylsilyl).

1-Cp-vinylphenyl-siro-inositol (formula VI)
Appearance: White powder Solubility: Insoluble in water, soluble in DMSO, DMF, ethylene glycol Molecular weight: EI-MS m / z 282 (M ⁺ )
¹ H-NMR (D ₂ O): δ 7.39 ppm (4H), 6.67 ppm (1H), 5.75 ppm (1H), 5.20 ppm (1H), 3.67 ppm (2H), 3.58 ppm (2H), 3.37 ppm ( 1H)

Method for producing boric acid selective binding gel particles using 1-Cp-vinylphenyl-siro-inositol In a plastic container, 1-Cp-vinylphenyl-siro-inositol 5.1 g (18.2 mmol), acrylamide Ethylene glycol was added to 4 g (56.3 mmol) and N, N-methylene-bisacrylamide 240 mg (1.6 mmol) to a liquid volume of 16 ml and dissolved at 50 ° C., and AIBN ( 2 ml of ethylene glycol in which 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved was mixed, and immediately the solution was heated to 90 ° C. to polymerize into a gel. This gel-like substance was taken out and extruded on a 0.5 mm stainless mesh to obtain gel particles of about 0.2 to 0.5 mm. The gel particles were washed with water and dialyzed to prepare gel particles introduced with scyllo-inositol as a functional group.
1-C-p-vinylphenyl-siro-inositol contained in the washing solution is quantitatively incorporated into 18 ml of gel particles from the results of TLC analysis. I found out.
TLC analysis uses silica gel TLC plates (with fluorescent agent), developed with a developing solvent of chloroform: methanol: water = 5: 5: 1, dried, and then irradiated with ultraviolet light (254 nm), and the spot size with an Rf value of 0.66 Compared.

Binding and liberation of boric acid by gel particles introduced with scyllo-inositol as a functional group Binding of boric acid using the gel particles prepared in Example 2, Example 4 and Example 6 was performed as follows. It was.
Three types of gel particles introduced with a functional group of scyllo-inositol (gel particles produced using 1-C-allyl-siro-inositol are called “SI-Al gel”, 1-Cp-vinylbenzyl-shiro -Gel particles produced using inositol are abbreviated as "SI-Bl gel", and gel particles produced using 1-Cp-vinylphenyl-siro-inositol are abbreviated as "SI-Pl gel". It put into a 100 ml beaker so that it might contain 5.8 mmol in inositol conversion. The bulk of each gel particle was 37 ml for SI-Al gel particles, 13 ml for SI-Bl gel particles, and 33 ml for SI-Pl gel particles.
These beakers were then charged with 50 ml of boric acid-containing water. This “boric acid-containing water” has a composition of boric acid 200 mM (containing 10 mmol boric acid), NaCl 300 mM, pH 9.5 (adjusted with 5 N NaOH). This solution was stirred while slowly warming with a mechanical stirrer and bound at 70 ° C. for 2 hours. Thereafter, the temperature was returned to room temperature, filtration was performed, the filtrate was adjusted to pH 9.5 with 5N NaOH, and this solution was designated as “treated water”. The remaining gel particles were each washed with water. After washing, each gel particle was placed in a beaker, and 50 ml boric acid eluent (0.2 N hydrochloric acid) was added thereto. The solution was slowly stirred at room temperature with a mechanical stirrer and released for 30 min. Thereafter, filtration was performed, and a solution obtained by adjusting the filtrate to pH 9.5 with 5N NaOH was designated as “boric acid recovery water”.

The boric acid concentration of the solution thus prepared was quantified by the azomethine H absorbance measurement method, which is a JIS standard boron measurement method.
The results are shown in Table 1.

結果として、供試したゲル粒子のいずれもが、ホウ酸を結合し、検出限界である0.01mM（ホウ素として0.11ppm）までホウ酸濃度を低下させることができることが判る。また、酸によりホウ酸を遊離することが可能であることが判る。

As a result, it can be seen that any of the gel particles tested can bind boric acid and reduce the boric acid concentration to the detection limit of 0.01 mM (0.11 ppm as boron). It can also be seen that boric acid can be liberated by acid.

Recovery of boric acid from seawater by gel particles introduced with scyllo-inositol as a functional group 92 ml of gel particles produced using 1-Cp-vinylphenyl-siro-inositol in the same manner as in Example 6 16 mmol in terms of scyllo-inositol (abbreviated as “SI-Pl gel”) is placed in a column of 4 cm in diameter and 25 cm in length, and 50 L of seawater passed through a 0.45 μm filter is added to a column temperature of 70 ° C. And passed at a flow rate of 0.5 ml / min. The “seawater” used had a composition of boric acid 0.42 mM (containing 21 mmol boric acid), NaCl 475 mM, pH 8.7. After 70 hours, the passed solution was cooled to room temperature to obtain “treated water”. Next, the gel particles in the column were washed with 300 ml of water (room temperature, 0.5 ml / min). After washing, 100 ml boric acid eluent (0.2 N sulfuric acid) was passed through the gel particles in the column (room temperature, 0.5 ml / min). Thereafter, a part of the passed solution was taken, and a solution adjusted to pH 8.7 with 5N NaOH was designated as “boric acid recovery water”.

The boric acid concentration of the solution thus prepared was quantified by the azomethine H absorbance measurement method, which is a JIS standard boron measurement method.
The results are shown in Table 2.

結果としてゲル粒子が、ホウ酸を結合し、酸によりホウ酸を遊離していることが判る。
次に、ホウ酸を回収した水溶液を15mlまで濃縮し、20℃に置くと、ホウ酸が析出した。析出したホウ酸をろ過し、乾燥後、781mgのホウ酸を得た。このように、海水50Lから781mgのホウ酸を得ることができることが判った。

As a result, it can be seen that the gel particles bind boric acid and release boric acid by the acid.
Next, the aqueous solution from which boric acid was recovered was concentrated to 15 ml and placed at 20 ° C., whereby boric acid was precipitated. The precipitated boric acid was filtered and dried to obtain 781 mg of boric acid. Thus, it was found that 781 mg of boric acid can be obtained from 50 L of seawater.

Claims (9)

A polymer, resin, or gel substance into which scyllo-inositol having boric acid binding ability is introduced as a functional group. A scyllo-inositol derivative in which at least one hydrogen bonded to the carbon skeleton of scyllo-inositol is substituted with a linker molecule for binding scyllo-inositol to an immobilization support. The scyllo-inositol derivative according to claim 2, represented by the following general formula (I):

Selection of boric acid having a scyllo-inositol group obtained by covalently binding the scyllo-inositol derivative according to claim 2 or 3 to a substance serving as a carrier or polymerizing the derivative with a monomer molecule for polymer polymerization Binding carrier. The boric acid selective binding carrier according to claim 4, wherein the carrier is a polymer, a resin, or a gel substance. 6. A boric acid-selective binding carrier having a scyllo-inositol group according to claim 4 or 5 is passed through a boric acid-containing solution or contacted in a batch system to selectively bind boric acid and remove it. The processing method of a boric acid containing solution including the process to carry out. A boric acid-selective binding carrier having scyllo-inositol groups according to claim 4 or 5, wherein boric acid is selectively bound and bound by passing a boric acid-containing solution or contacting in a batch system. A method for recovering boric acid, comprising a step of recovering the boric acid. The method for recovering boric acid according to claim 7, wherein the boric acid-containing solution is seawater. A boric acid-selective binding carrier having scyllo-inositol groups according to claim 4 or 5, wherein boric acid is selectively bound and bound by passing a boric acid-containing solution or contacting in a batch system. The manufacturing method of boric acid including the process of collect | recovering the performed boric acid.