JP4660793B2 - Adsorbing material carrying extraction reagent and method for producing the same - Google Patents

Description

The present invention relates to an adsorption material carrying an extraction reagent for separating and purifying metal ions, and a method for producing the same.

In order to quantify fission products, activation products, and actinide elements contained in environmental samples and radioactive waste, it is necessary to separate and purify metal ions as a pretreatment for measurement. Until now, separation and purification by an ion exchange method using a solvent extraction method (for example, see Non-Patent Document 1) using an extraction reagent or an ion exchange resin (for example, see Non-Patent Document 2) has been performed. However, the solvent extraction method has a problem that a large amount of harmful organic waste liquid is generated, and the ion exchange method has a low adsorption selectivity for specific metal ions.
Hideo Akaiwa “Extraction Separation Analysis” (4th edition), Kodansha, 1976 Mitsubishi Chemical Corporation Ion Exchange Resin Department "Ion Exchange Resin / Synthetic Adsorbent Manual Application" (8th edition), Mitsubishi Chemical Corporation, 1995

A solid-phase extraction material called extraction chromatography resin, in which the extraction reagent is supported on a solid, mainly polymer substrate, has been developed, and separation and purification of metal ions using it as an alternative to solvent extraction and ion exchange methods Attention has been paid. The shape of the extraction chromatography resin is beads, and the beads are packed into a column when separating and purifying metal ions. Examples of extraction reagents include octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide, diamylamyl phosphate, tri-n-butyl phosphate, dimethylglyoxime, bis (2-ethylhexyl) phosphate, bis (2 , 4, 4-trimethylpentyl) phosphinic acid, tri-n-octylphosphine oxide.

Since the polymer substrate of the extraction chromatography resin has a cross-linked structure, there is a drawback that the amount of the extraction reagent supported is small or only a part of the supported extraction reagent contributes to the adsorption of metal ions. Furthermore, there is a problem that it takes time for the diffusion of metal ions into the resin.

In view of the above prior art, the present invention imparts a graft (graft) polymer chain at a high density to the surface of a substrate such as a porous hollow fiber membrane, porous film, fiber, and nonwoven fabric, and carries an extraction reagent there. Thus, an object of the present invention is to provide an adsorbing material that can perform separation and purification of metal ions at a high capacity and at a high speed. There is no known example in which the extraction reagent is supported on the graft polymer chain to improve the separation and purification performance of metal ions.

The present inventors have reported that when a functional group capable of being dissociated positively or negatively is introduced into the graft polymer chain imparted to the base material, the graft polymer chain is extended by repulsion of electric charges. In addition, we found that proteins with charges opposite to those of graft polymer chains are stacked in multiple spaces, for example, 40 layers, in the space created between the graft polymer chains due to the elongation. In other words, the inventors have found that the graft polymer chain imparted to the substrate gives a useful structure for supporting molecules and ions. Therefore, I came up with the idea of applying this structure to support the extraction reagent.

As a result of intensive research, the present inventors have introduced a functional group having an extraction reagent supporting function into the graft polymer chain imparted to the base material, and by supporting the extraction reagent therein, metal ions can be separated efficiently. The present invention was completed by finding that it can be purified. The adsorbing material carrying the extraction reagent according to the present invention can carry the extraction reagent adsorbing metal ions at a high density because the graft polymer chain has a non-crosslinked polymer structure, and the diffusion transfer resistance of metal ions It can be minimized.

That is, the present invention is a material in which a functional group having an extraction reagent supporting function is introduced into a graft polymer chain imparted to a substrate, and the graft polymer chain is formed by graft polymerization of a polymerizable monomer. The present invention relates to an adsorption material carrying an extraction reagent.

As used herein, “functional group having an extraction reagent carrying function” means a functional group having a function of carrying an extraction reagent by itself and a functional group that can be converted into such a functional group by reaction with an appropriate reagent. Refers to the group. As the functional group having an extraction reagent carrying function that can be used in the present invention, a hydrophobic group, a cation exchange group, an anion exchange group, or a functional group combining them can be used. Examples of the cation exchange group include a sulfone group, a phosphate group, and a carboxyl group. On the other hand, examples of the anion exchange group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary amino group, and a quaternary ammonium base.

In order to carry an extraction reagent containing a hydrophobic group as a part of the extraction reagent, the graft polymer chain has an alkyl group, an alkylamino group, an epoxy group, a phenyl group, or a functional group that combines them. It is effective to have. Examples of the alkylamino group include octadecylamino group, dodecylamino group, octylamino group, butylamino group, and octadecanethiol group.

An example of a functional group that can be converted into a functional group having an extraction reagent carrying function is an epoxy group. Since the epoxy group has high reactivity, it can be converted into a functional group having an extraction reagent carrying function by reaction with an appropriate reagent. For example, by reacting an epoxy group with one or more of octadecylamine, dodecylamine, etc., a functional group having an extraction reagent supporting function can be introduced into the graft polymer chain.

As the polymerizable monomer used in the present invention, for example, a polymerizable monomer having an epoxy group can be polymerized on a substrate. Particularly useful as the polymerizable monomer having an epoxy group are glycidyl methacrylate and glycidyl acrylate.

Various polymerizable monomers can be used depending on the type of extraction reagent to be supported. Examples of the polymerizable monomer having a hydrophilic group include 2-hydroxyethyl methacrylate, vinyl pyrrolidone, dimethylacrylamide, and ethylene glycol dimethacrylate. On the other hand, examples of the polymerizable monomer having a hydrophobic group include alkyl methacrylate and alkyl acrylate. These polymerizable monomers can be copolymerized with the base material at an arbitrary ratio. The present invention is characterized in that it employs graft polymerization capable of arbitrarily combining various polymerizable monomers, thereby making it possible to combine functions.

There is no restriction | limiting in particular in the base material of the adsorption material which carry | supported the extraction reagent of this invention, What kind of material can be used if a polymerizable monomer can couple | bond. In the present invention, for example, polyolefin such as polyethylene and polypropylene, polytetrafluoroethylene, or a combination (mixture or copolymer) thereof can be used.

Also, the form is not particularly limited, and for example, existing fibers, fabrics, nonwoven fabrics, porous films, porous hollow fiber membranes, porous rods, or porous filters can be used.

As the graft polymerization method of the polymerizable monomer, for example, a reaction initiator polymerization method or an ionizing radiation polymerization method can be used. In either case, the desired degree of polymerization can be obtained by appropriately controlling the reaction conditions. In the case of using ionizing radiation, ultraviolet rays, electron beams, X-rays, α rays, β rays, γ rays, or the like can be used.

The combination of the extraction reagent and the functional group having the supporting function includes a combination of bis (2-ethylhexyl) phosphate and octadecylamino group, a combination of bis (2-ethylhexyl) phosphate and dodecylamino group, bis (2, 4, 4-trimethylpentyl) phosphinic acid and octadecylamino group, bis (2, 4, 4-trimethylpentyl) phosphinic acid and dodecylamino group, trioctylmethylammonium chloride and 6-aminohexanoic acid group, A combination of octylmethylammonium chloride and octadecylamino group and 6-aminohexanoic acid group, a combination of tri-n-octylphosphine oxide and octadecanethiol group, and the like can be mentioned.

Other functional groups include substances having both an amino group and a carboxyl group in one molecule, such as various amino acids and 6-aminohexanoic acid.

The present invention is also a method for producing an adsorbing material carrying an extraction reagent, characterized in that a polymerizable monomer containing a functional group having an extraction reagent carrying function is graft-polymerized on the surface of a substrate.

A functional material composed of an adsorbing material carrying the extraction reagent described so far is provided. The form of such a functional material can be appropriately changed according to the purpose and application of use. Examples thereof include an analysis kit or an analysis cartridge.

When the extraction reagent is supported by the method proposed by the present invention, the extraction reagent can be effectively used for collecting metal ions up to 100%. The advantage of the production method according to the present invention that the extraction reagent is supported on the graft polymer chain imparted to the substrate has been demonstrated. Such high values have not been reported for conventional materials. The adsorption material carrying the extraction reagent of the present invention is promising as a material with high utilization efficiency of the extraction reagent. Furthermore, the adsorption material carrying the extraction reagent of the present invention is based on an existing porous hollow fiber membrane or fiber, and a chemically and physically stable graft polymer chain is imparted to the extraction reagent. This makes it easy to handle as a material. Expansion of application is expected as an adsorbing material carrying an extraction reagent using existing materials.

Embodiments of an adsorbing material carrying an extraction reagent according to the present invention will be described in detail with reference to the drawings. This embodiment shows some examples of the present invention, and the present invention is not limited to this example. In the following examples, the above-mentioned various monomers can be used for the polymerizable monomer, the base material and the like.

The production route of the adsorbing material carrying the extraction reagent based on the porous hollow fiber membrane is shown in FIG. FIG. 2 shows the mechanism of adsorption of metal ions on the adsorbing material carrying the extraction reagent. Here, a combination of bis (2-ethylhexyl) phosphate as the extraction reagent and yttrium ion as the metal ion was selected. A polyethylene porous hollow fiber membrane (inner diameter 2 mm, outer diameter 3 mm, average pore diameter 0.4 μm, porosity 70%) was used as a substrate membrane, and an electron beam was irradiated at 200 kGy at room temperature in a nitrogen atmosphere. Glycidyl methacrylate was graft polymerized by immersing the irradiated substrate in a 10% by volume methanol solution of glycidyl methacrylate at 40 ° C for 15 minutes. At this time, the graft ratio defined by the weight increase rate was 200%. The obtained film is called a GMA graft polymerized film.

Thereafter, the GMA graft polymerized film was immersed in octadecylamine (C ₁₈ H ₃₇ NH ₂ ) at 80 ° C. for a predetermined time. By this reaction, a part of the epoxy group in the graft polymer chain was converted to an octadecylamino (C ₁₈ H ₃₇ NH) group. The conversion rate from the epoxy group to the octadecylamino group and the octadecylamino group density in the graft polymer chain were calculated according to the following formulas (1) and (2) from the weight increase of the film accompanying the reaction. The obtained film is called an octadecylamino film.
Conversion (%) = 100 [(W ₂ -W ₁ ) / 270] / [(W ₁ -W ₀ ) / 142] (1)
Octadecylamino group density (mol / kg) = 1000 (W ₂ -W ₁ ) / 270 / W ₁ (2)
Here, W ₀ , W ₁ , and W ₂ are the weights of the base film, GMA graft polymerized film, and octadecylamino film, respectively. Here, 142 and 270 are the molecular weights of glycidyl methacrylate and octadecylamine, respectively. FIG. 3 shows the relationship between the reaction time, the conversion rate, and the octadecylamino group density. The conversion increased with increasing reaction time, reaching a constant value of 64% in 3 hours. At this time, the octadecylamino group density was calculated to be 3.0 mol / kg.

Bis (2-ethylhexyl) phosphate (hereinafter referred to as HDEHP) was used as an extraction reagent. The extraction reagent was loaded on the octadecylamino membrane by immersing the octadecylamino membrane having various octadecylamino group densities in a 5 vol% ethanol solution of HDEHP at room temperature for 2 hours. After soaking, it was dried at 60 ° C. for 2 hours. The amount of the extracted reagent carried was calculated according to the following formula (3). The obtained membrane is called an extraction reagent carrying membrane.
Extraction reagent loading [mol / kg] = 1000 (W ₃ -W ₂ ) / 322 / W ₁ (3)
Here, W ₃ is the weight of the extraction reagent carrying membrane. 322 is the molecular weight of HDEHP. FIG. 4 shows the amount of HDEHP supported on octadecylamino films having various octadecylamino group densities. The amount of extraction reagent supported increased as the octadecylamino group density increased, reaching 2.1 mol / kg when the octadecylamino group density was 2.8 mol / kg. This is because when the octadecylamino group density is increased, the graft polymer chain is extended due to charge repulsion between amino groups.

FIG. 5 shows scanning electron micrographs of the cross sections in the film thickness direction of the GMA graft polymerized film, octadecylamino film, and extraction reagent supporting film. It was observed that the porous structure of the membrane was maintained after the introduction of octadecylamino group and loading of HDEHP.

In the case where the extraction reagent is supported on a material having a porous structure, it is effective to increase the adsorption rate of metal ions by allowing a solution containing metal ions to pass through the material. Therefore, as shown in FIG. 6, an extraction reagent-supporting membrane was attached to a syringe pump, and a solution containing metal ions was permeated from the inner surface to the outer surface of the membrane. Here, yttrim ions were selected as the metal ions selectively adsorbed by the extraction reagent HDEHP, and it was demonstrated that the adsorption material carrying the extraction reagent prepared according to the present invention efficiently captures metal ions.

A 50 mg-Y / L yttrium solution prepared by dissolving in 0.01M nitric acid was supplied to the inner surface of an extraction reagent-carrying membrane having a HDEHP loading of 1.4 mol / kg and permeated to the outer surface at a constant flow rate. The flow rate was varied in the range of 30 to 120 mL / h. The effluent from the outer surface was collected continuously to quantify yttrium in the effluent. Permeation of the liquid continued until the yttrium concentration in the feed liquid matched that in the effluent. FIG. 7 shows the relationship between the effluent volume and the yttrium concentration in the effluent, that is, the breakthrough curve, obtained by this experiment. The horizontal axis of the breakthrough curve is the value obtained by dividing the effluent volume by the volume of the membrane (excluding the hollow part), and the vertical axis is the value obtained by dividing the yttrium concentration in the effluent by that in the feed liquid. The breakthrough curves overlapped regardless of the yttrium solution flow rate. This indicates that yttrium ions are instantaneously moved and adsorbed from the pores of the membrane to the extraction reagent supported on the graft polymer chain. This is advantageous in industrial separation and purification operations.

From the breakthrough curve, the yttrium equilibrium adsorption capacity of the extraction reagent-supporting membrane with respect to the yttrium concentration in the feed solution was calculated. The equilibrium adsorption capacity Q was calculated by the following equation (4). Here, C ₀ , C and V are the concentration of the feed liquid, the concentration of the effluent and the volume of the effluent, respectively. The yttrium equilibrium adsorption capacity was 0.38 mol / kg. Ideally, yttrium ions, which are trivalent cations, and the extraction reagent HDEHP bind at a molar ratio of 1: 3. Therefore, the amount of yttrium adsorbed was 0.38 mol / kg while the amount of HDEHP supported was 1.4 mol / kg, indicating that 82% of the supported HDEHP contributed to the adsorption of yttrium. Furthermore, all yttrium adsorbed on the extraction reagent-carrying membrane was eluted by permeating 7M nitric acid through the membrane.

One of functional groups having an extraction reagent carrying function is a hydrophobic group represented by an alkyl chain. In Example 1, an extraction reagent was supported on a graft polymer chain having an octadecylamino group. Example 2 shows that a material exhibiting a higher metal ion adsorption capacity can be produced by supporting an extraction reagent on a graft polymer chain having a dodecylamino group.

The GMA graft polymerized membrane was immersed in dodecylamine at 80 ° C. for 5 minutes. By this reaction, 30 mol% of the epoxy groups in the graft polymer chain were converted to dodecylamino groups. At this time, the dodecylamino group density is 1.3.
mol / kg. The obtained film is called a dodecylamino film.

HDEHP was used as an extraction reagent. The extraction reagent was supported on the dodecylamino membrane in the same manner as in Example 1. The amount of HDEHP supported was 1.6 mol / kg. The obtained membrane is called an extraction reagent carrying membrane. From the inner surface of this membrane, the same 50 mg-yttrium / L yttrium solution as in Example 1 was supplied and allowed to permeate to the outer surface of the membrane. The flow rate was 120 mL / h. The breakthrough curve obtained by this experiment is shown in FIG. From the breakthrough curve, the yttrium equilibrium adsorption capacity of the extraction reagent-supporting membrane with respect to the yttrium concentration in the feed solution was calculated to be 0.57 mol / kg. Ideally, yttrium ions, which are trivalent cations, and the extraction reagent HDEHP bind at a molar ratio of 1: 3. Therefore, the amount of yttrium adsorbed was 0.57 mol / kg while the amount of HDEHP supported was 1.6 mol / kg, indicating that all of the supported HDEHP contributed to the adsorption of yttrium.

In Example 1 described above, an octadecylamino group was introduced into a polyethylene porous hollow fiber membrane to which glycidyl methacrylate (GMA) was imparted by graft polymerization to produce a hydrophobic membrane, and an acidic extraction reagent HDEHP was supported. However, in this Example 3, 6-aminohexanoic acid (6AHA) group was introduced as a functional group instead of octadecylamino group, and the basic extraction reagent Aliquat 336 (official name: tri-n-octylmethylammonium chloride) was supported. An example will be described. In this example, the Aliquat 336-supported film was prepared by selecting [PtCl ₆ ] ^2- as the adsorption model metal ion among platinum group elements (platinum, palladium, ruthenium, rhodium, etc.) selectively adsorbed on the Aliquat 336 The adsorption performance of was evaluated.

(Production of 6AHA film)
FIG. 9A shows a polyethylene porous hollow fiber membrane production route in which 6AHA groups are introduced as functional groups. GMA grafting using 0.8 M of 6-aminohexanoic acid (6AHA) solution adjusted to pH 13 with NaOH solution (16%) and dioxane, and maintaining at 80 ° C, using methanol as the polymerization solvent The polymer film (graft rate 200%) was immersed. The conversion rate and the density of the introduced 6AHA group were calculated from the following equation (5). The obtained hydrophobic membrane is called a 6AHA membrane.
Conversion [%] = [(W ₂ -W ₁ ) / 131] / [(W ₁ -W ₀ ) / 142] × 100 (5)
Here, W ₀ , W ₁ and W ₂ are the weights of the base film, the GMA graft polymerized film, and the 6AHA film, respectively.

(Supporting Aliquat336)
Next, Aliquat 336, whose structure is shown in FIG. 9B, is dissolved in a mixed solution in which the volume ratio of pure water to ethanol is adjusted to be ethanol / water = 2/1, and the Aliquat 336 concentration is 10%. The 6AHA film was immersed in the wt% support solution for 2 hours at room temperature. After immersion, it was dried at 40 ° C. and weighed. The carrying amount of Aliquat 336 is calculated by the following equation (6).
Aliquat336 loading [mol / kg] = 1000 (W ₃ -W ₂ ) / Mr / W ₁ (6)
Here, W ₃ is the weight of the Aliquat 336-supported membrane, and Mr is the molecular weight of Aliquat 336. The obtained membrane is called an Aliquat 336-supported membrane.

(Calculation of equilibrium adsorption capacity of platinum)
A 100 mg-Pt / L solution adjusted to pH 4 with hydrochloric acid was permeated through an Aliquat 336-supported membrane at a flow rate of 120 mL / min, and the concentration of the permeate was measured by ICP-AES at regular intervals. The equilibrium adsorption capacity Q was calculated by the above equation (4).

Hereinafter, the experimental results obtained will be described in detail.

(Platinum adsorption by Aliquat 336 supported film)
FIG. 10 shows a breakthrough curve when a pH 4 [PtCl ₆ ] ² -solution (100 mg-Pt / L) was passed through an Aliquat 336-supported membrane. The amount of platinum adsorbed was 0.37 mol-Pt / kg, which was sufficient as an adsorbing material.

As described above, the adsorbing material in which the 6-aminohexanoic acid (6AHA) group in Example 3 is introduced as a functional group and the basic extraction reagent Aliquat 336 (official name: tri-n-octylmethylammonium chloride) is supported is ， Has good adsorption characteristics.

In this Example 4, after introducing a 6-aminohexanoic acid (6AHA) group as a functional group in Example 3, the remaining epoxy group and octadecylamine (C ₁₈ H ₃₇ NH ₂ ) are reacted to obtain an extraction reagent. An example will be described in which Aliquat 336 is supported and palladium (Pd) is selected as the adsorption model metal ion.

The reaction conditions for the preparation of the adsorbent material carrying the extraction reagent Aliquat 336 according to this example of the present invention are shown in Table 1 below.

(Production of 6AHA film)
FIG. 11 shows a polyethylene porous hollow fiber membrane production route in which 6AHA groups are introduced as functional groups. The step of introducing the 6AHA group is the same as that described in Example 3 above.

The change in the conversion rate with respect to the reaction time is shown in FIG. The conversion increased with the reaction time and reached equilibrium in 10 hours. At this time, the conversion was 50% and the 6AHA group density was 2.3 mol / kg.

(Introduction of octadecylamine group)
Next, using the 6AHA film with various conversion rates, the epoxy group remaining after the reaction with the 6AHA group was reacted with octadecylamine (C ₁₈ H ₃₇ NH ₂ ) (FIG. 11 (4)). The change in the conversion rate of the epoxy group to the C ₁₈ H ₃₇ NH group is shown in FIG. The conversion rate of epoxy groups to C ₁₈ H ₃₇ NH groups decreased as the conversion rate of 6AHA groups introduced earlier increased. This is because the 6AHA group hinders the reaction between the epoxy group and the C ₁₈ H ₃₇ NH group. The final conversion rate was 40-50% when the introduced 6AHA group and C ₁₈ H ₃₇ NH group were combined. Here, a film obtained by introducing a C ₁₈ H ₃₇ NH group into a 6AHA film is called a 6AHA-C ₁₈ H ₃₇ NH film.

(Support of Aliquat 336 on 6AHA-C ₁₈ H ₃₇ NH membrane)
A 10% (v / v) solution of Aliquat 336 was prepared using ethanol and ethanol / water = 2/1 (volume ratio) as a solvent, and 6AHA-C ₁₈ H ₃₇ NH membrane was immersed (FIG. 11 (5)). ). FIG. 13 shows the supported amount of Aliquat 336 with respect to the conversion ratio of epoxy groups to 6AHA groups. When a mixed solvent of ethanol / water = 2/1 is used as a supporting solvent, it is supported in a larger amount than when ethanol is used, and a maximum of 1.2
mol / kg. This is because, in a mixed solvent of ethanol / water = 2/1, the graft polymer chain is extended by charge repulsion, and a space where Aliquat 336 can approach can be secured. On the other hand, the graft polymer chain does not extend in ethanol, so Aliquat 336 is difficult to approach and results in less loading. Therefore, it was demonstrated that a supported solvent with ethanol / water = 2/1 was preferable. A membrane carrying Aliquat 336 is referred to as an Aliquat 336 (x, y) membrane. Here, x and y indicate the conversion rate from the epoxy group to the 6AHA group and the conversion rate from the epoxy group to the octadecylamino group, respectively.

(Palladium adsorption performance by supported Aliquat 336)
A palladium solution of 100 mg-Pd / L (1M HCl) was passed through an Aliquat336 (14,26) membrane. The breakthrough curve at this time is shown in FIG. The palladium adsorption capacity calculated from the breakthrough curve was 0.30 mol-Pd / kg. The permeation flow rate was 60 mL / h, the permeation flux was maintained at 1.5 m / h, and no leakage of Aliquat 336 was confirmed. The supported Aliquat 336 was shown to be retained on the C ₁₈ H ₃₇ NH group without loss of palladium adsorption performance.

As described above, it can be seen that the adsorption material of the present invention according to the present example supports the extraction reagent Aliquat 336 and has good adsorption characteristics.

In Example 5, a hydrophobic membrane was prepared by introducing a C ₁₈ H ₃₇ S group into a polyethylene porous hollow fiber membrane to which glycidyl methacrylate (GMA) was applied by graft polymerization, and the neutral extraction reagent TOPO ( An example of supporting Tri-n-octylphosphine oxide) will be described. In this example, Bi (III) was selected as the adsorption model metal ion.

(Preparation of diol-C ₁₈ H ₃₇ S membrane)
The preparation route of the diol-C ₁₈ H ₃₇ S film in this example is shown in FIG. GMA graft polymerized film with a graft ratio of 180-200% prepared using methanol as the polymerization solvent was immersed in 0.5 MH ₂ SO ₄ at 60 ° C, diol groups were introduced, and then immersed in C ₁₈ H ₃₇ SH at 80 ° C. A diol-C ₁₈ H ₃₇ S membrane was prepared. Then, it dried at 60 degreeC overnight. The increase in the weight of the membrane before and after was measured, and the conversion rate from the epoxy group to each functional group was calculated by the following formula (7).
Conversion _{[%] = [(W 2} - W 1) / Mr] / [(W 1 - W 0) / 142] × 100 (7)
Here, W ₀ , W ₁ , W ₂ , and Mr are the weight of the base film, the weight of the GMA graft polymerized film, the weight of the functional group after introduction, and the molecular weight of the functional group, respectively.

(Preparation of extraction reagent carrying membrane)
A diol-C ₁₈ H ₃₇ S membrane was immersed in a TOPO (100%) solution at 60 ° C. for 12 hours. The structural formula of TOPO is shown in FIG. The immersed film was washed with pure water for 20 min × 3 times and dried at 60 ° C. overnight. The amount of the extraction reagent supported was calculated from the increase in the membrane weight before and after. The obtained film is called a TOPO-supported film.

(Adsorption of model metal ion Bi (III))
A Bi (III) solution dissolved in 1M HCl and adjusted to 1 mmol-Bi / L was permeated from the inner surface to the outer surface of the TOPO supported membrane at a constant flow rate (10 mL / h). Further, as a blank, a Bi (III) solution was similarly permeated through a diol-C ₁₈ H ₃₇ S membrane not supporting TOPO. FIG. 16 shows the breakthrough curve at that time. The Bi (III) adsorption capacity of the TOPO supported membrane was 0.52 mol / kg. This is the same value as the adsorption capacity of conventional bead-shaped resin (0.33 to 0.61 mol / kg-resin). In addition, Bi (III) was not adsorbed on the diol-C ₁₈ H ₃₇ S membrane not supporting TOPO, so Bi (III) was adsorbed on TOPO, not on diol and C ₁₈ H ₃₇ S groups. It was shown that

As described above, it can be seen that the adsorption material of the present invention according to the present example supports the extraction reagent TOPO and has good adsorption characteristics.

As described in Examples 1 to 5 above, various kinds of extraction reagents are supported on a material that is a hydrophobic membrane in which various functional groups having an extraction reagent supporting function are introduced into the graft polymer chain. Nuclides (metal ions) can be adsorbed. That is, by combining the supported extraction reagent with a hydrophobic membrane having a functional group appropriate for the supported extraction reagent, various and various nuclides can be adsorbed (FIG. 17).

Supported extraction reagents include those described in Examples 1 to 5 above, TBP (Tri-n-butylphosphate), octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphine oxide, diamylamyl phosphate. , Dimethylglyoxime, bis (2,4,4-trimethylpentyl) phosphinic acid may be used.

As described above, it has been shown that the adsorption material carrying the extraction reagent prepared according to the present invention can adsorb metal ions efficiently. Since the adsorption material carrying the extraction reagent of the present invention can separate and purify metal ions and their complexes from various liquids with high efficiency, it can be widely used for adsorption operations frequently used in analysis and water treatment techniques.

It is a figure which shows an example of the preparation path | routes of the adsorption material which carry | supported the extraction reagent which concerns on one Example of this invention. It is a figure which shows the mechanism of adsorption | suction of a metal ion by the extraction reagent carrying | support adsorption material which concerns on one Example of this invention. FIG. 5 is a diagram showing the relationship between the reaction time, the conversion rate to a functional group (here, octadecylamino group), and the octadecylamino group density in a reaction for introducing a functional group having an extraction reagent supporting function in one embodiment of the present invention. is there. The figure which shows the load of the extraction reagent (here, bis (2-ethylhexyl) phosphate, abbreviated as HDEHP in the figure) with respect to the functional group (here, octadecylamino group) density in the material in one embodiment of the present invention. is there. It is a scanning electron micrograph of the cross section of the adsorption material which carry | supported the extraction reagent produced based on the porous membrane in one Example of this invention. It is a figure which shows the apparatus which permeate | transmits a metal ion solution to the adsorption material which carry | supported the extraction reagent produced using the porous membrane as a base material in one Example of this invention. It is a figure which shows the breakthrough curve obtained by making an yttrium solution permeate | transmit the porous membrane which carry | supported HDEHP in the octadecylamino group in one Example of this invention. It is a figure which shows the breakthrough curve obtained by making an yttrium solution permeate | transmit the porous membrane which carry | supported HDEHP in the dodecylamino group in one Example of this invention. (A) is a figure which shows an example of the preparation path | route of the adsorption material which carry | supported the extraction reagent based on one Example of this invention, (b) is a figure which shows the structural formula of Aliquat336. It is a figure which shows the breakthrough curve obtained by making a Pt solution permeate | transmit the porous membrane which carry | supported Aliquat 336 to 6AHA group in one Example of this invention. It is a figure which shows an example of the preparation path | routes of the adsorption material which carry | supported the extraction reagent which concerns on one Example of this invention. (A) is a diagram showing in one embodiment, a change in the conversion rate to C ₁₈ H ₃₇ NH group of the epoxy groups on the reaction time of the present invention, (b), the conversion of 6AHA group of the epoxy groups is a diagram showing the conversion to C ₁₈ H ₃₇ NH group of the epoxy groups to. It is a figure which shows the load of Aliquat 336 with respect to the conversion ratio of the epoxy group to 6AHA group in one Example of this invention. In one Example of this invention, it is a figure which shows a breakthrough curve when the palladium solution of 100 mg-Pd / L (1 M HCl) is permeate | transmitted to the Aliquat 336 (14,26) membrane. (A) is a figure which shows an example of the preparation path | route of the adsorption material which carry | supported the extraction reagent based on one Example of this invention, (b) is a figure which shows the structural formula of TOPO. It is a figure which shows the breakthrough curve in one Example of this invention. FIG. 6 is a diagram for explaining that various kinds of nuclides can be adsorbed by combining a supported extraction reagent and a hydrophobic membrane having a functional group suitable for the supported extraction reagent in the adsorption material of the present invention. It is.

Claims (14)

A material obtained by converting at least a part of the functional group of the graft polymer chain imparted to the base material into a functional group having both a hydrophobic group and a hydrophilic group and having an extraction reagent supporting function, An adsorbing material carrying an extraction reagent, wherein the graft polymer chain is formed by graft polymerization of a polymerizable monomer. The extraction reagent according to claim 1, wherein the hydrophobic group and the hydrophilic group are selected from a cation exchange group , an anion exchange group, an alkyl group, an alkylamino group, an epoxy group, and a diol group . Adsorption material. The adsorbent material carrying the extraction reagent according to claim 1 or 2 , wherein the polymerizable monomer is glycidyl methacrylate or glycidyl acrylate. The adsorbing material carrying the extraction reagent according to claim 1 or 2 , wherein the polymerizable monomer is hydroxyl methacrylate, vinyl pyrrolidone, dimethylacrylamide, ethylene glycol dimethacrylate, alkyl methacrylate, or alkyl acrylate. The adsorbent material carrying the extraction reagent according to any one of claims 1 to 4 , wherein the substrate is composed of polyolefin, polytetrafluoroethylene, or a combination thereof. 6. The extraction reagent according to any one of claims 1 to 5 , wherein the substrate is in the form of a fiber, a fabric, a nonwoven fabric, a porous film, a porous hollow fiber membrane, a porous rod, or a porous filter. Adsorption material. The adsorbing material carrying the extraction reagent according to any one of claims 1 to 6 , wherein the graft polymerization is performed by a reaction polymerization method or an ionizing radiation polymerization method. Adsorption carrying the extraction reagent according to any one of claims 1 to 7 , wherein the extraction reagent is bis (2-ethylhexyl) phosphate, and the functional group having the extraction reagent carrying function is an octadecylamino group or a dodecylamino group. material. The extraction reagent is bis (2,4,4-trimethylpentyl) phosphinic acid, functional group having an extraction reagent bearing functionality is also octadecyl amino dodecyl amino group, according to any one of claims 1 to 7 An adsorbent material carrying an extraction reagent. The adsorbing material carrying the extraction reagent according to any one of claims 1 to 7 , wherein the extraction reagent is trioctylmethylammonium chloride, and the functional group having the extraction reagent carrying function is a 6-aminohexanoic acid group. The extraction reagent according to any one of claims 1 to 7 , wherein the extraction reagent is trioctylmethylammonium chloride, and the functional group having the extraction reagent supporting function is an octadecylamino group and a 6-aminohexanoic acid group. Adsorption material. The adsorbing material carrying the extraction reagent according to any one of claims 1 to 7 , wherein the extraction reagent is tri-n-octylphosphine oxide, and the functional group having the extraction reagent carrying function is an octadecanethiol group. A grafting polymer chain is imparted to the surface of the substrate by graft polymerization of a polymerizable monomer, and at least a part of the functional groups of the graft polymer chain has both a hydrophobic group and a hydrophilic group. And a method for producing an adsorbent material that is converted into a functional group having an extraction reagent carrying function and carries the extraction reagent. An analysis kit or an analysis cartridge composed of an adsorbent material carrying the extraction reagent according to any one of claims 1 to 12 .