WO2005102512A1

WO2005102512A1 - Adsorbents carrying extracting reagents and process for production thereof

Info

Publication number: WO2005102512A1
Application number: PCT/JP2005/007639
Authority: WO
Inventors: Kyoichi Saito; Shiho Asai; Takanobu Sugo
Original assignee: National University Corporation Chiba University
Priority date: 2004-04-21
Filing date: 2005-04-21
Publication date: 2005-11-03
Also published as: JP4660793B2; JP2005331510A

Abstract

Current extraction chromatographic resins, which are materials having both the characteristics of an extracting reagent used in solvent extraction and those of an ion-exchange resin used in ion exchange, have disadvantages of slow transfer of metal ions to the extracting reagent supported on the resin and low utilization of the extracting reagent supported thereon, and the invention provides an adsorbent carrying an extracting reagent which is freed from the disadvantages. The invention relates to an adsorbent for metal ions which is obtained by grafting a polymerizable monomer having the ability to carry an extracting reagent onto the surface of a substrate and making an extracting reagent supported on the obtained product. The functional group having the ability to carry an extracting reagent may be a hydrophobic group (such as alkylamino, alkyl, alkylthiol, or epoxy), a hydrophilic group (such as diol), or a combination of them.

Description

Specification

Adsorption material supporting extraction reagent and method for producing the same

Technical field

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

Background art

[0002] In order to quantify fission products, activation products, and actinoid elements contained in environmental samples and radioactive waste, it is necessary to separate and purify metal ions as a pretreatment for measurement. There is. So far, separation and purification have been performed by a solvent extraction method using an extraction reagent (for example, see Non-Patent Document 1) or an ion-exchange method using an ion-exchange resin (for example, see Non-Patent Document 2). However, the solvent extraction method generates a large amount of harmful organic effluents, and the ion exchange method has a problem in that the adsorption selectivity for specific metal ions is low.

Non-Patent Document 1: Hideo Akaiwa, "Extraction Separation Analysis Method" (4th edition), Kodansha, 1976

Non-Patent Document 2: Ion Exchange Resin Department, Mitsubishi Chemical Corporation “Ion Exchange Resin 'Synthetic Adsorbent Manual Application Edition” (8th edition), Mitsubishi Chemical Corporation, 1995

[0003] A solid-phase extraction material called an extraction chromatography resin, in which an extraction reagent is supported on a solid, mainly a polymer substrate, has been developed, and a method for separating and purifying metal ions using it has been developed by solvent extraction or ion exchange. It is attracting attention as an alternative to the law. The extraction chromatography resin is in the form of beads, and the beads are packed into a column when separating and purifying metal ions. Examples of extraction reagents include octyl (phenyl) -N, N-diisobutylcarbamoylmethylphosphonoxide, diamylamylphosphite, tri_n-butylphosphate, dimethylglycoxime, bis (2-ethylhexyl) phosphite, and bis (2-ethylhexyl) phosphite. (2,4,4-trimethylpentyl) phosphinic acid and tri-n-octylphosphinoxide.

[0004] Since the polymer base material of the extraction chromatography resin has a crosslinked structure, there is a drawback that the amount of the extraction reagent carried is small, or that only a part of the supported extraction reagent contributes to the adsorption of metal ions. . Furthermore, it takes time for the diffusion of metal ions into the resin. There is a problem of power.

Disclosure of the invention

Problems to be solved by the invention

[0005] In view of the above prior art, the present invention provides a high density graft (grafted) polymer chain on the surface of a substrate such as a porous hollow fiber membrane, a porous film, a fiber, or a nonwoven fabric. An object of the present invention is to provide an adsorbent material capable of separating and refining metal ions at a high capacity and at a high speed by supporting an extraction reagent on the substrate. There is no known example of improving the performance of separating and purifying metal ions by supporting an extraction reagent on a graft polymer chain.

Means for solving the problem

[0006] The present inventors have reported that when a functional group capable of dissociating positively or negatively is introduced into a graft polymer chain provided to a substrate, the graft polymer chain is elongated by repulsion of electric charge. They also found that proteins with charges opposite to the charge of the graft polymer chains were adsorbed in multiple layers, for example, 40 layers, in the space created between the graft polymer chains due to their elongation. Was. In other words, we have found that the grafted polymer chains provided to the substrate provide a structure useful for supporting molecules and ions. Therefore, I thought about applying this structure to support extraction reagents.

[0007] The inventors of the present invention have conducted intensive studies, and as a result, introduced a functional group having an extract-reagent carrying function into a graft polymer chain attached to a substrate, and carried the extract-reagent on the functional group. The present inventors have found that it is possible to efficiently separate and purify proteins, and have completed the present invention. The adsorbent material supporting the extraction reagent according to the present invention can support an extraction reagent that adsorbs metal ions at a high density because the graft polymer chain has a non-crosslinked polymer structure. It has the feature of minimizing the movement resistance.

[0008] That is, the present invention relates to a material in which a functional group having an extracting reagent-carrying function is introduced into a graft polymer chain provided to a base material, wherein the graft polymer chain grafts a polymerizable monomer. The present invention relates to an adsorbent material carrying an extraction reagent formed by the above method.

[0009] As used herein, the term "functional group having the function of supporting the extraction reagent" refers to a functional group capable of supporting the extraction reagent by itself and converted to such a functional group by reaction with an appropriate reagent. A functional group that can be used. Has an extraction reagent carrying function that can be used in the present invention As the functional group, a hydrophobic group, a cation exchange group, an anion exchange group, or a functional group obtained by combining them can be used. Examples of the cation exchange group include a sulfone group, a phosphoric acid 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.

[0010] Among the extraction reagents, in order to carry an extraction reagent containing a hydrophobic group in a part thereof, the graft polymer chain must have an alkyl group, an anolequinoleamino group, an epoxy group, a phenyl group, or It is effective to have a functional group combining them. Examples of the alkylamino group include an otadecinoleamino group, a dodecinoleamino group, an octylamino group, a butylamino group, and an octadecanethiol group.

[0011] A functional group that can be converted into a functional group having a function of supporting an extraction reagent is, for example, an epoxy group. Since the epoxy group has high reactivity, it can be converted into a functional group having a function of carrying an extraction reagent by reacting with an appropriate reagent. For example, by reacting an epoxy group with one or more of octadecylamine, dodecinoleamine and the like, a functional group having an extraction reagent-supporting function in the epoxy group 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. Glycidyl methacrylate / glycidyl atalylate is particularly useful as a polymerizable monomer having an epoxy group.

[0013] 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, dimethyl acrylamide, and ethylene glycol dimethacrylate. On the other hand, examples of polymerizable monomers having a hydrophobic group include alkyl methacrylate and alkyl acrylate. These polymerizable monomers are capable of copolymerizing the base material at an arbitrary ratio. The present invention is characterized by adopting a graft polymerization in which various kinds of polymerizable monomers can be arbitrarily combined, whereby the functions can be compounded.

[0014] The substrate of the adsorption material supporting the extraction reagent of the present invention is not particularly limited, and any material can be used as long as the polymerizable monomer can be bound thereto. In the present invention, for example, polyolefin such as polyethylene and polypropylene, polytetrafluoroethylene, or a combination thereof (mixture or copolymer) can be used. [0015] The form is not particularly limited. For example, existing fibers, fabrics, nonwoven fabrics, porous films, porous hollow fiber membranes, porous rods, or porous filters can be used.

[0016] As the graft polymerization method for the polymerizable monomer, for example, a reaction initiator polymerization method or an ionizing radiation polymerization method can be used. In any case, the desired degree of polymerization can be obtained by appropriately controlling the reaction conditions. When ionizing radiation is used, ultraviolet rays, electron beams, X-rays, braided rays, / 3 rays or gamma rays can be used.

[0017] As a combination of an extraction reagent and a functional group having a supporting function thereof, a combination of a bis (2-ethylhexyl) phosphate and an octadecylamino group, a combination of a bis (2-ethylhexyl) phosphite and a dodecylamino Combination of bis (2,4,4-trimethylpentyl) phosphinic acid and octadecylamino group, combination of bis (2,4,4-trimethylpentyl) phosphinic acid and dodecylamino group, Combination of octylmethylammonium chloride and 6-aminohexanoic acid group, combination of trioctylmethylammonium chloride and octadecylamino group and 6-aminoaminohexanoic acid group, tree η-octylphosphonoxide and octadecanethiol group And the like.

[0018] Other examples of the functional group include substances having both an amino group and a carboxyl group in one molecule, such as various amino acids and 6-aminohexanoic acid.

[0019] The present invention also relates to a method for producing an adsorbent material carrying an extraction reagent, wherein a polymerizable monomer containing a functional group having an extraction reagent-supporting function is graft-polymerized on the surface of the substrate. I do.

[0020] A functional material constituted by an adsorbent material supporting the extraction reagent described above is provided. The form of these functional materials can be changed as appropriate according to the purpose and application of use. Examples include an analysis kit or an analysis cartridge.

The invention's effect

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 an extraction reagent is carried on a graft polymer chain attached to a substrate has been demonstrated. No such high values have been reported for conventional materials. The adsorption material supporting the extraction reagent of the present invention is useful for the extraction reagent. It is promising as a material with high use efficiency. Furthermore, the adsorbent material supporting the extraction reagent of the present invention provides a chemically and physically stable grafted high molecular chain to an existing porous hollow fiber membrane or fiber as a base material, to which the extraction reagent is applied. Since it can be manufactured by supporting it, it has excellent handleability as a material. Its use is expected to expand as an adsorbent material that supports extraction reagents using existing materials.

Brief Description of Drawings

FIG. 1 is a diagram showing an example of a production route of an adsorption material supporting an extraction reagent according to one embodiment of the present invention.

FIG. 2 is a view showing a mechanism of metal ion adsorption by an extraction reagent-carrying adsorption material according to one embodiment of the present invention.

[Fig. 3] Reaction time, conversion to a functional group (here, octadecylamino group), and octadecyl in the reaction of introducing a functional group having a function of supporting an extraction reagent in one embodiment of the present invention. It is a figure which shows the relationship with an amino group density.

[FIG. 4] In one embodiment of the present invention, an extraction reagent (here, bis (2-ethylhexyl) phosphate) versus a functional group (here, octadecylamino group) density in a material, and HDEHP and FIG. FIG. 4 is a diagram showing the amount of support (abbreviation).

FIG. 5 is a scanning electron micrograph of a cross section of an adsorbent material carrying an extraction reagent prepared using a porous membrane as a substrate in one example of the present invention.

FIG. 6 is a view showing an apparatus for permeating a metal ion solution to an adsorbent material carrying an extraction reagent prepared using a porous membrane as a substrate according to one embodiment of the present invention.

FIG. 7 is a graph showing breakthrough curves obtained by permeating an yttrium solution through a porous membrane having HDEHP supported on octadecinoleamino groups in one example of the present invention.

FIG. 8 is a view showing a breakthrough curve obtained by permeating an yttrium solution through a porous membrane having HDEHP supported on dodecylamino groups in one example of the present invention.

[FIG. 9] (a) is a diagram showing an example of a production route of an adsorbent material supporting an extraction reagent according to one embodiment of the present invention, and (b) is a diagram showing a structural formula of Aliquat 336 .

FIG. 10 is a view showing a breakthrough curve obtained by permeating a Pt solution through a porous membrane carrying Aliquat 336 on 6AHA groups in one example of the present invention. FIG. 11 is a diagram showing an example of a production route of an adsorbent material supporting an extraction reagent according to one embodiment of the present invention.

[FIG. 12] (a) shows C H of an epoxy group versus reaction time in one example of the present invention.

18 37

It is a figure which shows the change of the conversion rate to an NH group, and (b) is a figure which shows the conversion rate of an epoxy group to a CHNH group with respect to the conversion rate of an epoxy group to 6AHA group.

18 37

FIG. 13 is a graph showing the amount of Aliquat 336 carried with respect to the conversion ratio of epoxy groups to 6AHA groups in one example of the present invention.

[FIG. 14] In one embodiment of the present invention, a 100 mg-Pd / L (1 M HC1) palladium solution was used.

It is a figure which shows the breakthrough curve at the time of making it permeate an Aliquat 336 (14, 26) membrane.

[FIG. 15] (a) is a diagram showing an example of a production route of an adsorbent material supporting an extraction reagent according to one embodiment of the present invention, and (b) is a diagram showing a structural formula of TOPO.

FIG. 16 is a view showing a breakthrough curve in one example of the present invention.

[FIG. 17] In the adsorbent material of the present invention, by combining a supported extraction reagent with a hydrophobic membrane having an appropriate functional group for the supported extraction reagent, it is possible to adsorb a wide variety of nuclides. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the adsorption material supporting the extraction reagent according to the present invention will be described in detail with reference to the drawings. The present embodiment shows some examples of the present invention, and the present invention is not limited to the present embodiment. In the following examples, the above-mentioned various ones can be used as the polymerizable monomer and the base material.

Example 1

[0024] Fig. 1 shows a production route of an adsorbent material supporting an extraction reagent using a porous hollow fiber membrane as a substrate. Figure 2 shows the mechanism of metal ion adsorption on the adsorption material supporting the extraction reagent. Here, a combination of bis (2-ethylhexyl) phosphate as the extraction reagent and yttrium ion as the metal ion was selected. Using a polyethylene porous hollow fiber membrane (inner diameter 2 mm, outer diameter 3 mm, average pore diameter 0.4 / m, porosity 70%) as a substrate film, electron beams were irradiated at 200 kGy in a nitrogen atmosphere at room temperature. By immersing the irradiated substrate in a 10% by volume glycidyl methacrylate solution in methanol at 40 ° C for 15 minutes, the glycidyl methacrylate can be graphed. Polymerized. At this time, the graft ratio defined by the weight gain was 200%. The obtained film is called GMA graft polymerized film.

[0025] Thereafter, the GMA graft polymerized film was applied to octadecinoleamine (CHNH) at 80 ° C for a predetermined time.

18 37 2

Dipped. By this reaction, a part of the epoxy group in the graft polymer chain was converted to an octadecylamino (CHNH) group. Octadecinole from epoxy groups in grafted polymer chains

18 37

The conversion to amino groups and the density of octadecylamino groups were calculated according to the following equations (1) and (2). The obtained film is called an octadecinole amino film. Conversion (%) = 100 [(W-W) / 270] / [(W-W) / 142] (1)

2 1 1 0

Octadecylamino group density (mol / kg) = 1000 (W-W) / 270 / W (2)

2 1 1

Here, W, W, and W are the base film, GMA graft polymerized film, and octa, respectively.

0 1 2

This is the weight of the decylamino film. Where 142 and 270 are the molecular weights of glycidyl methacrylate and octadecylamine, respectively. Fig. 3 shows the relationship between the reaction time, the conversion, and the density of amino groups. The conversion increased with increasing reaction time, reaching a constant value of 64% in 3 hours. At this time, the density of octadecinole amino groups was calculated to be 3.0 mol / kg.

[0026] As an extraction reagent, bis (2-ethylhexyl) phosphate (hereinafter referred to as HDEHP) was used. To support the extraction reagent on the octadecinoleamino membrane, immerse the octadecylamino film with various octadecinoleamino group densities in a 5% by volume ethanol solution of HDEHP at room temperature for 2 hours. It was done by doing. After immersion, it was dried at 60 ° C for 2 hours. The amount of the extraction reagent carried was calculated according to the following equation (3). The obtained membrane is called an extraction reagent-carrying membrane.

Extraction reagent loading [mol / kg] = 1000 (W-W) / 322 / W (3)

3 2 1

Here, W is the weight of the extraction reagent-carrying membrane. 322 is the molecular weight of HDEHP. Sa

Three

Figure 4 shows the amount of HDEHP supported on octadecinoleamino membranes with various octadecinoleamino group densities. The amount of the extraction reagent carried increased with an increase in the density of the octadecylamino group, and reached 2.1 mol / kg when the density of the octadecylamino group was ¾0.8 mol / kg. This is because when the density of octadecylamino groups increases, the grafted high molecular chain elongates due to charge repulsion between amino groups.

[0027] Cross-section in the thickness direction of GMA graft polymerized membrane, octadecylamino membrane, and membrane supporting extraction reagent The scanning electron micrograph of the sample is shown in FIG. It was observed that the porous structure of the membrane was maintained after the introduction of the octadecylamino group and the loading of HDEHP.

[0028] When an extraction reagent is carried on a material having a porous structure, it is effective to allow a solution containing metal ions to pass through the material in order to increase the metal ion adsorption rate. Therefore, as shown in Fig. 6, an extraction reagent-carrying membrane was attached to the syringe pump, and a solution containing metal ions was permeated from the inner surface to the outer surface of the membrane. Here, we selected yttrium ions as the metal ions selectively adsorbed by the extraction reagent HDEHP, and demonstrated that the adsorbent material supporting the extraction reagent produced by the present invention efficiently captures metal ions.

[0029] A 50 mg-Y / L yttrium solution prepared by dissolving in 0.01 M nitric acid was supplied to the inner surface of an extraction reagent-supporting membrane having a HDEHP-supporting amount of 1.4 mol / kg, and permeated to the outer surface at a constant flow rate. The flow rates varied from 30 to 120 mL / h. The effluent from the outer surface was continuously sampled and the amount of yttrium in the effluent was determined. The permeation of the liquid was continued until the yttrium concentration in the feed and the effluent corresponded. Figure 7 shows the relationship between the amount of effluent and the yttrium concentration in the effluent, that is, the breakthrough curve obtained from 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 solution. The breakthrough curves overlapped regardless of the flow rate of the yttrium solution. This indicates that yttrium ions move instantaneously from the pores of the membrane to the extraction reagent supported on the graft polymer chain and are adsorbed. This is very advantageous for industrial separation and purification operations.

[0030] From the breakthrough curve, the yttrium equilibrium adsorption capacity of the extraction reagent-carrying 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). Where C, C, and V are the concentration of the feed, the concentration of the effluent, and the volume of the effluent, respectively. I

0

The thorium equilibrium adsorption capacity was 0.38 mol / kg. Yttrium ion, a trivalent cation, and an extraction reagent, HDEHP, combine with a force ideally in a molar ratio of 1: 3. Therefore,

The amount of adsorbed yttrium was 0.38 mol / kg against the amount of HDEHP supported of 1.4 mol / kg, indicating that 82% of the supported HDEHP contributed to the adsorption of yttrium. Furthermore, yttrium adsorbed on the extraction reagent-carrying membrane was completely eluted by permeating 7M nitric acid through the membrane. [0031] [Number 1]

Example 2

[0032] One of the functional groups having the function of supporting the extraction reagent is a hydrophobic group S 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 was produced by supporting an extraction reagent on a graft polymer chain having a dodecylamino group.

[0033] The GMA graft polymer film was immersed in dodecinoleamine 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 was 1.3 mol / kg. The obtained film is called a dodecylamino film.

[0034] HDEHP was used as an extraction reagent. The loading of the extraction reagent on the dodecylamino membrane was carried out in the same manner as in Example 1. The HDEHP loading was 1.6 mol / kg. The obtained membrane is called an extraction reagent-carrying membrane. The same 50 mg-yttrium / L yttrium solution as in Example 1 was supplied from the inner surface of this film and allowed to permeate to the outer surface of the film. The flow rate was 120 mL / h. Figure 8 shows the breakthrough curve obtained from this experiment. From the breakthrough curve, the equilibrium adsorption capacity of the extraction reagent-carrying membrane with respect to the yttrium concentration in the feed solution was calculated to be 0.57 mol / kg. The yttrium ion, which is a trivalent cation, and the extraction reagent HDEHP bind ideally in a molar ratio of 1: 3. Therefore, the amount of adsorbed yttrium was 0.57 mol / kg with respect to the HDEHP carrying capacity Sl.6 mol / kg, indicating that all the supported HDEHP contributed to the adsorption of yttrium.

Example 3

[0035] In Example 1 described above, an octadecinoleamino group was introduced into a polyethylene porous hollow fiber membrane to which glycidyl methacrylate (GMA) was applied by graft polymerization to form a hydrophobic membrane. In this Example 3, a 6-aminohexanoic acid (6AHA) group was introduced as a functional group instead of the otatacinoleamino group, and the basic extraction reagent Aliquat 336 (formally Name: An example carrying tri-n-octylmethylammonium chloride) Will be described. In this example, among the platinum group elements (platinum, palladium, ruthenium, rhodium, etc.) that selectively adsorb to Aliquat 336, [PtCl broad was selected as the adsorption model metal ion, and the adsorption of the produced Aliquat 336-supported membrane was performed. The performance was evaluated.

6

(Preparation of 6AHA film)

FIG. 9 (a) shows a route for preparing a polyethylene porous hollow fiber membrane into which a 6AHA group has been introduced as a functional group. An equal volume of a 0.8 M aqueous solution of 6-aminohexanoic acid (6AHA) adjusted to pH 13 with a NaOH solution (16%) and dioxane are mixed and maintained at 80 ° C, and methanol is used as the polymerization solvent. The used GMA graft polymer film (graft ratio 200%) was immersed. The conversion and the density of the introduced 6AHA groups were calculated from the following equation (5). The obtained hydrophobic membrane is called a 6AHA membrane.

Conversion [%] = [(W-W) / 131] / [(W _ W) / 142] X 100 (5)

2 1 1 0

Where W, W and W are the base film, GMA graft polymerized film, and 6AHA film, respectively.

0 1 2

Is the weight.

[0037] (Loading of Aliquat 336)

Next, Aliquat 336 having the structure shown in Fig. 9 (b) was dissolved in a mixed solution in which the volume ratio of pure water to ethanol was adjusted to ethanol / water = 2/1. The 6AHA membrane was immersed in a supporting solution of wt% at room temperature for 2 hours. After immersion, it was dried at 40 ° C and weighed. The amount of Aliquat 336 carried is calculated by the following equation (6).

Aliquat 336 carrying amount [mol / kg] = 1000 (W _W) / Mr / W (6)

3 2 1

Here, W is the weight of the Aliquat 336 supported membrane, and Mr is the molecular weight of Aliquat 336. Obtained

Three

The resulting membrane is called 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 the Aliquat 336-supported membrane at a flow rate of 120 mL / min, and the concentration of the permeate was measured at regular intervals by ICP-AES. The equilibrium adsorption capacity Q was calculated by the above equation (4).

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

[0040] (Platinum adsorption by Aliquat 336-supported membrane)

Breakthrough when pH 4 [PtCl] solution (100 mg_Pt / L) is permeated through Aliquat 336 supported membrane

6

The lines are shown in FIG. The adsorption amount of platinum is 0.37 mol Pt / kg, which is sufficient as an adsorption material. It was a good life.

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

Example 4

[0042] In Example 4, after the 6-aminohexanoic acid (6AHA) group was introduced as a functional group in Example 3, the remaining epoxy group was reacted with octadecinoleamine (CHNH).

The following describes an example in which extraction reagent Aliquat 336 is supported and palladium (Pd) is selected as the model metal ion for adsorption.

[0043] Table 1 below shows reaction conditions for producing an adsorbent material supporting the extraction reagent Aliquat 336 according to this example of the present invention.

[Table 1] Table 1 Reaction conditions for production of Aliquat 336 support material according to Example 4 Graft polymerization

GMA concentration (vol%) 10

Solvent Methanol

Reaction temperature 353 K

Introduction of 6-aminohexanoic acid group

6-Aminohexanoic acid concentration 6AHA / water / dioxane

= 5/45/50 (w / w / w)

PH 13 (adjusted with 0.4 M NaOH) Reaction temperature 353 K Introduction of octadecylamino 堇

C ₁₈ H ₃₇ NH ₂ concentration 100%

Reaction temperature 353 K

Aliquat 336 loading

Aliquat 336 concentration (vol%) 10

Solvent Ethanol / water = 2/1 (v / v) (Preparation of 6AHA film)

FIG. 11 shows a route for preparing a porous hollow fiber membrane made of polyethylene into which 6AHA group was introduced as a functional group. The step of introducing the 6AHA group is the same as the step described in Example 3 above.

FIG. 12 (a) shows a change in the conversion with respect to the reaction time. The conversion increased with the reaction time and reached equilibrium in 10 hours. At this time, the conversion is 50% and the density of 6AHA groups is 2.3 mol / kg.

(Introduction of octadecylamine group)

Next, using the 6AHA membranes with various conversion rates, the epoxy group remaining after the reaction with the 6AHA group was reacted with octadecylamine (CHNH) (Fig. 11 (4)). Epoxy C H

18 37 2 18 37

FIG. 12 (b) shows the change in the conversion to the NH group. The conversion of epoxy groups to C H NH groups is

18 37

It decreased with an increase in the conversion of the 6AHA group introduced earlier. This is because the 6AHA group interferes with the reaction between the epoxy group and the CHNH group. The final conversion rate is

18 37

The combined 6AHA and C H NH groups resulted in a range of 40-50%. Here, 6AHA film has C

18 37

The membrane into which the HNH group has been introduced is called a 6AHA-CHNH membrane.

18 37 18 37

[0048] (Loading of Aliquat 336 on 6AHA-CH NH membrane)

18 37

Using ethanol and ethanol / water = 2/1 (volume ratio) as a solvent, a 10% (v / v) solution of Aliquat 336 was prepared, and the 6AHA-CHNH film was immersed (Fig. 11 (5)). Epoxy group to 6AHA group

18 37

FIG. 13 shows the supported amount of Aliquat 336 with respect to the conversion of. When a mixed solvent of ethanol / water = 2/1 was used as the supported solvent, the supported amount was larger than that when ethanol was used, and the maximum was 1.2 mol / kg. This is because in a mixed solvent of ethanol / water = 2/1, the grafted polymer chains are stretched due to charge repulsion, and a space accessible to Aliquat 336 can be secured. On the other hand, in ethanol, the grafted polymer chains did not elongate, so that the amount of Aliquat 336 carried was small, and the result was a small result. Therefore, it was demonstrated that a supported solvent with ethanol / water = 2/1 is preferable. The membrane supporting Aliquat 336 is called Aliquat 336 (x, y) membrane. Here, X and y indicate the conversion from the epoxy group to the 6AHA group and the conversion from the epoxy group to the octadecylamino group, respectively.

(Adsorption performance of palladium by supported Aliquat 336) A 100 mg-Pd / L (1M HC1) palladium solution was permeated through Aliquat 336 (14, 26) membrane. Figure 14 shows the breakthrough curve at this time. The adsorption capacity of palladium calculated from the breakthrough curve was 0.30 mo 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. It was shown that the supported Aliquat 336 was retained on the CHNH group without loss of palladium adsorption performance.

18 37

[0050] 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.

Example 5

In Example 5, a hydrophobic membrane was produced by introducing a CHS group into a polyethylene hollow hollow fiber membrane to which glycidyl methacrylate (GMA) was applied by graft polymerization, and a neutral extraction was performed.

18 37

An example in which the reagent TOPO (Tri-n-octylphosphine oxide) is carried will be described. In this example, Bi (m) was selected as the adsorption model metal ion.

[0052] (Preparation of diol-CHS film)

18 37

FIG. 15A shows a manufacturing route of the did-CHS film in this example. Methano in polymerization solvent

18 37

Of GMA graft polymer film with a graft ratio of 180-200%

twenty four

After immersion at 60 ° C and introduction of diol groups, immersion in CHSH at 80 ° C to form a diol-CHS film.

18 37 18 37 Then, it was dried at 60 ° C overnight. The amount of increase in the membrane weight before and after was measured, and the conversion from the epoxy group to each functional group was calculated by the following equation (7).

Conversion [%] = [(W-W) / Mr] / [(W-W) / 142] X 100 (7)

2 1 1 0

Here, W, W, W, and Mr are the weight of the base film and the weight of the GMA graft polymerized film, respectively.

0 1 2

Amount, film weight after functional group introduction, and molecular weight of functional group.

(Preparation of membrane supporting extraction reagent)

The diol-CHS film was immersed in a TOPO (100%) solution at 60 ° C for 12 hours. Figure 1 shows the structural formula of TOPO

18 37

This is shown in Fig. 5 (b). The membrane after immersion was washed with pure water three times for 20 min and dried at 60 ° C overnight. Based on the increase in membrane weight before and after, the amount of extraction reagent carried was calculated. The obtained film is called TOPO-supported film.

(Adsorption of Model Metal Ion Bi (m))

The Bi (m) solution, which was dissolved in 1M HC1 and adjusted to lmmo Bi / L, was supplied at a constant flow rate (10 (mL / h) through the TOPO-supported membrane from the inner surface to the outer surface of the membrane. As a blank, the Bi (m) solution was also permeated through the dioK: HS membrane, which did not support ΤΟΡΟ. then

18 37

Figure 16 shows the breakthrough curve. The Bi (m) adsorption capacity of the TOPO-supported membrane was 0.52 mol / kg. This value is about the same as the adsorption capacity of conventional bead-shaped resin (0.33 to 0.61 mol / kg-resin). Bi (m) was not adsorbed on the dio-C H S membrane without T〇P〇.

18 37

Therefore, it was shown that Bi (m) was adsorbed on T〇PO, not on the diol and CHS groups.

18 37

[0055] As described above, it can be seen that the adsorption material of the present invention according to the present example supports the extraction reagent ， and has good adsorption characteristics.

Example 6

[0056] As described in Examples 1 to 5 above, by supporting various extraction reagents on a material that is a hydrophobic membrane in which various functional groups having an extraction reagent support function are introduced into the graft polymer chain, Various · Various nuclides (metal ions) can be adsorbed. In other words, by combining a supported extraction reagent with a hydrophobic membrane having a functional group suitable for the supported extraction reagent, it is possible to adsorb a wide variety of nuclides (Fig. 17).

[0057] As the extraction reagent to be supported, in addition to those described in Examples 1 to 5 described above, ΤΒΡ (Tri-n-butylphosphate), octyl (phenyl) _Ν, Ν-diisobutylcarbamoylmethylphosphinoxide , Diamylamyl phosphate, dimethyldalioxime, bis (2,4,4-trimethylpentyl) phosphinic acid.

Industrial applicability

[0058] As described above, it was shown that the adsorption material supporting the extraction reagent produced by the present invention adsorbs metal ions efficiently. Since the adsorption material supporting the extraction reagent of the present invention can separate and purify metal ions and their complexes with various liquid forces and high efficiency, they can be widely used in adsorption operations frequently used in analysis and water treatment technology. it can.

Claims

The scope of the claims

[1] A material in which a functional group having an extraction reagent-carrying function is introduced into a graft polymer chain provided on a substrate, wherein the graft polymer chain is formed by graft polymerization of a polymerizable monomer. , An adsorption material carrying an extraction reagent.

2. The adsorbent material supporting an extraction reagent according to claim 1, wherein the functional group having the function of supporting the extraction reagent is a hydrophobic group, a cation exchange group, an anion exchange group, or a combination thereof.

3. The adsorbent material supporting an extraction reagent according to claim 1, wherein the functional group having an extraction reagent-supporting function is an alkyl group, an alkylamino group, an epoxy group, a diol group, or a combination thereof. .

[4] The adsorbent material supporting an extraction reagent according to any one of claims 1 to 3, wherein the functional group having the function of supporting the extraction reagent is one or more types.

[5] The adsorptive material carrying the extraction reagent according to any one of claims 1 to 4, wherein the polymerizable monomer is glycidyl methacrylate or glycidinoleate tallate.

[6] The polymerizable monomer according to any one of claims 1 to 4, wherein the polymerizable monomer is hydroxyl methacrylate, vinylpyrrolidone, dimethyl atalinoleamide, ethylene glycol dimethacrylate, alkyl methacrylate or alkyl acrylate. Adsorbent material supporting the extraction reagent described in 1.

[7] The adsorbent material carrying an extraction reagent according to any one of claims 1 to 6, wherein the substrate is composed of polyolefin, polytetrafluoroethylene, or a combination thereof.

[8] The extraction test according to any one of claims 1 to 7, wherein the substrate is in the form of a fiber, a cloth, a nonwoven fabric, a porous film, a porous hollow fiber membrane, a porous rod, or a porous filter. An adsorption material that carries a drug.

[9] The adsorbent material supporting the extraction reagent according to any one of claims 1 to 8, wherein the graft polymerization is performed by a reaction initiator polymerization method or an ionizing radiation polymerization method.

10. The method according to claim 1, wherein the extraction reagent is bis (2-ethylhexyl) phosphate, and the functional group having the function of supporting the extraction reagent is an octadecylamino group or a dodecylamino group. An adsorption material carrying the extraction reagent according to any one of the above.

11. The method according to claim 1, wherein the extraction reagent is bis (2,4,4-trimethylpentyl) phosphinic acid, and the functional group having the function of supporting the extraction reagent is an octadecylamino group or a dodecinoleamino group. An adsorption material carrying the extraction reagent according to any one of the above.

[12] The extraction reagent according to any one of claims 1 to 9, wherein the extraction reagent is trioctylmethylammonium chloride, and the functional group having a function of supporting the extraction reagent is 6-aminohexanoic acid group. Adsorbed material carried.

13. The method according to claim 1, wherein the extraction reagent is trioctylmethylammonium chloride, and the functional groups having the function of supporting the extraction reagent are an octadecylamino group and a 6-aminohexanoic acid group. An adsorbent material carrying the extraction reagent according to any one of the preceding claims.

[14] The extraction reagent according to any one of claims 1 to 9, wherein the extraction reagent is tri-n-octylphosphinoxide, and the functional group having the function of supporting the extraction reagent is an octadecanethiol group. Adsorbed material carried.

[15] A method for producing an adsorbent material that carries an extraction reagent by graft-polymerizing a polymerizable monomer having an extraction reagent-supporting function onto the substrate surface.

[16] An analysis kit or an analysis cartridge comprising the adsorption material carrying the extraction reagent according to any one of claims 1 to 14.