WO2005102512A1 - Adsorbants portant des reactifs d’extraction et procede de fabrication de ceux-ci - Google Patents

Adsorbants portant des reactifs d’extraction et procede de fabrication de ceux-ci Download PDF

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Publication number
WO2005102512A1
WO2005102512A1 PCT/JP2005/007639 JP2005007639W WO2005102512A1 WO 2005102512 A1 WO2005102512 A1 WO 2005102512A1 JP 2005007639 W JP2005007639 W JP 2005007639W WO 2005102512 A1 WO2005102512 A1 WO 2005102512A1
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Prior art keywords
extraction reagent
group
supporting
extraction
function
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PCT/JP2005/007639
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English (en)
Japanese (ja)
Inventor
Kyoichi Saito
Shiho Asai
Takanobu Sugo
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National University Corporation Chiba University
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Publication of WO2005102512A1 publication Critical patent/WO2005102512A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/285—Porous sorbents based on polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/26—Cation exchangers for chromatographic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/20—Anion exchangers for chromatographic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/62—In a cartridge

Definitions

  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • the cation exchange group include a sulfone group, a phosphoric acid group, and a carboxyl group.
  • 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.
  • the graft polymer chain 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.
  • the alkylamino group include an otadecinoleamino group, a dodecinoleamino group, an octylamino group, a butylamino group, and an octadecanethiol group.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • polyolefin such as polyethylene and polypropylene, polytetrafluoroethylene, or a combination thereof (mixture or copolymer) can be used.
  • 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.
  • a reaction initiator polymerization method or an ionizing radiation polymerization method can be used as the graft polymerization method for the polymerizable monomer.
  • the desired degree of polymerization can be obtained by appropriately controlling the reaction conditions.
  • ionizing radiation ultraviolet rays, electron beams, X-rays, braided rays, / 3 rays or gamma rays can be used.
  • 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 ⁇ -octylphosphonoxide and octadecane
  • Suitable 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.
  • 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.
  • 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 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.
  • 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.
  • 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 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.
  • 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.
  • 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. 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.
  • the present embodiment shows some examples of the present invention, and the present invention is not limited to the present embodiment.
  • the above-mentioned various ones can be used as the polymerizable monomer and the base material.
  • 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.
  • 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 / m, porosity 70%
  • the glycidyl methacrylate 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.
  • the GMA graft polymerized film was applied to octadecinoleamine (CHNH) at 80 ° C for a predetermined time.
  • CHNH octadecinoleamine
  • W, W, and W are the base film, GMA graft polymerized film, and octa, 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.
  • HDEHP bis (2-ethylhexyl) phosphate
  • W is the weight of the extraction reagent-carrying membrane.
  • 322 is the molecular weight of HDEHP.
  • 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 3 ⁇ 40.8 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.
  • an extraction reagent 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.
  • 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.
  • 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.
  • 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,
  • One of the functional groups having the function of supporting the extraction reagent is a hydrophobic group S represented by an alkyl chain.
  • 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.
  • 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.
  • 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.
  • 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 1 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.
  • GMA glycidyl methacrylate
  • 6AHA 6-aminohexanoic acid
  • Aliquat 336 An example carrying tri-n-octylmethylammonium chloride
  • 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.
  • W, W and W are the base film, GMA graft polymerized film, and 6AHA film, respectively.
  • 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).
  • W is the weight of the Aliquat 336 supported membrane
  • Mr is the molecular weight of Aliquat 336. Obtained
  • the resulting membrane is called Aliquat 336-supported membrane.
  • 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.
  • Example 3 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 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).
  • 6AHA 6-aminohexanoic acid
  • 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.
  • 6-Aminohexanoic acid concentration 6AHA / water / dioxane
  • 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.
  • FIG. 12 (b) shows the change in the conversion to the NH group.
  • the conversion of epoxy groups to C H NH groups is
  • 6AHA film has C
  • the membrane into which the HNH group has been introduced is called a 6AHA-CHNH membrane.
  • FIG. 13 shows the supported amount of Aliquat 336 with respect to the conversion of.
  • Aliquat 336 (x, y) membrane The membrane supporting Aliquat 336 is called Aliquat 336 (x, y) membrane.
  • 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.
  • the adsorption material of the present invention supports the extraction reagent Aliquat 336 and has good adsorption characteristics.
  • 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.
  • GMA glycidyl methacrylate
  • FIG. 15A shows a manufacturing route of the did-CHS film in this example.
  • W, W, W, and Mr are the weight of the base film and the weight of the GMA graft polymerized film, respectively.
  • 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.
  • 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.
  • a constant flow rate 10 (mL / h) through the TOPO-supported membrane from the inner surface to the outer surface of the membrane.
  • the Bi (m) solution was also permeated through the dioK: HS membrane, which did not support ⁇ . then
  • FIG 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 ⁇ P ⁇ .
  • the adsorption material of the present invention supports the extraction reagent , and has good adsorption characteristics.
  • 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.

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Abstract

Les résines chromatographiques d’extraction courantes, possédant des matériaux ayant à la fois les caractéristiques d’un réactif d’extraction utilisé dans l’extraction de solvants et ceux d’une résine d’échange d’ions utilisée dans l’échange d’ions, souffrent de l’inconvénient d’un lent transfert de ions de métal vers le réactif d’extraction supporté sur la résine et d’une faible utilisation du réactif d’extraction supporté sur celui-ci, et l’invention fournit un adsorbant portant un réactif d’extraction libéré de ces inconvénients. La présente invention porte sur un adsorbant pour ions de métal que l’on obtient par greffage d’un monomère polymérisable ayant la capacité de porter un réactif d'extraction à la surface d'un substrat et de fabriquer un réactif d'extraction appliqué sur le produit obtenu. Le groupe fonctionnel ayant la capacité de porter un réactif d'extraction peut être un groupe hydrophobe (comme un alkylamine, un alkyle, un alkylthiol, ou un époxy), un groupe hydrophile (comme un diol), ou une combinaison de ceux-ci.
PCT/JP2005/007639 2004-04-21 2005-04-21 Adsorbants portant des reactifs d’extraction et procede de fabrication de ceux-ci WO2005102512A1 (fr)

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Cited By (3)

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CN104941603A (zh) * 2015-05-11 2015-09-30 史清元 一种高效吸油离子交换树脂
CN113546610A (zh) * 2021-07-07 2021-10-26 北京科技大学 一种在硅基材料表面接枝二烷基次膦酸官能团的方法
WO2024125210A1 (fr) * 2022-12-16 2024-06-20 吉林大学 Procédé d'extraction d'ions minéraux à l'aide d'un matériau poreux inorganique chargé de liquide ionique

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JP4547327B2 (ja) * 2005-12-05 2010-09-22 株式会社日立ハイテクノロジーズ 分析方法
FR2896792B1 (fr) * 2006-01-27 2008-07-18 Millipore Corp Systeme et procede de purification d'eau
JP2008045906A (ja) * 2006-08-11 2008-02-28 Chiba Univ アフィニティビーズおよびその製造方法
JP5045916B2 (ja) * 2007-09-05 2012-10-10 株式会社イノアックコーポレーション 放射性核種捕捉材料、放射性核種捕捉用カートリッジ、製造方法及び分離方法
EP2915840A4 (fr) 2012-10-30 2016-08-10 Kuraray Co Particules poreuses d'un copolymère greffé, leur procédé de production et matière adsorbante les utilisant
JP6744538B2 (ja) * 2014-11-10 2020-08-19 国立研究開発法人量子科学技術研究開発機構 固体組成物及び固体組成物の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104941603A (zh) * 2015-05-11 2015-09-30 史清元 一种高效吸油离子交换树脂
CN113546610A (zh) * 2021-07-07 2021-10-26 北京科技大学 一种在硅基材料表面接枝二烷基次膦酸官能团的方法
CN113546610B (zh) * 2021-07-07 2022-04-22 北京科技大学 一种在硅基材料表面接枝二烷基次膦酸官能团的方法
WO2024125210A1 (fr) * 2022-12-16 2024-06-20 吉林大学 Procédé d'extraction d'ions minéraux à l'aide d'un matériau poreux inorganique chargé de liquide ionique

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