JPH076963B2 - Packing material for liquid chromatography - Google Patents

Description

TECHNICAL FIELD The present invention relates to a packing material for liquid chromatography for collecting, concentrating or separating metal ions.

BACKGROUND ART A chelate resin is known as a functional polymer having an ability to collect, concentrate, and separate a specific metal ion from a solution containing a metal ion. However, the conventional chelate resin is a nitrogen having a high coordination ability. Since most of them support a coordination group containing an atom or an ionic atom on a polymer, the ability to collect metal ions is generally high, but it has been pointed out that the selectivity is not always good (Hojo Shousei) , "Chelate resin / ion exchange resin", 1976, Kodansha; Coord. Chem. Rev. 59, 1-139.
(1984)). In addition, the conventional one takes a long time to adsorb metal ions (Toshishige Suzuki, Toshiro Yokoyama, "Collecting and Separation of Metal Ions by Chelating Resins", Science Area, 3
7,74-84 (1983)). On the other hand, a resin carrying a coordination group containing only oxygen atom as a coordination atom generally does not have a high coordination ability, but it is possible to express excellent selectivity because a coordination group in which an oxygen atom is macrocyclic is formed. In the case of (F.
Vogtle, “Host Guest Complex Chemistry,” Vol.I, 43-1
06 (1981), Springer-verlag; RMIzatt, JJChristen
sen) Toshiyuki Shono, Shozo Yanagida, Keiichi Kimura, co-translated "Science of Crown Neetel and Cryptand", 217-326 (1979).
Chemistry coterie). The present inventors have also studied the adsorption behavior of metal ions by synthesizing a resin carrying a 2-hydroxyacetophenone type coordination group containing only oxygen atoms as coordination atoms. As a result, high selectivity was exhibited for Cu (II) and Pd (II), and these metal ions were adsorbed very quickly, but the uniformity and adsorption amount of the resin were not sufficient.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention develops a high-performance 2-hydroxyacetophenone type chelate resin that is rapid, highly selective, and has high uniformity and adsorption amount, and uses the resin as a packing material for liquid chromatography. is there.

Here, the 2-hydroxyacetophenone type chelate resin is a resin having 2-hydroxyacetophenone as a chelate coordination group, and is 4-vinylbenzyloxy-2-hydroxyacetophenone. The resin obtained by copolymerizing the metal complex of (1) with various polymerization agents and various crosslinking agents, respectively.

Means for Solving the Problems The inventors of the present invention have earnestly studied to obtain a high-performance 2-hydroxyacetophenone type resin having rapid and high selectivity and high uniformity and adsorption ability. When synthesizing a resin, we tried a polymer synthesis method using a metal ion as a template (template synthesis method). As a result, the uniformity was improved and the adsorption time of the metal ion was significantly shortened. It was found that the spread of pH dependence can be reduced and that the metal ion trapping ability (adsorption ability) can be improved. Then, it was reached that Pd (II), Cu (II) and Ga (III) can be collected, concentrated and separated by using the chelate resin obtained by such a method as a packing material for liquid chromatography.

The 2-hydroxyacetophenone type chelate resin (non-template resin) and the chelate resin (template resin) obtained by the template method were synthesized by the scheme shown in FIG. 4 when synthesizing
-Vinylbenzyloxy-2-hydroxy-acetophenone (abbreviation MVS) was synthesized by reacting 2,4-dihydroxyacetophenone and P-chloromethylstyrene (abbreviation P-CMS) in ethanol in the presence of sodium hydroxide (Y .Fujii, K.Kikuchi, K.Matutani, K.Ota, M.Adachi, M.Sy
ouji, I.Haneishi, and Y.Kuwana, Chem.Lett., 1984,1487
−1490) .MVS Ni (II) and Al (III) complexes were synthesized using the corresponding synthetic method of salicylaldehyde complex.
Acrylamide (abbreviation AM) was used as a copolymerizing agent. In addition, methylenediacrylamide (abbreviation) is used as a cross-linking agent.
MDAA) was used. Tetrahydrofuran (abbreviation as solvent)
THF) and 2,2′-azobisisobutyronitrile (AIBN abbreviation) as a polymerization initiator, MVS, AM and MDAA
(Or its metal complex) was reacted at a molar ratio of 1: 5: 0.15 to synthesize a resin. For the resinized complex,
The resins were used after being treated with 6N hydrochloric acid to dissociate the metal ions. The resin was a white powder and was used by pulverizing it into 100-300 mesh. In addition, the resin using Ni (II) complex as the template was 1: 2 and the resin using Al (III) complex was the template.
Abbreviated as 1: 3 mold resin.

The composition of the resin is determined by elemental analysis (C, H, N) and MVS: A
The M: MDAA molar ratio was found to be 1: 5: 0.15 for all resins. In addition, divalent metal ions (Pd (II), Cu (II), Co
(II), Ni (II), Zn (II)) and the complexing ratio of the coordination groups on these resins are determined by the distribution coefficient of metal ion to the resin and PH.
It was found to be 1: 2 when determined from the blot of.

Table 1 shows the results of measuring the saturated adsorption amount of the above resin in the batch method using Cu (III) and the swelling degree of each resin.

As shown in the above table, the template resin has a metal ion saturated adsorption amount improved by about 10% as compared with the non-template resin. Also, the degree of swelling is 12 to 19% higher for the mold resin. This improvement in adsorptivity is due to the "effect of arranging the coordinating group at a position convenient for adsorbing metal ions" brought about by template synthesis.

FIG. 2 shows the PH dependence on the adsorption of various divalent metal ions of the above resins in the batch method.

In addition to the divalent metal ions shown in Fig. 2, Pd (II) and Cd (I
The adsorption of I) was also tested, but those metal ions were not adsorbed at all below pH 6. From these results, it was confirmed that the pH of the chelate resin was Pd (II) as a divalent metal ion at pH 6 or lower.
And Cu (II) were selectively adsorbed. Also, the difference in the adsorbed PH between Pd (II) and Cu (II) is 2
With the above, the chelate resin can be adjusted by adjusting the pH even in the batch method.
It was found that pd (II) and Cu (II) can be completely separated.

Figure 3 shows the adsorption of Ga (III) on the above resin by the batch method.
The H dependence is illustrated. In addition, AI (III) and In (III) were also tested, but those ions did not adsorb to the chelate resin at pH 5 or lower. Therefore, the chelate resin exhibits selectivity for Ga (III) as a trivalent metal ion. Ga (III) adsorption pH of the chelate resin shifts to the acidic side in the order of non-template resin <1: 2 template resin <1: 3 template resin,
It was found that the adsorption pH range was sharpened by template synthesis. The sharpening associated with the shift to the acidic side plays an important role in avoiding the precipitation of gallium (III) hydroxide.

FIG. 4 shows the measurement result of the metal ion adsorption time of the chelate resin in the batch method. The adsorption time was about 5 minutes with the template resin and 20 minutes with the non-template resin for both the Pd (II) and Cu (II) ions studied. The reason why the adsorption time of the template resin is reduced by 4 times compared with the non-template resin is that the time for rearrangement of metal ions found in the non-template resin can be shortened by "the effect of the position of the coordinating group by template synthesis" To be It was found that the adsorption time of the chelate resin is remarkably improved as compared with the conventional chelate resin which requires several hours or more.

Examples Examples will be described below.

Under the experimental conditions shown in FIG. 5, a metal ion adsorption experiment was performed by liquid chromatography using a template resin and a non-template resin as columns. As a result, as shown in FIG. 5, the amount of Cu (II) retained in the template resin was about 20% higher than that in the non-template resin. In addition, Pd performed under the same conditions
In the case of (II), it was about 50% higher. Furthermore, the flow rate of the solution containing metal ions could be set to 10 ml per hour.

Fig. 6 shows the experimental results of column separation of Cu (II) and Zn (II) using 1: 2 template resin as a packing material for solution chromatography. Since Zn (II) is not adsorbed, the retention capacity in the column is small and it flows out within a short time, but since Cu (II) is adsorbed, the retention capacity is large and the time until the outflow of Cu (II) is large.
We show that Zn (II) is different from Zn (II) and that Cu (II) and Zn (II) can be completely separated within the capacity of Cu (II).

Fig. 7 shows the results of elution of Cu (II) adsorbed on the resin with 0.001N hydrochloric acid and Pd (II) with 1N hydrochloric acid. It was found that the separation of both metal ions was complete, that they could be eluted within a short time, and that there was no tailing.

EFFECTS OF THE INVENTION The packing material for liquid chromatography according to the present invention is mainly composed of a 2-hydroxyacetophenone type chelate resin obtained by template synthesis, whereby Pd (II), Cu
(II) and Ga (III) ions can be adsorbed / concentrated / separated with high selectivity, quickly and with high collection ability. In the present invention, 2 obtained by template synthesis
The -hydroxyacetophenone type chelate resin can be used not only as a packing material for chromatography but also as an analytical reagent such as a masking agent, if necessary.

[Brief description of drawings]

FIG. 1 is an explanatory view of the method for producing the chelate resin, and FIGS. 2 to 7 are graphs showing the experimental results of the present invention.

Claims (1)

[Claims] 1. A packing material for liquid chromatography for collecting, concentrating or separating metal ions, comprising a 2-hydroxyacetophenone type chelate resin obtained by template synthesis.