JPS6254127B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for immobilizing a hetero-macrocyclic compound on the surface of a porous inorganic solid. More specifically, it relates to a method for supporting and immobilizing a hetero macrocyclic compound on the surface of a porous inorganic solid such as silica gel, alumina, zeolite, etc. by graft polymerizing the hetero macrocyclic compound having a vinyl group on the surface of the solid using ionizing radiation.

Hetero-macrocyclic compounds selectively incorporate ions into the vacancies within their molecules, solubilize inorganic salts and alkali metals in organic solvents, and facilitate various organic chemical reactions at room temperature and pressure. It has many excellent properties that were previously unknown, such as catalytic activity. Therefore, in recent years, it has attracted attention from chemists around the world, and they are competing to develop various types of organic synthesis, capture, separation, and analysis of heavy metals, resolution of optical isomers, ion-selective electrodes, and applications of their physiological activities to medicine and biochemistry. We are conducting applied research in an extremely wide range of fields. However, for large-scale industrial applications in the chemical, metal, and nuclear industries, as well as the environment and life sciences, hetero-macrocyclic compounds themselves are expensive, and they cannot be used as catalysts for organic synthesis. It has several drawbacks, such as difficulty in recovering it, and its solubility, physiological effects, and toxicity have not been clarified.

In order to eliminate the above-mentioned problems, it would be extremely advantageous industrially to make the hetero macrocyclic compound into a polymer or to carry and immobilize a small amount of the hetero macrocyclic compound on an inexpensive solid surface to make it insoluble. In other words, it is convenient and advantageous in all kinds of applications such as trapping and separation of heavy metals, columns for optical resolution, recovery and regeneration when used as an organic synthesis catalyst, and becomes industrially practical.

From this point of view, methods for supporting solids have been developed, for example, by reacting and curing a cyclic polyether having an amino group as a functional group with an epoxy compound on the surface of a solid support, thereby creating a strong adhesive force on the surface of the support. An immobilization method for forming a thin film is known [JP-A No. 53-6284], and a method for solidifying the aromatic ring of a cyclic polyether having an aromatic ring by chlorosilylation and reacting with silica is known [JP-A No. 53-6284].
50−69090] are known.

All of these methods are unsatisfactory in that after the introduction of the functional group, a chemical reaction involving complicated steps follows again.

In order to overcome these drawbacks, the present inventors have long investigated the polymerizability of hetero-macrocyclic compounds with vinyl groups by ionizing radiation, with the aim of polymerizing or immobilizing hetero-macrocyclic compounds, and further investigated the polymerizability of hetero-macrocyclic compounds with vinyl groups by ionizing radiation. As a result of various studies on methods for supporting and immobilizing a hetero-macrocyclic compound that maintains ion uptake ability on a solid surface at a high rate, the present invention was achieved.

The solid-supported hetero macrocyclic compound of the present invention is produced by adsorbing an organic solvent solution of a vinyl group-containing hetero macrocyclic compound on the surface of a porous inorganic solid such as silica gel, alumina, or zeolite as a carrier, and then ionizing it. Obtained by irradiation with radiation. It is known that when a liquid vinyl monomer adsorbed on the surface of a carrier is subjected to radiation polymerization, a so-called graft polymer is produced which is not extracted by any solvent. Furthermore, in this case,
It is also known that a large amount of so-called homopolymers extracted by solvents are produced as by-products. This not only causes a significant decrease in monomer utilization efficiency, but also forms an essential means of increasing the reaction efficiency between the carrier surface and the monomer by forming a high monomer concentration near the carrier surface. , is considered inevitable. Therefore, conventionally, only a method of creating an adsorption state using a liquid vinyl monomer alone is known, and there is no compatible method.

The present invention unexpectedly goes beyond this common sense and achieves high monomer utilization efficiency at low cost by adsorbing a dilute solution of a hetero macrocyclic compound having a vinyl group.
The present invention provides a method for immobilizing a hetero-macrocyclic compound on the surface of a porous inorganic solid, which is characterized by easy operation.

The immobilized hetero macrocyclic compound of the present invention is generally produced by the following method. A hetero-macrocyclic compound having a vinyl group is dissolved in an organic solvent, and the solution is adsorbed onto the surface of a porous inorganic solid such as silica gel, alumina, or zeolite in vacuum or under reduced pressure, and then ionizing radiation is irradiated onto it. .
The porous inorganic carrier used at this time is heated to 100℃ to 300℃ in advance.
It is preferable to use a material that has been dried for about 2 hours to remove adsorbed water at a temperature range of .degree.

Although the vinyl monomer used in the present invention has not been manufactured or commercially available, there are several synthetic methods reported so far [S. Koplow, TE Hogen Esch, and J.
Smid, Macromolecules, 6 , 133 (1973)], as well as those that can be radically or ionicly polymerized by ionizing radiation can be applied.

In the present invention, the solvent for the vinyl monomer may be any ordinary organic solvent that dissolves 0.5 wt% or more of the hetero macrocyclic vinyl compound, but preferably benzene is stable against ionizing radiation and is expected to have a protective effect. , toluene, etc. are recommended. As a method for adsorbing a solution of a hetero-macrocyclic vinyl compound onto a porous inorganic carrier, it is desirable to vacuum-degas the carrier and the solution separately and adsorb the solution under vacuum. In this case, the amount of solution required usually varies depending on the bulk density of the carrier, but it is sufficient that the carrier is sufficiently immersed, and the amount of the hetero macrocyclic vinyl compound, which is the solute, is based on 100 parts by weight of the carrier. On the other hand, the solution concentration is used in an amount corresponding to 0.5 parts to 30 parts, preferably 0.5 parts to 5 parts. Using an excessive solution or a solution in which a hetero macrocyclic vinyl compound is dissolved at a high concentration leads to a decrease in grafting efficiency and causes wasteful consumption of the hetero macrocyclic vinyl compound.

In the present invention, after the adsorption state is created in this way, the solvent may be distilled off as much as possible without exceeding the solubility by further operations such as heating under vacuum, reduced pressure, or normal pressure. Furthermore, even if the solvent is completely distilled off, the immobilized hetero-macrocyclic compound of the present invention can be obtained by irradiating the hetero-macrocyclic vinyl compound with ionizing radiation below its melting point; The operating steps are redundant and can be easily selected and implemented by experts in the field as needed as a means of controlling monomer concentration, etc.

It is preferable to perform radiation irradiation in a vacuum system with the solution adsorbed, and the ionizing radiation used at this time is γ.
Any radiation that can ionize substances, such as X-rays, β-rays, X-rays, and electron beams, can be used. The irradiation dose is preferably 3×10 ⁶ R or less at which a conversion rate close to 100% can be obtained; a larger dose may destroy the cyclic bonds of the macrocyclic compound. The hetero-macrocyclic compound thus obtained through radiation polymerization is made into a very small amount of polymer (homopolymer) that is not bonded to a carrier using an appropriate solvent.
When extracted and removed, an immobilized hetero macrocyclic compound (graft polymer) having a structure chemically bonded to a carrier is obtained. There is no longer any need to worry about the material being lost due to phenomena such as elution or peeling off in any solvent. This is a major feature of the immobilized hetero macrocyclic compound of the present invention. Furthermore, the immobilized hetero-macrocyclic compound of the present invention is characterized in that the amount of the hetero-macrocyclic vinyl compound used is extremely small relative to the carrier, and about 100% of it is consumed for immobilization, so that a small amount of hetero-macrocyclic vinyl compound can be used. The result is that the macrocyclic vinyl compound is effectively converted into an immobilized hetero-macrocyclic compound with a large specific surface area without losing its activity, which is extremely economical and easy to industrialize.

Next, in order to explain the present invention more clearly, examples will be shown.

Example 1 Silica gel dried in air at 200°C for 3 hours (specific surface area 420 m ² /g, size 0.2-0.5 mm) 3.9404
(g) was kept under vacuum at 10 ^-4 mmHg while 4'-vinylbenzo-15-crown-5 crude (purity approx. 70
%) 1.3693 (g) dissolved in benzene, concentration 19.1
% solution was degassed under vacuum, and the solution was poured onto silica gel for adsorption in a vacuum system. The weight of the monomer solution used at this time was 1.8 times the weight of the silica gel, and the state was such that all of the silica gel was immersed in the solution, with a liquid phase slightly visible in the upper layer. γ from ⁶⁰ Co at room temperature in a vacuum system
After irradiation for 2 hours at a dose rate of 1×10 ⁶ R/hr, the system was opened and the silica gel was removed and subsequently extracted with benzene using a Soxhlet extractor for 24 hours. After air-drying this, the silica gel that was further vacuum-dried at 50°C and weighed was 4.8008 (g), and the silica gel contained 0.8604 (g) of benzo-15-
Crown-5 was immobilized, and the weight increase rate (immobilization rate) relative to silica gel was 21.8%. The dry weight of the homopolymer extracted with benzene was 0.0207 (g), and 97.7% of the polymerized 4'-vinylbenzo-15 crown-5 was consumed for immobilization.

Example 2 Purified 4'-vinylbenzo-15-crown-5
0.0987 (g) (approx. 100% purity) of 3.1% benzene solution and dried 1.9711 (g) of silica gel
It was treated and adsorbed in the same manner as in Example 1. The weight of the monomer solution used at this time was 1.6 times the weight of the silica gel. The weight of the silica gel carrier obtained by irradiation, extraction, and drying under the same conditions as Example 1 was 2.0423 (g), and 0.0712 (g) of vinylbenzo-15-crown-5 was grafted onto the silica gel. Fixed. This is 3.6% in terms of weight increase rate (immobilization rate). In addition, the dry weight of the homopolymer extracted with benzene is 0.0025 (g), and the weight of the polymerized monomer is 0.0025 (g).
96.6% was consumed for immobilization.

Test Example 1 The metal ion uptake ability of the hetero macrocyclic compound immobilized on the inorganic carrier obtained in Examples 1 and 2 and its separation and selection characteristics were tested.

Test method: A solution of 4.0×10 ^-5 mol/picric acid dissolved in 0.1N aqueous alkali metal hydroxide solution.
Add 0.5 (g) of the immobilized hetero-macrocyclic compound to 25 ml, stir in a thermostatic water bath at 25°C for 4 hours, and then filter the solution. Measure the absorbance (UV, 357 nm) of the liquid and calculate the amount of cation taken up. did.

From the results, as shown in FIG. 1, it was demonstrated that the immobilized hetero-macrocyclic compound of the present invention is a carrier that clearly retains excellent metal ion trapping ability and its separation and selection function. In Figure 1, the numbers on the horizontal axis represent the size of the alkali metal ion in diameter (Å).
The number on the vertical axis indicates the percentage (%) at which the immobilized hetero macrocyclic compound of the present invention captures dissolved cations. In addition, the curves connected by circles and marks in the figure represent the immobilized hetero macrocyclic compounds of Example 1 and Example 2, respectively.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the size of alkali metal ions captured by the immobilized hetero macrocyclic compound of the present invention and the capture rate of dissolved cations.

Claims (1)

[Claims] 1. An organic solvent solution containing 0.5-30 parts by weight of 4'-vinylbenzo-15-cran-5, which is a hetero macrocyclic compound having a vinyl group, per 100 parts by weight of a porous inorganic carrier. A method of immobilizing a hetero macrocyclic compound on a porous inorganic carrier by irradiating the compound with ionizing radiation while the compound is adsorbed on the inorganic carrier. 2. The method for immobilizing a hetero macrocyclic compound on a porous carrier according to claim 1, wherein the porous inorganic carrier is silica gel.