JPS5823137B2 - Metal ion scavenger - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a metal ion scavenger made of a novel three-dimensional polyether.

In general, crown ethers have many properties, such as selective ion uptake due to the vacancies in their molecules, solubilization of inorganic salts and alkali metals in organic solvents, and catalysis of various organic chemical reactions at room temperature and pressure. It is known to have unique properties, and is used as catalysts for the production of various organic compounds, resolving agents for optical isomers, scavengers for heavy metals, analytical adsorbents, ion-selective electrodes, as well as for pharmaceuticals and agricultural chemicals. It is applied in an extremely wide range of fields.

However, conventional low-molecular-weight crown ethers are soluble in water and other solvents, so their applications are inevitably limited.

In order to improve these drawbacks of low-molecular-weight crown ethers, research has been conducted to create insoluble materials by incorporating crown ether structures into polymers, and as a result, crown ethers with functional groups such as amine groups were formed. Later, a method of polymerizing using this functional group was proposed, but
This method is complicated and cannot be said to be industrially practical.

The present inventors have conducted intensive research to obtain a material with the same function as crown ether and an insoluble polymer structure through simple operations, and as a result, they have succeeded in polymerizing a divinyl compound with polyether residues. By forming a cross-linked and cyclized structure, an insoluble polymer compound having a large number of pores composed of polyether networks and rings and capable of trapping metal ions in these pores is produced. They discovered scales and came up with the present invention.

That is, the present invention provides a metal ion scavenger comprising a three-dimensional polymer of a divinyl ether compound represented by the general formula n is an integer of 1 to 4.

This metal ion scavenger is prepared by adding one type or a mixture of two or more divinyl ether compounds represented by the general formula (I) to 0°C or more in the presence of a cationic polymerization initiator without a solvent or in a solvent. It is produced by stirring at -100°C, preferably -20°C to -178°C.

As a solvent in this case, a solvent commonly used in ordinary cationic polymerization, such as methylene dichloride, ethylene dichloride, carbon tetrachloride, toluene, nitromethane, etc., is used.

Further, as the cationic polymerization initiator, etherified boron trifluoride, tin chloride, aluminum chloride, aluminum sulfate/sulfuric acid/aqueous complex salt, iodine, etc. are used.

This polymerization initiator is 0.0% relative to the divinyl ether compound.
It is added in an amount of 0.01 to 10% by weight, preferably 0.5 to 5% by weight, and it may be added at once or in several portions.

After the polymerization is completed, a small amount of a base such as an amine is added to the reaction mixture to inactivate the polymerization initiator, and the gel-like three-dimensional polymer containing the solvent is crushed and washed with an appropriate organic solvent. Either dry as is, or perform further extraction with an organic solvent such as a benzene-ethanol mixture and then dry.

The obtained dried product is ground into particles of an appropriate size.

In the three-dimensional polymer obtained in this way, the size of the pores formed by polyether residues is smaller than that of the conventional method in which a crown ether derivative with the same pore size is bonded to a polymer substrate in advance. Although it is not always constant, there is no particular problem in using it, for example, to selectively separate alkali metal ions from an aqueous solution containing many types of mixed metal ions, or to use it as a phase transfer catalyst in organic chemical reactions.

The metal ion scavenger of the present invention has the ability to capture metal ions when brought into contact with them.

Therefore, the inorganic salt in the aqueous solution can be extracted by adding a powdered metal ion scavenger to an aqueous solution of the inorganic salt and stirring it, or by passing the aqueous solution through a column filled with a powdered metal ion scavenger.

Further, in a bimolecular reaction such as a reaction between alkyl bromide and potassium iodide or a reaction between alkyl bromide and potassium cyanide, the present invention can be used when reacting between different phases with each reactant as a discriminating phase. Metal ion scavengers have the effect of significantly accelerating the reaction.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Diethylene glycol divinyl ether 1 purified by distillation
Dissolve 0 g in 80 ml of methylene chloride, cool the container in a dry ice chloride bath, and add 0.1 T of boron trifluoride ether (hereinafter abbreviated as BTE) without stirring.
Polymerization was carried out for 1 hour by adding Ll, followed by an additional 0.1
When I added ml of BTE and continued stirring, about 20 ml of BTE was added and stirred continuously.
It gelled after minutes.

10 TL of ethanol containing a small amount of diethylamine was added, and the gel was finely ground using a spatula, transferred to a mortar, and ground.

This was washed with a mixture of ethanol and n-hexane, then with ether, extracted with a benzene-ethanol mixture for 12 hours, and then dried under reduced pressure.

Yield 10. O,! 11 (100 scary). 10 pieces of this dried material
Grind into a powder of 0 to 200 meshes, and 500,772
@0.01 mol/7 hydroxide MeOH (Me
-3 types of Li, Na or K) and picric acid 6.85
It was added to 25 TL of an aqueous solution containing 10 mol,/7 (becomes an alkali salt) and stirred for 5 hours, and then the change in the picrate concentration of the aqueous solution before and after addition of the powder was determined spectrally.

As a result, the amount of alkali metal captured by the polymer is Li+2
1.2x10-7 mol/, 9, Na” 19.
7 x 10'mol/, 9°K+17. IX
10-7mol/? Met.

Example 2 Under the polymerization conditions in Example 1, the amount of methylene chloride was 10 WLl, and the BTE was 0.1 at the same temperature.
When ml was added, polymerization occurred vigorously and was completed within 30 seconds.

Powder obtained by performing the same treatment as in Example 1 (yield 100%)
) as a result of measuring the alkali metal ion trapping ability of
L i +14.7X10”mol/, 9, Na
+14. OX 10-7mol/g, K+11,3
X 10-7 mol/, 9.

Example 3 Polymerization, post-treatment, and powdering (yield io
As a result of measuring the alkali metal ion trapping ability of the polymer under the same conditions, L i +23
．． I XIO-7mol/&, Na +17.3 x
10”mol/, ?, +15.3X 10-7m
It was ol/jJ.

Example 4 1.2-di(2-vinyloxyethoxy)benzene was produced by the following method.

i.e. catechol 62.9 and caustic soda 44.9
was dissolved in 1500 ml of n-butanol under heating reflux,
After adding dropwise 120 g of 2-rolethyl vinyl ether to this, the mixture was stirred for 14 hours and reflux was continued.

n-Butanol was distilled off, the residue was dissolved in chloroform, insoluble matter was removed, and the solution F was washed several times with a 3% caustic soda aqueous solution and water, and then dried by adding anhydrous sodium carbonate.

The solvent was removed and the residue was distilled under reduced pressure (bp, 128~b White crystals (mp, 42.5-44.5°C) were obtained.

Yield 43.04g (30.6%).

Elemental analysis value Calculated value C67, 18%, H7, 25%
Actual value 066.87%, H7,41% IR (KBr, cm-Re 1630,950,830 (
vinyl); 1600.1520.740 (1,2-substituted benzene); 1200 (aromatic ether); 1140 (aliphatic ether) NMR (CDC13, τ) 2.60-2.90 (4
H, benzene); 3.00-3.42 (2H, vinyl); 5.40-5.95 (12H, vinyl and
CH2-) The monomer thus obtained was polymerized under exactly the same polymerization conditions as in Example 1, and then post-treated and powdered (yield: 100
%), the alkali metal ion trapping ability was measured under the same conditions, and the results showed that L i +2
．． 7 x 10-7 mol/&, Na+3, 5 x 1
+4 to 0-7 mol/L'. OX10=7mol
/fl.

Reference Example Using the polymer powder obtained in Example 1, the effect of promoting the following reaction was investigated.

n 04 H9B r (organic phase) 10 NaI (aqueous phase) -
n-04H,I (organic phase) + NaBr (aqueous phase) 7,88
25 m of mol/13 sodium iodide aqueous solution
1 and 2.56 mol/13 of a benzene solution of n-butyl bromide was placed in a container, and a polymer powder corresponding to 1/10 unit mole of n-butyl bromide was added thereto, and a reflux condenser was attached to the container for 6 hours. The kneaded mixture was cooled and the residual n-butyl bromide concentration in the base was determined.

As a result, in the reaction without adding polymer, the reaction rate was 26.
2%, but that of the reaction with the addition of polymer was 76.
At 2%, a promoting effect of about 3 times was observed.

Claims (1)

[Scope of Claims] 1 A metal ion scavenger comprising a three-dimensional polymer of a divinyl ether compound represented by the general formula n is an integer of 1 to 4. 2. The metal ion scavenger according to claim 1, wherein the three-dimensional polymer is a homopolymer of one type of divinyl ether compound. 3. The metal ion scavenger according to claim 1, wherein the three-dimensional polymer is a copolymer of two or more divinyl ether compounds.