JPS5915323B2 - Method for producing alkali metal trap material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel alkali metal scavenger having an azacrown ether ring in its side chain.

Until now, polymers with an aza crown ether ring have been produced by condensation polymerization of an aza crown ether compound and a diacid chloride compound, polyaddition with a diisocyanate compound, thermosetting system with a diepoxide compound, or chloromethylated styrene polymer. A method based on a polymer reaction with 0 is known.

However, although polymers having an aza-crown ether ring obtained by these methods have no problem in exhibiting properties specific to an aza-crown ether ring, they generally have a drawback of poor mechanical strength5.

The present inventors improved the drawbacks of conventional polymers having aza-crown ether rings and developed a new method for producing aza-crown ether-containing polymers with excellent mechanical strength and alkali metal scavenging performance. As a result of intensive research, we first graft-polymerized a monomer with an epoxy group to a film-like or fibrous polyolefin.
Next, it was discovered that the object could be achieved by reacting an aza crown ether compound, and based on this knowledge, the present invention was completed.

That is, the present invention graft-polymerizes a vinyl monomer having an epoxy group or a vinyl monomer that does not react with at least one epoxy group onto a film-like or fibrous polyolefin, and then The present invention provides a method for producing an alkali metal scavenger, which is characterized by reacting a crown ether compound.

As the polyolefin used in the present invention, for example, polyethylene, polypropylene, etc. are used, and the shape of the polyolefin may be a film, a sheet, or a fiber.

It was completely unexpected that by the method of the present invention, an aza crown ether ring could be introduced into a polymer having no reactive groups, which was molded into a solid state. .

The vinyl monomer having an epoxy group used in the present invention is
There are no particular limitations as long as the monomer has an epoxy group and a vinyl group in its molecule. As such,
For example, glycidyl methacrylate ((the above reaction is
Generally, it is relatively slow at room temperature, and becomes extremely reactive when heated.

That is, it is stable in a processing bath and has properties that act effectively in curing, so it is suitable for practical use. There are no particular restrictions on the reaction solvent, but those that are highly reactive with epoxy groups are not good. Usually alcohols such as methanol and ethanol, N,N-dimethylformamide,
Acetone, tetrahydrofuran, etc. are used. The amount of the azacrown compound to be used is preferably slightly in excess of the epoxy groups in the graft polymer. If desired, equivalent or smaller amounts can be reacted.
The reaction temperature is suitably in the range of 55°C to 100°C. The thus obtained polymer having an azacrown ether ring is a suitable alkali metal scavenger.

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

Example 1 0.68741r polyethylene film, 60ml of tetrahydrofuran, and 10d of glycidyl methacrylate were placed in an ampoule, cooled and degassed repeatedly using liquid nitrogen, and sealed under a vacuum of 1 x 10-2 mmHt.

This ampoule was heated at 25℃, 0.18×106R/Hr, 2
γ-ray irradiation from CO6O was performed for an hour. The ampoule was opened and the film was taken out, subjected to sox-thread extraction using acetone, and then dried to obtain a grafted polyethylene film 1.22692f. The grafting rate was calculated from the weight increase to be 78.5%. This glycidyl methacrylate grafted polyethylene film 0.0246
0t1 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane with the following structure 1.031
, 10 d of methanol was placed in a test tube and reacted at 60° C. for 74 hours.

The weight of the reactant was 0.03100flN from nitrogen analysis:
It was 1.64%. Figure 1 shows the infrared absorption spectrum of the film. 910C from the IR spectrum of the film
The glycidyl group of M-1 disappears, absorption by 3450CM-1 hydroxyl group and tertiary amine, and 1125CM-1
The absorption of ether groups was observed. Example 2 0.99543y of polypropylene fibers, 20 ml of tetrahydrofuran, 5 ml of glycidyl methacrylate were placed in an ampoule, and the ampoule was repeatedly cooled and degassed using liquid nitrogen, and then sealed under a vacuum of 1 x 10-2 mmHf.

This ampoule was irradiated with gamma rays from CO6O at 25°C and 0.18 x 106 B/Hr for 5 hours. Open the ampoule, take out the fibers, perform socks extraction using acetone, dry and graft polypropylene fiber 3.0.
4270f was obtained. Based on the weight increase, the graft ratio was calculated to be 205.6%.
1,7,10,16-tetraoxa used in Example 1
1.03 t of 4,13-diazacyclooctadecane and 10 ml of methanol were placed in a test tube and reacted at 60°C for 74 hours.

The weight of the reactant was 0.87244f, which was determined by nitrogen analysis.
．． It was 55%. This fiber had the ability to adsorb alkali metals, such as sodium ions. That is, sodium picrate aqueous solution 1 x 10-4 mol/T2OrfLl
This fiber (0.10206f) was placed in a sample, and the decrease in the absorbance of the aqueous solution at 356 nm at 25°C was measured. The results are shown in Table 1. Example 3 The glycidyl methacrylate grafted polyethylene film used in Example 1 (
Grafting rate 78.5%) 0.02588t1 Glycidyl methacrylate grafted polypropylene fiber used in Example 2 (grafting rate 205.8%) 0.54200t
1 1,4,10-trioxer 7,1 with the following structure
3-diazacitalopentadecane 0.99% methanol,
5 ml of the mixture was placed in a test tube and reacted at 60°C for 72 hours.

The weight of the reactant is 0.03400 polyethylene film.
7 polypropylene fiber was 0.810657. Nitrogen analysis revealed that the polyethylene film was 2.41% and the polypropylene fiber was 3.61%. Polypropylene fibers adsorbed sodium ions. Graft fiber 0.10
029t to sodium picrate 1 x 10-4 mol/T
Table 2 shows the results of measuring the decrease in absorbance at 356 Nm when placed in 2Od.

The measurement method is the same as in Example 1. Example 4 Polypropylene fiber 2.41081t1 Tetrahydrofuran 6
0T1Le1 glycidyl methacrylate 10ml,. N
, N-Dimethylacrylamide (10ml) was placed in an ampoule, and cooling and degassing were repeated using liquid nitrogen.
It was sealed under a vacuum of -2 mmHt.

This ampoule was heated to 25℃, 0.15×106Vhr114
．． It was irradiated with gamma rays from CO6O for 1 hour. The ampoule was opened to obtain 4.74170f of grafted polypropylene fibers. The grafting rate was calculated from the weight increase and was 96.7%. According to N analysis, it was 3.465%. This co-grafted polypropylene fiber 0.61026t, 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane used in Example 1 0.70f1 ethanol 20m
1 was placed in an Erlenmeyer flask and reacted at 70°C for 50 hours. The weight of the reactant was 0.760f. N from N analysis
:4.24%.

[Brief explanation of the drawing]

Figure 1 shows polyethylene film A, glycidyl methacrylate grafted polyethylene film Bll, 7, l.
It is a graph showing the infrared absorption spectrum of O,l6-tetraoxa-4,13-diazacyclooctadecane-reacted glycidyl methacrylate grafted polyethylene film C.

Claims (1)

[Scope of Claims] 1. A method for producing an alkali metal scavenging material, which comprises graft polymerizing a vinyl monomer having an epoxy group to a film-like or fibrous polyolefin, and then reacting it with an azacrown ether compound. . 2. A film-like or fibrous polyolefin is graft-polymerized with a vinyl monomer having an epoxy group and at least one vinyl monomer that does not react with the epoxy group, and then reacted with an aza crown ether compound. A method for producing an alkali metal trapping material.