JPS6124588A - Polymerizable crown ether compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R<1> is H or CH3; R<2> is H or 1-5C alkyl; n is 1-5). USE:The compound has cation-complexing activity and high polymerizability, and gives a polymer having high mechanical strength and complexing activity. PREPARATION:The compound of formula II (e.g. ethylaminomethyl-15-crown-5, etc.) is made to react with preferably 1.0-1.5 times mol of the compound of formula III (e.g. acryloyl chloride) in water or an organic solvent (e.g. benzene) in the presence of an alkali such as triethylamine, preferably at 0-15 deg.C.

Description

[Detailed description of the invention] [Object of the invention] Production flI"Lt! One aspect of the present invention relates to a crown ether compound having polymerizability represented by the following general formula.

Crown ether compounds have the ability to form complexes with various cations and are beginning to be used in a wide range of fields such as organic synthesis, analytical chemistry, biochemistry, and pharmaceuticals, making them industrially interesting compounds.

Placement! υu1 Low-molecular crown ether compounds generally have relatively strong toxicity and high solubility in water and organic solvents, which limits their use, and requires considerable effort in industrial recovery, circulation, and use. There was a problem that it required

In order to solve these problems, polymerization of crown compounds has recently attracted attention and has been extensively studied. The polymer crown ethers known so far can be broadly classified into the following two types.

1) A polycondensation type crown polymer obtained by condensing two types of crown ethers having different functional groups that can be condensed with each other. 2) A vinyl polymerization type crown polymer obtained by polymerizing a crown ether having a vinyl group.

However, in the polycondensation type, the crown ring is immobilized in the polymer main chain, so the degree of freedom is reduced, and many of them have poor adsorption ability for metal ions. On the other hand, the vinyl polymerization type has a crown ring in the side chain of the polymer, so it has a greater degree of freedom.
It is also known that the selectivity of complex formation increases due to the cooperative effect of adjacent crown rings, and polymerization not only covers the drawbacks of low-molecular crowns but also makes the functions of crown ethers more prominent. We can also expect the possibility of it being realized.

Various vinyl-polymerized crown polymers have been researched based on this research, but conventional ones have steric hindrance and other problems because the raw material vinyl moamer is composed of a 7-benzocrown type with a crown ring attached to the aromatic ring. The polymerization of the vinyl groups does not proceed smoothly, and the resulting polymer has good complex-forming ability.) Its use is limited due to its weak mechanical strength and poor film-forming ability. (or the vinyl moamer itself) had problems such as extremely complicated synthesis.

The present inventors have solved the above problems and found that the polymerizable compound (monomer) itself, which is a raw material for a polymer, can be easily synthesized and that inhibits the polymerization reaction. As a result of extensive research in order to obtain a polymerizable crown ether compound that has no steric hindrance and the resulting polymer has excellent mechanical strength, the amine 7 group of aminomethyl crown ether was replaced with acrylic acid or methacrylic acid. The inventors discovered that a compound acylated with a residue can achieve the objective, and the present invention was completed.

1 Constitution of the Invention] That is, the crown ether compound of the present invention has the general formula % Formula % In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n is an integer from 1 to 5.

The lower alkyl group represented by R2 includes, for example, a linear methyl group, ethyl group, propyl group, butyl group, pentyl group, and a branched isopropyl group, isobutyl group, t-butyl group, etc. And from the viewpoint of extremely easy purification, a preferred example is one in which R1 is a hydrogen atom, R2 is an ethyl group, and n=2.3 in the above general formula.

The crown ether compound of the present invention is produced by adding aminomethyl crown ether to water or an organic solvent, as shown in the following formula.
It can be easily obtained by using acrylic acid chloride or methacrylic acid chloride in the presence of an alkali and the usual 5chotten-Baumann method. Ami/methyl crown ether, which is a raw material, can also be prepared using a known method (Japanese Unexamined Patent Publication No. 58-5
7377)).

The reaction is carried out at a low temperature of 0 to 50[deg.] C., preferably 0 to 15[deg.] C., and it is desirable to avoid polymerization by heating, especially when distilling off the solvent after the reaction is completed. The amount of acrylic acid chloride or methacrylic acid chloride used is suitably 1.0 to 1.5 times the amount of aminomethyl crown ether by mole.

[The crown ether compound of the present invention has high polymerizability because the steric hindrance around the vinyl group is alleviated compared to the vinyl monomer of conventional benzo crown ether.
The polymer can be easily obtained by conventional diyl polymerization methods such as radical polymerization. For example, a homopolymer of the compound of the present invention obtained by vinyl polymerization using AIBN as a polymerization initiator can yield a highly polymerized polymer having film-forming ability.

Furthermore, it can be easily copolymerized with 14 types of monomers such as ethylene, propylene, styrene, methyl acrylate, methyl methacrylate, and vinyl acetate, and has strong mechanical strength and excellent adsorption ability for metal ions. A copolymerized polymer is obtained.

Ju1 Wholesaler Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Ethylaminomethyl-15-crown-54,0QB (
i4mol), triethylamine (16,8mmol I
) and benzene 60III in a 100 ml three-tube flask, and add 1.57 g (16.8 mmol) of acrylic acid chloride to benzene (10
The solution was slowly added dropwise over 1 hour while stirring. After the addition was completed, the reaction was continued for another 10 hours while gradually returning the temperature to room temperature. After the reaction was completed, neutralization was performed using triethylamine (if not necessary) After that, the salt was filtered off and washed with a small amount of benzene.The solvent was distilled off from the filtrate under reduced pressure without applying heat, and silica gel chromatography was performed using hexane-acetone (85/15 v/v) as a developing solvent. Elute as,
Purification to obtain 3.41 g of colorless oil (yield 78%)
.

'It-NMR (CI) C1, ), δ; 1.15 (t,
3) 1), 3,08 4.07 (m, 23H), 5,5
3 5.75 (Kei, l1l), 6.20-6.87 (m
, 2H) MSh/c): 331 (M+), 276 (5), 219 (1B), 11
2 (42), 87 (100), 58 (49), 45 (3
1) IR(neat); am' 2920.2860.1645.1615.1450.
1120] し^(calcd, ); C+ al12.
Calculated value as NOa C; 57,99, )l; 8,82
, N; 4,23 Actual value C: 57,96, II; 8.9
3, N; 3,94 Examples 2 to 4 In Example 1, in place of the combination of ethylaminomethyl-15-crown-5 and acrylic acid chloride, Table 1
Three types of combinations shown below were synthesized and synthesized.

Table 1 Example 2 Ethylaminomethyl-18-crown-6 Acrylic acid chloride Example 3 Ethylaminomethyl-15-crown-5 Methacryl chloride Example 4 Ethylaminomethyl-18-crown-6 Methacrylic acid chloride reaction The process proceeds smoothly and the desired product is obtained in good yield (
70 to 80%), but care was taken not to apply heat when the target product was concentrated, such as during distillation of the solvent.

Table 2 shows the spectrum data and elemental analysis results of the polymerizable crown ether obtained.

Reference Example 1 1111 pm, Moamar (I) obtained in Example 1 was placed in an ampoule for LL sealing tube.
g, add 2.5 ml of benzene, and then add AI to this.
A solution of BNIB in benzene (0.5 ml) was added, the tube was replaced with nitrogen, the tube was sealed, and polymerization was carried out at 70° C. for 84 hours. After heating, the package was opened and poured into hexane with stirring, and the precipitated polymer was filtered off and dried under reduced pressure at 60° C. for 5 hours. As a result, 1.21 g of white solid polymer was obtained (yield: 8
1%).

Hereafter, the concentration of Moamer (1) was changed in the same manner, and
Copolymerizing Moamer (+) with styrene (II),
The results obtained are shown in Table 3.

As is clear from Table 3, the homopolymer is 80-90%
Both were obtained as white (or pale yellow) solids with a yield of . In IR, 162 due to the double bond of the monomer
The absorption band at 0 cm' disappeared, the signal of 'l(-NMH became broad, and the signal of onfin hydrogen was not observed. These polymers are soluble in methylene chloride, chloroform, etc. in addition to benzene. Styrene In the case of the copolymer with 'H-NMR, a small signal that is thought to be assigned to the phenyl hydrogen of the styrene monomer is seen, but this may be because the monomer is not completely removed.The molecular weight is determined by the vapor pressure equilibrium method. (Hitachi Model 115 Molecular Weight Measurement 811), the number average molecular weight of most polymers was about 35,000 to 40,000.

b The alkali cation extraction ability of the polymer (1) obtained with alkali cation a) was investigated according to the method of Pedersen and compared with model compound (11), and the results are shown in Table 4. In addition, the model compound (I[l) is ethylaminomethyl-
Example 1: 15-crown-5 and propionic acid chloride
It was synthesized in the same manner as above in the presence of triethylamine in a benzene solvent, and Table 5 shows its spectral data and elemental analysis results.

As is clear from Table 4, the extraction ability of cations with small ionic radii such as Li'' and Ng+ is higher than that of the model compound (II
There is almost no difference between I) and the polymer (I) of the present invention. On the other hand, for cations larger than K+, a large difference is observed between the two. This is due to the cooperative effect of adjacent crown rings, similar to the previously reported case of crown polymers, and 1 for large-sized cations.
: This is thought to be due to the formation of a 2-complex.

[Effects of the invention 1

Claims (1)

[Claims] A crown ether compound having polymerizability represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼. (In the formula, R^1 represents a hydrogen atom or a methyl group, R^2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 5.)