JPS5910723B2 - Method for producing macrocyclic hexamines containing polystyrene - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing macrocyclic hexaamines containing polystyrene, and more specifically, polystyrene is introduced into specific macrocyclic diamidetetraamines that are effective as adsorbents for heavy metal ions, and further reduction is performed. The present invention relates to a method for producing water-insoluble macrocyclic hexamines by treatment.

Heavy metal ion adsorbents conventionally used to remove heavy metal ions such as copper, nickel, and mercury contained in wastewater include activated carbon, diatomaceous earth, ion exchange resins, and chelate resins. However, among these, activated carbon, diatomaceous earth, and ion exchange resins have a disadvantage in that they have poor selectivity toward heavy metal ions, and chelate resins have particularly poor selectivity among heavy metal ions.
The present inventors have discovered that certain new macrocyclic hexamines have extremely excellent selective adsorption performance for heavy metal ions. The present inventors further conducted research to make these macrocyclic hexamines insoluble in water, thereby making them more useful compounds, and finally completed the present invention. That is, the present invention involves reacting a macrocyclic diamidetetraamine represented by the formula o□o C) (N''...(1) with functional group-containing polystyrene in a polar solvent, and then reacting the resulting product with The present invention provides a method for producing macrocyclic hexamines containing polystyrene, which is characterized by being reduced.

The macrocyclic diamidetetraamines represented by formula (I) used as raw materials in the method of the present invention are 18-N6-
diamide (correctly, 2,6-dioxo-1,4,7,
10,13,16-hexaaza-cyclooctadecane)
The size of the ring is 18, of which the number of nitrogen atoms is 6.

The reason why the number of ring members is set to 18 is that the size is suitable for trapping heavy metal ions inside the ring, and the reason why the number of nitrogen atoms that make up the ring is set to 6 is that the X-rays of the uranyl complex This is because diffraction shows a structure in which a uranium atom is placed at the center of six ligands, and it is considered to be stable as a complex. In the method of the present invention, the macrocyclic diamidetetraamines described above are first reacted with polystyrene containing a functional group.

The polystyrene used here is not particularly limited in terms of degree of polymerization, etc., as long as it is insoluble in water. Moreover, this polystyrene includes not only a styrene homopolymer but also a styrene-divinylbenzene copolymer and the like. Furthermore, the functional groups bonded to polystyrene include -CH, Cl, -Cl, -Br, -CO2H, -C
O2R. Examples include -SO, R (R represents an alkyl group), and chloromethyl group (-CH2Cj) is particularly preferred. The reaction of polystyrene containing a functional group with the above-mentioned macrocyclic diamidetetraamines may be carried out by stirring in a polar solvent such as chloroform under normal pressure at room temperature to elevated temperature for 1 to 3 days.

In the method of the present invention, the product obtained by the above reaction (
This is mainly a macrocyclic diamidetetraamine of formula (1) into which polystyrene has been introduced, that is, N-polystyryl-18-N6-diamide. ) is further reduced using a reducing agent or the like to produce the target large cyclic hexaamines having polystyrene. The large cyclic hexamines into which polystyrene has been introduced, obtained by this method, are determined by the ratio of the large cyclic diamidetetraamines represented by formula (1) to be subjected to the reaction and polystyrene, as well as the functionalities bonded to the polystyrene. Although it varies depending on the ratio of groups, for example, when polystyrene having chloromethyl groups (CH, Cl) as functional groups is used, the general formula [wherein R1 to R6 are hydrogen atoms or (where (
PS) indicates polystyrene.

). However, this excludes the case where all of R and ~R6 are hydrogen atoms. ] is obtained. In the compound of the general formula (), even a compound in which there is no substituent group in which all of R1 to R1 are hydrogen atoms has a certain degree of selective trapping property for heavy metal ions; The polystyrene-incorporated macrocyclic hexamines thus obtained have even better selective trapping properties for heavy metal ions, and also have high selectivity among heavy metal ions. Moreover, the capture rate of heavy metal ions is extremely high, and the capture and desorption of heavy metal ions is extremely easy.
Furthermore, since a polymer is introduced, it is insoluble in water, and its utility value is particularly great as a heavy metal ion adsorbent for seawater and the like. As is clear from the above description, the polystyrene-containing hexamines obtained by the method of the present invention are completely new compounds that exhibit excellent performance as heavy metal ion adsorbents.

In particular, it is significantly superior to conventional adsorbents in terms of selective adsorption, capture or desorption rate for heavy metal ions, and also has the property of very high heavy metal ion capture rate under seawater conditions (pH around 8.2). Therefore, macrocyclic hexamines containing polystyrene obtained by the method of the present invention can be suitably used for wastewater treatment, metal refining, concentration, etc. Next, the present invention will be explained in more detail using reference examples, synthesis examples, and application examples. Reference example 18-N6-diamide (2,6-dioxo-1,4,7
, 10,13,16-hexaaza-cyclooctadecane) iminodiacetic acid diethyl ester 18.91 (0
．． 1 mol) and tetraethylenepentaamine 1869f1
(0.1 mol) was dissolved in ethanol 111 and heated to reflux with stirring for 5 days.

Ethanol was distilled off from the reaction solution under reduced pressure, and the residue was diluted with benzene 1
00w11 was heated and extracted three times, and after cooling, benzene was distilled off under reduced pressure, and the precipitated crystals were recrystallized from benzene again to obtain colorless crystals 4.01 (yield: 15%). The analysis results of this crystal were as follows. 1 Melting point 130-132 C 2 element analysis value % Cl, H26O2N6 3 Mass spectrum peak m/E286 (M+) 243 (M+-CONH) 4 Nuclear magnetic resonance spectrum (deuterium chloroform solvent, TMS
Standard) 5 Infrared absorption spectrum (KBr tablet method) 337
001n-1 (νNH), 1640 (νCOO). 1
The crystal obtained from the result of 550 (ν00NH) or more is 18-N6-diamide (2,6-dioxo-1,4,7,10,13,16-hexaaza-cyclooctadecane) represented by the formula. I understand.

Synthesis example N-polystyryl-18-N6 (p-[1-(1,4,
Synthesis of 7,10,13,16-hexaaza-cyclooctadecyl)alkyl (copolymer of styrene and styrene) 1 Synthesis of chloromethyl polystyrene Purified in a round bottom flask equipped with a stirring device Polymerization degree 160
0-1800 polystyrene 20f! , add chloromethyl methyl ether 124TfL1 (1.54 mol),
Stir to dissolve at room temperature.

Anhydrous zinc chloride powder 3.14f1 (0.023ml) was added and stirred at room temperature (200C) for 10 hours. Under reduced pressure 1
Most of the excess chloromethyl methyl ether was distilled off from the reaction mixture at 0°C. Chloroform 150Tr on the residue
After adding L1 and stirring, insoluble matters were removed by filtration. Add the bottom liquid to 300 d of methanol, filter out the precipitate, and add 4
After drying under reduced pressure at 0° C. for 48 hours, chloromethyl polystyrene 159 was obtained. As a result of dissolving the obtained chloromethyl polystyrene in deuterated chloroform and measuring NMR,
The chloromethylation rate of phenyl rings in the raw material polystyrene was 60%. 2N-polystyryl-18-N6
- 3.951 (0.02 mol) of chloromethyl polystyrene synthesized in Diamide Synthesis 1 was added to 100 d of chloroform.
18-N6 dissolved in 50ml of chloroform
-Diamide 5.7f! (0.02 mono(h)) was added and reacted at room temperature for 48 hours with stirring.

After removing the precipitated polymer and washing it with 1N hydrochloric acid aqueous solution,
Subsequently, the resin was washed successively with distilled water, 1% potassium hydroxide aqueous solution, distilled water, ethanol, chloroform, and acetone, and dried under reduced pressure to obtain white resin 6.09. The analysis results are shown below. 0 elemental analysis value (%) C2lH34O2N6Ol8-
N6-diamide (mmol)/polystyrene (9) = 1
．． 300 Conversion rate (polystyrene immobilization rate) = 48% 0 Infrared absorption spectrum (KBr tablet method) 3400α-1
(νNH), 2920, 2820 (ν0H) 1660(
νoE0), 1540(ν00NH), 1460(δC
r) Reducing 3N-polystyryl-18-N6 diamide with N-
Grind polystyryl-18-N6-diamide in a mortar,
This powder 69 was added to a large excess of a THF solution of diporan (0.4 mol/', 200 d) while cooling little by little, stirred at room temperature for 5 hours, and then heated for an additional 5 hours.

The polymer was taken out, added to 200 d of 6N hydrochloric acid, and stirred for 10 hours while heating. Take the polymer again,
After washing with water, it was added to 200 d of a 1% aqueous potassium hydroxide solution and a neutralization reaction was carried out at room temperature for 1 hour.

Subsequently, the product was washed with distilled water, chloroform, and methanol acetone in this order, and then dried under reduced pressure to obtain a white resin 5.59.

O elemental analysis value (%) C2, H, 8N6 Ol8-N6 (m monoly/polystyrene●) = 1.3
00 conversion rate (polystyrene immobilization rate) = 47% O infrared absorption spectrum (KBr tablet method) 3350CWL-1 (
νNH), 2920.2820(ν0H), 1640(
δNH), 1460(δ0H)O Solubility Similar to N-polystyryl-18-N6-diamide, insoluble in organic solvents, mineral acids, and aqueous alkaline solutions.

The crystals obtained from the above results have the following structure: N-polystyryl-18-N6 (p[1-
It was found to be a copolymer of (1,4,7,10,13,16-hequinaazalcyclooctadecyl)alkyl]styreso and styrene.

Example of application (metal capture test) 1) Uranyl acetate UO2 (0C0CH,), aqueous solution and N
-Polystyryl-18-N6 powder was mixed and shaken at room temperature, and then evaporated.

Claims (1)

[Claims] 1. Macrocyclic diamidetetraamines represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ are reacted with functional group-containing polystyrene in a polar solvent, and the resulting product is then reduced. A method for producing macrocyclic hexamines containing polystyrene, characterized in that: 2 The functional groups of polystyrene are -CH_2Cl, -Cl
, -Br, -CO_2H, -CO_2R or -SO
The method according to claim 1, wherein _3R (R represents an alkyl group).