Heavy metal ion adsorbents

A heavy metal ion adsorbent represented by the following general formula: ##STR1## wherein l, m, and n are 2 or 3, respectively; R is an alkyl group containing 4 to 6 carbon atoms which is substituted by an amino group in the .omega.-position; and A is hydrogen or a synthetic resin.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to adsorbents for heavy metal ions. More 
particularly, it is concerned with novel adsorbents for heavy metal ions, 
which are cyclic tetramines containing specific substituents and synthetic 
resins with the cyclic tetramines bonded thereto. 
2. Description of the Prior Art 
Heavy metal ion adsorbents hitherto used to remove heavy metal ions 
contained in waste water, such as copper, nickel, mercury and the like 
ions include activated carbon, kieselguhr, ion exchange resins, chelate 
resins and the like. These adsorbents, however, have disadvantages; 
activated carbon, kieselguhr and ion exchange resins are inferior in 
selective adsorption ability for heavy metal ions, and chelate resins are 
inferior in selectivity, particularly among heavy metal ions. 
Thus, heavy metal ion adsorbents have long been desired which do not have 
the disadvantages of the conventional adsorbents. 
SUMMARY OF THE INVENTION 
The principal object of this invention is to provide heavy metal ion 
adsorbents having excellent adsorption characteristics: excellent 
selective adsorption ability for heavy metal ions generally and also 
between heavy metal ions. 
It has now been discovered that cyclic tetramines substituted by a specific 
substituent at a ring carbon atom and synthetic resins to which the cyclic 
tetramines are bonded, have excellent adsorption characteristics. 
Thus, this invention provides heavy metal ion adsorbents represented by the 
following general formula: 
##STR2## 
wherein l, m and n are 2 or 3, respectively; R is an alkyl group 
containing 4 to 6 carbon atoms which is substituted by an amino group in 
the .omega.-position; and A is hydrogen or a synthetic resin. 
DETAILED DESCRIPTION OF THE INVENTION 
In Formula (I), R is, as described above, C.sub.4 -C.sub.6 alkyl group 
containing an amino group in the .omega.-position. Typical examples are 
--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2, --CH.sub.2 CH.sub.2 
CH.sub.2 CH.sub.2 CH.sub.2 NH.sub.2, etc. In addition, those alkyl groups 
containing side chains can be used. 
Representative compounds represented by the general formula (I) are given 
below: 
Compounds represented by the formula (II): 
##STR3## 
Compounds represented by the formula (III): 
##STR4## 
Compounds represented by the formula (IV): 
##STR5## 
wherein (PS) is polystyrene. 
Compounds represented by the formula (V): 
##STR6## 
wherein (PS) is polystyrene. 
Heavy metal ion adsorbents represented by the general formula (I) in which 
A is hydrogen; i.e., cyclic tetramines with a specific substituent 
introduced therein can be synthesized by various procedures. In general, 
they are synthesized by reacting chain-like tetramines and 
.omega.-cyanoalkyl malonates, and reducing the resulting cyclic products. 
Preferred chain-like tetramines are, for example, triethylenetetramine, 
1,4,8,11-tetraazaundecane, 1,5,9,13-tetraazatridecane and the like. Of 
these compounds, 1,4,8,11-tetraazaundecane, for example, can be obtained 
by reacting ethylenediamine and 1,3-dibromopropane in the presence of 
potassium hydroxide in ethanol. 
Preferred .omega.-cyanoalkyl malonates are, for example, diethyl 
.omega.-cyanobutyl malonate, which can be formed by reacting diethyl 
malonate and 4-bromobutane nitrile, and the like. 
Cyclization reaction of the above tetramines and .omega.-cyanoalkyl 
malonate is effected by stirring them in a polar solvent capable of 
dissolving them, such as methanol, ethanol, dimethyl formamide or dimethyl 
sulfoxide while heating under atmospheric pressure over a period of from 3 
to 5 days. 
This cyclization reaction yields cyclic diamides represented by the general 
formula (VI): 
##STR7## 
wherein l, m and n are 2 or 3, respectively; R' is an alkyl group 
containing 3 to 5 carbon atoms which contains a cyano group in the 
.omega.-position. The thus obtained cyclic compounds are recrystalized 
from ethanol or the like, isolated and then reduced. This reduction 
processing can be carried out by, for example, the procedures using 
reducing agents such as lithium aluminum hydride, diborane, etc., the 
catalytic reduction process and the like process. 
This reduction converts the acid amido (--NHCO) of the ring into 
--NHCH.sub.2, and the cyano group (--CN) of the substituent into 
--CH.sub.2 NH.sub.2. This results in the formation of the compounds 
represented by Formula (I), which are the heavy metal ion adsorbents of 
this invention. 
Compounds represented by Formula (VI) which are formed by the above 
cyclization reaction are given below: 
Compounds represented by the formula (VII): 
##STR8## 
Compounds represented by the formula (VIII): 
##STR9## 
Reduction of the compounds represented by Formula (VII) yields the 
compounds represented by Formula (II), and reduction of the compounds 
represented by Formula (VIII) yields the compounds represented by Formula 
(III). 
In producing the heavy metal ion adsorbents represented by Formula (I) in 
which A is a synthetic resin, chain-like tetramines and .omega.-cyanoalkyl 
malonates are first subjected to the same cyclization reaction as 
described above. While the resulting cyclic products may be reduced 
immediately after the formation of ring and then bonded to a synthetic 
resin, it is preferred that the cyclic products are bonded to the 
synthetic resin, taking its reactivity into account, prior to the 
reduction thereof and then reduced. 
Synthetic resins which can be used in this invention, are those having 
functional groups or capable of having introduced therein the functional 
groups. For example, styrene based synthetic resins, acrylic acid based 
synthetic resins, polyvinyl alcohol resins and the like can be used. Of 
these synthetic resins, those containing benzene nuclei in the structure 
thereof are particularly preferred. These preferred synthetic resins are, 
for example, polystyrene, a copolymer of styrene and divinyl benzene, etc. 
They are usually used as ion exchange resins. 
Chemical bonding of the above described cyclic reaction products and 
synthetic resins are achieved by reacting the imino group (.dbd.NH) 
contained in the cyclic reaction products and functional groups such as 
--Cl, --Br, --I, --COOH, --COOR, --SO.sub.3 R and the like which are 
present in the synthetic resins or introduced therein. Of these synthetic 
resins, polystyrene with chloromethyl groups introduced therein as 
functional groups is most preferred in effecting the chemical bonding with 
the cyclic reaction products. Reaction conditions under which the chemical 
bonding is carried out are not especially limited, and it is sufficient to 
stir the above cyclic reaction product and the synthetic resin at room 
temperature or at elevated temperatures. After the above reaction, if 
necessary, reduction can be carried out. 
In this way, synthetic resins to which cyclic tetramines containing a 
specific substituent are bonded, as represented by Formulas (IV) and (V), 
can be obtained. 
Of the heavy metal ion adsorbents of this invention, cyclic tetramines 
represented by Formula (II) or (III) have excellent selective adsorption 
characteristics for heavy metal ions, and furthermore their selectivities 
among heavy metal ions are excellent. The presence of the specific 
substituent at the ring carbon atom increases the adsorption speeds of 
heavy metal ions and makes the adsorption and desorption markedly easy. 
Those heavy metal ion adsorbents prepared by chemically bonding cyclic 
tetramines to synthetic resins such as polystyrene and the like, as 
represented by Formula (IV) or (V) are insoluble in water, and thus they 
will find a wide variety of applications. 
Thus the heavy metal ion adsorbents of this invention can be extensively 
and effectively used in a wide variety of applications e.g., treatment of 
waste water, refining of metals, capturing useful metals from sea water, 
and concentration of metals in the isotope dilution analysis. 
We have succeeded in developing various kinds of heavy metal ion adsorbents 
during the course of conducting various experiments and researches. Among 
these heavy metal ion adsorbents, those represented by Formula (I) are 
presently considered to be the most excellent. 
Hereinafter, the general explanation of a group of heavy metal ion 
adsorbents developed by us will be made. 
Our heavy metal ion adsorbents are those prepared by chemically bonding 
large cyclic compounds containing therein at least one nitrogen or sulfur 
atom as hetero atoms of the ring and having one or more alkyl groups 
containing three or more carbon atoms of the main chain as substituents at 
one or more carbon atoms of the ring, said alkyl groups have one or more 
amino or mercapto groups at one or more carbon atoms of the 3 to 8 
positions, to synthetic resins. 
The number of atoms forming the ring of the large cyclic compound in the 
above absorbents is not especially limited in its size, but it is 
preferred that it is large enough to capture therein heavy metal ions. 
Thus, the number of atoms forming the ring of the large cyclic compound is 
desired to be 12 to 18. While the ring number of atoms other than the 
carbon atoms; i.e., hetero atoms is not especially limited, it is 
preferably 3 to 6. 
These hetero atoms include nitrogen, sulfur and oxygen. It is preferred 
that the hetero atoms contained in the ring are all nitrogen, or nitrogen 
and sulfur, or nitrogen and oxygen. In particular, it is most suitable 
that all of the hetero atoms are nitrogen. In addition, those rings where 
all of the hetero atoms are sulfur, or sulfur and oxygen, can be 
considered. These large cyclic compounds include structures in which the 
hetero atoms are adjacent to each other. In general, however, those 
structures where 2 to 3 carbon atoms are present between the hetero atoms, 
are preferred. 
The substituents introduced into one or more carbon atoms of the ring 
(usually one carbon atom) are alkyl groups containing at least 3 carbon 
atoms, usually 3 to 8 carbon atoms, and preferably 4 to 6 carbon atoms of 
the main chain, which are substituted by amino or mercapto groups at the 3 
to 8 positions of the main chain thereof (preferably in the 4 to 6 
positions and most preferably in the .omega.-position). These alkyl groups 
are, for example, 4-aminobutyl: --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 
NH.sub.2, 4-mercaptobutyl: --CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 SH, and 
the like. In the large cyclic compounds, the substituents, alkyl groups 
are introduced at one or more carbon atoms of the ring. Introduction of 
the substituents at the hetero atoms of the ring are not preferred. 
Introduction of alkyl groups containing only 1 to 2 carbon atoms or alkyl 
groups being substituted by the amino or mercapto group in the .alpha.- or 
.beta.-position of the main chain does not increase the adsorption ability 
appreciably as compared with those to which no alkyl group is introduced. 
Thus, no effect can be obtained by the introduction of alkyl groups of 1 
or 2 carbon atoms. 
In general, the large cyclic compounds can be synthesized in one or two 
steps by condensation reaction of the compounds containing --NH.sub.2, 
--NHX (X: sulfonyl, acyl, etc.), --OH, --SH or the like at the both ends 
of the molecular thereof (hereinafter referred to as "Group A Compounds") 
and the compounds containing --Cl, --Br, --I, --COOH, --COOR or --SO.sub.3 
R (R: alkyl or aryl) at the both ends of the molecular thereof 
(hereinafter referred to as "Group B Compounds"). It is difficult from the 
stand point of synthesis to introduce the above described substituents 
after the ring is formed by the condensation of Group A Compounds and 
Group B Compounds. Usually, therefore, it is advantageous that Group B 
Compounds in which the substituents have been introduced, and Group A 
Compounds are condensed. 
Among the condensation reactions of Group A Compounds and Group B Compounds 
(or Group B Compounds with substituents introduced therein), those 
condensations of compounds containing --NH.sub.2 at the both ends of the 
molecule of the compound, e.g., ethylenediamine etc. and compounds 
containing --Br at the both ends of the molecule of the compound, e.g., 
1,2-dibromoethane (or those to which the desired substituents have been 
introduced) yield the objective cyclic compounds in one step. However, 
those cyclic compounds prepared by reacting ethylenediamine, etc., and 
diester or dicarboxylic acids (or those to which the desired substituents 
have been introduced), etc., containing --COOR, --COOH at the both ends of 
the molecule of the compounds, have insufficient adsorption ability for 
heavy metal ions as they are. Therefore, it is necessary that these cyclic 
compounds are reduced to produce large cyclic compounds having sufficient 
adsorption ability. In the latter case, immediately after the formation of 
the ring, the cyclic compound obtained may be reduced to provide thereto 
sufficient adsorption ability and thereafter it may be bonded to a 
synthetic resin as described hereinafter. Taking the reactivity into 
account, however, it is preferred that the cyclic compound is bonded to 
the synthetic resin prior to the reduction thereof and it is then reduced. 
With regard to the substituents to be introduced into the large cyclic 
compounds, introduction of an alkyl group containing a cyano group 
previously into Group B Compounds or directly into large cyclic compounds 
is easier than that of an alkyl group containing an amino or mercapto 
group. Therefore, it is advantageous from the standpoint of synthesis that 
a large cyclic compound having an alkyl group substituted by an amino 
group as a substituent is prepared by introducing an alkyl group 
substituted by a cyano group into a cyclic compound, bonding the resulting 
cyclic compound to a synthetic resin, and then reducing the cyano group 
into an amino group along with reduction of the cyclic compound. 
For preparing those containing a mercapto group, a method comprising 
converting the above amino group into a hydroxy group by the use of 
nitrous acid and the like, and reacting the hydroxy group with phosphorous 
pentasulfide while heating, and other procedures can be employed. Some of 
the other procedures are given below: 
A substituent containing a carbon-carbon double bond is introduced during 
the cyclization reaction, and the resulting cyclic compound having the 
substituent is reacted with thioacetic acid or the like to introduce 
##STR10## 
to the carbon-carbon double bond. The resulting cyclic compound is then 
reduced with borane etc. and bonded to a synthetic resin, or first bonded 
to a synthetic resin and reduced with borane etc. Thus, the desired 
product is obtained. In accordance with another procedure, a substituent 
containing a hydroxy group is introduced during the cyclization reaction, 
the hydroxy group is replaced by chlorine by the use of sulfonyl chloride 
or the like, and the chlorine is then converted into a mercapto group by 
the use of thiourea or the like. 
The following are representative examples of combinations of Group A 
Compounds and Group B Compounds for production of the large cyclic 
compounds: 1,3-Diaminopropane and 1,3-dibromopropane are reacted in an 
ethanol solvent in the presence of potassium hydroxide to form 
1,5,9,13-tetraazatridecane. This 1,5,9,13-tetraazatridecane is condensed 
with 3-cyanopropyl malonic diester whereby a cyclic compound having a 
total number of the ring atoms of 16 containing 4 nitrogen atoms as hetero 
atoms of the ring can be obtained. 
According to another procedure, ethylenediamine ditocylate obtained by 
reacting tocyl chloride and ethylenediamine is reacted with a compound 
prepared by introducing a .omega.-cyanoalkyl group into ethyl 
bromoacetate. The resulting reaction product is condensed with 
diethylenetriamine whereby a cyclic compound having a total number of the 
ring atoms of 15 containing 5 nitrogen atoms as hetero atoms of the ring 
can be obtained. 
According to still another procedure, 1,4,8,11-tetraazaundecane and diethyl 
3-cyanopropyl malonate are condensed whereby a cyclic compound having a 
total number of the ring atoms of 14 containing 4 nitrogen atoms as hetero 
atoms of the ring can be obtained. 
Cyclic compounds containing atoms other than nitrogen as hetero atoms of 
the ring can be produced by several procedures. For example, 
ethyleneglycol is converted into disodium ethylenedioxide in methanol by 
the use of a sodium metal, the disodium ethylenedioxide is reacted with a 
compound prepared by introducing a .omega.-cyanoalkyl group to ethyl 
bromoacetate, and the resulting product is reacted with diethylenetriamine 
whereby a cyclic compound having a total number of the ring atoms of 15 
containing 3 nitrogen and 2 oxygen atoms as hetero atoms of the ring can 
be obtained. 
In accordance with another procedure, a .omega.-cyanoalkyl group is 
introduced into 1,6-dimethoxycarbonyl-2,5-dithiahexane and the resulting 
compound is reacted with diethylenetriamine whereby a cyclic compound 
having a total number of the ring atoms of 15 containing 3 nitrogen and 2 
sulfur atoms as hetero atoms of the ring can be obtained. 
The heavy metal ion adsorbents which we have developed are synthesized by 
bonding the above large cyclic compounds to the synthetic resins as 
described above, and if necessary, by reducing the resulting products. 
The chemical bonding of the large cyclic compounds and the synthetic resins 
is achieved by reacting functional groups such as --NH.sub.2, .dbd.NH, 
--OH, --SH and the like which are originally present in the large cyclic 
compounds or introduced thereto, and functional groups such as --Cl, --Br, 
--I, --COOH, --COOR, --SO.sub.3 R and the like which are present in the 
synthetic resins or introduced thereto. It is also possible to replace the 
functional groups of the large cyclic compounds with those of the 
synthetic resins. For example, when polyvinyl alcohol (containing --OH as 
a functional group) is employed as a synthetic resin, the groups --Cl, 
--Br, --I, --COOH, --COOR, --SO.sub.3 R and the like are preferably 
employed as functional groups of the large cyclic compounds. Of these 
synthetic resins, polystyrene with a chloromethyl group introduced therein 
as a functional group is most preferred in chemical bonding with a cyclic 
compound. 
Conditions under which the large cyclic compound and the synthetic resin 
are chemically bonded will vary depending upon their functional groups. 
For example, where a large cyclic compound containing an amino or imino 
group and polystyrene with a chloromethyl group introduced therein are 
employed, the chemical bonding can be carried out by stirring both at room 
temperature or elevated temperatures. 
After the large cyclic compound and the synthetic resin are chemically 
bonded, if necessary, the resulting product is reduced, and thus a large 
cyclic compound with a predetermined substituent introduced therein is 
obtained which has excellent adsorption ability for heavy metal ions. 
These large cyclic compounds bonded to synthetic resins have also excellent 
selective adsorption abilities for heavy metal ions like the heavy metal 
ion adsorption of this invention.

The following examples are given to illustrate this invention in more 
detail. 
EXAMPLE 1 
(1) Synthesis of Diethyl 3-Cyanopropyl malonate 
To a 1-liter three neck flask equipped with a stirrer, a condenser with a 
drying tube, and a dropping funnel were charged 500 milli liters of 
anhydrous ethanol and 23 g (1 mole) of a sodium metal. After the sodium 
metal was completely dissolved, 165 g (1.03 moles) of diethyl malonate was 
dropped through the dropping funnel at 50.degree. C. Then, 148 g (1 mole) 
of 3-cyanopropylbromide was dropped. The reaction mixture was refluxed 
with heating for 3 hours. After the major portion of the solvent was 
distilled away, 400 milli liters of water were added to the residue and 
the organic phase was isolated. On distilling the organic phase under 
reduced pressure, 186 g of diethyl 3-cyanopropyl malonate with a boiling 
point of 135.degree. C./4 mmHg was obtained (yield 82%). Infrared spectrum 
showed the peaks: 2250 cm.sup.-1 and 1740 cm.sup.-1. 
(2) Synthesis of 
3-(3-Cyanopropyl)-2,4-dioxo-1,5,8,11-tetraazacyclotridecane 
To a 2-liter three neck flask equipped with a cooler and a stirring device 
were charged 14.6 g (0.1 mole) of triethylenetetramine on the market and a 
solution prepared by dissolving 22.7 g (0.1 mole) of diethyl 3-cyanopropyl 
malonate synthesized in (1) in 1 liter of 95% ethanol. The resulting 
mixture was refluxed with heating and stirring for 5 days. The major 
portion of ethanol was distilled away from the reaction mixture under 
reduced pressure. The residues were cooled and crystals precipitated were 
collected. These crystals were recrystallized from ethanol. Thus, 6.9 g 
(0.025 mole) of crystals of 
3-(3-cyanopropyl)-2,4-dioxo-1,5,8,11-tetraazacyclotridecane (hereinafter 
referred to as "C-substituted cyclic diamide") was obtained (yield 25%). 
The analytical results of the crystals obtained are shown below: 
(1) Melting Point: 196.degree.-198.degree. C. 
(2) Elemental Analysis: C.sub.13 H.sub.23 O.sub.2 N.sub.5 
______________________________________ 
Found(%) Calculated(%) 
______________________________________ 
C 55.49 55.52 
H 8.61 8.19 
N 24.56 24.91 
______________________________________ 
(3) Peaks of Mass Spectrum: m/e: 281 (M.sup.+), 238 
(4) NMR Spectrum (heavy methanol solvent, TMS base): .delta. (ppm), 
3.48-3.90 (2H, m), 3.28 (1H, t, J=7.0 Hz), 2.95-3.20 (2H, m), 2.73 (8H, 
m), 2.58 (2H, t, J=7.0 Hz), 1.90 (4H, m). 
(3) Synthesis of 3-(4-Amino-n-butyl)-1,5,8,11-tetraazacyclotridecane 
To 30 ml of a solution of diborane (18 milli moles) in tetrahydrofuran was 
added little by little 5 milli moles of the C-substituted cyclic diamide 
obtained in (2). The mixture was allowed to stand for 30 minutes, and the 
tetrahydrofuran was distilled away by heating for 5 hours. To the residue 
was added 20 milli liters of 6 normal hydrochloric acid, and the resulting 
mixture was heated for 3 hours. Then, the solvent was distilled away under 
reduced pressure. The residue was further dissolved in a mixed solvent of 
ethanol-water (5:1) by heating, and then it was cooled. Thus, the 
hydrochloric acid salt of 3-(4-amino-n-butyl) 
-1,5,8,11-tetraaza-cyclotridecane precipitated. 
A column was charged with about 400 milli liters of an anionic exchange 
resin (Amberlite IRA-400) which had been washed with an aqueous solution 
of sodium hydroxide, and water. A solution prepared by dissolving the 
above hydrochloric acid salt in about 150 milli liters of water was flowed 
through the column and then about 500 milli liters of water was flowed 
down through the column. From the effluent so obtained, water was 
distilled away, and thus 
3-(4-amino-n-butyl)-1,5,8,11-tetraaza-cyclotridecane was obtained in high 
yield. 
EXAMPLE 2 
(1) Synthesis of Chloromethyl Polystyrene 
To a round bottom flask equipped with a stirring device was charged 20 g of 
polystyrene having a degree of polymerization of 1,600 to 1,800, available 
on the market, and 124 g (1.54 moles) of chloromethyl methyl ether. The 
polystyrene was dissolved in the ether by stirring at room temperature. To 
the solution was added 3.14 g (0.023 mole) of anhydrous zinc chloride 
powder, and the resulting mixture was stirred at room temperature 
(20.degree. C.) for 10 hours. The major portion of an excess of 
chloromethyl methyl ether was distilled away from the reaction mixture at 
10.degree. C. under reduced pressure. To the residue was added 150 milli 
liters of chloroform, and and mixture was filtered to remove the insoluble 
material. 300 milliliters of methanol were added to the filtrate, and the 
precipitates were filtered. On drying the precipitates at 60.degree. C. 
under reduced pressure, 15 g of chloromethyl polystyrene was obtained. The 
chloromethyl polystyrene was dissolved in heavy chloroform and measured in 
a degree of chloromethylation. NMR spectrum showed that the degree of 
chloromethylation per phenyl ring of the starting material, polystyrene, 
was 60%. 
(2) Bonding of C-substituted Cyclic Diamide and Chloromethyl Polystyrene 
In 30 milli liters of chloroform was dissolved 0.89 g of chloromethyl 
polystyrene (containing 4 milli moles of chloromethyl group) obtained in 
(1). To this solution was added 1.124 g (4 milli moles) of 
3-(3-cyanopropyl)-2,4-dioxo-1,5,8,11-tetraaza-cyclotridecane obtained in 
(2) of Example 1, and the resulting mixture was stirred at room 
temperature for 48 hours. Thus, an insoluble reaction product 
precipitated. This precipitate was filtered, washed with a 0.1 normal 
aqueous solution of hydrochloric acid, then washed with distilled water, 
an aqueous solution of 0.1 normal sodium hydroxide, distilled water, 
chloroform and methanol in this order, and dried under reduced pressure at 
80.degree. C. for 12 hours. As a result, 1.3 g of a white solid compound 
in which polystyrene was chemically bonded to the C-substituted cyclic 
diamide, was obtained. 
(3) Reduction of C-substituted Cyclic Diamide bonded to Polystyrene 
500 mg of the compound obtained in (2) was pulverized to 100-200 meshes, 
added little by little to 30 milli liters of a solution of diborane (14 
milli moles) in tetrahydrofuran while cooling, allowed to stand at room 
temperature for 30 minutes and then heated at 65.degree. C. for 5 hours. 
The solvent, tetrahydrofuran was distilled away from the reaction 
solution. To the residue was added 30 milli liters of a 6 normal aqueous 
solution of hydrochloric acid, and the resulting mixture was heated at 
70.degree. C. for 3 hours. The reaction product was filtered, washed with 
water, then washed with a 1 nomral aqueous solution of sodium hydroxide, 
distilled water, chloroform and finally methanol in this order, and dried 
under reduced pressure at 80.degree. C. for 12 hours. Thus, the objective 
product; i.e, C-substituted cyclic polyamine: 3-(4-amino-n-butyl) 
-1,5,8,11-tetraaza-cyclotridecane produced by the reduction of the 
C-substituted cyclic diamide which was bonded to polystyrene was obtained 
in the amount of 380 mg. This product was a white solid. 
The elemental analysis of the product was as follows: C, 74.91%; H, 9.49%; 
N, 9.35%. 
From these results, it was calculated that C-substituted cyclic polyamine 
(milli mole)/polystyrene (g)=1.34. Furthermore, it was found that the 
introduction ratio of C-substituted cyclic polyamine to chloromethylated 
styrene unit; i.e., conversion was 43%. 
(4) Metal Adsorption Test 
The compound (containing 0.18 milli mole of C-substituted cyclic polyamine) 
obtained in (3), in which 
3-(4-amino-n-butyl)-1,5,8,11-tetraaza-cyclotridecane was chemically bonded 
to polystyrene, was pulverized to 100-200 mesh, and added in an amount of 
134 mg to each of 3 milli liters of 0.02 mole aqueous solutions of copper, 
nickel and cobalt sulfates. After the equilibrium at 25.degree. C. was 
attained, the concentration of remaining metal ion was measured by the 
atomic absorption. The results obtained are shown in Table 1. In Table 1, 
the values in the brackets indicate the results obtained by using a 
compound in which 1,5,8,11-tetraaza-cyclotridecane containing no 
substituent at the ring carbon thereof was bonded to polystyrene, which is 
given for comparison. 
Table 1 
______________________________________ 
Initial Residual 
Metal Ion 
Concentration(ppm) 
Concentration(ppm) 
______________________________________ 
Cu.sup.2+ 
1270 1.5 (7) after 24 hours 
Ni.sup.2+ 
1174 0.25 (7) after 96 hours 
Co.sup.2+ 
1180 2.5 (22) after 96 hours 
______________________________________ 
(5) 100 mesh powder of a compound in which 
3-(4-amino-n-butyl)-1,5,8,11-tetraaza-cyclotridecane (C-substituted cyclic 
polyamine) was chemically bonded to polystyrene, was added to each of 3 
milli liters of 0.02 mole aqueous solutions of nickel and cobalt sulfates 
in such an amount that the amount of the C-substituted cyclic compound 
contained was 0.09 milli mole. In this case, the half-life period of metal 
ion remaining in the aqueous solution was measured at 25.degree. C. The 
results are as follows: 
______________________________________ 
Nickel ion 30 minutes (2 hours) 
Cobalt ion 30 minutes (2 hours) 
______________________________________ 
The values shown in the brackets indicates the results obtained by using a 
compound as an adsorbent in which 1,5,8,11-tetraaza-cyclotridecane was 
bonded to polystyrene, which are given for comparison. 
EXAMPLE 3 
(1) Synthesis of 
3-(3-Cyanopropyl)-2,4-dioxo-1,5,8,12-tetraaza-cyclotridecane 
The procedure of (2) of Example 1 was repeated with the exception that 
N,N'-bis(2-aminoethyl)-1,3-propylenediamine was used in place of 
triethylenetetramine. Thus, 
3-(3-cyanopropyl)-2,4-dioxo-1,5,8,12-tetraaza-cyclotetradecane 
(C-substituted cyclic diamide) was obtained in a yield of 30%. 
The analytical results of this C-substituted cyclic diamide are shown 
below: 
(1) Melting Point: 178.degree.-180.degree. C. 
(2) Elemental Analysis: C.sub.14 H.sub.25 O.sub.2 N.sub.5 
______________________________________ 
Found(%) Calculated(%) 
______________________________________ 
C 57.00 56.92 
H 8.68 8.53 
N 23.50 23.71 
______________________________________ 
(3) Peaks of Mass Spectrum: m/e: 295 (M.sup.+) 
(4) NMR Spectrum (heavy methanol solvent, TMS base) .delta. (ppm) 7.50 (2H, 
broad), 3.60-3.05 (4H, m), 3.20 (1H, t, J=6 Hz), 2.70 (8H, m), 2.41 (2H, 
s), 2.00 (2H, m), 1.70 (4H, m), 1.41 (2H, t, J=6 Hz) 
(2) Synthesis of 3-(4-Amino-n-butyl)-1,5,8,12-tetraaza-cyclotetradecane 
The C-substituted cyclic diamide (5 milli moles) obtained in (1) was added 
little by little while cooling to 30 milli liters of a solution of 
diborane (18 milli moles) in tetrahydrofuran, allowed to stand for 30 
minutes and then heated for 5 hours to distill away the tetrahydrofuran. 
To the residue was added 20 milli liters of 6 normal hydrochloric acid. 
The mixture was heated for 3 hours and the solvent was distilled away 
under reduced pressure. The residue was dissolved in a mixed solvent of 
ethanol-water (5:1) by heating. On cooling the solution obtained above, 
the hydrochloric acid salt precipitated. 
About 400 milli liters of an anion exchange resin (Amberlite IRA-400) which 
had been washed with aqueous solution of sodium hydroxide and water was 
charged to a column. The above hydrochloric acid salt dissolved in about 
150 milli liters of water was flowed through the above column, and further 
about 500 milli liters of water was flowed down through the column. On 
distilling away the water from the effluent obtained, colorless crystals 
were obtained in a yield of 70%. 
The analytical results of these crystals are shown below: 
(1) Melting Point: 132.degree.-133.degree. C. 
(2) Elemental Analysis: C.sub.14 H.sub.33 N.sub.5.H.sub.2 O 
______________________________________ 
Found(%) Calculated(%) 
______________________________________ 
C 59.17 58.09 
H 11.93 12.19 
N 24.19 24.20 
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(3) Peaks of Mass Spectrum: m/e: 271 (M.sup.+) 
(4) NMR Spectrum (heavy methanol solvent, TMS base) .delta. (ppm) 2.90-2.50 
(5H, m), 1.72 (2H, q), 2.30 (6H, s), 1.36 (6H, s, J=6 Hz) 
Analysis of the above date revealed that the crystal was 
3-(4-amino-n-butyl)-1,5,8,12-tetraaza-cyclotetradecane. 
(3) Metal Adsorption Test 
A compound in which 3-(4-amino-n-butyl)-1,5,8,12-tetraaza-cyclotetradecane 
was chemically bonded to polystyrene, was found in the same manner as in 
Example 2 except that the C-substituted cyclic diamide obtained in (1) was 
used. With this compound, the same adsorption test as in (4) of Example 2 
was conducted. The results obtained are shown in Table 2. The values in 
the brackets indicate the results obtained by using a compound in which 
1,5,8,12-tetraaza-cyclotetradecane was chemically bonded to polystyrene, 
which are given for comparison. 
Table 2 
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Initial Residual 
Metal Ion 
Concentration(ppm) 
Concentration(ppm) 
______________________________________ 
Cu.sup.2+ 
1270 2.5 (2.0) 
Ni.sup.2+ 
1174 18 (63) 
Co.sup.2+ 
1180 38 (134) 
______________________________________ 
A found value of the elemental analysis of the compound in which 
3-(4-amino-n-butyl)-1,5,8,12-tetraaza-cyclotetradecane (C-substituted 
cyclic polyamine) was chemically bonded to polystyrene, was as follows C, 
74.52%; H, 8.72%; N, 9.76%. 
From these results, it was calculated that C-substituted cyclic polyamine 
(m mole)/polystyrene (g)=1.35. Furthermore, it was found that the 
introduction ratio of C-substituted cyclic polyamine to chloromethylated 
styrene unit; i.e., converstion was 45%. 
(4) 100 mesh powder of a compound in which 
3-(4-amino-n-butyl)-1,5,8,12-tetraaza-cyclotetradecane (C-substituted 
cyclic polyamine) was chemically bonded to polystyrene, was added to each 
of 3 milli liters of 0.02 mole aqueous solutions of nickel and cobalt 
sulfates in such an amount that the amount of the C-substituted cyclic 
compound contained be 0.09 milli mole. In this case, the half-life period 
of metal ion remaining in the aqueous solution was measured at 25.degree. 
C. The results are as follows: 
______________________________________ 
Nickel ion 1 hour (6 hours) 
Cobalt ion 1 hour (24 hours) 
______________________________________ 
The values shown in the brackets indicate the results obtained by using a 
compound in which 1,5,8,12-tetraaza-cyclotetradecane was chemically bonded 
to polystyrene, which are given for comparison. 
EXAMPLE 4 
A compound in which 3-(4-amino-n-butyl)-1,5,9,13-tetraaza-cyclohexadecane 
was chemically bonded to polystyrene, was synthesized in the same manner 
as in Examples 1 and 2 except that 
N,N'-bis(3-aminopropyl)-1,3-propylenediamine was used in place of 
triethylenetetramine. 
The compound obtained is represented by the following formula: 
##STR11## 
wherein (PS) is polystyrene. With this compound, the same adsorption test 
as described in (4) of Example 2 was conducted. The results obtained are 
shown in Table 3. The values shown in the brackets indicate the results 
obtained by using a compound in which 1,5,9,13-tetraaza-cyclohexadecane 
was chemically bonded to polystyrene, which are given for comparison. 
Table 3 
______________________________________ 
Initial Residual 
Metal Ion 
Concentration(ppm) 
Concentration(ppm) 
______________________________________ 
Cu.sup.2+ 
1270 3.6 (8.6) 
Ni.sup.2+ 
1174 10 (112) 
Co.sup.2+ 
1180 19 (163) 
______________________________________ 
A found value of the elemental analysis of the compound in which 
3-(4-amino-n-butyl)-1,5,9,13-tetraaza-cyclohexadecane (C-substituted 
cyclic polyamine) was chemically bonded to polystyrene, was as follows: C, 
77.23%; H, 8.20%; N, 8.40%. From these results, it was calculated that 
C-substituted cyclic polyamine (milli mole)/polystyrene (g)=1.20. Further, 
it was found that the introduction ratio of C-substituted cyclic polyamine 
to chloromethylated styrene unit; i.e., conversion was 37%.