J. Cent. South Univ. Technol.

(2011) 18: 361−366

DOI: 10.1007/s11771−011−0704−8

Synthesis of 1,4-benzenedicarbonyl thiourea resins and

their adsorption properties for Ag(I)
WANG Zhong-nan(王仲南)1, 2, ZHONG Hong(钟宏)1, WANG Shuai(王帅)1,
LIU Guang-yi(刘广义)1, ZHANG Qian(张骞)1
1. School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
2. College of Chemistry and Environmental Engineering, Shaoguan University, Shaoguan 512005, China
© Central South University Press and Springer-Verlag Berlin Heidelberg 2011

Abstract: Several 1,4-benzenedicarbonyl thiourea resins (BTR) were synthesized through interfacial polymerization between 1,4-
benzenedicarbonyl diisothiocyanate and polyamine. Their structures were confirmed by FT-IR. The adsorption properties (including
the effect of adsorption time, pH, initial concentrations and temperature) of BTR-1, BTR-2 and BTR-3 for Ag(I) were investigated by
batch tests. The results show that the adsorption equilibria of BTR-1, BTR-2, BTR-3 for Ag(I) are achieved after about 10 h. Their
equilibrium adsorption capacities are 7.11, 6.75 and 6.23, respectively, and the adsorption process accords with G. E. Boyd equation
and Langmuir adsorption isotherm as well. The adsorption capacities increase with the increase of pH (the highest uptake values are
observed at pH being about 6−7). The thermodynamic parameters of BTR-1 were calculated. The results show that ∆HΘ and ∆SΘ are
6 958.8 J/mol and 64.28 J/(mol·K), respectively, and ∆GΘ at 20, 30, 40 and 50 °C are −11.79, −12.52, −13.16 and −13.8 kJ/mol,
respectively. The silver-loaded resins can be quantitatively eluted by a solution containing 6% thiourea in 1 mol/L HNO3.

Key words: acylthiourea polymer; resin; interfacial polymerization; adsorption; Ag(I)

groups locate in the main chain. With high content of

1 Introduction thiourea group and ordered structure, they often show
more excellent adsorption capacities and selectivity for
Precious metals usually tend to form stable precious metals. For example, in our previous works
complexes with ligands containing “soft” donor atoms. [12−14], some novel resins of poly(ester thiourea) were
As a donor containing N- and especially S-atom, thiourea prepared by monomer polymerization. The adsorption
is an excellent ligand to precious metal ions, which is capacities of ATR for Au(II) and Ag(I) are 4.65 and
widely used in the extraction, separation and recovery of 4.40 mmol/g, respectively, and that of PETU for Ag(I) is
precious metals. So, the investigations on the preparation 3.53 mmol/g.
and application of chelating resins with thiourea have In order to further research the adsorption properties
been attracting much attention, and many research results for noble metals of these thiourea resins from the
had been reported [1−4]. Thiourea polymers reported polymerization, in this work, several crosslinked
were mainly obtained in two ways: one was polymer acylthiourea polymers (1,4-benzenedicarbonyl thiourea
grafting, which meant to graft thiourea groups to the resins or BTR) were synthesized through the interfacial
framework of polymers, such as polystyrene [4−5], polymerization of 1,4-benzendicarbonyl diisothiocyanate
polyvinyl chloride [6], poly(ethylene glycol) [7], and polyamine. The synthesis process of BTR is more
phenolic aldehyde [8], chitosan [9], and silica gel [10]; convenient and efficient than that of ATR and PETU.
the other was monomer polymerization, such as the And their adsorption properties for Ag(I) were
polymerization of thiourea or bisthiourea and investigated.
formaldehyde [1−2], or the polymerization of
diisothiocyanate and diamine [11]. At present, most 2 Experimental
thiourea polymers reported are synthesized in the first
way. Thiourea groups in these resins often locate in 2.1 Reagent and apparatus
branches, and their adsorption performance is limited by Metal nitrate or chloride was used as source of
the relatively low reaction efficiency and low content of metal ions by dissolving exact nitrate or chloride in pure
thiourea groups. Contrarily, thiourea polymers obtained water. All chemicals are of analytical or chemical grade.
in the second way are reported less, in which thiourea The infrared spectra were recorded on a G510PFTIR

Foundation item: Projects(20476105, 50604016) supported by the National Natural Science Foundation of China
Received date: 2010−03−08; Accepted date: 2010−10−11
Corresponding author: ZHONG Hong, Professor, PhD; Tel: +86−731−88830603; E-mail: zhongh@mail.csu.edu.cn
362 J. Cent. South Univ. Technol. (2011) 18: 361−366
spectrophotometer. The adsorption experiments were was filtrated and washed repeatedly. Then, the resin was
carried out with a SHA-C thermostatic vibrator. suspended in elution solution in the iodometric flask. The
flask was shaken for a certain time in the thermostatic
2.2 Synthesis of BTR resin vibrator. The adsorption−desorption operation was
The synthesis of BTR included two steps. Firstly, repeated several times, and the adsorption capacity of
50 mmol ammonium thiocyanate (dried and triturated), resin was recorded.
20 mmol 1,4-benzenedicarbonyl dichloride, about 75 mL
methylene chloride (CH2Cl2) and 0.6 g PEG-400 were 3 Results and discussion
placed in a 250 mL flask equipped with a magnetic stirrer.
The mixture was stirred for about 3 h at room 3.1 Preparation of BTR
temperature. The orange suspension was formed. Then, The synthesis route of BTR is represented as
the reaction mixture was filtrated to remove the solvent. follows:
1,4-benzendicarbonyl diisothiocyanate was obtained as
orange solid. Secondly, in a 250 mL three-necked flask
with mechanical stirrer, 10 mmol 1,4-benzenedicarbonyl
diisothiocyanate dissolved in 50 mL CH2Cl2 reacted with
10 mmol diethylene triamine, or 8 mmol triethylene (2)
tetraamine or 6 mmol tetraethylene pentamine
(respectively dissolved in about 80 mL water) for 1−
1.5 h at room temperature and with continuous stirring,
and a yellow precipitate was formed. After being filtered,
washed with water, ethanol and small quantity of ether
successively, and then dried, several crosslinked
acylthiourea polymers (BTR-1, BTR-2, BTR-3) were
synthesized. The yields of BTR-1, BTR-2 and BTR-3 (3)
were 93.2%, 87.3% and 84.7%, respectively.
where for BTR-1, n=1; for BTR-2, n=2; for BTR-3, n=3.
FT-IR spectra of BTR are shown in Fig.1.
2.3 Adsorption procedure
2.3.1 Adsorption of BTR for metal ions
The adsorption behaviours of resins for Ag(I) and
other metals were carried out by batch method. 50 mg
BTR resin was placed into an iodometric flask
containing 25 mL Ag(I) or other metal ions solution at an
initial concentration of 0.1 mol/L. The pH was controlled
by acetic acid/sodium acetate buffer or HNO3 or
ammonia/ammonium chloride buffer. At desired
temperature, the flask was shaken in the thermostatic
vibrator at 150 r/min for a certain time. Then, the
solution was filtrated off. The concentrations of Ag(I),
Cu(II) and other metal ions in the solution were
determined by Volhard method, iodimetry method and
titration against EDTA, separately. Adsorption capacity
could be calculated by Fig.1 FT-IR spectra of BTR

Q=(c0−ce)V/m (1) The spectra show that N—H stretching vibration

where Q is the adsorption capacity (mmol/g), c0 is the appears at 3 365−3 240 cm−1，C=O stretching vibration
initial concentration of solution (mol/L), ce is the appears at about 1 674 cm−1, N — C — N stretching
concentration after adsorption (mol/L), V is the volume vibration appears at about 1 529 cm−1, and C=S
of solution (L), and m is the mass of the dry resin (g). vibration appears at about 1 263 and 1 109 cm−1. It is
2.3.2 Regeneration of BTR indicated that the resin contains functional groups of
Elution experiments were also performed by batch carbonyl and thiourea.
method. A solution containing 1 mol/L HNO3 and 6%
(mass fraction) thiourea was used as elution solution. 3.2 Adsorption capacities of BTR for metal ions
After reaching the maximum uptake for Ag(I), the resin The adsorption experiments of BTR for Ag(I) and
J. Cent. South Univ. Technol. (2011) 18: 361−366 363
some metal ions were carried out under the following adsorption equilibrium of BTR-1, BTR-2 and BTR-3 for
conditions: contact time 24 h, temperature 30 °C, initial Ag(I) is achieved. It is also shown that the adsorption
concentration of metal ions 0.1 mol/L, and natural rate of BTR for Ag(I) is slow. The adsorption data of
medium. The adsorption capacities for Ag(I), Cu(II), Fig.2 are treated according to the Boyd diffusion
Zn(II), Ca(II), Mg(II), Fe(Ⅲ) are presented in Table 1. equation of liquid film:
The obtained data display that for the same metal ion, the −ln(1−F)=kt (4)
adsorption capacity order of BTR is BTR-1>BTR-2>
BTR-3 basically. F is obtained by the expression F=Q/Qm, where Q
and Qm refer to the amounts (mmol/g) of Ag(I) absorbed
Table 1 Adsorption capacities of BTR for metal ions at time t (h) and at equilibrium, respectively, and k is the
Q/(mmol.g-1)
overall rate constant (h−1).
Resin The obtained results are presented in Fig.3 and
Ag(I) Cu(II) Zn(II) Fe(Ⅲ) Ca(II) Mg(II)
Table 2.
BTR-1 7.11 0.68 0.64 0.17 0.013 0.015
BTR-2 6.75 0.52 0.58 0.15 0.020 0.019
BTR-3 6.23 0.45 0.51 0.23 0.016 0.025

And it can also be seen that three BTRs have a high

selectivity for Ag(I). This may be attributed to the strong
affinity of silver towards sulphur as donor atom and the
particular structure of resin. Owing to the conjugation
among phenyl, carbonyl and thiourea, the softness of N
and S donor atoms as soft bases is raised. According to
the hard and soft acids and bases theory (HSAB), they
will interact more strongly with soft acid，such as Ag(I),
and on the other hand, they are weak to interact with
borderline or hard acid，such as Cu(II), Zn(II), Fe(III), Fig.3 Relationship of −ln(1−F) and t for BTR
Ca(II) and Mg(II) .
Table 2 Linear equations of adsorption kinetics of BTR
3.3 Adsorption behaviours of BTR for Ag(I) Resin Linear equation k/h−1 R2
3.3.1 Effect of contact time on adsorption and adsorption BTR-1 −ln(1−F)=0.197+0.397t 0.397 0.996
kinetics
BTR-2 −ln(1−F)=0.227+0.437t 0.437 0.996
The effect of contact time on the adsorption of BTR
for Ag(I) was studied at 30 °C, initial Ag(I) concentration BTR-3 −ln(1−F)=2.69+0.509t 0.509 0.994
of 0.1 mol/L, and pH value of 6.9. The results are
presented in Fig.2. It is obvious that a linear relationship exists between
−ln(1−F) and t. The rate constant k is 0.397, 0.437 and
0.509 h−1, respectively. This also reflects that the
adsorption rate order of BTR for Ag(I) is BTR-3>
BTR-2>BTR-1. This may have relationship with the
different lengths of main chain in BTR-3, BTR-2 and
BTR-1. It is suggested that the kinetics of adsorption
process of BTR is controlled by the diffusion through the
liquid film surrounding the solid adsorbents.
3.3.2 Effect of pH on adsorption
Adsorption experiments under controlled pH were
carried out under the conditions that the contact time is
10 h, the adsorption temperature is 30 °C, and the initial
concentration of Ag(I) is 0.1 mol/L. Considering the
Fig.2 Effect of contact time on adsorption hydrolysis of Ag(I), the highest pH value selected is 6.9
(natural). The results are shown in Fig.4.
It can be seen that the adsorption capacities increase It can be seen that the adsorption capacities increase
with the increase of contact time，and it is particularly with the increase of pH value. The highest uptake values
rapid in the initial stage of 4 h. And after about 10 h, the are observed at pH of about 6−7. The observed result that
364 J. Cent. South Univ. Technol. (2011) 18: 361−366
maximum uptake when c0 exceeds 0.1 mol/L. On the
other hand, at the same initial concentration (c0), the
adsorption capacity increases with the rise of the
temperature. The effect of temperature on the process
can be explained by two reasons: 1) increasing the active
sites available for the interaction with the rise of
temperature [16], and 2) rising temperature leading to
higher dehydration of Ag(I) and consequently their
interaction becoming more favorable [17].
The adsorption data are plotted according to
Langmuir equation:
ce/Q=ce/Qm+1/QmKL (5)
where ce is the equilibrium concentration of metal ions in
Fig.4 Effect of pH value on adsorption solution (mol/L), Qe is the absorbed value of metal ions
at equilibrium concentration (mmol/g), Qm is the
the uptake values decrease with pH value decreasing maximum adsorption capacity (mmol/g), and KL (L/mol)
may be attributed to the partial protonation of the amino is the Langmuir constant which is related to the energy
group and thiourea group [15]. This hinders the of adsorption. The results are presented in Fig.6 and
interaction of the resins and Ag(I) ion. Table 3.
3.3.3 Effect of initial concentration and temperature on
adsorption and isotherm
BTR-1 was selected to study the effect of initial
concentration of Ag(I) and temperature on the adsorption
and isotherm. The solution was controlled at pH=6.9.
The results are presented in Fig.5.

Fig.6 Langmuir isotherm for adsorption of Ag(I) on BTR-1

It can be seen that the plot of ce/Q vs ce gives a

straight line with the correlation coefficient exceeding
0.99. This implies that the adsorption process of Ag(I) on
BTR can be described by Langmuir equation.
Fig.5 Isotherms for adsorption of Ag(I) on BTR-1

The adsorption curves indicate that the adsorption 3.4 Adsorption thermodynamics of Ag(I)
capacity for Ag(I) increases with the increase of the Thermodynamic parameters could be calculated
initial concentration (c0) of Ag(I) at the same temperature, from Van’t Hoff equation [15−16]:
but increases slowly and is gradually close to the ln KL=−∆HΘ/RT+∆SΘ/R (5)

Table 3 Langmuir equation of BTR-1 and parameters

Temperature/℃ Langmuir equation Qm/(mmol·g−1) KL/(L·mol−1) R2

20 ce/Q=140.17ce+1.07 7.13 131 0.999 6

30 ce/Q=130.68ce+0.893 7.65 146 0.999 6
40 ce/Q=124.78ce+0.795 8.03 157 0.999 4
50 ce/Q=119.75ce+0.708 8.35 169 0.997 3
J. Cent. South Univ. Technol. (2011) 18: 361−366 365
where ∆HΘ and ∆SΘ are enthalpy and entropy changes,
respectively, R is the universal gas constant (8.314 4 Conclusions
J/(mol·K)) and T is the absolute temperature (K).
The plot of ln KL against 1/T gives a straight line 1) A series of novel 1,4-benzendicarbonyl thiourea
with the slope equal to −∆HΘ/RT and the intercept equal chelating resins (BTR) were synthesized through the
to ∆SΘ/R. The results are presented in Fig.7 and Table 4. interfacial polymerization between 1,4-
benzenedicarbonyl diisothiocyanate and polyamine. The
synthesis process is more convenient and efficient. The
yields of BTR-1, BTR-2 and BTR-3 are 93.2%, 87.3%
and 84.7%, respectively.
2) The equilibrium adsorption capacities of BTR-1,
BTR-2, BTR-3 for Ag(I) (contact time 24 h, temperature
30 °C, initial concentration of metal ions 0.1 mol/L, and
natural medium) are 7.11, 6.75, 6.23 mmol/g,
respectively. The adsorption capacity order of BTR is
BTR-1>BTR-2>BTR-3.
3) The adsorption process for Ag(I) is found in
accord with Boyd equation and Langmuir adsorption
isotherm as well. The obtained thermodynamic
parameters show that the adsorption process is
spontaneous and dominated by entropy change rather
Fig.7 Van’t Hoff plot for adsorption of Ag(I) on BTR-1
than enthalpy change, and the adsorption becomes more
favorable at higher temperatures.
Table 4 Results of Van’t Hoff plots and thermodynamic
4) The silver-loaded resins can be quantitatively
parameters
eluted by a solution containing 6% thiourea in 1 mol/L
∆HΘ/ ∆SΘ/ HNO3.
Fitting equation R2
(J·mol−1) (J·mol−1·K−1)
ln KL=7.732−837T−1 0.989 2 6 958.8 64.28 References
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