International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190

th
st
ICRTIET-2014 Conference Proceeding, 30 -31 August 2014

Mercaptozinc Succinate semiconductor initiated Ring Opening

Polymerization of -Caprolactone: Band gap study
L. Kannammal, M. Ponvigneshbabu, R. Anbarasan*
Department of Polymer Technology, Kamaraj College of Engineering and Technology,
Virudhunagar-626 001, Tamilnadu, India

ABSTRACT
A simple hybrid system was prepared by the acid-base
titration method. Thus obtained product was tested
towards the ring opening polymerization (ROP) of caprolactone (CL) in the presence of stannous octoate
(Sn(oct)2) as a catalyst at 1600C under N2 atmosphere
with mild stirring conditions. The ROP of -CL was
carried out at different [M/I] ratio and the polymer
samples obtained were characterized by analytical tools
like fourier transform infrared (FTIR) spectroscopy,
Particle size analysis(PSA), X-ray diffraction (XRD),
Gel permeation chromatography (GPC) and scanning
electron microscope (SEM).The FTIR-RI data
confirmed the ROP of -CL by metal salt as a chemical
initiator.
Keywords: semiconductor, synthesis, characterizations,
nano composite, band gap

literature [5]. Surface initiated ROP of lactones on iron

oxide nano particles was reported by Nan et al [6].
For the ROP of -CL, various functional groups like
OH [7-9], -CO2H [10], -SO3H [11], -NH2 [12-13], and
SH [14] were used. Among the functional groups
available for the ROP of -CL, the thiol group
occupies the first row because of its multi applications
such as easy hydrogen donor property, mild reducing
tendency, good surface binding capability and exhibits
excellent initiating efficiency towards the ROP of CL without any branching or cross linking. In the
present investigation such a valuable thiol group is
acting as an initiator for the ROP of -CL. By thorough
literature survey we could not find any report based on
the mercaptozinc succinate as an initiator for the ROP
of -CL.

II. EXPERIMENTAL
I. INTRODUCTION
Zinc in an eco friendly bio-metal and has wide
application in semi-conductor and biological fields [12]. The applications of zinc can be increased in the
biological field by making salt or introducing functional
groups. Mercaptoacetic acid (MAA) is a simple
molecule with two carboxyl functional group and one
thiol group. The thiol group is an active metal surface
binding group [3]. While referring the literature, we
found very few reports are available on the synthesis of
mercaptozinc succinate towards the ROP of -CL as an
effective initiator. In the present investigation we
follow this job as a challenge and successfully
synthesized the same towards the ROP of -CL as an
initiator. The novelty of the present investigation is the
study of band gap energy before and after hybrid
formation. The band gap energy of PCL-hybrid was
determined and critically compared.
PCL is one of the bio-medical polymers which are used
as a drug carrier in the pharmacology field such a nice
bio-compatible and bio-degradable candidate can be
synthesized by ROP. In 2011, organic acid catalysed
ROP of -CL was carried out and the synthesized
polymer was characterized by NMR, DSC, GPC and
SEM like analytical tools [4]. Doxifluridine initiated
ROP of -CL report is available in the

1. Materials
Mercapto succinic acid was purchased from Alfa Aesar,
India . Zinc carbonate was purchased from Loba
Chemie, India. Double distilled water (DD water) was
used for making solutions. -caprolactone, stannous
octoate were purchased from sigma Aldrich, USA and
used as received. Chloroform and diethyl ether were
purchased from spectra chemicals, India.
2. Synthesis of ROP of PCL
10 g ZnCO3 was dissolved in 100 mL double distilled
water under N2 atmosphere. 10 g MSA was added
slowly under vigorous stirring conditions at 450 C. The
stirring was further continued for 2 hrs. At the end of
the reaction content of the beaker was evaporated to
dryness. During the course of the reaction, thiol group
will act as a mild oxidising agent whereas the carboxyl
group will try to form a salt with equal possibility. The
particle size analysis report declared that, MSA formed
as a metal salt with ZnCO3. After the salt formation one
thiol group was remained free for further ROP of CL. Thus obtained white colour mercapto zinc
succinate was weighed and stored in a zipper lock
cover. The %yield was noted as 85%.

Divya Jyoti College of Engineering & Technology, Modinagar, Ghaziabad (U.P.), India

International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
th
st
ICRTIET-2014 Conference Proceeding, 30 -31 August 2014

1g -CL was accurately weighed and taken into a 25

mL RB flask. 0.001 g of Sn(oct)2 catalyst was charged
with the RB flask. 0.1 g of mercaptozinc succinate was
accurately weighed and added to the RB flask. Here,
the [M/I] ratio was maintained as 10. Similarly, [M/I]
ratios were varied such as 10, 50, 100, 200 and 400.
The contents were mixed for a minutes at room
temperature. After the thorough mixing, the RB flask
was transferred to oil bath and maintained at 1600C.
Now, the ROP of -CL started under N2 pursing with
mild stirring, the [M/I] =10, [M/C] =1000. The ROP of
-CL was continued for another 2 hours. After, 2 hours
the RB flask removed from the oil bath and cooled. 25
mL of chloroform was added with the already cooled
polymer and re-precipitated by the addition of 200 mL
of diethyl ether. Thus obtained white polymer was
noted as poly (caprolactone) and dried by freeze drying
method for overnight. After the freeze drying, the white
solid mass was weighed and stored in zipper lock cover.

the sample was measured by JSM 6300, Jeol product.

From the UV-absorption spectrum, the direct band gaps
were calculated for synthesized samples. The direct
band gap of the materials obeys the following relation,
Direct band gap:
Where is absorption coefficient, Eg is optical band
gap of the material, A is constant, h is Plancks constant
and is the frequency.

IV. RESULTS AND DISCUSSION

1. Characterization of MSA decorated Zn
system

Fig. 1: (a) FTIR spectrum; (b) PSA; (c) EDX; (d) XRD;
(e, f) UV-visible reflectance spectrum of (e) Zinc
carbonate; (f) Mercaptozinc succinate

Scheme 1 Reaction of Zinc salt initiated ROP of -CL

III. CHARACTERIZATIONS
3 mg of the sample was made as a disk with 200 mg of
spectral grade KBr and the FTIR spectrum was
measured between 400 and 4000 cm-1 with the help of
Shimadzu 8400S Japan, model instrument. Absorption
spectroscopy was done by a UV-visible NIR
spectrophotometer, Jasco V-570 instrument, USA.
Absorption scans were performed in the range of 260
700 nm. 1H and 13C nuclear magnetic resonance (NMR)
(500 MHz) spectra were obtained using an NMR
apparatus (Varian, Unity Inova-500 NMR) at room
temperature in D2O solvent. Differential scanning
calorimetry (DSC) and Thermogravimetric analysis
(TGA) were measured by using Universal V4.4A TA
Instruments under nitrogen atmosphere at the heating
rate of 10 K min1 from room temperature to 373 K.
Molecular weight determination of polymer samples
was carried out in gel permeation chromatography
(GPC) Perkin Elmer Series 200. Surface morphology of

1.1. FTIR study

The FTIR spectrum of MSA decorated Zn system is
given in Fig. 1(a). The O-H stretching of intercalated
water molecules appeared at 3407 cm-1. The C-H
symmetric stretching and anti symmetric stretching are
appeared as a hump at 2925 cm-1 and 2966 cm-1
respectively. The carbonyl stretching of MSA appeared
at 1724 cm-1. The C-H bending vibrations can be seen
at 1568 cm-1. A peak at 1404cm-1 is corresponding to CS stretching of MSA. The C-H OPBV appeared at 742
cm-1.

1.2.

Particle size analysis

The material prepared by acidbase titrations method

was subjected to particle size analysis. Fig. 1(b)
indicates the same. The pictures indicate two distinct
zones. The first zone is appearing between 200 and 300
nm (2%), where as the second zone is appeared
between 600 and 1000 nm. The appearance of two
different distinct regions confirmed the various possible
reactions. MSA contains one thiol group and two
carboxyl groups. The thiol group is a mild reducing
agent and carboxyl groups are ready to form salt with

Divya Jyoti College of Engineering & Technology, Modinagar, Ghaziabad (U.P.), India

International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
th
st
ICRTIET-2014 Conference Proceeding, 30 -31 August 2014

zinc carbonate. The two different reactions yielded two

different products. As a result of reduction reaction, the
MSA decorated Zn nano particle was obtained, where
as zinc salt was formed as a result of acid-base reaction.
The mild reduction reaction yield the formation of nano
meter sized zinc (200-300 nm). In the case of salt
formation a micrometer sized material was formed. On
comparing the percentage of material, a material
formed through acid-base titration is more than that of
the simple reduction reactions. Finally, one can
conclude that, there will be a mixture of both nano and
micrometer sized materials (ie) hierarchically structured
materials.

1.3.

EDX spectrum

Fig. 1(c) indicates the EDX spectrum of MSA

decorated zinc. The elements present here is carbon,
oxygen, sulphur and zinc. Carbon was appeared at 0.20.5 keV, oxygen appeared at 0.75 keV, sulphur
appeared at 2.25 keV and zinc appeared at 8.6 and 1.0
keV. The appearance of peaks corresponding to zinc,
sulphur, oxygen and carbon confirmed the formation of
zinc salts of MSA.

1.4.

e). The important peaks are explained here. The O-H

stretching of PCL appeared around 3437 cm-1 as a
broad peak. The C-H symmetric and anti symmetric
stretching were observed at 2867 and 2950 cm-1
respectively. The carbonyl stretching of linear polyester
of PCL appeared at 1737 cm-1. The ester C-O-C linkage
and C-H OPBV can be seen at 1182 and 728 cm-1
respectively. The C-S stretching of MSA appeared at
1416 cm-1. The metal oxide stretching of hybrid
appeared at 457 cm-1. It is very interesting to note that
while increasing the [M/I] ratio, the corrected peak area
of C=O (1737 cm-1) and C-H OPBV (728 cm-1) were
increased. In order to find out the order of reaction
based on the FTIR-RI, the plot of log [M/I] Vs log
[RI(C=O/C-H)]. Figure 2(f) was drawn and the slope value
was determined from the linear plot as 0.12. It means
0.1 mole of initiator is required to form 1 mole of PCL.
It also inferred that at higher [M/I] ratio due to the
availability of lower initiated species, the RI was very
high. It means at lower initiator concentration only the
molecular weight of PCL was drastically increased.

XRD study

Fig. 1(d) represents the XRD of zinc salt of MSA. The

diffractrogram exhibits one broad peak around 250
confirmed the d(111) crystal plane of zinc. The
appearance of broad peak confirmed the formation of
zinc salt of MSA with poor crystallinity. It means after
the salt formation reaction, the crystallinity of zinc was
depressed.

1.5.

UV-visible reflectance study

Fig. 1(e) and 1(f) confirmed the UV-visible reflectance

spectrum. Fig. 1(e) indicates the reflectance spectrum
of zinc carbonate with lower percentage of reflectance
value. Fig. 1(f) indicates the reflectance spectrum of
zinc salt of MSA with more than 90% reflectance value.
The appearance of such a higher reflectance value
confirmed the hydrophobic nature of the material.
Moreover, the shape of the plot is irregular. In
comparison, the hybrid exhibited the highest reflectance
value due to the metal salt formation.

Fig. 2: FTIR spectrum of PCL synthesized at various

[M/I] ratio (a) 10, (b) 50, (c) 100, (d) 200, (e) 400, (f)
plot of log [M0/I0] Vs. log(RI[C=O/C-H])

2.2. XRD analysis

2. Characterization of MSA decorated Zn

system
2.1. FTIR study
The figure 2 synthesized zinc salt was used as a
chemical initiator towards the ROP -CL and FTIR
spectrum was recorded for the sample synthesized at
various [M/I] ratio such as 10, 50, 100, 200, and 400.
The FTIR spectrum of PCL synthesized with the help
of Zn-salt at various [M/I] ratio is given in Figure 2(a-

Fig. 3: (a) XRD, (b) EDX, (c) SEM, (d-h) UV-visible

reflectance spectrum of Zinc salt initiated ROP of CL
Figure 3(a) represents the XRD of zinc salt. The
appearance of d(111) and d(200) confirmed the metal salt

Divya Jyoti College of Engineering & Technology, Modinagar, Ghaziabad (U.P.), India

International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
th
st
ICRTIET-2014 Conference Proceeding, 30 -31 August 2014

initiated ROP of -CL. After the chemical conjugation

with caprolactone unit, the crystallinity of metal salt
was increased. The appearance of sharp d(110) crystal
peak confirmed the crystalline nature of zinc salt.
Moreover PCL is a semi-crystalline polymer. At higher
temperature (600C) PCL chain underwent to reorganization process and hence increase of crystallinity.

2.3. EDX
Figure 3(b) represents the EDX of metal salt conjugated
PCL chains. Here also all the elements are seen. This
confirmed the chemical conjugation of metal salt with
PCL chains.

same time, due to the availability of more initiating

centres, the molecular weight of PCL was very low. (2)
At high [M/I] ratio (400), the number of initiating
species were found to be very low and hence restricted
number of initiating centre for the ROP of -CL. Now,
the entire monomeric -CL unit ring opened and
attached with the initiating centre. In such a way, the
polymerization reaction propagates and resulting with
the high molecular weight of PCL. Table 1 gives the
data about the role of [M/I] ratio on the molecular
weight of PCL.

2.4. SEM analysis

Figure 3(c) represents the surface morphology of metal
salt conjugated PCL system (M/I=10). The appearance
of broken stone like morphology confirmed the surface
morphology of PCL. Here, a particle with greater than
500 nm can be seen. Again this proved the presence of
metal salt in the PCL matrix. Above all one can see
more and more empty spaces and this will help us to
use the material in the bio-medical field as a drug
carrier.

Fig. 4: GPC of PCL synthesized at various [M/I] ratio

(a) 10, (b) 50, (c) 100, (d) 200, (e) 400

2.7. UV visible spectrum

2.5. UV-visible study

Figure 3(d-h) indicates the UV-visible reflectance
spectrum of PCL synthesized at various [M/I] ratio. It
was interesting to note that while increasing the [M/I]
ratio, the percentage of reflectance is also increased.
The increase in reflectance value confirmed the
increase in molecular weight of PCL and hydrophobic
nature of PCL. The increase in reflectance value with
the increase of [M/I] ratio explains the availability of
less number of initiating species for the ROP of -CL.
It means at lower initiator concentration, due to less
number of initiating species available for the ROP of
-CL was effective and produced a high molecular
weight of PCL. In conclusion, increase in molecular
weight leads to the hydrophobic structure of PCL. The
increase in molecular weight can be further confirmed
by GPC measurement.

2.6. GPC
The ROP of -CL by the zinc salt was confirmed by
GPC measurement. Figure 4(a-e) ensures GPC
chromatogram of PCL synthesized at various [M/I]
ratio such as 10, 50, 100, 200 and 400. The important
point noted here is while increasing [M/I] ratio from 10
to 400 both the Mw and Mn of PCL was increased. The
increase in Mw of PCL was obtained while increasing
the [M/I] ratio. It can be explained as follows: (1) At
lower [M/I] ratio, the availability of initiator species for
the ROP of -CL was very high. Due to this reason all
the monomer units were converted into polymer. At the

Fig. 5: UV-visible absorption spectrum of Zinc salt

initiated ROP of -CL
The UV-visible absorption spectrum of PCL
synthesized at various [M/I] ratio is given in Figure
5 (a-e). From the UV-visible absorption spectrum, the
band gap energy was calculated by plotting E(eV) Vs
(h)2 (Figure 6 (a-e)).

2.8. Energy band gap

It was found that while increasing the [M/I] ratio the
molecular weight of PCL was increased and with the
simultaneous increase of band gap energy. Figure 6f
plot of [M/I] ratio Vs band gap energy (eV) with a
linear plot. This proves that the molecular weight
having direct relationship with band gap energy. This is
due to the formation of encapsulated structure offered
by the coiled PCL chains.

Divya Jyoti College of Engineering & Technology, Modinagar, Ghaziabad (U.P.), India

International Journal of Advanced Engineering Research and Technology (IJAERT), ISSN: 23488190
th
st
ICRTIET-2014 Conference Proceeding, 30 -31 August 2014

Fig. 6: (a-e) Taucs plot of Zinc salt initiated ROP of

-CL, (f) plot of band gap Vs. [M/I]

V. CONCLUSIONS
From the above physicochemical studies, niche points
are summarized here as a conclusion. The FTIR
spectrum confirmed the presence of C-S, C=O and C-H
OPBV stretching in hybrid system. The particle size
analysis report declared that the metal salt formation
reaction is dominant one than the simple reduction
reaction. After the metal salt formation, the XRD
showed the poor crystalline nature. The UV-visible
reflectance value of the hybrid system exhibited the
hydrophobic nature of metal salt. After the structural
modification the band gap energy of zinc exhibited the
lower value. The FTIR-RI method proved 0.12 mole
initiator was required to form 1 mole of PCL. The
appearance of alkoxy proton and carbonyl carbon
signals confirmed the ROP of -CL by zinc salt. The
broken stone like morphology confirmed the formation
of PCL with high crystalline order (d(111)). The ring
opening nature of zinc salt was confirmed by varying
the [M/I] ratio and corresponding Mw were increased.
The taucs plot was confirmed that increase of band gap
with the increase of molecular weight of PCL. In over
all comparison, during the initiator preparation, the
acid-base titration reaction was dominant one and the
same led to the formation of metal salt.

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Divya Jyoti College of Engineering & Technology, Modinagar, Ghaziabad (U.P.), India