SYNTHESIS AND TEMPERATURE-RESPONSIVE BEHAVIOR OF N-

VINYLCAPROLACTAM-GRAFTED NR

S. PHETRONG, C. SANSUK, P. PAOPRASERT*

DEPARTMENT OF CHEMISTRY, FACULTY OF SCIENCE AND TECHNOLOGY, THAMMASAT UNIVERSITY, PATHUMTHANI, 12120
THAILAND

RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)

ABSTRACT
Temperature-responsive polymers are smart materials that respond to changes in temperature, making them suitable for
a range of applications. We report the synthesis and temperature-responsive behavior of N-vinylcaprolactam-grafted natural
rubber. The grafting reaction was carried out using deproteinized natural rubber (DPNR) latex, with 2,2 0 -azoisobutyronitrile
(AIBN) as the free radical initiator. The temperature responsiveness of the graft copolymers was investigated using water
swelling and contact angle measurement and compared with that of pure DPNR. The graft copolymer was found to be
temperature responsive in the range 32–34 8C, whereas the DPNR was not responsive to temperature. Since the temperature
responsiveness of graft copolymer is near the human body temperature, it can be used to fabricate biomedical and sensing
materials. Dye adsorption studies revealed the Langmuir isotherm, indicating monolayer coverage. The novel temperature-
responsive natural rubber demonstrated in this study has potential uses in a wide range of applications.
[doi:10.5254/rct.18.81663]

INTRODUCTION
Stimuli-responsive materials are smart materials because they can sense and respond to
changes in environmental conditions, such as pH, temperature, light, ionic strength, electric field, or
magnetic field.1–4 Changes in surrounding conditions trigger a change in the physical and chemical
properties of stimuli-responsive materials, such as their size, shape, hydrophobicity/hydrophilicity,
and degradation rate.2,5 These materials can therefore be used to fabricate responsive, active
devices that can be regulated and have new functionalities. These can be used in a range of
applications. Temperature is one of the most widely used external stimuli for such materials because
it is simple to modulate using temperature-programmed equipment or ambient conditions.
Temperature-responsive materials are generally those that undergo a volume transition or soluble-
to-insoluble change when placed in a solvent around the lower critical solution temperature
(LCST). One of the most widely studied temperature-responsive polymers is based on poly(N-
vinylcaprolactam) (PNVCL), which possesses an LCST of around 32–34 8C in water, which is near
the human body temperature.1,6,7 The non-toxicity, high water solubility, and biocompatibility of
PNVCL make it suitable for biomedical applications. In addition, PNVCL is relatively stable
against hydrolysis and does not produce toxic low molecular-weight amines due to the presence of
cyclic amide, rather than the aliphatic amides found in other polymers.8 However, the mechanical
properties of PNVCL are not particularly useful, and, therefore, significant efforts have been
directed toward improving its mechanical strength. Many temperature-responsive copolymers have
also been prepared that increase the strength and impart new properties to hybrid materials. N-
vinylcaprolactam (NVCL) has been graft copolymerized with several polymers or monomers, for
example, chitosan,9 dextran,10 graphene oxide,11 methacrylic acid,12 poly(acrylic acid),13
poly(ethylene oxide),14 polypropylene,15 and poly(vinyl chloride).16 NVCL-based copolymers
thus have the potential to be used in a wide range of applications.
Natural rubber (NR) is a well-known renewable elastomeric material obtained from the Hevea
brasiliensis tree in the form of a milky white fluid called latex.17 NR is a versatile material widely

*Corresponding author. Email: peerasak@tu.ac.th

417
418 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)

used in various applications. However, NR is poorly resistant to oxidation, weathering, and

exposure to ozone or other chemicals and solvents because of unsaturation of cis-polyisoprene in
NR.18,19 Several undesirable reactions, such as crosslinking or chain scission, occur on the
unsaturated backbones of cis-polyisoprene. Although the presence of double bonds makes cis-
polyisoprene susceptible to degradation, the double bonds are points at which new functionalities
can be added. Several chemical reactions have been used to modify NR, producing hybrid
structures with high strength and stability. Various monomers have been grafted with NR, including
dimethyl aminoethyl methacrylate,20 glycidyl methacrylate,21,22 methyl methacrylate,23–25
styrene,26–29 2-hydroxyethyl methacrylate,30,31 vinyl alcohol,32 ethyl acrylate,33 and maleic
anhydride.34 Recently, our group reported the synthesis of temperature-responsive natural rubber
crosslinked with poly(N-isopropylacryamide) (PNIPAM) and PNVCL. However, to date no
temperature-responsive materials have been reported via grafting with NR.
Although several monomers and polymers have been grafted, the main goal has been to
improve the thermal, chemical, and mechanical properties of the NR. The addition of responsive
functions to NR via grafting has not yet been reported. In this work, we thus developed a method for
grafting NVCL and deproteinized natural rubber (DPNR) latex, yielding rubber-based,
temperature-responsive materials. Grafting of hydrophilic monomers remains a challenge because
of the presence of surface proteins in the form of rubber particle shells. Monomers are not well
incorporated in the hydrophobic NR cores in latex and therefore often homopolymerize.35–37
Therefore, in this work, a grafting reaction was carried out using DPNR latex and 2,2 0 -
azoisobutyronitrile (AIBN) as an initiator. The temperature responsiveness of the graft copolymers
was measured and compared with that of pristine DPNR. Dye adsorption was investigated, to derive
the adsorption isotherms. These results show that temperature responsiveness can be introduced to
DPNR, which will expand its range of potential applications.

EXPERIMENTAL
MATERIALS

High-ammonia NR latex (60% dry rubber content (DRC)) was purchased from the Department
of Agriculture, Bangkok, Thailand. All other chemicals were purchased from Sigma-Aldrich (St.
Louis, MO, USA) and used as received, unless otherwise noted. NVCL (98%) was purified by
recrystallization in methanol. Organic solvents (Labscan, AR; Bangkok, Thailand) were used as
received. Deionized (DI) water was used throughout the experiments. PNVCL was synthesized
from NVCL via free radical polymerization using AIBN and used as a reference.

DEPROTEINIZATION OF NR LATEX

The NR latex (100 g) was commercial high-ammonia latex (60% DRC). The incubation of the
latex was performed with 0.1 wt% urea (0.2 g) in the presence of 1 wt% sodium dodecyl sulfate
(SDS, 2 g) dissolved in DI water (100 g). This mixture was then incubated for 30 min with
continuous stirring at room temperature (30 8C). The resulting latex was then purified by
centrifugation at 10 000 rpm for 1 h at 25 8C. The cream fraction was re-dispersed in 1 wt% SDS and
washed twice by centrifugation to prepare the DPNR latex (32% DRC).

GRAFTING OF NVCL ON DPNR BACKBONE

The DPNR latex (5 g) was placed in a 100 mL round-bottom flask. Then, SDS (0.15 g) as an
emulsifier and potassium hydroxide (KOH, 0.15 g) diluted in DI water was added with stirring.
 N–VINYLCAPROLACTAM–GRAFTED NR 419

Subsequently, NVCL monomer (50–150 phr with respect to DRC) was added continuously, and
the reaction mixture was heated at 80 8C for at least 30 min with continuous stirring. Next, 2,2 0 -
azoisobutyronitrile (AIBN) (5–15 phr with respect to DRC) as an initiator was dissolved with a
small amount of toluene and slowly charged into the reactor. The reaction was performed at the
desired polymerization temperature (80–100 8C). The reaction mixture was allowed to react for a
specified length of time (4–8 h). After that, the reaction mixture was cooled to room temperature and
coagulated using 5 wt% acetic acid solution. The modified product was purified by soxhlet
extraction in acetone for 24 h to remove contaminants, PNVCL homopolymer, and unreacted
monomer. The grafted product was dried under vacuum at 60 8C overnight. After drying, the grafted
product was dissolved with chloroform-d to investigate the grafting efficiency. The 1H (400 MHz)
nuclear magnetic resonance (1H-NMR) intensity of the product was used to determine the
percentage grafting efficiency.
Grafting efficiency (%G), a molar ratio between PNVCL and DPNR in the graft copolymer,
was determined from 1H-NMR spectra using the following equation:
I4:4
Grafting efficiencyð%GÞ ¼ 3 100;
I5:2
where I4.4 is the integrated signal area of the proton in –NCH– of the a position of the PNVCL unit
and I5.2 is the integrated signal area of the unsaturated methyne proton of the polyisoprene backbone
chain.

DETERMINATION OF TEMPERATURE RESPONSIVENESS

The grafted material and dry DPNR were cut into small pieces (1 3 1 cm2) and compressed to
remove air bubbles and reduce porosity by sandwiching them between two glass slides and heating
at 60 8C for 24 h. The samples were immersed in DI water for 2 h at temperatures of 28, 30, 32, 34,
36, and 38 8C. After gently removing the surface liquid using tissue paper, the weight of the
materials was measured and the swelling percentage was calculated to determine the responsive
temperature, from the following equation:
W2  W1
Swellingð%Þ ¼ 3 100;
W1
where W1 and W2 are the weight of the material before and after immersion, respectively.

ADSORPTION ISOTHERM STUDIES

A stock solution of 50 ppm was prepared by dissolving indigo carmine (0.05 g) in DI water (1
L). The working solutions (10–50 ppm) were prepared by diluting the stock solution with DI water.
Equilibrium adsorption was carried out by introducing 0.2 g of the rubber sample with 10 mL of
indigo carmine at concentrations of 10–50 ppm. The bottles were sealed and placed in a shaker at
room temperature for 1 week. The concentration of the residual dye was measured using a
ultraviolet (UV)–visible spectrometer at a kmax corresponding to the maximum adsorption for the
dye solution (kmax ¼ 610 nm). A calibration curve was constructed between absorbance and the
concentration of the dye solution (2–18 ppm) to obtain the absorbance-concentration profile. The
amount of adsorbed indigo carmine was calculated based on a mass balance equation, given by
ðC0  Ce ÞV
qe ¼ ;
W
where qe is the equilibrium adsorption capacity per gram dry weight of the adsorbent (mg g1), C0 is
420 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)

the initial concentration of indigo carmine in the solution (mg L1), Ce is the final or equilibrium
concentration of indigo carmine in the solution (mg L1), V is the volume of the solution (L), and W
is the dry weight of the rubber sample (g).

DYE ADSORPTION AND DESORPTION STUDIES

Indigo carmine dye was chosen to represent a water-soluble anionic drug. Thin rubber samples
(13 1 cm2) were prepared and compressed to remove air bubbles as described above. The samples
were then immersed in an aqueous solution of indigo carmine (10 ppm) for 1 week at 30 8C. Then,
the rubber samples were removed and dried at 60 8C for 24 h. After that, the rubber samples were
incubated in DI water and then placed in a temperature-controlled water bath at a range of
temperatures of 28, 30, 32, 34, 36, and 38 8C for 3 h. Aliquots were withdrawn for measurement
using UV–visible spectroscopy in the wavelength range 400–800 nm.

CHARACTERIZATION

CHN data were obtained using a CHN-2000 LECO analyzer. 1H (400 MHz) nuclear magnetic
resonance (NMR) spectra were obtained using an AVANCE Bruker NMR Spectrometer with
chloroform-d as solvent. The Fourier transform infrared (FT-IR) spectra were obtained using a
Perkin Elmer FT-IR (Spectrum GX model) and NaCl salt windows. Thermogravimetric analysis
(TGA) of the polymers was carried out using an SDTA851e Mettler Toledo analyzer. The samples
were heated at a rate of 10 8C min1 under a nitrogen atmosphere. The glass transition temperatures
(Tg) of the polymers were obtained using a DSC822e Mettler Toledo differential scanning
calorimeter. The samples were heated at a rate of 10 8C min1 under a nitrogen atmosphere. UV–
visible spectra were obtained using a UV-1700 PharmaSpec UV–visible spectrometer. The water
contact angle was measured using an OCA35 Dataphysics contact angle meter. The size of the
water droplet was 8 lL.

RESULTS AND DISCUSSION

SYNTHESIS AND CHARACTERIZATIONS OF GRAFT COPOLYMER

In this work, the synthesis of temperature-responsive NR is described. NVCL-grafted DPNR

(NVCL-g-DPNR) was prepared via free radical grafting in an aqueous system using AIBN as an
initiator. The NR latex was deproteinized prior to grafting because previous studies have shown that
deproteinization removes surface protein, improving grafting efficiency between monomer and cis-
polyisoprene in the particle core.35,37 Deproteinization was carried out using urea as the
deproteinizing agent.38,39 Urea can denature the surrounding proteins around the latex particles.
The DPNR was characterized using CHN analysis. It was found that the nitrogen content in DPNR
was less than that of the NR by 43%, while the percentage of carbon and hydrogen remained almost
unchanged (Table I). This result indicates that deproteinization of NR removed approximately 50%
of the protein from the NR latex, comparable with the results of a previous study.39
Grafting of NVCL onto DPNR was carried out in an aqueous system using AIBN as a free
radical initiator (Figure 1). Based on previous studies, AIBN is an excellent initiator for preparation
of PNVCL-based polymers.40,41 The formation of grafting copolymer is believed to proceed by two
possible pathways: a reaction between the free radicals and double bonds of the isoprene units, and a
hydrogen abstraction mechanism.42–46 The NVCL-g-DPNR was purified by stirring twice in
acetone to remove impurities, unreacted NVCL, and PNVCL homopolymer. The NVCL-g-DPNR
was characterized using FT-IR and 1H-NMR and compared with the DPNR and PNVCL. The FT-
 N–VINYLCAPROLACTAM–GRAFTED NR 421

TABLE I
ELEMENTAL ANALYSIS OF NR AND DPNR

Chemical composition

Sample name Carbon (%) Hydrogen (%) Nitrogen (%)

DPNR 84.19 12.88 0.43

NR 84.79 12.68 0.76

IR spectrum of NVCL-g-DPNR showed signature signals of both DPNR and PNVCL (Figure 2).
The FT-IR signals at 3440, 3255, 1631, and 1479 cm1 corresponded to O–H stretching, N–H
stretching, C¼O stretching, and C–N stretching of the caprolactam ring of the PNVCL,
respectively. The signal at 1442 cm1 corresponded to C¼C stretching of the polyisoprene. The FT-
IR results are consistent with those reported in previous work.40 The O–H stretching at 3390 cm1
was possibly due to the presence of moisture adsorbed on hydrophilic NVCL units. Images were
taken of the NVCL-g-DPNR, DPNR, and NVCL (Figure 1b). DPNR was a clear solid, whereas
NVCL was a white powder. The NVCL-g-DPNR was a yellowish solid and stiffer than the DPNR.
The rubber samples were characterized using 1H-NMR to confirm the formation of graft
copolymer and determine the grafting efficiency. The 1H-NMR spectrum of DPNR showed signals
at 5.2, 2.1, and 1.7 ppm, corresponding to C–H, CH2, and CH3, respectively (Figure 3), and
consistent with previous reports.47–49 The 1H-NMR spectrum of the PNVCL showed signals at 4.4,
3.3, 2.5, and 1.8 ppm, corresponding to CH–NH, CH2–NH, CH2–CO, and CH2, respectively. The
1
H-NMR spectrum of NVCL-g-DPNR showed signals corresponding to both DPNR and PNVCL.
The signal at 4.4 ppm corresponded to CH–NH of the PNVCL, whereas the signal at 5.2 ppm
corresponded to C–H of the isoprene units, confirming the successful grafting reaction. These
signals were used to calculate grafting efficiency, which was found to be 25%.

FIG. 1. — (a) Schematic representation for the synthesis of NVCL-g-DPNR from DPNR and NVCL and (b) their respective
images.
422 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)

FIG. 2. —FT-IR spectra of DPNR, PNVCL, and NVCL-g-DPNR.

Thin films of rubber samples were prepared and characterized using X-ray photoelectron
spectroscopy (XPS). The XPS spectra of DPNR and NVCL-g-DPNR shown signals of O1s, C1s,
Si2s, and Si2p at 532, 285, 153, and 102 eV, respectively (Figure 4). The presence of silicon signals
was due to the use of a silicon as a substrate for the measurement. However, only the XPS spectrum
of NVCL-g-DPNR showed a strong N1s signal at 399 eV. This was not observed in the DPNR
sample, due to the presence of amide groups of NVCL units in the grafted material.
To further confirm the formation of graft copolymer, a blend sample between DPNR latex and
PNVCL was prepared in water solution and dried as a thin film by placing on a glass plate. After
that, the film was peeled off and purified via stirring in acetone twice and dried in an oven at 60 8C
overnight. No PNVCL was detected in the 1H-NMR spectrum, as it was soluble in acetone.
Therefore, the presence of both PNVCL and DPNR in the NVCL-g-DPNR sample was attributed to

FIG. 3. — (a) 1H-NMR spectra of DPNR, PNVCL, and NVCL-g-DPNR and (b) signal assignments.
 N–VINYLCAPROLACTAM–GRAFTED NR 423

FIG. 4. —XPS spectra of DPNR and NVCL-g-DPNR. The inset shows the high-resolution spectra in the N1s region.

the formation of a grafted structure inseparable by stirring in acetone. This result also confirmed that
stirring in acetone twice effectively removed the unbound PNVCL homopolymer.
The thermal properties of the DPNR and NVCL-g-DPNR were characterized using DSC and
TGA. From the DSC thermograms, it was found that the Tg of DPNR and PNVCL were63.7 and
184.1 8C, respectively (Figure 5). NVCL-g-DPNR showed Tg of both DPNR and PNVCL
components at 61.6 and 175.7 8C. This suggests that the NVCL-g-DPNR sample consists of

FIG. 5. —DSC thermograms of DPNR, PNVCL, and NVCL-g-DPNR.

424 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)

FIG. 6. —TGA thermograms of DPNR, PNVCL, and NVCL-g-DPNR.

amorphous domains of DPNR and PNVCL. From the TGA thermograms, the DPNR started to
lose weight at 320 8C, consistent with the previous reports (Figure 6).46,50,51 PNVCL started to
lose weight at 100 8C due to breakage of the amide functional groups. The thermogram of the
NVCL-g-DPNR sample was similar to that of DPNR, but slightly more stable due to the presence
of PNVCL. This confirms the presence of both DPNR and PNVCL in the NVCL-g-DPNR
sample.
In this study, the effects of different reaction conditions and reagent concentrations on grafting
efficiency were investigated. First, the grafting efficiency as a function of NVCL concentration was
measured using an AIBN concentration of 10 phr and a reaction time of 6 h at 90 8C. It was found
that, as the NVCL concentration was increased from 50 to 150 phr with respect to DPNR, the
grafting efficiency increased from 11% to 38% (Figure 7a). This result indicates that, as the amount
of NVCL monomer increased, the percentage grafting efficiency also increased. Second, the effect
of AIBN concentration on grafting efficiency was studied using an NVCL concentration of 100 phr,
and a reaction time of 6 h at 90 8C (Figure 7b). When the AIBN concentration was increased from 5
to 15 phr, the grafting efficiency decreased from 21% to 10%. Increasing the initiator concentration
resulted in a lower grafting efficiency. We assume that the higher initiator concentration
preferentially reacted with the monomer rather than grafting onto the DPNR backbone, producing a
free polymer. A high concentration of AIBN might also lead to high termination rates of free
radicals. Third, the effect of reaction temperature on grafting efficiency was investigated using an
NVCL concentration of 100 phr, AIBN concentration of 10 phr, and a reaction time of 6 h (Figure
7c). It was found that, when the reaction temperature was increased from 80 to 100 8C, which is the
optimum working range for AIBN,52 the grafting efficiency decreased from 51% to 11%. The high
temperature might produce a high termination rate. Lastly, the effect of reaction time on grafting
efficiency was investigated using an NVCL concentration of 100 phr, AIBN concentration of 10
phr, and a reaction temperature of 90 8C (Figure 7d). When the reaction time was increased from 4 to
8 h, the grafting efficiency decreased from 29% to 6%. It was found that the use of a longer reaction
time decreased the grafted DPNR but increased the free PNVCL. A long reaction time might lead to
decomposition of the polymer.
 N–VINYLCAPROLACTAM–GRAFTED NR 425

FIG. 7. —Grafting efficiency as a function of (a) NVCL concentration, (b) AIBN concentration, (c) reaction temperature,
and (d) reaction time.

TEMPERATURE-RESPONSIVE CHARACTERISTICS

The temperature responsiveness of DPNR and NVCL-g-DPNR in water were characterized in

a temperature range of 28–38 8C. At 28 8C, NVCL-g-DPNR swelled by 25% of its original weight,
or about 12 times more than the DPNR, due to the presence of hydrophilic amide groups in the
NVCL units. Moreover, the NVCL-g-DPNR sample with higher grafting efficiency showed more
swelling than the sample with lower grafting efficiency because of higher hydrophilicity. As the
temperature was increased, the percentage of water swelling of the DPNR did not change, whereas
that of the NVCL-g-DPNR started to decrease when the water temperature exceeded 32 8C, and
became constant above 34 8C (Figure 8). The transition temperature of NVCL-g-DPNR was
therefore determined to fall in the range 32–34 8C, which is similar to the coil-to-globule transition
temperature of PNVCL.40,53 These results suggest that the presence of DPNR and a grafted
structure in the NVCL-g-DPNR did not significantly affect the transition temperature of the
PNVCL. This finding is consistent with other reports on temperature-responsive crosslinked
materials.54–58
The transition temperatures of DPNR and NVCL-g-DPNR were also determined using
temperature-controlled contact angle meters. At 28 8C, the contact angles of DPNR and NVCL-g-
DPNR were 104 and 538, respectively, indicating a greater hydrophobicity of DPNR than NVCL-g-
DPNR (Figure 9). The contact angles of the DPNR sample were almost constant over the measured
temperature range, confirming that the DPNR was not temperature responsive. In contrast, the
contact angles of the NVCL-g-DPNR sample started to increase as the temperature exceeded 32 8C,
reaching 798 at 38 8C. The increase in contact angle was due to the increase in hydrophobicity of the
NVCL units as a result of hydrogen-bond breakage between the water molecules and amide groups
in NVCL. The transition temperature determined from the abrupt change in contact angles was
about 32–34 8C, which is similar to those determined using the water swelling method.
426 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)

FIG. 8. —Water swelling percentage of DPNR and NVCL-g-DPNR in aqueous solutions at different temperatures.

DYE ADSORPTION AND DESORPTION STUDIES

To further confirm the temperature responsiveness of the NVCL-g-DPNR sample, the

adsorption and desorption were determined using indigo carmine as the anionic drug model. Indigo
carmine was selected due to its high solubility in water and intense absorbance in the visible region.
After the rubber samples had been immersed in indigo carmine solution for 1 week at room

FIG. 9. —Contact angles of DPNR and NVCL-g-DPNR at different temperatures.

 N–VINYLCAPROLACTAM–GRAFTED NR 427

FIG. 10. —UV–visible spectra of standard indigo carmine solution and solutions after immersion of DPNR and NVCL-g-
DPNR samples.

temperature, the grafted samples were found to absorb more dye than the DPNR, as illustrated by a
greater reduction in dye absorbance (Figure 10). Additionally, the NVCL-g-DPNR sample with
higher grafting efficiency absorbed more indigo carmine than the grafted sample with lower
grafting efficiency, as indicated by the greater reduction in absorbance. The larger amount of amide
groups of NVCL units within the grafted structure had numerous hydrogen-bond interactions with
the amino groups of the indigo carmine molecules.
Four well-known adsorption models, the Langmuir, Freundlich, Temkin, and Dubinin–
Radushkevich isotherms, were used to investigate the interaction between indigo carmine and
NVCL-g-DPNR (Table II).59–62 The Langmuir adsorption isotherm assumes that monolayer
coverage is formed on the surface of the adsorbent. The Freundlich adsorption isotherm describes
the adsorption characteristics of multilayer adsorption. The Temkin adsorption isotherm takes
account of indirect effects, such as heat, and the adsorbate/adsorbent interaction. Lastly, the
Dubinin–Radushkevich isotherm describes the adsorption model on both homogeneous and
heterogeneous surfaces, based on a pore filling mechanism. The mathematical equations of these
four models are shown in Table II.63–65 On the basis of the R values (R2) (Figure 11), the Langmuir
model showed the highest R2 of 0.91 and therefore the best fit to the experimental data among the
four models. This suggests that the monolayer adsorption of indigo carmine occurs more readily on
the surface of NVCL-g-DPNR.
The adsorption coefficients and parameters provide evidence on the mechanisms of
adsorption. The dimensionless constant (RL) value of between 0 and 1 indicates favorable
adsorption between indigo carmine and NVCL-g-DPNR (Table III). In addition, the adsorption
 428

TABLE II
EQUATIONS FOR THE ISOTHERMS AND THE COEFFICIENT OF DETERMINATION (R2)

Isotherm Nonlinear forma Linear forma Plota Parametera

Q 0 KL Ce 1 1
Langmuir59 qe ¼ 1þK L Ce qe ¼ Q10 þ Q0 K1L Ce qevs C1e
Freundlich60 qe ¼ KfCe1/n log qe ¼ log Kf þ 1nlog Ce log qe vs log Ce
Temkin61 qe ¼ RbTT lnðAT Ce Þ qe ¼ B ln AT þ B ln Ce qe vs ln Ce B ¼ RT
bT
Dubinin–Radushkevich62 qe ¼ (qs) exp (Kade2) ln qe ¼ ln (qs)  (Kade2) ln qe vs e2 e ¼ RTln½1 þ C1e 
E ¼ ½pffiffiffiffiffiffi
1 ffi
2K

ad
a
Ce is the equilibrium concentration of adsorbate (mg L1), qe is the amount of metal adsorbed per gram of the adsorbent at equilibrium (mg g1), Q0 is the maximum monolayer coverage
capacity (mg g1), RL is a dimensionless constant, KL is Langmuir isotherm constant (L mg1), Kf is Freundlich isotherm constant (mg g1), n is adsorption intensity, AT is Temkin isotherm
equilibrium binding constant (L mg1), bT is Temkin isotherm constant, R is universal gas constant (8.314 J mol1 K1), T is temperature at 303.15 K, B is constant related to heat of sorption (J
mol1), qs is theoretical isotherm saturation capacity (mg g1), Kad is Dubinin–Radushkevich isotherm constant (mol2 J2), and e is Dubinin–Radushkevich isotherm constant.
RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)
 N–VINYLCAPROLACTAM–GRAFTED NR 429

FIG. 11. —Plots of (a) Langmuir, (b) Freundlich, (c) Temkin, and (d) Dubinin–Radushkevich adsorption isotherms.

intensity (n) from the Freundlich isotherm is larger than 1, indicating the favorable adsorption of
dye onto NVCL-g-DPNR.66,67 Additionally, the value of mean sorption energy (E) from the
Dubinin–Radushkevich isotherm gives information about chemical and physical adsorption. The E
value of 0.71 kJ mol1 was less than 8 kJ mol1, revealing that the adsorption of indigo carmine by
NVCL-g-DPNR is through physical adsorption.65,68,69
After adsorption of indigo carmine, the rubber samples were removed, dried, and placed in
aqueous solution at temperatures in the range 28–38 8C (Figure 12). At temperatures above 32 8C,
the NVCL-g-DPNR sample released dye into the aqueous solution, as confirmed by the increase in
absorbance and change of color. In contrast, absorbance of indigo carmine from the DPNR sample
showed no change throughout the measured temperature range. It was also found that NVCL-g-
DPNR with higher grafting efficiency released more dye than the sample with lower grafting
efficiency. This is possibly because more dye was available from the sample with higher grafting
efficiency. These results clearly indicate that the NVCL-g-DPNR was temperature responsive,
whereas the DPNR was not. The NVCL-g-DPNR has potential uses in biomedical and sensing
applications, separation membranes, and as an activator for enzymes.70–72

TABLE III
LANGMUIR, FREUNDLICH, TEMKIN, AND DUBININ–RADUSHKEVICH ISOTHERM CONSTANTS FOR THE ADSORPTION OF
INDIGO CARMINE ONTO NVCL-G-DPNR

Langmuir constants Freundlich constants

Q0 (mg g1) KL (L mg1) RL R2 1/n n Kf (mg g1) R2

1.54 0.14 0.41 0.91 0.62 1.60 0.22 0.83
Temkin constants Dubinin–Radushkevich constants
bT (kJ mol1) AT (L mg1) B (J mol1) R2 qs (mg g1) Kad (mol2 kJ2) E (kJ mol1) R2
5.66 0.92 0.45 0.64 1.02 1 3 106 0.71 0.69
430 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)

FIG. 12. —UV–visible spectra of solutions after desorption of indigo carmine from (a) DPNR, (b) NVCL-g-DPNR (%G¼
24%), (c) NVCL-g-DPNR (%G ¼ 15%) samples at different temperatures, and (d) release profiles of indigo carmine from
DPNR and NVCL-g-DPNR samples at kmax ¼ 610 nm.

CONCLUSIONS
In this work, the graft copolymers between NVCL and DPNR were successfully prepared via
grafting reaction in emulsion. The grafted materials were rubber-like with thermal properties close
to those of pristine DPNR. The transition temperature of the graft copolymer was about 32–34 8C,
close to that of PNVCL. The dye adsorption studies showed a monolayer formation of the dye onto
the graft copolymer surface. The adsorbed dye could be released when the temperature of the
materials was raised above their transition temperature. These temperature-responsive, hydrogel-
like rubbers will be useful in a variety of biomedical applications. Potential consumer products
include smart bandages and facial masks with the ability to efficiently release medicine or other
healing ingredients, upon contact with human skin. The strategy presented in this work allows the
preparation of multi-stimuli–responsive rubbers through reactions with multiple responsive
materials, extending their properties of the rubbers.

ACKNOWLEDGEMENTS
This work is financially supported by the Thailand Research Fund (TRF) and the Faculty of
Science and Technology, Thammasat University (TRG5880199). The authors acknowledge the
Central Scientific Instrument Center (CSIC), Department of Chemistry, Faculty of Science and
Technology, and Thammasat University.
 N–VINYLCAPROLACTAM–GRAFTED NR 431

REFERENCES
1
H. Almeida, M. H. Amaral, and P. Lobão, J. Appl. Pharma. Sci. 2, 1 (2012).
2
J.-K. Chen and C.-J. Chang, Materials 7, 805 (2014).
3
M. A. Ward and T. K. Georgiou, Polymers 3, 1215 (2011).
4
T. B. Y. N. Gupta, M. Chandra, R. B. Sharma, and D. K. Setua, RUBBER CHEM. TECHNOL. 90, 159 (2017).
5
R. Liu, M. Fraylich, and B. R. Saunders, Colloid Polym. Sci. 287, 627 (2009).
6
M. R. Aguilar, C. Elvira, A. Gallardo, B. Vázquez, and J. S. Román, Topics Tissue Eng. (2013).
7
T. Yoshida, T. C. Lai, G. S. Kwon, and K. Sako, Expert Opin. Drug Deliv. 10, 1497 (2013).
8
T. Kavitha, I.-K. Kang, and S.-Y. Park, Colloids Surf. B 115, 37 (2014).
9
M. Prabaharan, J. J. Grailer, D. A. Steeber, and S. Gong, Macromol. Biosci. 8, 843 (2008).
10
H. Shi, W. Chen, and L. Zhang, Frontiers Chem. Eng. China 1, 72 (2007).
11
T. Kavitha, I.-K. Kang, and S.-Y. Park, Colloids Surfaces B: Biointerfaces 115, 37 (2014).
12
D. Crespy, A. Golosova, E. Makhaeva, A. R. Khokhlov, G. Fortunato, and R. Rossi, Polym. Int. 58, 1326 (2009).
13
X. Jiang, G. Lu, C. Feng, Y. Li, and X. Huang, Polym. Chem. 4, 3876 (2013).
14
K. Van Durme, S. Verbrugghe, F. E. Du Prez, and B. Van Mele, Macromolecules 37, 1054 (2004).
15
V. N. Kudryavtsev, V. Y. Kabanov, N. A. Yanul’, and S. A. Kedik, High Energy Chem. 37, 382 (2003).
16
R. Patel, S. H. Ahn, W. S. Chi, and J. H. Kim, Ionics 18, 395 (2012).
17
D. F. Graves, ‘‘Rubber,’’ in Handbook of Industrial Chemistry and Biotechnology, Kent, J. A., Ed., Springer, New York,
2007.
18
C. Gamlin, M. G. Markovic, N. K. Dutta, N. R. Choudhury, and J. G. Matisons, J. Therm. Anal. Calorimetry 59, 319
(2000).
19
W. Kangwansupamonkon, R. G. Gilbert, and S. Kiatkamjornwong, Macromol. Chem. Phys. 206, 2450 (2005).
20
P. C. Oliveira, A. Guimaraes, J. Y. Cavaille, L. Chazeau, and R. G. Gilbert, Polymer 46, 1105 (2005).
21
P. Juntuek, C. Ruksakulpiwat, P. Chumsamrong, and Y. Ruksakulpiwat, J. Appl. Polym. Sci. 122, 3152 (2011).
22
P. Suriyachi, S. Kiatkamjornwong, and P. Prasassarakich, RUBBER CHEM. TECHNOL. 77, 914 (2004).
23
P. Satraphan, A. Intasiri, V. Tangpasuthadol, and S. Kiatkamjornwong, Polym. Adv. Technol. 20, 473 (2009).
24
T. Kochthongrasamee, P. Prasassarakich, and S. Kiatkamjornwong, J. Appl. Polym. Sci. 101, 2587 (2006).
25
S. Zhang, L. Cao, F. Shao, L. Chen, J. Jiao, and W. Gao, Polym. Adv. Technol. 19, 54 (2008).
26
P. Suksawad, Y. Yamamoto, and S. Kawahara, Eur. Polym. J. 47, 330 (2011).
27
W. Arayapranee and G. L. Rempel, J. Appl. Polym. Sci. 109, 1395 (2008).
28
N. Pukkate, T. Kitai, Y. Yamamoto, T. Kawazura, J. Sakdapipanich, and S. Kawahara, Eur. Polym. J. 43, 3208 (2007).
29
L. Fukuhara, N. Kado, N. T. Thuong, S. Loykulant, K. Suchiva, K. Kosugi, Y. Yamamoto, H. Ishii, and S. Kawahara,
RUBBER CHEM. TECHNOL. 88, 117 (2015).
30
Y. Promdum, P. Klinpituksa, and J. Ruamcharoen, Songklanakarin J. Sci. Technol. 31, 453 (2009).
31
S. Amnuaypanich and P. Ratpolsan, J. Appl. Polym. Sci. 113, 3313 (2009).
32
W. Wongthep, S. Srituileong, S. Martwiset, and S. Amnuaypanich, J. Appl. Polym. Sci. 127, 104 (2013).
33
G. Adam, A. Sebenik, U. Osredkar, F. Ranogajec, and Z. Veksli, RUBBER CHEM. TECHNOL. 64, 133 (1991).
34
C. Nakason, A. Kaesaman, and P. Supasanthitikul, Polym. Testing 23, 35 (2004).
35
C. Nakason, A. Kaesaman, and N. Yimwan, J. Appl. Polym. Sci. 87, 68 (2003).
36
N. Pukkate, Y. Yamamoto, and S. Kawahara, Colloid Polym. Sci. 286, 411 (2008).
37
P. Wongthong, C. Nakason, Q. Pan, G. L. Rempel, and S. Kiatkamjornwong, Eur. Polym. J. 49, 4035 (2013).
38
L. Fukuhara, K. Miyano, Y. Yamamoto, H. Ishii, and S. Kawahara, Kobunshi Ronbunshu 72, 1 (2015).
39
S. Kawahara, W. Klinklai, H. Kuroda, and Y. Isono, Polym. Adv. Technol. 15, 181 (2004).
40
K. Selin, T. Özdemir, and A. Usanmaz, Macr. Sci. A 48, 467 (2011).
432 RUBBER CHEMISTRY AND TECHNOLOGY, Vol. 91, No. 2, pp. 417–432 (2018)

41
M. Webster, J. Miao, B. Lynch, D. Green, R. Jones-Sawyer, R. J. Linhardt, and J. Mendenhall, Macro. Mater. Eng. 298,
447 (2013).
42
Halimatuddahliana, H. Ismaila, and H. M. Akil, Int. J. Polym. Mater. 54, 1169 (2005).
43
H. Liu, C. Chuai, M. Iqbal, H. Wang, B. B. Kalsoom, M. Khattak, and M. Q. Khattak, J. Appl. Polym. Sci. 122, 973 (2011).
44
S. M. Tamboli, S. T. Mhaske, and D. D. Kale, J. Appl. Polym. Sci. 122, 973 (2011).
45
E. Manaila, M. D. Stelescu, G. Craciun, and L. Surdu, Polym. Bull. 71, 2001 (2014).
46
P. Nuntahirun, O. Yamamoto, and P. Paoprasert, Macr. Res. 24, 816 (2016).
47
J.-K. Chen and C.-J. Chang, Materials 7, 805 (2014).
48
D. Li, X. Zhang, J. Yao, G. P. Simon, and H. Wang, Chem. Commun. 47, 1710 (2011).
49
Y. I. Park, B. Zhang, C.-Y. Kuo, J. S. Martinez, J. Park, S. Mallapragada, and H.-L. Wang, J. Phys. Chem. C 117, 7757
(2013).
50
C. Kookarinrat and P. Paoprasert, Iran. Polym. J. 24, 123 (2015).
51
T. Chanroj and P. Paoprasert, RUBBER. CHEM. TECHNOL. 89, 251 (2016).
52
J. Brandrup, E. H. Immergut, and E. A. Grulke, Polymer Handbook, 4th ed., Vol. 2, John Wiley, New York, 1999.
53
K. M. Rao, B. Mallikarjuna, K. S. V. K. Rao, S. Siraj, K. C. Rao, and M. C. S. Subha, Colloids Surf. B 102, 891 (2013).
54
G. Yi, Y. Huang, F. Xiong, B. Liao, J. Yang, and X. Chen, J. Wuhan Univ. Technol.-Mater. Sci. Ed. 26, 1073 (2011).
55
X. Xia, and Z. Hu, Langmuir 20, 2094 (2004).
56
Y. Cai, W. Shen, S. L. Loo, W. B. Krantz, R. Wang, A. G. Fane, and X. Hua, Water Res. 47, 3773 (2013).
57
A. Hebeish, S. Farag, S. Sharaf, and T. I. Shaheen, Carbohydrate Polym. 102, 159 (2014).
58
A. Zadrazil and F. Stepánek, Colloids Surf. A 372, 115 (2010).
59
I. Langmuir, J. Am. Chem. Soc. 40, 1361 (1918).
60
H. Freundlich, Z. Chem. Ind. Kolloide 7, 193 (1910).
61
M. I. Temkin, J. Phys. Chem.(Moscow) 14, 1153 (1940).
62
C. Nguyen and D. D. Do, Carbon 39, 1327 (2001).
63
X. Chen, Information 4, 14 (2015).
64
A. O. Dada, A. P. Olalekan, A. M. Olatunya, and O. Dada, IOSR J. Appl. Chem. 3, 38 (2012).
65
A. U. Itodo and H. U. Itodo, Life Sci. J. 7, 31 (2010).
66
B. H. Hameed, D. K. Mahmoud, and A. L. Ahmad, J. Hazard Mater. 158, 65 (2008).
67
Y. S. Ho and G. McKay, Chem. Eng. J. 70, 115 (1998).
68
M. Jain, V. K. Garg, and K. Kadirvelu, J. Hazard. Mater. 162, 365 (2009).
69
M. B. Ibrahim and S. Sani, Open J. Phys. Chem. 4, 139 (2014).
70
J. Tobis, L. Boch, Y. Thomann, and J. C. Tiller, J. Membr. Sci. 372, 219 (2011).
71
M. Hanko, N. Bruns, J. C. Tiller, and J. Heinze, Anal. Bioanal. Chem. 386, 1273 (2006).
72
N. Bruns, W. Bannwarth, and J. C. Tiller, Biotech. Bioeng. 101, 19 (2008).

[Received July 2017, Revised August 2017]