Reactive and Functional Polymers 112 (2017) 2232

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Reactive and Functional Polymers

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Chemically modied natural rubber latex - poly(vinyl alcohol) blend

membranes for organic dye release
Janisha Jayadevan a, Rosamma Alex b, Unnikrishnan Gopalakrishnapanicker a,
a
Polymer Science & Technology Laboratory, Department of Chemistry, National Institute of Technology Calicut, NITC Campus (P.O), Kozhikode, Kerala 673601, India
b
Joint Director (Rt), Rubber Research Institute of India, Kottayam, Kerala, India

a r t i c l e i n f o a b s t r a c t

Article history: Novel blend membranes were prepared from chemically modied natural rubber latex (NRL) and poly(vinyl al-
Received 23 July 2016 cohol) (PVA) for release application. Chemical modication of NRL was done by grafting (dimethylaminoethyl
Received in revised form 27 December 2016 methacrylate) (DMAEMA) onto NR particles by using a redox initiator system viz; cumene hydroperoxide/
Accepted 3 January 2017
tetraethylenepentamine (CHP/TEPA), followed by dialysis for purication. The grafting was conrmed by dy-
Available online 05 January 2017
namic light scattering (DLS), fourier transform infrared (FT-IR) spectroscopy and nuclear magnetic resonance
Keywords:
spectroscopy (NMR). The grafted NRL was subsequently blended with PVA to make uniform membranes by sol-
Natural rubber latex vent casting at 60 2 C. The blend membranes were characterised by FT-IR spectroscopy, X-ray diffractometry
Poly(dimethylaminoethyl methacrylate) (XRD) and thermogravimetry (TGA). Moisture uptake, swelling and water contact angle experiments showed an
Redox initiated grafting increased hydrophilicity when the PVA content in the blend membranes was increased. Scanning electron micro-
Poly(vinyl alcohol) scopic investigations indicated the formation of pores in the membranes after a leaching cycle. The potential of
Blend membranes the membrane for the use in the release application was tested with model organic dyes rhodamine B, methyl
Organic dye release orange and uorescein. Results from the release study indicate that the membranes can be used for the release
of cationic dyes.
2017 Elsevier B.V. All rights reserved.

1. Introduction
Natural rubber latex (NRL) is a biomacromolecular system having
cis-polyisoprene particles dispersed in aqueous medium [1]. It is a slight
yellow milky liquid that undergoes coagulation by acids and electrolytes
at room temperature [2,3]. Average size of the polymer particles in NRL
is 0.023 m. The particles are covered by a layer of proteins and lipids.
These proteins and lipids are negatively charged, which provides colloi-
dal stability to the NRL [4]. However, the colloidal stability is very sensi-
tive to pH changes. This limits its use as a core material in latex form for
many applications. The products from NRL such as tubings, surgical
gloves and catheters nd extensive applications in the biomedical
eld [58]. The advantages of these products are their elasticity, exibil-
ity and resistance against splitting [9]. However, the products from NRL
show some disadvantages such as low resistance to thermal degrada-
tion, poor resistance to ozone and organic solvents and biological in-
compatibility to the human body [10].
In view of the above, many efforts are being implemented to modify
the features of NRL. There are three main approaches to improve the
properties of NRL which includes a change in its chemical microstruc-
ture, addition of compatible chemical reagents into it or blending it
Corresponding author.
E-mail address: unnig@nitc.ac.in (U. Gopalakrishnapanicker).
with other suitable polymers [1115]. It has been reported that the
properties of NRL can be efciently altered through graft
copolymerisation [1619]. Grafting of a second polymer onto NRL
using redox initiators is a preferred method for modifying NR both in so-
lution [20] and latex form [2123]. Such grafting may lead to a core-
shell structure; with a hydrophobic core and hydrophilic shell [19].
The core-shell type composite polymer emulsions possess structured
latex particles with ne-tunable properties [24,25]. The key feature in
this type of structured composite emulsions is the regulation of the
structure of the latex particles without changing the basic composition
[26]. This type of chemical modication results an enhanced colloidal
stability at a lower pH range, since the resultant hydrophilic shell can
act as an electrosteric stabiliser. The enhanced colloidal stability
makes latex resistant to any mechanical and chemical disturbances
and improves its processability [27].
Polyvinyl alcohol (PVA) is a water soluble synthetic polymer. It is a
macromolecule of great interest because of its desirable characteristics
such as hydrophilicity, good lm forming ability, resistance to oxidation
and excellent mechanical properties [28]. It has also been employed for
different pharmaceutical and biomedical applications [29,30]. PVA has
by now been identied as an excellent partner for many macromolecu-
lar systems [3133].
There are different reports on the utilization of NRL and PVA individ-
ually or along with other polymers for drug/dye delivery applications

http://dx.doi.org/10.1016/j.reactfunctpolym.2017.01.001
1381-5148/ 2017 Elsevier B.V. All rights reserved.
 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232 23

Scheme 1. Chemical modication of NRL.

[3439]. A few articles report their combination with improved proper-
ties for similar applications [40]. However no reports are available on
chemically modied NRL/PVA blends for dye/drug release applications.
The goal of the present work is to modify NRL physico-chemically, and
to develop novel membranes for release applications. The study initially
focuses on the chemical modication of NRL with dimethylaminoethyl
methacrylate (DMAEMA) by using a redox initiator system (cummene
hydroperoxide/tetraethylene pentamine) (CHP/TEPA). The modied
NRL has then been physically blended with PVA to form high quality
membranes. The grafting has been monitored by DLS, FT-IR and NMR.
The blended systems have been characterised by using FTIR, XRD, TGA
and SEM. Pore generation has been achieved for the membranes by a
swelling-deswelling cycle. The efciency of the membranes for controlled
release has been conrmed by three model organic dyes rhodamine B,
methyl orange and uorescein.
2. Materials and methods
2.1. Materials
Natural rubber latex (34% DRC) used in this study was a commercial
sample procured from a rubber plantation at Thekkumkutty, Calicut,
Kerala, India. Dimethylaminoethyl methacrylate (DMAEMA) monomer
and the tetraethylene pentamine (TEPA) co-initiator were purchased
from Aldrich, Germany. Sodium dodecyl sulfate (SDS) and cumene hy-
droperoxide (CHP) were procured from Alfa Aesar, Briton. PVA used
for blending was purchased from Aldrich, USA with a molecular weight
in the range 89,00098,000 g/mol. The dyes used for the release studies
such as rhodamine B, methyl orange and uorescein were purchased
from Merck, India.
2.1.1. Preparation of chemically modied latex
The chemically modied latex was prepared by grafting a water sol-
uble polymer poly dimethylaminoethyl methacrylate (PDMAEMA) onto
the surface of hydrophobic NR particles by an in situ polymerization of
dimethylaminoethyl methacrylate (DMAEMA) monomer. The process
was initiated by the redox couple cumene hydroperoxide (CHP)/
tetraethylenepentamine (TEPA). The grafting procedure for NRL is
shown in (Scheme 1). The composition of the reagents used for the ex-
periment is given in (Table 1).
In the grafting process, the mixture of NRL, DMAEMA, CHP and SDS
was agitated initially for 1 h in N2 atmosphere. TEPA solution was
added shot wise for 1 h, at an interval of 5 min, to initiate polymeriza-
tion. The system was cooled in an ice/water bath during the process
and held at a low temperature for the rst 8 h of reaction. After that
gradual warming to room temperature, another 16 h were given for
the completion of the reaction. Separation of the reaction products
Table 1
Reaction conditions for graft co-polymerization of DMAEMA on
NRL surface.
Ingredients Quantity (g)
Rubber latex 83.5
DMAEMA 2.5, 5, 10, 15, 20
CHP 0.1
TEPA 0.1
SDS 1
24 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232

Fig. 1. Structures of organic dyes used for the dye release studies.

was done by dialysis, using a dialysis membrane of pore size 14 kDa, for were then separately mixed with modied NRL in 1:1 proportion and
24 h, by changing the water after 5 h and 17 h. poured onto glass moulds and kept at room temperature for 24 h and
then in a hot air oven at 60 2 C for complete drying.

2.1.2. Preparation of the blend membranes

The chemically modied NRL was subsequently blended with a syn-
thetic hydrophilic polymer PVA. Initially, PVA was completely dissolved
in distilled water at concentrations 2.5, 5 and 10% (w/v). The solutions

Fig. 2. Illustration of chemical modication of NRL using redox initiators.

 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232 25

Fig. 3. Chemical reaction mechanism showing graft copolymerisation.

2.2. Dynamic light scattering 2.3. FT-IR

The change in NR particle size before and after grafting was exam- The grafted linkages and the compatibility of blended systems
ined using a Malvern ZS nano instrument at 25 C for 1 min. were examined by FTIR spectroscopy using a spectrometer (Thermo Ni-
colet 5700, USA) in the range of 4000 to 500 cm1. The grafted and blend-
Table 2 ed systems were scanned as such in ATR (Attenuated Total Reectance)
Particle sizes, grafting ratio (G %) and grafting efciency (GE %) after grafting process. mode.
Composition Particle size (nm) Grafting ratio (G %) Grafting efciency (GE %)

NR 576.6
2.4. 1H NMR
2.5PDNR 583.2 5.7 30.9
5PDNR 634.5 15.2 58.2
10PDNR 713.8 22.3 80.0 The formation of graft on the NR particle was conrmed by 1H NMR
15PDNR 784.5 26.0 86.0 technique. The dried membranes of NRL were dissolved in deuterated
20PDNR 594.7 10.0 24.3 chloroform and 15PDNR were dissolved in DMSO depending on the
26 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232

dissolution and analysed using a Bruker proton NMR (500 MHz) at

25 C.

2.5. X-ray diffractometry

The crystallinity examination was done by using a Rigaku miniex

600 benchtop X-ray diffractometer. The X-ray source was Cu K with
a scanning range of 390 with a speed of 15 per minute.

2.6. Thermogravimetric analysis

Thermal stability of the grafted and blended membranes was

monitored by using a thermogravimetric analyser TGA Q50
instrument. All the experiments were performed in the temperature
range of 25700 C under at a heating rate of 10 C min1 in nitrogen
atmosphere.
Fig. 4. FT-IR spectra of NR and 15PDNR.

Fig. 5. 1H NMR spectrum of (a) natural rubber (b) 15PDNR.

 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232 27

2.7. Moisture uptake and swelling ratio

For the determination of moisture uptake, the membranes were cut

into 10 mm 10 mm size and kept in desiccators with calcium chloride
for 24 h and then weighed to obtain an initial weight (Wo). They were
then placed in desiccators with saturated sodium chloride. The speci-
mens were periodically taken out and weighed until their weight be-
came constant (Wc). The percentage of moisture uptake was
calculated from (Wc) and the initial weight (Wo) using the equation
[40]:

Wc  Wo
Moisture uptake%  100:
Wo 1

The swelling ratio was determined by drying the 10 mm 10 mm

size membranes at 60 2 C overnight. The membranes were weighed
(W0) and immersed in 5 mL of distilled water at room temperature for
48 h. After removal of excess water, the hydrated lms were reweighed
(Wh). The swelling ratio was calculated from the increased
weight (Wh Wo) compared to the initial membrane weight (Wo).
The hydrated membranes were later dried at 60 2 C overnight and
weighed again to nd the percentage of leaching out from the mem-
branes [40].

2.8. Morphology

The morphology of the blended membranes before swelling and

after deswelling was examined by using a Hitachi Su 66,000 SEM. The
samples were gold coated in a sputter coater and the morphologies
were captured at an appropriate magnication.

2.9. Water contact angle measurement

Static water contact angle measurements were made by placing the

substrate at room temperature on the sample stage and recording the
contact angle at RT using the instrument Digidrop GBX, France. A typical
experiment starts with the positioning of 2 L Millipore water droplet
on the membrane surface using a microsyringe with a 20 gauge needle.
Using the instrument camera, images were captured to measure the
angle formed at the liquid-solid interface [41]. To minimize the experi-
mental errors, contact angles were measured at three different positions
for each sample [42]. For blend membranes, static contact angle mea-
surements are difcult to perform as the water drop disappears into
the membrane immediately.
Fig. 6. FTIR spectra of blends and PVA.
the resultant solutions was monitored continuously using a UVvisible
spectrophotometer [3739,41,44].
3. Results and discussion
The grafting executed on NR with PDMAEMA is a topology-con-
trolled process [1]. The grafting was done by using the redox initiator

2.10. Anti-microbial activity

Anti-microbial studies on the samples were done by the agar diffu-

sion method [43]. The membranes were cut in 10 mm 10 mm dimen-
sion and placed on Mueller Hinton agar plates (Merck, Germany) which
had been previously seeded with 0.1 mL of inoculums containing the
tested bacterium, Escherichia coli. The plates were then incubated at
37 C for 24 h.

2.11. Dye loading and releasing studies

Dye release studies were done using three model organic dyes rho-
damine B, methyl orange and uorescein (Fig.1). Rhodamine B and
methyl orange are hydrophilic dyes and uorescein is slightly soluble
in water. The samples of dimensions 10 mm 10 mm were immersed
in 5 mL water until reaching equilibrium. Then they were taken out
and wiped with tissue paper and immersed in 5 mL of dye solutions
(0.5 wt%) for 48 h. After a xed, time the samples were taken from
the dye solutions, washed with distilled water and wiped with a tissue
paper to remove the dye adhering onto the surface. The samples were
immediately immersed in 5 mL of distilled water. The absorbance of Fig. 7. XRD diffractograms of NR, 15PDNR and their blends.
28 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232

Fig. 8. TGA and DTG plots of grafted and blended membranes.

system consisting of CHP as a hydrophobic oxidising agent and TEPA as
a hydrophilic reducing agent. The process proceeds through a free-rad-
ical chemistry. Free radicals are initially generated from the redox initi-
ators. They subsequently abstract labile hydrogen from polyisoprene to
create a graft site at the particle-water interface, so that efcient subse-
quent propagation from this graft site, with a hydrophilic monomer, is
possible. In addition, a transfer reaction leading to the formation of ho-
mopolymer in the water phase, and cross-linking of the seed polymer
may occur [45]. The schematic representation for the redox initiated
grafting is shown in Fig. 2. The proposed mechanism of chemical reac-
tion for the grafting of PDMAEMA onto NR surface (abbreviated as
PDNR) by using the redox initiator couple CHP/TEPA was shown in
Fig. 3.
3.1. Evaluation of grafting
For the grafting process the quantities of the initiators were kept
constant, i.e. in 1:1 ratio, where as the amount of the monomer
DMAEMA was varied from 2.5 to 20 phr of NRL for grafting. After the
completion of reaction, the chemically modied latex was puried by
dialysis using a dialysis membrane [46]. The modied NRL displayed
an enhanced colloidal stability in the pH range of 28 while the unmod-
ied system exhibited stability only in the basic range [47,48]. This is
due to the electrosteric stabilising effect induced by the grafted hydro-
philic poly(dimethylaminoethyl methacrylate). The grafted systems
with different phr of monomers are abbreviated as NR-g-2.5PDMAEMA
[2.5PDNR], NR-g-5PDMAEMA [5PDNR], NR-g-10PDMAEMA [10PDNR],
NR-g-15PDMAEMA [15PDNR] and NR-g-20PDMAEMA [20PDNR].
From the DLS studies (Table 2), the diameter of NR particles has been
found to be increased after grafting initially with 2.5 phr of DMAEMA.
It has also been seen that diameter regularly increases with an increase
in the quantity of the monomer up to 15 phr. The diameter enhance-
ment is denitely due to the increase in the chain length of the graft
on NRL surface, with increase in the concentration of DMAEMA. The in-
crease in particle size is regular up to 15 phr of the monomer DMAEMA
but decreases after it, typically for 20 phr of the monomer. This can be
attributed to the possibility for the formation of more homopolymers
than the graft [45].
The grafting parameters such as grafting ratio (G %) and grafting ef-
ciency (GE %) were calculated for all grafted systems using the equations:
W 2 W 0
G%  100 2
W0

GE% W 2 W1
 100 3
where, W0 = Weight of initial substrate, W1 = Weight of total product
(copolymer and homopolymer) and W2 = Weight of pure graft copoly-
mer [49,50]. The grafting ratio and grafting efciency for systems were
presented in (Table 2). The results are complimentary to the results
from DLS.
The graft formation was further conrmed by ATR-FTIR analysis.
Fig.4 shows the ATR-FTIR spectra of NR and 15PDNR scanned in the
range of 4000 cm1to 500 cm1. The spectra show the characteristic
peaks of saturated aliphatic sp3C\\H bond at 28472964 cm 1
for both NR and 15PDNR. The peak at 3293 cm 1 is due to the
presence\\OH group from the moisture absorbed by NR. This peak in-
tensity has been found to be decreased in the case of 15PDNR. The
peak at 1660 cm1indicates C _C stretching in polyisoprene. A distinct
peak at 1736 cm 1 for the 15PDNR sample, not seen for NR, due to
C _O stretching of the ester group derived from PDMAEMA grafted
onto NR conrms the grafting process.
1
H NMR spectra of dried membranes of NR and 15PDNR are shown
in Fig.5a and b respectively. In the spectrum of NR, the unsaturated
methyne proton gives a resonance signal at 5.16 ppm (a). The reso-
nance signal of alkyl protons are seen in the range of 1.71
2.13 ppm(b, c and c). In the 1H NMR spectrum of 15PDNR also the un-
saturated methyne protons of NR backbone gives a resonance signal at
5.15 ppm (a). The methylenoxy proton resonance of the grafted
DMAEMA unit appears at 4.01 ppm (b). The N-methylic protons show
a signal at 2.30 ppm (c) and the N-methylenic protons show signal at

Table 4
Table 3 Erosion study of the membranes before dye loading and releasing.
Increase in moisture uptake and swelling ratio as the increase in PVA content.
Composition Erosion (%) Erosion (%)
Composition Moisture uptake (%) Swelling ratio (%) Cycle 1 Cycle 2

15PDNR 1.75 0.08 10.02 1.50 15PDNR 0.08 0.02 0.00 0.00
15PDNR/2.5PVA 2.02 1.00 63.47 2.39 15PDNR/2.5PVA 2.05 0.07 0.03 0.04
15PDNR/5PVA 2.58 1.08 95.00 4.04 15PDNR/5PVA 2.25 0.10 0.15 0.02
15PDNR/10PVA 7.20 0.09 160.16 4.49 15PDNR/10PVA 2.77 0.02 0.18 0.01
 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232 29

Fig. 9. SEM micrographs before swelling (a) and after deswelling (b):(A) 15PDNR, (B) 15PDNR/2.5PVA(C) 15PDNR/5PVA (D) 15PDNR/10PVA.

2.49 ppm [51,52]. These results further conrm the successful execution
of grafting.
3.2. Evaluation of blended membranes
The physical modication of the chemically modied NRL, with PVA
in the ratios 15PDNR/2.5PVA, 15PDNR/5PVA and 15PDNR/10PVA re-
sulted in transparent membranes due to enhanced compatibility of
modied NRL with PVA due to possible interactions involving the func-
tional groups.
3.2.1. FT-IR
Fig. 6 shows the FTIR spectra of PVA, 15PDNR and the blend mem-
branes (15PDNR/2.5PVA, 15PDNR/5PVA and 15PDNR/10 PVA) scanned
in the range of 1000 to 4000 cm1. In the FTIR spectra, 15PDNR shows
distinct peaks at 28532962 cm1 due to C\\H stretching, 1659 cm1
due to C _C stretching, 13701445 cm1 due to C\\H bending and
832 cm1due to C _CH wagging. However it gives an additional peak
at 1736 cm1 corresponding to the C _O stretching of ester group de-
rived from PDMAEMA grafted onto NR. The peak at 1639 cm1 corre-
sponds to the C\\O stretching in PVA [53]. The PVA gives a broader
peak at 3316 cm1due to the stretching vibration of \\OH group. The
30 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232
Fig. 10. Water contact angle of the surface of the membranes.
blend membranes produce a broader peak in the range of 3050
3500 cm1. These are attributed to weaker hydrogen bonding interac-
tions between the PVA and 15PDNR compared to the neat PVA [53,54].
The major peaks of NRL, PVA and PDMAEMA are found in the grafted
and blended membranes. No additional peaks apart from those of the
basic materials are found for the polymer blends.
3.2.2. XRD
XRD patterns at 2 = 590 for NR, 15PDNR, 15PDNR/2.5PVA,
15PDNR/5PVA, 15PDNR/10PVA and NR/PVA are shown in Fig. 7. The
NR, 15PDNR and NR/PVA do not show any peak indicating their amor-
phous nature. Pure PVA shows a 2 peak at 19.51 due to the semicrystal-
line nature being emerged from its strong inter and intramolecular
hydrogen bonding between the polymer chains. In the blends, the peak
intensity has been found to be increased as the PVA concentration in-
creased. The enhancement in crystallinity can be attributed to the inter-
molecular hydrogen bonding between PVA and 15PDNR after physical
blending.
3.2.3. TGA
Thermograms of NR, 15PDNR and blended membranes are shown in
Fig. 8. NR shows a degradation peak at 347 C where as the modied NR
shows the degradation at 364 C. After blending with PVA, there is a
further improvement in the thermal stability of the membranes (366
371 C). This can be correlated with the increased crystallinity of the
blends as evident from the diffractograms (Fig.6). As discussed, the crys-
tallinity is primarily due to the intermolecular hydrogen bonding be-
tween PVA and grafted PDMAEMA part on NR.
Fig. 11. Antibacterial test: (1) NR, (2)15PDNR, (3) PVA, (4) 15PDNR/2.5PVA (5) 15PDNR/5PVA and (6) 15PDNR/10PVA against Escherichia coli.
3.2.4. Moisture-uptake and swelling ratio studies
The moisture uptake and swelling ratio of 15PDNR and the different
blended membranes are presented in Table 3. These parameters have
been found to be increased with an increase in concentration of PVA
in the blend membranes. These changes are due to the increased hydro-
philicity of the blended membranes when the amount of PVA is in-
creased [40]. Upon deswelling, the blended samples have been found
to show a reduction in weight. This has been attributed to the leaching
out of unreacted PVA in the matrix. A second cycle of experiments do
not show any weight reduction as shown in Table 4. The leaching out
of unreacted PVA generates pores throughout the matrix which are
ideal for drug or dye release.
3.2.5. Morphology studies
The SEM photomicrographs of 15PDNR and different blend mem-
branes are shown in Fig.9. No pores have been found in the systems
prior to water treatment. However, pores have been found to be formed
in the matrix after treatment. Number of the pores, their dimensions
and distributions has been found to be increased for the blends with
higher percentages of PVA.
3.2.6. Water contact angle measurement
Water contact angle measurements were used to monitor the
changes on the surfaces of the thin membranes and the enhancement
in hydrophilicity. Contact angle of 73 2 and 59 4 were found for
NR and 15PDNR respectively. NR membranes show the highest value
of contact angle due to their higher hydrophobicity because of the iso-
prene hydrophobic part in the polymer. While a lower contact angle
was seen for 15PDNR owing to the presence of the hydrophilic grafted
part polydimethylaminoethyl methacrylate. Upon increasing the PVA
content in the blends the contact angle has been found to be decreased
from 54 4 to 25 2 as shown in Fig.10. This is denitely due to the
higher hydrophilicity deriving from PVA.
3.2.7. Anti-microbial analysis
The Fig.11 shows the antibacterial test results of NR, 15PDNR, PVA
and the blend membranes against Escherichia coli. It can be seen from
the gure that no bacterial inhibition zone has been developed for NR
and PVA. However, in the case of the 15PDNR, a distinct inhibition
zone of about 2.3 cm has been found to be developed. For the blends
also, inhibition zones are formed with 2 cm, 1.3 cm and 2 cm diameter
respectively for 15PDNR/2.5PVA, 15PDNR/5PVA and 15PDNR/10PVA.
It is reported that at pH = 7, PDMAEMA is partially charged (hydrophil-
ic) and partially uncharged (hydrophobic) and is thus amphipathic in
nature [55]. Hence the DMAEMA based copolymers have been found
to exhibit bactericidal activity [56]. Upon grafting it onto NR, the resul-
tant PDNR also gains antibacterial activity. This property is retained in
the blend also as attested by Fig. 11.
 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232 31

Fig. 12. Dye release through membranes with respect to time.

3.2.8. Dye release study
The effects of grafting and blending on the release prole of the NRL-
PVA systems were studied by using three model dyes viz.; rhodamine B
(cationic dye), methyl orange (anionic dye) and uorescein (slightly sol-
uble in water). The dye release was monitored by UVvis spectrometer at
554 nm, 461 nm and 490 nm wavelength for rhodamine B, methyl or-
ange, and uorescien dyes respectively in water (Fig.12). Rhodamine B
shows a controlled release prole up to six hours. Since Rhodamine B is
a cationic dye there is a chance of electrostatic attraction between the
dye and the negative charge from the hydroxyl group of PVA present in
the blend membrane to favour a controlled release feature. However
methyl orange is an anionic dye and there may occurs an electrostatic re-
pulsion between the dye and the hydroxyl group in the blend membrane
leading to a fast release prole. For uorescein which is partially ionic
shows approximately a constant and low release prole. The results indi-
cate that the modied NRL-PVA membranes are ideal for the release of
cationic dyes. Schematic representation of this study is shown in Fig.13.
4. Conclusions
A functional modication of natural rubber latex (NRL) has been done
by grafting with DMAEMA followed by blending with PVA. Dynamic light
scattering experiments indicated the enlargement of NRL dimension after
grafting; which was subsequently conrmed by FT-IR spectroscopy inves-
tigation. Blending of the grafted NRL with PVA resulted in transparent
membranes. These membranes were characterised by FT-IR, XRD, TGA
and SEM. The leaching out of the unreacted PVA was found to generate
pores within the membranes which are ideal for dye release. An

Fig. 13. Schematic representation of dye loading and release study.

32 J. Jayadevan et al. / Reactive and Functional Polymers 112 (2017) 2232
investigation of release of three dyes viz.; rhodamine B, methyl orange
and uorescein by the blend membranes revealed that cationic dyes/
drugs are most effectively released by them.
Acknowledgments
U.G. acknowledges the support by DST, New Delhi through the re-
search fund SR/S1/OC-40/2011.
J.J. is grateful to MHRD, Govt. of India for the research fellowship.
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