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Synthesis, characterization and properties of a bio-

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based elastomer: polymyrcene†

Cite this: RSC Adv., 2014, 4, 61343
Preetom Sarkara and Anil K. Bhowmick*b

An environmentally benign emulsion polymerisation technique was exploited to prepare a bio based
polymer from a naturally occurring monoterpene, b-myrcene. The structure of the polymer was
ascertained by spectroscopic measurements. Density functional theory was employed to determine the
ground state optimised structure of b-myrcene. The persulfate initiated polymyrcene possesses 3,4 and
1,2 vinyl defects along with 1,4 microstructures, whereas the redox analogue contains solely 1,4 addition
Received 29th August 2014
Accepted 7th November 2014
products. The synthesised polymer displayed a substantially high molecular weight (upto 92 860 Da for
persulfate polymyrcene) and subzero (
73  C) glass transition temperature along with shear thinning
DOI: 10.1039/c4ra09475a
behaviour within the experimental conditions, thereby rendering itself as a promising entrant in the
www.rsc.org/advances domain of bio-based elastomers.

polymers with terpenes as either functional entities or as the

Introduction main constituent.8 To make use of the chemical functionalities
The outbreak of synthetic elastomer technology and elastomers (unsaturation, functional groups) present in terpene molecules,
as a strategic material is well documented in the history of various chemical strategies and a wide range of polymerisation
World War II. The basic building blocks of synthetic elastomers techniques9–19 had been studied. Unlike the terpenes used in
are either derived from petrochemical resources (fossil fuel) or the aforementioned reports, the acyclic monoterpene: 7-methyl-
part of them contains petro-based synthons. As these resources 3-methylene-1,6-octadiene or b-myrcene resembles the classical
dwindle with time, along with their price volatility and envi- chemistry of other petro based unsaturated hydrocarbons. b-
ronmentally adverse effects, the scientic community is in dire myrcene is a component of essential oil of various plants like
search of a suitable replacement of the current petro based wild thyme, ylang–ylang, bay, cannabis, parsley, hops and its
elastomers by sustainable alternatives.1 This paradigm shi of use as a fragrance and avours are known from antiquity.20
surge is reected in the announcement of the Genencor and Commercially, b-myrcene is prepared from the pyrolysis of b-
Amyris company to launch BioIsoprene® as a replacement for pinene. Its use as a potential diesel fuel additive aer hydro-
its petro based analogue.2,3 Thus, it is evident that the impetus genation is also reported in literature.21 Interestingly, very little
for growth in this domain will surely rely on the development of thrust has been given to exploit this natural product in the eld
environmentally benign methodologies which utilise abundant of elastomer and tyre technology. Kobayashi et al.22 prepared
bio-resources. poly(3-methylenecyclopentene) using a combination of ring-
Nature produces rubber latex in over two thousand plant closing metathesis and cationic polymerization starting from
species by bio-synthetic (isopentenyl pyrophosphate) route.4 On myrcene. Loughmari et al.23 reported co-ordination polymeri-
the other hand, terpenes or terpenoids refer to one of the largest sation of b-myrcene. Marval and Hwa24 studied the polymeri-
families of naturally occurring compounds and are secondary sation of myrcene using Ziegler-type catalyst. Recently, Choi
metabolites synthesized mainly by plants, particularly coni- and Ritter25 reported a free radical copolymerisation of myrcene
fers.5,6 Though most terpenes share isoprene (2-methyl-1,4- with diethyl fumarate and styrene, utilising water soluble b-
butadiene) as an elementary unit (‘isoprene rule’),7 nature cyclodextrin complex. All of the methodologies mentioned
does not produce any polymer out of it. Thus, due to their essentially rely on either utilisation of volatile organic
abundance in nature, there has been great interest in producing compounds (especially solvents) or specialised techniques
(catalyst), and were not carried out with application in mind.
a
Thus, despite some studies on terpene-based polymers, the
Department of Chemistry, School of Basic Science, Indian Institute of Technology
Patna, Patna - 800013, India
increasing leap for environmentally benign methodologies
b
Rubber Technology Centre, Indian Institute of Technology Kharagpur, Kharagpur - demands further development and implementation of a green
721302, India. E-mail: [email protected]; [email protected]; Fax: polymerisation technique in this domain which will supple-
+91 3222 220312; Tel: +91 3222 283180 ment the dearth of bio based synthetic elastomer. Being a
† Electronic supplementary information (ESI) available: Wide angle XRD analysis, solvent less and mature system along with its multitude of
particle morphology of the latex emulsion. See DOI: 10.1039/c4ra09475a

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advantages (faster rate, high molecular weight products), Table 1 Recipe for persulfate-initiated emulsion polymerization
emulsion polymerisation26,27 is cynosure in this area.
Ingredients Amount (g, in phra)
With our quest to develop a bio-based elastomer by
employing a green technique, we herein report the persulfate as Monomer 100
well as redox initiated emulsion polymerisation of b-myrcene DI water 250
and intend to give an insight into the chemical structure and Sodium dodecyl sulphate (SDS) 2.5
the properties of the synthesised polymer. Vulcanisate proper- Ammonium persulfate (APS) 0.35
Sodium bicarbonate (NaHCO3) 1.5
ties of polymyrcene was rst reported by Johanson et al.,28
a
Parts per hundred parts of rubber.
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although there was no work on the structure or characterisation

or optimisation of the experimental conditions to obtain the
best properties of the pristine polymer. Surprisingly, this poly-
mer did not nd attention for a long time aer the preliminary Thereaer, the b-myrcene monomer was added slowly over a
investigation. We feel that further studies should be done to period of 10 min and le as such for a further 20 min so as to
exploit its commercial viability in view of recent focus on obtain a stable emulsion. Then, the reactor was ushed twice
sustainable and green elastomer. To the best of our knowledge, with nitrogen and the temperature was set to 70  C. Aqueous
this is the rst report of its kind which presents an in-depth solution of the initiator (APS) was added into the reaction
analysis of the microstructure of the as obtained polymer mixture drop-wise over 20 min in two intervals. The reaction
using environmentally benign emulsion polymerisation tech- was continued for 20 h to obtain a stable latex. Initially, the
nology along with theoretical calculation and elucidation of colour of the reaction mixture was off white, but with the
properties. The optimised structure of b-myrcene was deter- progress of the reaction a light blue tinge appeared due to the
mined using Density Functional Theory (DFT) calculation. The particle growth in the emulsion medium (Tyndall effect). Aer
reactivity of the molecule was ascertained with the help of the stipulated time, the latex was coagulated using excess
frontier molecular orbital theory and electrostatic potential acidied ethanol with continuous stirring. The obtained poly-
(ESP) mapping. Thermal stability, various transitions and myrcene (PMy) was taken out, washed profusely with DI water to
mechanical and dynamic mechanical properties of the syn- remove the traces of emulsier and subsequently dried at 50  C
thesised polymer were measured and the ndings were corre- in vacuum for 24 h. The polymerisation is shown in Scheme 1.
lated with the microstructure. Furthermore, the particle nature Polymerisation was also carried out at different temperatures
of the emulsion latex was also reported. (60–80  C) and different times (4–24 h).

Redox initiated emulsion polymerisation of b-myrcene

Experimental
According to the recipe furnished in Table 2, redox initiated
Materials
emulsion polymerisation was performed following strict addi-
b-Myrcene (99%) was purchased from Sigma Aldrich company tion sequence. At rst, DI water, potassium oleate, potassium
and the inhibitor, butylated hydroxytoluene was removed by chloride and potassium phosphate tribasic buffer were charged
shaking with 2(M) NaOH solution. Sodium dodecyl sulphate into a round bottom ask and stirred at 250 rpm for 20 min.
(SDS, 99%) was procured from Loba Chemie, India and used as Subsequently, b-myrcene was introduced into the ask and
received. Ammonium persulphate (APS, 98%) and sodium mixed thoroughly for a further 20 min. Upon obtaining a stable
bicarbonate (NaHCO3, 99%) were obtained from E. Merck emulsion, SHS, FeSO4 and Na-EDTA were added to the mixture.
(India). Ferrous sulphate heptahydrate (FeSO4$7H2O, 98%) was Thereaer, the reactor was ushed with nitrogen to remove
purchased from Alfa Aesar India. Ethylenediaminetetraacetic
acid sodium salt, potassium oleate, potassium phosphate
tribasic (K3O4P), potassium chloride (KCl), sodium hydroxy-
methane sulnate (SHS) and tert-butyl hydroperoxide solution
(Luperox® TBH70X), were purchased from Sigma Aldrich
company and used without further purication. All other
chemicals were reagent-grade commercial products and used as
received without further purication. Deionised water (DI) was
taken for all the experiments.

Persulfate initiated emulsion polymerisation of b-myrcene

Persulfate initiated emulsion polymerisation of b-myrcene was
carried out following the recipe mentioned in Table 1. The
general procedure followed for the emulsion polymerisation
was as follows: at rst, the emulsier (SDS), DI water and buffer
(NaHCO3) were added into the round bottom ask and mixed
thoroughly at 250 rpm for 20 min to form the micelle. Scheme 1 Emulsion polymerisation of b-myrcene.

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Table 2 Recipe for redox-initiated emulsion polymerization of the optimised structure was generated using ArgusLab 4.0.1
a
soware.
Ingredients Amount (g, in phr )
Differential scanning calorimetry measurements were
Monomer 100 recorded in a Perkin Elmer DSC8000 under nitrogen atmo-
DI water 180 sphere. The following heating protocol was followed: the
Potassium oleate 4.5 sample was heated from
96  C to +100  C, equilibrating at
Potassium chloride 0.3 +100  C for 2 min, cooling from +100  C to
96  C, equilibrating
Potassium phosphate tribasic 2.0
tert-Butyl hydroperoxide solution (TBHP) 0.06
at
96  C for 2 min, reheating from
96  C to +100  C. The
heating or cooling rates were 5  C min
1 in all the cases. To
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Ferrous sulphate heptahydrate (FeSO4, 7H2O) 0.01

Ethylenediaminetetraacetic acid sodium salt 0.05 eliminate the thermal history, transition temperature was
Sodium hydroxymethane sulnate (SHS) 0.05 reported from the second heating run. Thermogravimetric
a
Parts per hundred parts of rubber. analysis were carried out using SDT Q600 (TA Instruments)
under nitrogen ow at a ramp rate of 10  C min
1.
The dynamic mechanical properties of synthesised polymer
traces of air, followed by the injection of TBHP solution into the were measured using a DMA-Q800 machine in tension mode.
ask. The polymerisation was allowed to proceed for 20 h at All the samples (11  6.3  0.24 mm) were analyzed at a
25  C. The obtained latex was then coagulated using excess constant frequency of 1 Hz, at a heating rate of 3 C min
1 and
acidied ethanol. The as obtained polymer was washed profusely strain amplitude of 30 mm over a temperature range of
100  C
with DI water and dried in vacuum oven at 50  C for 24 h. to +100  C. Because of low strength of the synthesised polymer,
the glass bre cloth was impregnated with a solution of the
polymer in chloroform and a thin lm of uniform thickness was
deposited on it followed by drying at room temperature. Glass
Measurements and characterisation bre cloth was chosen as it did not show a glass transition
Polymer molecular weight was determined by Agilent PL-GPC within the temperature range of interest.29 Only the Tan Delta
50 instrument, using PLgel 5 mm Mixed-D column equipped peak was taken into account from this experiment.
with a refractive index detector and tetrahydrofuran as the The rheological measurements were performed using a
eluent (sample concentration 1 mg ml
1). The GPC data were MCR302 Anton Paar Modular Compact Rheometer having
recorded at 25  C at a ow rate of 1 ml min
1 (polystyrene parallel plate geometry of 8 mm diameter and with a 1.1 mm
standards were used for calibration). In order to determine the gap in between the plates. Frequency sweep experiments were
gel fraction of the synthesised polymers, the samples were conducted at 30  C and at a constant strain of 0.2% in the
extracted using THF under reux condition for 8 h. The gel frequency range between 0.1 to 10 Hz. Temperature sweep
percentage was calculated as the ratio of dried polymer weight experiments were carried out at 0.2% constant strain and 1 Hz
to its original value. frequency in between
10  C to +100  C temperature employing
The FT-IR spectra were recorded in Universal Attenuated a ramp rate of 3  C/min.
Total Reectance mode (UATR) using Perkin Elmer Spectrum The stress–strain behaviour of the synthesised polymyrcene
400 machine in a spectral range of 4000–650 cm
1 with a total of was recorded using Tinius Olsen H5KS UTM machine with a 5 N
8 scans per sample (resolution 4 cm
1). load cell at room temperature and a cross-head speed of 25 mm
1
H NMR and 13C NMR spectrum were recorded in a AVANCE min
1. The samples for tensile testing were prepared by solu-
III 400 Ascend Bruker instrument operating at 400 MHz. CDCl3 tion casting technique. As the samples were weak, attempt to
was used as a solvent and the chemical shi values were prepare the dog-bone type tensile specimen by using standard
reported in d (ppm) relative to the 1H signals from the internal ASTM (D412) cutter created wrinkles and defects in the
standard tetramethylsilane (TMS). The peak for deuterated samples. Hence, it was decided to prepare rectangular
solvent appeared at d ¼ 7.19 ppm for 1H NMR and d ¼ 77.22 samples.30 The dimensions of the rectangular tensile specimen
ppm for 13C NMR. were: length ¼ 35 mm, width ¼ 7.5 mm, thickness ¼ 0.5 mm.
Raman spectroscopy was recorded using an STR 750 series Wide angle X-ray diffraction analysis was carried out using
(Seki Technotron/Technos Instrument India) Raman spec- Rigaku TT RAX3 XRD machine in the range of 2q from 10 –50
trometer with a 633 nm He–Ne laser source and a grating of 600 (scan rate 3 per min) with CuKa (0.154 nm) as radiation source
lines per mm. The samples were placed on the sample stage and at 50 kV and 100 mA.
the laser focused on a specic area of the samples using 50 The morphology of the latex was characterised using eld
objective lens of the attached microscope (Olympus BX-51). The emission scanning electron microscope (Hitachi, S-4800
results reported are an average of data collected over 5 different FESEM) at an accelerating voltage of 10 kV. The latex was
points. diluted with water and sonicated prior to casting and drying on
Density functional theory (DFT) calculation was carried out silicon wafer and thereaer coated with gold by using Hitachi E-
using Gaussian-09 soware. The geometry (optimised structure) 1010 ion sputter system. The particle nature of the latex was
and frequency of b-myrcene were calculated with Becke's three- analysed by dynamic light scattering (DLS) method using
parameter hybrid functional (B3LYP) method by using 6-311G Delsa® Nano Submicron Particle Size and Zeta Potential
(d, p) as basis set. The electrostatic potential map (ESP) density Particle Analyzer PN A54412 from Beckman Coulter with a laser

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as a light source and a detector that detected the scattered light

at an angle of 165 .
All the experimental results on characterisation and poly-
merisation were based on three measurements.

Results and discussion

Synthesis of polymyrcene (PMy) by emulsion polymerisation
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Ammonium persulfate initiated emulsion polymerisation of b-

myrcene was performed at 70  C at atmospheric pressure. High
temperature was maintained to furnish sufficient free radicals
for the polymerisation process. Sodium dodecyl sulphate (SDS)
was used as a surfactant and sodium bicarbonate was used as a
buffer. Based on the polymer molecular weight and percentage
yield, the optimised reaction conditions (polymerisation time
and reaction temperature) for persulfate initiated process were
frozen, and all the analysis was carried out using the polymer
synthesised at the optimised set of reaction conditions. To
facilitate the polymerisation process at room temperature,
redox emulsion technique was also carried out. Na-EDTA was
used as a sequestering agent, sodium hydroxymethane sulnate
(SHS) was used as an oxidant, ferrous sulphate heptahydrate
(FeSO4, 7H2O) as a reductant and tert-butyl hydroperoxide
(TBHP) as a free radical generator.

Time and temperature dependence of PMy synthesis

In order to investigate the effect of time and temperature on the
PMy synthesis, the persulfate initiated emulsion polymerisation Fig. 1 (a) Temperature dependence of PMy synthesis on yield and
molecular weight, (b) time dependence of PMy synthesis on yield and
was carried out at rst at ve different temperatures of 5  C
molecular weight.
interval and for a xed reaction time of 20 h. The lower and
upper limit of the temperature is such chosen to ensure
complete initiator decomposition in the former case (well above
molecular weight and yield values for the synthesised PMy at
the half life temperature of the initiator species) and preventing
different conditions. Redox initiated polymerisation yields
destabilisation of the dispersion medium (i.e. water) of the
polymer with high molecular weight in comparison to persul-
polymerisation system respectively. Fig. 1a shows that with
fate initiated one (Table 3). This is because the redox reaction
increasing temperature, both molecular weight and percentage
was carried out at room temperature, and the side reactions and
yield exhibit increasing trend upto 70  C, aer which a reversion
chain transfer effects are suppressed which facilitate the
trend is followed. This can be attributed to the fact that with
production of high molecular weight polymer. Due to micro
increase in temperature, the propagation rate of the reaction
crosslinking between the growing chains (two nos of residual
increases; but at high temperature, thermal decomposition of
unsaturation in the polymer structure), the gel content of the
the polymer chains predominates, thereby reducing the
synthesised polymer increases with increasing reaction
molecular weight and percentage yield value. Thus, 70  C was
temperature and time. For the redox system, the high gel
chosen as the optimum reaction temperature. To study the
content value is in good agreement with other studies.25
effect of time on the polymerisation reaction, aliquots were
taken out from the reaction mixture at 4 h time interval and
upto 24 hours followed by GPC measurements and yield FT-IR and NMR characterisation of the synthesised PMy
calculation. Fig. 2 represents the FT-IR spectra of b-myrcene and PMy20 h.
It is evident from Fig. 1b that percentage yield increases with The weak peak at 3093 cm
1 in the monomer represents the
reaction time and the molecular weight reaches its maximum ]C–H stretching of C1, C3 and C4, which disappears upon
value of 92 860 Da at 20 h. In line with the temperature effect, at polymerisation. The broad absorption peaks at 2970, 2931 and
higher reaction time, chain scission occurs which produces 2860 cm
1 in the monomer are assigned to the –CH3, –CH2 and
oligomers and hence there is a decreasing trend of molecular –CH asymmetric stretching vibration respectively, which get
weight at long reaction time.27 Therefore, from the cumulative broadened due to the formation of more number of such groups
study of temperature and time dependence, the optimum in the polymer. The strong absorption peak at 1596 cm
1 is
reaction condition for the persulfate initiated emulsion poly- assigned to C1]C2 and C3]C4 stretching frequency (Fig. 2).
merisation was xed at 70  C for 20 h. Table 3 summarises the Due to conjugation, this stretching appears at lower wave

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Table 3 Molecular weight and percent yield of persulfate and redox initiated PMy

Sample Time (h) Temperature ( C) Mn (Da) PDI % Gel % Yield

PMy60  C 20 60 43 270 (250)a 2.64 5 83.0 (0.4)

PMy65  C 20 65 73 570 (280) 2.51 7 87.0 (0.3)
PMy70  C 20 70 92 860 (300) 2.48 12 96.0 (0.6)
PMy75  C 20 75 88 650 (590) 2.42 14 91.0 (0.8)
PMy80  C 20 80 85 850 (490) 2.55 14 83.0 (0.4)
PMy4 h 4 70 33 970 (490) 1.77 2 87.0 (0.3)
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PMy8 h 8 70 60 580 (220) 2.25 5 89.0 (0.3)

PMy12 h 12 70 69 450 (500) 2.27 8 91.0 (0.6)
PMy16 h 16 70 75 140 (380) 2.26 9 93.0 (0.5)
PMy20 h 20 70 92 860 (300) 2.48 12 96.0 (0.4)
PMy24 h 24 70 63 550 (450) 3.02 12 98.0 (0.5)
PMyredox 20 25 109 780 (410) 3.13 17 66.0 (0.7)
a
Values in the parenthesis indicate the standard deviation based on three measurements.

during polymerisation, the small residual peak in these two

regions is due to the formation of 3,4 structure (C1]C2 is
preserved) and 1,2 vinyl (C3]C4 is preserved) structure in the
polymer as ascertained from the NMR analysis discussed in the
next section. The small peak at 735 cm
1 is due to the –CH2
rocking vibration which is preserved in the polymer with lower
intensity due to restriction of rocking movement in the
macromolecular chains.

1 13
H and C NMR characterisation of the synthesised PMy
The H and 13C NMR (inset) spectra of b-myrcene are presented
1

in Fig. 3a. Fig. 3b and c represents 1H and 13C NMR spectra of

persulfate initiated polymyrcene (PMy20 h) respectively. The
spectral signals are well assigned to various magnetically
different protons and carbons. The structure of the monomer is
Fig. 2 FT-IR spectra of b-myrcene and PMy20 h.
much like an isoprene unit, except the methyl group is replaced
by an aliphatic chain having an isolated unsaturation (i.e.
C7]C8). Thus, the polymer may have four different types of
microstructure viz. 1,4-cis, 1,4-trans, 1,2 vinyl and 3,4-poly-
number value. A small peak at 1641 cm
1 can be ascribed to the
myrcene. The spectral assignments are in good accord with the
presence of isolated C7]C8 in the structure. The disappearance
available literature.23,31 The sequencing of the carbon atoms are
of the former C]C peaks and simultaneous broadening of the
adopted from the literature.23,31
latter one indicates the consumption of C1]C2 and C3]C4 1
H NMR data of PMy20 h (CDCl3, 400 MHz, d ppm). 5.32 [3%
during the polymerisation process followed by formation of
H]; 5.04 [3,7,30 ,70 ,700 and 7% H]; 4.69 [4% H]; 4.68 [100 H]; 1.96
C2]C3 and simultaneous retention of the isolated unsatura-
[1,4,5,6,10 ,40 ,50 ,60 ,300 ,400 ,500 ,600 ,1%,5%,6% H]; 1.60 [10,100 ,1000 ,10%
tion. The connement of C–H bending peak for tri substituted
H]; 1.52 [9,90 ,900 ,9% H]. (Please see gures for designation).
alkene (here C7) at 824 cm
1 even aer polymerisation reiter-
The protons of the two methyl groups attached to C8 in all
ates that the isolated double bond is indeed preserved during
the microstructures appear at upeld values (d ¼ 1.60 ppm
polymerisation (which is evident from theoretical calculation
and 1.52 ppm). The methylene protons of all the micro-
discussed later). The characteristics absorption peaks around
structures appear as a broad peak at 1.96 ppm. The upeld
1444 and 1376 cm
1 are due to the –CH2 and –CH3 bending
shi of all these protons relative to their monomer can be
vibration of C5–C6 and C9–C10 centres respectively. Aer
ascribed due to the generation of long chain macromolecules
polymerisation, generation of more methylene unit is reected
which shield each other from the external magnetic eld (cf.
in the relative increment of the corresponding peak area at 1444
Fig. 3a and b).
cm
1. The strong absorption peaks around 992 and 889 cm
1 in
According to the literature report32,33 available on NMR
the monomer is due to the sp2 C–H bending vibration of C1, C3
studies of polyisoprene, the peaks above 4.5 ppm indicates the
and C4 centres respectively. While the sharp decrease in the
olenic protons of 1,2 vinyl addition (5.32 ppm of 3% H). A close
intensities of these bands in the polymer is due to the
look into the peak around 4.6 ppm reveals the presence of two
consumption of these two unsaturations (C1]C2 and C3]C4)
splitting pattern at 4.69 ppm (4% H of 1,2 vinyl) and 4.68 ppm

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Fig. 3 (a): 1H and 13C NMR spectra of b-myrcene, (b): 1H NMR spectrum of PMy20 h, (c): 13C NMR spectrum of PMy20 h, (d): 1H NMR spectrum of
PMyredox, (e): 13C NMR spectrum of PMyredox.

(100 H of 3,4 structure). The olenic ]CH– for both 1,4-cis, 1,4- polymyrcene consists of 47% 1,4-cis and 1,4-trans mixture, 29%
trans as well as ]CH– of C7 appears as a single peak at 5.04 1,2 vinyl and 24% 3,4 structure. As no signature peak for 1,4-cis
ppm. Taking these three peaks (d ¼ 5.04, 4.69 and 4.68 ppm) and 1,4-trans structure was obtained, exact percentage of these
into account, it is estimated that the persulfate initiated microstructures could not be determined.

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13
C NMR data of PMy20 h (CDCl3, 400 MHz, d ppm). 154.34 Raman spectra of synthesised PMy
[2 C]; 137.5 [2, 20 C]; 131.54 [8,80 ,800 ,8% C]; 124.69
00
Raman spectra of b-myrcene and its polymer were recorded to
[3,7,30 ,70 ,700 ,3%,7% C]; 107.14 [100 ,4% C]; 40.37 [2% C] 39.97 [300 C]; compliment the observation of FTIR measurement. These are
37.86 [5 C]; 37.61 [500 C]; 37.40 [50 ,5% C]; 29.71 [10 C]; 29.07 [1% represented in Fig. 4. Raman band at 3006 cm
1 is assigned to
C]; 28.34 [1 C]; 27.98 [40 ,400 C]; 27.16 [4 C]; 27.01 [6,60 C]; 26.84 [600 the aliphatic ]C–H stretching mode of C1, C3 and C4 centre
C]; 26.51 [6% C]; 25.86 [10,100 ,1000 ,10% C]; 17.71 [9,90 ,900 ,9% C]. which gets diminished aer polymerisation. The combined
The 13C NMR spectrum of persulfate initiated PMy shows –CH2 and –CH3 asymmetric stretching bands appear as a broad
several sharp peaks and few overlapped peaks in the region of d band at 2913 cm
1 in the spectrum of the monomer which are
¼ 25–30 ppm. Due to long macromolecular chains, the exact
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intensied aer polymerisation. Raman bands at 1632 and 1670

degeneracy of the peaks in 13C NMR spectra is very much cm
1 in the monomer are ascribed to the presence of conju-
unlikely. Peak at 154 ppm suggests the formation of 3,4 structure gated (C1]C2 and C3]C4) and isolated (C7]C8) unsaturation
in the polymer. 2C and 20 C in -cis and -trans structures respec- respectively. It is anticipated that aer polymerisation, the
tively appear at lower ppm (d ¼ 137.5 ppm), as they are part of newly formed unsaturation (C2]C3) and the isolated one
the main chain of the polymer. The retention of peaks around (C7]C8 as present in the monomer) appear as a single peak
131.5 and 124.6 ppm in polymer (131.5 and 124.2 ppm respec- around 1668 cm
1. A broad band around 1435 cm
1 in the
tively in monomer) indicates that the isolated unsaturation monomer is assigned for –CH2 bending which shis to higher
(C7]C8) is indeed preserved and polymerisation took place at wave number value of 1444 cm
1 aer polymerisation due to the
C1]C2 and C3]C4 position. The peak for 3C, 30 C, 3%C along formation of more such units, whereas the peak position due to
with C7 appears at the same position (d ¼ 124.69 ppm). The –CH3 bending at 1381 cm
1 remains unaltered even aer
vinyl carbons i.e. 100 C (of 3,4 structure) and 4%C (of 1,2 vinyl) polymerisation (though its intensity gets enhanced probably
appeared as a single peak at 107.1 ppm. As in 1H NMR, the two due to macromolecular entanglement aer polymerisation).
methyl carbons attached to the C8 centre for all the micro- The peaks at 1287 and 1327 cm
1 in the polymer are due to the
structures were detected at up-eld values (d ¼ 25.8 and 17.7 wagging vibration of the methylene unit.
ppm). Due to the presence of attached hydrogen with 300 C, it
showed an upeld value (d ¼ 39.9 ppm) compared to 2%C (d ¼
40.37 ppm). Due to -cis structure, 5C is least shielded followed
Theoretical studies
by 500 C. The close proximity of the polymer chains with 50 C and
5%C leads to the higher shielding effect which reduces the In order to understand the relation between chemical structure
chemical shi values. All other methylene protons (1, 4 and 6 and reactivity, and to provide an insight into the electronic
Cs) appear in the range of 29.7–26.5 ppm and are overlapped properties, Density Functional Theory (DFT)34 calculation was
with each other. performed with Becke's three-parameter hybrid functional
1
H NMR data of PMyredox (CDCl3, 400 MHz, d ppm). 5.14 (B3LYP) method using 6-311G (d, p) as a basis set. Calculations of
[3,7,30 ,70 H]; 2.02 [1,4,5,6,10 ,40 ,50 ,60 H]; 1.64 [10,100 H]; 1.27 [9,90 H]. molecular geometries and energy levels of polymers employing
As shown in Fig. 3d, the 1H NMR spectrum of redox initiated DFT is difficult due to their inherent macromolecular nature, but
polymyrcene shows a single peak at 5.14 ppm corresponding to the calculation can be approximated using repeat unit of the
olenic protons (3,7,30 ,70 H) of ]CH– units. The absence of any same.35 Fig. 5a represents the optimised structure of b-myrcene
other peak in the range of 4.5 to 5.5 ppm indicates that neither molecule in the ground state computed by B3LYP/6-311G (d, p)
3,4 structure nor 1,2 vinyl structure has formed and the micro- level. The frontier orbitals of the same are also presented in
structure predominantly contains 1,4 addition product (mixture Fig. 5b. It can be seen that though the HOMO is spread over the
of 1,4-cis and 1,4-trans). No distinct peak for all other methylene entire molecule, the LUMO is mainly localised onto the conju-
and methyl protons is observed, rather a bimodal peak (d ¼ 2.02 gated double bonds, i.e. C1]C2 and C3]C4 positions. Based on
ppm and 1.64 ppm) followed by a hump (d ¼ 1.27 ppm) is the B3LYP/6-311G (d, p) calculation, the energy of HOMO and
obtained in the 1H NMR spectrum. LUMO is found to be
6.355 and
1.078 eV respectively, thereby
13
C NMR data of PMyredox (CDCl3, 400 MHz, d ppm). 139.01 indicating possible charge transfer from HOMO to LUMO and
[2,20 C]; 131.41 [8,80 C]; 124.43 [3,7,30 ,70 C]; 37.09 [5,50 C]; 30.42 [1 subsequent accumulation of charges on the conjugated double
C]; 29.65 [10 C]; 26.97 [4,6,40 ,60 C]; 25.70 [10,100 C]; 17.70 [9,90 C]. bond makes it very much avid towards polymerisation. The value
The 13C spectrum (Fig. 3e) of redox initiated polymyrcene of ground state dipole moment of b-myrcene calculated by
also does not contain the signature peak of 200 C (of 3,4 structure) B3LYP/6-311G (d, p) level is 0.4922 Debye. To envisage the charge
and 100 ,4% C (of 3,4 structure and 1,2 vinyl structure respectively), distribution three dimensionally, electrostatic potential mapping
indicating that the microstructure is devoid of 3,4 and 1,2 vinyl (ESP) of the b-myrcene monomer was done. It can be used to
defects. Due to lower reaction temperature, the side reactions evaluate the electronic distribution around the molecular surface
are suppressed in the case of redox polymerisation, thereby and has been used35 for predicting sites and relative reactivity
leading to polymyrcene that is rich in 1,4 microstructure. The towards electrophilic attack. From the ESP mapping, it is clear
chemical shi values of all the other methylene and methyl that C1, C2, C3, C4 are surrounded by a greater density of
carbons are well in accordance with those of persulfate initiated negative charge, thus making this site potentially more prone
polymyrcene. towards polymerisation. Thus, combining the spectroscopic
analysis and theoretical studies, it is evident that the

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Fig. 4 Raman spectra of b-myrcene and PMy20 h.

2,20 ,300 ,2% C position in all of the microstructures prevents close

packing of the chains, thereby rendering the polymer
amorphous.

Thermal analysis of the synthesised polymer

Glass transition temperature (Tg) of a polymer plays an impor-
tant role in dictating whether a particular polymer is in the
rubbery state at room temperature. Elastomers are amorphous
in nature and thus should have a Tg much below the ambient
temperature, preferably at sub-zero range. Fig. 6a shows the
DSC thermograms of persulfate and redox initiated polymer.
For persulfate initiated polymyrcene, the DSC thermogram of
second heating run shows a distinct baseline shi at around

Fig. 5 (a) The ground state optimized structure of b-myrcene in

B3LYP/6-311G (d, p), (b) the molecular orbitals and their energies of b-
myrcene molecule in the ground state in B3LYP/6-311G (d, p), (c)
electrostatic potential map for optimised b-myrcene molecule, high
electrostatic potential: relative absence of electron; low electrostatic
potential: relative abundance of electron.

polymerisation of b-myrcene proceeds via C1]C2 and C3]C4

pathways and the isolated unsaturation (C7]C8) remains
unaltered.

Wide angle X-ray diffraction analysis of the synthesised PMy

X-ray diffraction analysis was performed to study the crystalline
nature of the synthesised polymyrcene. The XRD plot (Fig. S1†)
of the synthesised polymer shows a broad hump at 2q ¼ 19 . Fig. 6 (a) DSC thermograms of persulfate and redox initiated poly-
Thus, the polymer lm displayed a typical pattern of an amor- myrcene, (b) TGA thermograms of persulfate and redox initiated
phous polymer, much like a natural rubber. Branching at polymyrcene.

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73  C which corresponds to the glass transition temperature

of the polymer. The transition temperature value is close to that
of the natural rubber reported in literature,36 thereby implying
rubber like behaviour of the synthesised polymer. The redox
variety of the polymer showed inexion point at
60  C,
approximately 13  C higher than the persulfate initiated
species. This shi of temperature to higher value can be
attributed to both increase in molecular weight which increases
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entanglement, thereby restricting segmental mobility, higher

gel content and 1,4 addition rich microstructure which facili-
tates dense packing compared to its persulfate initiated
analogue. Fig. 6b represents the thermal decomposition curve
of both persulfate and redox initiated polymyrcene. Unlike
natural rubber, which shows a single degradation peak, the
synthesised polymer exhibits two step degradation pattern. In
the case of persulfate initiated polymyrcene, the sample weight
gradually falls aer onset of degradation, until it reaches
425  C beyond which the polymer degrades off quickly. In the
case of redox initiated polymer, it shows a plateau aer rst
weight loss and falls off rapidly upon reaching 427  C. As
analysed from the NMR spectra, the persulfate initiated poly-
myrcene contains 3,4 and 1,2 vinyl defects in its microstructure
in comparison to redox initiated polymyrcene which contains
only 1,4 microstructure. The effect of microstructure on the
degradation of polybutadiene rubber is documented in the
literature.37

Rheological studies and mechanical properties of the

synthesised polymer
The tan d versus temperature plot for both persulfate and redox
polymyrcene are presented in Fig. 7a. The tan d peak and hence
the glass transition temperature of the persulfate and redox
polymyrcene was found to be around
53.3 and
50.0  C
respectively. The numerical values follow the same trend as in
DSC analysis. The higher Tg's are due to dynamic heating rate in
the experiment. The monotonous decrease of complex viscosity
with increasing angular frequency for both the samples is
evident from Fig. 7b. It is anticipated that due to high molecular
weight and defect free microstructure (1,4 microstructure aids
in much dense packing) the complex viscosity for redox poly-
myrcene shows such higher value.
In order to understand the ow behaviour of the synthesised
polymer, Power law model38 was employed. Power law relates
complex viscosity (h*) with angular frequency (u) by ow Fig. 7 (a) tan d overlay plot for persulfate and redox polymyrcene, (b)
plot of complex viscosity versus angular frequency for persulfate and
consistency index (k) and ow behaviour index (n) by the redox polymyrcene, (c) tensile stress–strain plot of synthesised poly-
following equation: myrcene (inset shows a representative strip of polymyrcene used in
tensile measurements).
h* ¼ ku(n
1). (1)

Aer linear curve tting, from the slope, ow behaviour

The tensile stress–strain plot of the synthesised polymer is
index for both the polymers was found to be less than one (n < 1),
presented in Fig. 7c. The strips were prepared by casting a
indicating pseudoplastic nature (shear thinning behaviour).38
solution of synthesised polymer in chloroform on Teon® petri-
PMyredox, having higher ‘n’, is less shear thinning than PMy20 h.
dish and driving off the solvent at room temperature. The
The tan d value at 0  C (indirect measure of wet skid resistance)
stress–strain curve for persulfate initiated polymyrcene
and 60  C (indirect measure of rolling resistance) for the syn-
(unvulcanised and gum) shows higher tensile strength value
thesised polymer are presented in Table 4.

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Table 4 Rheological analysis of synthesised polymyrcene

Sample Tga ( C) tan db at 0  C tan db at 60  C Flow behaviour indexb (n)

PMy20 h
53.3 0.238 0.199 0.167 (R2 ¼ 0.9948)

PMyredox
50.0 0.236 0.240 0.250 (R2 ¼ 0.9988)
a b
Data presented from dynamic mechanical analyser. Data presented from modular compact rheometer.
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Table 5 Mechanical properties of the synthesised polymyrcene

Sample Modulus@20% (kPa) Ultimate stress (kPa) Breaking stress (kPa) EAB (%)

PMy20 h 2.22 (0.05)a 97.8 (0.7) 42.2 (0.5) 60 (2)

PMyredox 1.18 (0.01) 36.7 (0.6) 8.9 (0.4) 46 (1)
a
Values in the parenthesis indicate the standard deviation based on three measurements.

(97.8 kPa) and higher elongation (upto 60%) than the redox molecular weight of 1,09 780 Da. The absence of peak in the
polymyrcene. It is anticipated that presence of 3,4 and 1,2 vinyl range of d ¼ 4.5 to 5.5 ppm in the 1H NMR spectrum indicated
microstructure leads to higher physical entanglement in the that it contained predominately 1,4 microstructures. Spectro-
case of persulfate polymyrcene which aids in higher elongation scopic measurements coupled with DFT calculation conrmed
and tensile strength. The relatively high 1,4-trans content in the participation of conjugated double bond in the polymeri-
redox polymyrcene hinders such phenomenon. Table 5 presents sation process and simultaneous conservation of the isolated
the mechanical properties of the polymyrcene polymers. These one. The complex viscosity data was tted to Power Law model
values are similar to other unvulcanised and gum rubbers.39 and the nding revealed the pseudoplastic behaviour of the
Hence, this elastomer may nd application as a single rubber, synthesised polymer. The amorphous nature, glass transition
in polymer blends, composites as well as in adhesives. temperature and thermal stability of the synthesised poly-
myrcene were found to be similar to those of other rubbers, thus
paving the way for its application as an elastomer of the future.
Analysis of particle morphology of the latex emulsion
To analyse the particle nature of the latex, dynamic light scat-
tering method was used and the particle nature of the latex was Acknowledgements
further conrmed from FESEM images. The particle size Part of the work and analysis of the results were carried out at
distribution and mean particle size of the polymyrcene latex Indian Institute of Technology Kharagpur. PS would like to
taken at different time intervals are presented in Fig. S2.† The acknowledge the facilities provided by IIT Kharagpur.
particle size increases from 52.6 nm at 4 h to 72.1 nm at 24 h at
70  C. The FESEM images (Fig. S3†) were taken by drop casting
the latex emulsion on silicon wafer and subsequently driving off References
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