Article

Polymers and Polymer Composites

2021, Vol. 29(9S) S1446–S1456
Copolymerization of palm oil with sulfur © The Author(s) 2021
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DOI: 10.1177/09673911211054269
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oil industry

Amin Abbasi1 , Wan Zaireen Nisa Yahya1 , Mohamed Mahmoud Nasef2 ,

Muhammad Moniruzzaman1 and Ali Shaan Manzoor Ghumman1 

Abstract
Nowadays, most of the world’s palm oil is being produced in Malaysia and Indonesia; however, the demand for this vegetable
oil as an edible oil is declining in many countries since consuming palm oil in excess can result in serious health problems.
Consequently, finding new applications such as the production of bio-based polymers to make use of this cheap and abundant
vegetable oil seems necessary. Herein, we report the copolymerization of palm oil with sulfur with different feed ratios via
inverse vulcanization. The copolymers are then characterized using Fourier-transform infrared spectroscopy, differential
scanning calorimetry and X-ray diffraction analysis. The results confirmed the formation of the polymers and their stability
against depolymerization. Altogether, the obtained sulfur-palm oil copolymers showed great properties such as thermal stability
up to 230°C under a nitrogen atmosphere and rubbery properties at room temperature. Although the Thermogravimetric
analysis (TGA) thermograms had previously confirmed the high conversion of elemental sulfur into the polymeric structure by
comparing the initial sulfur content and the final polysulfide content in the polymer, some unreacted elemental sulfur was also
observed in the final product. Sulfur-palm oil (S-Palm oil) is a new green polymer that helps to find a new use for palm oil as a big
industry as well as sulfur which is underutilized and left in stockpile as a byproduct in gas and petroleum refineries.

Keywords
Inverse vulcanization, elemental sulfur, palm oil, sulfur-based polymers, bio-based polymers, vegetable oil

Received 3 May 2021; accepted 2 October 2021

Introduction
Modern human life cannot be imagined without polymers and plastics. Polymers play an essential role in modern technology
and industry; however, it is only in recent decades that the unavoidable disadvantages of conventional polymers on the en-
vironment and as a consequence on human life are being considered very seriously.1,2 Most of the polymers produced so far are
petroleum-based which are not only expensive but also extremely harmful to the environment. It is estimated that in 2018 only,
around 359 million metric tons of different plastics were produced worldwide.3 Most of these plastics are non-biodegradable and
dependent on petroleum, making it difficult to come up with an appropriate solution for their waste and environmental
management.4,5 Biopolymers, on the other hand, are sustainable polymers that are produced using bio-based monomers which
directly decrease the dependency of polymers on petro-based monomers,6,7 and in many cases, they are also biodegradable.
Vegetable oils are a great source of bio-based monomers that have demonstrated great potential in the production of
biopolymers which are mainly utilized in composites, food packaging, insulators, plasticizers, adhesives, and also medical
devices.7–9 Palm oil, in particular, is a cheap vegetable oil that is being produced in high amounts in countries such as Malaysia
and Indonesia both of which are responsible for 86% of the global palm oil production.10,11 In 2019, around 18,469,258
million tons of palm oil were only exported from Malaysia. The fact that the demand for this vegetable oil is decreasing as an
edible oil in many countries indicates the necessity of finding new applications (such as polymer production) for this abundant
green feedstock to maintain the current production level and also to boost the domestic palm oil industry.12

1
Chemical Engineering Department, Universiti Teknologi PETRONAS, Seri Iskandar, Perak
2
Department of Chemical and Environmental Engineering, Malaysia Japan International Institute of Technology, Universiti Teknologi Malaysia, Kuala Lumpur,
Malaysia

Corresponding authors:
Amin Abbasi, Chemical Engineering Department, Universiti Teknologi PETRONAS, Seri Iskandar, Perak 32610, Malaysia.
Email: amin_18000407@utp.edu.my
Wan Zaireen Nisa Yahya, Chemical Engineering Department, Universiti Teknologi PETRONAS, Seri Iskandar, Perak 32610, Malaysia.
Email: zaireen.yahya@utp.edu.my
Abbasi et al. S1447

Palm oil, in particular, has already been investigated in the production of polymers in a number of reports.13 Mas’ud et al.14
studied the polymerization of waste palm cooking oil employing cationic polymerization under microwave irradiation using a
trifluoride-etherate catalyst. Also, the polymerization of 2-(vinyloxy) ethanol with palm oil using the base-catalyzed
transesterification is reported by Kalita et al.15 In another report, Tajau et al.16 investigated the usage of palm oil in the
production of epoxidized palm olein and diol as a novel polymeric precursor for drug delivery purposes. The need for initiators
and catalysts together with low conversion of palm oil into polymeric structure were the main limitations of these poly-
merization processes.14–16 Inverse vulcanization is a recently developed technique that is proven to be very effective and
economical to produce sulfur-based polymers using petro-based or bio-based monomers including vegetable oils.7,17
Nowadays, sulfur, with an annual production of almost 70 million tons, mostly comes as a byproduct of natural gas and
petroleum refineries making it a very cheap and readily available material.18–20 With the high supply and low market demand
for sulfur globally, elemental sulfur is, for the most part, left piled up in open spaces in gas and petroleum refineries which
raises environmental concerns making it inevitable to search for a new way to convert it to less harmful materials for the
environment. Inverse vulcanization first reported in 2013 is a solvent- and initiator-free polymerization method which makes it
possible to produce sulfur-based polymers using either petro-based or bio-based monomer(s).21–23 The octet ring structure of
elemental sulfur (S8), if heated above its floor temperature (159°C), will be opened, and forms a biradical linear chain of sulfur
atoms accompanied by a color change of sulfur melt from yellow to orange. If heating continues, the opened chains of
elemental sulfur will homopolymerize and form a pure polysulfide.24,25 Due to the nature of sulfur, pure polysulfide is not
stable, and it undergoes depolymerization after only a short period resulting in the reformation of elemental sulfur
crystals.7,26,27 Adding a comonomer with one or more vinylic C=C bonds to the sulfur melt with free radicals results in the
production of stable sulfur-based polymers.21,23,27 Depending on the nature of the comonomer(s) and the reaction parameters,
sulfur-based polymers have shown a wide range of properties from linear thermoplastics to highly crosslinked thermosets.7,28
So far, petro-based monomers are mostly used in the investigation of sulfur-based polymers. However, some bio-based
monomers such as farnesene,19 myrcene,19 squalene,29 limonene,30 and diallyl disulfide31 were also reported. Oil of some
vegetables including corn,32 rubber seed,33,34 canola,35 soybean,36 rice bran,37 castor,37 cottonseed,38 sunflower,39 linseed,39
olive,39 and algae40 were also studied in the production of sulfur-based polymers. Nevertheless, the complex chemical
structure of vegetable oils together with their unknown mechanism of reaction makes it practically very difficult to control the
properties of the products.23 The copolymerization of vegetable oils with elemental sulfur opens up a new approach not only to
find new applications for sulfur but also to produce cheap polymers that can act as a good alternative for petro-based polymers
in a number of applications.
Palm oil can be used as a comonomer to be copolymerized with elemental sulfur in an inverse vulcanization process due to
its unsaturated fatty acid portion.41,42 Depending on the plant breed and also the growing environmental conditions, the
percentage of different triglycerides in palm oil can vary.28 Figure 1 shows the fatty acid composition of a typical palm oil
species in which C:D represents the ratio of the number of carbon atoms to the number of C=C bonds.11 It can be observed that
palm oil is consisted of about 50 wt% unsaturated fatty acids including oleic, linoleic, and linolenic acids with 39.2, 10.1, and
0.4 wt%, respectively.11
In our recent reported paper proceeding, we briefly presented the preliminary copolymerization of sulfur with palm oil with
a limited study of different feed ratios and also a narrow investigation of the product properties.41 Herein, a full report
including the copolymerization of sulfur with palm oil using different feed ratios and a detailed investigation of their properties
together with a full comparison between sulfur-palm oil and the other reported sulfur-oil polymers is presented that not only
proposes a new application for palm oil and as a consequence helps the domestic palm oil industry but also suggests an
innovative use of the stockpile of sulfur to reduce the environmental concern of its pollution in soil. The effect of different feed
ratios on the properties of the obtained polymer is discussed. The sulfur–palm oil polymers (poly (S-Palm oil)) were produced

Figure 1. Fatty acid composition (wt%) of typical palm oil.11

S1448 Polymers and Polymer Composites 29(9S)

under chosen reaction parameters (including reaction time and reaction temperature) based on the preliminary results to obtain
homogenous polymeric phases without releasing a huge amount of harmful gas during the polymerization. The obtained
polymers by the inverse vulcanization technique were characterized using Fourier-transform infrared spectroscopy (FTIR),
differential scanning calorimetry (DSC), and X-ray diffraction analysis (XRD). A comparison study of the properties of the
obtained poly (S-Palm oil) with reported bio-based sulfur polymer using other vegetable oils as monomers is outlined. Poly (S-
Palm oil) suggests a potential application for the abundant and readily available palm oil which can help the domestic palm
industry. The obtained poly (S-Palm oil) can be directly used for environmental-friendly applications such as mercury removal
due to the affinity of sulfur to mercury,35,37 oil spill removal,43 slow-release fertilizers,36 and palladium capture,30 to name a
few.

Materials and methods

Materials
Elemental sulfur 99.9% and refined palm oil were purchased from PC Laboratory Reagent, Malaysia, and Malaysian local
suppliers, respectively, and were used without further purification.

Copolymerization of poly (S-Palm oil)

Initial monitoring of reaction conditions helped to select the reaction conditions at which a homogenous polymeric phase can
be achieved. Different wt% ratios of sulfur to palm oil, that is, 50:50, 60:40, 70:30, and 80:20, were copolymerized using
inverse vulcanization. In each case, elemental sulfur was initially melted in a glass tube at 170°C employing a thermostatic oil
bath with continuous stirring. After the ring-opening of sulfur chains began, observable by the color change of the molten
sulfur from yellow to orange, the palm oil was gradually added to the melt to prevent a sudden decrease in the melt
temperature. The reaction melt was continuously stirred for 1 h while maintaining the temperature (170°C), and subsequently,
the product was let to be cooled at room temperature. As a matter of comparison, the same reaction conditions (170°C and 1 h)
were utilized to produce pure polysulfide (sulfur as the only monomer) without adding palm oil as a comonomer in this case.
As a reference for DSC and XRD, this pure polysulfide was tested exactly after polymerization to minimize the depoly-
merization of sulfur chains back to elemental sulfur. The mechanism of polymerization of sulfur with palm oil using inverse
vulcanization is shown in Figure 2, based on the fact that most unsaturated fatty acid portion of palm oil consists of oleic acid
and linoleic acid.

Characterization of poly (S-Palm oil)

A PerkinElmer Frontier model spectrophotometer model equipped with Universal ATR Accessory was employed to perform
FTIR in a frequency range of 4000-500 cm 1 with eight scans at a resolution of 4 cm 1. A TA Instruments Q2000 equipment
was also employed to run the DSC tests under a nitrogen atmosphere in a temperature range of 50 to 200°C at a heating rate

Figure 2. Polymerization of sulfur with palm oil using inverse vulcanization.

Abbasi et al. S1449

Figure 3. Poly (S-Palm oil) with different feed ratios (wt%): (a) 50:50, (b) 60:40, (c) 70:30, and (d) 80:20.

of 10 °C/min. A Malvern PANalytical X’Pert powder diffractometer provided with a Cu anode material (Kγ1 = 1.540598 Å,
Kα2 = 1.544426 Å) at 40 mA in transmission geometry utilizing a capillary spinner was used to conduct the XRD mea-
surements. The morphology of the polymers was also studied using a Zeiss EVO LS 15 microscope after the gold coating
(using Emitech K550X sputter coater) of the already fractured samples in liquid nitrogen.

Results and discussion

The obtained copolymers using different feed ratios are shown in Figure 3. It can be observed that the obtained copolymers
mainly consist of a dense brownish polymer phase which becomes lighter by increasing the sulfur content and a liquid phase
which is assumed to be the saturated portion of palm oil that did not take part in the polymerization process. The preliminary
results showed that the polymers obtained by more than 80 wt% initial sulfur content were not firm against depolymerization
even in short times and thus, 80 wt% sulfur was chosen as the maximum amount of initial sulfur content. Poly (S-Palm oil)s at
all studied compositions showed no solubility in conventional organic solvents including toluene, chloroform, tetrahydrofuran
(THF), dimethylformamide (DMF), n-hexane, ethanol, methanol, 2-propanol, acetonitrile, and 1,4-dioxane. It is also
necessary to mention that Poly (S-Palm oil)s at all percent compositions were not strongly stable against depolymerization by
time, and after about a month, it can be observed that elemental sulfur is separating from the polymeric structure. This phase
separation proved to be faster with increasing the initial sulfur content and in humid environments.

Composition of poly (S-Palm oil)

Figure 4 illustrates the FTIR spectra of poly (S-Palm oil) with different feed ratios together with the spectrum of pure palm oil
as a reference. The FTIR spectrum of palm oil is indistinguishable from those of other vegetable oils due to the similarity of the
composition of different varieties of vegetable oils.32,39 In the case of pure palm oil, the tiny peaks at 1655 cm 1 and
3006 cm 1 are due to the vinylic C=C double bond stretching and vinylic C-H stretching vibration, respectively, while the
copolymers do not show such peaks.36,39 Instead, a small peak at 965 cm 1 appeared in the case of copolymers which
represents the C-H rocking vibrations in the vicinity of C-S bonds.32,39 The disappearance of the vinylic peaks together with
the appearance of C-H rocking vibrations in the vicinity of C-S bonds confirmed the consumption of the vinylic C=C bonds

Figure 4. Fourier-transform infrared spectroscopy spectra for (a) palm oil and the obtained poly (S-Palm oil) copolymers: (b) 50:50, (c) 60:
40, (d) 70:30, and (e) 80:20.
S1450 Polymers and Polymer Composites 29(9S)

Figure 5. Differential scanning calorimetry thermograms for (a) fresh polysulfide (100:0) and the obtained S-Palm oil copolymers: (b) 70:30
and (c) 80:20.

and the formation of the Poly (S-Palm oil).36,39 Furthermore, the variation of molar ratios does not affect the FTIR spectra as
the S-palm oil polymers are well-formed for all compositions.

Thermal properties of poly (S-Palm oil)

Elemental sulfur starts to degrade at around 210°C. It was previously shown by the TGA thermograms that the degradation
onset temperatures of the copolymers with 70 and 80 wt% sulfur take place sooner at around 200°C, whereas copolymers with
50 and 60 wt% initial sulfur contents show higher onset temperatures (about 230°C) compared with elemental sulfur.41 Poly
(S-Palm oil) with all feed ratios showed a different weight-loss trend in DTG curves compared with elemental sulfur which
itself confirms the formation of a polymeric structure.41 This trend for poly (S-Palm oil), regardless of its feed ratio, consisted
of a rapid first degradation step (sulfur content of the polymer) accompanied by a slight second step and finally a gradual
reduction in the weight percentage.31,39,41
Poly (S-Palm oil) 70:30 and poly (S-Palm oil) 80:20 due to their distinct TGA trends together with fresh pure polysulfide as
a reference were selected for DSC analysis (Figure 5). Sulfur in its elemental state demonstrated two melting peaks at around
109 and 119°C due to the presence of two different crystalline structures.44,45 The copolymers also show these two peaks
suggesting the incomplete conversion of elemental sulfur into the polymeric structure. The presence of these peaks might also
be due to the depolymerization of some sulfur chains after some time.19,35,46 Fresh pure polysulfide, on the other hand, only
reveals the second peak. Poly (S-Palm oil) 70:30 and poly (S-Palm oil) 80:20 demonstrate different melting peak areas which

Figure 6. X-ray diffraction analysis patterns for (a) elemental sulfur, (b) fresh polysulfide and the obtained S-Palm oil copolymers: (c) 50:50,
(d) 60:40, (e) 70:30, and (f) 80:20.
Table 1. Comparing the properties of poly (S-Palm oil) with other reported inverse vulcanized polymers using vegetable oils.
Abbasi et al.

Physical appearance
and solubility Chemical composition Thermal stability and properties Morphological properties Structural properties

Palm oil -Brown rubbery -No thiol groups are present since no -Two-step TGA degradation -Not reported. -Amorphous nature
material. signal was observed in the range of pattern.41 of the copolymers
1
-No solubility in 2250–2600 cm . -Copolymers with 50 and 60 wt% was approved.
toluene, -Formation of C-S bonds was initial sulfur content onset to -XRD revealed the crystalline peaks
chloroform, THF, confirmed due to the signal at degrade at 230°C, while due to the
DMF, n-hexane, 965 cm 1 confirming the formation copolymers with 70 and 80 wt% presence of
ethanol, of the copolymer. initial sulfur degrade at 200°C.41 unreacted sulfur.
methanol, 2- -Signals related to C=C bonds -DSC showed some unreacted
propanol, disappeared confirming the elemental sulfur since melting
acetonitrile, and consumption of vinylic groups. peaks associated with elemental
1,4-dioxane. sulfur were observed.
-No Tg was observed in the
experimental range ( 50 to
250°C).
Rubber seed -Dark brown -Disappearance of signals associated -Three-step degradation pattern. -Smooth surface was observed for the -P-XRD revealed the amorphous
oil33,34 rubbery material. with cis-alkene characteristics at -The first step of the decomposition copolymer with 50 wt% S at lower nature of the copolymer with very
-Soluble in THF. 3009 cm 1 (related to C=C-H is due to the degradation of the magnification (20 μm), whereas less intense crystalline peaks related
-Partly soluble in stretching) and 1660 cm 1 loosely bonded S-S chain and zooming in showed composite to the sulfur which shows the high
Chloroform. (associated with C=C stretch) and unreacted sulfur. morphology with some isolated conversion of the sulfur for
-Not soluble in appearance of the new signal at -The second step represents the particles of unreacted sulfur at 2 µm. copolymer with 50 wt% S.
DMF, n-hexane, 804 cm 1 showing the rocking of C- decomposition of the unreacted -Similar composite morphology was -Crystalline peaks appeared for all
methanol, H bond in the vicinity of C-S bond, polyunsaturated fatty of the oil observed for other obtained other copolymers obtained from
toluene, ethanol, confirmed the formation of the domain. copolymers from rubber seed oil. rubber seed oil due to the presence
N-dimethyl copolymer. -Tg 6.41oC was observed for the of the unreacted sulfur.
formamide, and -No thiol group were observed as no copolymer containing 50 wt%
water. signal related to them appeared at sulfur, and 7.85 oC for poly (S-
1
2250-2600 cm . RSO) 70 wt% S.
Canola -Dark brown -The disappearance of C=C stretch at -Two-step TGA degradation pattern. -Composite morphology. -Crystalline peaks appeared for all
oil35,37,43,49 rubbery material. 1613 cm 1 and the alkene stretch at -Polymer starts to degrade at 230°C -Isolated sulfur particles appeared on the copolymers in the PXRD
-Soluble in pyridine. 3035 cm 1 indicated the successful followed by a second step at surface which became denser with diffractogram, which became more
conversion of vinylic bonds. 340°C. increasing the initial sulfur content. assertive with the increase in initial
-Step change was observed at sulfur content.
17°C for copolymer with 50 wt
% initial sulfur content.
-Melting peaks appeared in DSC
thermogram due to the presence
of elemental sulfur.

(continued)
S1451
Table 1. (continued)
S1452

Physical appearance
and solubility Chemical composition Thermal stability and properties Morphological properties Structural properties

Corn oil32 -Light brown -Peaks at 1655 and 3009 cm 1 which -Two-step TGA degradation, the -Composite-morphology with unreacted -PXRD showed only peaks related to
rubbery material. are related to pure corn oil first step onsets at 200°C followed sulfur particles that were trapped in the unreacted sulfur, confirming the
-Insoluble in CH3Cl, associated with C=C and C=C-H, by the second step at 385°C. copolymer. amorphous structure of the
CH3OH, respectively, disappeared in the -Melting peaks were observed in the -Copolymers with higher sulfur loading copolymers.
CH3CN, and spectrum of all copolymers DSC thermogram related to showed porous structure which may be
(CH3)2CO. confirming the consumption of elemental sulfur. due to the H2S gas release.
vinylic bonds. -No Tg was observed in the tested
-No signal related to thiol group was range.
observed.
-New signal at 797 cm 1 confirmed the
formation of the C-S bonds.
Soybean oil36 -Remains brown -The absence of signals at 3008 and -No melting point and step change -Homogenous surface with sulfur loading -Diffractogram revealed the presence
color rubbery 1653 cm 1 indicated the successful point were observed in the tested up to 50 wt%. of crystalline sulfur in all
material for up to addition of sulfur. No signal appeared range of DSC for the copolymer. -Copolymer with higher sulfur loading copolymers.
80 wt% initial in the range of 2250–2600 cm 1 -Melting peaks due to the presence of showed composite morphology with
sulfur. which means no thiol groups are unreacted sulfur appeared. crystals of unreacted sulfur.
-Becomes brittle present in polysulfide. A signal
light brown color appeared at 465 cm 1 which is
material with associated with the S-S bonds.
90 wt% initial
sulfur.
-Solubility not
reported.
Rice bran oil37 -Brown rubbery -No thiol groups. -Two-step TGA degradation pattern. -Composite morphology with sulfur -Not reported.
material. -Disappearance of C=C and C=C-H -First major loss onsets at 230°C and particles embedded in the copolymer
-Solubility not group confirming the consumption of the second at 325°C. structure.
reported. vinylic bonds. -Tg= 13°C, for copolymer with
50 wt% initial sulfur, no Tm which
shows copolymer is amorphous in
nature.
Castor oil37 -Light brown -No thiol groups. -Two-step TGA degradation, first -Composite morphology with sulfur -Not reported
rubbery material. -Disappearance of C=C and C=C-H onsets at 230°C followed by the particles embedded in the copolymer
group confirming the consumption of second step at 325°C. structure.
vinylic bonds. -Tg = 24°C was observed for
copolymer with 50 wt% initial
sulfur content.
-Melting peaks were observed
related to sulfur in the DSC
thermogram.

(continued)
Polymers and Polymer Composites 29(9S)
Table 1. (continued)
Abbasi et al.

Physical appearance
and solubility Chemical composition Thermal stability and properties Morphological properties Structural properties

Cottonseed -Brown color -Mercapto functional group (S-H) was -Two-step thermal degradation. -Not reported. -Not reported.
oil38 material. present in the copolymer as no signal -No Tg was observed in the tested
-Solubility not was observed at 2550-2600 cm 1. range.
reported. -Signals related to C=C and C=C-H -Amorphous.
disappeared in the copolymer
spectrum.
-Signals in Raman spectrum at 430 and
465 cm 1 related to S-S bonds.
Algae oil40 -Black color with -Absorption of hydrocarbon moieties -Two-step thermal degradation. -Not reported. -The copolymer with 90 wt% sulfur
sulfur wt% of 50 around 3000 (C-H stretch), 1375, -The first step onsets at 200°C showed peaks of crystallinity, but
and brown with and 1445 cm 1 (C-H bending followed by the second at 385°C. these peaks did not resemble the
sulfur wt% of 70– vibration). A small peak at 1658 cm 1 -Tg was found to be 32°C for α-S8, but partially with β-S8. A
80. (C=C stretch) indicates the presence copolymer with 50 wt% initial significant portion of the residual
-Soluble in CHCl3, of double bonds also supported by sulfur content. sulfur exists as γ-S8
THF, and solid-state NMR. It also shows broad -DSC thermogram showed melting -No peaks were observed for
C2H2Cl4. spectra at around 2000–4000 cm 1 peaks related to sulfur for the copolymer with 50 and 70 wt%
-Insoluble in C6H14. (which represents the residual copolymer containing 90 wt% S. sulfur indicating the amorphous
sulfur). nature of these polymers and the
complete conversion of sulfur.
Sunflower, -Brown rubbery -IR spectra of all copolymers resemble -Three-step degradation pattern was -SEM revealed that copolymer consists of -The crystallinity peaks associated with
olive, and material. widely the pristine vegetable oil. The observed, the first step onsets at two components possessing different sulfur increased with increasing the
linseed oil39 -Partly soluble in signals that appeared at 3010 and 200°C, the second at 300°C, shapes; one owns a smooth and sulfur content in the copolymer,
H3C(CH2)5CH3. 1650 cm 1 are attributed to C-H followed by the third step at network-like surface embedding the which indicates the presence of
bonds and C=C double bonds, 550°C. other in it (which is the residual or residual sulfur.
respectively, which are not visible in -No Tg was observed. unreacted sulfur). By increasing the
the spectra of copolymers, indicating -Peaks related to the phase transition amount of sulfur in the copolymer, the
the addition of sulfur to double of elemental sulfur appeared due amount of interpenetrating polymeric
bonds. New signals were seen in to the presence of the unreacted network decreased, and the isolated
spectra of composites at 803 and sulfur. particles increased.
965 cm 1 which represent the C-H
rocking vibrations in the vicinity to a
C-S bond another indication of
successful reaction.

DSC: differential scanning calorimetry; XRD: X-ray diffraction analysis; THF: tetrahydrofuran; DMF: dimethylformamide.
S1453
S1454 Polymers and Polymer Composites 29(9S)

is a result of different amounts of unreacted sulfur in their structures.19,35,36,46 No glass transition temperature (Tg) can be observed
for the copolymers in the experimental temperature range of 50 to 250°C. The copolymers are rubbery at room temperature, and
hence, it is expected that poly (S-Palm oil) exhibits Tg of less than 50°C. The lack of presence of any melting and crystallization
peaks related to the copolymer structure also suggests the possible amorphous structure of Poly (S-Palm oil).

Structural properties of poly (S-Palm oil)

The XRD diffractograms of poly (S-Palm oil) with different feed ratios, elemental sulfur, and fresh pure polysulfide are
presented in Figure 6. Poly (S-Palm oil) with all percent compositions and fresh polysulfide shows similar XRD patterns to
that of elemental sulfur. The crystalline peaks that appeared in the case of the copolymers are due to the unreacted elemental
sulfur and also that sulfur content that was initially reacted into the polymeric structure but depolymerized after some time.
The absence of any crystalline peak other than those of elemental sulfur in the XRD patterns of the copolymers confirms the
amorphous structure of the polymeric structure similar to other comparable sulfur-based polymers.29,47,48 The presence of
elemental sulfur peaks in XRD patterns also indicates that palm oil, regardless of its feed ratio, cannot stabilize all of the initial
sulfur content into the polymeric structure.19,47

Comparing poly (S-Palm oil) with other reported inverse vulcanized polymers using vegetable oils
As it was mentioned earlier, there are already some vegetable oils investigated as monomers to be copolymerized with
elemental sulfur using the inverse vulcanization technique. These vegetable oils include corn,32 rubber seed,33,34
canola,35,37,43,49 soybean,36 rice bran,37 castor,37 cottonseed,38 sunflower,39 linseed,39 olive,39 and algae.40 Due to the
similar composition of different vegetable oil species, most of the properties of different poly (S-oil) products are similar to
each other; however, they also illustrate some differences which are reviewed in detail in Table 1.
Except for algae oil which yields a black color product in the case of low sulfur loadings, all the investigated sulfur-based
polymers using vegetable oils have demonstrated different shades of brownish color which becomes lighter by increasing
the initial sulfur content.32,40 Poly (S-Palm oil) showed zero solubility in conventional organic solvents such as toluene,
chloroform, THF, DMF, n-hexane, ethanol, methanol, 2-Propanol, acetonitrile, and 1,4-dioxane. Besides rubber seed oil
which was fully soluble in THF and partially soluble in chloroform,34 poly (S-Canola oil) which was proved to be soluble in
pyridine,43 poly (S-Algae oil) in CHCl3, THF, and C2H2Cl4,40 and also polymers made using sunflower, olive, and linseed oils
which were partially soluble in H3C(CH2)5CH3,39 no solubility was reported for other sulfur-based polymers using vegetable
oils. In general, vegetable oils with more linolenic acid and linoleic acid portions result in highly crosslinked sulfur-based
polymers.
Due to the composition similarity of different vegetable oils, the reported sulfur-based polymers using vegetable oils
demonstrated similar FTIR spectra confirming the consumption of the vinylic bonds and the formation of the polymeric
structure.27 TGA thermograms of poly (S-Palm oil) with different percent compositions showed a two-step degradation
pattern similar to most of the reported polymers.32,37,38,40,41 However, polymers made by using rubber seed, sunflower, olive,
and linseed oils showed a three-step weight loss pattern.33,34,39 The first weight loss onsets at around 200–230°C for all the
reported polymers. Just like poly (S-Corn oil),32 poly (S-Soybean oil),36 poly (S-Sunflower oil),39 poly (S-Linseed oil),39 poly
(S-Olive oil),39 and poly (S-Cottonseed oil),38 no Tg was detected in the case of poly (S-Palm oil) in the experimental
temperature range; nevertheless, poly (S-rubber seed oil),33,34 poly (S-canola oil),37 poly (S-algae oil),40 poly (S-Rice bran
oil),37 and poly (S-Castor oil)37 (all with 50 wt% initial sulfur content) exhibited glass transition temperatures at 6.41, 17,
32, 13, and 24°C, respectively. Regardless of the feed ratio, vegetable oils, in general, are not capable to stabilize all the
initial sulfur content against depolymerization over time, and thus, melting peaks resembling the phase transition of different
crystalline structures of elemental sulfur can be detected in the DSC thermograms of their resultant sulfur-based polymers. The
area of these peaks can be utilized to calculate the exact amount of elemental sulfur left embedded in the copolymers.32,36,37
Except for poly (S-algae oil)40 with 50 and 70 wt% initial sulfur contents, other reported sulfur-based polymers using
vegetable oils showed peaks identical to elemental sulfur in their XRD patterns which are in line with the DSC results. This
indicates the amorphous nature of these polymers and the presence of unreacted or depolymerized sulfur in the structure of the
polymers. All in all, utilizing vegetable oils as comonomers in inverse vulcanization results in brown color amorphous highly
crosslinked thermosetting polymers with some unreacted or depolymerized sulfur particles embedded inside the structure.

Conclusion
The copolymerization of palm oil with sulfur using inverse vulcanization was reported. 170°C and 1 h were chosen as reaction
conditions based on the preliminary results to copolymerize sulfur with palm oil using different percent compositions (S:Palm
oil), that is, 50:50, 60:40, 70:30, and 80:20. Fourier-transform infrared spectroscopy, DSC, and XRD were employed to
investigate the properties of the obtained copolymers. Poly (S-Palm oil) demonstrated a brownish color solid phase, which
became lighter by increasing the initial sulfur load, and a liquid phase consisting of the saturated portion of palm oil. The
obtained polymers showed no solubility in conventional organic solvents. Poly (S-Palm oil) is not firm against depoly-
merization after a long period and only after a few months, the phase separation of the reactants can be visually observed.
Fourier-transform infrared spectroscopy confirmed the successful reaction of the monomers and the formation of the
Abbasi et al. S1455

polymeric structure. In general, the obtained polymers with all percent compositions demonstrated a high thermal stability.
Poly (S-Palm oil) with all feed ratios showed some amount of unreacted or depolymerized elemental sulfur confirmed by DSC
and XRD indicating that palm oil regardless of its weight ratio is not able to stabilize all the sulfur content into the polymeric
structure. The obtained poly (S-Palm oil) suggests a new application for the openly stored elemental sulfur in gas and
petroleum refineries and thus helps reducing its environmental effects while also proposes a new application for palm oil that
directly boosts the palm oil industry. Poly (S-Palm oil) as it is can be utilized in several applications such as mercury removal,
oil spill removal, slow-release fertilizers, and palladium capture.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding
The authors disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This work was
supported by Yayasan Universiti Teknologi PETRONAS (Y-UTP) through cost centers 015LC0-080 and 015LC0-065.

ORCID iDs
Amin Abbasi  https://orcid.org/0000-0003-4212-1663
Wan Zaireen N Yahya  https://orcid.org/0000-0002-8211-3329
Mohamed M Nasef  https://orcid.org/0000-0002-0192-5107
Ali Shaan Manzoor Ghumman  https://orcid.org/0000-0002-3239-9250

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