Journal of Polymer Research (2020) 27: 191

https://doi.org/10.1007/s10965-020-02134-0

ORIGINAL PAPER

One-step hydroxylation of rubber seed oil and synthesis of green

polyurethane networks thereof
George Justine 1 & S. Athul 1 & C. P. Reghunadhan Nair 1

Received: 9 July 2019 / Accepted: 24 April 2020 / Published online: 2 July 2020
# The Polymer Society, Taipei 2020

Abstract
The unsaturation in Rubber seed oil (RSO) was converted to polyhydroxy compound (HY-RSO) in a single step reaction using
potassium permanganate solution under carefully controlled conditions. The HY-RSO polyol so formed was reacted with
methylene diisocyanate (MDI) to synthesize polyurethane prepolymer (PU) containing terminal isocyanate groups. Moisture
aided curing of the prepolymer led to crosslinked polyurethanes bearing additional urea linkages. The cross-linked poly(ure-
thane-urea)‘s mechanical, thermal and thermo-physical properties increased with increase in the isocyanate-content in the
precursor. These properties were better than those of a PU network derived from castor oil as a reference polyol. It was
demonstrated for the first time that RSO could effectively be converted to a value-added hydroxyl derivative for eventual
conversion to many useful materials including polyurethanes for related applications.

Keywords Rubber seed oil . Hydroxylation of unsaturated oil . Potassium permanganate . Polyurethane-urea

Introduction
Polyurethanes (PU) are promising materials for diverse appli-
cations ranging from packing materials for delicate electronic
equipment to providing thermal insulations in rocketry [1, 2].
The versatility of polyurethanes originates from their amena-
bility for modifications in many ways. The main raw materials
for the production of polyurethane are polyols and
diisocyanates. Conventionally, petroleum derived polyols
are used for the production of PU. As the petroleum wells
are drying up fast, the availability of polyols is going to be a
big concern in future. So, currently there is a move to look for
alternate, naturally available raw materials [3], particularly
from a renewable resource, Rubber seed oil (RSO) is a non-
edible oil abundantly available in many countries. It is seldom
used for any good commercial purposes. The unsaturated fatty
acid content of it is constituted by oleic, linoleic and linolenic
segments present in varying extents.
* C. P. Reghunadhan Nair
cpr@cusat.ac.in; cprnair@gmail.com
1
Department of Polymer Science and Rubber Technology, Cochin
University of Science and Technology, Kalamassery,
Cochin - 682022, India
The unsaturation and the ester groups of this oil have some
scope for chemical modifications to render RSO a useful raw
material. Majority of the methods for converting the
unsaturation in oils and fats to alcohol groups is via epoxidation
of the double bond followed by ring-opening of the epoxide to
generate one OH group per double bond [4, 5]. But Okieimen
[6] and coworkers employed a different route involving partial
trans-esterification of the oil with a polyhydric compound like
glycerol. In this process, the derived polyol will have all the OH
groups centered on one side of the oil molecule. This will result
in polyurethanes with all urethane linkages concentrated on one
side of the molecule. This can lead to an imbalance in the
distribution of the urethane groups across the RSO-PU net-
work. Patent application U.S. 6,433,121 claims a method for
the production of oligomeric polyols based on epoxidized veg-
etable oils [7]. The ring-opening of the epoxy group is then
done to generate hydroxyl groups. This way PU foams were
also prepared [8, 9]. A modified process for making polyure-
thane foams from RSO via the polyol route was also reported
[10, 11]. In this case, the OH groups were introduced through
glycerolysis of the ester part. It can be seen that all the reported
methods warrant cumbersome procedure which are multi-step,
energy-intensive and non-quantitative. In that case, it cannot be
recommended as a method for hydroxylation of the oils. The
number of OH groups generated per unsaturation is also limited
to a maximum of one only.
191 Page 2 of 9
Though there are many reports on hydroxylation of RSO
[12], none of them describes any direct method for hydroxyl-
ation using the unsaturated groups on them. The unsaturated
groups are known to react with alkaline KMnO4 to form vic-
inal diols. This is an accepted method for qualitative identifi-
cation of unsaturated organic compounds (where KMnO4 is
discolored). However, this method has never before been ex-
plored as a method for quantitative hydroxylation of unsatu-
rated compounds. The reason is that KMnO4 is an aggressive
oxidant that it may not stop the reaction at the diol level. It can
further oxidize the formed alcohols. Moreover, the reaction
between an olefin and KMnO4 may not be easy as the olefin
is generally not soluble in water. But, we found a solution for
the dispersion of these oils in water using a dispersing agent.
The oxidation beyond hydroxylation was precluded by
employing an extremely dilute solution of KMnO4 at near
zero temperature condtions. Under these conditions, the reac-
tion of KMnO4 with an olefin was found to be quick and
quantitative. The matter is the subject of an Indian patent [13].
This paper describes for the first time, the conversion of
RSO to a vicinal dihydroxy polyol (HY-RSO) by a single-step
process. A known quantity of rubber seed oil (200 g) was
dispersed in de-ionized water (1000 mL) using potassium ole-
ate as the dispersant at a concentration of 2 × 10 −3 M.
Potassium oleate might not appear as the right choice for the
dispersant as this also contains unsaturation capable of under-
going hydroxylation via KMnO4. It was however used as it is
cheap and easily available. At such low concentration (2 ×
10−3 M), its oxidation (hydroxylation) was found not to affect
adversely the overall dispersing property of it. The formation
of OH groups is confirmed by OH value determination in
addition to analyses by NMR techniques. This synthesis of
polyol can be considered “green” as it is made from RSO
(green source) using KMnO4 in an aqueous medium (green
conditions). This is the first ever report of synthesis of polyol
from unsaturated oil by a direct route.
Experimental methods
Materials
Rubber seed oil was procured from M/s, Pavalam Industries,
Madurai, India. The lightly brown, clear, free flowing liquid
had an iodine value 153 g/100 g. Proton NMR further con-
firmed its composition and purity.
Methylene diphenyl isocyanate (MDI) better known as Bis
(4-isocyanato phenyl) methane (BIPM) was a gift sample re-
ceived from Indian space research Organization and it has a
NCO content of 99.1% as estimated by the butyl-amine meth-
od. RSO was further analyzed by NMR for the number of
unsaturated groups. Potassium permanganate, Ethyl methyl
ketone (EMK) etc. were purchased from NICE Chemicals,
J Polym Res (2020) 27: 191
Cochin; India. EMK was further purified by keeping it over
freshly dried and powdered potassium carbonate and then
distilling.
Methods
Hydroxylation of rubber seed oil (RSO)
Calculated quantities of dilute potassium permanganate solu-
tion (prepared as a 0.005 N solution in 0.0001 N aqueous
NaOH) was cooled below 2C and then added drop-wise to
the RSO dispersion in deionized water.. While doing so, care
was taken for the total system not to exceed a temperature of
2 °C. After the addition was over, the system was kept stirred
for one and half hour. Since the reaction occurs inside micelle
of micron size, the transport of the oxidant across the micelle
is quite rapid.
The formed product was extracted with ethyl acetate which
was removed in vacuum. The obtained product was further
purified by dissolving it in ethyl acetate and warming after
adding charcoal. The filtered solution after solvent recovery
was then characterized by NMR and for OH value. Yield
70%.
Synthesis of polyurethane
In the first step, the hydroxylated RSO (Hy-RSO) was made to
react with BIPM under dry conditions. Dibutyl tin dilaurate
(DBTDL) at 0.25% (by weight) was used as catalyst to com-
pensate for the reduced reactivity of the secondary OH groups
generated as a result of hydroxylation. BIPM was used in
excess so as to get NCO-terminated pre-polymer. HY-RSO
mixed with DBTDL was added drop-wise to BIPM calculated
for different NCO/OH values and kept stirred for one hour at
ambient temperature.
As the viscosity of the system increased, Methyl Ethyl
Ketone (EMK) was added in small portions to reduce the
viscosity and to prevent formation of lumps. The final product
was a clear lacquer which was cast over a clean surface and
was allowed to get cured using atmospheric moisture at room
temperature. Sample of different compositions for Attenuated
total reflectance (ATR) were cast the same way. The relative
humidity was 80 to 90% at ambient temperature of 28 to
32 °C.
Characterization
Nuclear magnetic resonance (NMR) spectroscopic analyses
were carried out on a Bruker Avance IIITM, 400 MHz
NMR spectrophotometer. CDCl3 was used as the solvent,
while attenuated total reflection analyses were performed on
the samples using a Thermo Nifcolet AVATAR 370 FTIR
Nicolet AVATAR 370 DTGS in the range 4000-400 cm−1with
J Polym Res (2020) 27: 191 Page 3 of 9 191

ATR instrument - Perkin Elmer spectrum 20.e solvent. The

cure characteristics were monitored with a Rubber Process
Analyzer RPA 2000 (Alpha Technologies) with a frequency
of 0.833 Hz and a strain of 0.2 degree.

Dynamic mechanical analyses Dynamic Mechanical Analyses

of the samples were done using a DMA Q800TM Series of
TA Instruments® under non-isothermal conditions, at a
heating rate of 30C per minute and the equilibrium point
was set as 300C. The test was run up to 200 C for each case.

Mechanical properties

The mechanical properties of the samples were determined by

ASTM D 882 procedure and using Shimadzu AG-I™ SPL
10kN Universal Testing Machine at a strain rate of 50 mm
per minute. The test was conducted at room temperature with
a 12X5cm × 0.5 m rectangular strip. Tensile strength, Elastic
moduli, and maximum strain etc. of the samples were evalu-
ated. The average of 5 test results is reported along with their
standard deviation.

Iodine value estimation This was done as per ASTM D5554–

15 for the RS oil.

OH value determination It was done as per a modified ASTM

D1639–90 and ASTM D1957–90, where maleic anhydride
was used in place of acetic anhydride. Care was taken to
ensure that no part of maleic anhyride gets sublimed and lost.

Results and discussions

The RSO, on the average contains 5 double bonds which can
be represented as a mixture of three isomers in any proportion.
Fig. 1 shows the structure of a typical RSO bearing one C18
chain on each of its arm. The unsaturation on each arm is
indicated as below. The first number indicates the number of
carbon atoms in the fatty acid and the second, the number of
unsaturation in these three arms.
18: 0 (stearic),18:2(linoleic),18:3 (linolenic)
or
18: 1 (oleic), 18:1(oleic), 18:3(linolenic)
or
18: 2(linoleic), 18:1 (oleic), 18:2 (linoleic)
The total number of double bonds amounts to 5. Average
molecular weight (theoretical) of RSO is 842.The purity of
RSO was confirmed from its iodine value (refer experimental
part) and NMR analyses..The liquid had an iodine value
155 g/100 g(Theoretical value 151 g/100 g. The near zero acid
value was yet another evidence for the absence of hydrolysis
of the ester groups. The proton NMR (Fig. 2) showed the
proportion of protons on the terminal methyl groups to those
Fig. 1 Composition of RSO
on the glycerol unit of the fatty acid as 4.98/2.71 = 1.83, while
the value expected of the non-hydrolyzed product is 9 /5 =
1.80, in close agreement with the expected structure. All these
are in support of the purity of the product as the proprietary
purification method was not disclosed by the manufacturer.
Hydroxylation
Hydroxylation of rubber seed oil was done by treatment with
alkaline KMnO4.(ref.: Experimental part). The reaction was
carried out in cold conditions where the temperature was not
allowed to exceed 2 °C. Formation of the hydroxyl derivative
was confirmed from its OH value and further by NMR anal-
ysis. In one typical case, hydroxylation was limited at 60%
and the product was isolated as usual (whose NMR details are
described later). The OH value for the completely hydroxyl-
ated product (with 10 OH groups) was obtained as 530-
191 Page 4 of 9
Fig. 2 Proton NMR spectrum of
RSO (CDCl3)
540 mg KOH/g. For 60% hydroxylation, the OH value is 340-
350 mg KOH/g.
Synthesis of PU
Earlier reports on polyurethanes from HY- RSO were based
on polyols derived from partial glycerolysis of RSO. Several
reports deal with epoxidation of unsaturated oils followed by
hydrolysis as a means for developing the polyols. While the
former method leads to localization of OH groups on one side
(the glycerol part), the present method ensures even distribu-
tion of these groups on the fatty acid arms of the molecule.
The second method is very cumbersome and invokes multi-
steps. Moreover, it provides only oneOH group per
unsaturation. We report here for the first time, the direct hy-
droxylation of RSO to HY-RSO by reaction with an extremely
dilute KMnO4 solution at very low temperatures, providing
Fig. 3 Expected composition of HY-RSO
J Polym Res (2020) 27: 191
vicinal dihydroxy groups per unsaturation in a quantitative
way. The idealized structures of RSO as well as HY-RSO
are shown in Figs. 1 and 3 respectively.
Analyses
Spectral analyses of RSO and HY-RSO
HY-RSO was characterized by FTIR and NMR. FTIR showed
the absorptions characteristic of OH groups at around
3400 cm−1 which were not present in RSO. Detailed charac-
terization was done by proton NMR. NMR of RSO (Fig. 2)
showed signals corresponding to the unsaturation at 5.4 ppm
with a relative signal intensity of 7.08. This was compared to
the signals at 4.2 ppm corresponding to the four methylene
protons on glycerol unit that are invariant (intensity 2.55, i.e. 1
proton =0.64 unit). The signals at 5.4 ppm includes the central
J Polym Res (2020) 27: 191 Page 5 of 9 191

Fig. 4 Proton NMR of fully

hydroxylated HY_RSO in
DMSO-d6

C-H hydrogen of glycerol unit. From these, it can be easily
estimated that the unsaturated hydrogens in this molecule are
(7.08–0.64)/0.64 = 10. As the double bonds are isolated, each
double bond possesses two unsaturated hydrogens. Thus, the
RSO used in this study contains 5 double bonds. Obviously,
this is an average number and that the RSO is constituted by a
mixture of oils of different saturated and unsaturated fatty acid
arms such that the average unsaturation corresponds to 5 dou-
ble bonds, as it is represented in Fig. 1. A good NMR spectral
assignment of RSO has been done by Onoji etal [14].
On hydroxylation, the unsaturated hydrogens disappeared
totally from the vicinity of 5.4 ppm (Fig. 3) and the new
protons corresponding to the -(OH)H-C-C-H(OH) protons ap-
peared fresh at 2.3 ppm.
In Fig. 4 is shown an NMR spectrum of a fully hydroxyl-
ated RSO. Referring to the NMR, the protons corresponding
to the methylene units of glycerol appear at a chemical shift of
4.2 ppm with an intensity of 2.55 units. This corresponds to a
signal intensity of 0.6 units per hydrogen. The intensity of
unsaturated proton at 5.4 ppm is 3.05(a.u). So the number of
hydrogen actually responsible for this signal is (3.05–0.64)/
0.64 = 3.76. So the residual unsaturation is 3.76/2 = 1.88.
Therefore, out of 5 double bonds 5–1.88 = 3.12 double bonds
are already hydroxylated. So, the extent of hydroxylation in
this case is (3.12/5) *100 = 62.4 as against the target of 60%
(that was experimentally planned). The proton NMR of partly
hydroxylated RSO, (HY-RSO) is shown in Fig. 2.
The CH-OH signal of the hydroxylated derivative appears
at 2.3 ppm along with the allylic protons. The intensity of the
allylic protons expected i to the CH-O- is 6.01–1.8 =
4.21 units. This corresponds to 6.57 protons. Since the hy-
droxylation occurs in vicinal mode, this equals 3.28 vicinal
hydroxyl (one pair) groups. This closely matches with the
expected number of hydroxylated double bonds of 3.20. The
NMR of partially hydroxylated RSO is shown in Fig. 3.
However, the HY-RSO used for polyurethane synthesis were
the fully (100%) hydroxylated one. [i.e. 10 OH groups].
Similarly, the proton counting in NMR corresponded ex-
actly to the fully hydroxylated structure of HY-RSO..The like-
ly isomers in 100% hydroxylated RSO are shown in Fig. 3
(one possibility).
Synthesis of polyurethane
Polyurethane was synthesized from HY-RSO and BIPM tak-
en in the [NCO]/[OH] ratio ranging from 1.1 to 1.5 (refer
Table 1)). In this case, the polyol used has an OH functionality
of 10 (i.e.10 OH groups per molecule) as all double bonds in
RSO are hydroxylated. This reaction was carried out in a RB
flask under nitrogen atmosphere with mechanical stirring. The
polyol mixed with DBTDL catalyst was added to BIPM drop-
wise. The reaction was instantaneous and moderately exother-
mic. The addition of HY-RSO was done in such a way that the
isocyanate remains always in excess.
This precursor was diluted with required quantity of EMK
prior to casting thin films. The formation of PU is depicted in
Fig. 5.

Table 1 Typical reactant

concentrations for synthesis of Sl [NCO]/[OH] weight of weight of HY- weight of cross-link
polyurethanes at different NCO/ no Equivalent Ratio BIPM (g) RSO (g) DBTDL (mg) density(mol/L),
OH equivalent ratios theoretical

1 1.1 13.75 105 294 16.9

2 1.2 15 105 297 18.4
3 1.3 16.25 105 300 20.0
4 1.4 17.5 105 303 21.5
5 1.5 18.75 105 306 23.0
191 Page 6 of 9 J Polym Res (2020) 27: 191

Fig. 5 Formation of
polyurethane-urea network from
HY-RSO.

Cure optimization Characterization of polyurethane by FTIR/ ATR

This was done using a rheometer with the prepolymer of OH
/NCO ratio of 0.7(NCO/ OH =01.4) at ambient temperature
(28–320 C) and humidity (RH = 80–90%). The analysis was
done using a parallel plate rheometer. The rheogram shown in
Fig. 6 manifests a rapid modulus build-up at ambient temper-
ature and RH. The curing at ambient conditions is complete in
less than 10 min.
The ATR analysis (Fig. 7) showed the complete disappear-
ance of the NCO peak at 2249 cm−1 and the appearance of
C=O of the urethane at 1705 cm−1(urethane carbonyl), indi-
cating formation of the expected polymer. The other peaks
observed were assigned as: 1643 cm−1 (C = O bond urea),

Casting of thin PU films

The NCO-terminated polyurethane prepolymer (viscous

liquid) was initially synthesized using NCO/OH ratios of
1.1 to 1.5. It was then cast in to thin sheets after dilution
with EMK. The curing took place by the reaction of NCO
groups with atmospheric moisture generating amine whose
reaction with NCO led to a urea-linked PU network. Thus,
the final network is poly (urethane-urea) with RSO base.
This experiment was repeated for all the pre-polymers of
NCO/OH ratios 1.1 to 1.5. Fig. 6 Rheogram of polyurethane pre-mix (NCO/OH ratio = 1.3)
J Polym Res (2020) 27: 191
Fig. 7 ATR of cured resin
1599 cm−1 is C=C stretching of aromatic ring,while the one at
1533 cm-1is attributed to C-N stretching. Figure 7 shows a
representative ATR spectrum of a typical composition of the
PU-PUR matrix (with the apparent NCO/OH ratio of 1.1. The
absorption at around 1700 cm−1 corresponds to the carbonyl
group of polyurethane and the one at 1637 cm−1, to the car-
bonyl group of urea. By considering the absorbance of these
two groups, one should normally be able to estimate the rela-
tive concentrations of the two groups in different systems and
make a first cut assessment of the crosslink density. However,
the quantitative estimation of both warrants materials that can
act as standards for these. For want of it, the crosslink density
couldn’t be estimated from ATR spectral studies.
Mechanical properties
Tensile properties The tensile properties of the films of
polyurethane–urea at different [NCO]/[OH] ratio are depicted
25
Tensile strength (N./mm )
20
15
10
5 different NCO/OH ratio are depicted in Fig. 8. The scatter in
0
1.1 1.2 1.3 1.4
Reactant ratio (NCO/OH)
Fig. 8 Tensile properties of the crosslinked PU from RSO (Top:Tensile
strength, bottom:Tensile modulus)
Page 7 of 9 191
Table 2 Crosslink densities of the various PU networks calculated from
DMA and from chemical structure.
NCO/OH Tg Modulus at Molecular weight Theoretical
equivalent (°C) Tg + 40 °C between crosslinks Molecular weight
ratio (MPa) from DMA. (Mc,g/ between crosslinks
mol) (Mc), g/mol
1.1 125 3.95 3180 463
1.2 148 16.60 807 466
1.3 150 15.53 855 477
1.4 154 41.27 320 478
1.5 156 40.66 331 480
in Fig. 8. As per this figure, the properties get optimized at a
ratio of 1.3 to 1.4. The moduli get optimized at a [NCO]/[OH]
ratio of 1.3–1.4. Therefore, the system can be considered to
have an optimum formulation at a NCO/OH ratio of 1.3 to 1.4.
Elongation was found increasing systematically with an in-
crease in NCO/OH ratio implying the formation of a tough
polymer networks. It is to be remarked that these properties
are higher than those of the polyurethane derived from castor
oil (bench mark) at comparative molar ratios [15]. As per this,
the tensile strength of castor oil-PU ranges from 0.8 to 15 MPa
at an NCO/OH ratio of 1–1.3, while the elongation for the
same ranges from 15 to 50%. We got a tensile strength as
22–25 MPa for the [NCO]/[OH] ratio of 1.0–1.3 for HY-
RSO. The reported elongation for castor oil based polyure-
thane17 is 15–50% while for the HY-RSO system, the corre-
sponding values are 70–150% for the same NCO/OH ratio.
A higher elongation and a higher tensile strength imply that
the presence of HY-RSO offers a stronger and tougher poly-
urethane network in contrast to the one based on castor oil of
the same reactant ratio17. The thermo-physical properties of
the RSO-derived PU in comparison to the castor oil-derived
PU under identical conditions of the nature of the diisocyanate
and the reactant stoichiometry are compiled in Table 2. These
systems possess a higher Tg than the familiar PU systems.
Tensile modulus(N./mm )
2
In fact, the cured matrix contains both urethane and urea
groups. The urea group though rigid it offers avenues for
strong H-bonding with NH and OH groups thus sering as a
good cross linking site. Therefore, in a matrix containing both
urea and urethane, the proportion of urea decides, a priori, the
cross-link density and associated properties.
The tensile properties of the films of polyurethane–urea at
data are also indicated. As per this, the properties get opti-
mized at a an NCO/OH ratio of 1.3. The moduli get optimized
1.5 at ratios of 1.3–1.4. Therefore, the system was considered to
have the optimum properties at a reactant ratio of 1.3 to 1.4.
Interestingly the elongation went on increasing with increase
in reactant ratio, as shown in Fig. 9.
191 Page 8 of 9 J Polym Res (2020) 27: 191

Fig. 11 Linear variation of sub Tg storage modulus with reactant ratio

Fig. 9 Variation of elongation with reactant ratio

Theoretical calculations of CLD However, it was possible to

The Tg values derived from tan (δ) max in DMA of these PU
calculate the theoretical cross-link density from the chemical
are higher in comparison to other PUs reported. The high Tg
structure with the same assumption that the urea group (PUR)
indirectly confirm the multi OH- functionality of the polyol. In
contributes towards cross-linking and the urethane only to
fact, the OH groups in this type of polyols exist as vicinal, in the
chain extension [16]. The urea groups contributing to the stiff-
sense, the OH groups exist in pairs on adjacent carbons.. Thus,
ness as these groups are quite rigid and capable of H-bonding
there is a tendency for the urethane groups to exist adjacent to
from either directions. This was more evident in DMA spectra
each other. This local clustering is responsible for the abnormally
(Fig. 10) of the cured polyurethanes with varying NCO-
high Tg values and the high mechanical properties of these poly-
content in the precursor. The storage modulus variation with
urethanes. It was noted that at any point above the Tg, the storage
increase in NCO content is tremendous.
modulus at a given temperature increases linearly with the reac-
The theoretically computed CLD are compiled in Table 2.
tant ratio (NCO/OH). This is demonstrated in Fig. 11 for a typical
The values expressed as the molecular weight between cross-
case. The NCO groups in excess of what is needed to react with
links (Mc) are in close match with the Mc values determined
the available OH groups are hydrolysed to amines on exposure to
by DMA studies.
moisture which then react with NCO groups to form urea groups
in the network polymer. Figure 11 conveys, in fact, the impact of
DMA studies Figure 10 shows the DMA spectra of polyure-
urea linkages in deciding the modulus of these cross-linked poly
thanes prepared at different [NCO]/[OH] ratios. The influence
(urethane-urea) network polymers.
of the reactant ratio in increasing the moduli is obvious from
the DMA Profile.
CLD from DMA DMA profiles were used to calculate the CLD
values using the equation [15],

Mc ¼ 3E=RTd

where T is the absolute temperature at which the modulus

(E)is determined, d – polymer density, and R – the universal
gas constant. Usually the temperature is chosen as Tg + 40 °C.
The Mc values thus calculated and complied in Table 2 are
found to be in close match with the theoretical values except in
one two data. Naturally as the NCO content increases, the Mc
diminishes.

Glass transition temperature (Tg) The Tg values taken from

the tan(δ) max from DMA (refer Table 2) shows an increase on
increasing the isocyanate content. This happens because at
Fig. 10 DMA profiles of polyurethanes formed at varying [OH]/[NCO] higher isocyanate-content, the contribution of the rigid
ratio polyurea fraction towards Tg is significant. These Tg values
J Polym Res (2020) 27: 191
(125–156 °C) are higher than those of d from castor oil
(109 °C)17.
Conclusions
It was demonstrated that rubber seed oil, a material otherwise
of not much commercial value can be converted into a value-
added polyol. This is achieved by a single-step, direct hydrox-
ylation process under controlled conditions using alkaline
KMnO4 though a green route. The polyurethanes derived
from these OH-rich polyols are mechanically strong and
tough. These properties increased with an increase in the
[NCO]/[OH] ratio in moisture-cured samples. The poly
(urethane-urea) systems possessed higher Tg than the usually
encountered polyurethanes. This is attributable to the multi-
functionality of the polyol (HY-RSO). The curing through air-
borne moisture increased the relative concentration of urea
over urethane in the cross-linked polymer that increased Tg
as well as the modulus of the network. Since hydroxylation is
controllable, polyols of desired OH value can be obtained.
Further studies are under way to derive other useful precursors
like maleated RSO for green unsaturated polyester resin,
acryloyloxy RSO as green, anaerobic adhesive etc.
Acknowledgments
The authors thank Kerala State Council for Science
Technology and Environment, Kerala, India for finan-
cial support.
Role of each author Author 1. Part of this work is taken from
the Master’s Degree (in Technology, M-Tech) research disser-
tation of the first author (Mr.George.J) under the supervision of
the third author (Prof. CPR Nair). Mr.George was responsible
for generating part of the data as per direction of the 3rd author.
Author 2.The second author (Athul.S) generated the data as
was necessary and were demanded by the reviewers in addi-
tion to those generated per direction of the third author.
Author 3. Third author (Prof. CPR Nair) conceived the
idea, planned for its execution and compiled the data generat-
ed by the first and second authors into a research paper. He is
also responsible for compiling the data in to this research
paper.
Affidavit I, Dr. C.P.Reghunadhan Nair hereby affirm that the
contents of this paper are known to the other two contributors
(authors). They have vetted the changes marked in the revised
texts. We have sincerely attempted to make the element of
plagiarism close to zero in this paper.
This paper is submitted on behalf of, and with the concurrence
of all the three authors (J George, S Athul and CPR Nair).
CPR Nair.
Page 9 of 9 191
Compliance with ethical standards
Conflict of interest The authors hereby declare that there is no conflict
of interest for this manuscript’s preparation and publishing.
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