Bull. Mater. Sci., Vol. 38, No. 5, September 2015, pp. 1155–1161. © Indian Academy of Sciences.

Synthesis and characterization of castor oil-based polyurethane for

potential application as host in polymer electrolytes

S IBRAHIM1,*, A AHMAD2 and N S MOHAMED3

1
Institute of Graduate Studies, University of Malaya, 50603 Kuala Lumpur, Malaysia
2
School of Chemical Sciences and Food Technology, Faculty of Science and Technology,
Universiti Kebangsaan Malaysia, 46300 Bangi, Selangor, Malaysia
3
Center for Foundation Studies in Science, University of Malaya, 50603 Kuala Lumpur, Malaysia

MS received 21 January 2014; accepted 20 May 2015

Abstract. Polyurethane (PU) based on polyol, derived from castor oil has been synthesized and characterized
for potential use as a base material for electrolytes. Transesterification process of castor oil formed a polyol
with hydroxyl value of 190 mg KOH g–1 and molecular weight of 2786 g mol–1. The polyols together with
4,4′-diphenylmethane diisocyanate were used to synthesize the desired bio-based PU. The molecular structure of
PU was investigated by Fourier transform infrared (FTIR) spectroscopy. The disappearance of NCO peak in
the FTIR spectrum at 2270–2250 cm–1 showed that diisocyanate has completely reacted to form PU. Morpho-
logical characteristic of the PU film was analysed using scanning electron microscopy, whereas thermal char-
acteristics of the materials were characterized using dynamic mechanical analysis and thermal gravimetric
analysis. The cross-sectional micrograph showed that the prepared film was highly amorphous and homo-
geneous. Thermal studies revealed that the film had low glass transition temperature, –15.8°C, and was
thermally stable up to 259°C. These observations indicated the synthesized PU possessed favourable proper-
ties to act as a base material in polymer electrolytes.

Keywords. Castor oil; transesterification; polyol; 4,4′-diphenylmethane diisocyanate; polyurethane.

1. Introduction In order to meet specific requirement, their structures can

be tailored by selecting appropriate polyols and polyiso-
Polyurethanes (PUs) are versatile materials and widely cyanates. In industry, only a few diisocyanates or poly-
used in both industry and everyday life. They can be used isocyanates are commonly used, while a variety of
for many applications, such as tubings, footwear, industrial polyols are available. Therefore, the choice of polyol
machinery, coatings and paints, elastic fibres, rigid insu- typically determines the properties of the created PUs.6 In
lations, soft flexible foam, medical devices, and many addition to petroleum-based polyols, vegetable oils such
others.1–3 PUs are included in both thermoplastic and as soybean oil, canola oil, palm oil, sunflower oil, corn
thermosetting polymers. Research and development in the oil, linseed oil and nahar seed oil7–9 have been exten-
field of PUs is increasing year to year showing the rapid sively studied as bases for various polyols used for the
growth in PU industry. The polymers are mainly pro- manufacture of PUs for different applications.
duced by the isocyanation of diisocyanate (NCO) with The preparation of polymers from vegetable oils is
polydiol (OH) of various molecular weights.4 Large currently receiving increasing attention because of the
selections of polyols and isocyanates are available, which economic and environmental concerns.10–13 Raw materials
permit the design of polymers for many applications. based on vegetable oils have a number of excellent pro-
PUs serve the mankind in its various roles such as flexi- perties for producing valuable polymers such as PU,
ble, rigid, semi-rigid, elastomers, surface coatings, and alkyd, polyester, amide and epoxy resins. Vegetable oils
adhesives. A review on the background and history of are triglycerides of fatty acids. In order to use these com-
urethane foams and elaborations on their potential future pounds as starting materials for PU synthesis, it is neces-
utility has been written by Khemani.5 sary to functionalize them to form polyols. Castor oil
The properties of PU depend on certain factors such as (Ricinus communis) from the family of Euphorbiaceae is
the content of the reactive groups, the degree of cross- a promising starting raw material for PU due to low
linking and the entanglement of the reacting monomers. toxicity and availability as a renewable agricultural
resources. The major constituent in the castor oil is rici-
noleic acid (12-hydroxy-cis-9-octadecenoic acid), which
*Author for correspondence (salmiah01@gmail.com) is a hydroxyl containing fatty acid. The most common
1155
1156 S Ibrahim et al

chain lengths in these fatty acids are 18 and 20 carbon was reacted with MDI to obtain flexible films. Trans-
atoms which can be either saturated or unsaturated, esterification of castor oil was performed under nitrogen
where unsaturation of the double bonds are located at atmosphere. The set-up consisted of four-necked glass
the 9, 12, and 15 carbon. By using enzymes or chemicals reactor of 1000 ml capacity with 250 mm height and
to modify the unsaturated fatty acid and introducing 150 mm in diameter equipped with a mechanical stirrer.
hydroxyl functional groups, castor oils could be con- Heating was carried out by means of 1000 ml heating
verted into polyol. There are many literatures on modi- mantle. Nitrogen was supplied at a constant flow rate to
fied castor oil PU for application in bridge decking, avoid any oxidation reaction within the reactor. One of the
adhesives and thermal insulation.14–16 However, modifica- necks of the reactor was equipped with a reflux condenser.
tion of PU for use as host in polymer electrolytes has not The reactor was filled with castor oil and 15 wt% of gly-
yet been reported in the literature. PU has unique multi- cerol was added to it. The percentage of the mixture was
phase structure formed from soft segment and hard seg- fixed according to the Patton formula18 to obtain the
ment in the polymer chains. Soft segment could hydroxyl value of below 200 mg KOH g–1. The mixture
contribute as polymeric solvent to solvate the cation and was slowly heated until it reached 210°C. The tempera-
hard segment could function in maintaining the electro- ture was maintained at this value under constant stirring
chemical stability. Therefore, it would be used as PU at 200 rpm. The small amount of reaction mixture was
polymer electrolytes in the fabrication of electrochemical taken out and mixed with methanol in the ratio of 1 : 4 to
devices.17 check the solubility of the mixtures. A clear and homoge-
The aim of this work is to synthesize PU from renew- neous solution was obtained, indicating the formation of
able resource, castor oil with desired properties for appli- monoglycerides. The mixture was allowed to cool to
cation as host material in polymer electrolytes as an 120°C before it was latter continuously stirred at ~ 200–
alternative to petrochemical-based PU. Nevertheless, there 220°C after the addition of an appropriate amount of
is no report related to the potential of castor oil-polyol- phthalate anhydride. The progress of condensation reac-
based PU as host in polymer electrolytes. The synthesis is tion and its stability were confirmed by checking its acid
carried out at room temperature without additives, value according to the procedure recommended in ASTM
cross linkers and chain extenders. The work comprises of D1639-90E. For this purpose, samples were taken out at
the transesterification of castor oil followed by polymeri- regular intervals and checked for an acid value using the
zation of PU. The materials were characterized including titration method and phenolphthalein was used as indica-
optical, morphological and thermal properties. Although tor. The time required to complete the reaction was about
there are many methods and sources to synthesize PU, the 10 h. The resulted polyol was stored in dark bottles away
transesterification of polyol from castor oil could give from direct sun light. The produced polyol was mixed
highly amorphous PU with low molecular weight and low thoroughly with MDI using a digital magnetic stirrer at
glass transition temperature, Tg, value. Unlike crystalline room temperature condition in the weight percentage
phase, the polymeric chain in the amorphous phase is (wt%) ratios of 20 : 80 (NCO : OH) and 40 : 60 (NCO : OH).
more flexible, which results in enhancement of segmental MDI was slowly added to polyol and THF was used as
motion to enable easy ion migration. the solvent. The complete reaction of PU was confirmed
by the disappearance of NCO peak at 2270 cm–1 in Fourier
transform infrared (FTIR) spectra. The resulting solution
2. Experimental
was poured into a Teflon mould and left for slow evapo-
ration of solvent. To ensure complete curing, the films
2.1 Materials
produced were kept in a desiccator before they were cha-
racterized. For polymer electrolytes preparation, compo-
Castor oil, glycerol (99.9%), ethanol (99%), methanol,
sition of NCO : OH that formed PU was dissolved in
potassium hydrogen phthalate, phthalate anhydride, potas-
10 ml THF before the addition of lithium iodide in differ-
sium hydroxide, phenolphthalein and tetrahydrofuran
ent wt% (10–40 wt%) and stirred for 4 h. The homogene-
(THF) were supplied by R&M Marketing, Essex, UK,
ous solutions were then casted in Teflon Petri dishes and
while 4,4′-diphenylmethane diisocyanate (MDI) and
left at room temperature for slow drying until free-
lithium iodide (LiI) were obtained from Merck and
standing films were obtained.
Aldrich, respectively. All the reagents were of analytical
grade and used without further purification.
2.3 Analytical measurements
2.2 Preparation of castor oil-based PU films
The interaction of chemical structures of polyol and PU
The PU films were obtained by two steps of procedures. prepared using castor oil was characterized using
In the first step, the castor oil was modified to obtain Perkin-Elmer Frontier FTIR/MIR spectrophotometer
polyol of desired acid value and in the subsequent step it through attenuated total reflectance (ATR) scanning from
 Castor oil-based PU as host in polymer electrolytes 1157

550 to 4000 cm–1 with a resolution of 2 cm–1. The mo- range of 10 Hz–5 MHz with amplitude of 100 mV at
lecular weight, Mw, of polyol and PU-based castor oil was room temperature. The samples were sandwiched by two
determined by the gel-permeation chromatography (GPC) polished stainless-steel blocking electrodes. The values of

from the Nyquist plots obtained. Conductivity, σ values

technique using the Waters equipment with refractive bulk resistance, Rb, of the electrolytes were determined
index detector, Water 717 plus Autosampler and Water
600 Controller. THF was used as the eluent with flow were calculated using equation
rate of 1 ml min–1 at 16 bar. Dynamic mechanical analy-
σ=
sis (DMA) was performed in order to determine the glass t
,
transition temperature, Tg, of the synthesized PU. The Rb A
analysis was performed using Perkin Elmer DMA 8000
where t is the thickness of the electrolyte and A the elec-
of 1 Hz. Rectangular PU film specimens of 20 × 10 ×
dynamic mechanical analyser with a film-tension mode
trolyte–electrode contact area.
0.60 mm (length × thickness × width) were used for the
analysis. The samples were cooled and held isothermally 3. Results and discussion
at –60°C before the temperature was increased to 180°C

tained from the peaks of the tan δ curves. The thermogra-

at a rate of 2°C min–1. Tg values of the samples were ob- Scheme 1 shows the transesterification of castor oil-based
polyol. Esterification began after phthalate anhydride was
vimetric analysis (TGA) was carried out in added to the mixture of oil and glycerol and after some-
order to study thermal stability of the PU films. The TGA time, water was collected and the mixture turned into a
was done using the Setaram LABSYS Evo simultaneous clear brownish solution. From the titration that was done
thermal analyser. The experiment was carried out under at a certain interval of time during the heating and stirring
nitrogen atmosphere from 30 to 600°C at 10°C min–1 processes, the calculated acid value of the reaction was
heating rate. The morphology of the cross-section of found to decrease gradually throughout the reaction. This

scanning electron microscope at ×2000 magnification

polymer films was observed using ZEISS EVO MA 10 proves that the reaction has progressed and polyester
polyol was formed. The polyol obtained has an acid value
with 10 kV electron beam. Sample was fractured and of 3 mg KOH g–1. The hydroxyl value of the polyol was
coated with gold using sputter coating machine for 90 s obtained using 848 Titrino Plus equipment and its value
before the analysis. Conductivity measurements of the is 190 mg KOH g–1. According to Petrovic, polyols with
polymer electrolytes were done using impedance spec- OH numbers of about 200 mg KOH g–1 and less give
troscopy, Solartron SI 1260 impedance/Gain-Phase Ana- semi-rigid PUs of moderate or low crosslinking density
lyser. The measurements were performed over frequency when crosslinked with diisocyanate.19 Figure 1 shows FTIR

Scheme 1. Schematic representation of the preparation of castor oil-based polyol.

1158 S Ibrahim et al

spectra of castor oil and synthesized castor oil-based In this work, molecular weight of samples was deter-
polyol. The characteristic band of ester group C=O stret- mined by using gel-permeation chromatography. From
ching appears at 1730 cm–1 and that of O–H functional the chromatogram that was not shown here, the molecular
group at 3550 cm–1. These bands confirm the esterifica- weight of castor oil is 1023 g mol–1, close to the value
tion reaction of polyol. reported by other researcher which is 963 g mol–1.14 The
As mentioned earlier, PU films were produced by the synthesized castor oil-based polyol gives a molecular
reaction of MDI with castor oil-based polyol. Two differ- weight of 2786 g mol–1. This value is suitable to form
ent PU formulations were used (table 1). Formulation 1 flexible PU.25,26 The molecular weight of synthesized PU
contains NCO and OH in the weight ratio of 20 : 80, while in this work is 11,942 g mol–1. Table 2 summarizes the
Formulation 2 contains NCO : OH ratio of 40 : 60. Figure molecular weight of samples.
2 presents the FTIR spectra of the synthesized castor oil-
based PU in the region 550–4000 cm–1. For Formulation
2, the presence of peak at 2270 cm–1 indicates that the
isocyanate has not completely reacted. The absence of
peak at 2270 cm–1 is an indicative of the absence of NCO
groups in the structure of Formulation 1 (NCO : OH
(20 : 80)). On the other hand, new peaks at 1512 and
3369 cm–1 corresponding to –NH vibration (–NH–C=O–)
and absorbance band around 1740 cm–1 characteristic of
the C=O group are present in the FTIR spectra.20 Accord-
ing to Narine et al,21 the band around 1740 cm–1 indicates
that the hydrogen bonded C=O group vibration region is
overlapped with the free C=O group vibration region. The
absence of the isocyanate peak and appearance of amine
and carbonyl peaks indicate a complete conversion of
monomers to urethane.22–24 Therefore, for further investi-
gation, only Formulation 1 was used. It is referred as PU
in the following paragraphs. The photograph of castor
oil-based PU film is shown in figure 3. Figure 2. FTIR spectra of castor oil-based polyurethane.

Figure 3. Photograph of castor oil-based polyurethane film.

Figure 1. FTIR spectra of castor oil and polyol.

Table 2. Values of molecular weight of castor
oil, polyol and polyurethane.
Table 1. Weight ratio of NCO : OH in different formulations.
Sample Molecular weight, Mw (g mol–1)
Formulation NCO : OH Physical observation
Castor oil 1023
1 20 : 80 Soft and flexible Polyol 2786
2 40 : 60 Rigid and brittle Polyurethane 11,942
 Castor oil-based PU as host in polymer electrolytes 1159

Table 3. Decomposition temperatures, Td and percentage weight losses of polyurethane

film.
Weight loss (%)
Total weight Residue after
Td1 258–330°C Td2 313–430°C Td3 410–560°C loss (%) 600°C (%)

4.7 47.7 34.8 87.2 12.8

Figure 4. Tangent delta and storage modulus as a function of Figure 5. Thermogravimetric and derivative thermogravimet-
temperature for polyurethane. ric curves of polyurethane.

Figure 4 depicts the plot of storage modulus, E and thermally stable from room temperature until the
tan δ vs. temperature of PU film. E is slightly decreased temperature started to decompose. The second step of
from –60 to –40°C, then decreases rapidly after –40°C thermal degradation, Td2, is observed from 313°C up to
until a rubbery plateau is observed in higher temperature. 400°C. The third step of thermal degradation, Td3, begins

tan δ reaches its maximum peak simultaneously. The plot

This change corresponds to glass–rubber transition and at 429 to 550°C. Td2 corresponds to the liberation of free

shows one tan δ peak, indicating homogeneous nature of

isocynate and Td3 is attributed to the decomposition of
soft segment of the PU.29,30 The TGA result suggests that

given by the peak maximum (α relaxation) of tan δ vs.

the film. The value of glass transition temperature, Tg, is the PU is stable from ambient temperature up to 259°C.
The morphology of cross-sectional area of the castor
temperature curve. The Tg value obtained for the PU film oil-based PU film is shown in figure 6. As seen in the
is –15.8°C. Tg values of PUs are depending on the proper- figure, the film is smooth and no phase separation is
ties of the synthesized polyols, therefore the values could observed. The smooth morphology of the film shows
vary from –50 to 80°C. Júnior et al reported the value of that the film is highly amorphous. This characteristic is
thermoplastic PU based on castor oil is –30°C whereas favourable for a host of polymer electrolytes as ion
Liu and co-workers27 obtained a Tg value of 22.3°C for conduction occurs in amorphous region.
castor oil-based PU. On the other hand, Yeganeh and In order to determine whether the synthesized PU can
Shamekhi28 obtained values of Tg between 47 and 61°C be used as host in polymer electrolytes, a doping salt, LiI
for the PUs synthesized from different compositions of has been added to the biopolymer. The plot of
castor oil and glycolysed poly(ethylene terphthalate) conductivity of PU polymer electrolytes with the addition

tine PU is 1.18 × 10–11 S cm–1 increased to 4.92 ×

(PET). of salt is illustrated in figure 7. The conductivity of pris-
Illustrated in figure 5 are thermogravimetric and deri-
vatives of thermogravimetric curves for PU. Three 10–8 S cm–1 with the addition of only 10 wt% LiI. The
decomposition stages are observed. Table 3 lists the conductivity increased by three orders of magnitudes

to 1.42 × 10–6 S cm–1 upon the addition of 30 wt% of LiI.

decomposition temperatures, Td, and the percentage weight compared to pristine PU and reached maximum value up
loss after decompositions. The first degradation stage,
Td1, is observed at 259°C which achieves a maximum Further addition of salt resulted in a decrease in conduc-
temperature, Tmax, at 271°C. The Td1 is corresponding to tivity. The increase in conductivity was contributed by
the degradation of urethane linkages. From the first the number of conducting species in the electrolyte
degradation stage, it can be concluded that the film is caused by dissociation of LiI ions. This occurred due to
1160 S Ibrahim et al

conductivity value upon the addition of salt up to 1.42 ×

10–6 S cm–1 with the addition of 30 wt% of LiI. These
results indicated that the castor oil-based PU possessed
favourable properties for the application as host in poly-
mer electrolytes.

Acknowledgements

We are grateful to the University of Malaya for financial

support under Postgraduate Research Fund, PPP Grant
no. PG073/2012B. A highly gratitude goes to the Minis-
try of Education, Malaysia for the scholarship under the
Graduate Scheme Program MyBrain15 given to
Salmiah Ibrahim.

Figure 6. SEM image of cross-section of castor oil-based

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