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Synthesis of Waste Cooking Oil-Based Polyol Using Sugarcane Bagasse

Activated Carbon and Transesterification Reaction for Rigid Polyurethane
Foam

Article  in  Materials Science Forum · March 2016

DOI: 10.4028/www.scientific.net/MSF.846.690

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Materials Science Forum Submitted: 2015-01-11
ISSN: 1662-9752, Vol. 846, pp 690-696 Revised: 2015-09-25
doi:10.4028/www.scientific.net/MSF.846.690 Accepted: 2015-09-26
© 2016 Trans Tech Publications, Switzerland Online: 2016-03-04

Synthesis of Waste Cooking Oil-Based Polyol Using Sugarcane

Bagasse Activated Carbon and Transesterification Reaction for Rigid
Polyurethane Foam
Syuhada Mohd Tahir1, a*, Wan Norfirdaus Wan Salleh1, b,
Nur Syahamatun Nor Hadid1, c, Nor Fatihah Enderus1, d
and Nurul Aina Ismail1, e
1
Faculty of Applied Sciences, Universiti Teknologi MARA Pahang,
26400 Bandar Tun Razak Jengka, Pahang, Malaysia
syuhadamohdtahir@pahang.uitm.edu.my, wanfirdaus89@yahoo.com, sya_hadid@yahoo.com,
te_ndrus@yahoo.com, nurulaina@pahang.uitm.edu.my

Keywords: Polyol, Polyurethane foam, Transesterification reaction, Waste cooking oil

Abstract. This study was carried out to determine the potential of waste cooking oil (WCO) in
preparation of rigid polyurethane (PU) foam. The raw WCO was first filtered and adsorbed by using
sugarcane bagasse activated carbon in order to purify the oil. Next, the adsorbed WCO was used to
synthesize polyol via transesterification reaction. The WCO-based polyol was then combined with
other chemicals at various ratios to form PU rigid foam. The adsorbed WCO showed the decrease in
both free fatty acid percentage and viscosity, from 4.3 % to 0.77 % and from 106 mPa.s to 72.5
mPa.s, respectively. No alteration of functional group observed after adsorption as proven by FTIR
spectroscopy. The FTIR spectrum of WCO-based polyol showed the formation of OH absorption
peak and supported by the increase in hydroxyl value from 0 to 148.79 mgKOH/g after reaction.
The formation of urethane linkages (NHCO) backbone in PU foam was confirmed using FTIR. The
properties of PU foam are highly dependent on the chemical composition. The density and
compressive strength of 60:54:90:40 of glycerol:water:polyol:amine polyurethane foam are 277.7
kg/m3 and 0.10 MPa, respectively. This study showed that WCO exhibit promising potential as raw
material for PU formation.

Introduction
Today polyurethane (PU) has become the most important polymeric material due to its
mechanical and chemical properties. There are several types of PU; rigid foam, paint and flexible,
depends on the type of reactants and process used [1]. The most used PU are in form of rigid and
foam [2]. The applications of PU include industrial product such as footwear, construction,
automobile, medical devices and more.
PU is a polymer formed from exothermic reaction of isocyanate with polyol [3]. Generally, most
PU is synthesized by using petroleum-based polyol. Over the past decades, the price of petroleum
increase drastically and the source is depleting. This problem makes petroleum-based polyol is not
practical anymore [1]. Thus, attention is being shifted to preparation and application of bio-based
polyol that are synthesized using vegetable oil. Vegetable oil is suitable as raw material due to its
universal availability, lower price than petroleum and inherent biodegradability. Several types of
vegetable oil have been used to produce polyol such as soy bean oil, linseed oil, sunflower oil and
palm oil [4]. However, the use of vegetable oil faced challenges due to competition in food supply
consumptions and high production cost.
The latest approach is to synthesize polyol by using waste cooking oil (WCO), a highly
abundance, under utilized raw material. The similarities in organic structure of WCO to vegetables
oil make it suitable as starting material, hence can be derivatized into polyol using the same route
used to produce vegetable oil-based polyol [5]. The main problems with WCO are the oil
contamination from food residue and low number of hydroxyl value.

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 Materials Science Forum Vol. 846 691

Several reactions had been used in previous studies in order to produce WCO-based polyol such
as epoxidation [6], hydroxylation [5,7,8] and ozonolysis [9]. However, most of these existing
methods produced low number of hydroxyl and require long reaction time. In this study,
transesterification reaction had been chosen to derivatize WCO into polyol because of the low
reaction temperature and short reaction time as well as high hydroxyl number in the polyol obtained
[10]. The WCO was first refined using filtration and adsorption using sugarcane bagasse (SCB)
activated carbon.

Methodology
To prepare the sugarcane bagasse (SCB) activated carbon, SCB was first washed, dried, cut and
heated in oven at 80 oC for 24 hour to dry it out. Next, SCB was ground to 1.0 mm mesh and sieved
to 150 micron. 10 g of ground SCB was weighed and activated with 500 ml 1M KOH solution and
put in oven for 6 hour at 150 oC. The SCB was collected by filtration. Next, the carbonization was
carried out furnace at 800 oC for 1 hour to drive out all the volatile organic compounds and leave
behind carbon and minerals (ash). After being cooled down to room temperature, the SCB was
rinsed with 0.1 M HCl and deionized water until the pH 7 achieved. The product was then dried
overnight in an oven at 105 ˚C to remove moisture [11,12,13].
The WCO sample collected was filtered using filter paper to remove any foreign materials. 100
mL of filtered WCO was heated to temperature 95-125 oC. Then, 0.5g of SCB adsorbent was added
into the WCO and stirred at 500 RPM and 110 ˚C for 24 hour and finally filtered. The WCO before
and after adsorption was analyzed using FTIR spectroscopy, hydroxyl value (HV) (TP-AATM-109-
01) and free fatty acids percentage (%FFA) (ASTM D5555–95) [11].
The first stage of synthesizing WCO-based polyol is preparation of polyhydric solution. The
polyhydric solution was prepared by mixing diethanolamine (DEA), monoethylene glycol (MEG)
and potassium acetate (PA) at ratio of 90:7:3. The solution then stirred until dissolved and left
overnight. WCO-based polyol was prepared using transesterification by mixing WCO with
polyhydric solution at ratio of 80:20 WCO-to-polyhydric. The mixture was heated at 185 oC to 195
o
C for 20 minutes [10]. The WCO-based polyol obtained was analyzed using FTIR spectroscopy,
HV, %FFA, acid value and viscosity.
For the preparation of WCO-based polyurethane was conducted by first mixing WCO-based
polyol, glycerol, water and amine at different three ratio compositions in a round bottom flask under
elevated temperature. Then, the resin was mixed with 2,4-diphenylmethane diisocyanate (MDI) at
1:1 ratio [14]. During the polymerization reaction, the reaction times (cream time, gel time, tack-
free time, rise time) was taken to study the effect of amine catalyst and glycerol. The structure
WCO-based polyurethane produced was confirmed using FTIR spectroscopy and the apparent
density and compression strength was analyzed.

Result And Discussion

Waste Cooking Oil. FTIR analysis of WCO before and after adsorption as shown in Fig.1 proved
that the adsorption process did not alter the functional groups presence [5]. The lightening in colour
will increase the commercialisability of the final product and the reduced viscosity will increase the
processability of polyol produced. The properties of WCO before and after adsorption were
compiled in Table 1.

Table 1 Properties of WCO before and after adsorption

Properties Raw WCO Adsorbed WCO
% FFA 4.4 % 0.77 %
Acid Value (AV) 8.756 mgKOH/g 1.53 mgKOH/g
Viscosity 106 mPa.s 72.5 mPa.s
Colour Dark brown Yellow
692 Main Tendencies in Applied Materials Science

Waste Cooking Oil-Based Polyol. FTIR spectroscopy analysis was carried out to confirm the
formation of polyol. Fig. 1 shows the FTIR spectra of adsorbed WCO and WCO-based polyol. The
presence of absorption peaks of O-H (3318.12 cm-1) and C=O (1743.71 cm-1) proved that the
transesterification reaction was successfully carried out and WCO-based polyol was obtained [14].
The result supported by the significant increase in OH value as shown in Table 2.

Table 2 Properties of adsorbed WCO and WCO-based polyol

Properties Adsorbed WCO WCO-based polyol
OH value 0 mgKOH/g 148.79 mgKOH/g
Viscosity 72.5 mPa.s 162.5 mPa.s
Colour Yellow Dark brownish yellow
pH - 10.47 pH

O-H stretching C=O stretching

Raw WCO

Adsorbed WCO

%T

WCO-based Polyol

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
cm-1

Fig. 1 FTIR spectra of raw, adsorbed WCO and WCO-based polyol

Waste Cooking Oil-Based Polyurethane. Rigid polyurethane foam was prepared by using
different ratio compositions of glycerol:water:WCO-based polyol:amine (Table 3 and Table 4) and
the quantity of MDI used is at 1:1 ratio to the resin mixture. The effect of the catalyst and glycerol
on reaction times (cream time, gel time, tack-free time, rise time) is shown in Fig. 2 and Fig. 3,
respectively. Based on the result obtained, the reaction times are shorter when the amount of
catalyst increased. This is due to the faster formation of complex intermediate when more amine
catalyst added that can donate electrons from nitrogen to the carbonyl carbon of the isocyanate
group [2]. The main function of glycerol in production of polyurethane is as the crosslinking agent
or plasticizer, in which it holds the monomer chains together. Based on the result obtained, it is
observed that the less glycerol used, the reaction became faster and the foams obtained are softer
and more flexible.
 Materials Science Forum Vol. 846 693

Table 3 Chemical composition for preparation of rigid PU foam

Chemicals Composition
1 2 3
Glycerol 60 60 60
Water 54 54 54
WCO-based polyol 90 90 90
Diethanolamine 20 30 40
MDI 21 g 22 g 23 g

600

500

400
Time (s)

Gel time
300
Cream time
200 Rise time
100 Tack-Free time

0
1 2 3
Composition

Fig. 2 Effect of catalyst on reaction times

Table 4 Chemical composition for preparation rigid PU foam

Chemical Composition
1 2 3
Glycerol 60 50 40
Water 54 54 54
WCO-based polyol 90 90 90
Diethanolamine 40 40 40
MDI 23 g 22 g 21 g
694 Main Tendencies in Applied Materials Science

300

250

200
Time (s)

Gel time
150
Cream time
100 Rise time
Tack-Free time
50

0
1 2 3
Composition

Fig. 3 Effect of glycerol on reaction times

FTIR spectroscopy analysis was carried out to determine the presence of functional group in the
WCO-based polyurethane. Fig. 4 shows the FTIR spectrum of WCO-based polyurethane. The
successful formation of polyurethane can be proven by the presence of amide (NH) at 3720.90 cm-1,
urethane carbonyl (C=O) at 1741.52 cm-1, C-N-H at 1512.36 cm-1, C-O-C at 1231.16 cm-1 and the
absence of hydroxyl (OH) absorption peak at around 3000 cm-1 [3]. Fig. 5 shows the reaction of
polyol with isocyanate to produced PU [15].

WCO-based Polyol

%T

WCO-based PU

4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 650.0
cm-1

Fig. 4 FTIR spectrum of WCO-based polyurethane

 Materials Science Forum Vol. 846 695

O H2 H2 O O
C C OH H2
+ C N N C
R C N H2 C
C C OH
H2

WCO-based polyol Diisocyanate

O O
H2 H2 H2 H2 H H2 H
O C C N C C O C N C N C

C O

WCO-based Polyurethane
R

Fig. 5 Reaction between WCO-based polyol with isocyanate

Compression and density test was analyzed to determine the strength of the polyurethane
produced with ratio of 60:54:90:40 of glycerol:water:polyol:amine. Compression test was
conducted at crosshead speed 50.0 mm/min. The compressive strength was carried out by imposing
the load in the foam rise direction because the direction has three times the strength [14]. From the
result obtained, the maximum load for WCO-based PU is 0.25 kN and the maximum stress is 0.10
MPa. When force is applied to the polymer, the cellular structure is compacted and stress will be
spread throughout the polymer uniformly. However, due to presence of foreign constituent in the
polymer, the force fails to spread uniformly leading to decrease in compressive strength of WCO-
based PU produced [14].
Density test was carried out to determine the specific weight of PU. The PU was cut into 1 cm ×
1 cm × 1 cm dimension. The density of WCO-based PU is 277.7 kg/m3. The high density indicates
the high degree of crosslinking in the PU structure [3]. The PU produced with density 30 kg/m3 to
200 kg/ m3 will withstand temperature down to -196 oC [16].

Conclusion
The adsorption process of WCO using prepared SCB activated carbon did not alter the organic
structure of WCO. The WCO-based polyol was successfully synthesized using transesterification
reaction with hydroxyl value of 148.79 mgKOH/g, which is comparable to the commercially
available polyol. The process is attractive and economical due to the utilization of WCO, the cheap
and readily available raw material. The WCO-based polyurethane was successfully synthesized
with adequate physical properties.

Acknowledgements
The authors gratefully acknowledge the support from Universiti Teknologi Mara Pahang in terms
of financial and facilities provided.
 696 Main Tendencies in Applied Materials Science

References
[1] Zhang, L., Jeon, K.H., Malsam, J., Herrinton, R. and Macosko, W.C., (2007). Substituting
soybean oil-based polyol into polyurethane flexible foam. Polymer, 48, 6656-6667.
[2] Wood, G., (1990). The ICI Polyurethane Book. Netherland.
[3] Badri, K.H., (2012). Biobased polyurethane from palm kernel oil-based polyol.
Polyurethane, Dr. Fahmina Zafar (Ed.), ISBN. 978-953-51-0726-2, InTech, DOI: 10.5772/47966.
Available from: http://www.intechopen.com/book/polyurethane/biobased-polyurethane-from-palm-
kernel-oil-based-polyol.
[4] Miao, S., Wang, P., Su, Z. and Zhang, S., (2013). Vegetable oil based polymer as future
polymeric biomaterial. Acta Biomaterialia.
[5] Ferraro, L.G., Alvarenga, F.B.D.S., Gelfuso, M.V. and Thomazini, D., (2014). Investigation
to obtain polyols from residual frying oils. Material Science Forum, 775-776, 351-356.
[6] Maznee, T.N., Hazimah, T.I., Ooi, A.H., and Salmiah, T.L., (2007). A polyol from used
frying oil (P-UFO). MPOB information ISSN 1511-7871.
[7] Setia, F., & Dwi, D. (2012). The Optimization of Diphenyl Methane Diisocynate
Polymerization Process with the Used Frying Oil Polyalcohol to Foam Polyurethane Using RSM,
1–7.
[8] Sipaut, C.S. @ Nasri, M., Sundang, M., Saalah, S., Hoon, T. C., Ibrahim, M.N.M., Rahman,
I.A. and Abdullah, A.A., (2012). Synthesis and characterization of polyols from refined cooking oil
for polyurethane foam formation. Cellular Polymers, 31 (1), 19-38.
[9] Hwa, L. and Aloysius Yuli, W., (2013). Synthesis of polyol from edible oil waste with
ozonolysis technology.
[10] Badri, K.H., Ahmad, S.H and Zakaria, S., (2000). Development of zero ODP rigid
polyurethane foam from RBD palm kernel oil. Journal of Material Science Letters, 19, 1355-1356.
[11] Wanahari, R. and Nordin, M.F.M., (2012). The recovery of used palm cooking oil using
bagasse as adsorbent. American J. of Engineering and Applied Sciences, 59 – 62.
[12] Jin, J., Tanaka, S., Egashira, Y. and Nishiyama, N., (2010). KOH activation of ordered
mesoporous carbons prepared by a soft-templating method and their enhanced electrochemical
properties. Carbon, 48, 1985-1989.
[13] Mitome, T., Uchida, Y., Egashira, Y., Hayashi, K., Nishiura, A. and Nishiyama, N., (2013).
Adsorption of indole on KOH-activated mesoporous carbon. Colloids and Surfaces A:
Physiochemical and Engineering Aspects, 424, 89-95.
[14] Badri, K.H., Dawi, L.I.M. and Aziz, A.A.N., (2013). Rigid polyurethane foam from
glycolysed polyethylene terephthalate dissolved in palm-based polyol. Sains Malaysiana,42(4), 449
– 457.
[15] Fridrihsone, A., Stima, U., Lazdina, B., Misane, M. and Vilsone, D., (2013).
Characterization of polyurethane network structure and properties based on rapeseed oil derived
polyol. European Polymer Journal, 49(6), 1204 – 1214.
[16] Chuayjuljit, S., Sangpakdee, T. and Saravari, O., (2007). Processing and Properties of Palm
Oil-based Rigid Polyurethane Foam. J. Met. Mat. Mi.17, 17–23.

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