ISBN 978-1-84626-xxx-x

Proceedings of 2009 International Conference on Environmental Science and Technology

Bangkok, Thailand, 23-25 April, 2010, pp. xxx-xxx

Effect of H3PO4 to Et3PO4 Ratio on Synthesis of Cellulose

Phosphate from Oil Palm Biomass
Rohaizu R.,Wanrosli W. D. +, Arniza, G.
Bioresource, Paper and Coatings Division

School of Industrial Technology, Universiti Sains Malaysia, 11800 Pulau Pinang, Malaysia

Abstract. This study investigated the effect of orthophosphoric acid (H3PO4) to triethylphosphate (Et3PO4) ratio in
the synthesis of cellulose phosphate (CP) from oil palm empty fruit bunch microcrystalline cellulose (OPEFB-MCC).
Cellulose phosphate is prepared via a phosphorylation process. Here, the H3PO4/P2O5/Et3PO4/hexanol sequence was
used. It is the interest of this study to ascertain the reaction of these chemicals in terms of their value on
phosphorylation as a potential process to increase the phosphorus content of CP. It is believed that during this reaction,
the esterification of the free hydroxyl groups of the cellulose occurred. The H3PO4/Et3PO4 ratios applied were 0.16,
1.00, and 1.84. The effect of the H3PO4/Et3PO4 ratio on phosphorus content, resulting yield, water swelling and
structure molecule of CP are discussed. This study is a part of an attempt to produce CP from oil palm lignocellulosic
wastes which will be reported in due course.

Keywords: cellulose phosphate; oil palm empty fruit bunch microcrystalline cellulose; H 3PO4/P2O5/Et3PO4/hexanol
sequence; H3PO4/Et3PO4 ratio; phosphorus content

1. Introduction

Due to the sustainable and renewable production of fibres from non-wood materials, these viable sources are
now viewed as feasible alternatives to conventional fibre production. To be more competitive, the qualities of
these fibres have to be fixed in view of the fact that their properties significantly influence the derived end
products. In this matter, oil palm fibre had been found as an appropriate material from which high quality
cellulose content [1] can be derived. Oil palm is a rich source of fibre yet to be extensively commercialised. At
present there is an abundance of oil palm biomass residue in oil palm mills still perceived as waste by-products.
Preferably a solution that utilises these plentiful by-products to replace non-renewable sources should be
realised. This will be a positive impact towards a more sustainable development.

Thus measures must be undertaken to ensure that procedures carried out should positively contribute and be
beneficial to conservation efforts and sustainable development. To produce biopolymers in a sustainable manner,
the operation undertaken must have a significant effect to the environment and at the same time towards
development. Recently there have been numerous innovations to increase profits from oil palm biomass fibre by
producing higher value products [2, 3]. In this study, cellulose which is documented as a major constituent in
fibre and oil palm biomass was used as a trait [4, 5]. But the limited usage of pure cellulose in industries has led
to a synthesis of cellulose derivatives. The idea of this study is to emphasise on cellulose derivatives application
and development. The unique characteristics of cellulose derivatives therefore accord it more advantages for
application purposes [6, 7, 8].

Cellulose phosphate (CP) is a cellulose derivative. The incorporation of cellulose into phosphate alters the
significance of cellulose application by endowing the material advantageous phosphate characteristics. Specific
effects may thus be obtained without changing the general characteristics of the cellulose. The special
characteristics that cellulose inherits by this incorporation are the reduction in the flammability of the material
and an increase in ion exchange capability [7, 8, 9]. Flame resistance provides advantage to CP especially for
utilisation in the manufacturing of textile and paper. This property has an adequate capability to execute thermal
insulation of materials resulting in increased material protection upon exposure to sufficient heat [7, 8, 9]. CP is
also identified as a cation-exchange material. The ion-exchange capability of phosphate advances the application
of CP as an absorbent material. With these properties, CP can function as a membrane that binds the traced
metal ions for measurement [10], which also have to be separated from certain treated materials [11].
___________________
 Corresponding author. Tel.: + 604-653-2354; fax: +604-657-3678.
E-mail address: wanrosli@usm.my

CP is classified as a value added biomaterial. The development progress of this material in medical science
is outstanding and tremendous [5, 6, 12]. With calcium-binding ability, CP has been used for the treatment of
kidney stones where other medical and surgical procedures are inappropriate. The ability of CP to induce the
formation of calcium phosphate (mineralisation process) allows it to be used as an implant material in
orthopaedic applications. Calcium phosphate is endowed with properties resembling human bone; therefore it
has been proven to be valuable in artificial tissue engineering. The improvement on this implant material so as
CP can mineralise at a higher extent than other materials, can only be done via phosphorylation [13].

In the previous study, it has been shown that CP can successfully be synthesised from oil palm empty fruit
bunch (OPEFB). However for the intent of application purposes, a higher degree of OPEFB-CP substitution
should be achieved. The objective of this study is to investigate the effect of orthophosphoric acid (H3PO4) to
triethylphosphate (Et3PO4) ratio in CP synthesis from OPEFB. For this purpose, OPEFB first has to be converted
to pure cellulose pulp by a pulping process to liberate α-cellulose. Then a bleaching process has to be performed
by using total chlorine free (TCF) bleaching sequences [14, 15] to eliminate the remaining lignin that gives a
brownish colour to the pulp. Then the cellulose pulp will be converted via a hydrolysis process to produce
microcrystalline cellulose (MCC). MCC is a proper form of cellulose that can be used as a feed-source for the
phosphorylation process in order produce CP.

2. Materials and Methods

2.1 Preparation of Microcrystalline Cellulose (MCC)

OPEFB cellulose was prepared using the environmentally benign process as described by Wan Rosli et al.
(2003) and Leh et al. (2008) [14, 15]. The procedure involved water prehydrolysis of the OPEFB, which was
then followed by soda pulping. The unbleached pulp was afterwards bleached using a TCF sequence of oxygen
(O), ozone (Z) and peroxide (P) to a Kappa no. of 1.4. For the preparation of MCC, the bleached pulp was
subsequently hydrolysed with 2.5M HCl whilst keeping the solid liquor ratio at 1:20 and refluxing at 105 oC±2
o
C for 15 minutes. After hydrolysis, the material was thoroughly washed with distilled water before air drying.
Powdered OPEFB-MCC was then obtained by grinding the sample in a ball mill.

2.2 Synthesis of cellulose phosphate

Phosphorylation of MCC was carried out using the method described by Granja et al. (2001) [16]. 4.0 g of
MCC powder was swollen consecutively in distilled water, ethanol and hexanol for 24 hours to activate the
cellulose surface. Phosphorylation reaction was carried out in the four-neck round bottom flask equipped with a
nitrogen inlet, a condenser, a thermometer, and a mechanical stirrer. MCC was then dispersed in 29 mL 1-
hexanol. Then a solution of 50 g phosphorus pentaoxide (P2O5) in various ratios of H3PO4 to Et3PO4 was added
portion wise to the suspension. The reaction was allowed to proceed under constant stirring and nitrogen
atmosphere at 50oC for 72 h. After chemical treatment, modified MCC were rinsed with hexanol, ethanol, and
then dialysed against distilled water to remove excessive reagents. The resulting yield was then dried at room
temperature.

2.3 Characterisation methods

Quantification of phosphorous requires its conversion into dissolved orthophosphate. This is then followed
by colorimetric determination of the dissolved orthophosphate. A sulfuric acid-nitric acid mixture was used as
oxidants for the Kjeldahl digestion procedure to oxidise organic matter and thereby release phosphorus as
orthophosphate. Phosphorus concentration was determined spectrometrically at 880 nm by the ascorbic acid
colorimetric method. For water sorption measurement, 10 mg of samples was allowed to hydrate in excess
distilled water at room temperature in centrifuge polyethylene tubes. After centrifugation at 4000 rpm for 10 min
following removal of the excess water, the samples were then periodically weighed several times. Water sorption
as expressed by % swelling was determined via the difference of weight before and after swelling. DSC
thermograms were obtained using a Perkin Elmer DSC6 with ca. 3 mg of material in sealed aluminium pans and
heated from ambient temperature to 300oC at a heating rate of 10oC/min under a flowing nitrogen atmosphere.
FTIR was performed on a Nicolet Avatar 360 using the KBr method.

3. Results and Discussion

This study illustrates how chemical ratio between H3PO4 and Et3PO4 influence phosphorus content and
properties of CP. Hence the results obtained are present as described. The effect of H 3PO4/Et3PO4 ratio on
phosphorylation process concerning phosphorus content, resulting yield and water swelling of the CP are shown
in Table 1.

Table 1: Effect of H3PO4/Et3PO4 ratio on of phosphorus content, yield and water swelling of CP

H3PO4 / Et3PO4 P (%) Yield (%) Water swell (%)

0.16 10.34 72.17 172

1 12.80 62.44 468

1.84 20.66 45.56 1142

Table 1 shows that manipulating the H3PO4/Et3PO4 ratio significantly influenced the resulted phosphorus
content and yield percentage of CP. As the H3PO4 concentration increased, the phosphorus content of the
samples also increased but it was vice versa for the percentage of yield. We suggest that increasing the
concentration of the H3PO4 will enhance the substitution reactivity of the hydroxyl groups to the phosphate
group in anhydroglucose units of cellulose molecule. But it seemed that the phosphorylation process degraded
more MCC, hence less CP was obtained. This indicates that there was probably a competition between
phosphorylation and hydrolysis of the resulted product from the reaction [5, 13]. The previous study showed that
the phosphorylation process responds to the duration and temperature of the reaction. While in this study, we
proved that the phosphorylation process also responds to the H3PO4/Et3PO4 ratio.

Macroscopically, the water swelling ability of CP was significantly higher compared to 3% of

microcrystalline cellulose (MCC) (3%). Our observation showed that CP swells considerably in water. Higher
DS value of CP resulted in higher swelling ability. This was obtained from the incorporation of phosphate group
with the MCC which formed an ion-exchange material and the crystallinity of CP decreased. The solubility of
cellulose was relatively low in a lot of solvent; this is due to the hydrogen bond between cellulose molecules and
the crystalline region of molecular structure. After the phosphorylation process, the solubility of the resulted
cellulose increased. This is because of the substitution between the hydroxyl group and the phosphate group in
cellulose molecule resulting from the fractured hydrogen bond. The presence of a larger group of phosphate than
hydroxyl group in the cellulose molecule distracts the arrangement of crystalline pattern in the molecule
structure. The phosphate group inside the cellulose granules would be able to create a repulsive force that might
enhance inter- and intramolecular space and allow more water molecules to be absorbed. The phosphorylation
process also consequently fabricated the amorphous region in the molecule structure and increased the swelling
ability of modified cellulose in water.

To analyse the crystallinity of CP, thermal properties of MCC and CPs were examined using differential
scanning calorimetry (DSC). According to the results, what we observed could have been the phenomena related
to the morphological changes between MCC and CPs structure. We found that part of the crystalline region in
MCC molecule was transformed to the amorphous region which can be observed as T g. When the phosphate
group was introduced to the MCC as a main chain, Tg can be observed at the CPs thermograms around 162oC.
This could not be obtained at the MCC thermogram (Fig. 1). Tg value for each samples showed no large
difference among them even though the H3PO4/Et3PO4 ratio and the DS value of each samples were different.
From this result we can conclude that the T g value for each samples was not affected by the H3PO4/Et3PO4 ratio
and the value of DS.

Fig. 1: DSC thermograms of (a) MCC and CP with H3PO4/Et3PO4 ratio (b) 0.16 (c) 1.00 (d) 1.84
 Fig. 2: FTIR spectra of (a) MCC and CP with H3PO4/Et3PO4 ratio (b) 0.16 (c) 1.00 (d) 1.84

Fig. 2 shows the FTIR spectra between MCC and its phosphorylated form. After phosphorylation, a few
peaks that were earlier present in the MCC spectrum vanished and several new bands appeared, attributed to the
phosphate group. New absorption peaks which characterised CP were indicated by the vibration bands of PO4 at
1027 cm-1, P=O at 1377 cm-1, and P-H at 2360 cm-1 (Fig. 2 b,c,d) [17]. Although the reaction was carried out
under different H3PO4/Et3PO4 ratio it seemed that each phosphorylated samples showed similar changes in
absorption peaks. The resulted spectrums suggest that the molecule structures of derived CP products are
probably comparable.

4. Conclusion

From the results obtained, we recognise that the synthesis of cellulose phosphate from OPEFB MCC had
been significantly influenced by the H3PO4/Et3PO4 ratio. Experiment data demonstrated that phosphorus content,
resulting yield and water swelling ability of CP change regularly with the increasing of H 3PO4/Et3PO4 ratio. As
the phosphate group was incorporated into the MCC chain, we observed the formation of an amorphous region
and the water swelling ability of the modified MCC also increased. The FTIR result for CPs can confirm the
existence of a phosphate group. The phosphate group which had also been used to point out the molecular
structure of resulted CP was not affected by the H3PO4/Et3PO4 ratio. Perhaps, the most significant aspect of this
work is the possibility to increase the profits from the previously unused oil palm biomass residue. The
synthesised product can be utilised to generate more advanced materials with huge potential in various
biomaterial applications.
5. Acknowledgement
The authors express their gratitude to Universiti Sains Malaysia for the research university grant scheme
1001/PTEKIND/8140151.

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