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Preparation and Characterization of Cellulose Acetate from Pineapple (Ananas

comosus) Leaves

Article  in  Key Engineering Materials · July 2018

DOI: 10.4028/www.scientific.net/KEM.772.8

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Key Engineering Materials Submitted: 2018-04-12
ISSN: 1662-9795, Vol. 772, pp 8-12 Accepted: 2018-04-25
doi:10.4028/www.scientific.net/KEM.772.8 Online: 2018-07-04
© 2018 Trans Tech Publications, Switzerland

Preparation and Characterization of Cellulose Acetate from Pineapple

(Ananas comosus) Leaves
Marycris P. Egot1,2,3,a and Arnold C. Alguno1,2,b
1
Material Science Laboratory, Department of Physics, MSU-Iligan Institute of Technology, Iligan
City, Philippines 9200
2
Premier Research Institute of Science and Mathematics, MSU-Iligan Institute of Technology, Iligan
City, Philippines 9200
3
Physics Department, University of Science and Technology of Southern Philippines, Cagayan de
Oro City, Philippines 9000
a
marycris86@gmail.com, barnold.alguno@g.msuiit.edu.ph

Keywords: pineapple leaves, cellulose, cellulose acetate, alkali treatment, bleaching treatment

Abstract. Pineapple leaves was utilized for the fabrication of cellulose acetate. It underwent a series
of process that includes alkaline treatment using sodium hydroxide aqueous solution, bleaching
treatment using acetate buffer and aqueous sodium chlorite, and acetylation using acetic anhydride.
The preparation of cellulose acetate was done in different acetylation times (8, 16, 24 and 32 hours).
The cellulose acetate samples were then characterized using fourier transform infrared spectroscopy
(FTIR) to elucidate the vibrational move, thermal gravimetric analysis (TGA) and differential
thermal analysis (DTA) to investigate the thermal property of the material and scanning electron
microscopy (SEM) to examine the surface morphology. FTIR result showed significant decrease in
absorption intensity of the O-H stretch after the acetylation which indicates the substitution of
hydroxyl group by acetyl group. On the other hand, the emergence of C=O stretch of the ester group
and C-O stretch of acetyl group can be observed which indicates the formation of cellulose acetate.
TGA and DTA also shows enhanced thermal stability of cellulose acetate prepared in 16 hrs
acetylation period. Increasing the reaction time to 24 hrs and 32 hrs resulted to significant decrease in
thermal stability. SEM images revealed the deterioration on the physical structure of cellulose after
24 hrs acetylation.

Introduction
Cellulose acetate is one of the important biopolymer used in the production of fabrics, films,
cigarette filters, separation technology, molded goods and plastics and medical applications [1]. It has
been considered for many applications because of its excellent physical, chemical and biological
properties. Cellulose acetate is the byproduct of cellulose modification. Cellulose which is composed
β-1,4-anhydro-D-glucopyranose units has high reactive hydroxyl groups that can be substituted by
acetyl group to form cellulose acetate [2].
Cellulose is the most abundant natural polymer which can be found in plants, bacteria, marine
animals, algae, fungi, and minerals [3]. Production of cellulose from some of these sources presents
some challenges and limitations. For the case of bacteria, production of cellulose offers high
production cost and large-scale production for commercial use is impossible. The use of marine
animals and algae also presents risk of endangering water animals. Wood, which is the largest
producer of cellulose, requires high energy consumption and demands high levels of pressure.
Among other cellulose sources, plant is being considered due to its abundance, availability,
renewability and low cost.
Recently, utilization of agricultural waste such rice straw, sugarcane bagasse, sawdust and
pineapple leaves has been considered to address the environmental, esthetic and health problems.
Wide variety of plants has already been studied for the production of cellulose acetate. One example
is sugarcane bagasse has been successfully synthesized to cellulose acetate and was applied for

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 Key Engineering Materials Vol. 772 9

membrane preparation [4]. Rice husk was also successfully utilized for cellulose acetate production
with 66% yield in the presence of acetic anhydride and iodine as a catalyst [5]. Empty fruit bunches of
oil palm [6], acacia mangium pulp [7], cotton [8] and more plants was also used to synthesize
cellulose acetate. To the best of our knowledge, pineapple leaves remained less explored for cellulose
acetate production. Philippines is one of the largest producer of pineapple (Ananas comosus) in the
world and an estimated of 699 thousand metric ton [9] of pineapple was produced recently and
together with this large pineapple production, tons of pineapple leaves waste was also generated each
year. It has been reported that pineapple leaves contains 70-82% cellulose [10] and has been utilized
for cellulose nanocrystals production via alkali-treatment, bleaching treatment and acid hydrolysis
[11]. In this study, preparation of cellulose acetate from pineapple leaves was investigated.
Purification of the leaves by alkali and bleaching treatment were done to extract the cellulose and
acetylation using acetic acid was done to produce cellulose acetate.

Methodology
Materials and equipment. Pineapple (Ananas comosus) leaves was gathered from Del Monte
pineapple plantation located in Bukidnon, Philippines. Sodium hydroxide (NaOH) pellets Merck
brand, sulfuric acid (H2SO4) and glacial acetic acid (CH3COOH) was purchased from Elmar
Marketing (Iligan City, Philippines). Sodium chlorite (NaClO2) in powder form was purchased from
Sigma-Aldrich. Acetic anhydride (CH3CO)2O was obtained from the Chemistry Lab of USTP.
The resulting cellulose acetate samples were characterized using scanning electron microscopy
(JEOL JSM-6510LA) for the surface morphology. Fourier transform infrared spectroscopy (Perkin
Elmer) was used to determine the functional group of the samples. Thermogravimetric analysis/
differential thermal analysis (Shimadzu 60H) for the thermal stability of the samples.
Research methods. The pineapple leaves (PL) was washed several times with water then chopped
into small pieces using a blender and sun dried for several days. The dried PL leaves was grounded in
a mill and was treated with a 2% (w/w) sodium hydroxide (NaOH) aqueous solution for 4 h at 100oC
under constant mechanical stirring. It is then washed several times with distilled water until the alkali
was completely removed and air-dried for several days. After the treatment, the material was
bleached with a solution made up of equal parts (v:v) of acetate buffer (27 g NaOH and 75 ml glacial
acetic acid, diluted to 1 L of distilled water) and aqueous sodium chlorite (1.7 wt% NaClO2 in water).
This bleaching treatment was performed at 80oC for 4 h. The bleached material was washed
repeatedly with distilled water and then air-dried for several days.
Preparation of cellulose acetate includes dissolving 1 g of dried cellulose in a solution composed
of 40 mL of glacial acetic acid, 10 mL of acetic anhydride and six drops of sulfuric acid into a flask.
The sulfuric acid served as a catalyst for the reaction. The reaction was then allowed to take place at
different acetylation time (8 hrs, 16 hrs, 24 hrs and 32 hrs) in room temperature. The mixture was
gently poured in 400 mL of distilled water to stop the reaction and filtered. The produced cellulose
acetate was then air-dried.

Results and Discussion

The FTIR spectra of the treated pineapple leaves and cellulose acetate samples were shown in
Figure 1. The hydroxyl (OH) group can be found between 3500-3100 cm-1. High intensity of the
hydroxyl group of the treated pineapple leaves sample is associated to its high cellulose content after
the alkali and bleaching treatment. After the acetylation for 8 hours, significant decrease of the
intensity along hydroxyl group can be observed which indicates the substitution of hydroxyl group by
acetyl group. It has been reported that the degree of substitution and increase in yield of cellulose
acetate is influenced by proper delignification of the raw leaves material [5]. The formation of
cellulose acetate can also be monitored by the absorption band 1,724 cm-1 which corresponds to C=O
ester stretching and 1,222 cm-1 band assigned to C-O stretching of acetyl group. Cellulose samples
subjected to 16 hrs reaction time presents the lowest intensity bands on its OH group which may
10 Composite Materials Science and Technology

indicate the highest substitution have occurred during the period. After 24 hours, the hydroxyl group
starts to re-appear and increased C-O stretching band can be observed. Cellulose subjected to 32
hours acetylation shows higher number of OH and C-O group which may indicate the deterioration of
the overall composition of cellulose acetate sample. It has been reported that longer reaction time
degrades and hydrolysis the cellulose acetate [12, 13]. The acetic anhydride reacts through
nucleophilic attack with the hydroxyl groups in the cellulose. Rapid surface acetylation happens
initially and then cellulose was dissolved in the medium as the time progressed [14].

Fig. 1. FTIR spectra of PL cellulose and cellulose acetate samples in different acetylation times.
Figure 2 shows the thermal gravimetric curves of PL cellulose and cellulose acetate samples.
Thermal gravimetric curves showed three thermal events for the cellulose sample. The first curve
observed between 0 and 260oC was due to the desorption of water adsorbed in cellulose acetate and
evaporation of volatile compounds. The second curve between 260oC and 400oC was due to the
decomposition of cellulose acetate and lignin chains. And the last curve from 400oC to 600oC was a
total mass loss due by carbonization of the products. The onset degradation temperature of cellulose
can be observed at ~260oC and maximum decomposition at ~340oC. The onset and maximum
temperatures of the cellulose acetate samples prepared at 8 hrs and 16 hrs acetylation periods was
relatively higher which can be observed at ~300oC and ~400oC, respectively. The increase of thermal
degradation indicates enhanced thermal stability of the cellulose after acetylation. Moreover,
tremendous decrease in the thermal stability which takes place at temperature between 0 and 100oC of
cellulose acetate samples prepared at 24 hrs and 32 hrs acetylation period can be observed which may
indicate degraded structure of the cellulose acetate.

Fig. 2. TGA curves of PL cellulose and acetate samples in different acetylation times.
Figure 3 shows the differential thermal curves of the samples. The PL cellulose, 8 hrs and 16 hrs
samples shows two main exothermic reactions during degradation which is related to the random
dissociation of the glycosidic bonds in the cellulosic chains and the degradation of the cycloglucose
units. The shift of the two exothermic curves to higher temperatures can be observed in the 16 hrs CA
sample indicates that it is thermally more stable than the other samples. Moreover, an endothermic
 Key Engineering Materials Vol. 772 11

reaction can initially be observed in the 24 hrs and 32 hrs samples followed by an exothermic reaction
which corresponds to the early decomposition of the cellulose chains.

Fig. 3. DTA curves of PL cellulose and cellulose acetate samples.

(a) (b)
Fig. 4. Surface morphology of (a) PL cellulose and (b) cellulose acetate after 24 hours acetylation period.
Figure 4 shows the surface morphology of the cellulose sample and cellulose acetate prepared
after 24 hrs. Very well-oriented fiber textures are seen in the micrograph of pineapple leaves cellulose
before acetylation. The alkali and bleaching treatment resulted to high quality cellulose characterized
by clean fiber structure which is necessary for cellulose swellability and increase in the affinity of the
cellulose hydroxyls toward the acetylation. After 24 hrs acetylation, a cylindrical shaped micro-sized
fiber with perforated layer can be observed which indicates deterioration on the physical structure of
the cellulose acetate sample. This was primarily caused by dissolution of pineapple leaves cellulose
in acetic anhydride at longer time. The morphology of the resulting cellulose acetate from pineapple
leaves is similar to the observation made by Bahmid et.al. [6] who used empty fruit bunches from oil
palm.

Conclusion
Cellulose acetate was produced by purification of the pineapple leaves followed by acetylation
acetic anhydride and sulfuric acid as a catalyst. The acetylation was successfully done at different
reaction times. The effect of different reaction time on the chemical, thermal and morphology of the
cellulose from pineapple leaves was investigated using the Fourier transform infrared
spectroscopy(FTIR), thermal gravimetric analysis (TGA)/ differential thermal analysis (DTA) and
scanning electron microscopy (SEM), respectively. FTIR spectra shows increased reaction time up to
16 hours resulted to decrease in OH and formation of C=O ester groups and C-O groups which
indicates the development of cellulose acetate. TGA and DTA showed the enhanced thermo stability
of the cellulose acetate prepared in the 16 hrs reaction time compared to the other samples. Increasing
the reaction time to 24 hrs and 32 hrs shows re-appearance of OH group, decrease in the degradation
 12 Composite Materials Science and Technology

temperature and perforated fiber structure which indicates deterioration of the over-all composition
of the cellulose acetate from pineapple leaves. This research shows that pineapple leaves can be
utilized to develop an inexpensive and biodegradable cellulose acetate that can effectively replace
raw materials from fossil fuels as starting material in polymer industries. In the future work, it is
recommended to investigate the percent yield, crystallinity, molecular weight, mechanical properties
and degree of substitution. It is also suggested to utilize cellulose acetate for membrane application.

Acknowledgments
The first author would like to acknowledge the support of the DOST through the Accelerated
Science and Technology Human Resource Development Program for the scholarship grant.
DOST-PCIEERD for the equipment used in the characterization of the samples. University of
Science and Technology of Southern Philippines (USTP) for providing the laboratory space and
necessary materials.

References
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Materials, Springer 2016.
[4] R.G. Candido, G.G. Godoy and A.R. Goncalves: Carbohydrate Polymers Vol. 167 (2017),
p. 280–289.
[5] A.M. Das, A.A. Ali and M.P. Hazarika: Carbohydrate Polymers Vol. 112 (2014), p. 342–349.
[6] Bahmid, N., Syamsu, K. and Maddu, A.: Production of Cellulose Acetate from Oil Palm Empty
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[9] Information on https://psa.gov.ph/fruits-crops-bulletin/pineapple.
[10] S. Yahyam and Y. Yusof: Comprehensive Review on the Utilization of PALF, Advanced
Materials Research (2013).
[11] dos Santos, R. et.al., Cellulose nanocrystals from pineapple leaf, a new approach for the use of
this agro-waste, Industrial Crops and Products 50 (2013) 707– 714.
[12] Li, J. et.al., Microwave-Assisted Solvent-Free Acetylation of Cellulose with Acetic Anhydride
in the Presence of Iodine as a Catalyst. Molecules 14 (2009) 3551-3566.
[13] Hu W., Chen S., Xu Q. and Wang H., Solvent-free acetylation of bacterial cellulose under
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