Cellulose Triacetate Synthesis from Empty Bunches Palm oil’s

Cellulose
Theo Doohan

Cardiovascular disease and asthma are non-comunicable disease which had many patients, so
membrane in oxygen generator for oxygen separation is needed. One type of membrane is
cellulose triasetate. For make membrane, synthesis of cellulose triasetate is needed. Therefore,
the goal of this experiment are to determine the optimum composition of cellulose and acetic
glacial acid and temperature of the process. The result of this experiment represent that the
composition cellulose and acetic glacial acid and the temperature of process give impact of
substitution degree of cellulose triacetate. Then, the synthesized cellulose triacetate were
charaterized by NMR test. Hence, the conclusion of this experiment are 1 : 17,5 (gr/mL) for
composition and 50 oC for the temperature of the process of synthesis cellulose triacetate.

Keyword : cellulose, cellulose triacetate, substitution degree

INTRODUCTION
According data from Basic Health Research 2013, there are 2,650,340 who have
cardiovascular disease and 4.5 % from population of Indonesia have asthma (Kesehatan, 2013).
Cardiovascular disease and asthma sufferers need support instrument like oxygen concentrator.
One type technology of oxygen concentrator is membrane. Membrane technology works
through diffusion process with high pressure through polymer. Cellulose triacetate is one type
of membrane that can use for separation oxygen from air (Stern, 1994). Cellulose triacetate can
be synthesized by acetylation reaction of cellulose powder from Leucaena tree. Then, for
acetylation process use H2SO4 as catalyst (Hindi & Abohassan, 2015). Beside that, one type of
resources that can use for synthesis cellulose triacetate is empty bunches coconut oil’s cellulose
(Dewanti, 2018).
Therefore, empty bunches palm oil’s cellulose can be used for synthesis cellulose
triaceate through acetylation process with H2SO4 as catalyst, composition cellulose and glacial
acetic acid variation, temperature process, and acetylation time variation. The objective of this
research were to determine composition celullose : glacial acetic acid, acetylation time, and
validation chemical compund through NMR test.

EXPERIMENTAL
Materials
 The cellulose from empty bunches palm oil is obtained from Polytech Indonesia.
Sulfuric acid (98 %), glacial acetic acid (98 %), acetic anhydride (98 %) were purchased from
Univar. All chemicals were used as received without further purification.
Acetylation of empty bunches palm oil’s cellulose
Cellulose from empty bunches palm oil was acetylated using acetic anhydride as
acylation agent, sulfuric acid as catalyst, and glacial acetic acid as solvent. First of all, galcial
acetic acid (10 mL, 17.5 mL, and 25 mL) was added to cellulose (1 gram), then the mixture
was stirred at 50 oC for 1 h. After that, the system was added mixture of acetic anhydride (5
mL) and sulfuric acid (0.2 mL) at 50 oC for 45 min, 60 min, or 75 min. After the reaction, the
mixture was dripped to cool water bath until white solid appeared and solid-liquid separated
through filtration. The solid obtained were washed with distilled water until pH became neutral
to remove the unreacted anhydride, sulfuric acid, and acetic acid by-product. Then, the
acetylated empty bunches palm oil’s celluloses were oven-dried at 80 oC to constant weight.

FTIR Analysis
FTIR spectra from Zhimadsu was used for test carbonil and hydroxile element of
sample at ambient temperature. The range of wavenumber between 400 cm-1 and 4000 cm-1.
The result of FTIR can be used for determine the percentage of acetyl group and degree of
substitution (DS). Degree of subtitution of the sampel obtained was calculated from the ratio
between the absorbances of drawstring C=O (1750 cm-1) and OH (3400 cm-1). The ratio
between these absorbances is related to the percentage of acetyl groups (% AG). The value of
the percentage of acetyl groups relates to DS according to equation (1) and (2) (Silva, et al.,
2017).

% 𝐴𝐺 = 43.69 (1 − 𝑒 −0.947 𝑥 )2.153 (1)

Where x = ratio between the absorbances of the drawstring C=O (1750 cm-1) and OH (3400
cm-1)
162 × % 𝐴𝐺
𝐷𝑆 = (4300−42 × % 𝐴𝐺) 100 (2)

NMR Analysis
NMR Analysis was used to identify chemical compound based on properties of
magnetic atomic nuclei. The sampel was dissolved in choroform and then was tested at ambient
temperature with FT-NMR MHz in LIPI.

RESULTS AND DISCUSSION

The chemical reaction of cellulose from empty bunches palm oil is represented in the
reaction scheme 1, where Cellulose-OH represents the hydroxyl groups present on the
polymeric component of cellulose from empty bunches palm oil. The acetic anhydride has to
react mainly with the hydroxyl groups of cellulose.

Cellulose Cellulose

Sheme 1 : Acetylation of Cellulose

Effect of composition ratio on the change of functioal group
Fig 1 depicts the effect of changing the composition ratio on the change of functional
group. According to FTIR result, there were a OH groups peak from wavenumber 3339.41 cm-
1 with absorbance 18.48 % in composition ratio 1 : 25 (gr/mL). However, there was no OH
group absorbance in composition ratio 1 : 10 (gr/mL) and 1 : 17.5 (gr/mL). High absorbance
in composition ratio 1 : 25 (gr/mL) due to the modified cellulose is hydrophilic so in
atmospheric condition, it will absorb water. Beside that, the OH group peak appear because the
more glacial acetic acid caused the condition of reaction under strong acid so the cellulose will
be degradated (Nabili, et al., 2017). In the other side, there was no OH group absorbance in
composition ratio 1 : 10 (gr/mL) and 1 : 17.5 (gr/mL) due to the amount of glacial acetic acid
and temperature 50 oC were enough to make the cellulose swelling (increased surface area of
cellulose) and the intermolecular hydrogen bonds decreased. Therefore, cellulose will be
reacted easier and hydroxyl groups of cellulose will be substitued with acetyl groups
(Tristantini & Sandra, 2018).
Furthermore, there were carboxyl groups in wavenumber 1735 cm-1 with absorbance
3.56% in composition ratio 1 : 10 (gr/mL). In composition 1 : 17.5 (gr/mL), there was
wavenumber 1738.34 cm-1 with absorbance 3.11 %. Beside that, there was wavenumber
1637.09 cm-1 with absorbance 10.15 % in composition ratio 1 : 25 (gr/mL). Absorbance in
composition ratio 1 : 25 (gr/mL) is higher than the others because the more glacial acetic acid,
the more collision between reactants. But, absorbance in composition ratio 1 : 17.5 (gr/mL) is
lower than composition 1 : 10 (gr/mL) because the rate of swelling of cellulose in composition
1 : 17.5 (gr/mL) and at the same time, there was a little degradation of cellulose (Gaol, et al.,
2013).
 Fig 1. Effect of composition ratio on the change of functional group

Effect of acetylation time on the change of functioal group

Fig 2 shows the effect of acetylation time on the change of functional group. When the
acetylation time was increassed from 45 min to 75 min, there wasn’t OH group absorbance in
range wavenumber 3000 – 3700 cm-1. This is due to amount of glacial acetic acid and
temperature 50 oC were enough to make the cellulose swelling (increased surface area of
cellulose) and the intermolecular hydrogen bonds decreased. Therefore, cellulose will be
reacted easier and hydroxyl groups of cellulose will be substitued with acetyl groups
(Tristantini & Sandra, 2018). Furthermore, there were carboxyl groups in wavenumber
1733.21 cm-1 with absorbance 1.18% at 45 min acetylation time. At 60 min, there was
wavenumber 1738.34 cm-1 with absorbance 3.11 %. Beside that, there was wavenumber
1735.48 cm-1 with absorbance 2.94 % at 75 min. At 60 min acetylation time, the higher
absorbance was got. This is due to 60 min was the optimum acetylation time. If the acetylation
time was short, the gain of cellulose triacetate would decrease. Otherwise, If the acetylation
time was long, the cellulose would degraded slowly (Nemr, et al., 2017).
 Fig 2. Effect of acetylation time on the change of functional group

Degree of Substitution (DS)

Fig 3 depicts the effect of composition ratio and acetylation time on DS. There was no
significant change on DS. This is due to the reaction was already equilibrium state (Nabili, et
al., 2017). Then, the composition ratio 1 : 17.5 (gr/mL) has the higher DS than the others
because the amount of glacial acetic acid and temperature 50 oC were enough to make the
cellulose swelling (increased surface area of cellulose) and the intermolecular hydrogen bonds
decreased. Therefore, cellulose will be reacted easier and hydroxyl groups of cellulose will be
substitued with acetyl groups (Tristantini & Sandra, 2018). Furthermore, DS for composition
ratio 1 : 10 (gr/mL) was a little bit lower than 1 : 17.5 (gr/mL). Next, DS for composition ratio
1 : 25 was lower than the others. This is due to the more glacial acetic acid caused the condition
of reaction under strong acid so the cellulose will be degradated (Nabili, et al., 2017).
 3 2,80 2,869 2,871 2.870
2,77
2,43
2,5

2
DS

1,5

0,5 0,25 0,25 0,26

0
1 : 10 1 : 17.5 1 : 25
Composition ratio (gr/mL)

45 min 60 min 75 min

Figure 3. Effect of composition ratio and acetylation time on DS at 50 oC

Confirming of Acetylated Empty Bunches Palm Oil’s Cellulose

H-NMR spectra of modified empty bunches palm oil’s cellulose
Validation modified empty bunches palm oil’s cellulose used H-NMR spectroscopy.
Firstly, the solid modified cellulose dissolved in chloroform (solvent). The H-NMR spectrum
of the soluble modified cellulose from composition ratio 1 : 17.5 (gr/mL) and acetylation time
60 min is shown in Fig. 4. The chemical shift from range 1.8 – 2.3 ppm showed there were 3
peak that idetified of methyl protons from acetyl groups. Then, the weak signals of chemical
shift in the range 3.5 – 5.1 ppm represent hydroxyl protons and methylene protons in glucose
anhydride ring (Huang, et al., 2014). According to the peak of H-NMR, the acetylation reaction
was successful.
 Fig 4. H-NMR of aceylated empty bunches palm oil’s cellulose coresponding composition ratio 1 :
17.5 (gr/mL), teperature 50 oC, and acetylation time 60 min.

C-NMR spectra of modified empty bunches palm oil’s cellulose

Beside H-NMR, validation modified cellulose also used C-NMR shown in Fig 5. There
was carbon C6 substitued with acetyl groups in the peak 62 . Then, Carbon C1 and C4 didn’t
subsitute for OH groups that shown in 100.659 dan 76.231 respectively. On the other side, peak
70 – 75 showed there were carbon C2, C3, and C5 that only appeared in high DS. After that,
there were carbon binded carboxyl carbon in 170.010 ppm for C6, signal 169.9 ppm for C3, and
signal 169.6 ppm for C2. This was also indicating the acetylation reaction was successful.
 Fig 5. C-NMR of aceylated empty bunches palm oil’s cellulose coresponding composition ratio 1 :
17.5 (gr/mL), teperature 50 oC, and acetylation time 60 min.

CONCLUSION
This research has shown that empty bunches palm oil’s cellulose can be made to be
cellulose triacetate through acetylation reaction. The acetylation was performed optimum (high
DS = 2.871) under this conditions (composition ratio 1 : 17.5 (gr/mL), 5 mL acetic anhydride,
0.2 mL sulfuric acid, temperature process 50 oC, and acetylation time 60 min). Then, according
FTIR result, H-NMR, and C-NMR indicating successful of acetylation reaction.

REFERENCES
Dewanti, D. P., 2018. Potensi Selulosa dari Limbah Tandan Kosong Kelapa Sawit untuk
Bahan Baku Bioplastik Ramah Lingkungan. Jurnal Teknologi Lingkungan, 19(1), pp. 81-88.
Gaol, M. R. L. L. et al., 2013. PEMBUATAN SELULOSA ASETAT DARI α -SELULOSA
TANDAN KOSONG KELAPA SAWIT. Jurnal Teknik Kimia USU, Volume 2, pp. 33-39.
Hindi, S. S. Z. & Abohassan, R. A., 2015. Cellulose Triacetate Synthesis from Cellulosic
Wastes by Heterogeneous Reactions. Bioresources.com, pp. 5030-5048.
Huang, k. et al., 2014. ACETYLATION MODIFICATION OF RICE STRAW FIBER AND
ITS THERMAL PROPERTIES. CELLULOSE CHEMISTRY AND TECHNOLOGY, Volume
48, pp. 199-207.
Kesehatan, B. P. d. P., 2013. Riset Kesehatan Dasar. Jakarta: Kementrian Kesehatan RI.
Nabili, A., Fattoum, A., Brochier-Salon, M. & Bras, J., 2017. Synthesis of cellulose
triacetate-I from microfibrillated date seeds cellulose (Phoenix dactylifera L.). Iranian
Polymer Journal.
Nemr, A. E., Ragab, S. & Sikaily, A. E., 2017. Rapid Synthesis of Cellulose Triacetate from
Cotton Celluose and Its Effect on Specific Surface Area and Particle Size Distribution. Iran
Polym Petrochemical Institut, pp. 1-12.
Silva, F. B. et al., 2017. Preparation and Characterization of Cellulose Triacetate as Support
for Lecitase Ultra Immobilization. Molecules 2017, Volume 22, pp. 1 - 9.
Stern, S. A., 1994. Polymers for gas separation: the next decade. Journal of Membran
Science, pp. 1-65.
Tristantini, D. & Sandra, C., 2018. Synthesis of cellulose acetate from palm oil bunches and
dried jackfruit leaves. EDP Science.