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OPEN Ferric perchlorate hydrate as a new

catalyst for highly efficient
esterification of cellulose at room
temperature
Safaa Ragab , Ahmed Eleryan  & Ahmed El Nemr *
Ferric perchlorate was tested for the first time as a new catalyst to accelerate the esterification of
microcrystalline cellulose (MCC) at room temperature in a less amount of acetic anhydride compared
to the amount used in the conventional methods. It was possible to manufacture cellulose acetate
(CA) with a high yield of up to 94%. The influence of changes in reaction time, catalyst amounts, and
acetic anhydride on the characterization of cellulose acetate produced was investigated. The optimum
condition for esterification of 2.0 g (12.34 mmol) MCC was found to be: 10 mL (105.98 mmol) ­AC2O,
200 mg (0.564 mmol, anhydrous basis) of Fe(ClO4)3·xH2O and 1 h reaction time at room temperature.
The substitution degree of CA was investigated by FTIR and 1H-NMR spectroscopy. Thermal
stability of CA was studied using TGA, DTA and DSC analyses. The degree of polymerization and the
polydispersity index (PDI) were obtained using Gel permeation chromatography (GPC). This study
verified the direct and efficient synthesis of di- and tri-cellulose acetate in one–pot reaction using
Fe(ClO4)3·xH2O as a catalyst without using solvent.

This work is a part of a research topic that continues to give much attention about the use of catalyst materials
for one-pot organic reactions. Ester is widespread in nature and is also widely used in industry and cellulose
acetate being the most popular ester ­products1,2. The most important cellulose ester is cellulose acetate, which is
a nonirritant, biodegradable for many degree of substitution and some cellulose acetates are nontoxic and water
insoluble cellulose d­ erivative3,4. Cellulose acetate is a partially acetylated cellulose with an acetyl content ranging
from 29.0 to 44.8%, which is comparable to mono, di-, and tri-acetate. Plastics, films, photographic, lacquers,
fabrics, and dialysis or reverse osmosis membranes are only a few of the industrial uses of cellulose acetate. Fur-
thermore, cellulose acetate is used to coat tablets with semipermeable coatings, especially in osmotic pump-type
tablets and microparticles for controlled drug ­release5–8. Cellulose acetate, has been used in electrophoresis as
a mean of separating the lipoprotein c­ lasses9. Cellulose acetate is the most commonly used and tested material
for natural gas s­ weetening10.
From an economic and environmental standpoint, conducting one–pot reactions at room temperature under
solvent-free conditions and using heterogeneous catalysts have become increasingly important in recent years.
In general, the catalyst must possess a number of characteristics, including low cost, ease of handling and trans-
portation, and high effectiveness. Ferric perchlorate is extremely useful in organic chemistry because it is cheap,
readily accessible, and effective for a variety of purposes requiring Lewis acid ­catalysis11–13. Ferric perchlorate
has been used to form and cleave carbon–oxygen bonds in ethers, esters, alcohols, epoxides, tetrahydropyranyl
ethers, and acetals due to its v­ ersatility11,14.
In one pot, primary and secondary benzylic alcohols with nitriles were converted to various substituted
amides using an efficient reagent, ferric perchlorate hydrate supported on silica g­ el15. It’s worth noting that
Fe(ClO4)3·xH2O does not need a stoichiometric amount of base because, unlike all other metals, it can form the
dionato chelate complex without deprotonation and even in Brønstedt acidic m ­ edia16,17. Ferric perchlorate has
been used in the creation of carbon–carbon bonds. The ferric perchlorate catalyzed Michael reaction of β-esters
with methyl vinyl ketone and methyl acrylate as acceptors yielded products in 99% yield after the catalyst was
removed by simple ­filtration17. Ferric perchlorate was successfully used to oxidize Hantzsch 1,4-DHPs11,18. Oxi-
mes were also converted into aryl hydrazones in the presence of Fe(ClO4)3 in 1,2-dichloroethane19. Recently, El

National Institute of Oceanography and Fisheries, NIOF, Kayet Bey, El‑Anfoushy, Alexandria, Egypt. * email:
ahmedmoustafaelnemr@yahoo.com

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Nemr and his coworkers have reported N-iodosuccinimide (NIS), I­ 212, ­FeCl321, ­Zncl222, ­MnCl223, ­ZrOCl424 and
­ iCl225 as Lewis acid catalysts in esterification of cellulose.
N
The findings of cellulose acetate synthesis published in the literature showed a long reaction time, the use of an
excess of acetic anhydride, and high temperature application, all of which may increase the cost-effectiveness. As
a result, we hypothesized that using less acetic anhydride and using room temperature as the reaction tempera-
ture for the development of cellulose acetate would be advantageous in terms of reaction simplicity and product
properties. As a result, in previous work experiments, we attempted to test various catalysts for cellulose acetate
synthesis. Based on these hypothesis, the aim of this work is to demonstrate for the first time the use of Ferric
perchlorate hydrate as an efficient and green catalyst for the synthesis of cellulose acetate under solvent-free
conditions. In the presence of acetic anhydride at room temperature, ferric perchlorate was successfully used in
a catalytic amount to transform microcrystalline cellulose directly to the corresponding acetates with various
degrees of substitution in excellent yields in a one-pot reaction. The prepared cellulose acetate was characterized
using FTIR, TGA, DTA, DSC, NMR, and GPC.

Material and methods

Materials. Microcrystalline cellulose (MCC) was procured from Chemieerzeugnisse und Adsorptions tech-
nique AG. Switzerland. Fluka analytical provided acetic anhydride and ethyl alcohol. Ferric perchlorate hydrate
(Fe(ClO4)3·xH2O) was purchased from Merck.

Method. In a round flask (100 mL), 2.0 g (12.34 mmol) of MCC was combined with varying amounts of ace-
tic anhydride [10 (105.98 mmol), 12 (127.18 mmol), and 16 (169.58 mmol) mL], and then the catalyst ferric per-
chlorate hydrate was applied in four different amounts [50 (0.141 mmol), 100 (0.282 mmol), 200 (0.564 mmol)
and 300 (0.847 mmol) mg]; the catalyst should be added to the acetic anhydride before the addition of the MCC
to maintain the reaction temperature constant at room temperature). The reaction mixture was then stirred
at room temperature for different period of time (0.5, 1, 2, 3, and 4 h). After the reaction time was completed,
about 10 mL of ethyl alcohol was added drop by drop, followed by 100 mL of distilled water, and the mixture
was allowed to precipitate for 1 h. The white precipitate was filtered out and washed several times with distilled
water before being washed with a small amount of 70% ethanol (10 mL). The products were obtained by drying
the wet precipitate for 24 h at 50 °C in a drying oven and then weighing i­t7,8,12,20–23.

Characterization. To analyze the functional groups, all of the products were characterized using a Bruker
FTIR Model Vertex 70 spectrometer coupled to an ATR unit in the spectral range of 4000–400 ­cm–1. The Jeol
Nuclear Magnetic Resonance Spectrometer 500 MHz was used to obtain 1H-NMR in C ­ DCl3. Infrared spec-
trometry was used to assess the DS values of the cellulose acetates, which were then confirmed using 1H-NMR
spectrometry. The molecular weight, degree of polymerization, and polydispersity of a substance were also cal-
culated using gel permeation chromatography (GPC) (Agilent Technologies-1260 infinity II series) using tet-
rahydrofuran 1.0 mL/min as mobile phase at room t­ emperature7. Thermogravimetric analysis (TGA, DSC, and
DTA) was carried out with the SDT650-Simultaneous Thermal Analyzer instrument in the temperature range
of room temperature to 900 °C, with a ramping temperature of 5 °C per minute under atmosphere of nitrogen
gas (100 mL/min).

Determination of DS. The degree of substitution (DS) of CA was identified experimentally and confirmed
theoretically by integrating the areas of FTIR peaks and verified by integrating the areas of 1H-NMR peaks as
previously ­stated7,8,12,20–23,26–28.

Results and discussion

In this paper, we expedited direct esterification of MCC to their corresponding cellulose acetates using acetic
anhydride containing various amounts of inexpensive and available Fe(ClO4)3·xH2O as a new catalyst for cel-
lulose acetylation. From our point of view, this reaction takes place through ferric perchlorate which plays an
important role as Lewis acid catalyst where it accelerates the acetylation process by activating the acetyl portion
of the acetic anhydride, then facilitates attacking the oxygen atom of the cellulose by the electron pairs on it and
then allows the loss of the acetic acid molecule to complete the acetylation process (Scheme 1)12,14,20,22.
Initially, a routine study for direct esterification of MCC with catalytic amount of ferric perchlorate hydrate
(50 mg) in various amounts of acetic anhydride (10, 12, and 16 mL) and reaction times (0.5–4 h), was carried
out at room temperature. However, all samples of micro crystalline cellulose were easily converted to acetylated
cellulose (Samples 1–15) by that method (Table 1). Interestingly, in the course of this work, we have noticed that
such a reaction proceeds optimally by increasing the time reaction from 0.5 to 4 h not by increasing the amount
of ­AC2O from 10 to 16 mL (Table 1). Sample 3 reflects ideal conditions for preparing cellulose di-acetate as a final
product where the percentage yield is 87.32% ­(DSexp, 2.62) (cellulose di-acetate typically has a DS range of 2.4 to
2.6, while DS over 2.7 should be referred to as cellulose tri-acetate) (Table 1). The proposed method showed that
we are able to control the synthesis of cellulose di-acetate and cellulose tri-acetate by controlling the amount of
catalyst, acetic anhydride and reaction time without the use any additional solvent such as ionic liquid solvent
(Table 1). Therefore the cellulose di-acetate was directly prepared without the need for back hydrolysis from the
cellulose tri-acetate species, which is typically required for industrial applications.
To establish the generality of this method, a series of experiments have been performed under the same previ-
ous conditions except the catalytic amount of ferric perchlorate hydrate was (100 mg) (Samples 16–30) (Table 1).
After 0.5 h reaction time in different quantities of acetic anhydride, a sluggish acetylation reaction was occurred
with low yield (79.61, 72.37 and 70.65%) (Samples 16, 21 and 26, respectively), whereas the other products were

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Scheme 1.  Acetylation mechanism of MCC by using acetic anhydride and ferric perchlorate as c­ atalyst7,8,12,20–23.

acetylated in high product yields (90.49 to 93.66%). In the case of 10 mL of acetic anhydride and from 1 to 2 h,
the product yield began to increase. After just two hours at room temperature in 10 mL of acetic anhydride, we
were able to obtain the highest product yield of cellulose tri-acetate (Sample 18 in 93.66% yield) ­(DSexp, 2.81),
while with increasing time to 3 or 4 h, the hydrolyses occurred and the product yield decrease from 93.66 to
90.90% (Samples 18–20). In the case of 12 mL of the acetic anhydride, the product yield began to increase from
91.24 to 92.87% by increasing the time from 1 to 4 h, so the reaction time has found to be an effective effect in
Samples 22–25) (Table 1). With increasing the acetic anhydride to 16 mL, the acetylation reaction takes one
hour to give 90.51% yield (Sample 27), then after that the product yield was not much affected by the passage of
time from 1 to 4 h. From the above mentioned results, we have conclude that the reaction yield did not affected
by changing the amounts of acetic anhydride from 10 to 16 mL while it strongly affected by the catalytic amount
of ferric perchlorate hydrate (100 mg) (Table 1).
We investigated another catalytic amount of ferric perchlorate mediated by acetic anhydride after the success
of this reaction. Indeed, 200 mg ferric perchlorate in various amounts of acetic anhydride (10, 12 and 16 mL) with
different time reactions (0.5–4 h) successfully converted MCC to acetylated cellulose in 76.26 to 93.82 percent
yield, demonstrating ferric perchlorate’s catalytic capacity and impact (Samples 31–45) (Table S1). A quick acety-
lation occurred with an excellent yield (93.82%, ­DSexp 2.82) after a relatively short reaction time of 1 h in 10 mL
of acetic anhydride (Sample 32). Despite the longer reaction time, the product yield fell from 90.27 to 88.51%
(Samples 33–35). Using a higher volume of acetic anhydride (12 and 16 mL) in different reaction periods (0.5 to
4 h) yielded no important results (Samples 36–45) (Table 1). To determine the standard experimental protocol,
we used 2 g of MCC and treated it with A ­ C2O (10, 12 and 16 mL) at room temperature in the presence of ferric
perchlorate (300 mg) for various reaction times (0.5–4 h) (Table 1) (Samples 46–60). The best acetylation yield
was carried out using of 300 mg of Fe(ClO4)3·xH2O in 12 mL of ­AC2O for 0.5 h at room temperature to give
Sample 51 in 93.84% yield (­ DSexp, 2.82). The fastest formation of cellulose acetates with excellent yield at room
temperature was the most important finding of the current methodology. The functions of reaction times and
the amount of the reagent ­AC2O are limited, so they will not have much of an impact on product yield, whereas
the obvious effect was due to the different quantities of ferric perchlorate used in the various reactions. This
method of making cellulose acetate is thought to be one of the simplest in terms of reactant amounts, and the
reaction takes place at room temperature. The solubility test for the prepared samples showed that all samples
with DS higher than 2.6 are soluble in C ­ H2Cl2 and DMF while the samples with DS between 2.3 and 2.6 have a
good solubility in acetone and DMF, which is very important from the industrial point of view (Table 1). This
results of solubility in acetone is very important for the industrial production of acetone-soluble cellulose acetate
for different commercial applications.

Fourier transform infrared spectroscopy (FTIR). FTIR was used to analyze the microcrystalline cel-
lulose and the prepared cellulose acetate. Figure 1 displays the FTIR analyses of cellulose acetates (Samples 10,
18, 32, and 51) and microcrystalline cellulose. The absorption band at 3388.93 ­cm–1 in the FTIR of microcrys-
taline cellulose is due to OH v­ ibration7,8,12,20,22. The FTIR spectra in Fig. 1 display several distinct functional
groups after the acetylation process. The key feature absorption bands appeared at (1741–1748 ­cm–1) which were
assigned to carbonyl (C=O) as well as a diminishing in the strength of the band at 3388.93 ­cm−1 which was attrib-
uted to OH vibration, and the peak at (1365–1372 ­cm–1) was attributed to (C–H) in acetyl group. Furthermore,
the sharp absorption peak at (1212–1222 ­cm–1) has been attributed to carbon–oxygen (C–O) stretching in a

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Sample no Fe(ClO4)3 (mg) Ac2O (mL) Contact time (h) CA yield (g) Yield % of CA DSExp DSFTIR Solvent
1 50 10 0.5 3.215 90.55 2.72 2.68 CH2Cl2, DMF
2 50 10 1.0 2.758 77.70 2.33 2.31 Acetone, DMF
3 50 10 2.0 3.100 87.32 2.62 2.60 CH2Cl2, DMF
4 50 10 3.0 3.273 92.19 2.77 2.75 CH2Cl2, DMF
5 50 10 4.0 3.287 92.58 2.78 2.75 CH2Cl2, DMF
6 50 12 0.5 2.600 72.95 2.19 2.00 DMF, DMAC
7 50 12 1.0 2.776 78.20 2.35 2.32 Acetone, DMF
8 50 12 2.0 3.060 86.20 2.59 2.55 Acetone, DMF
9 50 12 3.0 3.300 90.97 2.73 2.71 CH2Cl2, DMF
10 50 12 4.0 3.282 92.46 2.77 2.76 CH2Cl2, DMF
11 50 16 0.5 2.672 75.28 2.26 2.22 DMF, DMAC
12 50 16 1.0 2.583 72.77 2.18 2.10 DMF, DMAC
13 50 16 2.0 2.821 79.46 2.38 2.36 Acetone, DMF
14 50 16 3.0 3.013 84.88 2.55 2.52 Acetone, DMF
15 50 16 4.0 3.131 88.18 2.65 2.64 CH2Cl2, DMF
16 100 10 0.5 2.826 79.61 2.39 2.35 Acetone, DMF
17 100 10 1.0 3.255 91.68 2.75 2.78 CH2Cl2, DMF
18 100 10 2.0 3.325 93.66 2.81 2.80 CH2Cl2, DMF
19 100 10 3.0 3.297 92.88 2.77 2.76 CH2Cl2, DMF
20 100 10 4.0 3.227 90.90 2.73 2.70 CH2Cl2, DMF
21 100 12 0.5 2.5691 72.37 2.17 2.00 DMF, DMAC
22 100 12 1.0 3.239 91.24 2.74 2.71 CH2Cl2, DMF
23 100 12 2.0 3.237 91.18 2.74 2.71 CH2Cl2, DMF
24 100 12 3.0 3.289 92.65 2.78 2.75 CH2Cl2, DMF
25 100 12 4.0 3.297 92.87 2.79 2.76 CH2Cl2, DMF
26 100 16 0.5 2.508 70.65 2.12 2.10 DMF, DMAC
27 100 16 1.0 3.213 90.51 2.72 2.69 CH2Cl2, DMF
28 100 16 2.0 3.100 86.47 2.59 2.56 Acetone, DMF
29 100 16 3.0 3.233 91.08 2.73 2.70 CH2Cl2, DMF
30 100 16 4.0 3.212 90.49 2.72 2.70 CH2Cl2, DMF
31 200 10 0.5 3.246 91.44 2.74 2.71 CH2Cl2, DMF
32 200 10 1.0 3.331 93.82 2.82 2.82 CH2Cl2, DMF
33 200 10 2.0 3.205 90.27 2.71 2.70 CH2Cl2, DMF
34 200 10 3.0 3.263 91.90 2.76 2.72 CH2Cl2, DMF
35 200 10 4.0 3.142 88.51 2.66 2.65 CH2Cl2, DMF
36 200 12 0.5 3.111 87.62 2.63 2.60 Acetone, DMF
37 200 12 1.0 3.285 92.55 2.78 2.75 CH2Cl2, DMF
38 200 12 2.0 3.179 89.55 2.69 2.66 CH2Cl2, DMF
39 200 12 3.0 3.294 92.78 2.78 2.77 CH2Cl2, DMF
40 200 12 4.0 3.287 92.60 2.78 2.77 CH2Cl2, DMF
41 200 16 0.5 2.710 76.26 2.29 2.26 DMF, DMAC
42 200 16 1.0 3.295 92.80 2.78 2.79 CH2Cl2, DMF
43 200 16 2.0 3.122 87.94 2.64 2.63 CH2Cl2, DMF
44 200 16 3.0 3.231 91.01 2.73 2.72 CH2Cl2, DMF
45 200 16 4.0 3.246 91.44 2.74 2.71 CH2Cl2, DMF
46 300 10 0.5 3.243 91.35 2.74 2.73 CH2Cl2, DMF
47 300 10 1.0 3.057 86.12 2.58 2.53 Acetone, DMF
48 300 10 2.0 3.078 86.70 2.60 2.59 Acetone, DMF
49 300 10 3.0 3.167 89.21 2.68 2.67 CH2Cl2, DMF
50 300 10 4.0 3.126 88.05 2.64 2.61 Acetone, DMF
51 300 12 0.5 3.284 93.84 2.82 2.80 CH2Cl2, DMF
52 300 12 1.0 3.191 89.90 2.70 2.70 CH2Cl2, DMF
53 300 12 2.0 3.177 89.49 2.68 2.66 CH2Cl2, DMF
54 300 12 3.0 3.261 91.84 2.76 2.75 CH2Cl2, DMF
55 300 12 4.0 3.213 90.52 2.72 2.70 CH2Cl2, DMF
56 300 16 0.5 3.171 89.29 2.68 2.65 CH2Cl2, DMF
Continued

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Sample no Fe(ClO4)3 (mg) Ac2O (mL) Contact time (h) CA yield (g) Yield % of CA DSExp DSFTIR Solvent
57 300 16 1.0 3.221 90.73 2.72 2.71 CH2Cl2, DMF
58 300 16 2.0 3.240 91.27 2.74 2.72 CH2Cl2, DMF
59 300 16 3.0 3.170 89.30 2.68 2.67 CH2Cl2, DMF
60 300 16 4.0 3.050 85.91 2.58 2.57 Acetone, DMF

Table 1.  Acetylation of MCC (2.0 g) using acetic anhydride in presence of Fe(ClO4)3·xH2O (50, 100, 200, and
300 mg) at room temperature and different times (0.5–4 h).

100%

80%
Transmittance [%]

MCC
60%
3900 3400 2900 2400 1900 1400 900 400

100%

80%

Sample-10
60%
3900 3400 2900 2400 1900 1400 900 400

95%

75%

Sample-18
55%
3900 3400 2900 2400 1900 1400 900 400

90%

70%

Sample-32
50%
3900 3400 2900 2400 1900 1400 900 400
100%

80%

60%
Sample-51
40%
3900 3400 2900 2400 1900 1400 900 400
Wavenumber cm –1

Figure 1.  FTIR analysis of samples 10, 18, 32, and 51.

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Figure 2.  Cellulose tri-acetate 1H-NMR spectrum (DS = 2.82), Me stands for methyl protons in the acetyl
group, H for anhydroglucose protons, and subscripts for Me or H positions on the anhydroglucose.

–O–(C=O)–CH3 group. C–O stretching in C–O–C linkages of cellulose, hemicellulose, and lignin was allocated
a broad band at (1031–1038 ­cm–1)21,23.

1
H‑NMR spectrum. Figure 2 represents the 1H-NMR analysis of acetylated cellulose (Sample 32) in 10 mL
­ C2O with 200 mg ferric perchlorate hydrate (Fe(ClO4)3·xH2O) as a catalyst and stirring at room temperature
A
for 1 h. Two signal clusters can be seen on the hydrogen atoms (Fig. 2). The resonance of seven anhydroglucose
protons were found at (= 3.53–5.06 ppm), while the three methyl protons of the acetate group were found at δ
1.93–2.12 ppm) (Fig. 2)7,8,12,20–23. The reaction product (Sample 32) had a DS value of 2.91, which was derived
from the 1H-NMR spectrum which confirmed the results obtained from the D ­ SExp and ­DSFTIR. 1H-NMR spec-
trum proved that the formation of cellulose tri-acetate in Sample 32 is obvious.

Gel permeation chromatography (GPC). GPC was used for evaluating the degree of polymerization,
weight average molecular weight (Mw), molecular weight distribution (MWD), Number average molecular
weight (Mn), z average molecular weight (Mz), and the polydispersity index (Mw to Mn (PDI)) of prepared
cellulose acetate. The polydispersity index and molecular weight averages are thus very useful in revealing the
width of a polymer distribution. The molecular weight of a polymer-based product is an important property
to know. A bell curve represents a molecular weight distribution, with the high end indicating high molecular
weight and the low end indicating low molecular weight. The presence of a broad molecular weight distribution
peak indicates that the sample is highly polydisperse, containing a variety of molecules of varying molecular
weights. A sharp molecular weight distribution peak indicates that a monodisperse sample has mostly one small
molecular range. Table 2 shows that as the catalyst concentration rises from 50 to 300 mg, the weight average
molecular weight (Mw) and degree of polymerization (DP) also decrease. The DP and Mw did not changed
substantially when the reaction time was increased from 0. 5 to 4 h or when the volume of acetic anhydride used
was increased from 10 to 16 mL. Also, in this research, it was observed that, all the studied samples using GPC
had a small polydisperses (Table 2).

Thermal stability analysis. The thermal degradation of cellulose acetate has been studied by thermogravi-
metric analysis (TGA). Also the activation energy of decompostion of cellulose acetate has been determined
from differential thermal analysis (DTA). Figure 3 showed dynamic TGA and DTA curves of cellulose acetate
products with heating rate of 5 °C/min under 100 mL/min flow of ­N2. The thermal degradation of the prepared
cellulose acetate has three series of degradation distinct zone. Initially, dehydration process was occurred at
100 °C due to the evaporation of bonding water on cellulose acetate in which depending on the hypophlicity
of the cellulose acetate. However, there has not significant weight-loss at 100 °C. Then, the second zone has a
rapid loss in weight due to the decompsition of cellulose acetate equal to (79–88%). Obviously, the temperature
of decompostion of all examined cellulose acetates was founed to be approxmatily from 310 to 375 °C. The

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Sample no. Mn (g/mol) MW (g/mol) MZ (g/mol) PDI DP

5 12,061 45,280 116,825 3.754 167
10 11,788 46,362 116,362 3.933 174
15 13,257 51,227 135,354 3.864 201
18 13,974 50,895 134,143 3.642 189
25 7902 31,406 93,652 3.974 117
29 10,173 37,700 113,978 3.706 144
32 8041 25,936 58,973 3.225 96
39 11,358 33,793 76,444 2.975 127
42 6831 24,139 64,857 3.534 90
46 4249 11,901 33,891 2.801 45
51 5416 14,936 36,104 2.780 55
56 8798 25,467 62,149 2.895 98

Table 2.  GPC analysis of selected samples of cellulose acetate prepared using different amount of ferric
perchlorate catalyst and different amount of acetic anhydride. The DP calculated values were calculated
and normalized depending on the DS as previously ­reported7,8. Mn number average molecular weight, Mw
weight average molecular weight, Mz z average molecular weight, PDI polydispersity index, DP degree of
polymerization.

decomposition rate gradually decreases to a constant weight reflecting carbonization in the final region. The
active temperature corresponding to maximum degradation rates (Tp) for the highest molecular weight cellulose
acetate (15) is found to be 351.33 °C, while that for the other cellulose acetate products was (343.05–352.76 °C).
Figure 4 shows DSC curves of cellulose acetate samples. An exodothermic peak was observed at around 100 °C
for prepared cellulose acetates due to crystalization of water, this exodothermic event is in agreement with that
observed in the TG ­analysis29. Another two exothermic peaks are observed around 310 and 330 °C assigned to
prepared cellulose acetates crystallization. The broad enothermic peak around 360 °C can be assigned to melting
of the crystalline regions of cellulose ­acetates7,8,12,20–23.

Comparison the present work with some of the previous work. Different catalysts and methods
have been reported for the synthesis of cellulose acetate with different degree of substitution. We previously
reported different new catalysts for the synthesis of cellulose acetate using different reaction methods. The
method reported in this work is superior in comparison with the literature work since the proposed reaction
method is occurred at room temperature and in relatively short time. Also the high yield obtained in the present
work is higher than many reported methods and comparable to the others (Table 3).

Conclusion
The objectives of this work was to find new efficient and inexpensive catalyst for successful esterification of
microcrystalline cellulose under simple conditions with varying degrees of substitution (­ DSEXP = 2.12–2.82). It
has been demonstrated that using different methods of analysis such as FTIR spectrometer, 1H-NMR, GPC, and
thermogravimetric analysis (TGA, DSC, DTA) proved that the di- and tri-cellulose acetate can be produced from
microcrystalline cellulose using the proposed method. This esterification process often requires no solvent, a
small amount of A ­ C2O, and a Lewis acid catalyst (Fe(ClO4)3·xH2O), and it takes place at room temperature, in a
short amount of time, and in a one-pot reaction system. With a ­DSEXP value of 2.82, the higher yield of acetylated
product is about 94%, and the reaction was completed in 1 h at room temperature. The acetylated product’s DP
(201) and MW (51,227 g/mol) values were found to be significantly higher in a small amount of catalyst (50 mg)
than in a large amount of catalyst (100–300 mg). The presence of Lewis acid Ferric perchlorate hydrate catalyst is
crucial for the direct conversion of microcrystalline cellulose to acetylated products, according to the findings.
The effectiveness of ferric perchlorate hydrate as a catalyst has been verified.

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Figure 3.  TGA and DTA analysis of (a) Samples 5, 10, 15; (b) Samples 18, 25, 29; (c) Samples 32, 29, 42; (d)
Samples 48, 51, 57.

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Figure 3.  (continued)

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Figure 4.  DSC analysis of (a) Samples 5, 10, 15; (b) Samples 18, 25, 29; (c) Samples 32, 29, 42; (d) Samples 48,
51, 57.

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Figure 4.  (continued)

No Catalyst Reaction Temp Yield % References

1 Fe(ClO4)3 25 °C 94.00 This work
20
2 NIS 140 °C 71.83
21
3 FeCl3 MW irradiation 90.58
12
4 I2 MW irradiation 100.00
22
5 ZnCl2 MW irradiation 95.83
23
6 MnCl2 140 °C 91.00
24
7 ZrOCl·8H2O MW irradiation ~ 100.00
30
8 NaOH 100 °C 84.00
31
9 H2SO4 60 ± 5 °C 87.08
32
10 SO3H/PhSO3H-carbon 80 °C 48–77
33
11 H2SO4 25 °C 91
34
12 I2 80 °C 40–60

Table 3.  Comparison between the yields of cellulose acetate using different catalysts. MW irradiation
microwave irradiation in closed teflun cup as reported in leteratures.

Data availability
Data sharing is not applicable to this article.

Received: 15 February 2022; Accepted: 21 March 2022

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Acknowledgements
We are grateful to Science, Technology & Innovation Funding Authority (STDF) of Egypt for financial support
for the project no. IG-34795.

Author contributions
S.R. prepared the original manuscript, A.E. conduct the experimental work, and A.E.N. supervised the research
work and conducted the characterization and revised the manuscript.

Funding
Open access funding provided by The Science, Technology & Innovation Funding Authority (STDF) in coopera-
tion with The Egyptian Knowledge Bank (EKB).

Competing interests
The authors declare no competing interests.

Additional information
Correspondence and requests for materials should be addressed to A.E.N.
Reprints and permissions information is available at www.nature.com/reprints.

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