Biomacromolecules 2005, 6, 1843-1845

1843

Solvent-Free Process to Esterify Polysaccharides

Atanu Biswas,* R. L. Shogren, and J. L. Willett
Plant Polymer Research Unit, National Center for Agricultural Utilization Research, USDA/Agricultural
Research Service, 1815 N. University Street, Peoria, Illinois 61604
Received March 7, 2005; Revised Manuscript Received April 21, 2005

A novel process for the preparation of acetates of polysaccharides is described herein. The process involves
the acetylation of polysaccharides with acetic anhydride in the presence of iodine as a catalyst. No solvent
is required to bring about the acetylation. The method is simple, rapid, and characterized by a high conversion
ratio. Conversion of cellulose and starch into their corresponding acetate derivatives has been demonstrated.
Introduction
Cellulose, the most abundant natural polymer, is of
tremendous economic importance.1 Over 90% of cotton and
50% of wood are made of cellulose. Wood and cotton are
the major resources for all cellulose products such as paper,
textiles, construction materials, cardboard, as well as cellulose
derivatives, such as cellulose esters2 and ethers.3 Similarly,
starch acetates have been known for over 100 years and have
found applications.4 However, cellulose acetates are industrially more important, and it is estimated that annually 1.5
billion pounds of cellulose acetates are manufactured globally. Cellulose acetate, Figure 1, is widely used in textiles
because of its low cost, toughness, gloss, high transparency,
natural feel, and other favorable aesthetic properties. Cellulose acetate fibers in cigarette filters are designed to absorb
vapors and accumulate particulate smoke components. Cellulose acetate is also used as a carrier for photographic negatives, motion picture film (celluloid), microfilm, microfiche,
and audio tape.1
Although cellulose and starch have the same glucosebased repeat units, these two polysaccharides vastly differ
in properties and reactivities.5 The properties of cellulose
and starch can be manipulated widely by various physical,
chemical, or enzymatic treatments. In recent years, there has
been strong emphasis to develop new cellulose and starchbased materials due to the biodegradability and renewable
aspects of these materials.
Acetylation of starch6 and cellulose7 with acetic acid or
acetic anhydride8 has been known for a long time. Recently,
the use of a new ionic liquid to dissolve9 cellulose and
prepare cellulose acetates has been reported.10 However, a
very dilute solution, only 4 wt % of cellulose in ionic liquid
could be used and it took 23 h to get a degree of substitution
(DS) of 2.74.
Acetic anhydride by itself is unable to acetylate starch or
cellulose. Cellulose needs a preactivation step that weakens
the intermolecular interactions within it. Thus, cellulose pulp
This article is dedicated to the memory of Dr. Conrad J. Kowalski,
1947-2004.
* To whom correspondence should be addressed. Phone: 309-681-6406.
Email: biswasa@ncaur.usda.gov.

10.1021/bm0501757

is treated with certain reagents, which cause a rupture or

weakening of its intermolecular bonds. Likewise, acetic
anhydride reacts11 with starch only at 180 C in the presence
of acetic acid to give starch acetate with a DS of 1.2-2.6.
Although these acetates are very useful products, the
processes involved in acetylation are sometimes not environmentally friendly and may need solvents such as methylene chloride or extreme conditions7 with sulfuric or
perchloric acid as a catalyst. To manufacture cellulose acetate
approximately 4.0-4.5 kg of acetic acid per kilogram of
cellulose is used. Most of the acetic acid, about 3.5-4.0 kg,
remains unreacted and is recovered from aqueous solution
along with sulfuric acid and other chemicals used in the
process. Thus, minimizing the amount of solvent or reagent
will be of great benefit.
We would like to report here a simple solvent-free 10
min method to acetylate cellulose, starch, and other polysaccharides. It was surprising to find that acetic anhydride
in the presence of a catalytic amount of iodine is an excellent
acylating reagent12 for both starch and cellulose. Iodine
activates the carbonyl group of acetic anhydride making the
latter more reactive, Figure 2. This acetic anhydride-iodine
combination works only in the absence of a solvent. Instead
of acetic anhydride when cellulose was heated with a mixture
of acetic acid and iodine no acetylation occurred.
Experimental Section
a. Materials. Cellulose samples (7% moisture) were
obtained from Weyerhaeuser Company and Aldrich. Corn
starch, Buffalo 3401 (4.7% moisture), was obtained from
CPC International. Acetic anhydride and iodine were obtained from Aldrich and used as is. Pierce Reacti-Vial glass
vials, 10 mL, equipped with magnetic stirrer were used as
reactors and Pierce Reacti-Therm heating block was used
as the heat source. Proton NMR scans of cellulose triacetates
were run in CDCl3 using Bruker Instruments DRX 400
spectrometer. NMR samples of starch acetates were prepared
from 10 mg of product and 0.7 mL of D2O and heated at 80
C with stirring for 3 h.
b. Typical Procedure. In a glass vial equipped with
magnetic stirrer, 1.7 g of starch (10.4 mmol of anhydroglu-

This article not subject to U.S. Copyright. Published 2005 by the American Chemical Society
Published on Web 05/05/2005

1844

Biomacromolecules, Vol. 6, No. 4, 2005

Communications

Figure 1. Structure of cellulose triacetate. n is typically 400-1000.

Figure 2. Mechanism of iodine catalyzed acetylation.

cose units or AGU), 1.9 g (15.6 mmol) of acetic anhydride,

and 120 mg (0.47 mmol) of iodine were heated at 100 C
for 10 min. The reaction mixture was then cooled to room
temperature and treated with a saturated solution of sodium
thiosulfate (2 mL) with stirring. The mixture color changed
from dark brown to colorless, indicating the transformation
of iodine to iodide. The mixture was poured into 50 mL of
ethanol and stirred for 15-30 min. The product was filtered
and washed with water and then dried in a vacuum oven at
60 C. The degree of substitution (DS) of the starch was
1.6. The starch acetate (1.53 g) was obtained in 65% yield.

There could be some loss due to the water-solubility of starch

acetate.
Acetylation of cellulose was carried out under identical
conditions using a mixture of cellulose (0.57 g), acetic
anhydride (1.9 g), and iodine (0.04 g). The cellulose acetate
was obtained in 94.8% yield. It had a DS of 2.8, i.e., in
average 2.8 mole of acetyl group per mole of AGU.
c. Determination of Degree of Substitution. The DS was
determined by proton NMR (see Figure 3) and by titration
with aqueous sodium hydroxide solution.13
Results and Discussion
The effects of the amounts of acetic anhydride and iodine
on the product DS, yields, and reaction efficiencies are
summarized in Table 1. Yields were calculated based on the
amount of polysaccharide used and the DS of the acetate.
For example, 162 g cellulose will give 280 g of cellulose
acetate with DS of 2.8 if the yield is 100%. Thus, for no. 1,

Figure 3. Proton NMR of cellulose acetate (DS 2.8), entry no. 1, in CDCl3.

Biomacromolecules, Vol. 6, No. 4, 2005 1845

Communications
Table 1. Acetylation of Polysaccharides at 100 C for 10 min
polysaccharide, g

Ac2O (gms)/
iodine (gms)

degree of
subsitution

yield
(%)

reaction
efficiency

1. cellulose, 0.57
2. cellulose, 0.43
3. cellulose, 0.43
4. cellulose, 0.85
5. starch, 1.7
6. starch, 0.57
7. starch, 0.57

1.9/0.04
1.9/0.02
1.9/0.01
1.9/0.04
1.9/0.12
1.9/0.12
1.9/0.04

2.8
2.8
2.8
2.8
1.6
1.6
1.3

94.8
70.0
57.5
82.0
64.3
46.5
59

53.16%
40.11%
40.11%
79.28%
90.6%
30%
24.12%

lower yield of starch acetates may be due to increased

solubility that resulted in some losses during workup. For
these acylation reactions, we found that the optimum reaction
temperature was 100 C. The ability to use a high concentration of polysaccharides in acetic anhydride, 25-50 wt %,
makes this process attractive for practical purposes. These
reactions including kinetics, molecular weights, and heterogeneities will be described in more details in future publication.
Conclusions

0.57 g of cellulose gave 0.933 g of product which corresponds to 94.8% yield. Reaction efficiency (RE) is proportion
of acetic anhydride added that actually reacts to form
cellulose acetate. The following equation
100 DS/(moles AA added/mole glucose) ) 100 DS
(weight of polysaccharide)/1.58 (weight of anhydride)
was used to calculate the reaction efficiency. Thus, for no.
1, RE ) 100 2.8/(1.9/102)/(0.57/162) ) 53.16%. For no.
5, RE ) 100 1.6/(1.9/(102)/(1.7/162) ) 90.6. So all
anhydride reacted in no. 5, whereas only 59% reacted in no.
1 since there was a large excess of anhydride in 1. After 10
min of heating, in the presence of 5 mol % of iodine, based
on the polysaccharide, both cellulose, entry no. 1, and starch,
entry no. 5, reacted with acetic anhydride to give the acetates.
Cellulose triacetate, entry no. 1, was obtained in 94% yield.
However, a yield of 64% and a DS of 1.6 for starch acetates
were both lower as compared to those for cellulose acetates.
There could be some loss due to the water solubility of starch
acetate. We observed that iodine helped the dissolution of
cellulose in acetic anhydride in 5 min at 100 C. Below 5
mol % iodine, the reaction mixture was heterogeneous. For
starch, the reactions were heterogeneous and that may
account for lower DS of starch acetates. Decreasing the
iodine amount to 2.5 mol % still gave the cellulose acetate
with DS of 2.8, entry no. 2, but in lower yield. Further
decrease of iodine to 1.25 mol % still gave cellulose acetate
with DS of 2.8, entry no. 3. Entry no. 4 highlights the best
result for cellulose, where 79.28% of acetic anhydride was
consumed to give acetate in 82% yield. It was difficult to
add more cellulose in a small volume of acetic anhydride
due to high porosity and low bulk density of cellulose.
However, for starch, with 1.25 mol % iodine, we obtained
starch acetate with DS of 1.3, entry no. 7. Increasing iodine
amount did not have any effect on the DS of cellulose acetate,
entry no. 2, and starch acetates, entry no. 6.
The amount of the anhydride, when increased, did not
affect the course of the reaction for either cellulose or starch.
We still obtained cellulose acetate with a DS of 2.8, entry
no. 2, and starch acetate with a DS of 1.6, entry no. 6. The

This work describes a simple, efficient, and solvent-free

rapid method of preparing polysaccharide acetate, such as
cellulose and starch acetates. We have demonstrated here
for the first time that iodine could be used as a catalyst to
acetylate polysaccharides using acetic anhydride. As shown
in Figure 2, it is proposed that iodine acts as a Lewis acid
catalyst, drawing electrons away from the carbonyl carbon
and making it more positively charged and thus more reactive
with alcohols.
Acknowledgment. We gratefully acknowledge Dr. H. N.
Cheng and Dr. A. C. Sau Hercules Incorporated, Wilmington,
DE, for helpful discussions. We thank Mr. Jim Wiley of
Weyerhaeuser Company, Federal Way, WA, for the gift of
dissolving pulp samples, Dr. David Weisleder for the NMR
work, and Janet Berfield and Stephanie Oedewaldt for
carrying out the reactions. Mention of a trademark or
proprietary product does not constitute a guarantee or
warranty of a product by the U.S. Department of Agriculture
and does not imply its approval to the exclusion of other
products that also can be suitable.
References and Notes
(1) Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.;
Wiley: New York, 1993; Vol. 5, p 496.
(2) Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.;
Wiley: New York, 1993; Vol. 10, p 598.
(3) Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.;
Wiley: New York, 1993; Vol. 5, p 541.
(4) Wurzburg, O. B. Modified Starches: Properties and Uses; CRC
Press: Boca Raton, FL, 1986; p 136.
(5) Richardson, S.; Gorton, L. Anal. Chim. Acta 2003, 497, 27.
(6) Wolff, I. A.; Olds, D. W.; Hilbert, G. E. J. Am. Chem. Soc. 1951,
73, 346.
(7) Bikales, N. M., Segal, L., Eds.; Cellulose and Cellulose DeriVatiVes,
High Polymers Series, Vol. V; Wiley-Interscience: New York, 1971.
(8) Larock, R. C. ComprehensiVe Organic Transformations; VCH: New
York, 1989; p 980.
(9) Swatloski, R. P.; Spear, S. K.; Holbrey, J. D.; Rogers, R. D. J. Am.
Chem. Soc. 2002, 124, 4974.
(10) Wu, J.; Zhang, J.; Zhang, H.; He, J. S.; Ren, Q.; Guo, M.
Biomacromolecules 2004, 5, 266.
(11) Shogren, R. L. Carbohydr. Polym. 2003, 52, 319.
(12) Phukan, P. Tetrahedron Lett. 2004, 45, 4785.
(13) Mullen, J. W.; Pacsu, E. Ind. Eng. Chem. 1942, 34, 1209.

BM0501757