Acetylated Starch Co2
Acetylated Starch Co2
Acetylated Starch Co2
X
3
i 1
b
i
x
i
X
3
i 1
b
ii
x
2
i
X
3
i 1
X
3
j 1
b
ij
x
i
x
j
(4)
Due to singularity issues in the matrix calculations, the
quadratic term of catalyst ratio (x
2
3
) was excluded from
the model. All regression coefcients (b
i
, b
ii
and b
ij
) and the
intercept (b
o
) were calculated using Mathcad
1
(Mathsoft)
software. A t-test (for statistical signicance) was per-
formed for regression coefcient and the non signicant
terms were deleted from the model [17].
3 Results and discussion
3.1 Catalyst screening experiments
A number of basic salts were screened at standard con-
ditions (15 MPa, 908C, catalyst to starch ratio of 0.1 mol/
mol AGU, and 1 h reaction time) to evaluate their catalytic
performance. After reaction, the product was washed
thoroughly with water to remove unreacted reagents
568 H. Muljana et al. Starch/Sta rke 2010, 62, 566576
2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.starch-journal.com
and catalyst and dried at 508C and 5 mbar till constant
weight. After work-up, the products were obtained as white
granular powders. The DS of the products was sub-
sequently determined by
1
H NMR.
K
2
CO
3
is the best catalyst in the series and gives the
highest DS value (Fig. 2). The least active catalyst is
Mg(OAc)
2
with the lowest DS (0.08) value. The acetic
anhydride conversion was far from quantitative after 1 h
reaction time and was between 40 and 47% for all cata-
lysts. To obtain insights in catalyst structure-performance
relations, the DS of the product was related to the pK
b
[18]
of the catalyst in water. Although the system under study is
not an aqueous system, the acetylation reaction takes
place in the starch matrix, which, certainly at the beginning
of the reaction, contains considerable amounts of water.
The results are given in Fig. 2.
It is clear that the DS decreases with the basicity of the
salt. The only exception is NaOAc, which gives a much
higher DS than expected. A reduction of the DS at lower
basicity of the catalyst is expected on the basis of the
proposed reaction mechanism (Scheme 1) [1921]. The
rst step in the mechanism involves the deprotonation of a
starchOH group by the base to form the intermediate
starch alkoxide (STO