Azhar Abbas et al., J.Chem.Soc.Pak., Vol. 37, No.

02, 2015 277

Green Synthesis, Thermal Analysis and Degradation Kinetics of

Cross-Linked Potato Starch
1
Azhar Abbas, 1 Muhammad Ajaz Hussain*, 1 Muhammad Amin, 1 Rizwan Nasir Paracha,
1
Muhammad Ameer and 2 Mazhar Hussain
1
Department of Chemistry, University of Sargodha, Sargodha 40100, Pakistan.
2
Institute of Chemical Sciences, Bahauddin Zakariya University, 60800 Multan, Pakistan.
majaz172@yahoo.com*

(Received on 7th April 2014, accepted in revised form 11th August 2014)

Summary: Succinylation of starch was carried out with succinic anhydride homogeneously using
N,N-dimethylacetamide (DMAc) at 70°C for 24 h. Starch succinates (SS) were then cross-linked
using 1,1′-carbonyldiimidazole (CDI). This green method for cross-linking of SS using CDI is being
reported for the first time. The SS and cross-linked starch succinate (CLSS) were characterized by
FTIR spectroscopy and thermal analysis. The CLSS was found thermally more stable than SS as
degradation maxima (Tdm) of CLSS (311°C) was 70°C higher than Tdm of SS (241°C) noted for
first and major step of degradation. Additionally, initial (Tdi) and final (Tdf) degradation
temperatures of CLSS were higher than SS which is indicative of extra thermal stability imparted
after cross-linking of starch via succinylation. Thermal degradation kinetics were calculated using
Friedman, Broido and Chang methods. Energy of activation (Ea) was calculated for each step of
degradation for SS and CLSS. Order of reaction (n) was calculated from Chang model and it was
found that degradation in first step follows first order kinetics in SS and CLSS.

Keywords: Cross-linking, Degradation kinetics, Starch, Succinic anhydride, Thermal analysis.

Introduction

Starch and its cross-linked derivatives are
widely used in various commercial applications like
paper making, pharmaceutical and medicinal fields
[1-4]. In order to improve thermal stability and
mechanical properties, starch is modified by blending
with other materials [5], esterification [6-8],
oxidation and cross-linking [9-15].
The cross-linked starch has several desirable
features, e.g., high temperature resistance, tensile
texture, improved viscosity, high shear force, etc [16-
20]. The cross-linking of starch is usually carried out
using glutaraldehyde as cross-linking agent. But,
glutaraldehyde gives aldehyde side products which
are toxic hence not desirable. Alternatively,
activated-dicarboxylic acids are being used as cross-
linking agents for polysaccharide materials [21, 22].
Such cross-linked polysaccharides are used in
pharmaceutical and food industries, ion separation
filters and membranes, antibody and enzyme
separation membranes [23]. One major drawback in
dicarboxylic acid mediated cross-linking of
polysaccharides is low DS due to less reactivity and
necessary work up procedure. Therefore, need was
felt to look for more efficient cross-linking
methodology.
Herein, we present novel and green
synthesis of cross-linked starch via succinylated
intermediate using a green in situ carboxylic acid
*
To whom all correspondence should be addressed.
activating agent, i.e., CDI. The succinyl moiety also
acts as a spacer arm and may enhance thermal
stability of starch after cross-linking. We are also
focused on thermogravimetric analysis and
degradation kinetics to elucidate thermal behavior of
SS and its cross-linked products, i.e., CLSS.
Experimental
Reagents and chemicals
Potato starch (Uni-Chem) was dried under
vacuum at 50°C overnight before use. 1,1′-
carbonyldiimidazole (CDI), N,N-dimethylacetamide
(DMAc) and DMF were obtained from Sigma-
Aldrich and used as such. Lithium chloride was
obtained from Guangdong Gaunghua, China.
Succinic anhydride, other reagents and solvents
(Fluka) were of analytical grade.
Measurements
IR Prestige-21 (Shimadzu, Japan) was used
to acquire FTIR spectra. Thermal decomposition
temperatures of the starch succinate (SS) and cross-
linked starch succinate (CLSS) were analyzed using
TA Instruments equipped with a thermo-balance
(SDT Q600 USA). Temperature effects on samples
were noted thermogravimetrically at heating rate of
10°C/min under N2.
Azhar Abbas et al.,
Dissolution of starch in DMAc/LiCl
Dried starch (1.0 g, 6.16 mmol) was added
in DMAc (30 mL) and heated at 100°C for 1 h.
Lithium chloride (0.5 g) was added and reaction
mixture was further heated at 135°C for 45 min. the
resultant starch solution was optically clear and used
for chemical modifications.
Succinylation of starch using succinic anhydride
Succinic anhydride (3.70 g, 37.0 mmol) was
added in parts to starch solution and reaction
proceeded for 24 h at 70°C. The reactions mixture
was precipitated and subsequently washed thrice with
2-propanol. The SS obtained was dried under vacuum
at 50°C.
Yield: 1.27 g (70%); DS: 1.32; FTIR (KBr):
3444 (OH), 2947 (CH2), 1726 (CO Ester), 1458
(CH2) cm-1.
Cross-linking of starch-succinate using 1,1′-
carbonyldiimidazole
The SS (1.0 g, 3.38 mmol) was dissolved in
DMAc (25 mL). CDI (548 mg, 3.38 mmol) was
added and reaction was preceded at 80°C for 24 h.
The reaction mixture was precipitated and washed
thrice with 2-propanol. The product obtained as white
powder was dried under vacuum at 50°C.
Yield: 1.12 g (62%); DS: 1.30; FTIR (KBr):
3421 (weak signal, OH), 2951 (CH2), 1724 (CO
Ester), 1453 (CH2) cm-1.
Degree of substitution (DS)
SS (100 mg) was dissolved in 1M aq.NaOH
(50 mL) and stirred overnight. pH of reaction mixture
was adjusted at 7 with help of HCl (0.01 M aq.).
Afterwards, measured amount of 1M aq.NaOH was
added. Extra amount of NaOH was back titrated
against 0.1M HCl solution to restore pH at 7. DS of
succinylation was then calculated using following
formula;
=[ . × ( )]/[ − ( )× . )]
where, n.NaOH is moles of NaOH added after
saponification, M (Ru) is molar mass of repeating
anhydroglucose unit, Ms is the mass of sample and
Mr (RCO-) is molar mass of ester as a substituent.
Thermal analysis and degradation kinetics
DTG curves were drawn from TG curves.
From TG and DTG curves, Tdi, Tdm and Tdf were
assessed for comparison of thermal stability of each
J.Chem.Soc.Pak., Vol. 37, No. 02, 2015 278
step in SS and CLSS. Friedman (eq. 1) [24], Chang
(eq. 2) [25] and Broido (eq. 3) [26] models were used
to calculate kinetic parameters.
where, in eq. 1-3, dα/dt (rate of weight loss) was
taken from DTG curve; n is the reaction order; Ea is
the activation energy; R is the gas constant; Z is
frequency factor of decomposition reaction; T is the
absolute temperature recorded; 1-α is the weight of
sample left at a certain temperature; y is (wt-w∞)/(w0-
w∞); w∞ is final weight; w0 is initial weight; wt is
weight at a given time t.
Results and Discussion
Synthesis and characterization
Succinylation of starch was performed under
homogenous reaction conditions. Starch was reacted
with succinic anhydride [27, 28]. The starch
succinates obtained were cross-linked using CDI.
CDI first reacts with free COOH groups on succinyl
moieties attached on starch to make their
imidazolides [29-31]. Imidazolide groups generated
in situ react with free OH of starch to yield cross-
linked product. Additionally, CDI if remains
unreacted towards COOH, it may cross-link starch
hydroxyls in the form of ester which is an additional
benefit of the reagent. The reaction scheme for the
synthesis of starch succinate (SS) and cross-linked
starch succinate (CLSS) is depicted in Fig. 1 and
results are accumulated in Table-1.
Table-1: The conditions and results of starch (1g)
with reagents to form esters of starch.
Yield
Samples Molar ratio DS Solubility
(g/ %)
SS 1:6a 1.32 1.27/70 DMAc, DMF, DMSO
CLSS 1:1b 1.30 1.12/62 DMAc, DMF, DMSO
a
Anhydroglucose unit : Succinic anhydride; bStarch succinate :
CDI
Azhar Abbas et al., J.Chem.Soc.Pak., Vol. 37, No. 02, 2015 279

O O
OH
O O
O O O
O
HO O O
OH
O O
O O
O RO RO
O O
70oC, 24 h N O
O O O
O
N C N
N
O
OH o
80 C, 24 h
O O O
O O O
O O
O O
O RO O
O O RO
O
O O
HO O O
OH
O O O
O O

R = H or Succinate O O

Fig. 1: Synthesis of starch-succinate from succinic anhydride and its crosslinking.

COEster

CH2
CH2
OH

COC, CO
(a)

(b)
Transmittance, %

(c)

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber, cm-1
Fig. 2: FTIR (KBr) spectra of pure starch (a), SS (b) and CLSS (c).

The degree of substitution (DS) was found The SS and CLSS were characterized using
1.32 for SS as calculated from acid-base titration FTIR spectroscopy. FTIR spectrum of SS showed a
after saponification. Both SS and CLSS were soluble distinct ester peak at 1726 cm-1 indicating successful
in DMSO, DMAc and DMF. However, SS was succinylation of starch. Other characteristic peaks of
partially soluble in water while CLSS was water free OH were found at 3444 cm-1 as a broad signals
insoluble even upon heating. and COC of polymer backbone centered at 1029 cm-1
while CH2 stretching appeared at 1458 cm-1.
However, FTIR spectrum of CLSS showed still intact
Azhar Abbas et al., J.Chem.Soc.Pak., Vol. 37, No. 02, 2015 280

and distinct ester peak at 1724 cm-1 and all other thermal stability imparted to SS after cross-linking.
characteristic peaks were comparable with SS as Thermal data of SS and CLSS is reported in Table-2.
expected. Distinct ester peak along with all
characteristic signals of starch indicated successful
formation of SS and CLSS. An overlay FTIR
spectrum of starch, SS and CLSS is shown in Fig. 2.

Thermal Analysis and Degradation Kinetics

Cross-linking is an important parameter to

enhance heat resistant properties in biopolymeric
materials. Such heat resistant biopolymers are used
for film formation and coating applications.
Therefore, it is important to study thermal properties
of cross-linked starch derivatives. Thermal analysis
and degradation kinetic of SS were studied before
and after cross-linking. Thermal decomposition
temperatures, Tdi, Tdm and Tdf were drawn from TG Fig. 4: Overlay DTG curves of SS(--) and CLSS( ̶ ).
and DTG curves. Thermal analysis has revealed two
step degradation profiles for SS and CLSS where 2nd Table-2: Results of thermogravimetric analysis for
step corresponds to furfural formation in starch-succinate at10°C/min.
Tdi Tdm Tdf Weight loss Char yield
polysaccharides [30] and is not being discussed here. Sample Steps
(°C) (°C) (°C) % at Tdf Wt. (%)
Therefore, first and major degradation step of SS and SS
I 114.27 241.26 387.78 64.55 4.81 at
CLSS was compared for thermal properties. The II 543.18 653.29 743.87 89.11 845.10°C
I 176.43 311.41 407.31 60.56
overlay TG and differential TG (DTG) curves of SS CLSS II 552.06 639.08 728.77 83.80
0.36 at
916°C
and CLSS are shown in Figs. 3, 4, respectively. III 764.29 846.88 893.05 98.30
Tdi, Tdm, Tdf = Initial, maximum, final thermal decomposition
temperatures in °C.

Thermal kinetics was also calculated using

three different kinetic models, i.e., Friedman, Broido
and Chang. Friedman, Broido and Chang plots of SS
and CLSS are shown in Figs. 5, 6 and 7, respectively.

The different kinetic parameters, e.g., order

Fig. 3: Overlay TG curves of SS (--) and CLSS ( ̶ ).
Degradation started at 114°C (Tdi) and
completed at 388°C (Tdf) with Tdm 241°C for first
step of thermal degradation of SS where total weight
loss observed was 65%. Whereas, in CLSS,
degradation started and ended later as Tdi and Tdf
appeared at 176 and 407°C, respectively. Similarly,
Tdm (311°C) of CLSS was 70°C higher than SS
(Tdm 241°C) which is indicative of significant
of reaction (n), activation energy (Ea) and frequency
factor (Z) were drawn from thermal data. The Ea
values for the first step degradation of SS as
calculated from Friedman (28.42 kJ/mol) and Chang
(29.47 kJ/mol) models were in good agreement.
CLSS showed Ea values of 35.94 and 38.51 kJ/mol
for first step degradation as calculated by Friedman
and Chang models, respectively. The relatively
higher Ea values for CLSS as compared to SS
indicate higher thermal stability in the cross-linked
product. Order of reaction (n) was also calculated
from Chang model and found that degradation
follows first order kinetics for SS and CLSS. Hence,
it is confirmed from thermal analysis and degradation
kinetics that CLSS has higher thermal stability than
SS. The results of thermal kinetics of SS and CLSS
are summarized in Table-3.
Azhar Abbas et al., J.Chem.Soc.Pak., Vol. 37, No. 02, 2015 281

-2.46
-2.54
-2.21
-2.56 -2.475
-2.26

ln(dα/dt)
ln(dα/dt)
ln(dα/dt)

-2.58 -2.49
-2.31 -2.6
-2.36 -2.505
-2.62
-2.41 -2.64 -2.52
2.4 2.45 2.5 1.179 1.186 1.193 0.956 0.960 0.964
1000/T (K-1) 1000/T (K-1) 1000/T (K-1)

Fig. 5: Friedman plots ln dα/dt vs. 1000/T (K-1) of step I, II and III (left to right) of thermal degradation of SS
(∆) and CLSS (□).

-2.07 -0.57
-0.72
-2.15 -0.62
-0.79
-2.23 -0.67

ln (ln1/y)
ln (ln1/y)

-0.87
ln (ln1/y)

-2.31 -0.94 -0.72

-2.39 -1.02 -0.77
-2.47 -1.09 -0.82
2.24 2.26 2.28 1.120 1.125 1.130 0.914 0.917 0.920
1000/T (K-1) 1000/T (K-1) 1000/T (K-1)

Fig. 6: Broido plots ln (ln1/y) vs. 1000/T (K-1) of step I, II and III (left to right) of thermal degradation of SS
(∆) and CLSS (□).

-1.7 -1.81 -1.26

ln[(dα/dt)/(1-α)n]
ln[(dα/dt)/(1-α)n]

ln[(dα/dt)/(1-α)n]

-1.75 -1.86 -1.31

-1.8 -1.92 -1.36
-1.85 -1.97 -1.41
-1.9 -2.03 -1.46
-1.95 -2.08 -1.51
2.24 2.26 2.28 1.120 1.125 1.130 1.135 0.897 0.900 0.903
1000/T (K-1) 1000/T (K-1) 1000/T (K-1)

Fig. 7: Chang plots ln [(dα/dt)/(1- α)n] vs. 1000/T (K-1) of step I, II and III (left to right) of thermal
degradation of SS (∆) and CLSS (□).

Table-3: Kinetics parameters of starch-succinate under nitrogen atmosphere.

Sample Step Method |r| n Ea (kJ/mol) lnZ ∆H* ∆S* ∆G*
Friedman 0.999 - 28.42 6.06 24.14 222.31 138.44
I Broido 0.999 - 39.48 - 35.21 199.87 137.97
Chang 0.999 1 29.47 6.39 25.20 219.26 137.93
SS
Friedman 0.999 - 138.47 17.32 130.77 130.20 251.36
II Broido 0.999 - 139.27 - 131.57 125.50 247.80
Chang 0.999 1 137.16 16.17 129.46 130.28 250.12
Friedman 0.999 - 35.94 6.84 31.09 217.06 157.88
I Broido 0.999 - 56.57 - 51.68 175.71 154.32
Chang 0.997 1 38.51 7.53 33.66 210.75 156.76
Friedman 0.994 - 75.95 8.14 68.36 211.15 260.96
CLSS II Broido 0.999 - 82.16 - 75.25 205.93 263.09
Chang 0.999 1 86.69 9.78 78.78 210.08 270.40
Friedman 0.999 - 267.02 29.03 257.36 35.21 298.42
III Broido 0.999 - 269.13 - 259.43 33.07 297.99
Chang 0.999 1 265.90 27.42 256.20 46.55 310.49
Azhar Abbas et al.,
Conclusion
Succinylation of starch was achieved under
homogeneous reaction conditions using succinic
anhydride. Moreover, cross-linking of succinylated
starch was achieved using CDI. Result of thermal
studies and degradation kinetics has revealed that
thermal properties of the starch succinate were
significantly improved after cross-linking. Due to
extra ordinary thermal stability imparted after cross-
linking, CLSS could be a material of choice for
surface coating applications.
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