Int J Plast Technol

https://doi.org/10.1007/s12588-018-9205-z

RESEARCH ARTICLE

Optimization of reaction condition for carboxylicpropyl

starch from potato starch

Nisarg K. Prajapati1 · N. K. Patel2 · Vijay Kumar Sinha1

Received: 15 December 2016 / Accepted: 1 May 2018

© Central Institute of Plastics Engineering & Technology 2018

Abstract  Starch from potato was converted to carboxypropyl starch (CPS) by

etherification using Monochloropropanoic acid and sodium hydroxide. The reaction
was optimized against temperature, concentration and reaction time. The optimized-
product has a large degree of substitution of 0.734, which compared favorably to
other forms of starch. Fourier Transform Infrared spectra were used to characterize
the product and potato starch. Digital photographs of starch and product showed the
expected amorphous structure while that of the CPS converted beads and smooth
surface morphology.

Keywords  Potato · Starch · Carboxyproply starch · Degree of substitution ·

Optimization

Introduction

Starch was early recognized as an important dietary component, and Hippocrates,

about 380 B.C., states that starch has a certain medical value. Abu Mansus, an Ara-
bian teacher and pharmacologist, about 975 A.D., was well acquainted with vari-
ous uses of starch, and even describes its conversion by saliva into a material which
was called “artificial honey” and used for treating wounds [1]. This is probably one
of the first references to the enzymic hydrolysis of starch to dextrin and maltose
[2]. Starches are inherently unsuitable for most applications and, therefore, must be

* Vijay Kumar Sinha

nisarg31.prajapati@gmail.com
1
Industrial Chemistry Department, V. P & R. P. T. P. Science College, Affiliated to Sardar Patel
University, Vallabh Vidyanagar, Gujarat 388 120, India
2
Institute of Science & Technology for Advanced Studies & Research, Vallabh Vidyanagar,
Gujarat 388 120, India

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modified chemically and/or physically to enhance their positive characteristics and/

or to minimize their defects. Starch derivatives are used in food products as thicken-
ers, gelling agents and encapsulating agents, in papermaking as wet-end additives
for dry strength, surface sizes and coating binders, as adhesives (corrugating, bag,
bottle labeling, laminating, cigarettes [tipping, side-seam], envelopes, tube-winding
and wallpaper pastes), for warp sizing of textiles, and for glass fiber sizing [3, 4].
Various starch products are used to control fluid loss in subterranean drilling, work-
over and completion fluids (for oil, gas or water production). Modified starches are
also used in tableting and cosmetic formulations [5, 6]. Some starch is incorporated
into plastics to enhance environmental fragmentation and degradation. Thermoplas-
tic starch and starch–polymer composites can replace petroleum-based plastics in
some applications. Newer applications include use of nondigestible starch as neutra-
ceuticals. The future of starch may include a role in detergents.
The structural morphology of Starch of d-glucopyranose polymers linked
together by α-1,4 and α-1,6 glycosidic bonds (Scheme 1). In forming these bonds,
carbon number 1 (C1) on a d-glucopyranose molecule reacts with carbon number
4 (C4) or carbon number 6 (C6) from an adjacent d-glucopyranose molecule [7].
Because the aldehyde group on one end of a starch polymer is always free, starch
polymers always have one reducing end [8, 9]. The other end of the polymer is
called the non reducing end. Depending on the number of polymeric branches

Scheme 1  Schematic diagram of starch

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present in a starch molecule, there could be a large number of nonreducing ends.

The glycosidic linkages in starch are in the alpha (α) configuration. Formation of
and α linkage is determined by the orientation of the hydroxyl (–OH) group on
C1 of the pyranosering. The linkage allows some starch polymers to form heli-
cal structures. The importance of the helical geometry of starch polymers is dis-
cussed at various times throughout this text. To illustrate the significance of the α
linkage, starch is sometimes compared to cellulose, a glucose polymer with β-1,4
bonds between subunits [10–12]. This seemingly trivial difference results in large
differences between starch and cellulose polymers, most notably in structural
configuration, physicochemical properties, and susceptibility to certain enzymes.
Starch ether production and starch hydroxypropylation improve the starch’s
water retention capacity, because of intermolecular bond established between
the water molecules and the starch macromolecule new sites. The modified form
of starch is a green polymer with significant importance in pharmacy, medicine,
cosmetics and food industries, in addition to many other industrial applications
[13, 14].

Materials and methods

Materials

Potato received from Indian market, mono chloro propionic acid, Sodium hydrox-
ide and Sodium chloride are purchased from SD fine chemicals. Water used in the
surfactant tests was purified by water purification system.

Starch extraction

Starch was extracted from matured potato after thorough cleaning. Potatoes
were cut in small slices and kept in saline water (0.1 M NaCl) to prevent bacte-
rial effects. The slices were crushed in a mixture with an excess of saline water.
So obtained milky pulp was filtered through nylon cloth to collect the separation
granules [15]. Residual material was crushed and filtered repeatedly to collect
mixture of starch. Filtrate thus collected contained starch granules and fine lighter
impurities which were removed by a number of saline water washing.
To remove potassium matters associated with starch its suspension in 0.1 M NaCl
was mechanically stirred with toluene for an hour. Starch was allowed to settle and
then the supernatant toluene layer with soluble and insoluble potassium matter at
water-toluene interference was siphoned out. The processes were repeated till potas-
sium matter was completely removed. The complete remove potassium matter was
ensured when the water toluene junction has no such extracted matter finally; the
starch was washed with saline water and stored in cool place. Sodium chloride was
removed by repeated washing with distilled water [16, 17].

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Preparation of carboxypropyl starch from potato starch

Potato starch was used after drying to constant weight. About 5.0  g of potato
starch was weighed and added to 250  ml Schott bottle and followed by 100  ml
of water:solvent in appropriate ratio. Then, 10  ml of 30% (w/v) sodium hydrox-
ide added drop-wise and stirred for an hour. The carboxypropylation reaction was
started by adding 6.0 g sodium monochloroacetate with reaction mixture placed in
thermo stated water bath with horizontal shaker. The reaction mixture was heated up
to reaction temperature of 45 °C and shaken for 3 h of reaction time. The mixture
was then filtered and the residue was suspended in 300 ml of methanol overnight.
The suspended methanol solution was then neutralized using glacial acetic acid. The
residue was filtered and dried to constant weight. The procedure used to study the
effect of the process parameters on carboxymethylation was similar to that of with
some modifications. The parameters to prepare carboxypropyl starch from potato
and the initial values used are as follows different types of solvents (water, dimeth-
ylformamide, methanol, dimethylsulfoxide, isopropyl alcohol, ethanol and butanol),
water and solvent ratio (20:80), reaction period (120 min), amount of sodium mono-
chloroacetic acid (6.0 g), concentration of NaOH (10 ml of 30%) and reaction tem-
perature (45 °C)[18].

Determination of degree of substitution

Absolute values of degree of substitution (DS) were determined by potentiometric

titration. The dried carboxylicpropyl starch 1  g were transferred to 250  ml Erlen-
meyer flask and suspended in distilled water (100  ml) until they dissolved com-
pletely. An excess of 0.1  N NaOH 10  ml solution was added with stirring and
stirring was continued for 15 more minute before solution was heated to boil for
15–30 min. While the solution was hot excess NaOH was back titrated with 0.1 N
HCL to a phenolphthalein end point. The amount of acid consumed was recorded
and the DS was calculated according to Eq. [19].
DS = 0.162A∕(1 − 0.058A)
A = (BC − DE)∕F

A = acid consume per gram of sample; B = NaOH solution added, ml; C = normal-
ity of NaOH; D = HCl required for titration of excess NaOH, ml; E = normality of
HCl; F = CPS used g; 162 = grams molecular mass of anhydroglucose unit of starch;
88.11 = net increase in molecular mass of anhydroglucose unit for each carboxypro-
ply group substituted.

Infrared spectroscopy

All measurements were carried out using the KBr method. The samples were dried
in an oven at 60  °C. About 0.2  mg of sample and 2  mg of KBr were mixed and

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ground finely and the mixture was compressed to a form a transparent disk. The
infrared spectra of these samples were recorded with a Perkin–Elmer Spectrometer
(Model spectrum BX) between 400 and 4000 cm−1.

Surface morphology analysis

Photographs of these samples were taken by using model Canon IXUS 170 20MP
Digital Camera with a superior performance of 10× zoom.

Results and discussion

Infrared spectroscopy of carboxyproply starch

The IR spectra of all the CPS samples synthesized show the typical absorptions of
the Starch backbone as well as the presence of the carboxyproply ether group at
1632 cm−1 (Fig. 1) shows the IR spectrum of starch from potato. It is evident that
the broad absorption band at 3441.26  cm−1, is due to the stretching frequency of
the –OH group as well as intermolecular and intermolecular hydrogen bonds. The
band at 2926 cm−1 is due to C–H stretching vibration. The bands around 1464 and
1381  cm−1 are assigned to –CH2 scissoring and –OH bending vibration, respec-
tively. The band at 1053  cm−1 is due to OCH–O–CH2 stretching (Fig.  2) shows a
representative spectrum of carboxyproply starch. Clearly, evident is a broad sorp-
tion band at 3300  cm−1, due to the stretching frequency of the –OH group and a
band at 2901 cm−1 attributable to C–H stretching vibration. The presence of a new
and strong absorption band at 1563  cm−1 confirms the presence of C ­ OO- group.
−1
The bands around 1419 and 1326  cm are assigned to –CH2 scissoring and

Fig. 1  Extracted starch from potato

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Fig. 2  Inferred spectroscopy of carboxylic propyl starch

–OH bending vibration, respectively. The band at 901 cm−1 is due to OCH–O–CH2

stretching.

Effect of various solvents

Figure 3 the extent of carboxypropyllation, expressed as degree of substitution when

the reaction was carried out in seven different solvent mediums. A maximum DS
of 0.5428 was obtained with isopropyl alcohol as the solvent medium. The role of
the solvent in the carboxypropyllation reaction is to provide miscibility and acces-
sibility of the etherifying reagent to the reaction centers of the starch chain rather
than glycolate formation. The differences in the extent of carboxypropyllation can
be explained by taking into consideration their solvent polarities and stereochem-
istry. The reaction efficiency increases as the polarity of the solvent decreases. The
results obtained are in good agreement with the literature but the solvents, isopro-
pyl alcohol and butanol with same polarity did not produce the CPS with the same
DS value. Isopropyl alcohol was the best choice, which is in agreement with other
reported solvents.

0.6

0.5
degree of substuon

0.4

0.3

0.2

0.1

0
H2O Methanol Isopropyl Butanol MSDO Ethanol
alcohol
type of solvent

Fig. 3  Effects of various solvents on degree of substitution of carboxyproply starch

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Effect of ratio of water and isopropyl alcohol

As shown in Fig.  4, the carboxyproplyation reaction was carried out in six differ-
ent water: isopropyl alcohol ratios. The observation increasing percentage of iso-
propyl alcohol with the increase degree of substation. The maximum of 0.5487
was obtained with 100% isopropyl alcohol ratio. The ratio of solvent volume
water:isopropanol is one of the vital aspect in obtaining optimum DS value. The
solvent is used as a medium for the substitution of CMC functional groups to take
place. The effect of the solvent system with regard to the reaction is related to its
miscibility, the ability to dissolve the etherifying agents and to swell the starch to
improve the accessibility of the etherifying agent into starch structure. Without sol-
vent, the reaction will be deterred. The accurate ratio of solvent will enhance the
substitution reaction and if the ratio is not appropriate, the substitution reaction will
be impeded. From Fig. 4, the optimum ratio of water:isopropanol is 00:100 with DS
of 0.5487. Higher DS is obtained due to the lower swelling in high organic solvent.
The polarity of the solvent decreases as the number of carbon atoms increases in the
solvent.

Effect of various reaction periods

As shown in Fig. 5, the carboxypropyllation reaction was carried out in seven dif-
ferent reaction periods. A maximum DS of 0.734 was obtained with 210 min as the
reaction period. There was an increase in the DS with reaction period up to 210 min
and thereafter it decreases. The increase in DS value by prolonging the reaction time
could be due to the favorable time effect on the swelling ability of the potato starch
granules, as well as the diffusion and absorption processes of the reactants with
improved contacts between the etherifying agents and starch.

Effect of reaction temperature

The influence of the reaction temperature on the DS is shown in Fig. 6. The tem-
perature for the carboxypropyllation reaction process was varied from 35 to 75 °C.

0.6

0.5
Degree of substuon

0.4

0.3

0.2

0.1

0
0 20 40 60 80 100 120
isopropyl alcohol %

Fig. 4  Effects of various percentage isopropyl alcohol ratio on degree of substitution of carboxyproply

starch

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0.8
0.7

Degree of substuon
0.6
0.5
0.4
0.3
0.2
0.1
0
0 50 100 150 200 250 300 350
Reacon period/minutes

Fig. 5  Effects of various reaction periods on degree of substitution of carboxypropyl starch in isopropyl

alcohol solvent

0.8

0.7

0.6
Degree of substuon

0.5

0.4

0.3

0.2

0.1

0
0 10 20 30 40 50 60 70 80
Temperature/C0

Fig. 6  Effects of various reaction temperatures on degree of substitution of carboxypropylstarch isopro-

pyl alcohol solvent

The DS value increased with the increases in reaction temperature, approaching its
maximum point at 55 °C. The maximum values of DS achieved were 0.734 respec-
tively. By increasing the temperature, reaction point of view temperature which cre-
ated more favorable environment for the reaction to take place. On the other hand,
the values of DS decreased sharply by further increment in the reaction temperature
from 55 to 75 °C. The drop in DS was from 0.734 to 0.427. This observation could
be explained by considering the reduction in the gelatinization temperature of the
starch molecules. Although the gelatinization temperature for potato starch is in the
range of 69–71 °C, it has been reported earlier that in the reaction media, the pres-
ence of solvent with high electron polarizability and ions, such as chloride, bromide
and iodide, was found to reduce the gelatinization temperature. In this study, isopro-
panol tends to form hydrogen bonds with the starch molecules, whereas the loose
end of this alcohol molecule, which was the alkyl chain, tends to disrupt the neigh-
boring hydrogen bonds between starch molecules. Both effects tend to decrease the
gelatinization temperature of the starch.

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Effect of various concentrations of sodium hydroxide

As shown in Fig.  7, the effect of sodium hydroxide concentration was studied by

varying the concentration of the sodium hydroxide solution. It was observed that the
DS of CPS increased with sodium hydroxide concentration and attained a maximum
DS of 0.734 at an alkali concentration of 10 ml of 25% (w/v). At particular alkali
strength, the DS was maximum after which it started declining. This observation can
be explained by considering the carboxypropylation process, where two competitive
reactions take place simultaneously.
The first involves reaction of the Starch hydroxyl with sodium hydroxide and then
prepared salt of starch reacted with mono chloro propionic acid to give (carboxylic
propyl starch) CPS as shown in Scheme 2.

Photographic study

The photographs in Fig. 8 shows structure ofpotato starch (II) is in white in color
amorphous material properties. The carboxypropylation (II) with the degree of sub-
stitution 0.734 is light brown in color, beads form and has a crystal surface. There-
fore, carboxypropylation reaction has resulted in the surface morphology changes
from a white amorphous to a brown smooth structure.

Conclusion

In this study, the optimization of the carboxypropylation reaction conditions of potato

starch has been successfully carried out. The optimized reaction conditions are: 25%
concentration of aqueous NaOH, 210  min of reaction time, 55  °C of reaction tem-
perature, were: pure isopropyl alcohol as the solvent medium, which have produced a
degree of substitution value of 0.734. Optimum carboxypropylation reaction conditions

0.8

0.7

0.6
Degree of substuon

0.5

0.4

0.3

0.2

0.1

0
10 15 20 25 30 35
Percentage NaOH

Fig. 7  Effects of various concentrations of sodium hydroxide on degree of substitution of carboxypropyl

starch in isopropyl alcohol solvent

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HO HO
HO HO NaO HO
HO NaOH HO
O HO HO O HO HO
O O O O
HO O O OH HO O O OH
OH OH
OH OH OH OH
Starch Na salt of starch

ClCH2CH2COOH
O

OH

HO
O HO
HO
O HO HO
O O
HO O O OH
OH
OH OH
carboxylic propyl starch

Scheme  2  The reaction is that sodium hydroxide reacts with extracted starch and then reaction with
monochloro propionic acidprepare carboxylic propyl starch Eq

Fig.  8  I Photographs of starch waste, II carboxypropyl starch from patato with the degree of substitution
of 0.734 at magnification 20X

shown in this study can be further exploited to prepare industrial products providing
much more opportunity for multi-applications of carboxypropylation starch.

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