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Synthesis and characterization of cationized starches for application in

flocculation, finishing and sizing

Article  in  Egyptian Journal of Chemistry · January 2009

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7 Egypt. J. Chem. 52, No. 1, pp. 73- 89 (2009)

Synthesis and Characterization of Cationized

Starches for Application in Flocculation, Finishing
and Sizing
A. Hebeish, A. A. Aly, A. El-Shafei and S. Zaghloul
Textile Research Division, National Research Centre, Giza,
Egypt.

C ATIONIZED starches of different nature were developed

g……through the reaction of starch and hydrolyzed starches with 3-
chloro-2-hydroxypropyl tri-methyl ammonium chloride (commercialy
known as Quat-188) in the presence of sodium hydroxide. Different
factors affecting these reactions were investigated. These factors
include the Quat-188 and sodium hydroxide concentrations, the
reaction time and the temperature. The extent of cationization reaction
was measured through monitoring the nitrogen content. Optimal
reaction conditions were achieved as Quat-188 (12.35mmole), NaOH
(15 mmole) -Quat-188 : NaOH ratio (1:1.25)- at a temperatured 70oC
for 180 min. The starch and cationized starch derived therefrom were
characterized by FTIR spectroscopy and scanning electron microscope
(SEM). Optimal conditions for the cationization were used to
cationize these hydrolyzed starches with their different molecular
masses. The derivatives so obtained were used as sizing agents,
flocculants. They were also used as additives in the Durable Press (DP)
finishing of cotton fabric. The efficiency of the cationized starch
derivatives, when applied in these domains depends on the molecular
size of the parent starch and on the extent of cationization.

Keywords: Starch, Cationization, Finishing, Flocculant and Warp

sizing.

Cationic starches bearing primary or tertiary or quaternary amino groups can be

prepared by reacting starch, respectively with either 3-chloro,2-
hydroxypropylamine with 1, 1, 1, N-tris (3-chloro- 2-hydroxypropylamine) and
with glycidyl trimethyl ammonium acetate in presence of sodium hydroxide
solution(1). All these syntheses were carried out in an aqueous medium which
caused the acceleration of some side reactions. Cationic starches were also
prepared by reacting starch with two amines containing either 3-chloro, 2-
hydroxy or epoxy groups in the presence of sodium hydroxide, using the dry
process(2,3). Several types of cationic starch, bearing various amino groups, i.e.
primary, secondary and tertiary or quaternary ammonium salts were prepared
and used as flocculants(4). They were also compared as dye absorbers(5).
74 A. Hebeish et al.
!
In this work, starch was cationized via its reaction with 3-chloro-2-
hydroxypropyl tri-methyl ammonium chloride "known commercialy as Quat-
188" under different conditions. Optimal conditions were used for the
cationization of the hydrolyzed starches. Cationized starch products derived from
starch and the hydrolyzed starches were analyzed for nitrogen and characterized
using FTIR and SEM. These products were applied as flocculants as well textile
sizes and durable press cotton finishes.

Experimental
Materials
Mill scoured and bleached cotton fabric (100%) was supplied by Misr
Company for Spinning and Weaving, El-Mehala-El-Kubra, Egypt. Quat-188 (3-
chloro-2-hydroxypropyl) tri-methyl ammonium chloride was supplied by Fluka,
Germany. Starch was supplied by Cairo Company for Starch and Glucose, Cairo,
Egypt. Sodium hydroxide, ethanol, isopropanol, hydrochloric acid, acetic acid ,
lauric acid, citric acid (C6H8O7.H2O), sodium hypophosphite monohydrate
(NaH2PO2.H2O), Fe (III) chloride, and sodium carbonate were laboratory grade
chemicals.

Cationization procedures for starch quaternization with Quat-188 (St-Q-188)

An aqueous solution of sodium hydroxide was added to a known amount of
Quat-188 and the mixture was added to a known amount of starch. Isopropanol
as a remaining part of the solvent was also added while stirring well. The
mixture was then transferred into a thermostated water bath at different
temperatures (40º-80ºC) and the reaction was allowed to proceed for different
durations (30-180 min). Then each reaction product was neutralized with an
acetic acid solution and washed with an ethanol/water mixture (80/20 (v/v) ratio)
and precipitated with acetone before drying at 40o-50ºC. Further details
concerning the reaction conditions are given along with the results.

Preparation of Fe(III) laurate

Lauric acid (5g) was suspended in H2O (500ml) in a 1L beaker and stirred at
60º-70ºC. An aqueous solution of sodium hydroxide (10%) was added dropwise
to adjust the pH to 10.5. Stirring was continued until the sodium laurate was
dissolved completely. The Fe(III) laurate was precipitated by adding aqueous
Fe(III) chloride (10%) dropwise to the so obtained solution. The pH was adjusted
to 6 and 8 by controlling the addition of Fe(III) chloride solution. The suspension
was then transferred to 1L measuring flask, 30 Cm3 of the Fe(III) laurate
suspention were diluted to 1L(6).

Flocculation procedure
The flocculation dispersion was added in different doses to a series of
250Cm3 beakers containing 100Cm3 of Fe(III) laurate solution and the mixtures
were mechanically stirred at 200 rpm for 30 sec. After 10 min the dispersion was
filtered. The transmission% of the filtrate was estimated using the colorimeter
apparatus(6).
Egypt. J. Chem. 52, No. 1 (2009)
 Synthesis and Characterization of Cationized Starches … 75

Fabric treatment for finishing

Unless otherwise indicated, the conventional pad-dry-cure method was
applied. Thus, the pad-bath was prepared containing citric acid (C6H8O7.H2O)
(80g/l), sodium hypophosphite monohydrate (NaH2PO2.H2O) catalyst (80 g/l)
and the cationized starches, prepared at different loadings of Quat-188 (0, 5, 10
and 20 g/l) as well as selected additives, namely ionic and non-ionic wetting
agents as detailed in the text. The padding of the fabrics was affected to a 100%
wet pick up. The padded fabrics were fixed in pin frames, dried at 85ºC for 5 min
and cured at 180 ºC for 90 sec. All the cured samples were washed at 50ºC for 5
min and conditioned before testing and analysis.

Sizing operation
Cooking process
An aqueous dispersion of the starch or of each of the modified starches under
investigation was prepared at a loading of 10% solid content. The dispersion was
then homogenized before heating by making use of a mechanical stirrer for
10min. Cooking was affected by heating the sample under continuous stirring in
a thermostated water bath where the temperature was raised from 25° to 95°C
then kept constant at 95°C for 30 min cooking to bring about a paste. The
temperature of this paste suspension system was lowered to 25°C. Meanwhile,
the stirring was reduced to the minimum degree within 15 min(7).

Sizing procedure
The aqueous slurries of the starch or of the modified starches in dispersion
were prepared at 10% loadings. They were cooked under the conditions
described above, then applied to a light cotton fabric sample. The application
was performed according to the pad-dry technique. The samples were dried at
100°C for 3 min. The sized cotton samples were monitored for the amount of the
size add-on%, size removal %, the tensile strength and the elongation at break.
The percent sizing add-on can be calculated as follows:
W1 – W0
Size add-on% = x 100
W0
W0= Weight of sample before sizing.
W1= Weight of sized sample before washing.

Desizing
Desizing was carried out by boiling the sized samples with tap-water for
15min, using a material to liquor ratio of 1:20. Each sample was then dried at
105°C and weighed.
W1 – W2
Size removal (%) = x 100
W1 – W0
W0= Weight of sample before sizing.
W1= Weight of sized sample before washing.
W2 = Weight of sized sample after washing.

!!Egypt. J. Chem. 52, No. 1 (2009)

76 A. Hebeish et al.
!
Testing and analysis
- The nitrogen percentage of the modified hydrolyzed starches was
estimated according to the microkjeldahl method(8).
- FTIR analysis. A Thermo Nicolet FTIR Spectrophotometer (Model- Nexus 870
FTIR) was used with the potassium bromide (KBr) pellet method, for the
FTIR studies.
- Scanning electron microscopy was applied, using a scanning electron probe
microanalyzer (JXA-840A) Japan. The specimens in the form of films were
mounted on the specimen stubs and coated with a thin film of gold by the
sputtering method. The micrographs were taken at a magnification of 1000
using (kv) accelerating voltage.
- The transmission% of the filtrate was estimated using a calorimeter standard
colorimeter apparatus(6).
- The carboxyl content was determined according to the Cirino method (9).
- The Crease recovery angle: Standard methods were used to measure the
wrinkle recovery angles (AATCC test method 66-1984).
- The tensile strength and elongation at break were determined according to ASTM
procedure D- 2296-66T(10).
- CIE whiteness index was measured on treated fabric samples using a
spectrophotometer, type ICS TEXICON Limited, England.

Results and Discussion

It has been reported(11) that the reaction of starch with (3-chloro-2-

hydroxypropyl) tri-methyl ammonium chloride in the presence of sodium
hydroxide, in aqueous solution proceeds as follows:
Cl - CH2 - CH – CH2-N+ (CH3)3Cl + NaOH

OH
H2C – CH – CH2 N+ (CH3)3Cl + NaCl (1)

St-OH + H2C – CH – CH2 N+ (CH3)3Cl NaOH

O
St - O – CH2-CH – CH2 N+ (CH3)3Cl (2)

OH
Cl - H2C – CH – CH2 N+ (CH3)3Cl + NaOH

OH
CH2 – CH – CH2 – N+ (CH3)3Cl + NaCl (3)

OH OH

Egypt. J. Chem. 52, No. 1 (2009)

 Synthesis and Characterization of Cationized Starches … 77

The above reaction scheme signifies the disadvantages of the cationization of

starch using a method that is based solely on an aqueous medium for the
synthesis of a cationic starch, using Quat-188 in the presence of an alkaline
medium. During the cationization of starch, several reaction steps occur
simultaneously, as suggested by Equations 1 –3. In this reaction scheme:
a) The chlorohydrin form of the reagent is converted to the epoxy intermediate (2,
3- epoxypropyl tri methyl ammonium chloride), (Eq. 1);
b) The epoxy agent reacts with the starch itself in the presence of an alkaline
medium (Eq. 2);
C) The epoxy unit is converted, via hydrolysis, to the non-reactive 2, 3-di
hydroxyl derivative (Eq. 3).
d) Considering the above reaction scheme, the magnitude of the cationization of
the starch would be dependent upon the NaOH concentration, the reaction
temperature, the reaction duration, the solvent used and the material to liquor
ratio as well as to the method of application. The results obtained along with
their appropriate discussion are given below.

Effect of sodium hydroxide concentration on cationization of starch

Figure 1 shows the dependence of the extent of the reaction, expressed as
nitrogen percent, between starch and Quat-188 on the NaOH concentration when
the reaction was carried out in a medium consisting of a water/isopropanol
mixture (2:3). The results show clearly that increasing the NaOH concentration
up to 15 mmole causes a significant enhancement in the extent of the
cationization reaction. Thereafter, a further increase in the alkali concentration
brings about a decrease. In short, the cationization reaction exhibited a maximum
at 15 of mmole NaOH when the reaction was conducted under the conditions
outlined in the footnote of Fig. 1.

Fig. 1. Effect of sodium hydroxide concentration on the cationization of starch.

Starch,(2 g) ; Quat 188 ( 12.35mmole); H2O: isopropanol (2:3); time, (60 min);
temperature, ( 70oC), material to liquor ratio (1:2.5).
!!Egypt. J. Chem. 52, No. 1 (2009)
78 A. Hebeish et al.
!
The favourable effect of NaOH, when used at a concentration up to 15 mmole
is a manifestion of its catalyzing action which needs a specific NaOH
concentration to enable optimisation of the cationization reaction (Reactions 1 & 2).
Above this specific concentration (i.e. 15 mmole NaOH), hydrolysis of the reactant
intermediate (Reaction 3) along with de-etherification most probably take place,
thereby lowering the opportunity of the competing cationization to occur. That is
why the extent of cationization decreases at higher NaOH concentrations.

Effect of Quat-188 concentration on cationization of starch

Figure 2 shows the nitrogen percent, a measure for the extent of the reaction,
as a function of Quat-188 concentration when the latter was reacted at different
concentrations (6-18 mmole), with starch (2 g), in presence of Quat-188 : NaOH
ratio (1:1.25). A mixture of water: isopropanol (2:3) was used as the
cationization medium. The reaction was carried out at 70 ºC for 60 min using a
material to liquor ratio (1:2.5).

Quat-188 concentration (mmole)

Fig. 2. Effect of Quat-188 concentration on the cationization of starch.

Starch, (2 g) ; Quat-188 : NaOH (1:1.25 mole); water : isopropanol (2:3); time, (60 min);
temperature, (70C). material to liquor ratio (1:2.5).

The results of Fig. 2 signify that the extent of the reaction increases
considerably as the Quat-188 concentration increases up to 18 mmole. Higher
Quat-188 concentrations induce gelatinization of the samples. The enhancement
of the extent of cationization by increasing the Quat-188 up to certain
concentration could be interpreted in terms of greater availability of the Quat-
188 molecules in the vicinity of starch hydroxyl groups. The latter are immobile
and their reaction would rely on the intensive presence of Quat-188 molecules in
the proximity of the hydroxyl groups of starch.

Egypt. J. Chem. 52, No. 1 (2009)

 Synthesis and Characterization of Cationized Starches … 79

Effect of reaction temperature and duration on cationization of starch

Table 1 shows the effect of temperature and duration on the extent of the
reaction occurring between starch and Quat-188 in presence of NaOH. Starch
(2g) was reacted with Quat-188 (18 mmole). Starch: Quat-188 molar ratio (1:1.5)
in presence of NaOH (23 mmole) were used as Quat188: NaOH molar ratio
(1:1.25) at different temperatures (40º -80ºC). The reactions were carried out for
various lengths of time (30-240 min) using water: isopropanol mixture (2:3) as
the reaction medium.

TABLE 1. Effect of reaction temperature and duration on the nitrogen percent of

cationized starch.

Nitrogen percent

Temperature (ºC )
Time (min)
40 50 60 70 80

30 0.65 0.80 0.90 2.95 2.80

60 1.00 1.46 3.00 3.20 3.00
90 1.35 2.05 3.05 3.40 3.15
120 1.35 2.55 3.35 3.55 3.25
180 1.85 2.70 3.35 3.70 3.35
240 1.60 2.40 2.90 3.50 3.00

Reaction conditions
Starch, (2 g); Quat 188 (18 mmole); Quat 188 : sodium hydroxide, (1:1.25 ratio); water:
isopropanol (2:3); material to liquor ratio(1:2.5) were used for the study.

The results (Table 1) disclose that the nitrogen percent increases on

increasing the reaction duration, to reach maximum at 180 min. It then decreases
at longer durations. The enhancement in the extent of the cationization reaction
suggests that cationization is the major reaction within the first 180 min.
Cationization prevails over the side reactions by virtue of better contact among
reactants and better opportunity for molecular collision as the reaction proceeds
within 180 min. Longer durations seem to act in favour of side reactions, namely,
de-etherification and hydrolysis.

Table 1 also shows that the nitrogen percent increases on raising the reaction
temperature up to 70ºC, to reach maximum value after which it decreases. This
chain of events was observed irrespective of duration of the reaction, within the
range studied. This indicates that within a temperature range of (40o-70ºC), the
cationization reaction prevails over the de-etherification and hydrolysis reactions.
The reverse is the case at temperatures that are higher than this range.
A temperature above 70ºC functions in favour of de-etherification and hydrolysis.
!!Egypt. J. Chem. 52, No. 1 (2009)
80 A. Hebeish et al.
!
Based on the results of Table 1, it may be concluded that the cationization
reaction is best carried out at 70ºC for 180 min.

Characterization of the cationized starch

Starch before and after being reacted with Quat-188 were characterized by
FTIR analysis and by scanning electron microscope (SEM). Given below are the
results of this investigation.

Characterization by FTIR analysis

FTIR spectra of starch and of Quat-188 (Q-188), as starting materials are
shown in Fig. 3 & 4, respectively. The spectrum of the starch that was modified
with Quat-188 (St-Q) is shown in Fig. 5.

Fig. 3. FTIR spectrum of starch.

Fig. 4. FTIR spectrum of (Quat-188).

Fig. 5. FTIR spectrum of cationized starch (St-Q).

Egypt. J. Chem. 52, No. 1 (2009)

 Synthesis and Characterization of Cationized Starches … 81

In Fig. 3 the broad band at 3393 cm-1, for starch, is due to the stretching mode
of O-H groups. The adsorption band at 1648 cm-1 is attributed to
an intermolecular H-bond involving the carboxyl group. The bands at 1155 cm-1,
2931 cm-1 are assigned to C-O and C-H stretching, respectively.

The FTIR spectrum of Quat-188 in Fig. 4 reveals that the broad band at
3419cm-1 is of an OH stretch vibration, the band at 1479cm-1 is assigned to the
C=N stretching. The band at 675 cm-1 is due to the C-Cl adsorption band.

This difference also appears in the spectrum assing for the product of the
reaction of starch with Quat-188 (Fig. 5). The presence of an additional band at
1417cm-1, assignable to the C=N stretching vibration which is not present in
starch, is clear proof of a cationic moiety on to the backbone of the starch.

Furthermore, the band corresponding to C-Cl at 675 cm-1 for Quat-188 (Fig.4)
was absent in the spectrum of the cationic product. This confirms that chlorine is
librated during the reaction.

Characterization by SEM
The surface characteristics of the aforementioned cationized starches were
investigated by scanning electron microscope (SEM), as shown in Fig. 6 & 7. It is
understandable that SEM is the right technique for the direct observation of
microstructure of spherulites of size in the range between 0.1-10 m. Cleary
Fig. 6 & 7 show that there are differences between starch and the cationized starch,
prepared by reacting starch with Quat-188. The granules are different in shape.

Fig 6. Scanning electron micrograph of hydrolyzed starch.

Fig 7. Scanning electron micrograph of (St+Q-188).

!!Egypt. J. Chem. 52, No. 1 (2009)
82 A. Hebeish et al.
!
Figure 7 shows the surface morphology of the cationized starch (St-Q-188).
There are small and very fine particles of starch connected to each other due to
their cationization with Quat-188. The particles have approximately
homogeneous shapes, being typically 5 m to10 m in size.

Utilization of the prepared cationized starches in flocculation, finishing and

sizing
Starches having different degrees of hydrolysis were prepared by subjecting
the starch to different concentrations of reagentes (0.1, 0.3, 0.5 M) of
hydrochloric acid, at 50oC, for 120 min using a starch to liquor ratio of (1:2.5).
The hydrolyzed starches so obtained were reacted with Quat-188 in an alkaline
medium to yield different cationized starches. An evaluation of the application of
these products as flocullants and as textile sizing and finishing agents was
undertaken.

Cationized starches as flocculants

For convenience simplicity, the reaction products of the hydrolyzed starches-
Quat-188 (cationized starches) are refered to as Derivative I, Derivative II and
Derivative III, as outlined in the footnote of Tables 2 & 3. Tables 2 & 3 depict
the effect of the derivative dose on the transmission % of the filtrates of these
cationized starches, when they were used as a flocculant at pH 6 and at pH 8,
respectively. As is evident, flocculation using the cationized starches is more
effective at pH 6 than at pH 8. As a consequence, a less amount of flocculant is
consumed at pH 6 than at pH 8, to give rise to as 98-99% transmission. Greater
extensions of the cationized starch molecules at pH 6, due to protonation, may
account for this. The addition of the cationized starch to the Fe(III) laurate
suspension creates attraction between the suspended laurate particles, bearing
their negative charges and the amino groups of the cationized starch.

TABLE 2. Flocculation properties of different cationized starches, at pH=6.

Dose of
flocculant Derivative I Derivative II Derivative III
(ppm)

Transmission (%) Transmission (%) Transmission (%)

0.00 65 65 65
0.05 92 98 92
0.1 97 99 96
0.2 94 93 97
0.3 90 92 94
0.4 87 85 89
0.5 87 83 87
0.6 85 70 84

Derivative I: Starch hydrolyzed with 0.1M HCl, prior to cationization with Quat-188
Derivative II:Starch hydrolyzed with 0.3M HCl, prior to cationization with Quat-188
Derivative III:Starch hydrolyzed with 0.5M HCl, prior to cationization withQuat-188
Egypt. J. Chem. 52, No. 1 (2009)
 Synthesis and Characterization of Cationized Starches … 83

TABLE 3. Flocculation properties of different cationized starches at pH= 8.

Dose of Derivative I Derivative II Derivative III

cationized
starch (ppm) Transmission (%) Transmission (%) Transmission (%)

0.00 57 57 57
0.1 84 89 91
0.2 92 93 93
0.3 94 97 88
0.4 92 98 84
0.5 87 96 82
0.6 84 92 80

Derivative I: Starch hydrolyzed with 0.1M HCl, prior to cationization with Quat-188
Derivative II:Starch hydrolyzed with 0.3M HCl, prior to cationization with Quat-188
Derivative III:Starch hydrolyzed with 0.5M HCl, prior to cationization with Quat-188

At the same time, the modified starch molecules that are attached to the solid
particles still have free active centres that can be adsorbed on the remaining free
surface of other particles. These results are "bridging" between solid particles,
thereby leading to formation of large flocs having a three dimensional network
structure. Beside bridging, the addition of cationized starch would increase
charge neutralization to the axtent that the zero zeta potential value would be
attained. It is understandable that the maximum flocculation occurs at the
optimal (or higher) dose value when the zeta potential value amounts to zero. By
further increasing the dose of cationized starch, deflocculation takes place, under
the influence of the repulsion that is caused by the already adsorbed cationic
starch on the particle surfaces.

It is also seen (Tables 2 & 3) that increasing the degree of hydrolysis of the
starch prior to cationization, exerts some influence on the transmission %. For
example, when the flocculation was carried out at pH 6, 99% transimission was
attained using Derivative II at a dose of 0.1 ppm. 97% transimission values were
attained with both Derivative I and III using doses of 0.1 ppm and 0.2 ppm,
respectively.

Table 3 shows that, at pH 8, 98% transimission was attained using Derivative

II at a dose of 0.4 ppm, while 94% transimission was attained using Derivative I
at a dose of 0.3 ppm. With respect to Derivative III, 93% transimission was
attained when using it at a dose of 0.2 ppm.

It may generally be concluded that the flocculation efficiency of the three

cationized hydrolyzed starches is greater at pH 6 than at pH 8. For a given pH
and at the optimal dose, the flocculation efficiency follows the order:
Derivative II > Derivative I  Derivative III

!!Egypt. J. Chem. 52, No. 1 (2009)

84 A. Hebeish et al.
!
However, the cationized starch derivatives that were examined, function as
effective flocculants even at pH 8.

Nature of the derivatives: Three starch derivatives with various properties were
obtained by controlling the molecular mass of the starch, by using different
concentrations of HCl and introducing Quat-188 moiety in the molecular
structure of the so obtained hydrolyzed starches. Utilization of the three
derivatives in flocculation studies, brought into focus a number of salient
features (Tables 2 & 3).

Cationized hydrolyzed starches (Derivatives I, II and III) proved to be the

best in flocculation, irrespective of the molecular mass of the parent starch or the
pH of the flocculation system. Doses in the range 0.1-0.6 ppm were required to
bring about transmission values ranging from 93-99%.

Differences in the values of the transmission %-which are taken as a measure

of the flocculation efficiency, observed upon using the said derivatives, could be
ascribed to differences in the mode of interaction of these derivatives with Fe(III)
laurate. By virtue of their positively charged surfaces, cationized starches
(Derivatives I, II, III) would be attracted, easily adsorbed forming bridging with
the negatively charged laurate particles. Such a strong mode of association of
these derivatives to form floc, with the particles, diminishes the role of the pH
and the molecular mass of the derivatives during flocculation.

Finishing
In an attempt to establish an effective formaldehyde-free, durable press (DP)
finishing system for cotton fabrics, the starch-based derivatives I, II, and III were
independently incorporated into a finishing formulation containing citric acid
(CA) and sodium hypophosphite (SHP). CA acts as the crosslinking agent, and
SHP serves as the catalyst for the esterification and the crosslinking of cotton
with the CA. The finishing treatment was carried out as per the conventional
pad-dry-cure method(11). The performance of the finished fabrics was assessed of
through monitoring the nitrogen content, the carboxyl content, the crease
recovery angle (CRA), the strength properties and the whiteness index.

Nitrogen content: Table 4 shows the effect of incorporation of each of the

three starch derivatives, (Derivatives I, II, and III) on the DP performance of the
cotton fabrics, when these derivatives were individually used at different
concentrations. Obviously, all of the fabric samples that were finished in
presence of the derivatives and thoroughly washed acquire measurable amounts
of nitrogen content. The nitrogen content tends to increase by increasing the
derivative concentration in the finishing formulation as well as by decreasing the
molecular mass of starch, using higher concentrations of HCl.

Egypt. J. Chem. 52, No. 1 (2009)

 Synthesis and Characterization of Cationized Starches … 85

TABLE 4. Effect of incorporation of different hydrolyzed starches, cationized with

Quat-188, at different concentrations, on the performance properties of
finished cotton fabrics.

Blank Fabric finished in presence of

properties Untreated Fabric Derivative I Derivative II Derivative III

fabric finished
without 5 10 20 5 10 20 5 10 20
derivative g/l g/l g/l g/l g/l g/l g/l g/l g/l
(0 g/l)
D CRAo
(W+F) 163 218 219 221 228 225 227 228 226 229 232

W CRAo 170 230 280 315 327 285 318 328 292 320 329
(W+F)
T.S (kg)
26 18 22 22 20 21 20 19 19 19 18
Elong.at
break (%)
7 8 13 13 14 12.5 12.5 14.5 12 12 14
N* (%)
--- --- 0.43 0.49 0.53 0.48 0.52 0.66 0.47 0.53 0.68
COOH
mEq/100
g sample
1.30 57.5 53.3 51.2 47.4 56.4 51.3 38.1 56.5 51.5 47
W. I
175 159 115 133 138 117 133 143 120 125 134

Citric acid (80g/l), CA: SHP molar ratio, 1:1, drying, 85C/5 min, curing, 180C/90sec.
N*, the residual nitrogen content on the finished fabric after washing.
D CRAo, dry crease recovery degree
W CRAo, wet crease recovery degree
Derivative I, Starch hydrolyzed with 0.1M HCl then cationized with Quat-188
Derivative II, Starch hydrolyzed with 0.3M HCl then cationized with Quat-188
Derivative III, Starch hydrolyzed with 0.5M HCl then cationized with Quat-188.

No nitrogen could be detected in absence of these derivatives. This indicates

that the starch derivatives (with different hydrolyzed parent starches) are
involved in reactions occurring between CA and cotton cellulose.

Carboxyl group content: The results of Table 4 reveal that the finished cottons are
characterized by a considerable loading of carboxyl groups. This is observed for the
presence and for the absence of the starch derivatives in the finishing formulation,
irrespective of the concentration and nature of the derivatives used. Nevertheless, the
magnitude of the carboxyl group content is greater in absence of the derivatives than in
the presence of the derivatives. It also tends to decrease on increasing the concentration
in the finishing formulation. Decreasing the molecular size of the parent-hydrolyzed
starch of the derivative has practically no effect on the magnitude of the carboxyl group
content. This implies that: (a) beside crosslinking, esterification of cotton cellulose with
CA occurs, via single ended reaction, (b) esterified cotton, brought about by such
!!Egypt. J. Chem. 52, No. 1 (2009)
86 A. Hebeish et al.
!
single-ended reaction, undergoes reaction with the starch derivatives and (c) the latter
reaction of the derivatives relies on its concentrations and nature, being more favoured
at high concentration and lower molecular mass values.

Whiteness index: Table 4 shows that DP finishing using CA as a crosslinking

agent and SHP as a catalyst brings about a significant decrease in the whiteness
index. As expected, the use of a polycarboxylic acid (CA) in the finishing
formulation is accompanied by yellowing of the cured cotton fabric. As evident
from Table 4, the whiteness index decreases considerably after finishing. This
was observed when finishing was conducted in the presence of the starch
derivatives and in the absence of the starch derivatives, in question. Decreasing
the molecular mass of the parent-hydrolyzed starch of the derivatives, as well as
increasing the concentration of the derivative have practically no effect on the
magnitude of the whiteness index.

Crease recovery: Table 4 depicts that the dry crease recovery and the wet
crease recovery of the fabrics increase significantly after finishing in the presence
of the starches derivatives and in the absence of the starch derivatives. Certainly
the increment is higher in the wet state. The magnitude of the increment in both the
dry crease recovery and the wet crease recovery is dependent to some extent on the
concentration and the nature of the derivative. With derivatives I, II, and III (Table
4), there is a tendency that the greater concentration of the derivatives and the
lower molecular mass of the parent-hydrolyzed starch of such derivatives increase
the crease recovery. However, the incorporation of the derivatives in the finishing
formulation brings about significant dimensional stability, as evidenced by the
striking enhancement in the wet crease recovery. The reactions of CA with cotton
cellulose, via crosslinking and single ended esterification, with involvement of the
starch derivatives in such reactions would account for the enhancement of crease
recovery of the cotton fabric.

Strength properties: As expected, the improvement in crease recovery is

accompanied by losses in strength properties. As evident from Table 4, the tensile
strength and elongation at break decrease considerably after finishing. This was
observed when the finishing was conducted in presence of the derivatives and in
the absence of the derivatives. However, the presence of the derivative acts in
favour of the strength properties, as evidenced by the greater strength properties
(both tensile strength and elongation at break values) in the presence of the
derivatives than in absence of the derivatives. The latter seems to protect the cotton
cellulose from the hydrolyzing action of CA, particularly during curing. As a result,
the molecular degradation of cotton cellulose would be less, Hence the strength
properties are less affected by the finishing treatment. However, the protection by
the derivative against the rigidity conferred on cotton cellulose by crosslinking and
the avoidance of any adverse effect on the strength properties cannot be ruled out.

Sizing
Table 5 shows the sizing performance of the aforementioned three starch
Derivatives I, II and III. The values of the size add-on that was obtained using
derivatives II and III are almost equal. They are significantly lower than the value
Egypt. J. Chem. 52, No. 1 (2009)
 Synthesis and Characterization of Cationized Starches … 87

obtained with derivative I. The higher molecular mass of the parent-hydrolyzed

starch of derivative I, compared with those of derivatives II and III, may account
for this. Size removal for the three derivatives follows the order: Derivative III >
Derivative II > Derivative I, indicating again the effect of the molecular size of the
parent hydrolyzed starches of the derivatives. Derivatives based on III, with the
lowest molecular mass for all of the samples, display the highest removal.

TABLE 5. Sizing performance of different starch derivatives based on cationization

of hydrolyzed starches using Quat-188.

Sizing agent Size Size Tensile Elongation

add-on removal strength at break
(%) (%) (kg) (%)

Blank --- --- 22 13

Derivative I 25.45 95 32 15

Derivative II 15.92 98 36 17

Derivative III 16.82 100 38 20

Derivative I: Starch hydrolyzed with 0.1M HCl, then cationized with Quat-188.
Derivative II: Starch hydrolyzed with 0.3M HCl, then cationized with Quat-188.
Derivative III: Starch hydrolyzed with 0.5M HCl, then cationized with Quat-188.

The results of strength properties of the sized light fabrics indicate the
advantages to be gained by the use of Derivative III by virtue of the advantages
in bringing about higher tensile strengths and elongations at break (Table 5). The
tensile strength and elongation at break increase that is brought about by
decreasing the molecular size of the parent hydrolyzed starches of the derivatives
follow the order: Derivative III > Derivative II > Derivative I.

Fabric sized with the lowest molecular mass of the parent-hydrolyzed starch
derivative (i.e. Derivative III ) displays a superior tensile strength than fabric sized
with derivatives whose molecular masses are greater, as represented by Derivatives
II and I (Table 5). This indicates that the lowest molecular mass of the derivative is
able to form more uniform, stronger and adhered film sizes on the fabric than can
the higher molecular masses. This points to the advantages of the use of modified
starches that have been derived from hydrolyzed starches, with respect to better
film forming properties, stronger adhesion and more uniform coverage.

Conclusion

We conclude that the conditions appropriate for synthesis of cationized starch

through reaction of the latter with Quat-188 (3-chloro, 2-hydroxypropyltrimethyl
ammonium chloride) were established; a point which necessitates systematic
!!Egypt. J. Chem. 52, No. 1 (2009)
88 A. Hebeish et al.
!
study concerning dependence of the extent and rate of the cationization reaction
on certain parameters. Hence the reaction was carried out under a variety of
conditions including concentration of Quat-188 (6-19 mmole), sodium hydroxide
concentration (0-25 mmole), duration (30-240 min) and temperatures (40-80C).
The extent of the cationization reaction was expressed as %N as the reaction
products were monitored for their nitrogen content.

Results conclude that, the most appropriate conditions for synthesis of

cationized starch can be drawn as follows: Hydrolyzed starch (12.35 mmole) and
Quat-188 (18.5 mmole) at 70oC for 180 min. In other words, hydrolyzed starch :
Quat-188 molar ratio (1:1.5) are reacted in presence of NaOH (23 mmole), which
means Quat188: NaOH molar ratio (1:1.25), using water: isopropanol mixture at a
ratio of 2:3 as the reaction medium. Material to liquor ratio (1:2.5) is employed.

References

1. Jouko, K.; Hendrik, L. and Karl, N. et al., Preparation and characterization of

cationic corn starch with a high degree of substitution in dioxane–THF–water media
US. Patent APP 20030177915 (2003).

2. Khalil, M. I. and Farag, S., Preparation of some cationic starches using the dry
process. Starch/ Stärk, 50, 267 (1998).

3. Reinhard, S. and Fisher, et al., Process for dry cationization of starch. US patent,
4785087 (1988).

4. Pal, S.; Mal, D. and Singh, R. P., Cationic starch: an effective flocculating agent.
Carbohydrate Polymers, 59, 417 (2005).

5. Khalil, M. I. and Aly, A. A., Use of cationic starch derivatives for the removal of
anionic dyes from textile effluents . J. Appl. Poly. Sci. 93, 227 (2004).

6. Khalil, M. I. and Aly, A. A., Evaluation of some starch derivatives containing amide
groups as flocculants. Starch- Stärk, 53, 323 (2001).

7. Hari, P. K. and Behere, P.K., 10th International Symposium on Warp Sizing,

Denkendorf. Germany Dec. 9 (1992).

8. Vogel, A. I., "Elementary Practical Organic Chemistry" Part 3"Quantitative Organic

Analysis" Longman Group Ltd. 2nd ed., 652 (1975).

9. Cirino, O. V. and Rowland, S. P., Text.Res J. 46, 272 (1964).

10. ASTM Test Methods, In: “Book of Standard Philadephia” and D-1682 part 24 (1972).

11. Hashem, M.; Refai, R. and Hebeish, A. Crosslinking of partially carboxymethylated

cotton fabric via cationization. Journal of Cleaner Production, 13, 947 (2005).

(Received 22/11/2007;
accepted 20 / 1/2009)

Egypt. J. Chem. 52, No. 1 (2009)

 ‫… ‪Synthesis and Characterization of Cationized Starches‬‬ ‫‪89‬‬

‫ﺗﺤﻀﯿﺮ وﺗﻮﺻﯿﻒ اﻧﻮاع ﻣﻦ اﻟﻨﺸﺎ اﻟﻜﺎﺗﯿﻮﻧﻰ ﻟﺘﻄﺒﯿﻘﮭﺎ ﻛﻤﻮاد ﺗﺠﻤﯿﻊ‬

‫وﺗﺠﮭﯿﺰ وﺗﺒﻮﯾﺶ‬
‫ﻋﻠﻰ ﻋﻠﻰ ﺣﺒﯿﺶ‪,‬اﻣﺎل اﺣﻤﺪ ﻋﻠﻰ ‪,‬أﻣﯿﺮة ﻣﺤﻤﺪ اﻟﺸﺎﻓﻌﻰ و ﺳﻌﺪ زﻏﻠﻮل ﻣﺮﻋﻰ‬
‫ﻗﺴﻢ ﺑﺤﻮث اﻟﻨﺴﯿﺞ ‪ -‬اﻟﻤﺮﻛﺰ اﻟﻘﻮﻣﻰ ﻟﻠﺒﺤﻮث ‪ -‬اﻟﺠﯿﺰة – ﻣﺼﺮ‪0‬‬

‫ﯾﺴﺘﮭﺪف اﻟﻌﻤﻞ اﻟﻤﻌﺮوض ﻓﻰ ھﺬه اﻟﻤﻘﺎﻟﺔ ﺗﺤﻘﯿﻖ ھﺪﻓﯿﻦ رﺋﯿﺴﯿﯿﻦ‪.:‬‬

‫ﯾﺸﻤﻞ اﻟﮭﺪف اﻷول ﺗﻄﻮﯾﺮ ﻣﺸﺘﻘﺎت اﻟﻨﺸﺎ ﺑﻤﺎ ﯾﻼﺋﻢ اﺳﺘﺨﺪاﻣﮭﺎ اﻟﺘﺠﺎرى ﻓﻰ ﻣﺠﺎل‬
‫ﺻﻨﺎﻋﺔ اﻟﻨﺴﯿﺞ ﺑﯿﻨﻤﺎ ﯾﺸﺘﻤﻞ اﻟﮭﺪف اﻟﺜﺎﻧﻰ ﻋﻠﻰ ﺗﻄﺒﯿﻖ ھﺬه اﻟﻤﺸﺘﻘﺎت ﻓﻰ ﻣﺠﺎﻻت‬
‫ﻣﺨﺘﻠﻔﺔ ﻓﻰ اﻟﺼﻨﺎﻋﺎت اﻟﻨﺴﺠﯿﺔ ﻣﺜﻞ إﺳﺘﺨﺪام ھﺬه اﻟﻤﺸﺘﻘﺎت ﻛﻤﻮاد ﺗﺠﻤﯿﻊ ‪,‬‬
‫واﺳﺘﺨﺪاﻣﮭﺎ ﻛﻤﻮاد ﺑﻮش ﺑﺎﻹﺿﺎﻓﺔ إﻟﻰ اﺳﺘﺨﺪاﻣﮭﺎ ﻓﻰ ﻣﺠﺎل اﻟﺘﺠﮭﯿﺰ اﻟﻨﮭﺎﺋﻰ‬
‫ﻟﻠﻤﻨﺴﻮﺟﺎت اﻟﻘﻄﻨﯿﮫ‪ .‬وﻟﺘﺤﻘﯿﻖ ھﺬه اﻻھﺪاف ﺗﻢ ﺗﺤﻀﯿﺮ ﻧﺸﺎ ﻣﻌﺎﻟﺞ ﺑﻤﺎدة اﻻﻣﯿﻦ‬
‫اﻟﺮﺑﺎﻋﻰ اﻟﻨﺸﻂ )اﻟﻜﻮات‪ (188 -‬ﻟﻠﻮﺻﻮل اﻟﻰ ﻃﺮق ﻣﻨﺎﺳﺒﺔ ﻹدﺧﺎل اﻟﻤﺠﻤﻮﻋﺎت‬
‫اﻟﻔﻌﺎﻟﺔ اﻟﻤﻄﻠﻮﺑﺔ ﻓﻰ اﻟﺘﺮﻛﯿﺐ اﻟﺠﺰﺋﻰ ﻟﻠﻨﺸﺎ ‪.‬‬
‫وﻓﯿﻤﺎ ﯾﻠﻰ ﻣﻠﺨﺺ ﻟﻤﺎ اﻧﺘﮭﺖ اﻟﯿﮫ ھﺬه اﻟﺪراﺳﺔ‪:‬‬

‫‪ -1‬اﻟﺘﺤﻮﯾﺮ اﻟﻜﯿﻤﯿﺎﺋِﻰ ﻟﻠﻨﺸﺎ ﺑﺎﺳﺘﺨﺪام اﻻﻣﯿﻦ اﻟﺮﺑﺎﻋﻰ اﻟﻨﺸﻂ )اﻟﻜﻮات‪.(188-‬‬

‫ﺗﻢ اﻟﺘﺤﻮﯾﺮ اﻟﻜﯿﻤﯿﺎﺋﻰ ﻟﻠﻨﺸﺎ اﻟﻤﺤﻠﻞ ﻣﺎﺋﯿﺎ ﺑﺎﺳﺘﺨﺪام اﻻﻣﯿﻦ اﻟﺮﺑﺎﻋﻰ اﻟﻨﺸﻂ‬
‫)اﻟﻜﻮات‪ (188-‬ﻓﻰ وﺟﻮد ھﯿﺪروﻛﺴﯿﺪ اﻟﺼﻮدﯾﻮم ﻛﻌﺎﻣﻞ ﺣﻔﺎز وﺗﻢ ھﺬا اﻟﺘﻔﺎﻋﻞ‬
‫)‪ 19-6‬ﻣﻠﯿﻤﻮل( وھﯿﺪروﻛﺴﯿﺪ‬ ‫ﺑﺎﺳﺘﺨﺪام ﺗﺮﻛﯿﺰات ﻣﺨﺘﻠﻔﮫ ﻣﻦ اﻟﻜﻮات‪188-‬‬
‫اﻟﺼﻮدﯾﻮم )‪25 -0‬ﻣﻠﯿﻤﻮل ( ﻟﻤﺪة ﺗﺘﺮواح ﺑﯿﻦ )‪ 240-30‬دﻗﯿﻘﺔ( ﻋﻨﺪ درﺟﺎت ﺣﺮارة‬
‫ﻣﺨﺘﻠﻔﺔ ﺗﺘﺮواح ﺑﯿﻦ )‪ 80-40‬درﺟﮫ ﻣﺌﻮﯾﺔ( وﻗﺪ ﺗﻢ ﻣﺘﺎﺑﻌﺔ اﻟﺘﻔﺎﻋﻞ ﺑﺘﺤﺪﯾﺪ ﻧﺴﺒﺔ‬
‫اﻟﻨﯿﺘﺮوﺟﯿﻦ ووﺟﺪ أن أﻓﻀﻞ ﻧﺴﺒﺔ ﻧﯿﺘﺮوﺟﯿﻦ ﺗﻢ اﻟﺤﺼﻮل ﻋﻠﯿﮭﺎ ﻓﻰ اﻟﻈﺮوف اﻟﺘﺎﻟﯿﺔ‪.‬‬

‫ﻋﻨﺪ ﺗﻔﺎﻋﻞ )‪ 12.35‬ﻣﻠﯿﻤﻮل( ﻣﻦ اﻟﻨﺸﺎ اﻟﻤﺤﻮر ﻣﻊ )‪ 18.5‬ﻣﻠﯿﻤﻮل( ﻣﻦ‬

‫اﻟﻜﻮات‪ 188-‬ﻋﻨﺪ )‪ 70‬درﺟﮫ ﻣﺌﻮﯾﺔ( وﻟﻤﺪه )‪ 180‬دﻗﯿﻘﺔ( ﻓﻰ وﺟﻮد )‪ 23‬ﻣﻠﯿﻤﻮل(‬
‫ﻣﻦ ھﯿﺪروﻛﺴﯿﺪ اﻟﺼﻮدﯾﻮم ﺑﺎﻟﻄﺮﯾﻘﮫ ﺷﺒﮫ اﻟﺠﺎﻓﮫ ﺑﺎﺳﺘﺨﺪام ﻣﺤﻠﻮل ﻣﺨﻠﻮط ﻣﻦ اﻟﻤﺎء‬
‫واﻟﻜﺤﻮل اﻻﯾﺰوﺑﺮوﺑﯿﻠﻰ ﺑﻨﺴﺒﮫ )‪ (3:2‬ﻋﻠﻤﺎً ان اﻟﻨﺴﺒﮫ ﺑﯿﻦ اﻟﻨﺸﺎ اﻟﻤﺤﻮر اﻟﻰ‬
‫اﻟﻜﻮات‪ 188-‬ھﻰ )‪ (1.5:1‬ﺑﯿﻨﻤﺎ اﻟﻨﺴﺒﮫ ﺑﯿﻦ اﻟﻜﻮات‪ 188-‬اﻟﻰ اﻟﺼﻮدﯾﻮم‬
‫ھﯿﺪروﻛﺴﯿﺪ ھﻰ )‪.(1.25:1‬‬

‫‪ -2‬اﻟﺘﻄﺒﯿﻖ اﻟﺼﻨﺎﻋﻰ ﻟﻠﻨﺸﺎ اﻟﻤﺤﻮر ﺑﺎﺳﺘﺨﺪام اﻻﻣﯿﻦ اﻟﺮﺑﺎﻋﻰ اﻟﻨﺸﻂ )اﻟﻜﻮات‪.(188-‬‬

‫ﺗﻢ ﺗﻮﺻﯿﻒ اﻟﺒﻮﻟﯿﻤﺮ اﻟﻨﺎﺗﺞ ﺑﺎﺳﺘﺨﺪام ﻣﻮﺟﺎت اﻻﺷﻌﮫ ﺗﺤﺖ اﻟﺤﻤﺮاء وﻛﺬﻟﻚ‬
‫اﻟﻤﯿﻜﺮوﺳﻜﻮب اﻻﻟﻜﺘﺮوﻧﻰ وﺗﻢ اﻟﺘﻄﺒﯿﻖ ﻟﮭﺬا اﻟﺒﻮﻟﯿﻤﺮ اﻟﻨﺎﺗﺞ ﻛﻤﺎدة ﺗﺠﻤﯿﻊ وﻓﻰ‬
‫ﻣﺠﺎل ﺗﺒﻮﯾﺶ وﺗﺠﮭﯿﺰ اﻟﺨﯿﻮط اﻟﻨﺴﺠﯿﺔ‪.‬‬

‫)‪!!Egypt. J. Chem. 52, No. 1 (2009‬‬

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