International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:12 No:06
137
A Study of Physico-Chemical Properties, Exhaust
Dyeing of Cotton with Synthesized azo-reactive Dyes
and Their Printing Applications
B. Ahmad1*, I. A. Bhatti1, H. N. Bhatti1, M. Abbas2
1.
Department of Chemistry & Biochemistry, University of Agriculture, Faisalabad.
2. Haaris Dyes and Chemicals Pvt. Ltd. Faisalabad.
*
[email protected]
Abstract-- Three sulfatoethylsulfone reactive dyes have been
synthesized and were applied to mill desized, bleached and
mercerized cotton fabric. Effect of different dyeing parameters
i.e. salt concentration, dyeing time, dyeing temperature and pH
of dye solution were being optimized by exhaust dyeing method.
The fixation (%F) of the synthesized dye molecules with the
cotton fabrics was also studied. Cotton fabric was printed with
the three synthesized dyes by printing paste formulation with
sodium alginate as a thickening agent. Dyed and printed cotton
fabrics exhibited excellent to good fastness results.
Index Term--
Vinylsulfone, Pad-thermosol dyeing, Reactive
dye, Printing, Color strength, Fastness.
I.
INTRODUCTION
In case of dyeing of cotton with reactive dyes, dyes forms
linkage with hydroxyl group of the fiber by either substitution
or addition reactions to make covalent linkages. These
physically powerful covalent bonds would be supposed to lead
to excellent wash fatness results. For reaction with cellulosic
fibers, reactive dyes rely on an elevated pH and big amounts
of electrolytes to prevail over the repulsion between cotton
and reactive dyes to support dyeability. During dyeing
application, dye absorption on the fabric and dye hydrolysis
may occur. The application of reactive dyes to cellulosic fibers
considers costly in terms of dye wasted, and due to the use of
electrolyte and alkali. This results in an increase of
environmental pollution [1].
The major setback is dye hydrolysis/ the reaction of
dye with water by blocking the reactive sites, so the dye
cannot build covalent bond with fibers which then results in
the depletion of dye. Hydrolysis of dye by water is fast at
elevated pH values. Attention has focused on the introduction

of different groups by means of pretreatment of fabric which
results in the increase of dye uptake and dye fixation ratio [2].
Advancements has been prepared in lowering salt 
prerequisites for a few newly synthesized reactive dyes, but

salt concentrations are still at high rates [3].
Exhaustive dyeing of cellulosic fibers with reactive
dyes usually needs the existence of electrolyte (NaCl or
Na2SO4), which restrains negative charge formation at the
fabric surface and endorses rate of dye uptake and fixation
rate. Amount of electrolyte present can vary depending on the
depth of obligatory color, dyeing method and the structure of
the dye used.
Textile printing with cellulosic fiber is an imperative way of
decoration with reactive dyes. For textiles printing by means
of reactive dyes, sodium alginates or combination with
polysaccharides are frequently employed as thickening agent,
but in case of viscose or bi-functional reactive dyes, a reaction
takes place among thickening agents and dyes which may
results in improper printing results on fabrics [4]. Sodium
alginate holds hydroxyl groups however the reaction among
alginate and reactive dye can be restricted by common anionic
repulsion of the alginate’s carboxyl groups and the reactive
dye’s vinylsulfonic groups [5]. Different synthetic thickeners
i.e. polyacrylic acids and polymaleic acids can also be used as
substitute to avoid such problems as they do not respond to
reactive dyes. Printing experiments with the help of natural
thickeners have revealed that unusual additives can avoid
rigidity of fabrics [6].
The aim of this research is to optimize dyeing
parameters for exhaust dyeing and to achieve reasonable
fastness applications with newly synthesized vinylsulfone
reactive dyes. In the printing studies with reactive dyes,
environmental-friendly thickening agent was used to permit
fine value printing and to reduce water pollution [6-7].
II.
MATERIALS AND METHOD
A. Materials
Pre-treated cotton fabric was procured from NoorFatima Textile Pvt. Ltd., Faisalabad. The fabric was bleached,
scoured and mercerized before dyeing. All the solvents and
chemicals utilized in the research work were of laboratory
reagent ranking and used with no further purification.
B.
Equipments
For color measurement; Datacolor FS 600 spectrophotometer
with software;
UV/ Vis. Spectrophotometer (CE- 7200) for measurement of
absorbance;
Lab- scale pH meter;
Crock-meter for testing rubbing fastness;
Launder-o-meter for washing fastness;

Fado-meter with xenon arc lamp for light fastness;
C. Dye Synthesis
Synthesis of polyfunctional vinylsulfone based
reactive dye B-1 was conceded out by preliminary preparation
of the H-acid (1- amino- 8- hydroxynapthalene- 3, 6 –
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International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:12 No:06
disulfonic acid) coupling component according to the standard
procedure. One mole of cyanuric chloride (2,4,6 -trichloro- 1,
3, 5- triazine) was condensation with three moles of H-acid in
three subsequent condensation reactions. The condensation
mixture was afterward coupled by means of the diazonium salt
aqueous solution of vinylsulfone para-ester (VSPE)
intermediate. The coupling reaction between condensed
product and diazotized salt solution was completed at pH 6.5
with the pattern of the desired Vinyl sulfone reactive dye B-1.
This dye was afterward filtered and dried out in a vacuum
oven at 70- 80 0C. Reactive dyes B-2 and B-3 were further
synthesized by using J- acid (6- amino- 1- naphthol- 3 –
sulfonic acid) and γ- acid (6- amino- 1 naphthol- 4- sulfonic
acid) respectively. In dye’s chemical structures, the substituent
X and Z are being explained in table I.
Z
N
NH
N
N
X
X
NH
N
N
X
X
OH
N
N
N
Chemical Structure for Dye B3
D. Optimization of dyeing conditions
Z
OH
NH
N
N
OH
NH
N
X
Z
Z
N
OH
N
Z
Chemical Structure for Dye B2
X
N
Z
X
N
NH
X
Z
N
N
N
X
HN
N
NH
OH
Z
Chemical Structure for Dye B1
X
N
N
X
N
X
HN
Z
N
N
N
N
NH
N
OH
OH
OH
OH
138
To find out the optimum conditions of dyeing of pretreated (bleached, scoured and mercerized) cotton fabric, the
electrolyte concentration, dyeing time, pH, and dyeing
temperature were fluctuated accordingly. Sixteen dye baths,
considering a group of three for each variable were practiced.
Four dye baths were prepared with pH 7, 9, 10 and
11 on the basis of weight of cotton fabric (3g) and 1% dye
solution. The fabric was then dyed at selected pH values
keeping rest of conditions at constant i.e. 5g salt (NaCl), 30
minutes dyeing time, and 90 0C dyeing temperature. Another
group of four dye baths each was containing 4, 6, 8, 10 g
sodium chloride (NaCl) as an electrolyte was prepared. Four
dye baths, each containing the 1% dye concentration were
prepared for varying dyeing time such as 40, 50, 60 and 70
minutes. Similarly a set of four dye baths was prepared and
cotton fabrics were dyed for the selected duration by varying
the temperature i.e. 50, 60, 70 and 80 0C.
The above selected conditions were regarded as the
optimum dyeing conditions for dyeing of mill pre-treated
cotton fabric. Dyeing procedure at selected dyeing conditions
was repeated for three of newly synthesized vinylsulfone
reactive
dyes
B1,
B2,
and
B3
respectively.
E. Exhaustion and fixation studies
For all dyeing of selected conditions, absorbance of
the original as well as the exhausted dye- baths were measured
by means of a UV/ Vis. Spectrophotometer (CE- 7200) at λmax
with 1cm quartz cells for all dyes. Percentage of dye
exhaustion (%E) was estimated with the given equation [8].
%E = [1- (C2/ C1] × 100
Where C1 and C2 are the quantities of the dye bath before and
after dyeing process, respectively.
Unsettled/ unfixed dye commencing onto the cotton
fabrics was extracted further by means of 25% pyridine-water
solution and afterward was measured spectrophotometrically
[9].
F. Fastness properties
The mill pre-treated and dyed cotton fabric samples
were sponged down twice with warm water at 70- 80 0C for 45 minutes, then under tap water and finally were dried in dry
cleaner (SDL- ATLAS) [10]. Fastness tests were employed as
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International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:12 No:06
follows: colorfastness to crocking (ISO 105- X12),
colorfastness to light (ISO 105- B02), colorfastness to
washing (ISO 105- CO3), colorfastness to perspiration (ISO
105- E04), colorfastness to chlorinated water (ISO 105- E03),
colorfastness to dry cleaning (ISO 105- D01) were also
performed according to the standard methods specified by
American Association of Textile Chemists and Colorists and
International Organization for Standardization (AATCC &
ISO).
G. Printing paste preparation and printing procedure
Printing paste was prepared by mixing biopolymer/
thickener 3% (Sodium Alginate), 8% Urea as well as 6%
NaHCO3. To the printing paste 3% w/w synthesized dye was
added. The viscosity of the print paste mixture was determined
by Viscometer. Spindle number 6 and 20 rpm: the viscosity
was fine-tuned to 2300 cps by adjoining the thickener.
Printing was carried out using laboratory scale printing
machine (Mini- MDF 702) for each of three newly
synthesized dyes i.e. B1, B2 and B3 respectively. The prints
were steamed, washed off twice with warm water, further
rinsed well in tap water to remove unfixed dyes/ thickener and
consented to dry in open air. Color strength (%) and different
fastness tests were also been employed on the prints obtained
by three synthesized dyes [4] [1].
III.
RESULTS AND D ISCUSSIONS
A series of three vinylsulfone reactive dyes were
prepared with H-acid (1- amino- 8- hydroxynapthalene- 3, 6 –
disulfonic acid) J- acid (6- amino- 1- naphthol- 3 – sulfonic
acid) and γ- acid (6- amino- 1 naphthol- 4- sulfonic acid)
respectively through a series of condensation, diazotization
and coupling reactions.
A. Optimization of dyeing conditions
The relative % fixation and exhaustion values of the
synthesized reactive dyes B1, B2 and B3 obtained at different
optimized conditions are given in Fig. 1, 2 and 3 respectively.
The outcome of dyeing temperature on the
exhaustion (%E) as well as fixation (%F) for dye B1 is given
in Fig. 1. It is clearly shown that the exhaustion (%E) values
increased with increase in dyeing temperature for up to 80 0C.
This phenomenon can be attributed to improved solubility of
color component at higher temperatures. Same increasing
trend with dyeing temperature can also be observed with dyes
B2 and B3 in Figs. 2 and 3 respectively. The increases in the
fixation (%F) values for dyes are due to better dye uptake at
higher temperatures. For reactive dyes, due to stumpy
migrating control, cautious management of dye exhaustion as
a result of temperature is stipulated [9].
Effect of dyeing time resting on the exhaustion (%E)
and fixation (%F) values for three of synthesized reactive dyes
can be observed with an increasing trend with increase in
dyeing time and reaches maximum value up to 70 min. The
exhaustion values ranges from 68% to 85% as shown in the
graphs. A further increase in dyeing time may result in
decrease in exhaustion value. This may be attributed to
139
decomposition of coloring component at longer times [11].
The longer the dyeing time, the higher is the exhaustion values
until dye exhaustion attains equilibrium and there is slight
decrease in the exhaustion value after further increase in time
over
70min.
The exhaustion (%E) and fixation (%F) values found
whilst different salt concentrations used for exhaustion and
fixation studies are shown in Fig. 1, 2 and 3 respectively.
Effect of salt on the dye exhaustion and fixation rate can be
observed with an increase of salt concentration [12]. This can
be attributed of negative charge of cotton by sodium ions in
the dye bath. Maximum fixation efficiency was obtained 10g
of salt i.e. 79% in case of dye B1 which is shown in Fig.1.
The best exhaustion value is obtained at pH 10 i.e.
86% for dye B2. The outcome of dye bath’s pH can be traited
to the correlation among dye structure plus cotton. On higher
pH, this could develop H-bond with cellulosic- hydroxyl
groups of cotton fabric [9]. But further rise in pH made the
dye and fabric further anionic which repelled each other and
caused lesser dyeability on elevated pH. The fixation (%F)
values obtained for the reactive dyes on cotton fibers boosted
by decreasing pH of application. In addition to this, at low pH,
the vinyl sulfone reactive dye is ubiquitous only at low
concentration in the dye-bath [13].
B. Colorfastness
Light fastness of every synthesized azo-reactive dyes
rating 4-5 for the mill pre-treated dyed cotton fabrics which
illustrated fastness results are moderate to very good.
Colorfastness to crocking rating 3-5 for dyed cotton fabrics
which demonstrated good to excellent results for all the dyes.
The light and washing fastness of the reactive dyes rating 4-5
which demonstrated good to excellent results. Results
obtained for colorfastness to perspiration and colorfastness to
chlorinated water were satisfactory i.e. 3-4. Fastness to dry
cleaning ranging 3-5 for the dyes demonstrated good to
excellent results for the cotton dyed with three reactive dyes
[14].
C. Printing results
The color strength (%) results of the prints obtained
by three synthesized reactive dyes with a specified printing
paste are shown in Fig. 4. It is associated to the shift rate of
the printing mixture on the cotton and the selected thickener
i.e. sodium alginate. Dye B2 showed satisfied printing quality
and color strength value i.e. 84%. Reactive dye printing also
illustrated some additional reactions among the dye and the
hydroxyl groups of water and the crosslinking of the thickener
used [15]. Printed cotton fabrics showed good fastness
properties which were measured by grey scale.
IV.
CONCLUSIONS
Synthesis of the three vinylsulfone based reactive
dyes i.e. B1, B2 and B3 were carried out by subsequent
condensations which followed by diazotization- coupling
route with H-acid (1- amino- 8- hydroxynapthalene- 3, 6 –
disulfonic acid), J- acid (6- amino- 1- naphthol- 3 – sulfonic
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International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:12 No:06
acid) and γ- acid (6- amino- 1 naphthol- 4- sulfonic acid)
respectively. Exhaustion and fixation applications of these
reactive dyes were carried out with pre-treated (bleached,
scoured and mercerized) cotton fabric to optimize dyeing
conditions, which showed good to satisfactory results. This
designated that the dyes have fine attraction and solubility to
the pre-treated cotton fabric. Fastness results obtained by three
of reactive dyes were good to excellent measured by grey
scale. The satisfactory rating of fastness properties could be
referred to the covalent bonding linkages between the dye and
the cotton fiber. Printing was attributed on cotton fabric with
printing paste using sodium alginate as a thickening agent
which showed good fastness properties.
sulphonic acid". Arabian Journal of Chemistry, vol. 4, pp. 279285.
S ostar S, Schneider R. (1999). "A study of fabric stiffness with
guar gum in reactive printing". Dyes and Pigments, Vol. 41, pp.
167-175.
[15]
T ABLE I
Dye #
Z
SO2CH2CH2OSO3Na
SO3Na
B2
SO2CH2CH2OSO3Na
SO3Na
B3
SO2CH2CH2OSO3Na
SO3Na
100
REFERENCES
S.M. Burkinshaw, S.N. Chevli, D.J. Marfell, (2000). "Printing of
nylon 6,6 with reactive dyes part I: preliminary studies". Dyes and
Pigments, Vol. 45, pp. 235-242.
Zolriasatein A.A. (2012). "The application of poly(amidoamine)
dendrimers for modification of jute yarns: Preparation and dyeing
properties". Journal of Saudi Chemical Society, In press.
Ahmed N.S.E. (2005). "The use of sodium edate in the dyeing of
cotton with reactive dyes". Dyes and Pigments, Vol. 65, pp. 221225.
Schneider R, Šostar-Turk S. (2003). "Good quality printing with
reactive dyes using guar gum and biodegradable additives". Dyes
and Pigments, Vol. 57, pp. 7-14.
Perrin Akcakoca Kumbasar E, Bide M. (2000). "Reactive dye
printing with mixed thickeners on viscose". Dyes and Pigments,
Vol. 47, pp. 189-199.
Kampyli, V. (2007). "Triazinyl reactive dyes for the exhaust
dyeing of cotton: Influence of the oxido group on the reactivity of
chloro and m-carboxypyridinium leaving groups". Dyes and
Pigments, Vol. 74, pp. 181-186.
Patel D.R., Patel J.A., Patel K.C. (2009). "Synthesis and evaluation
of a series of symmetrical hot brand bis azo reactive dyes using
4,4′-methylene-bis-metanilic acid on various fibre". Journal of
Saudi Chemical Society, Vol. 13, pp. 279-285.
El-Shishtawy R.M., Nassar S.H., Ahmed N.S.E. (2007). "Anionic
colouration of acrylic fibre. Part II: Printing with reactive, acid and
direct dyes". Dyes and Pigments, Vol. 74, pp. 215-222.
Son, Y.A. (2005). "A study of heterobifunctional reactive dyes on
nylon fibers: dyeing properties, dye moiety analysis and wash
fastness". Dyes and Pigments, Vol. 66, pp. 231-239.
Mokhtari J, Phillips D.A.S., Taylor J.A. (2004). "Synthesis and
evaluation of a series of trisazo, monochloro-s-triazinyl (MCT)
reactive dyes for cotton". Dyes and Pigments, Vol. 63, pp. 51-63.
Ali S, Hussain T, Nawaz R. (2009). "Optimization of alkaline
extraction of natural dye from Henna leaves and its dyeing on
cotton by exhaust method". Journal of Cleaner Production, Vol.
17, pp. 61-66.
Kraska J, Boruszczak Z, Łandwijt B. (1999). "Synthesis and
properties of reactive dyes, derivatives of 3,10-bis(3′aminopropylamino)-6,13-dichlorotriphenodioxazin-4,11disulphonic acid". Dyes and Pigments, Vol. 43, pp. 1-6.
Javaid Mughal M. (2012). "Dye fixation and decolourization of
vinyl sulphone reactive dyes by using dicyanidiamide fixer in the
presence of ferric chloride". Journal of Saudi Chemical Society, In
press.
Patel D.R., Patel K.C. (2011). "Synthesis and characterization of
reactive
dyes
based
on
2-phenyl-3-[4′-(4″aminophenylsulphonamido)]phenyl-4(3H)-quinazolinone-6-
40
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
X
B1
ACKNOWLEDGMENT
The authors are very grateful to Higher Education
Commission (HEC) of Pakistan for financial assistance under
Indigenous PhD 5000 Fellowship Program.
[1]
140
%E and %F values at different salt concentrations for
Dye B1
80
%E
60
%F
20
0
Salt 4g
100
Salt 6g
Salt 8g
Salt 10g
%E and %F values at different dyeing times for Dye
B1
80
%E
60
%F
40
20
0
40min
100
80
60
40
20
0
50min
60min
70min
%E and %F values at different dyeing temperatures for
Dye B1
%E
%F
Temp.
50C
Temp.
60C
Temp.
70C
Temp.
80C
%E and %F values at different pH for Dye B1
100
80
60
40
20
0
%E
%F
PH 7
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PH 9
PH 10
pH 11
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International Journal of Basic & Applied Sciences IJBAS-IJENS Vol:12 No:06
Fig. 1. Exhaustion (%E) and fixation (%F) values at different dyeing
parameters for dye B1.
%E and %F values at different salt concentrations
for Dye B2
141
%E and %F values at different salt concentrations for
Dye B3
100
100
80
80
60
60
40
%E
40
%F
20
%E
%F
0
20
Salt 4g
0
Salt 4g
Salt 6g
Salt 8g
Salt 6g
Salt 8g
Salt 10g
%E and %F values at different dyeing times for Dye
B3
Salt 10g
100
%E and %F values at different dyeing times for Dye
B2
80
100
%E
60
80
%E
60
%F
40
%F
40
20
0
40min
20
50min
60min
70min
0
40min
100
50min
60min
70min
%E and %F values at different dyeing temperatures for
Dye B3
%E and %F values at different dyeing temperatures
for Dye B2
100
80
80
60
%E
%F
60
%E
40
40
%F
20
20
0
0
Temp.
50C
Temp.
60C
Temp.
70C
Temp.
50C
Temp.
80C
100
100
80
80
%E
%F
40
Temp.
70C
Temp.
80C
%E and %F values at different pH for Dye B3
%E and %F values at different pH for Dye B2
60
Temp.
60C
20
%E
60
%F
40
20
0
PH 7
PH 9
PH 10
0
pH 11
Fig. 2. Exhaustion (%E) and fixation (%F) values at different dyeing
parameters for dye B2.
PH 7
PH 9
PH 10
pH 11
Fig. 3. Exhaustion (%E) and fixation (%F) values at different dyeing
parameters for dye B3.
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142
Printing Results with three reactive dyes
90
80
60
50
40
30
Color strength (%)
70
20
10
0
B1
B2
B3
Dyes
Fig. 4. Printing results with three synthesized reactive dyes.
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