Synthesis and evaluation of technical properties of novel cationic mono-s-chloro triazinyl (MCT) reactive dyes on cotton

Article abstract of DOI:10.1002/jccs.201100516

Two novel cationic mono-s-chloro triazinyl (MCT) reactive dyes together with their analogues were synthesized via reacting an N,N-dimethyl dodecylamine with p-nitrobenzyl bromide. The resultant was reduced using stannous chloride and hydrochloric acid to produce the primary amine. The quaternary ammonium salt containing primary amine was then diazotized and coupled to H-acid/J-acid reacted with cyanuric chloride and sulfanilic acid. The analogue dyes were prepared via the same route without quaternary ammonium salt making stage. The dyes were characterized using FTIR, ¹H NMR, UV-Vis spectroscopy and elemental analysis. The substantivity, exhaustion and fixation of the dyes were investigated on cotton fabric. It was found that these functional dyes could be effectively introduced to cotton for achieving simultaneous coloration and functional finishing effects. All the dyed fabrics exhibited softening efficacy. The washing and light fastness of the dyed samples were further studied.

Full text of DOI:10.1002/jccs.201100516

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Article
Synthesis and Evaluation of Technical Properties of Novel Cationic Mono-s-chloro
Triazinyl (MCT) Reactive Dyes on Cotton
Marzieh S. Javadi and Javad Mokhtari*
Department of Textile Engineering, Faculty of Engineering, University of Guilan, P. O. Box 3756, Rasht, Iran
(Received: Aug. 26, 2011; Accepted: Dec. 16, 2011; Published Online: Mar. 26, 2012; DOI: 10.1002/jccs.201100516)
Two novel cationic mono-s-chloro triazinyl (MCT) reactive dyes together with their analogues were syn-
thesized via reacting an N,N-dimethyl dodecylamine with p-nitrobenzyl bromide. The resultant was re-
duced using stannous chloride and hydrochloric acid to produce the primary amine. The quaternary am-
monium salt containing primary amine was then diazotized and coupled to H-acid/J-acid reacted with
cyanuric chloride and sulfanilic acid. The analogue dyes were prepared via the same route without quater-
nary ammonium salt making stage. The dyes were characterized using FTIR, 1H NMR, UV-Vis spectros-
copy and elemental analysis. The substantivity, exhaustion and fixation of the dyes were investigated on
cotton fabric. It was found that these functional dyes could be effectively introduced to cotton for achiev-
ing simultaneous coloration and functional finishing effects. All the dyed fabrics exhibited softening effi-
cacy. The washing and light fastness of the dyed samples were further studied.
Keywords: Cationic reactive dye; Dyeing; Quaternary ammonium group.
INTRODUCTION
In recent years, the most prominent developments in
textiles.9 Although high solubility enables dyes to more
readily form positive ions in aqueous solution, thereby in-
hibiting bacterial growth by adsorbing onto bacterial sur-
faces.4
dye chemistry and application have been announced in the
field of functional dyes.1-6 They are important class of the
synthesis colouring materials and have attracted much at-
tention due to their potential functions for specialty and
high-technology applications.
Several disperse dyes possessing quaternary ammo-
nium salts have been synthesized.4,6 However, less work
has been done in the field of soluble dyes such as reactive
dyes. In this paper, the main goal is to design a reactive dye
combined with a quaternary ammonium to benefit the de-
sired properties of both reactive dye and quaternary ammo-
nium moiety. For this purpose, two novel reactive dyes
containing quaternary ammonium moiety (Scheme I) are
Reactive dyes are attached to suitable fibres via cova-
lent bond. They are known for their bright colours and very
good to excellent light and wash fastnesses; however, their
resistance to chlorine bleach is poor.7 Several broad classes
of reactive dyes are available. Most of them are intended
for cellulosic fibres. There are two classes of chromo-
phores for reactive dyes, namely anthraquinone and azo.
Azo dyes and pigments constitute by far the most important
chemical class of commercial organic colorant. They ac-
count for around 60-70% of the dyes used in traditional tex-
tile applications.8
1
synthesized. The dyes are characterized using FTIR, H
NMR, melting point and UV/visible spectrophotometer.
The technical properties of the dyes are also studied via ex-
amining mechanical properties (Tear Strength, Abrasion
Resistance, Flexibility, and Crease recovery angle tests) of
the dyed substrates.
Quaternary ammonium salt (QAS) is one of the major
components of cationic surfactant. These compounds are
widely used as disinfectants due to having a positively
charged quaternary nitrogen. They inflict on microbes via a
variety of detrimental effects, including damage to cell
membranes, denaturation of proteins and disruption of the
cell structure.6 During inactivation of bacterial cells, the
quaternary ammonium group remains intact and retains its
antibacterial ability as long as the compound is attached to
EXPERIMENTAL
Instrumental and analysis methods
The UV/Vis absorption spectra of dyes (in water)
were recorded using a Cintra 10 UV/visible spectropho-
tometer (GBC Co., Australia).
Thin layer chromatography (TLC) was used for mon-
itoring reactions. This technique was performed using alu-
minium plates coated with silica gel 60 F254 (Merck) as
* Corresponding author. E-mail: j.mokhtari@guilan.ac.ir
J. Chin. Chem. Soc. 2012, 59, 793-801
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2,4,6-trichloro-s-triazine (2.43 g, 0.013 mol) was dissolved
in acetone (15 mL). The solution was then added dropwise
to a mixture of crushed ice (40 g) and water (40 mL) to pre-
pare a fresh suspension of 2,4,6-trichloro-s-triazine. To the
resulting suspension, an aqueous solution of H-acid (0.01
mol in 40 mL water) was added very slowly at below 5 °C,
pH 3-4. The reaction was continued for 2 h with stirring
and completion of the reaction was determined with the aid
of Ehrlich’s reagent and TLC. The synthesis route is shown
in Scheme II.
Scheme I Structures of dyes
Scheme II Synthesis route for compounds 1 and 2
stationary phase and a mobile phase consisting of n-bu-
tanol: acetone: water (2:2:1). The developed plates were vi-
sualized under both short and long wavelength ultraviolet
light (254 nm, 365 nm).
Synthesis of compound 2
Sulfanilic acid (0.011 mol) was dissolved in water
(30 mL) at pH 7. The solution was then added very slowly
to the reaction mixture prepared in previous section at
40-45 °C and pH 5-6. The mixture was stirred for 2 h and
completion of the reaction was determined with the aid of
Ehrlich’s reagent and TLC. The synthesis route is shown in
Scheme II (Yield 94%, black in colour).
The FTIR spectra of dyes were determined on a
Nicolet magna-ir 560 infrared spectrometer (USA) using
KBr pellets.
1
The H NMR spectra of dyes were recorded on a
Bruker AVANCE-500 MHZ (USA) spectrometer.
The melting points of the products were determined
via capillary method using a Barnstead electrothermal
9200 (UK).
Synthesis of compound 3
Compound 3 was synthesized according to ref 4. 4-ni-
tro benzyl bromide (0.0092 mol) was dissolved in acetone
(20 mL) in a two-neck flask. A mixture of SnCl2/2H2O
(0.0324 mol) and concentrated hydrochloric acid (36%,
0.14 mol) was added dropwise to the flask at room temper-
ature. The whole mixture was allowed to react at 45-50 °C
for 12 h. The pH was adjusted to 8-10 with sodium hydrox-
ide aqueous solution (10%). The mixture was filtered to re-
move impurities. The filtrate was then evaporated under
vacuum to obtain product. The synthesis route is shown in
Scheme III (Yield 92%, yellow in colour).
Elemental analyses for carbon, hydrogen and nitro-
gen were carried out at the Department of Chemistry,
Guilan University, on a Carlo Erba 1108 elemental ana-
lyser.
Synthesis of intermediates and dyes
Materials
P-nitrobenzyl bromide, N,N-dimethyl dodecylamine,
cyanuric chloride, H-acid (92%), J-acid (90%), sulfanilic
acid, sodium nitrite,stannous chloride and hydrochloric
acid (36%) were all obtained from Aldrich Co. and used as
received.
Synthesis of dye 1
Compound 3 (0.0085 mol) was dissolved in concen-
trated hydrochloric acid (36%, 0.1238 mol) and water (15
mL) at 0-5 °C. An aqueous solution of sodium nitrite (30%,
Synthesis of compound 1
Compound 1 was synthesized according to ref10.
794
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JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Novel Cationic MCT Reactive Dyes for Cotton
Scheme III Synthesis route for dyes 1 and 2
Synthesis route for compounds 6, 7 and
Scheme V
dyes 3, 4
0.009 mol) was added to the solution dropwise to prepare
diazonium salt. The reaction was continued for 2 h to com-
pletion, which was controlled by TLC.
in colour).
Synthesis of dye 3
Sodium nitrite (0.018 mol) was dissolved in concen-
Compound 2 (0.0094 mol) was dissolved in water
(100 mL) with stirring at 5-10 °C and pH 7-8. To the solu-
tion, the prepared diazonium salt was then added dropwise
to produce the dye. The pH of the reaction mixture was ad-
justed to 7-8 by dropwise addition of aqueous sodium hy-
droxide solution (10%) and the reaction was continued at
the same temperature for 3-5 h to completion, which was
controlled by TLC and reacting the mixture with b-naph-
thol. The product was salted out with sodium chloride, fil-
trated and dried. The residue was dissolved in acetone and
indiscerptible salt was filtrated off. Finally, the filtrate was
evaporated under vacuum to obtain the product. The syn-
thesis route is shown in Scheme III (Yield 70%, violet in
colour).
trated sulfuric acid (0.225 mol) at 5-15 °C. Compound 7
(0.0075 mol) was added dropwise to the solution with stir-
ring. The pH was adjusted to 4 by dropwise addition of ace-
tic acid (0.122 mol). The diazotisation was completed over
2 h. Compound 2 (0.0094 mol) as coupling component was
dissolved in water (100 mL) with stirring. The prepared
diazonium salt solution was then added dropwise to the
coupling component solution. The pH was adjusted to 7-8
by dropwise addition of aqueous sodium hydroxide solu-
tion and the reaction was continued at 5-10 °C for 3-5 h.
The product was salted out with sodium chloride, filtrated
off and dried. The obtained residue was dissolved in ace-
tone; the indiscreptible salt was filtrated off. Finally, the fil-
trate was evaporated under vacuum to obtain the product.
The synthesis route is shown in Scheme V (Yield 71%, ma-
roon in colour).
Synthesis of dye 2
By following the procedures for dye 1, dye 2 was pre-
pared using J-acid instead of H-acid (Scheme IV). J-acid
was reacted with cyanuric chloride and then followed re-
acting with sulfanilic acid according to ref 11. The synthesis
route is shown in Scheme IV (Yield 73%, red in colour).
Synthesis of dye 4
Dye 4 was prepared in the same procedures of dye 3
using J-acid instead of H-acid. The synthesis route is
shown in Scheme V (Yield 73%, orange in colour).
Characterisation of compounds and dyes
Scheme VI Synthesis route for compounds 4 and 5
In order to characterise the compound and the dyes,
they were submitted to UV-Vis spectroscopy, melting point
determination, FT IR and 1H NMR spectroscopy and ele-
mental analysis.
By UV-Vis spectroscopy, wavelength of maximum
absorption (lmax) and molar absorptivity coefficients
(emax) of the dyes were determined using beer-lambert law
eq. (1).
Synthesis of compound 6
Compound 6 was synthesized according to ref 4. The
A = elC
(1)
synthesis route is shown in Scheme V.
where A is absorbance, e is molar absorptivity coefficient
and C is concentarion in mol/l, l is pass length of cell (1
cm).
Synthesis of compound 7
Compound 7 was synthesized according to ref 4. The
synthesis route is shown in Scheme V. (Yield 84%, yellow
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Solutions of the four novel dyes, achieved in distilled
Colour strength (K/S) of dyes on fabric
Reflectance measurements on the dry dyed fabrics
were carried out using a Data colour Spectra Texflash
specrophotometer using D65 illumination; the dyed fiber
was folded twice so as to provide four layers and the aver-
age of three reflectance measurements, taken at different
positions, was used.
water, were prepared in the concentration range 0.01-0.03
g/l and the absorbance of each solution was measured at the
lmax of the dye using 1 cm cells and a Cintra 10 spectro-
photometer. The molar absorptivity coefficients (emax) of
the dyes were determined and are shown in Table 1.
The synthesised compound s and dyes were subjected
to melting point determination. The results are shown in
Table 1.
Measurement of the SER5F profiles of dyes
The SER5F (S, substantivity; E, exhaustion; R5, reac-
tivity after 5 min; and F, fixation) profiles of the dyes were
determined according to refs 11-13. The SER5F profiles of
the dyes were compared at the same depth of shade (1%
o.m.f). Most of researchers14 suggested that the use of urea
can make dyeing faster. Therefore, the effect of urea on the
dye adsorption was evaluated in this test.
FT IR and 1H NMR data and elemental analysis reults
for compounds 2, 3 and 7 and dyes 1-4 are shown in Tables
2 and 3, respectively.
Dyeing
Plain woven cotton fabric (138.8 g/m2) was pur-
chased from domestic producer. The fabric were scoured in
a 1% nonionic detergent for 30 min at 50 °C with a liquor to
fabric ratio of 40:1, then rinsed thoroughly in tap water and
dried in the open air. Dyeing were carried out using a
Roaches dyeing machine (Mathis Labomat BFA 12): 5 g
pieces of fabric were dyed at a liquor ratio of 20:1, using
stainless steel dye pots, each of 200 cm3 capacity. The dye-
ing method used is depicted in Fig. 1. At the end of dyeing,
the dyed fabric was removed and rinsed in cold water.
Washing the dyed fabric was performed at liquor ratio of
30:1 with 3 g/l detergent and 2 g/l sodium carbonate at 100
°C for 15 min. An initial series of dyeing was carried out at
four different alkali values using of 5, 10, 15 and 20 g/l by
adding sodium carbonate. No additional electrolyte, level-
ing agent or alkali was used. Having determined the opti-
mum alkali, further experiments were carried out to deter-
mine the optimum salt of dyeing. For this purpose, a series
of dyeing were set off at four different salt values of 10, 20,
30 and 40 g/l by sodium chloride. Subsequent dyeing was
carried out on 1 g pieces of fabric, at four depths of shade
(1, 2, 4 and 6% o.m.f.).
Determination of the migration indices of dyes
Migration refers to the movement of a dye molecule
from one site to another on the textile substrate via a de-
sorption process into the dyebath. By this mean, a uniform
dyeing over the whole of the textile substrate can be
achieved. Because a reactive dye forms a covalent bond
with cellulose under alkaline conditions, migration must
take place primarily during the neutral salting phase in or-
der to achieve a uniform dyeing. This is particularly the
case with high substantivity (S) dyes. Opportunity for mi-
gration after the addition of alkali will be limited. The mi-
gration properties of reactive dyes can be readily estimated
using a simple test, which seeks to define a migration index
(MI) for an individual dye when applied under a given set
of conditions.11,13,15 In order to determine the migration in-
dex, a typical method is described. 4 pieces of plain cotton
and two baths (dye and blank bath) were used. Dye bath
contain dye, salt and water and 2 pieces of fabrics D1 and
D2. Blank bath contain salt and water and 2 pieces of fab-
rics B1 and B2. The two baths were set at 80 °C and exhaus-
tion allowed to proceed for 30 min, thereafter sample D2
from the dye bath was swapped with sample B2 from the
blank bath, excess liquor being squeezed off when carrying
out the transfer. Sample B2 was rolled inside sample D1 be-
fore being returned to the dyebath. In a similar manner,
sample B1 was rolled inside sample D2 before being re-
turned to the blank bath.
The process was continued for 30 min at the same
temperature (to allow migration to occur in the blank bath)
before the alkali was then added. The dyeing was continued
according to the dyeing profile of dyes. The patterns were
then removed, washed and dried. The migration index of a
Fig. 1. Dyeing profile for reactive dyes.
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CHEMICAL SOCIETY
Novel Cationic MCT Reactive Dyes for Cotton
dye can be calculated using eq. (2).
ric, the lower is the flexibility, and vice versa. Therefore,
the inverse of flexural rigidity gives an indication of fabric
flexibility.
MI = (K/S) of fabric B1 *100/ (K/S) of fabric D2 (2)
Fastness testing
G = WC3
(3)
Colour fastness was determined according to the re-
spective international standards: The wash fastness proper-
ties of dyes were assessed using the ISO105-C01:1993(E)
and ISO105-C04:1993(E) wash fastness test. The change
in shade and the degree of cross staining were assessed vi-
sually using grey scales. Light fastness properties of dyes
were assessed using the ISO105-B02:1994(E) light fast-
ness test. The change in shade was assessed visually using
blue scales.
where G represents flexural rigidity, mg/cm; W represents
fabric mass per unit area, mg/cm2; and C represents bend-
ing length, cm.
Crease Recovery Angle
Crease angle measurements were made by AATCC
Standard Test Method 66 using a M003A Shirley Crease
Recovery Tester.
Softening properties
RESULTS AND DISCUSSION
The softening properties of the functional group in-
corporated in the cationic reactive dyes were evaluated via
examining mechanical properties (Tear Strength, Abrasion
Resistance, Flexibility, and Crease recovery angle tests) of
the dyed substrates using the following method:
The samples were divided into two sections: 1. The
samples which only dyed with novel dyes in different con-
centration; 2) The samples were dyed with dyes 1 and 2
then finishing with cationic softener (Celloube CM). For
finishing, the dyed fabric was padded in softener solution
(10 g/l) with pick up 70% and dried at 100 °C. Then, soft-
ener properties were evaluated by means of Tear Strength,
Abrasion Resistance, Flexibility, and Crease recovery an-
gle tests.
Structure characterization
UV-Vis spectra of the dyes were determined in the
aqueous solution. The corresponding lmax and molar ab-
sorptivity coefficient (emax) were summarized in Table 1.
Data in Table 1 show that the presence of H-acid in dyes 1
and 3 related to J-acid in dyes 2 and 4 caused a bathochro-
mic effect (36-40 nm) in dyes 1 and 3. This could be due to
an extra sulphonic acid present on the dayes containg H-
acid.16
It was found that alkyl chain did significantly affect
the lmax in all of the dyes. Quaternary ammonium group
present on the dye structures is more powerfully electron-
withdrawing and attracted electron as chromophore and led
to hypsochromic shift in dyes 3 and 4 in compared with
dyes 1 and 2, respectively. Absorption of dyes 3 and 4 was
decreased due to having alkyl chain. Steric hindrance may
be an important factor. Usually, emax is a widely accepted
measurement of tinctorial strength. However, assessing the
tinctorial strength of dyes is quite difficult and, in some
cases, controversial results could be obtained. As a general
rule, steric hindrance always causes a reduction in tinctorial
Tear Strength
The control and dyed fabrics were tested for tear
strength in the warp direction using a MICRO 250 (Shirley,
UK) tensile tester according to ASTM D 2261. A gauge
length of 3 in. and a crosshead speed of 2 in/min were used
for testing. Five samples were tested for each condition,
and the average of the readings was calculated.
Abrasion Resistance
Abrasion resistance was measured in terms of the
number of abrasion cycles required for failure with a 1 lb
load on a MARTINDALE 2000 Abrasion tester according
to ASTM D 3886. Five specimens were tested, and the av-
erage reduction of fabric mass of the sample is reported.
Flexibility
Table 1. The characteristics of compounds and dyes
lmax
emax
(dm3mol-1cm-1)
Sample Name
Mp (°C)
(nm)
Compound 2 Decompose at 250
Compound 3 Decompose at 274
Compound 7 Decompose at 286
-
-
-
-
-
-
Bending lengths of the samples were measured using
SDL003 Shirley stiffness tester. Fabric flexibility was mea-
sured in terms of flexural rigidity according to ASTM D
1388 using eq. (3). The higher the flexural rigidity of a fab-
Dye 1
Dye 2
Dye 3
Dye 4
Decompose at 385
Decompose at 381
Decompose at 400
Decompose at 400
552
512
536
500
25620
21767
22931
20019
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Table 2. FTIR, 1H NMR and elemental analysis of compounds
Table 3. The FTIR, 1H NMR and Elemental Analysis of dyes
Compound
FTIR, 1H MNR and Elemental Analysis
Dye
FTIR, 1H MNR and Elemental Analysis
FTIR (KBr, í, cm-1): 3444 (-OH); 1407 (C-N); 1039
(C-Cl); 1189 (S=O Stretching). 1H NMR (500 MHz,
D2O, d, ppm): 1.8-2.7 (3 singlet, 3H, -SO3H), 2.85
(singlet, 1H, benzene C-NH), 3.27 (singlet, 1H,
naphthalene C-NH), 4.6 (singlet, 1H, aromatic C-
OH), 6.5-8 (broad peak, 4H, 1-naphthalene), 8-8.5
(complex, 4H, 1-benzene). Anal Calcd for
FTIR (KBr, í, cm-1): 3442 (-OH); 1622 (N=N); 1043 (C-
Cl). 1H NMR (500 MHz, D2O, ä, ppm): 1.9 (singlet, 3H,
-SO3H); 4.1 (singlet, 2H, aromatic C-NH); 4.68 (singlet,
2H, CH2Br); 5.1 (singlet, 1H, aromatic C-OH); 7-9
(complex, 11H, aromatic ring). Anal Calcd for
1
2
C26H16BrClN7Na3O10S3: C, 36.02%; H, 1.86%; N,
11.31%; found: C, 36.07%; H, 1.9%; N, 11.26%.
C19H14ClN5O10S3: C, 37.78%; H, 2.34%; N, 11.60%;
found: C, 37.2%; H, 2.86%; N, 11.78%.
FTIR (KBr, cm-1): 3446 (-OH); 1618 (N=N); 1042 (C-Cl).
1H NMR (500 MHz, D2O, ä): 1.9 (singlet, 2H, -SO3H);
4.1 (singlet, 2H, aromatic C-NH); 4.6 (singlet, 2H,
CH2Br); 5.2 (singlet, 1H, aromatic C-OH); 7-8.4
(complex, 12H, aromatic ring). Anal Calcd for
C26H17BrClN7Na2O7S2: C, 40.83%; H, 2.24%; N, 12.82%;
found: C, 41.02%; H, 2.31%; N, 12.75%.
FTIR (KBr, í, cm-1): 3420, 1629 (-NH2). 1H NMR
(500 MHz, D2O, d, ppm): 3.9 (singlet, 2H, -NH2),
4.62 (singlet, 2H, -CH2Br), 6.3-7.1 (complex, 4H,
benzene). Anal Calcd for C7H8N: C, 45.19%; H,
4.33%; N, 7.53%; found: C, 44.56%; H, 4.38%; N,
7.40%.
2
3
FTIR (KBr, í, cm-1): 3453 (-OH); 2923, 2853
FTIR (KBr, í, cm-1): 3408 (-NH2); 2922, 2851
(-CH2(CH2)10CH3). 1H NMR (500 MHz, D2O, d,
ppm): 0.8-0.82 (triplet, 3H, -(CH2)11-CH3); 1.2
(singlet, 18H, -N+(CH3)2-(CH2)2-(CH2)9-CH3); 1.5
(complex, 2H, -N+(CH3)2-CH2-CH2-C10H21); 1.8
(triplet, 2H, -N+(CH3)2-CH2-C11H23); 2.7 (singlet,
6H, -N+(CH3)2-C12H25); 3.9 (singlet, 2H, aromatic C-
NH2); 4.3 (singlet, 2H, -CH2-N+(CH3)2-C12H25); 6.5-
7.2 (complex, 4H, 1-benzene). Anal Calcd for
C21H39BrN2: C, 63.14%; H, 9.84%; N, 7.01%; found:
C, 63.59%; H, 10.03%; N, 7.25%.
(CH3(CH2)10 CH2-); 1619 (N=N); 1401 (-N+(CH3)2-);
1041 (C-Cl). 1H-NMR (500 MHz, D2O, ä, ppm): 0.54
(broad peak, 3H, -(CH2)11-CH3); 0.88 (broad peak, 18H,
-N+(CH3)2-(CH2)2-(CH2)9-CH3); 1.2 (broad peak, 2H,
-N+(CH3)2-CH2-CH2-C10H21); 1.75 (triplet, 2H,
-N+(CH3)2-CH2-C11H23); 1.85 (singlet, 6H, -N+(CH3)2-
C12H25); 2.62 (broad peak, 3H, -SO3H); 4.02 (singlet, 2H,
aromatic C-NH); 4.68 ( singlet, 2H, -CH2-N); 4.88
(singlet, 1H, aromatic C-OH); 6.5-9 (broad peak, 11H,
aromatic ring). Anal Calcd for C40H47ClN8Na3O10S3: C,
47.97%; H, 4.70%; N, 11.19%; found: C, 47.80%; H,
4.81%; N, 11.25%.
7
3
FTIR (KBr, í, cm-1): 3427 (-OH); 2923, 2854 (CH3(CH2)10
CH2-); 1574 (N=N); 1405 (-N+(CH3)2-); 1039 (C-Cl). 1H-
NMR (500 MHz, D2O, ä, ppm): 0.62 (broad peak, 3H,
-(CH2)11-CH3); 0.98 (broad peak, 18H, -N+(CH3)2-(CH2)2-
(CH2)9-CH3); 1.4 (broad peak, 2H, -N+(CH3)2-CH2-CH2-
C10H21); 1.7 (triplet, 2H, -N+(CH3)2-CH2-C11H23); 1.86
(broad peak, 2H, -SO3H); 2 (singlet, 6H, -N+(CH3)2-
C12H25); 3.6 (singlet, 2H, aromatic C-NH); 4.55 ( singlet,
2H, -CH2-N); 5.2 (singlet, 1H, aromatic C-OH); 7-9
(broad peak, 12H, aromatic ring). Anal Calcd for
strength,6 which readily explains our experimental results,
as shown in Table 1. The structure of dyes 1 and 2 is small,
providing little steric hindrance, and thus absorption did
not decrease due to alkyl chain.
4
The FTIR spectra of the dyes show the absorbance
bands at wavenumbers, n, of 1039, 1407, 3444, and 1182
cm-1, which can be attributed to the C-Cl, C=N, OH, and
S=O stretching vibrations, respectively. The results corre-
spond with the literature data. Also, there is only one peak
in the region of 1575-1630 cm-1 for the dyes, which can be
attributed to stretching vibration of N=N group. Asymmet-
ric and symmetric stretching vibrations for alkyl chain are
shown at wavenumbers 2920-2960 cm-1 and 2830-2880
cm-1, respectively. These peaks only can be observed in the
FTIR spectra of the dyes 3 and 4.
C40H48ClN8Na2O7S2: C, 53.48%; H, 5.39%; N, 12.47%;
found: C, 53.41%; H, 5.48%; N, 12.43%.
the abovementioned intermediates such as the yields (Y%),
melting points and appearance of the crystals were reported
at the end of each preparation section. The FTIR, 1H NMR
spectra and elemental analysis of intermediates and dyes
are given in Tables 2 and 3, respectively.
The chemical structures of the synthesized dyes were
also confirmed by 1H NMR analysis. By comparing the 1H
NMR spectra of the dyes, there are peaks at chemical shift,
d, 0.54-1.85 ppm at the spectrum of dye 3, 0.62-1.7 ppm at
the spectrum of dye 4, which confirms the presence of the
alkyl chain group. The physical and chemical properties of
Evaluation of technical properties of dyes
The change in shade for effect of variation in the al-
kali and salt concentration of the dyes at 1% o.m.f depth of
shade were assessed (Figs. 2 and 3). In aqueous solutions,
depending on the pH within the fiber, hydroxyl groups of
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JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Novel Cationic MCT Reactive Dyes for Cotton
Table 4. SER5F profile for the novel dyes
cellulose will be ionized to a greater or lesser extent, also
the soda ash affects on the fixation and hydrolyses of dyes;
therefore determination of optimum concentration for soda
ash is necessary. Fig. 3 reveals that the dyes show a maxi-
mum colour yield at 20 g/l alkali.
Dye
1
2
3
4
3 (with urea) 4 (with urea)
%S
65
72
67
70
2
78
87
70
75
12
68
82
58
63
19
81
85
60
67
18
61
76
53
59
17
70
81
50
64
17
%E
%R5
%F
As shown in Fig. 2, the colour yield of dyes initially
increases with salt concentration, reaching a ‘plateau’ in
the presence of 40 g/l. The role of salt in the dyeing process
is to suppress the repulsion between the negative charge on
the surface of the cellulose and the anionic dye, thereby in-
creasing its substantivity for the cotton. This effect will
progressively increase as the concentration of salt is in-
creased, leading to a higher colour yield.
E-F
S: substantivity, E: exhaustion, R5: reactivity after 5 min, F:
fixation.
spectively) levels than dyes 1 (65%) and 3 (82%). High
substantivity and exhaustion are desirable properties of
dyes for environmental and an economical point of view.
This may be attributed to the fact that dyes 2 and 4 have
lower solubility than dyes 1 and 3, which have extra sul-
phonic acid groups present in their H acid coupling compo-
nent.
Dyeing properties of the dyes
In order to predict the likely (level) dyeing and fast-
ness properties of the dyes under (bulk) exhaust dyeing
conditions, the SER5F profiles of the dyes were measured
and compared. The results are shown in Table 4. Dyes 2 and
4 both exhibit higher substantivity (%S, 78% and 81%, re-
spectively) and higher exhaustion (%E, 85% and 87%, re-
The comparison of substantivity (%S) and exhaustion
(%E) of dyes 1 and 2 with those of dyes 3 and 4 (quar-
ernized dyes) shows that dyes 3 and 4 carrying cationic
group in dye structure led to higher substantivity and ex-
haustion. This observation can be attributed to a corre-
sponding increase in the attractive ion-ion interaction oper-
ating between the cationic groups in the dye molecule and
the anionic groups (ionized hydroxyl groups) present in the
fiber. On the other hand, there is a decrease of solubility
due to the presence of hydrocarbon chain group in the mo-
lecular structures of dyes 3 and 4.
The fixation (%F) levels of dyes 3 (63%) and 4 (67%)
are lower than those of dyes 1 (70%) and 2 (75%). This may
be attributed to the fact that these dyes contain hydrocarbon
chain group, and this group prevents the dyes to be ad-
sorbed on substrate.
Fig. 2. Effect of salt concentration on colour yield.
Urea is commonly used for dyeing and printing. It is
capable of the bursting the aggregation and associate the
dye being adsorbed on the fabric. In the presence of urea,
results in Table 4 show that the substantivity, exhaustion
and fixation of dyes 3 and 4 which are the cationic reactive
dye decreased on cotton. The reduction in colour yield
when the urea is added to dye bath could be due to decrease
aggregation of the dye molecules in the dyebath, leading to
increase of solubility and prevention of the dye being ad-
sorbed on to the cotton.
A useful indicator of the ease of washing off of the
hydrolysed reactive dye, in order to achieve good wet fast-
ness properties, can be obtained by examination of the dif-
ference between the exhaustion (E) and fixation (F) val-
Fig. 3. Effect of alkali concentration on colour yield.
J. Chin. Chem. Soc. 2012, 59, 793-801
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Article
Javadi and Mokhtari
ues.11,13 A high ‘E-F’value means a large amount of hydro-
lysed dye needing to be washed out during the rinsing and
‘soaping’ stages. This will result in potentially lengthy
washing sequences, especially if the dye possesses a high
substantivity (S).
Table 5. Migration indeces and fastness properties of the novel
dyes
Wash fastness Wash fastness Light fastness
Migration
Dye
ISO105-
ISO105-
ISO105-
index (MI)
C01:1993(E) C04:1993(E) B02:1994(E)
Comparing the E-F values for the dyes indicate that
dye 1 due to small structure offer lower E-F value (2%)
than the others (12-19%), indicating less amount of hydro-
lysed to be removed from the substrate. This could be at-
tributed to higher solubility of dye 1 due to more sulphonic
acid groups present on its structure (3 suphonic acid group
on dye 1 and 2 sulphonic acid group on dye 2). Dyes 3 and 4
show higher E-F values (18-19%) in compared with dyes 1
and 2. This could be attributed to the cationic alkyl chain
present on their structure. The use of urea decreased the
E-F values of dyes 3 and 4 (17%), indicating that urea facil-
itated the removal of the hydrolysed dyes.
1
2
3
4
77
72
61
59
5
5
5
5
5
5
5
5
5
4-5
5
4-5
Table 6. Softening properties of the novel dyes
Dye
1
2
3
4
1*
31.55 30.52 32.46 36.70 35.28 35.06
14.5 14.12 14.82 15.05 14.9 14.77
0.002 0.002 0.004 0.002 0.004 0.004
2*
E (%)
TS (N)
RFM (g)
BL (cm)
2.6
2.6
0.26
92
2.6
0.26
102
2.55
0.25
104
2.35
0.2
2.35
0.2
FR (mg/cm) 0.29
CRA 95
100
100
Migration indices of dyes
E: Elongation, TS: Tear Strength, RFM: Reduction of Fabric
Mass, BL: Bending Length, FR: Flexural Rigidity, CRA: Crease
Recovery Angle.
The migration index (MI) of a dye is often a reflection
of its substantivity; highly substantive dyes exhibiting a
low migration index and vice versa. Table 5 shows that the
migration indices of dyes 1 (77%) and 2 (72%) is much
better than dyes 3 (61%) and 4 (59%). These observations
could be attributed to the high solubility of dyes 1 and 2 in
dyebath. Hence, dyes 1 and 2 likely represent better level
dyeing properties than the other two novel dyes.
*Finished.
regular use of a fabric softener results a reduction of fric-
tion between the fabric components; therefore it would in-
crease fabric flexibility, reduce wrinkling and abrasion re-
sistance, increase fiber elongation and improve tear strength.
Since quaternary ammonium salts are extremely important
softener derivatives, the above mentioned tests were em-
ployed for dyed fabric. The results are summarized in Table
6. For evaluation purpose, two comparisons have been cho-
sen: 1. Comparing softness properties of dyed fabrics with
cationic reactive dyes only; 2. Comparing softness proper-
ties of dyed fabrics with cationic reactive dyes 1 and 2, then
the dyed fabric finished with cationic softening agent.
Tear strength
Fastness properties of dyes
The results of fastness tests for dyes 1-4 on cotton
fabric were summarized in Table 5. The wash fastness of
the dyes was assessed using the ISO105-C01:1993(E) and
ISO105-C04:1993(E) wash fastness test at 40 °C and 95
°C. The change in shade and the degree of cross-staining
were assessed visually using grey scales. The wash fast-
ness, as expected, of each dye fixed to cotton fabrics was
very good at each of the four depths of shade employed.
The light fastness of dyes was assessed using the ISO105-
B02:1994(E). The change in shade was assessed visually
using blue scale. Results indicated the light fastness of dyes
is moderate. These results also reveal that quarternization
of the dyes has no significant effect on the fastness proper-
ties of the dyes.
Table 6 shows the tear strength of the fabrics dyed
with cationic reactive dyes. As can be seen, dyes 1 and 2
provide lower tear strength in compared to dyes 3 and 4.
This effect could be attributed to quaternary ammonium
moiety of the dyes. Samples dyed only with dyes 1 and 2
were compared with samples dyed with dyes 1 and 2, then
finished with cationic softener agent. The results show that
tear strengths of the samples are almost the same, confirm-
ing the role of quaternary ammonium moiety of dyes 3 and
4. Finally, it proves the effectiveness of simultaneous dye-
ing and finishing of the novel cationic reactive dyes.
Softening properties
Finishing is a comprehensive term referring to pro-
cesses in which fabric is treated with chemical agents after
production. Textile softener is a result of chemical technol-
ogy; they give feeling of softness and slick hand in fabrics.
Consensus of the studies discussed below suggests that
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J. Chin. Chem. Soc. 2012, 59, 793-801

JOURNAL OF THE CHINESE
CHEMICAL SOCIETY
Novel Cationic MCT Reactive Dyes for Cotton
Abrasion Resistance
Incorporation of quaternary ammonium group to dye
structure of dyes 1 and 2 imparts softening properties in the
dyed fabric. Also several properties of the substrate dyed
with these dyes could be mentioned as being similar or top
of those for separately dyed and then cationic softener fin-
ished substrate. It is concluded that dyeing and softening
finishing are simultaneously employed in one step. These
dyes have excellent wash fastness, whilst their light fast-
ness on fabric is moderate.
Table 6 shows the abrasion resistance of the fabrics
dyed with cationic reactive dyes. As can be seen, dyes 1
and 2 offer lower mass reduction in compared to dyes 3 and
4, revealing more softening property for the novel cationic
reactive dyes.
Flexibility
Table 6 shows flexibility results for the fabrics dyed
with cationic reactive dyes. Dyes 1 and 2 offer higher flexi-
bility rigidity than dyes 3 and 4. Furthermore, samples dyed
with dyes 1 and 2 and then finished with cationic softening
agent lowers the flexibility rigidity.
REFERENCES
1. Xie, K.; Liu, Y.; Li, X. Mater. Chem. Phys. 2007, 105, 199.
2. Xie, K.; Liu, Y.; Li, X. Mater. Chem. Phys. 2007, 105, 204.
3. Liu, J.; Sun, G. Dyes Pigm. 2008, 77, 380.
4. Liu, S.; Ma, J.; Zhao, D. Dyes Pigm. 2007, 75, 255.
5. Freeman, H. S.; Hauser, P. J.; Chen, X.; Nakpathom, M. An-
nual Report. National Textile Center; November 1999,
C98-S04. http://www.ntcresearch.org (Accessed March 7,
2012)
Crease Recovery Angle
Table 6 shows crease recovery angle results for the
samples dyed with cationic dyes. Dyes 3 and 4 offer higher
crease recovery angle in compared with dyes 1 and 2. In ad-
dition, even samples which were separately dyed with dyes
1 and 2 then followed by finishing with cationic softening
agent do not provide the same crease recovery angle as
dyes 3 and 4 offer.
6. Ma, M.; Sun, Y.; Sun, G. Dyes Pigm. 2003, 58, 27.
7. Fox, M. R.; Sumner, H. H. In The Dyeing of Cellulosic
Fibres; Preston, C., Ed.; The Dyers’ Company Publication
Trust: Bradford, 1986; Chapter 4, pp 142-195.
8. Christie, R. M. Colour Chemistry; The Royal Society of
Chemistry: Cambridge, 2001; pp 45-46.
CONCLUSIONS
Four novel dyes were synthesized in good yield. Two
of them have quaternary ammonium salt in their structures.
Replacement of H-acid with J-acid in the molecular struc-
tures of the dyes offered bathochromicity in visible spectra.
Incorporating the QAS alkyl chain on dye structure led to
hypsochromic shift in visible absorption spectra. Cotton
fabrics were dyed using the novel cationic reactive dyes.
The technical properties of the dyes were evaluated with
SER5F profile and migration properties. These tests showed
that dyes 2 and 4 offer high substantivity and exhaustion
because they have lower solubility than dyes 1 and 3. Dyes
3 and 4 exhibited low fixation due to having big structure,
resulting in low adsorption on fabric. Dyes 3 and 4 have
lower migration indices than dyes 1 and 2 due to their low
solubility. The results show that the cationic reactive dyes
either improve or affect fabric properties.
9. Gao, Y.; Cranston, R. Text. Res. J. 2008, 78, 60.
10. Suwanruji, P. The Design, Synthesis and Application of Easy
Wash off Reactive Dyes; A Dissertation Submitted to the
Graduate Faculty of North Carolina State University 2004.
11. Mokhtari, J.; Phillips, D. A. S.; Taylor, J. A. Dyes Pigm.
2004, 63, 51.
12. Bent, C. J.; Davies, P. A.; Phillips, D. A. S. J. Soc. Dye. Col-
our. 1982, 98, 326.
13. Mokhtari, J.; Phillips, D. A. S.; Taylor, J. A. Dyes Pigm.
2005, 64, 163.
14. Cockett, K. R. F.; Rattee, I. D.; Stevens, C. B. J. Soc. Dye.
Colour. 1969, 85, 461.
15. Bradbury, M. J.; Collishaw, P. S.; Phillips, D. A. S. J. Soc.
Dye. Colour. 1992, 108, 430.
16. Gordon, P. F.; Gregory, P. Organic Chemistry in Colour;
Springer-Verlag: New York / Berlin / Heidelberg, 1983; pp
96-104.
J. Chin. Chem. Soc. 2012, 59, 793-801
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