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Dispersant-free disperse dyes for polyester an eco-

friendly approach

C. R. Meena, Saptarshi Maiti, N. Sekar, Sandeep More & R. V. Adivarekar

To cite this article: C. R. Meena, Saptarshi Maiti, N. Sekar, Sandeep More & R. V. Adivarekar
(2016): Dispersant-free disperse dyes for polyester an eco-friendly approach, The Journal of
The Textile Institute, DOI: 10.1080/00405000.2016.1222858

To link to this article: http://dx.doi.org/10.1080/00405000.2016.1222858

Published online: 19 Aug 2016.

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Download by: [Eastern Michigan University] Date: 03 November 2016, At: 21:54
The Journal of The Textile Institute, 2016
http://dx.doi.org/10.1080/00405000.2016.1222858

Dispersant-free disperse dyes for polyester an eco-friendly approach

C. R. Meenaa, Saptarshi Maitia, N. Sekarb, Sandeep Morea and R. V. Adivarekara
a
Department of Fibres and Textile Processing Technology, Institute of Chemical Technology, Mumbai, India; bDepartment of Dyestuff Technology,
Institute of Chemical Technology, Mumbai, India

ARTICLE HISTORY
ABSTRACT Received 30 January 2016
Disperse dyes contain around 30–60% of dispersing agents as well as dyeing with disperse dyes Accepted 5 August 2016
requires around 2–5  g/L of dispersing agent for faultless dyeing of polyester and other hydrophobic
KEYWORDS
fibres. Dispersing agents are not absorbed by the fibres and a large quantity of dispersing agent creates Eco-friendly; effluent load;
unavoidable load on the effluent treatment. Dispersant-free disperse dyes seem to have an acceptable dispersant-free disperse
solution to this existing problem. These dyes can work in absence of dispersing agents and thus are called dyes; polyester; fastness
as dispersant free disperse dyes. In this work, dispersant-free disperse dyes were synthesised by coupling
diazotised p-nitroaniline with the different components like sulfomethylated aniline and m-toluidine.
These synthesised dyes were applied successfully on polyester which resulted into uniform dyeing, good
build-up and desired colour yield. The dyeing was dependent on the pH and the optimum pH was 5 similar
to that employed in conventional polyester dyeing. The fastness properties obtained were good and
comparable with the conventional dyes. Whereas the chemical oxygen demand levels of the dispersant-
free disperse dyes were much lower than those from commercial disperse dye.

Introduction stability and its consequences: inadequate levelness and unac-

ceptable reproducibility (Navratil, 1990). Thus, in the conven-
While developing new disperse dyes, it must be taken into
tional disperse dyeing of polyester, dispersing agents are usually
account that the dyeing effluents are affecting our environment,
added to increase the dispersion stability and solubility of dis-
and steps to minimise such pollution have to be taken effectively
perse dyes. However, after the dyeing process is finished, they
(Koh, Kim, & Kim, 2003). The need for environmental friendly
are not adsorbed onto polyester and discharged as effluents with
dyes for polyester is increasing. In addition, there are rising global
the residual dyeing liquor, which increases the chemical oxygen
legislative pressures to reduce the impact of dyeing processes on
demand (COD) and biological oxygen demand (BOD) values
the environment through reductions in effluent discharge as well
of the effluent (Lee, Han, Lee, Choi, & Kim, 2002; Lee & Kim,
as in the use of energy and materials (Koh & Park, 2008).
1999a,1999b; Lee, Lee, Choi, & Kim, 2005).
The first temporarily solubilised disperse dyes were synthe-
In this work, synthesis of dispersant-free disperse dyes in the
sised in 1922 (Lee, Lee, & Kim, 2003). The dyes, especially those
range of yellow such as golden-yellow and yellow-brown was car-
of the Ionamine range, contained N-methylsulfonic acid group
ried out. The correlation between the dye structure and spectral
that gave temporary solubility to the dye molecules. These dyes
properties is discussed. These dyes are used as dispersant-free
when hydrolysed in the dyebath while dyeing form insoluble
disperse dyes for polyester for which the performance properties
species that get adsorbed onto the surface of the hydrophobic
are investigated.
fibre and diffuse into it (Green & Saunders, 1923).
Disperse dyes are used in aqueous dyebaths in the form of
fine dispersions because their solubility in water is very low, even Experimental
at high dyeing temperatures. During manufacture, dispersing
Materials and methods
agents are incorporated into the dye powders to confer the dyeing
properties (Odvarka & Schejbalova, 1994). The dispersing agents Ready-for-dyeing polyester (100%) fabric (weight 70  gm/m2,
are divided into two classes by the chemical point of view, such ends per inch 105 & picks per inch 94) was purchased from
as surfactants and water-soluble polymers/oligomers. The dis- Piyush Sydicate, Mumbai, India.
persing agents used in dyes are usually anionic polyelectrolytes The required chemicals and reagents such as p-nitroaniline,
(Heimann, 1981). aniline, m-toluidine, sodium nitrate, sodium carbonate, hydro-
One of the severe problems encountered in dyeing of poly- chloric acid, sodium acetate and sodium chloride (analytical
ester at high temperatures with disperse dyes is poor dispersion grade) were purchased from SD Fine Chem. Ltd. Mumbai. The

CONTACT  R. V. Adivarekar  rv.adivarekar@ictmumbai.edu.in

© 2016 The Textile Institute
2    C. R. Meena et al.
Figure 1. Sulfomethylation of aniline.
required dyes such as, Yellow Brown REL 200% (C I Disperse
Orange 61) and Yellow Brown K2RS (C I Disperse Orange 30)
were supplied by Colorband Dyestuffs Pvt. Ltd.
All dyeings were carried out using Flexi dyer machine
(Rossari Labtech, Mumbai, India). The infrared (IR) spec-
tra were recorded on a FTIR-8400S, Fourier Transform IR
Spectrophotometer, Shimadzu, Kyoto, Japan. The dispersi-
bility was evaluated by filtering time and filter residue under
standard conditions in aqueous media using the AATCC Test
Method 146-2006.
Evaluation of % dye exhaustion
The exhaustion of dye on the polyester fabric was also measured
by DMF extraction method (30 min at 150 °C). The absorbance
of the solution extracted was determined using UV–Vis 8500
spectrophotometer. The percentage exhaustion was calculated
using equation:
(1)
/
Exhaustion (%) = Ct C0 × 100,
where Ct is the amount of dye extracted from a dyed fabric at
time t and C0 is the amount of dye in the initial dyebath.
Colour measurements
Dyed fabrics were simultaneously evaluated in terms of
CIELAB colour space (L*, a* and b*) values and colour
strength in terms of K/S. In general, the higher the K/S value,
the higher the depth of the colour on the fabric. L* corre-
sponds to the brightness (100 represents white, 0 represents
black), a* to the red–green coordinate (+ve represents red,
−ve represents green) and b* to the yellow–blue coordinate
(+ve represents yellow, −ve represents blue). As a whole, a
combination of all these enables one to understand the tonal
variations. Four locations on the dyed fabric were arbitrarily
chosen and L*, a* and b* values were measured by spectro-
photometer. The CIE L*a*b* colour difference between any
two points was calculated. The levelling properties of the dyes
on polyester fabric were assessed using the mean of five such
colour difference results (Lee et al., 2005).
The colour properties of the dyed samples were determined
with Spectra Scan 5100+ under the illuminant D65 using 10°
standard observer. The K/S values were determined using
expression;
K∕S = (1 − R)2 2R,
/
(2)
where R is the reflectance at complete opacity, K is the absorption
coefficient and S is the scattering coefficient.
Fastness testing
Rubbing fastness of the dyed samples was determined using auto-
matic Crockmeter (World Traders & Co. Bombay) using the stand-
ard ISO 105 X 12 method. Sublimation fastness of the polyester dyed
samples was tested on Sublimation tester, RBE Electronics Engg. Pvt.
Ltd. Mumbai, India, using the ISO 105-F04 method. The light fast-
ness of the dyed samples was tested on Q-Sun Xenon Test Chamber
using the AATCC 16-2004 method. Washing fastness testing was
done by the standard method ISO 2-105-C10: 2006 (E). The shade
change, together with staining of adjacent fabrics, was rated accord-
ing to appropriate SDC grey scales.
COD analysis
The COD value of dispersant-free disperses dyes and commercial
disperse dyes were measured according to the test method IS:
3025 (Part 58) Reaffirmed 2006.
Sulfomethylation of aniline (Groggins, 1995)
A three-neck round-bottom flask was charged with aqueous
sodium bisulfite (0.04808 mol) and formaldehyde (0.04808 mol)
was added with stirring, followed by heating for 30 min at 70 °C
to form the adduct (2). After cooling to room temperature, ani-
line (1) (0.04808 mol) was added to the mixture and temperature
was held for 3 h at 25–30 °C, followed by heating at 35 °C for
an additional hour. The reaction scheme is shown in Figure 1
and was monitored using GCMS. Heating was continued until
all the aniline was consumed. After completion of reaction, the
required pure product (3) was obtained by following protocol
already established.
Sulfomethylation of m-toluidine (Groggins, 1995)
Aqueous sodium bisulfite (0.04808 moles) was charged to a
round three-neck flask with stirrer and heating mantle and
formaldehyde (0.04808 mol) was then added with stirring, fol-
lowed by heating 30 min at 70 °C to form the adduct (2). After
cooling to room temperature, m-toluidine (4) (0.04808 mol)
was added and the temperature held for 3hr at 25–30 °C, fol-
lowed by heating at 35 °C for an additional hour. The reaction
scheme is shown in Figure 2. Following the reported protocol,
the product (5) was separated and purified.
 The Journal of The Textile Institute   3

Figure 2. Sulfomethylation of m-toluidine.

Figure 3. Synthesis of dispersant-free disperse dyes.

Diazotisation & coupling (Pope & Willette, 1913) Characteristic IR: 3379.05 (–NH), 1595.02 (–N=N–) cm−1.
p-Nitroaniline (6) (0.01448  mol) was dissolved in acetone at
0–5 °C. Then concentrated hydrochloric acid (0.05068 mol) and Dye-2
sodium nitrite (0.014480 mol) were added slowly under constant
Elemental analysis: C, 45.16; H, 3.52; N, 15.05; Na, 6.17; O, 21.49;
stirring at 0–5 °C and the reaction was continued for 3–4 h. The
S, 8.61.
reaction was monitored using starch paper and the diazotised
Characteristic IR: 3284.55 (–NH), 1596.95 (–N=N–) cm−1.
product (7) was separated.
Sulfomethylated aniline (3) (0.014480 mol) and sulfometh-
ylated m-toluidine (5) (0.014480 mol) synthesised above were Dyeing of polyester
dissolved separately in water and then 35% hydrochloric acid was
Polyester fabric was dyed in a Flexi dyer dyeing machine using
added dropwise at room temperature. The prepared diazonium
M: L 1:20. The dyebaths were prepared with the synthesised dyes
salt (7) was added to the corresponding solution and the temper-
without using any dispersing agent and maintained at pH 5 with
ature was maintained between 0–5 °C. The solution was stirred
acetic acid. The dyebath temperature was raised at a rate of 1 °C/
for 2–3 h and allowed to reach room temperature. Then sodium
min to 130 °C, maintained at this temperature for 60 min, and
acetate solution (1 M) was added to adjust the pH between 4 and
rapidly cooled to 60 °C. The dyed fabrics were rinsed and then
5. Finally, saturated sodium chloride solution was added to the
reduction cleared in an aqueous solution of 2 g/L sodium hydrox-
above solution; the precipitate formed was filtered and washed
ide and 2 g/L sodium hydrosulphite at 80 °C for 30 min.
several times. Finally, after drying in a vacuum oven at room
temperature, the respective dyes (Dye-1 & Dye-2) were obtained
in pure form. The reaction scheme is illustrated in Figure 3. Results and discussion
Characterisation of dyes
Dye-1
The IR spectra were recorded in order to confirm the func-
Elemental analysis: C, 43.58; H, 3.09; N, 15.64; Na, 6.42; O, 22.33; tional groups and get the data, for Dye-1 showed absorption
S, 8.95. bands at 3379.05 cm−1(–NH), 1595.02 cm−1 (–N=N–) as evident
4    C. R. Meena et al.

Table 1. Filtration of synthesised dyes.

Filter rating
Dye Filtration time (s) Filter residue scale
1 55 4–5
2 51 4

Table 2.  Effect on pH on exhaustion (%) value of Dye-1 & Dye-2 on polyester
fabric (1% shade, M: L 1:20).

Exhaustion (%)
pH Dye-1 Dye-2
4 78.4 77.7
5 90.5 91.0
6 88.0 88.1
7 79.7 78.9
8 74.0 75.5
9 67.4 68.5
Figure 4. FTIR spectra of Dye-1. 10 61.1 60.6

Figure 6. Colour build-up of Dye-1 & Dye-2 on polyester fabric (pH 5, M: L 1:20).

Table 3. The colour data of Dye-1 & Dye-2 on polyester fabrics.

CIE L*a*b* values

Dye L* a* b* Colour name
Figure 5. FTIR spectra of Dye-2. 1 62.63 22.008 57.288 Golden yellow
2 56.669 31.144 55.865 Yellow brown

from Figure 4. Whereas, Dye-2 revealed absorption bands at
3284.55 cm−1 (–NH), 1596.95 cm−1 (–N=N–) group as shown
in Figure 5. The purity was confirmed by elemental analysis as
mentioned already.
The dispersibility test was evaluated by filtering time and filter
residue of dispersant-free disperse dyes. Table 1, illustrates the fil-
ter residue scale which is rated from one (poor) to five (excellent).
All the synthesised dyes showed good dispersibility in aqueous
media as it was found near a rating of 4–5 and was compared to
that of the standard rating of commercial dyes.
Spectral properties of dyes
The absorption maxima of the synthesised dyes (Dye-1 & Dye-2)
varied from 491.6 to 497.2, respectively, which was golden-yellow
to yellow-brown shade.
Effect of dyebath pH
The exhaustion % at different pH of dyebath is given in Table 2 of
Dye-1 and Dye-2. The trend in exhaustion % remained same for
both the dyes for polyester dyeing and good colour yields were
obtained. The maximum colour yield was observed at pH 5 for
both the dyes and was of the tune of 90%. The colour yields at
pH 7 and 8 were lower than those at pH 5 and also the dyeings
showed some unevenness. Therefore, the optimum pH condition
for dyeing was concluded as pH 5 which was normally within
the range of pH stability of the two aforementioned commercial
dyes. The colour yield at pH  4 was not satisfactory owing to
the low conversion rate of dye of soluble dye into the insoluble
form. The colour yield on the polyester fabric increased contin-
uously throughout the whole dyeing procedure, implying grad-
ual increase in the conversion of dye. The low dye uptake and
poor levelling at pH 10 are attributed to the rapid conversion of
dye causing a collapse in the dyebath dispersion stability. Thus,
the exhaustion of dyebath in terms of exhaustion % was highly
dependent on the pH of the dyebath with maximum exhaustion
of 90.5 and 91.0%, respectively, for Dye-1 & Dye-2 obtained at
pH 5 (Lee et al., 2005).
Effect of dye concentration
Figure 6 shows the build-up of the dyes at pH  5 in terms of
K/S values at various depths of dyeing such as 0.5–3%. Dye-1 &
 The Journal of The Textile Institute   5

Table 4. Colour differences between four points of polyester fabric. Table 7. The rubbing, light and sublimation fastness of Dye-1 & Dye-2 (1% shade)
on polyester fabric.
Dye Colour differences
  Fastness
1 2 3 4 5 Average
1 0.504 0.409 0.236 0.507 0.440 0.419 Rubbing
2 0.306 0.342 0.462 0.267 0.532 0.381 Dye  Dry Wet Light Sublimation
1 4–5 4–5 5 4–5
2 4–5 4 4–5 4
Table 5. COD values of dispersant-free disperse dyes and commercial disperse dye.

Yellow Brown K2RS It is clear from Table 7 that rubbing and sublimation fastness
COD Yellow Brown REL 200% (C I Disperse Orange
(mg/L)
were very good for both dyes. The light fastness for Dye-1 and
Dye-1 (C I Disperse Orange 61) Dye-2 30)
  518 789 447 843
Dye-2 was moderate to good, probably because of having same
chromophoric system.

Dye-2 exhibited good build-up on the polyester and the colour
strength of these dyes reached saturation at depth of dyeing of
2.0% shade with no distinct increase in K/S values at 3% shade
depth of dyeing. It is also clear that the extent of exhaustion of
both dyes decreases with increasing dye concentration. This is
believed to be because of the lowering of dye substantivity at a
higher dye concentration as a result of increasing dye aggrega-
tion. Additionally, at a high dye concentration the numbers of
available dye sites on the fibre decreases and competitive hydrol-
ysis increases, resulting in a lower extent of exhaustion of both
dyes (Youssef, Mousa, Farouk, Allam, & El-Kharadly, 2007).
Colour assessment
The colour data as shown in Table 3 are in agreement with the
spectral data of the two synthesised dyes. The dyes gave gold-
en-yellow and yellow-brown hues on polyester fabrics.
Table 4 gives the average of 5 results for the colour differences
at four random locations on 1% shade (pH 5, M: L 1:20) polyes-
ter-dyed fabric. All the dyes showed very little colour differences
between locations, showing that levelling was good (Odvarka &
Schejbalova, 1994).
Comparison with a commercial disperse dye
It is clear from Table 5 that COD levels of dispersant-free disperse
dyes, Dye-1 (518 mg/L) and Dye-2 (447 mg/L), respectively, were
lower than commercial disperse dye. Low COD levels of dis-
persant-free disperse dyes are probably due to the fact that no
dispersant was used during synthesis.
Fastness properties
The colour fastness tests carried out for all the dyed fabrics were
done at pH 5, which was obtained as the optimum pH of dyeing.
The results of the wash fastness tests for Dye-1 & Dye-2 on pol-
yester are summarised in Table 6 and showed good to excellent
wash fastness.
Table 6. The wash fastness of dyes 1–2 (1% shade) on polyester fabric.
   Staining
Change
Dye in colour Acetate Cotton Nylon Polyester Acrylic Wool
1 4–5 4–5 4–5 4 5 5 4–5
2 4–5 4–5 4–5 4 4–5 5 4–5
Conclusions
Polyester fabrics were successfully dyed with the dyes without
using dispersing agent. The colour yield on polyester was depend-
ent on the dyeing pH and the optimum result was obtained at
pH 5 similar to that employed in conventional polyester dyeing.
Therefore, no modification of dyeing process is needed for the
application of synthesised dyes. The dyes gave golden-yellow to
yellow-brown hues on polyester and showed good build-up and
levelling properties. The dyes exhibited good to excellent wash
fastness while rubbing, sublimation and light fastness results
were good and moderate to good and mainly dependent on the
structure of dyes. The COD levels of dispersant-free disperse
dyes were considerably lower than those of commercial disperse
dye, which is probably attributed to the absence of dispersants in
the dispersant-free disperse dyes. This research gives a pathway
for the development of a range of dispersant-free disperse dyes
which is used for uniform dyeing of polyester which eliminates
the use of dispersing agents thereby reducing effluent load and
could be promising as eco-friendly dyes.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by UGC-SAP (CAS); INSPIRE Department of
Science & Technology, Government of India.
References
Green, A. G., & Saunders, K. H. (1923). The ionamines: A new class of
dyestuffs for acetate silk. Journal of the Society of Dyers and Colourists,
39, 10–16.
Groggins, P. H. (1995). Unit processes in organic synthesis (5th ed., 375–
376). New Delhi: Tata Mcgraw-hill.
Heimann, S. (1981). Textile auxiliaries: Dispersing agents. Review of
Progress in Coloration and Related Topics, 11, 1–7.
Koh, J., Kim, J. D., & Kim, J. P. (2003). Synthesis and application of a
temporarily solubilised alkali-clearable azo disperse dye and analysis of
its conversion and hydrolysis behaviour. Dyes and Pigments, 56, 7–26.
Koh, J., & Park, J. (2008). One-bath dyeing of PET/cotton blends with
azohydroxypyridone disperse dyes containing a fluorosulfonyl group.
Fibers and Polymers, 9, 128–133.
Lee, J. J., Han, N. K., Lee, W. J., Choi, J. H., & Kim, J. P. (2002). Dispersant-
free dyeing of polyester with temporarily solubilised azo disperse dyes
from 1-substituted-2-hydroxypyrid-6-one derivatives. Journal of the
Society of Dyers and Colourists, 118, 154–158.
6    C. R. Meena et al.
Lee, J. J., Lee, W. J., Choi, J. H., & Kim, J. P. (2005). Synthesis and application
of temporarily solubilised azo disperse dyes containing β-sulphatoethyl
sulphonyl group. Dyes and Pigments, 65, 75–81.
Lee, J. J., Lee, W. J., & Kim, J. P. (2003). Dispersant-free dyeing of polyester
with temporarily solubilized azo disperse dyes from indole derivatives.
Fibers and Polymers, 4, 66–70.
Lee, W. J., & Kim, J. P. (1999a). Dispersant-free dyeing of polyester with
temporarily solubilised disperse dyes. Journal of the Society of Dyers and
Colourists, 115, 370–373.
Lee, W. J., & Kim, J. P. (1999b). The rate of hydrolysis of temporarily
solubilised disperse dyes. Journal of the Society of Dyers and Colourists,
115, 270–273.
Navratil, J. (1990). Dyeing behaviour of aqueous solutions of dispersant-
free disperse dyes in the high-temperature dyeing of polyester (Part 1).
Journal of the Society of Dyers and Colourists, 106, 283–288.
Odvarka, J., & Schejbalova, H. (1994). The effect of dispersing agents on the
dyeing of polyester with a disperse dye. Journal of the Society of Dyers
and Colourists, 110, 30–34.
Pope, F. G., & Willette, W. I. (1913). Colour and constitution of azomethine
compounds. Part III. Journal of the Chemical Society, Transactions, 103,
1258–1263.
Youssef, Y. A., Mousa, A. A., Farouk, R., Allam, E. E., & El-Kharadly,
E. A. (2007). Dyeing of nylon 6 fabric with a bifunctional
sulphatoethylsulphone reactive disperse dye. Journal of the Society of
Dyers and Colourists, 123, 312–316.