The synthesis and application of novel 2-chloro-4-Alkylthio triazinyl reactive dyes

Article abstract of DOI:10.1016/j.dyepig.2012.08.016

Two hetero bi-functional reactive dyes (red and yellow) each containing both a sulphatoethylsulphonyl and 2-chloro-4-Alkylthio-s-triazinyl reactive group have been synthesised and their dyeing properties including exhaustion, colour strength on fabric (visual colour yield), fixation and wash fastness compared with market leading products. Under the alkaline application conditions employed, both the dyes, a yellow and a red, having a novel bridging group, exhibited good build-up, fixation and wet fastness properties being essentially comparable with leading commercial products. The concept of synthesising a substituent that can be introduced into a dye as a linking group to impart increased reactivity to a chlorotriazine has been demonstrated to be viable and effective.

Full text of DOI:10.1016/j.dyepig.2012.08.016

Dyes and Pigments 96 (2013) 397e402
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Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
The synthesis and application of novel 2-chloro-4-alkylthio triazinyl reactive dyes
*
Khalid Pasha , John A. Taylor
Textiles and Paper, School of Materials, University of Manchester, PO Box 88, Manchester M60 1QD, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Two hetero bi-functional reactive dyes (red and yellow) each containing both a sulphatoethylsulphonyl
and 2-chloro-4-alkylthio-s-triazinyl reactive group have been synthesised and their dyeing properties
including exhaustion, colour strength on fabric (visual colour yield), fixation and wash fastness compared
with market leading products. Under the alkaline application conditions employed, both the dyes,
a yellow and a red, having a novel bridging group, exhibited good build-up, fixation and wet fastness
properties being essentially comparable with leading commercial products. The concept of synthesising
a substituent that can be introduced into a dye as a linking group to impart increased reactivity to
a chlorotriazine has been demonstrated to be viable and effective.
Received 16 July 2012
Received in revised form
13 August 2012
Accepted 15 August 2012
Available online 1 September 2012
Keywords:
Reactive dyes
Cotton
Ó 2012 Elsevier Ltd. All rights reserved.
Sulphatoethylsulphone
Chloroalkylthiotriazinyl dyes
Exhaust dyeing
Fixation
1. Introduction
cotton, include the nature (electronegativity) of the leaving group,
the number and type of heterocyclic atoms in the heteroaromatic
Since the introduction of the hetero bi-functional range of
Sumifix Supra reactive dyes, the thrust of much synthetic effort,
both academic and industrial, on reactive dyes, has focussed on
utilising existing reactive systems but in novel arrangements or
combinations. The current market is dominated by two major
classes of reactive systems i.e. Michael type acceptors and hal-
oheterocyclic. Several approaches towards optimisation of the
application properties of derived dyes have been adopted. Ciba
disclosed a wide range of combinations of different reactive groups
in a single dye molecule. These included dyes possessing a mono-
fluorotriazine in combination with a sulphatoethylsulphone [1e4],
ring and other ring substituents. 2,4-Dichloro-6-methylthio-[1,3,5]
triazine (Fig. 1, Structure 1) has been known and used in other
chemical industries, especially agrochemicals, for many years. Its
synthesis has been reported in the literature by several different
routes [13] and [14].
Monochlorotriazines derived from 2,4-6-alkylthio-[1,3,5]
triazine, of the type depicted in Structure 2(a) as shown in Fig. 2,
having an alkylthio substituent have received little attention.
Carboxymethylthiol-triazine
and
carboxyethylthiol-triazines
studied by Lehr [15] and cysteamine crosslinked triazine systems
to give tri- and tetra functional chlortriazinyl dyes [16] were also
reported. Nitrogen is more electronegative than sulphur and
therefore, more electron withdrawing by an inductive effect.
However, both atoms possess a lone pair of electrons and so can
function as electron donators by a mesomeric effect. Sulphur being
a much larger atom, than nitrogen, cannot donate its lone pair of
electrons as effectively as nitrogen. Hence an alkylamino or aryla-
mino substituent is more electron donating (deactivating with
respect to nucleophilic substitution), overall, than an alkylthio
group when attached to a triazine ring.
with
a thiosulphatoethyl sulphonyl group [5], an alkoxy-
chlorotriazinyl group [6] and a difluorochloropyrimidinyl group [7].
Triazinyl derivatives containing a cyanamino group were disclosed
by [8] Sandoz and [9e12] by Hoechst, although this group
contributes minimally to fixation. Factors which determine the ease
with which a haloheterocyclic, or related, system undergoes acti-
vated heteroaromatic substitution such as hydrolysis on fixation to
* Corresponding author. Textile Engineering Department, NED University of
Engineering and Technology, University Road, Karachi 75270, Pakistan. Tel.: þ92 21
99261261.
In order to evaluate this concept, novel hetero bi-functional dyes
incorporating both a 2-alkylthio-4-chlorotriazine and a sulphatoe-
thylsulphonyl (masked vinyl sulphone) group were prepared.
E-mail addresses: Khalid@neduet.edu.pk, drkpasha@hotmail.com (K. Pasha).
0143-7208/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dyepig.2012.08.016

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K. Pasha, J.A. Taylor / Dyes and Pigments 96 (2013) 397e402
reaction mixture (250 ml) was filtered to remove any insoluble
Cl
N
S
impurities and the product (structure shown in Fig. 3) was
precipitated by the portion wise addition of potassium chloride
(25 g, 10% w/v) to the stirred solution. Solid was collected and dried
under reduced pressure. Rf 0.73, PABSES 0.60, h.p.l.c. retention time
0.79 min, (M-Hþ) 356.7, molecular weight 357, 1H-NMR, dH
(300 MHz, D2O): 7.85 ppm (2H, doublet, aromatic, ortho to SO2),
7.7 ppm (2H, doublet, aromatic, ortho to NH), 4.2 ppm (4H, triplet
and singlet, eSO2eCH2e, and eCH2eCl), 3.65 ppm (2H, triplet, e
CH2eOSO3H), Found: C, 25.25%; H, 1.95%; N, 3.10%; S, 13.55%.
C10H11NO7ClS2$K (84%) requires C 25.50%, H 2.3%, N 3.0%, S 13.60%,
yield 3.4 g, 76%, Mole In (M.I.) 470. Effective agent (ea) strength 84%.
N
N
Cl
CH3
Fig. 1. Structure 1, Dichloromethylmercapto-[1,3,5] triazine.
2.3. Yellow dye
2. Experimental
2-Aminonaphthalene-3,6,8-trisulphonic acid (55.9 g, 0.1 mol,
Moles In 559, strength 68.50%) was dissolved in sodium carbonate
in water (100 ml) at 3e5 ꢀC together with sodium nitrite (6.9 g,
0.1 mol). The solution was added to hydrochloric acid (0.25 mol,
36%) at 0e5 ꢀC and the mixture stirred for 1 h. The resulting dia-
2.1. Materials
}
Proton NMR spectra were recorded using a Bruker DPX 300
instrument equipped with a proton/carbon, z-gradient, dual probe
with an automatic sample changer. The solvent used was deute-
rium oxide >99.9 atom% D, with tetramethyl silane as an internal
standard.
zonium salt suspension was added to
a stirred solution of
(3-aminophenyl) urea (22.9 g. 0.1 mol, M.I. 229) in water (250 ml) at
4e6 ꢀC. The pH was raised to 6e6.5 with aqueous sodium carbonate
solution (10% w/v) and maintained at this value for 2 h. The mixture
was filtered to remove a small quantity of insoluble material and
the resulting solution added to a freshly prepared, stirred suspen-
sion of cyanuric chloride (18.5 g, 0.1 mol), 0e5 ꢀC and pH 6e6.5.
After 1.5 h reaction was essentially complete and the temperature
was raised to 30e35 ꢀC, for 1.5 h to destroy any excess cyanuric
chloride. The solution was filtered to remove any insoluble impu-
rity and sodium chloride was added slowly to the stirred filtrate.
The precipitated dichlorotriazine was collected and dried. Rf 0.39,
Yield 74 g, 82%. M.I. 903. E.a. 77%.
Sodium hydrogen sulphide (1.56 g, 0.02 mol) was added portion
wise to a solution of the freshly prepared dichlorotriazine dye
(9.03 g, 0.01 mol), at 8e10 ꢀC; temperature was allowed to rise to
16e18 ꢀC, at pH 8e9.5. After completion of the reaction, as judged
by t.l.c. and h.p.l.c. (2 h), the mixture was filtered to remove
insoluble impurities and a solution of N-chloroacetyl para amino-
Mass spectra were obtained using two different techniques, FAB
(fast atom bombardment) and MALDI (matrix assisted laser
desorption ionisation). Elemental analyses for carbon, hydrogen,
nitrogen and sulphur were carried out on a Carlo Erba 1108
elemental analyser. Thin layer chromatography was performed on
aluminium plates coated with silica gel, 60 F254 (Merck). The eluent
system used was iso-butanol:n-propanol:ethyl acetate:water
(2:4:1:3), unless otherwise stated. The developed plates were
visualised under both short and long wavelength ultraviolet light.
Procion Yellow MX-3R and Procion Red MX-8B were available
commercially. Samples of 3-aminoacetanilide, 2-aminonaph-
thalene-3,6,8-trisulphonic acid and benzidine-2,20-disulphonic
acid were generously provided by DyStar.
The strength of any given dyestuff sample was estimated from
the ratio of its actual molecular weight (MW) to its effective
molecular weight (Mole In) estimated by titanous chloride titration
method [17], each water-soluble dyestuff usually being contami-
nated with varying amounts of non-coloured (mainly inorganic)
materials.
phenyl-b-sulphatoethyl sulphone was added (7.05 g, M.I. 470,
1.5:1 M ratio) at 16e18 ꢀC to the stirred filtrate at 20 ꢀC and at pH
6e6.5. After 4 h the mixture was filtered, the filtrate collected and
the product was precipitated with potassium chloride (26 g,
8% w/v). The resulting solid, yellow dye (structure shown in Fig. 4)
was collected and dried under vacuum. Rf 0.18. (M-OSO3H)þ 915.43,
(M-SO3)þ 932.43, mol. Wt. 1012.45 R.T (h.p.l.c.) 3.50 min. Yield
3.67 g, 24%, M.I. 1512. E.a. strength 72.7%, εmax 22,368 molꢁ1 cmꢁ1 l.
2.2. 4-(-
b
-[Sulphatoethyl-]sulphonyl-) chloroacetanilide
-sulphatoethyl sulphone (2.92 g, 0.01 mol,
Para aminophenyl-
b
M.I. 292) was stirred in distilled water (20 ml), sodium carbonate
solution (10% w/v) was added drop wise and the pH was raised to 5.
Chloroacetyl chloride (2.82 g, 0.025 mol) was added drop wise, at
4e6 ꢀC, and the pH was maintained at 4e5 with sodium carbonate
(10% w/v) solution, with control by t.l.c. Completion of the reaction
was also indicated by a negative test with Ehrlich’s reagent. The
2.4. Red dye
A solution of 1-hydroxy-8-aminonaphthalene-3,6-disulphonic
acid, H-acid (38.8 g, 0.1 mol M.I. 388), in water at pH 6.5,
was added to a stirred, freshly prepared, suspension of cyanuric
chloride (18.45 g, 0.1 mol) in aqueous acetone 0e5 ꢀC and the cold
mixture stirred for 3 h, after which reaction was essentially
complete. The resulting solution of N-dichlorotriazinyl H-acid was
filtered to remove a small amount of insoluble material. Concur-
rently, diazotisation of 2-aminonaphthalene-1,5-disulphonic acid
Fig. 2. Structure 2, (a) X ¼ eSCH3 (b) X ¼ eNHR(Ar).
Fig. 3. Structure 3, N-chloroacetyl para aminophenyl-b-sulphatoethyl sulphone.

K. Pasha, J.A. Taylor / Dyes and Pigments 96 (2013) 397e402
399
Table 1
Quantities of salt and alkali applied.
(% Dye o.m.f.)
Glaubers salt (g/l)
Soda ash (g/l)
1
2e9
35
50
20
20
Fig. 4. Syn. yellow dye.
ensure almost complete primary exhaustion [18] and [19]. A set of
eighteen dyeing tubes was needed to measure the substantivity,
exhaustion and fixation of each dye. The liquor ratio used for 2.5 g
fabric was 10:1. Each dyeing tube was prepared as follows:
(52 g, 0.1 mol, M.I. 520) was accomplished with sodium
nitrite (6.9 g, 0.1 mol) and hydrochloric acid (0.25 mol, strength
35%) at 3e4 ꢀC. The resulting suspension of diazonium salt was
added to the freshly prepared solution of N-dichlorotriazinyl
H-acid at pH 6e6.5 and at 8e10 ꢀC. After 60 min the reaction was
essentially completed and product was salted out by slowly
adding sodium chloride (15% w/v) to the stirred solution and
dried under reduced pressure. Rf 0.53. R.T. (h.p.l.c.) 1.89 min.
Yield 108 g, 65%. M.I. 1808. E.a. strength 45%.
This red dichlorotriazinyl dye (18.08 g, 0.01 mol, M.I. 1808) was
dissolved in water at 8e10 ꢀC, the pH of the solution was raised to
8 to 9 with sodium carbonate solution (10% w/v). Sodium hydrogen
sulphide (1.95 g, 0.025 mol) was added directly portion wise to this
solution at 8e10 ꢀC and the temperature slowly raised to about
18 ꢀC at pH 8e9, with control by t.l.c. and h.p.l.c. After 1.5 h, the
solution was filtered, the filtrate was collected and excess
2.6.1. Dyebath 1 (control)
The required weight of dye solution, Glaubers salt solution and
water were added to the dyeing tube and placed in the dyeing
machine at 60 ꢀC. After 60 min the tube was removed from the
dyeing machine and immediately dipped into tap water for
a couple of minutes to cool to room temperature. Later the optical
density of the solution was measured and used as the control to
calculate the substantivity and exhaustion.
2.6.2. Dyebath 2e5
The same weights of dye, salt and water were added to make
each of dyebaths 2e5 as were used in making dyebath 1. The only
difference was that a 2.5 g piece of cotton was added to each dye-
bath. The tubes were then placed in a dyeing machine at 60 ꢀC for
10, 20, 30 and 60 min. After the required period, each tube was
removed from the dyeing machine and cooled to room temperature
by dipping in cold water. Excess liquor was squeezed back into the
tube by applying the same pressure to each fabric from tubes 2e5.
To ensure consistency in squeezing out excess liquor each piece of
fabric was weighed after squeezing until the same weight was
achieved. The dye solutions (excess liquor) from tubes 2e5 were
kept at room temperature and later their optical densities were
measured to allow calculations of the substantivity and exhaustion
of the dyes.
N-chloroacetyl para aminophenyl-b-sulphatoethyl sulphone
(7.05 g, 0.015 mol, M.I. 470) was added. The reaction was stirred at
room temperature at pH 6e6.5 (sodium carbonate solution). After
3 h, the solution was filtered, the filtrate collected and the product
was precipitated by slow portion wise addition of potassium
chloride (55 g, 13.75% w/v). The resulting precipitated red dye
(structure shown in Fig. 5) was collected and dried under vacuum.
Rf 0.20, (M-OSO3H)þ 1003.51, (M-SO3)þ 1020.51, molecular weight
1100.51, h.p.l.c. retention time 2.14 min, yield 18 g, 63%, M.I. 2833,
E.a. 42.72%, εmax. 31,250 molꢁ1 cmꢁ1 l.
2.5. Exhaust dyeing method
Each dye was applied to bleached unmercerised woven cotton at
five depths, viz. 1%, 2%, 4%, 6% and 9% dye o.m.f. at 60 ꢀC and liquor
ratio 10:1, using the quantities of Glauber’s salt (exhaustion for
30 min) and soda ash (fixation for 60 min) shown in Table 1. After
dyeing, the fabric was rinsed well with cold and hot water before
soaping at the boil for 10 min. Finally the fabric was rinsed with
cold water and air dried at room temperature.
2.6.3. Dyebath 6 (control B)
The same weight of dye, salt and water were added as in control
A without fabric and placed in dyeing machine for 60 min at 60 ꢀC.
Then a measured amount of alkali (sodium carbonate solution) was
added and the tube was replaced in the dyeing machine at 60 ꢀC.
After 60 min the tube was removed, cooled to room temperature
and the optical density of the solution was measured to calculate
the value of fixation.
2.6. SER5F profiles of dyes
2.6.4. Dyebaths 7e12
Dyebaths 7, 8, 9, 10, 11 and 12 were made up as for dyebath 6
(control B). The exception was that in dyebath 6 there was no fabric,
whereas a piece of fabric weighing 2.5 g was added in each of
dyebaths 7e12. After the completion of the exhaustion period
(60 min) the measured amount of alkali was added to each tube and
The SER5F profile (substantivity, exhaustion, reactivity and
fixation) of each dye was measured at 3% dye o.m.f., under similar
dyeing conditions to those used for the assessment of build-up,
except that in this case time spent by dyes in the dyebath, in
presence of fabric and salt before addition of alkali, was 60 min to
Fig. 5. Syn. red dye.

400
K. Pasha, J.A. Taylor / Dyes and Pigments 96 (2013) 397e402
30
25
20
15
10
5
later optical densities of these solutions were measured along with
other solutions collected during the whole exercise. These values
were used to determine the amount of unfixed dye removed during
washing off and therefore, gave the true fixation.
2.7. Optical density measurements
Optical densities were measured using a Pye Unicam PU 8700
spectrophotometer. All readings were taken at room temperature
in the presence of aqueous buffer (pH 7).
2.8. Substantivity, exhaustion and fixation
0
These were calculated as follows.
0
0.05
0.1
0.15
0.2
Tube 1 ¼ OD1 ¼ Control A.
Amount of dye appliedto cotton (mmoles/10 gm)
0
Tubes 2e5 ¼ OD2e5 ¼ 10, 20, 30 and 60 min in salt only.
Tube 6 ¼ OD6 ¼ Control B.
Tubes 7e8 ¼ OD7e12 ¼ 60 min salt and 5, 10, 20, 30, 45 and
60 min in alkali.
Synth yellow dye
Comm S.S Yellow 3RF
Fig. 6. Colour yield (k/s) versus dye applied (Sumifix Supra yellow 3RF and synthesised
yellow dye).
Tubes 13e18 ¼ OD13e18 ¼ wash off of tube 7e12 respectively.
ꢃ Percent substantivity ¼ (OD1ꢁODn)/OD1
n ¼ from tube 2 to tube 5.
then the tubes were returned to the dyeing machine for 5, 10, 20,
30, 45 and 60 min for tubes 7, 8, 9, 10, 11 and 12 respectively. At the
end of the designated time each tube was removed from the dyeing
machine and cooled to room temperature by dipping in cold water;
excess liquor was removed by squeezing the fabric. Again the
amount of excess liquor remaining on the fabric was controlled by
weighing and squeezing each fabric to constant weight
i.e., 5.5 ꢂ 0.1 g. The solutions were used to measure optical densities
to determine the exhaustion and fixation.
ꢃ Percent exhaustion ¼ (OD6ꢁODn)/OD6
n ¼ from tube 7 to tube 12.
ꢃ Percent fixation after n minutes ¼ ((OD6ꢁOD7e12ꢁOD13e18)/
OD6) ꢄ 100
2.6.5. Dyebaths 13e18
Distilled water (47.5 ml) was measured and added to the dyeing
tubes 13e18 and placed in the rotadyer at 95 ꢀC. When the
temperature reached the desired value, squeezed fabric from dye-
baths 7e12 were placed in tubes 13e18 respectively, then the tubes
were placed again in the rotadyer at 95 ꢀC for 30 min. After that
tubes were removed from the dyeing machine, cooled to room
temperature and excess liquor was squeezed back into the tube and
2.9. Wash fastness I.S.O. 105: CO6/C2S test
This test assesses both the change (or loss) of colour and staining
of adjacent fabrics that occurs during washing. Samples were dried
in air at room temperature and assessed for any change of colour
and staining of the adjacent multi-fibre strip.
2.10. Dye e fibre bond stability in aqueous alkali
35
30
25
20
15
10
5
For each dye, a given weight of cotton fabric was dyed at 3% dye
(o.m.f.). A measured amount of buffer solution (pH 12) was placed
100
90
80
70
60
50
40
30
20
10
0
0
0
0.05
0.1
0.15
0.2
Amount of dye aplliedto cotton (mmoles/100 gm)
0
10 20 30 40 50 60 70 80 90 100 110 120 130
Time in minutes
Commercial S.S Red 3BF
Synth. red dye
Comm S.S Yellow 3RF
Synth yellow dye
Fig. 7. Colour yield (k/s) versus dye applied (Sumifix Supra red 3BF and synthesised
red dye).
Fig. 8. SER5F profile of yellow dyes.

K. Pasha, J.A. Taylor / Dyes and Pigments 96 (2013) 397e402
401
Table 3
100
90
80
70
60
50
40
30
20
10
0
Results showing dyeefibre bond stability.
Dye
K/S values
Before test
Dye loss (%)
After test
Sumifix Supra yellow 3RF
Syn. yellow
Sumifix Supra red 3BF
Syn. red
17.05
14.97
15.87
16.03
14.21
12.76
14.69
15.23
16.66
14.77
7.44
5.00
While commercial Sumifix Supra Red 3BF built up better than
synthesised red dye overall.
0
10 20 30 40 50 60 70 80 90 100 110 120 130
3.2. SER5F profiles
Time in minutes
The SER5F profiles were measured at 3% depth of shade on the
fibre. The values of optical density measurements were converted
into respective percentages and are depicted graphically in Fig. 8
and Fig. 9. From SER5F profiles of both the synthesised yellow and
red dyes it can be seen that both exhibit marginally lower fixation
in medium shades (3% o.w.f.) than the commercial Sumifix Supra
analogues. For both the synthesised dyes the maximum level of
substantivity achieved after 60 min was less than that of the cor-
responding Sumifix Supra dyes.
The lower substantivity values of synthesised yellow and red
dyes relative to commercial products, Sumifix Supra Yellow 3RF and
Sumifix Supra Red 3BF, is attributed to the carboxamidomethylthio
linking group used to attach vinyl sulphone reactive group to the
chlorotriazine residue. This appears to contribute less to sub-
stantivity, hence exhaustion and fixation than the more usual
triazineeNHearyl linkage of commercial dyes.
Comm S/S Red 3BF
Synth. red dye
Fig. 9. SER5F profile of red dyes.
in each dyeing tube so as to ensure the liquor to fabric ratio is 20:1
[20] and [21]. When the temperature of the rotadyer and buffer
solutions had reached 80 ꢀC, dyed samples of fabric were placed in
separate tubes and left for 60 min with continuous rotation at 80 ꢀC.
After 60 min the samples were washed with distilled water (5 min
cold wash, 10 min boiling water then 5 min cold wash) and dried at
room temperature. K/S values of each fabric were measured using
a Datacolor International Spectraflash 600 spectrophotometer and
any reduction in the colour strength occurring during the test was
assessed.
2.11. Variation in colour yield with changes in dyeing temperature
3.3. Staining properties
Each dye was applied at 3% o.m.f at 50 ꢀC, 60 ꢀC, 70 ꢀC and 80 ꢀC
at 10:1 liquor ratio using 2.5 g pieces of knitted cotton fabric,
presence of Glauber’s salt (60 g/l) and soda ash (20 g/l). After
dyeing, fabrics were washed and dried at room temperature and
the colour strength of each dyed fabric was assessed (k/s values).
Staining properties of both the synthesised yellow and red dyes
were assessed using multifibre strip in CO6/C2S test. Both dyes
showed no staining on any of the fibres of multifibre strip as shown
in Table 2. Similar results were observed for commercial Sumifix
Supra Yellow 3RF and Sumifix Supra Red 3BF.
3.4. Dye-fibre bond stability in aqueous alkali
3. Results and discussion
The dye fibre bond stability of synthesised yellow and red dyes
under alkaline conditions appeared superior to that of commercial
Sumifix Supra dyes as less dye loss being observed on treatment
with hot aqueous alkali as shown in Table 3. The established
observation [22] that dye fibre bond formed by the reaction of vinyl
sulphone with the cellulose cleaves more under alkaline conditions
than to the dye fibre bond formed by halo triazinyl dyes, might
suggest that in case of synthesised yellow and red dyes more
covalent bonding to cotton occurred via triazinyl linkage as
compared to commercial Sumifix Supra Yellow 3RF and Sumifix
Supra Red 3BF. This is in accordance with our expectations that the
presence of alkylthio group enhanced the reactivity of chloro group
of triazine ring.
3.1. Build-up properties of yellow and red dyes
The visual colour yields of the dyed fabrics were expressed as k/s
values. In order to facilitate the comparison of the build-up prop-
erties of the these dyes, k/s values versus dye concentrations in
millimoles per 100 g of fabric were plotted, as depicted graphically
in Fig. 6 and Fig. 7.
At pale and medium depths of shade of yellow dyes, commercial
Sumifix Supra Yellow 3RF was marginally superior but at heavy
depths of shade the novel synthesised yellow dye built up better.
Table 2
I.S.O. 105: CO6/C2S test results.
4. Conclusion
Dye
Staining
Secondary Bleached
cellulose un-mercerised
Nylon 6.6 Polyester Acrylic Wool
The concept of synthesising a substituent which can be intro-
duced into a dye as a linking group to impart increased reactivity to
a chlorotriazine has been demonstrated to be viable and effective.
The improved dye-fibre bond stability, under alkaline dyeing
conditions, of the synthesised yellow and red dyes, compared to
their Sumifix Supra analogues, was in agreement with the concept.
acetate
cotton
S.S. yellow 3RF
Syn. yellow
S.S. red 3BF
Syn. red
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5

402
K. Pasha, J.A. Taylor / Dyes and Pigments 96 (2013) 397e402
[14] Koopman H, Uhlenbroek JH, Haeck HH, Daams J, Koopmans MJ. Investigations
on herbicides II: 2-alkyloxy- and 2-aryloxy-4,6-dichloro-1,3,5-triazines
2-alkylthio- and 2-arylthio-4,6-dichloro-1,3,5-triazines. Recl. Trav. Chim.
Pays-Bas 1959;78:967e80.
[15] Lehr F. Synthesis and application of reactive dyes with heterocyclic reactive
systems. Dyes Pigments 1990;14:239e62.
Both the synthesised yellow and red dyes having a novel bridging
group broadly performed similar to their commercial Sumifix Supra
analogues. Use of mixed reactive system, as tried in synthesised
novel yellow and red dyes, might display even better build up and
fixation in conjunction with more substantive chromophores.
[16] Smith B, Berger R, Freeman HS. High affinity, high efficiency fibre-reactive
dyes. Color Technol 2006;122:187e93.
References
[17] Murtagh V, Taylor JA. A simple titrimetric method for the estimation of
reactive dye fixation on cellulosic fabrics. Dyes Pigments 2004;63:17e22.
[18] Bent CJ, Davies PA, Phillips DAS. Latest development in the batchwise
application of hot-dyeing reactive dyes to cellulosic knitwear. JSDC 1982;98:
326e34.
[1] Sumifix Supra and Sumifix dyes. Osaka, Japan: Sumitomo Chemical Ltd.
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