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Dyeing of nylon with reactive dyes. Part 3: Cationic reactive dyes for nylon

Article in Dyes and Pigments · December 2008

DOI: 10.1016/[Link].2006.11.010

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 Dyes and Pigments 76 (2008) 610e623
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Dyeing of nylon with reactive dyes. Part 3: Cationic reactive

dyes for nylon
A. Soleimani-Gorgani1, J.A. Taylor*
Textiles and Paper, School of Materials, University of Manchester, Sackville Street, Manchester M60 1QD, UK
Received 31 October 2006; received in revised form 29 November 2006; accepted 29 November 2006
Available online 22 December 2006

Abstract

Several reactive dyes, solubilised by the incorporation of one or two cationic groups were synthesised. Each possessed either a single mono-
or dichlorotriazine reactive group, or a hetero-bifunctional (monochlorotriazine/sulphatoethylsulphone) reactive system. All dyes fixed effi-
ciently to nylon under alkaline dyeing conditions with fixation and build up being fully comparable to market’s leading anionic reactive dyes.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Reactive dyes; Nylon; Fixation efficiency; Cationic dyes

1. Introduction bromoacrylamides [12], chlorotriazines and vinylsulphones

[13,14], as well as some disperse types [15].
Anionic (acid) dyes are commonly used to colour nylon The most notable commercial reactive dyes for nylon have
[1,2]. These attach to nylon via electrostatic linkages between probably been the Stanalan [16] and Eriofast [17] ranges. In
the cationic, protonated amino end groups of the nylon (NHþ 3) order to render reactive dyes for nylon attractive to potential
and the anionic sulphonate groups of the dye (DyeeSO 3 ). customers it is necessary that any such products exhibit a use-
However, in this type of attachment the wet fastness is usually ful balance of technical and commercial properties. Desirable
less than ideal and some staining of adjacent fabrics takes technical features include high fixation, good build-up and
place during laundering. The first commercially successful co- fastness properties.
valent attachment of dyes to textiles is generally attributed to We have recently reported that molecular size and shape, as
Rattee and Stephen [3e6] who demonstrated that dyes con- well as degree of sulphonation, are important determinants of
taining a dichlorotriazine reactive group could be covalently anionic reactive dye fixation [18,19] on nylon. Greater sul-
attached to cotton [7e10]. Nowadays reactive dyes, which in- phonic acid group concentration leads to greater electrostatic
corporate one or more electrophilic reactive groups, are the attraction with the positively charged fibre (nyloneNHþ 3 under
dominant class used for dyeing cellulosic fibres. However, acidic conditions), and final exhaustion (K/S )2 and fixation ef-
only relatively small quantities of reactive dye are used on ny- ficiency were observed to increase with increasing degree of
lon and the focus of most of the published work has been sulphonation [19]. Additionally, the build up of anionic reac-
a comparison of the relative efficacies, on nylon, of existing tive dyes is limited by the number of amino sites present on
water soluble cellulose reactive dyes possessing electrophilic the fibre and also by steric hindrance.
reactive groups such as chlorodifluoropyrimidines [11], Reactive groups, capable of reacting with the terminal
amino groups of nylon, belong to one of the two major classes.
* Corresponding author. Tel.: þ440 161 306 4112; fax: þ440 161 955 8150. Hetero-aryl halides react by a bimolecular activated hetero-
E-mail address: [Link]@[Link] (J.A. Taylor). aromatic nucleophilic substitution (SNAr) reaction. Activated
1
Present address: Institute of Colourants, Paint and Coatings, Teheran, Iran. Michael type acceptors function by the nucleophilic addition

0143-7208/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/[Link].2006.11.010
 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623 611

of a terminal amino group to the b-carbon of an activated dou- through the column, maintained at 40  C, in a fixed ratio
ble bond of the reactive dye. Such reactions would be expected A:B (70:30) at the standard gradient rate 2 ml/min, and the
to occur only when the amino end groups in the fibre are non- samples were analysed spectroscopically using a diode array
protonated and nucleophilic. Under the usual acidic applica- detector at a wavelength range from 250 to 650 nm. Elemental
tion the effective concentration of un-protonated amino groups analyses for carbon, hydrogen, nitrogen and sulphur were car-
on nylon is low and fixation tailed off before all the formally ried out at the Department of Chemistry, University of Man-
available amino groups had reacted with dye. chester, on a Carlo Erba 1108 element analyser. Mass
Lewis and Ho [20] proposed that when dyeing at 95  C, the spectrometry was performed using two different techniques,
pKa of the amino conjugate acid in nylon 6.6 would be about fast atomic bombardment and MALDI (matrix assisted laser
8. At high pH, the carboxylic acid group of nylon will be es- adsorption ionisation) at Hall Analytical, Manchester.
sentially fully de-protonated and the fibre will be strongly an- Scoured, modified nylon 6.6 Tactel Coloursafe fabric was sup-
ionic. Thus anionic dyes will experience strong electrostatic plied by Du Pont (UK).
repulsion from the nylon. Conversely cationic dyes would be Commercial reactive dyes invariably contain additional ma-
expected to be strongly attracted to anionic fibre, via ione terials such as dedusting agents, salt and water. The effective
ion attractive forces, whilst at the same time maximising the agent (e.a.) content of each dye was determined by titration
concentration of nucleophilic amino end groups and thus the against titanium(III) chloride [13e15]. As titanium(III) chlo-
number of sites for reaction with electrophilic reactive groups. ride is readily oxidised by air it was standardised prior to
In order to test this postulate some reactive cationic dyes were use by titration against a standard dye (Procion Orange MX-
prepared and evaluated. 2R). The dye (0.1 g) was dissolved in distilled water
(100 ml) and potassium sodium tartrate buffer (20 ml,
20% w/v) was added. The solution was boiled under argon
2. Experimental and titrated against titanium(III) chloride solution (0.1 N)
and the strength of each dye described by its Mole In, that
Visible absorption spectra were recorded using a Phillips is, the mass in grams of dye which contains one mole of dye.
model PU 8700 UV/visible spectrophotometer. Thin layer
chromatography (TLC) was performed using aluminium plates
coated with silica gel 60 F254 (Merck) as stationary phase, 2.1. Preparation of dyes
and a mixture of isobutanol:n-propanol:ethyl acetate:water in
the ratio 2:4:1:3 as mobile phase. The developed plates were A series of dyeings were conducted using the novel reactive
visualised under visible, short and long wavelength ultraviolet dyes listed in Table 1. These were prepared as described below.
light (254 nm, 365 nm). High performance liquid chromatog-
raphy (HPLC) was performed using a Hewlett-Packard 1100 2.1.1. m-Aminophenyltrimethylammonium salt
liquid chromatograph with a 10 cm, Purospher RP-18 (5 mm) This was prepared by the two routes depicted in Schemes 1
packing and LiChroCART 125-4 HPLC column cartridges. and 2.
The mobile phases used were aqueous 0.25% CHAP solution
(dicyclohexylammonium phosphate) as solvent A and acetoni- [Link]. m-Aminophenyltrimethylammonium salt (method
trile (HPLC grade) as solvent B. These solvents were passed 1). meta-Nitroaniline (1) (0.945 mol, 130 g), was stirred

Table 1
Synthesised novel reactive dyes used for dyeing, Tactel Coloursafe
X

N N
NHCONH2 Cl
HN N Cl
+ N
(CH3)3N N N N + N
Cl (CH3)3N N
N N X
H N(CH2-CH3)2
(Dye 1 to Dye 3) (Dye 4 to Dye 7)
Dye No. of cationic groups XH (A) Reactive group
1 1 Cl Dichlorotriazinyl
2 2 m-(Trimethylammonio-)phenylamino Monochlorotriazinyl
3 1 4-(2-Sulphatoethylsulphonyl)phenylamino Monochlorotriazinyl and vinylsulphone
4 1 Cl Dichlorotriazinyl
5 1 Phenylamino Monochlorotriazinyl
6 2 m-(Trimethylammonio-)phenylamino Monochlorotriazinyl
7 1 4-(2-Sulphatoethylsulphonyl)phenylamino Monochlorotriazinyl and vinylsulphone
612 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623

O
O NH2 HCl
N+
N+ O-
O Fe,98-100°C
1)HBr(47%)-90°C
Reflux, 22hrs
2)Methanol,25h
HCl
95-100°C, 5 atm H3C N+ -CH3
(Autoclave) H3C N+ CH3 Br
NH2 Br-
CH3 CH3
(1) (2) (3)

Scheme 1. Synthesis of m-aminophenyltrimethylammonium salt (method 1).

NHCOCH3 NH2
NHCOCH3

DMS H2SO4 CH3

CH3
-CH OSO -
+ 3 3
NH2 N+ N
CH3 CH3
H3C H3C
(4) (5) (6)

Scheme 2. Synthesis of m-aminophenyltrimethylammonium salt (method 2).

with aqueous hydrogen bromide solution (47%, 156 ml, a previously prepared suspension of iron dust (57.5 g), in dis-
0.72 mol/mol), with good agitation at 30  C. The suspension tilled water (191 ml), and hydrochloride acid (12 N, 3.5 ml).
was then heated to 90  C for 30 min. On cooling to room tem- The mixture was heated under reflux for 45 min, maintaining
perature, the solid was collected, washed with acetone the temperature by controlling the rate of addition. The result-
(200 ml), and dried under reduced pressure, at 20  C. This ing suspension was refluxed for 22 h, cooled to 25  C and so-
was stirred with methanol (200 ml), and heated in an autoclave dium carbonate (w20 g) was added very carefully with
for 25 h at 95e100  C and at 5 atm pressure. The resulting stirring, to pH 8. The resulting suspension was filtered through
pale brown crystalline solid was collected, stirred with meth- ‘‘Hyflo’’ to give a clear brown solution of filtered m-amino-
anol (250 ml), collected and washed with further methanol phenyltrimethylammonium bromide (3) which was used
(100 ml). The almost dry solid was stirred with dilute aqueous directly.
ammonia (5 g þ 250 ml water), for 5 min and collected, stirred
with methanol (200 ml), followed by diethyl ether (200 ml) [Link]. m-Aminophenyltrimethylammonium salt (method 2). 3-
and the resulting 3-nitrophenyl-trimethylammonium bromide Aminoacetoanilide hydrochloride (4), (18 g, 0.12 mol), was
was dried at room temperature. 3-Nitrophenyl-trimethylam- dissolved in distilled water, and the pH was raised to 7. Dime-
monium bromide (50 g, 0.19 mol), was added slowly to thylsulphate (DMS) (50.4 g, 0.4 mol) was added to the

H
+ - H2N CO N
N NCl NHCONH2

pH, 5.5-6 N NH2

+ N
T, 0-5°C
+
N(CH3)3 NH2 +
(CH3)3N

T, 5-14°C Cl
pH, 4-5 N N

Cl N Cl
NHCONH2 Cl

+ N
(CH3)3N N N N

N N Cl
H

Scheme 3. Synthesis of Dye 1.

 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623 613

resulting suspension of 3-aminoacetoanilide and the mixture NHCONH2 Cl

heated to 50  C; the pH was maintained at 7 by the slow + N
addition of sodium hydroxide (2 N). The reaction was moni- (CH3)3N N N N
tored by TLC and HPLC and the product hydrolysed without N N Cl
isolation. Concentrated sulphuric acid was slowly added drop- H
wise to the stirred solution of 3-(acetylaminophenyl)trimethy- NH2
lammonium chloride (5) at room temperature; the mixture was
T, 30-40°C
stirred at 90e100  C for 1 h, with control by HPLC and TLC,
pH, 6-6.5 +
to produce a solution of m-aminophenyltrimethylammonium N(CH3)3
methosulphate (6), which was used directly without isolation.

2.1.2. 1-(3-Trimethylammoniophenylazo)-2-ureido-4-(4,6-
NHCONH2 Cl
dichloro-[1,3,5]triazin-2-ylamino)benzene (Dye 1)
+ N
This was prepared by the route depicted in Scheme 3. (CH3)3N N N N
A solution of sodium nitrite (2.5 g, 0.036 mol), in distilled
water (20 ml), was slowly added, at 0e5  C, to a solution of N
H
N NH
the above m-aminophenyltrimethylammonium salt (4.8 g,
0.032 mol) in water (20 ml) and hydrochloric acid (36%,
+
40 ml, 0.08 mol). After stirring for 30 min at 0e5  C and (CH3)3N
pH less than 2, excess nitrous acid was destroyed by adding
a small amount of sulphamic acid. The resulting solution of di- Scheme 4. Synthesis of Dye 2.
azonium salt was added slowly to a solution of m-ureido-ani- 2.1.4. 1-(3-Trimethylammoniophenylazo)-2-ureido-4-[4-
line (4.8 g, 0.032 mol), at pH 5.5e6. The mixture was stirred chloro-6-[40 (b-sulphatoethylsulphonyl)phenylamino]-
for 30 min at pH 6 and at 0e5  C. The resulting yellow solid, [1,3,5]triazin-2-ylaminobenzene (Dye 3)
1-(3-trimethylammoniophenylazo)-2-ureido-4-aminobenzene, This was prepared by the route depicted in Scheme 5.
was collected after removing some of the solvent under Sodium hydroxide (2 N) was added slowly to a suspension of
reduced pressure. 4-(2-sulphatoethylsulphonyl)aniline (PABSES) (9 g, 0.032 mol),
A freshly prepared suspension of 2,4,6-trichloro-s-triazine in distilled water (200 ml), at 0e5  C up to pH 2, followed by
(5.9 g, 0.032 mol) was made by adding a solution of this mate- the slow addition of sodium carbonate solution (2 N) up to pH
rial in acetone (20 ml) to crushed ice (10e20 g). The solution of 4. A freshly prepared suspension of 2,4,6-trichloro-s-triazine
1-(3-trimethylammoniophenylazo)-2-ureido-4-aminobenzene, (5.9 g, 0.032 mol), in acetone (30 ml), and crushed ice (10e
in distilled water (100 ml), at 5  C and at pH 4 was added to this 20 g), was added very slowly to the resulting stirred solution
suspension. The mixture was stirred for 30 min with control by of 4-(2-sulphatoethylsulphonyl)phenylamino at below 5  C
TLC (Rf ¼ 0.64) and h.p.l.c. (tR ¼ 1.2 min). The resulting and at pH 3.5. After 1 h the reaction was essentially complete
solid, 1-(3-trimethylammoniophenylazo)-2-ureido-4-(4,6- and 2,4-chloro-6-[40 (b-sulphatoethylsulphonyl)phenylamino]-
dichloro-[1,3,5]triazin-2-ylamino)benzene, was collected by [1,3,5]triazin-2-ylaminobenzene, so produced, was used with-
filtration. The dye was very sparingly soluble in water. Calc. out further isolation.
for C19H20N9OCl2: C, 49%; N, 27%. Found: C, 26%; N, A solution of 1-(3-trimethylammoniophenylazo)-2-ureido-
14%. Mol. In was 885 (52% e.a.). Mass m/e: [(460e463) ¼ M]. 4-aminobenzene prepared as described above (Section 2.1.2)
was added slowly to a solution of 2,4-dichloro-6-[40 (b-sulph-
2.1.3. 1-(3-Trimethylammoniophenylazo)-2-ureido-4-[4- atoethylsulphonyl)phenylamino]-[1,3,5]triazin-2-ylaminoben-
chloro-6-(3-trimethylammoniophenylamino)-[1,3,5]triazin- zene, at 30e40  C and at pH 5. The mixture was stirred for
2-ylaminobenzene (Dye 2) 30 min at pH 6 and the resulting yellow product 1-(3-trimethy-
This was prepared by the route depicted in Scheme 4. lammoniophenylazo)-2-ureido-4-[4-chloro-6-{40 (b-sulphatoe-
A solution of m-aminophenyltrimethylammonium chloride thylsulphonyl)}phenylamino]-[1,3,5]triazin-2-ylaminobenzene
(4.8 g, 0.032 mol) in distilled water was slowly added to a so- was collected by filtration (HPLC (tR ¼ 4.1 min) and TLC
lution of 1-(3-trimethylammoniophenylazo)-2-ureido-4-(4, (Rf ¼ 0.58)). The dye was very sparingly soluble in water
6-dichloro-[1,3,5]triazin-2-ylamino)benzene prepared as de- and the Mol. In was determined by elemental analysis: 832
scribed above (Section 2.1.2) at 30e40  C, and at pH 6, (87% e.a.). Calc. for C27H29N10S2O7ClNa (725.5): C,
with control by HPLC (tR ¼ 1.4 min) and TLC (Rf ¼ 0.68). 44.6%; N, 19.2%; S, 8.8%. Found: C, 38.9%; N, 19.24%; S,
The desired product, 1-(3-trimethylammoniophenylazo)-2- 7.55%. Mass spectrum m/e: 607 (M  SO4Na), 667
ureido-4-[4-chloro-6-(3-trimethylammoniophenylamino)-[1,3, (M  N2H3CO), 711 (M  CH3), 726 (M).
5]triazin-2-ylamino]benzene, was collected by filtration.
Calc. for C28H34N11OCl2: C, 55%; N, 25.2%. Found: C, 2.1.5. 4-(3-Trimethylammoniophenylazo)-3-amino-N,N-
19.2%; N, 8.76%. Mol. In ¼ 1754 (35% e.a.). Mass m/e: 611 diethylaniline
(M þ H). This was prepared by the route depicted in Scheme 6.
614 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623

Cl
Cl
N N
N N pH, 3.5-4
Cl N NH
N T, 0-5°C
Cl Cl
(A)

SO2CH2CH2OSO3H
H
H2N CO N

N NH2
N
+
(CH3)3N

NHCONH2 Cl
+ N
(CH3)3N N N N

N N NH
H

SO2CH2CH2OSO3H

Scheme 5. Synthesis of Dye 3.

A solution of 3-trimethylammoniophenyl diazonium chlo- acid (2 N) was added dropwise to a stirred solution of the
ride (2.475 g, 0.015 mol), prepared as described (Section resulting 4-(3-trimethylammoniophenylazo)-3-acetylamino-
2.1.2), was added slowly to a solution of N,N-diethyl N,N-diethylaniline, under reflux, at 90e100  C for 30 min
m-amino acetanilide (3.09 g, 0.015 mol), at pH 5.5e6. The with control by TLC (Rf ¼ 0.33) and HPLC (tR ¼ 0.651 min)
mixture was stirred for 30 min at pH 6 and at 0e5  C, to obtain an orange solid, 4-(3-trimethylammoniophenylazo)-
with control by TLC and HPLC Concentrated hydrochloric 3-amino-N,N-diethylaniline.

H3C
+ H
N2 N
O O
N N(CH2-CH3)2
HN CH3 N(CH3)3 N
+

(CH3)3N
+
N(CH2-CH3)2
pH,5.5-6
T, 0-5°C HCl
T, 90-100°C

H2N

N N(CH2-CH3)2
N

(CH3)3N
+

Scheme 6. Synthesis of 4-(3-trimethylammoniophenylazo)-3-amino-N,N-diethylaniline.

 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623 615

The Mol. In was determined by titration against titaniu- The product was essentially homogeneous as judged by TLC
m(III) chloride [21e25] (400) and microanalysis (405). Mi- (Rf ¼ 0.64) and HPLC (tR ¼ 4.89 min). Calc. for C22H27N8Cl2
croanalysis, Calc. for C19H28N5 (326): C, 69.9%; N, (474): C, 55.7%; N, 23.62%. Found: C, 37.2%; N, 15.75% cor-
21.47%. Found: C, 55.6%; N, 17.4% (80% e.a.). Mass m/e: responding to Mol. In ¼ 710 (67% e.a.). Mol. In by titanous
326/327 (M þ H). titration 704. Mass m/e: 472e475 (M).

2.1.6. 4-(3-Trimethylammoniophenylazo)-3-(4,6-dichloro- 2.1.7. 4-(3-Trimethylammoniophenylazo)-3-[4-chloro-6-

[1,3,5]triazin-2-ylamino)-N,N-diethylaniline (Dye 4) (phenylamino)-[1,3,5]triazin-2-ylamino]-N,N-
This was prepared by the route depicted in Scheme 7. diethylaniline (Dye 5)
A solution of 2,4,6-trichloro-s-triazine (1.15 g, 0.006 mol) This was prepared by the route depicted in Scheme 8.
in acetone (10 ml) was added to crushed ice (5 g) and the re- Aniline (0.558 g, 0.006 mol) was slowly added to a solution
sulting suspension was added to a stirred solution of 4-(3-tri- of dichlorotriazinyl orange reactive dye, 4-(3-trimethylammo-
methylammoniophenylazo)-3-amino-N,N-diethylaniline (2 g, niophenylazo)-3-(4,6-dichloro-[1,3,5]triazin-2-ylamino)-N,N-
0.006 mol), in distilled water (50 ml), at below 5  C and at diethylaniline, prepared as described above at 30e40  C and
pH 4. The mixture was stirred for 30 min at pH 4e5 with at pH 6 with control by TLC (Rf ¼ 0.44), and HPLC
control by TLC and HPLC and the resulting product, 4-3-trime- (tR ¼ 1.027 min). The desired monochlorotriazinyl orange re-
thylammoniophenylazo)-3-(4,6-dichloro-[1,3,5]triazin-2-yla- active dye, 4-(3-trimethylammoniophenylazo)-3-[4-chloro-6-
mino)-N,N-diethylaniline, was precipitated by slow addition of (phenylamino)-[1,3,5]triazin-2-ylamino]-N,N-diethylaniline,
potassium chloride (KCl, 20% w/v), and isolated by filtration. was precipitated by slow addition of potassium chloride
(15% w/v), isolated by filtration. Mol. In by titanous titration
H2N 995. Calc. for C28H33N9 Cl (530): C, 63.7%; N, 23.7%. Found:
C, 33.6%; N, 12.5% corresponding to Mol. In ¼ 1006 (53%
N N(CH2-CH3)2 e.a.). Mass m/e: 531 (M).
N

Cl 2.1.8. 4-(3-Trimethylammoniophenylazo)-3-[4-chloro-6-(3-
(CH3)3N+
trimethylammoniophenylamino)-[1,3,5]triazin-2-ylamino]-
pH,4.5-5 N N
T, 5-10°C
N,N-diethylaniline (Dye 6)
Cl N Cl
This was prepared by the route depicted in Scheme 9.
A freshly prepared suspension of 2,4,6-trichloro-s-triazine
Cl in ice/acetone (1.15 g, 0.006 mol) was added to a stirred solu-
N tion of m-aminophenyltrimethylammonium chloride (0.91 g,
N Cl 0.006 mol), in distilled water (100 ml), at below 5  C and at
N pH 4. The mixture was stirred for 30 min, at pH 4e5, to
HN give a solution of 3-[N-(4,6-dichloro-[1,3,5]triazine-2-ylami-
no)]phenyltrimethylammonium chloride. A solution of 4-(3-
N N(CH2-CH3)2 trimethylammoniophenylazo)-3-amino-N,N-diethylaniline,
N (2 g, 0.006 mol), in distilled water, was slowly added and the
resulting solution stirred at 30e40  C, and at pH 6, for 2 h.
(CH3)3N
+
The product, 4-(3-trimethylammoniophenylazo)-3-[4-chloro-
6-(3-trimethylammoniophenylamino)-[1,3,5]triazin-2-yla-
Scheme 7. Synthesis of Dye 4. mino]-N,N-diethylaniline, was precipitated by slow addition of

H
Cl N N
Cl
N N N

N Cl
NH2 HN N(CH2-CH3)2
N
HN
N
T:30°C N
N N(CH2-CH3)2
pH:6-6.5
N
N(CH3)
+
(CH3)3N
+

Scheme 8. Synthesis of Dye 5.

616 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623

H
Cl N N Cl
NH2

N N T, 0-5°C N N
+
pH, 3.5-4
N(CH3)3 Cl N Cl N(CH3)3 Cl
+
+

H2N
T, 30-40°C
N N(CH2-CH3)2
pH, 5.5-6
N

(CH3)3N
+

+
(CH3)3N NH

N N

HN N Cl
N
(CH3)3N N
+
N(CH2-CH3)2

Scheme 9. Synthesis of Dye 6.

potassium chloride (KCl, 25% w/v) to the stirred solution and 2.2. Dyeing
collected to give a product which was essentially homoge-
neous, as judged by TLC Calc. for C31H41N10Cl (588): C, Dyeings were carried out using a Roaches dyeing machine
63.2%; N, 23.7%. Found: C, 36.2%; N, 12.6% corresponding (Mathis Labomat BFA 12): 5 g pieces of fabric were dyed at
to Mol. In ¼ 1069 (55.5% e.a.). Mol. In by titanous titration a liquor ratio of 20:1, using stainless steel dye pots, each of
970. Mass m/e: 295(M þ H), corresponding to a strong doubly
charged ion.
Cl N Cl

N N

2.1.9. 4-(3-Trimethylammoniophenylazo)-3-[4-chloro-6- NH
[40 (ß-sulphatoethylsulphone)phenylamino]-[1,3,5]triazin-
2-ylamino]-N,N-diethylaniline (Dye 7)
HO3SOCH2CH2O2S +
This was prepared by the route depicted in Scheme 10. N(CH3)3
A solution of 2,4-dichloro-6-[40 (b-sulphatoethylsulphonyl)-
phenylamino]-[1,3,5]triazine (2.5 g, 0.006 mol), (Section T, 30-40°C N
2.1.4, Scheme 5) was added slowly to a solution of 4-(3-trime- pH, 5.5-6 N(CH2-CH3)2 N
thylammoniophenylazo)-3-amino-N,N-diethylaniline (2 g,
0.006 mol) (Section 2.1.5, Scheme 6), at 30e40  C and at NH2
pH 4e5.5 and the mixture was stirred for 30 min. The orange Cl
product, 4-(3-trimethylammoniophenylazo)-3-[4-chloro-6- SO2CH2CH2OSO3H
[40 (b-sulphatoethylsulphonyl)phenylamino]-[1,3,5]triazin-2- N N
ylamino]-N,N-diethylaniline, was precipitated by slow addition
HN N N
of potassium chloride (KCl, 25% w/v) and isolated by H
filtration. The product was essentially homogeneous as N
judged by TLC (Rf ¼ 0.35) and HPLC (tR ¼ 4.99 min). N
Calc. for C30H37N9S2 O6Cl (718.5): C, 50.1%; N, 17.53%; N(CH2-CH3)2
H, 5.14%. Found: C, 48.4%; N, 17%; H, 5.1% corresponding (CH3)3N
+
to Mol. In ¼ 748 (96% e.a.). Mol. In by titanous titration
774. Mass m/e: 740(M  H þ Na), 600(M  SO4Na). Scheme 10. Synthesis of Dye 7.
 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623 617

200 cm3 capacity. The dyeing method used is depicted in Table 2

Fig. 1. At the end of dyeing, the dyed fabric was removed Composition of McIlvaine buffers in a total volume of 80 cm3
and rinsed in cold tap water for 5 min. An initial series of dye- pH 0.2 M Na2HPO4/cm3 0.1 M citric acid/cm3
ings was carried out at four different pH values using McIl- 4 30.9 49.1
vaine buffers, as shown in Table 2 [24], for pH values of 4, 6 50.6 29.4
6 and 8 and by adding sodium hydroxide to disodium hydro- 8 77.8 2.2
gen phosphate (pH 10). No additional electrolyte, levelling
agent or alkali was used. Having determined the optimum
2.2.3. Dye fixation
pH, subsequent dyeings were carried out on 5 g pieces of fab-
Only a proportion of the total dye, which exhausts onto the
ric, at four depths of shade (0.18%, 0.36%, 0.72%, and 1.44%
substrate, reacts to form covalent linkages, whilst the remain-
o.m.f.).
ing dye is attached by ionic bonds and by van der Waals’
Dyes 1e3 and 7 were sparingly soluble and were dispersed
forces. Therefore, in order to determine the degree of dye fix-
by milling overnight with pea gravel in the presence of dis-
ation the following procedure was used. A sample (1 g) of
persing agent (Zetex DA-N, 0.5 cm3) to give very finely di-
dyed fabric was immersed in 150 cm3 of 20% aqueous pyri-
vided dispersions.
dine solution, the temperature was raised rapidly to boiling
and the treatment continued under reflux until no further dye
2.2.1. Colour strength (K/S ) of dyes on fabric was removed from the fibre, which took approximately 3 h.
Reflectance measurements on the dry dyed fabrics were The stripped dyeing was thoroughly rinsed in tap water and al-
carried out using a Datacolor Spectraflash 600 specrophotom- lowed to dry at room temperature. The percentage of ex-
eter using D65 illumination; the dyed fibre was folded twice so hausted dye fixed was determined by a method used by
as to provide four layers and the average of three reflectance several earlier workers [11e15,18,19] using Eq. (2), where
measurements, taken at different positions, was used. (K/S )1 and (K/S )2 represent the colour strength of dyeing
before and after stripping, respectively.
2.2.2. Dye exhaustion ðK=SÞ2
The extent of dye exhaustion was determined spectrophoto- %F ¼  100 ð2Þ
ðK=SÞ1
metrically. The absorbance of each dye bath solution before
and after the dyeing process was measured using 1 cm quartz This method assumes, at least at the concentrations of dyes
cells housed in a Philips PU 8720 UV/visible scanning spec- employed, that (K/S ) values are proportional to the concentra-
trophotometer at the lmax of each dye. The percentage dye tion of dye on fabric. The overall percentage fixation, %T, was
bath exhaustion (%E ) was calculated using Eq. (1), where evaluated from Eq. (3).
A0 and A1 are the absorbances of the dye bath before and after %F  %E
dyeing, respectively. %T ¼ ð3Þ
100
However, exhaustion (%E ) could not be readily determined
A0  A1 for the dyes of sparing solubility (Dyes 1e3 and 7); therefore
%E ¼  100 ð1Þ in the place of percentage of total fixation (%T ), the percent-
A0
ages of fixation (%F ) were calculated.
As Dyes 1e3 and 7 were only sparingly soluble in water,
%E could not be determined. 2.2.4. Determination of effective agent content of dyes
The effective agent content of each dye was determined by
100
titration against titanium(III) chloride as previously described
98°C
[18,19,21e24]. Invariably, the products as isolated contained
salt and water, Mole In (MI) represents the mass, in grams of
Temperature (°C)

80 dye as isolated, which contains 1 mol of ‘‘pure’’ dye. To confirm

the results obtained by titration against titanium(III) chloride,
60 the percentage effective agent contents of the dyes were also de-
termined by microanalysis. In the latter method the average of
40°C the figures for carbon and nitrogen only were used. As Dyes
40
1e3 and 7 were only sparingly soluble in water the effective
30°C agent content of each dye was determined by microanalysis.
20
0 20 40 60 80 100 120 140 160 180
2.2.5. Visible absorption spectra of dyes
Time (min)
Solutions of the seven novel dyes, achieved in the cases of
Dye and Buffer
Dyes 1e3 and 7 in acetone and, for Dyes 4e6 in distilled wa-
ter, were prepared in the concentration range 0.01e0.12 g l1
Fig. 1. Dyeing profile used. and the absorbance of each solution was measured at the lmax
618 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623

of the dye, using 1 cm cells and a Philips model PU 8720 spec- H+ H+

NH2-PA-COO- HOOC-PA-NH2 HOOC-PA-NH3+
trophotometer. The molar extinction coefficients (3max) of the
dyes were determined and are shown in Table 3. Fig. 2. Protonation/deprotonation of nylon with varying acidity.

3. Results and discussion

so as to determine the optimum application pH. Buffers of
3.1. Visible absorption spectra of dyes pH 4, 6, 8 and 10 were made as described above (Section 3)
and the dyes applied for over 60 min at 98  C.
Dyes 1e3 were all yellow; Dyes 4e7 were all orange. The As the results in Table 4 indicate, Dye 1 (at 0.18% o.m.f.),
lmax of the former group varied from 390 nm (Dye 2) to Dyes 3e5 (at 0.36% o.m.f.), fix more efficiently at pH 8,
400 nm (Dye 3) and the latter from 481 nm (Dye 6) to whilst Dye 2 (at 0.72% o.m.f.) and Dye 6 (at 1.44%, o.m.f.)
486 nm (Dye 7). The individual members of each of the two fix best at pH 10. Dyes 1e3 are only sparingly soluble, thus
groups were based on a common chromophore, and reactive measurement of the absorbance of each dye bath both before
group (single monochlorotriazine) but differed only in ‘‘sec- and after the dyeing process was not accurate. Therefore in
ond leg’’ substituent attached to the halotriazine. The introduc- these cases the percentage of exhaustion (%E ) could not be
tion of successively more powerfully electron-withdrawing determined and in the place of percentage of total fixation
groups into the ‘‘second leg’’ attached to the halotriazine re- (%T ), the percentages of fixation (%F ) were calculated.
sulted in a slight hypsochromic shift. The order of reducing Very low values of colour strength (K/S )1 were not recorded.
lmax for the group comprising Dyes 1e3 was as follows: Dye 7 possesses the same mixed monochlorotriazinyl/vinyl-
Dye 3, lmax 400 nm, 4-(2-sulphatoethylsulphonyl)aniline sulphone hetero-bifunctional reactive system as Dye 3; with
(PABSES) as ‘‘second leg’’ is more bathochromic than Dye the former dye the optimum dyeing yield was obtained at
1, chlorine as ‘‘second leg’’, lmax 392 nm, and Dye 2 m-ami- pH 8 and because of the difficulties associated with sparing
nophenyltrimethylammonium chloride as ‘‘second leg’’ sub- solubility, Dye 7 was also applied at pH 8.
stituent, lmax 390 nm. In the second group (Dyes 4e7) lmax The dependence of exhaustion and fixation on pH for the
reduces as follows: Dye 7, lmax 486 nm, 4-(2-sulphatoethyl- different dyes is shown in Figs. 3e8.
sulphonyl)aniline as ‘‘second leg’’, Dye 4, chlorine lmax The optimum pH for dyeing nylon 6.6 with cationic reac-
392 nm, Dye 5, aniline lmax 482 nm and Dye 6 m-aminophe- tive dyes was found to be between pH 8 and 10, where good
nyltrimethylammonium lmax 481 nm. exhaustion and fixation were achieved without the need for
The molar extinction coefficient of two groups of dyes var- electrolyte or proprietary levelling agent.
ied slightly, but was approximately 13,000e14,000 As all the dyes (Dyes 1e7) carried cationic groups, the ob-
(mol1 cm1) and 20,000e28,000 (mol1 cm1), respectively. served increase in dye uptake (K/S value) that accompanied
the increase in pH of application can be attributed to
3.2. Effect of pH on dyeing performance
Table 4
In the presence of water, depending on the pH within the (K/S )1, (K/S )2,, %F of all dyes and also %E, %T of soluble dyes (Dyes 4e6) at
fibre, the amino and carboxylic acid groups will be ionised different pH values
to a greater or lesser extent, according to the equilibrium Dye pH 4 6 8 10
shown in Fig. 2. 1 (0.18% dye o.m.f.) (K/S )1 0.51 0.73 1.22 1.15
Under basic conditions, the cationic reactive dye will be ad- (K/S )2 0.37 0.52 1.2 0.74
sorbed onto the anionic carboxylate groups in the fibre via %F 72.5 71.2 98.4 64.3
ioneion linkages. Consequently pH is a key parameter in 2 (0.72% dye o.m.f.) (K/S )1 e e 1.2 1.9
(K/S )2 e e 1.1 1.8
influencing the level of exhaustion and therefore probably final %F e e 91.6 94.7
fixation of the cationic reactive dye to nylon. It was thus nec- 3 (0.36% dye o.m.f.) (K/S )1 1.61 2.2 2.3 2.4
essary to determine the best application pH for each dye type (K/S )2 0.87 1.6 2 1.7
in order to achieve optimum colour yield and dye fixation. A %F 54 72.7 87 71
series of dyeings were evaluated, in buffers of different pHs, 4 (0.36% dye o.m.f.) (K/S )1 e 4.4 6 5.9
(K/S )2 e 3 5.4 4.4
%E e 60 100 90
Table 3 %T e 40 90 67.7
Molar extinction coefficients 3max and absorption maximum lmax of dyes 5 (0.36% dye o.m.f.) (K/S )1 e e 5.88 6.5
1 1 (K/S )2 e e 4.83 5.6
Dye lmax/nm 3max/mol cm l
%E e e 68 70
1 392 13 625 %F e e 82 86
2 390 12 500 %T e e 56 60.3
3 400 14 690 6 (1.44% dye o.m.f.) (K/S )1 2.89 3.16 3.31 2.33
4 485 27 512 (K/S )2 1.85 2.5 2.8 1.88
5 482 20 985 %E 90 90 100 80
6 481 20 157 64 79 84.6 80.7
7 486 28 649 %T 57.6 71.2 84.6 64.5
 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623 619

Dye 1 Dye 5
1.4 120 7 61
(K/S)1 (K/S)1
1.2 (K/S)2 100 6 (K/S)2 60
%F %T
1 5
80
59
0.8
K/S

%F
60 4

K/S

%T
0.6 58
40 3
0.4 57
20 2
0.2
1 56
0 0
0 2 4 6 8 10 12 0 55
pH 0 2 4 6 8 10 12
pH
Fig. 3. (K/S )1 (exhaustion), (K/S )2 (fixed dye) and % fixation (%F ) for Dye 1
at different pHs (0.18% dye o.m.f.). Fig. 7. (K/S )1 (exhaustion), (K/S )2 (fixed dye) and % total fixation (%T ) for
Dye 5 at different pHs (0.36% dye o.m.f.).

Dye 2
2 95
(K/S)1 Dye 6
1.8 94.5 3.5 90
(K/S)2
1.6 (K/S)1
%F 94
1.4 3 (K/S)2 80
1.2 93.5 %T
K/S

%F 70
1 2.5
0.8 93 60
0.6 92.5 2 50
K/S

%T
0.4
92
0.2 1.5 40
0 91.5
0 2 4 6 8 10 12 30
1
pH 20
0.5
10
Fig. 4. (K/S )1 (exhaustion), (K/S )2 (fixed dye) and % fixation (%F ) for Dye 2
at different pHs (0.72% dye o.m.f.). 0 0
0 2 4 6 8 10 12
pH

Fig. 8. (K/S )1 (exhaustion), (K/S )2 (fixed dye) and % total fixation (%T ) for
Dye 3 Dye 6 at different pHs (0.36% dye o.m.f.).
3 90
(K/S)1
(K/S)2 80
2.5
%F 70
2 60 a corresponding increase in the attractive ioneion interaction
50 operating between the cationic groups in the dye molecule
K/S

%F

1.5
40 and the anionic carboxylate groups present in the fibre.
1 30
20
0.5
10 3.3. Build-up properties of dyes on nylon
0 0
0 2 4 6 8 10 12
Having established that the optimum dyeing pH was 8
pH
for Dyes 1, 3, 4 and 5 and assumed to be 8 for Dye 7
Fig. 5. (K/S )1 (exhaustion), (K/S )2 (fixed dye) and % fixation (%F ) for Dye 3 (by comparison with Dye 3) and pH 10 for Dyes 2 and 6,
at different pHs (0.36% dye o.m.f.). the build-up properties of the dyes (Dyes 1e7) were deter-
mined using the dyeing profile shown in Fig. 1. The
strengths of the dyes were determined by microanalysis
Dye 4 and/or titration against titanium(III) chloride [25] and the re-
7
(K/S)1
100 sults are shown in Table 5.
90
6 (K/S)2
%T 80
5 70
60 Table 5
4
K/S

%T

50 Effective agent contents of dyes

3 40
Dye Mr Mol. In Strength/%
2 30
20 1 463 885 52
1
10 2 611 1754 35
0 0 3 725.5 832 87
0 2 4 6 8 10 12
4 474 707 67
pH 5 531 1000 53
6 588 1019 58
Fig. 6. (K/S )1 (exhaustion), (K/S )2 (fixed dye) and % total fixation (%T ) for
7 719 774 93
Dye 4 at different pHs (0.36% dye o.m.f.).
620 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623

Table 6 lists the build up (K/S data values) and percentage 8

Dye 1
fixation (%F ), exhaustion (%E ) and percentage of total fixa- 7 Dye 2
Dye 3
tion (%T ) obtained on dyeing nylon 6.6 with all novel cationic
6
reactive dyes and two commercial products, Eriofast Red B
and Eriofast Yellow R. It shows the percentage obtained on 5

(K/S)1
dyeing nylon with soluble dyes (Dyes 4e6, Eriofast Red B 4
and Eriofast Yellow R) at optimum application pH.
3
Results are depicted graphically in Figs. 9e17. In order to
obviate discrepancies arising from the different molecular 2

weights and effective agent contents of the dyes, build-up 1

data were plotted using milli-molar concentrations of dye 0
o.m.f.; therefore the dye concentration on the x-axis has 0 5 10 15 20 25
been expressed in milli-moles of dye per kilogram of fibre. mol x 10-3 of dye / kg fabric
Initially, the three hypsochromic dyes were based on Fig. 9. (K/S )1 values of Dyes 1e3.
a common chromophore, Dye 1 possesses a single dichlor-
otriazinyl reactive group and one cationic group, Dye 2 pos-
sesses a single monochlorotriazinyl reactive group and two 6
Dye 1
cationic groups, while Dye 3 possesses a single cationic Dye 2
5
Dye 3
4

(K/S)2 3
Table 6
2
(K/S )1, (K/S )2, %F, of all dyes and %E and %T of soluble dyes (Dyes 4e6 and
commercial dyes) at optimum pH 1
Dye %Depth/o.m.f. 0
0 5 10 15 20 25
0.36 0.72 1.44 1.8
mol x 10-3 of dye / kg fabric
1 (K/S )1 2.23 3.57 5.71 6.8
(K/S )2 1.8 2.7 4.2 5.1 Fig. 10. (K/S )2 values of Dyes 1e3.
%F 81 75.6 73.5 75
2 (K/S )1 0.99 1.9 2.8 3.4
(K/S )2 0.99 1.8 2.5 3 120
%F 100 94.7 89.3 88
3 (K/S )1 2.3 3.13 4.7 5.01 100
(K/S )2 2 2.9 4 4.2
80
%F 87 86 85.1 84
4 (K/S )1 6 11.3 19.4 21.5
%F

60
(K/S )2 5.4 9.7 16.5 18.2
%E 100 95 88 84 40
%F 90 86 85 84.6 Dye 1
Dye 2
%T 90 81.7 75 71.1 20
Dye 3
5 (K/S )1 3.75 7.5 14.81 17 Anionic dye
(K/S )2 3.54 7.13 13.17 15.43 0
0 5 10 15 20 25
%E 100 100 99 96
mol x 10-3 of dye / kg fabric
%F 94.4 95 89 90.76
%T 94.4 95 88 87.13 Fig. 11. %F values for Dyes 1e3 and an anionic reactive dye.
6 (K/S )1 3.31 5.6 11.1 12.93
(K/S )2 2.8 4.5 8.76 10
%E 100 85 85 81
%F 84.6 78.9 79 77.34 25
%T 84.6 69.5 67 62.6 Dye 4
Dye 5
7 (K/S )1 2.24 3.57 5 5.65 Dye 6
20 Dye 7
(K/S )2 2 3.1 4.3 4.45
%F 89.3 86.8 86 78.76
15
(K/S)1

Commercial yellow dye (K/S )1 2.9 5.8 11.3 13.4

(K/S )2 2.87 5.6 10.5 12.5
10
%E 100 100 96 95
%F 98.9 96.5 93 93.3
%T 98.9 96.5 89 88.62 5
Commercial orange dye (K/S )1 2.64 5.28 9.9 12.6
(K/S )2 2.54 5.05 9 11.5 0
0 5 10 15 20 25 30
%E 100 100 96 94
%F 96.2 95 90 91 mol x 10-3 of dye / kg fabric
%T 96.2 95 86 85
Fig. 12. (K/S )1 values of Dyes 4e7.
 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623 621

20 120
Dye 4
18 Dye 5
16 Dye 6 100
Dye 7
14
80
12
(K/S)2

%T
10 60
8
6 40
4 Dye 4
Dye 5
2 20
Commercial Yellow dye
0 Commercial Orange dye
0 5 10 15 20 25 30 0
0 5 10 15 20 25
mol x 10-3 of dye / kg fabric
mol x 10-3 of dye / kg fabric
Fig. 13. (K/S )2 values of Dyes 4e7.
Fig. 17. %T values for two commercial reactive dyes for nylon and Dyes 4
and 5.

100
90 group but has an additional reactive group (vinylsulphone).
80
Dyes 1e3 are sparingly soluble and gave very low visual
70
60 colour yield (K/S ) due to the hypsochromic nature of the
%T

50 chromophore. The vinylsulphone group of reactive dyes, in-

40 cluding hetero-bifunctional types Dye 3, is usually formed,
30 in situ, during dyeing in the presence of alkali. The most
20 Dye 4

10
Dye 5 important precursor for dyes of this type is the b-sulphatoe-
Dye 6
0 thylsulphone, which forms the corresponding reactive, vinyl-
0 5 10 15 20 25 sulphone in the alkaline dye bath by elimination of sulphate.
mol x 10-3 of dye / kg fabric At a lower dye bath pH value, the sulphatoethylsulphone is
Fig. 14. (%T ) values of Dyes 4e6. relatively stable and an alkali-moderated, b-elimination step
is required to generate the reactive vinylsulphone form
[26,27].
From the results displayed in Table 6 and Figs. 9e11, it
25
Commercial Yellow dye can be seen that the initial exhaustion (K/S )1 of Dye 1 is
Dye 4
20 Dye 5 higher than that of Dyes 2 and 3, but that all dyes behave
Commercial Orange dye very similarly in terms of fixed dye (K/S )2. Fig. 11 suggests
15 that cationic dyes exhibit better fixation efficiency compared
(KS)1

with anionic dyes (Dye 4), from an earlier study [18,19] in

10
which it was shown that the build up and fixation of anionic
5
dyes tail off long before all the formally available amine
groups were reacted with dye; that its build up was likely
0 to be limited, not by the number of amino sites present,
0 5 10 15 20 25 but more by steric hindrance and/or electrostatic repulsion.
mol x 10-3 of dye / kg fabric Thus at pH (8e10) essentially most of the amino groups
Fig. 15. (K/S )1 values of the commercial dyes and Dyes 4 and 5. will be present in the free, un-protonated form and hence
highly nucleophilic and reactive towards electrophilic reac-
tive groups. Additionally at this high pH essentially all of
20
18
Commercial Yellow dye the carboxylate acid groups will be de-protonated and hence
Dye 4
16 Dye 5 anionic. Under these conditions, therefore, both electrostatic
Commercial Orange dye attraction between dye and fibre and availability of nucleo-
14
12
philic amino groups will be maximised. It was readily dem-
(K/S)2

10 onstrated that high F/E values were attainable with cationic

8 dyes relative to anionic dyes and thus four novel orange,
6 cationic reactive dyes (Dyes 4e7) were evaluated. All
4 dyes were monocationic, except Dye 6 which was a bis-cat-
2 ionic species. Both Dyes 5 and 6 possess a single mono-
0 chlorotriazinyl reactive group; Dye 4 a single
0 5 10 15 20 25 dichlorotriazinyl reactive group and Dye 7 a bifunctional
mol x 10-3 of dye / kg fabric (monochlorotriazinyl and sulphatoethylsulphone) reactive
Fig. 16. (K/S )2 values of two commercial reactive dyes for nylon and Dyes group. The evaluation of this series of novel dyes was hin-
4 and 5. dered by widely varying solubility. Dyes 4e6 were readily
622 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 76 (2008) 610e623

soluble in water whereas Dye 7 was only sparingly soluble; 4. Conclusions

therefore, measurement of the absorbance of the dye bath
(Dye 7) before and after the dyeing process was not accu- At high pH the build up and fixation of anionic reactive
rate, and so the percentage of exhaustion (%E ) could not dyes on nylon is limited by electrostatic repulsion between
be readily determined. dye and anionic carboxylate groups present in the nylon.
Fig. 12 shows that the initial exhaustion of Dye 4 is mar- At low pH the effective concentration of anionic carboxyl-
ginally higher than that of Dyes 5 and 6, but that all of these ate groups is greatly reduced, and that of cationic protonated
are much greater than that of Dye 7. Build up, initial and final amino groups increased, leading to electrostatic attraction be-
exhaustion of Dye 7 were very much lower than the other tween dye and fibre but a massive reduction in the concentra-
dyes; this might be related to lack of solubility of Dye 7. tion of free amino groups, the nucleophilic species responsible
Figs. 12e14 show that the bis-cationic monochlorotriazinyl for reactive with dye.
(MCT) dye, Dye 6, shows less build up, than Dyes 4 and 5; Under alkaline conditions the fixation and build up of
less initial and final exhaustion than the monocationic mono- cationic reactive dyes on nylon are excellent. Because cova-
chlorotriazinyl (MCT) dye, Dye 5. It is possible that one cat- lent bond formation between dye and nylon is efficient, the
ionic group interacts efficiently with one anionic carboxylate resulting dyeing exhibit excellent wet fastness. Monoca-
group of nylon, whereas with the bis-cationic Dye 6 a greater tionic dyes appear to build up better than bis-cationic types;
build-up of positive charge, as dye fixes, impedes approach of this may be associated with the build up of positive charge
further bis-cationic dye. This suggests that, although the on the fibre as more dye fixes leading to reduced electro-
monochlorotriazins, Dyes 5 and 6, are significantly less reac- static attraction between dye and fibre at heavy depths of
tive than the dichlorotriazine, Dye 4, they are still sufficiently shade.
reactive to react efficiently with the amino end groups of ny-
lon under the chosen application conditions. Dye 7 was only Acknowledgement
sparingly soluble and conclusions about the stability of the
second reactive group were thus difficult to draw. In the We wish to express our gratitude to UMIST and to Profes-
next step, Dyes 4 and 5 were compared with two commer- sor D.A.S. Phillips for financial support (to A.S.-G.).
cially available reactive dyes for nylon.
Figs. 15e17 show that the initial and final exhaustion of
monocationic MCT (Dye 5) and monocationic DCT (Dye 4) References
were better than the two commercial dyes. They (especially
[1] Broadbent Arthur D. Basic principles of textile coloration. Bradford:
Dye 5) gave very high fixation, similar to the commercial Society of Dyers and Colourists; 2001. p. 268.
dyes. [2] Burkinshaw SM, Chevli SN, Marfell DJ. Printing of nylon 6,6 with reac-
tive dyes. Dyes and Pigments 2000;45:235.
[3] Stephen WE. GB785120; 1957-10-23.
[4] Stephen WE. GB785222; 1957-10-23.
3.4. Wash fastness properties of dyes [5] Rattee I. GB797946; 1958-07-09.
[6] Rattee I. GB798121; 1958-07-16.
The wash fastness of Dyes 1e7 were assessed using the [7] Stead CV. In: Shore J, editor. Colorants and auxiliaries. Bradford: Society
ISO 105CO6/C2S wash fastness test at 60  C [28]. The change of Dyers and Colourists; 1990.
[8] Fox MR, Summer HH. The dyeing of cellulosic fibres. Bradford: Dyers
in shade and the degree of cross-staining were assessed visu- Company Publication Trust; 1986.
ally using grey scales and the results are presented in Table 7. [9] Renfrew AHM. Reactive dyes for textile fibres. Bradford: Society of
The wash fastness, as expected, of each dye fixed to nylon 6.6 Dyers and Colourists; 1999.
fabrics was very good at each of the four depths of shade [10] Christie RM. Colour chemistry. Cambridge: Royal Society of Chemistry;
employed. 2001 [chapter 8].
[11] Burkinshaw SM, Gandhi K. The dyeing of conventional decitex and mi-
crofibre nylon 6,6 with reactive dyes-I. Chlorodifluoropyrimidinyl dyes.
Dyes and Pigments 1996;32:101.
Table 7 [12] Burkinshaw SM, Gandhi K. The dyeing of conventional and microfibre
Wash fastness results of dyes in the ISO 105CO6/C2S nylon 6,6 with reactive dyes-2. a-Bromoacrylamido dyes. Dyes and Pig-
ments 1997;33:259.
Dye Staining [13] Burkinshaw SM, Wills AE. The dyeing of conventional and microfibre
Secondary Bleached Nylon Polyester Acrylic Wool nylon 6,6 with reactive dyes-3. Vinyl sulphone and chlorotriazine dyes.
cellulose un-merc. 6.6 Dyes and Pigments 1997;34:243.
acetate cotton [14] Burkinshaw SM, Son Young-A, Bide MJ. The application of hetero bi-
functional reactive dyes to nylon 6,6: process modifications to achieve
1 5 5 5 5 5 5
high efficiencies. Dyes and Pigments 2001;48:245.
2 5 5 5 5 5 5
[15] Burkinshaw SM, Collins GW. Dyes and Pigments 1994;25:31.
3 5 5 5 5 5 5
[16] DyStar. USP 5,803,930; 1998.
4 5 5 5 5 5 5
[17] Ciba, [Link].
5 5 5 5 5 5 5
[18] Soleimani-Gorgani A, Taylor JA. Dyeing of nylon with reactive dyes.
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