Reactive Dye

doi: 10.1111/cote.
12114
Developments in the chemistry of reactive

dyes and their application processes Coloration
David M. Lewis
Technology
Department of Colour Science, The University of Leeds, Leeds, LS2 9JT, UK
Email: d.m.lewis@leeds.ac.uk
This review describes the immense impact of reactive dyes on the textile industry. Their use on cellulosic
fibres is especially important, but their growing popularity on polyamide substrates is notable. Detailed
information is given about developments both in the chemistry of reactive systems and in the chemical
technology involved in their application to a variety of fibre types. It is also pointed out that further research is Society of Dyers and Colourists
necessary to improve dye–fibre fixation efficiency, especially when dyeing full shades on cellulosic fibres. This
work is necessary to address the current environmental problem of colour in dyehouse effluent. The potential
solutions reviewed include multifunctional reactive dyes, cationic reactive dyes, and cellulose fibre
modification.
The author is currently Emeritus Research Professor in the Reactive dyes may be loosely defined as chromophores
Department of Colour Science at the University of Leeds that contain pendant groups capable of forming covalent
and in the School of Design. Prior to joining the University
bonds with nucleophilic sites in fibrous substrates. Provid-
of Leeds in 1987, he was employed at the International
Wool Secretariat (IWS), Ilkley, as a Principal ing these covalent bonds are stable to conditions encoun-
Development Scientist, and at CSIRO, Division of Textile tered in laundering, the wash fastness properties of the
Industry, Geelong, Australia, as a Senior Research colorations will be outstanding.
Scientist. He is a former Professor of Colour Chemistry Reactive dyes have also become more widely used on
and Head of Department (1987–2004). He is a cofounder
polyamide materials as a means to produce dyeings and
and Research Director of Inovink Ltd (security printing),
Perachem Ltd, and Green Chemicals plc. Inovink Ltd has prints of excellent wash fastness; reactive dyes for wool are
a successful business in high-security printing. Perachem seen as alternatives to chrome dyes. Certain classes of
Ltd has developed new technologies in cotton flame- reactive dyes have a positive effect on the amount of wool
proofing and in novel hair dyeing. The author is a former damage produced when dyeing at the boil and above.
President of the Society of Dyers and Colourists (1993–
In addition to the detailed descriptions given in this
1994) and was appointed to honorary membership in
January 2006. He has been a Liveryman of the Worshipful review, the reader is referred to very useful texts on reactive
Company of Dyers since 1995. Publications include 244 dyes and their application [1–8].
refereed papers, 62 patents, eight book chapters, and two
edited books.
Brief history of available reactive dyes
Bearing in mind that the last review on reactive dyes was
published in 2000, it is worthwhile refreshing readers with
Introduction a very brief summary of their history.
Reactive dyes are a highly successful class of modern
synthetic dyes owing to their wide shade gamut, their Halo-s-triazines
flexibility in application, and the excellent fastness The early work at ICI (UK) established that dichloro-s-
properties they offer when dyed on wool, silk, cotton, triazine (DCT) dyes could be cheaply synthesised by the
and regenerated cellulosic fibres. Earlier reviews [1,2] reaction of so-called ‘amino dye bases’ (chromophore-NH2)
covered the subject up until 2000; undoubtedly, the with cyanuric chloride, a material that was already avail-
period since then has seen major contraction in European able in large tonnages from their Agrochemical Division.
dye manufacturing and perhaps, coupled with REACH Horrobin [9] expertly summarised the hydrolysis chemistry
legislation, a slackening of the launching of new chem- of these dyes.
istries designed to improve reactive dye performance. It is It is not widely appreciated that monochloromonohydr-
important to note, however, that a major contributor to oxy-s-triazine dyes are capable of efficient bonding to wool,
this slowdown was the legislation that came into force as the keto form of the hydroxy-s-triazine ring predominates
during the 1990s – many years before REACH, the when they are applied under mildly acidic conditions [10].
framework of which was only loosely described during The acid sensitivity of the dye–fibre bonding observed
2006–2007. when these dyes are applied to cellulosic substrates is not
Subjects covered in this review include: the chemistry of apparent in the case of wool.
reactive groups, the application of reactive dyes to cellu- Better storage stability in aqueous print pastes prompted
losic fibres, nucleophilic sites, substantivity effects, cellu- the development of lower-reactivity monochloromonoamino-
losic fibre printing, multifunctional reactive dyes, novel s-triazine (MCT) dyes (Procion H – now Procion P dyes).
reactive dyes (not yet commercialised), the application of Cyanuric fluoride was developed by Bayer (Germany) as an
reactive dyes to natural and synthetic polyamide fibres, intermediate to produce monoaminomonofluoro-s-triazine
cellulosic fibre modification to enhance reactive dye fixa- (MFT) reactive dyes [11]. Subsequently, these dyes have
tion, and the use of crosslinking agents for covalent fixing of gained significant importance for printing and long-liquor
dyes on fibres. dyeing [sold as Novacron F dyes by Huntsman (USA)].
382 © 2014 The Authors. Coloration Technology © 2014 Society of Dyers and Colourists, Color. Technol., 130, 382–412
Lewis developments in the chemistry of reactive dyes and their application processes
Halopyrimidines In the early 1970s, ICI developed homobifunctional dyes

The 2,4,5-trichloropyrimidine dyes [12] were introduced in by simply reacting 2 mol of a dichloro-s-triazine dye with
1958 (Reactone and Drimarene dyes). The halopyrimidines, 1 mol of a diamine such as p-phenylene diamine to give a
when compared with the halotriazines, are much less bis-monochloro-s-triazine dye; in this way the technically
activated towards nucleophilic substitution, and thus these important Procion HE, HEXL, and XL+ ranges of reactive
dyes are fixed at 95 °C in the exhaust dyeing of cellulosic dyes were developed.
fibres. The dyes are synthesised by condensation of the In the mid-1990s, Ciba launched Cibacron LS (now
amino dye base with 2,4,5,6-tetrachloropyrimidine [13–15]. Novacron LS from Huntsman) bifunctional dyes based on
More reactive fluorochloropyrimidine dyes (FCP) dyes, bis-monofluoro-s-triazines; these dyes were prepared from
prepared from 2,4,6-trifluoro-5-chloropyrimidine, are mar- the condensation of 2 mol of difluoro-s-triazine dye with a
keted as the Levafix EA range (by DyStar, Germany) and suitable diamine (e.g.a, x diaminopropane). These dyes
Drimarene R/K ranges (by Clariant, Switzerland). A modi- were of such a molecular size as to be highly substantive to
fied group, the 2,4-difluoropyrimidyl-6-yl residue, is uti- cellulose and thus could be dyed in the presence of reduced
lised in the Drimarene HF range [2,16]. salt, e.g. 40 g l1 of sodium sulphate – hence the use of the
LS suffix (Low Salt). The monofluoro-s-triazines are signif-
Haloquinoxalines icantly more reactive than the monochloro-s-triazine dyes
Reactive dyes containing 2,4-dichloroquinoxaline (DCQ) and are thus fixed on cotton at pH 10.5–11 at 60 °C rather
reactive residue were developed by Bayer and marketed as than 80 °C. The high substantivity of these dyes can lead to
Levafix E (now DyStar) [17]. unlevel dyeings in dyeing machines with low rates of fibre–
liquor interchange.
Vinylsulphones In 1980, Sumitomo (Japan) launched the first complete
Dyes containing masked vinylsulphone residues were first range of heterobifunctional reactive dyes, which contained
sold by Hoechst (Germany) as Remalan Fast dyes for wool both a monochloro-s-triazine and a sulphatoethylsulphone
and then relaunched as Remazol reactive dyes for cellulose; group attached to the same dye molecule; these were named
the most common masking group used in commercial dyes Sumifix Supra.
is a b-sulphato residue and occasionally a b-chloro residue An important difference in the Sumifix Supra range of
[18]. dyes was the fact that all were prepared by the condensation
of a parent dichloro-s-triazine dye with m-base, 1-amino-
Acrylamide and substituted acrylamides benzene-3-sulphatoethylsulphone. It was claimed by Sumi-
The early Primazin (BASF) reactive dyes for cotton con- tomo [21] that the use of m-base, rather than the cheaper p-
tained the b-chloropropionamido group attached to a base, produced a range of dyes that were of high compat-
chromophore. ibility in mixture shades; this is because corresponding p-
Originally sold by Ciba (Switzerland) but now by Hunts- base dyes show wider variations in individual dye reactiv-
man, the Lanasol reactive dye range, containing the a- ity. As well as being of high combinability, these dyes,
bromoacrylamido group, remains the most popular for wool when used on cellulosic substrates in the temperature range
dyeing [19,20]. 60–80 °C, gave repeatable fixation values; thus, if there
were temperature variations from front to back of a dyeing
Polyfunctional reactive dyes machine, shade reproducibility would not be compromised.
The first polyfunctional reactive dye range comprised the A typical structure of a Sumifix Supra dye is shown in
dichloro-s-triazinyl dyes, but the likelihood of actually Structure 2.
achieving two dye–fibre bonds by the reaction of both The concept of heterobifunctionality was further devel-
electrophilic sites with cellulose hydroxyl residues is quite oped commercially by Ciba with their Cibacron C range
low owing to the competing hydrolysis reaction. The most (now Novacron C from Huntsman) dyes, designed particu-
important bifunctional dye is Remazol Black B (CI Reactive larly for pad–batch application; many of these dyes were
Black 5 – Structure 1), first marketed in 1957 and now based on the reactive 2-vinylsulphonylethylamino-4-fluoro-
widely used for navy blue and black shades on wool, cotton, s-triazine residue. In this case the reactive electrophilic
and viscose. groups in the dyes were designed to be of similar reactivity;
SO2CH2CH2OSO3Na
NaO3SOH2CH2CO2S O NH2
N N
N N
H
NaO3S SO3Na
Structure 1 CI Reactive Black 5
In cold pad–batch applications, CI Reactive Black 5 is having the reactive vinylsulphone residue attached through
capable of giving total fixation values >90% in moderate an aliphatic amine to fluorotriazine imparted flexibility to
depths of shade; in long-liquor applications it gives total the reactive group, which increased the likelihood of
fixation values (%T) of the order of 70% owing to its only reaction with the cellulosate anions; in addition, aliphatic
moderate substantivity. vinylsulphone-alkylamine-halotriazine residues improved
© 2014 The Authors. Coloration Technology © 2014 Society of Dyers and Colourists, Color. Technol., 130, 382–412 383
Cl
SO3Na
N N
H H
N N NH
N O
SO2CH2CH2OSO3Na
NaO3S SO3Na
Structure 2 Sumifix Supra Brilliant Red 2BF
the water solubility of the dyes in this range compared with type were exemplified. The introduction of the very success-
analogous dye ranges containing dyes with aromatic vinyl- ful reactive group made from condensation of the dye base
sulphone-arylamine-halotriazine residues. with 2,4,6-trifluoropyrimidine was outlined; this dye was
The halopyrimidine-based dyes may also be viewed as preferred over the so-called NTCP system, derived from the
heterobifunctional, as each dye contains at least two reaction of an amino chromophore with 2,4,6-trichloro-5-
halogen leaving groups; these carbon–halogen sites are cyanopyrimidine. The flagship range of Drimarene HF dyes
selectively activated because the pyrimidine ring is asym- probably incorporates a vinylsulphone group and a 2,4-
metric; thus, in the case of 2,4-difluoro-5-chloropyrimidine difluoropyrimidine-6-yl group in the dye molecule. These
dyes, the 4-fluorocarbon site is most reactive, reacting with dyes offer very high exhaustion/fixation efficiencies when
cellulose in the presence of sodium carbonate at 60 °C; for applied to cotton in long-liquor processes; cited values for
the 2-fluorocarbon electrophilic site to react efficiently with Drimarene Orange HF-2GL at 1/1 standard depth were
cellulose, a temperature increase of some 10 °C would be exhaustion 96% and fixation 91% (in contrast to the corre-
required. The 2,4-difluoropyrimidyl-6-yl residue as utilised sponding values from dyeing with an FCP dye, Drimarene
in the Drimarene HF range is likely to be effectively Orange K-GL: exhaustion 98% and fixation 77%) [28].
bifunctional in its reaction with cellulose. Other trifunctional dyes capable of giving high fixation
In 2005, a special reactive dye conference was held in efficiencies (T values) from long-liquor dyeing processes,
Manchester, celebrating 50 years of innovation through the approaching 90% in medium depths of shade, have been
introduction of Procion dyes for cotton in 1955. Trends in the developed. Thus, Everlight have a trifunctional range
status of the reactive dye making/application industries were (Everzol ED), and it is believed that some of the Procion
summarised [22]. Other topics addressed included the light HE-XL+ dyes are tris-monochloro-s-triazines; the latter may
fastness of reactive dyed substrates [23], opportunities to be prepared by the reaction of 3 mol of a dichloro-s-triazine
develop polymeric reactive dyes to obtain improved dye–fibre dye with 1 mol of a trifunctional amine. As early as 1975,
covalent bonding efficiencies [24], synthesis and application Hoechst launched the trifunctional dye Remazol Red SBB
of a vinylsulphone disperse dye from supercritical carbon (CI Reactive Red 181), which is shown in Structure 3;
dioxide [25], the synthesis of rotoxane complexes of reactive Hoechst also patented dyes of this type [29].
Cl
SO3Na
NaO3S N N
H H
N O N N N(CH2CH2SO2CH2CH2Cl)2
NaO3S SO3Na
Structure 3 Remazol Red SBB
dyes, which exhibit improved fastness properties, even-to- Dye makers are undoubtedly working on more intensely
severe oxidation, and reductive clearing [26,27], and details of absorbing chromophores to reduce the impact of colour in
the Drimarene reactive dye systems marketed by Clariant effluent when dyeing ternary shades with dye mixtures.
[28]. The chemistry of the preparation of the Drimarene dyes Heterobifunctional trisazo dyes are important in this con-
was detailed, and the special application conditions for each text and were studied by Mokhtari et al. [30]. Even though
hydrolysed dye will also show increased colour intensity in sodium sulphate and running with cotton fabric for 30 min;
dyehouse effluent, it should be noted that fixation efficien- 20 g dm3 of trisodium phosphate was then added, and the
cies are much higher at lower application levels; thus, if the fixation step was continued for 1 h.
dyer could obtain a deep shade using 2% owf dye as against Figure 1 shows that there is rapid uptake of this dye
5% owf with current dyes, then clear environmental molecule in the ‘salt-only’ phase of dyeing and extremely
advantages would accrue. rapid covalent fixation of the sorbed dye with the fibre on
addition of alkali. These kinetics indicates a potential for
The application of reactive dyes to unlevel dyeing; therefore, machines such as jets should be
cellulosic fibres selected to give good mechanical interchange between the
dye liquor and the goods being dyed. A further important
Long-liquor or ‘exhaustion’ dyeing
feature emerging from this study is the T value of 72%; this
A major use of reactive dyes is in long-liquor dyeing
value indicates that 28% of the dye originally applied is lost
processes (exhaustion dyeing), and for these processes to
to the dyehouse effluent; if deeper shades than the 2% owf
operate efficiently, three factors apply:
dye applied in this case are used, the dye discharge problem
1 Dye substantivity must be as high as possible during the
increases greatly. These issues of unfixed dye contamina-
so-called neutral exhaustion phase (typically 30 min at
tion of water courses were highlighted in published Sumi-
the required dyeing temperature) – dye uptake by the
tomo studies (Table 1) [33].
fibre under these conditions involves minimal covalent
This table shows that, in full-depth dyeings, between 30
bonding, and most of the sorbed dye can usually be
and 50% of the originally applied dye is discharged to
removed by cold water rinsing; the amount of dye sorbed
wastewater. Although Table 1 was published in 1996, it
at this stage may be expressed as %S (substantivity
still needs emphasising today because it quantitates the
factor). The substantivity of the dye for the fibre during
major problems encountered in the reactive dyeing of
this phase of dyeing is almost wholly related to the
cellulosic fibres to full shades. A more recent paper by
amount of electrolyte present in the dyebath – concen-
Kwok et al. [34] quantitates the absorbance values of
trations of sodium sulphate between 60 and 80 g dm3
reactive dye effluent when dyeing with fluoro-s-triazine
are normally used.
dyes.
2 Following the above substantivity phase, an addition of
Colour in the effluent is a pressing problem and needs to
alkali (usually sodium carbonate) is made, and dyeing is
be addressed in a variety of ways; possible solutions to the
continued for a further 30 min to bring about covalent
problem include the development of new reactive dyes,
bonding of the dye with the fibre – dyebath exhaustion at
with fixation efficiencies >95% at 6% depth, or the chemical
this stage is referred to as %E (exhaustion factor).
modification of the substrate. A significant number of
3 At the end of dyeing, repeated rinsing in cold water and
publications dealing with methods to clean up reactive
then in boiling water, until no more colour is removed, is
dyes from effluent have appeared in the period pertinent to
carried out to remove all non-covalently bound dye. The
this review [35–38]. Colour uniformity of reactive dyeings
amount of dye desorbed in these processes can be
on Tencel was studied by Syed and Wardman [39] using
measured spectrophotometrically, and hence the total
physical measurement from microscope analysis of fibre
efficiency of dye–fibre covalent bonding can be calcu-
cross-sections.
lated as %T (total fixation factor). In some cases it may be
useful to know the degree of fixation of the sorbed dye,
Pad–batch, pad–steam, and pad–bake piece dyeing
and this is referred to as %F; this factor is related to E
processes
and T by the simple relationship %T = %F 9 %E/100.
Padding processes now account for <25% of cotton fabric
Exhaustion/fixation plots are very useful when studying
dyeing procedures; this drop in popularity is because the
reactive dye compatibility in long-liquor dyeing [31].
industry has to respond to a high fashion market which
Typical exhaustion/fixation curves for a sulphatoethylsul-
increasingly demands short runs to a particular shade.
phonyl dye, CI Reactive Blue 19 (Remazol Brilliant Blue R),
Moreover, it is costly to put together a padding system
are reproduced [32] in Fig. 1. The dyeing process used to
containing significant excess pad liquor that contains
obtain these results involved setting the dyebath at pH 7.0 at
relatively high concentrations of dye, some 20 l of which
a 10:1 liquor ratio with 2% owf dye and 80 g dm3 of
is simply washed to drain at the end of padding. In terms of
2% Remazol Brilliant Blue R (60 °C)

100 Table 1 The fixation yield of various reactive red dyes (from
90 Douthwaite et al. [33])
80
70 S = 68.3%
Dyea
Percent
60 E = 88.1% 3% owf 6% owf

50
F = 81.8%
40
30 T = 72.1% MCT/VS 76 68
20 MFT 64 56
Uptake %
10 Fixation % MFT/VS 61 50
0 DFMCP 74 67
0 10 20 30 40 50 60 70 80 90 VS 68 58
Time, min MCT/MCT 57 49
Figure 1 S, E, F, and T profiles for a typical long-liquor reactive a MFT, monofluoro-s-triazine; VS, vinylsulphone; DFMCP,
dyeing process [32] difluoromonochloropyrimidine; MCT, monochloromonoamino-s-triazine.
energy saving, pad–batch (24 h) is an important procedure, borate, all typically used at a concentration of 100 g
batching being carried out at 30 °C in a constant temper- dm3 [43,44]. The results indicated that fabrics pretreated,
ature environment. even at pH 6.5, by padding and drying such an ‘activator’
Continuous pad thermofix dyeing of cotton/polyester resulted in subsequent ink-jet prints that exhibited high
blends with mixtures of disperse and reactive dyes has been levels of reactive dye fixation similar to or even better
studied by DyStar [40,41]. The main limitation is the than corresponding prints produced on alkali-pretreated
limited colour depth achieved, which was ascribed to fabrics.
insufficient dye solubility and thus low diffusion rates,
rather than to low reactivity of the dye [40]. Additions of Resist printing of cotton with inks containing sodium sulphite
dicyandiamide and moisture injection had a beneficial In resist printing, the resist agent prevents fixation of
effect on colour yields [41]. prepadded background colour by chemical means (resist
agent inhibits dye fixation) or physical means (resist agent
Printing processes inhibits dye absorption), in both cases giving a white print
Screen printing against a solid colour background. The process offers real
Rotary screen printing makes up the most important part of opportunities if reactive dyes are selected; it is important
the market [42]. When printing cotton fabrics, reactive dyes that the ground shade does not fix during the drying process
of the highest possible solubility are required, and their prior to the printing process, otherwise white images cannot
print paste stability is of paramount importance – alkaline be produced. Broadbent and Lewis [45] described the
(sodium carbonate) print pastes containing alkali-stable following procedure: pad the fabric with a pad liquor
dyes (e.g. MCT or sulphatoethylsulphone) are preferred containing a sulphatoethylsulphone reactive dye (Remazol)
because they can be stored overnight without significant and sodium formate (pH 6.5), dry at 70–80 °C, overprint
hydrolysis. with an ink containing either sodium sulphite or, for
illuminated prints, sodium sulphite plus a monochloro-s-
Ink-jet printing of cellulosic substrates with reactive-dye- triazine reactive dye (Procion P/PX); fixation is achieved by
based inks steaming at 102 °C for 8–10 min; finally, soap off to yield
Currently commercial ink-jet textile printing operations either a white and/or a coloured print on a coloured
require the pretreatment of cellulosic fabrics with pad background. The fact that good colour yields are obtained
liquors containing a thickener and alkali (such as sodium with the illuminating triazine dyes indicates that, under the
carbonate or sodium bicarbonate). Surprisingly, the above conditions used, sulphite reduction of the chromophores
pretreatment procedure can also use neutral fixation selected is not occurring.
‘activators’ such as sodium acetate, sodium formate, The reactions occurring during the process are repre-
sodium trichloroacetate, sodium cyanate, or sodium sented in Schemes 1 and 2.
DYE–SO2 –CH2 –CH2 –OSO3Na + OH → DYE–SO2 –CH=CH2 + NaHSO4

DYE–SO2 –CH=CH2 + SO3−(2Na+) + H2O → DYE–SO2 –CH2 –CH2 –SO3Na + NaOH
Inactive sulphonate dye
Scheme 1 Reaction of sulphatoethylsulphone dye with sulphite
Cl SO3Na
N N
Na2SO3
H H
DYE N N DYE N N
N N
NH2 NH2
Monosulphonate-triazine
Monochlorotriazine dye
dye
Cell-OH
Cell-OH
N
H
DYE N N
NH2
Scheme 2 Reaction of monochloro-s-triazine dye first with sulphite and then with cellulose
When using sodium formate, high levels of dye fixation towards subsequent covalent reaction with the cotton
were achieved for pad liquors possessing the Remazol dye substrate.
in its preactivated vinylsulphone form, while pad liquors The reactions occurring during the process are repre-
containing sodium acetate gave equivalent results even sented in Schemes 3 and 4.
when the Remazol dye was still in its sulphatoethylsul-
phone form. Weakly acidic pad liquors (pH 6.5) enabled the Commerical developments in the reactive
production of ground-shade fabrics having 4–5 days stabil- dye field during the period 1999–2014
ity (i.e. no dye–fibre bonding or dye hydrolysis), whereas
It is interesting to survey commercial progress by dye
ground fabrics prepared using alkaline pad liquors required
manufacturers during the period 1999–2014. I have chosen
immediate printing to prevent unwanted ground dye fixa-
these dates because previous coverage of this topic was
tion occurring.
admirably done by the Taylor review in 2000 [2].
Resist printing with secondary amines [44]
Patent analysis
In terms of the dye class selection, this system covers the
A patent analysis is to be found in the Appendix, where the
opposite situation to the above sulphite process; in this
list of patents gives an indication that the main thrust by
case, monohalo-s-triazine reactive dyes and sodium for-
dye manufacturers is to develop reactive dyes for cotton that
mate are padded on cotton fabrics, dried, and then ink-jet
offer:
printed with a suitable secondary-amine-based ink for-
deeper shades by increasing colour intensity (extinction
mulation to produce a white image on a solid ground
coefficient) – especially blacks;
colour after steam fixation and soaping off. A coloured
better dye–fibre fixation efficiencies through the intro-
image can be achieved by overprinting the resist-printed
duction of three or more reactive groups on the dye
areas with a coloured ink formulation containing either
molecule;
a vinylsulphone or a sulphatoethylsulphone reactive
higher light fastness;
dye; the latter dyes form a new reactive dye via reaction
optimised mixtures for deep-shade dyeing;
with the secondary amine and so are not deactivated
H3C
Cl NCH2CH2SO3Na
N N
H CH3NHCH2CH2SO3Na H
DYE N N DYE N N
Resist
N N
NH2 NH2
Monochlorotriazine dye
No dye–fibre reaction possible
Scheme 3 Reaction of monohalo-s-triazine dye with N-methyltaurine [44]
alkali
DYE SO2CH2CH2OSO3Na DYE SO2CH=CH2
Sulphatoethylsulphone dye Vinylsulphone dye
CH3NHCH2CH2SO3Na
Cell-OH
DYE SO2CH2CH2N CH2CH2SO3Na DYE SO2CH2CH2OCell
CH3
Scheme 4 Reaction of sulphatoethylsulphone dye with N-methyltaurine [44]
trichromatic combinations of improved levelness and dichloro-s-triazine dyes (or difluoromonochloropyrimidine

light fastness, especially in paler shades. dyes) with two moles of cysteamine and subsequent
reaction of the two pendant primary amines with cyanuric
Recent introductions chloride; the preparation route is summarised in
New ranges designed to make a considerable impact in Scheme 5.
terms of deeper shades, better fixation properties, and hence
environmental impact have been forthcoming. Cl
Eriofast (Huntsman). This range of reactive dyes for
N
polyamide fibres currently includes the following: Eriofast H
Black M, Eriofast Navy M, Eriofast Blue 3G, Eriofast Blue DYE N N + 2 HSCH2CH2NH3Cl
3R, Eriofast Orange 4R, Eriofast Red 2B, Eriofast Red B, N
Eriofast Yellow 5G, and Eriofast Yellow R. The Eriofast
Cl
Navy M has been registered with the Colour Index as a
completely new metal-free molecule.
Huntsman have also put together an Eriofast XKS range
solely for ink-jet printing of cotton and polyamide textiles.
Avitera SE (Huntsman). These dyes have three reactive
groups per dye molecule – they were introduced at ITMA
2011. These multifunctional reactive dyes were especially SCH2CH2NH3Cl
designed for cellulosic fibres, and are claimed to save
N
energy and time and reduce water consumption; a special H
DYE N N
auxiliary to assist the washing-off of unfixed dye is Eriopon
LT. Notable dyes are Avitera Yellow SE (CI Reactive Yellow N
217), Avitera Red SE (CI Reactive Red 286), and Avitera
SCH2CH2NH3Cl
Blue SE (CI Reactive Blue 281).
Remazol Ultra RGB (DyStar). These dyes are designed for
deep-shade dyeing. It is claimed that the chromophore Cl N Cl
strength is such that, to achieve the same depth as when
dyeing ternary shades with commodity reactive dyes, some 2
N N
50% less Remazol RGB dyes may be used. Washing-off
times are greatly reduced to a maximum of two soapings
using the special auxiliary Sera Fast C-RD. Of particular Cl
note are the two black dyes for cellulosic fibres, Remazol
Onyx RGB (a neutral black) and Remazol Midnight Black Cl
RGB. For deep blacks on wool, DyStar have recently
N
launched Realan Black MF-PV, which outperforms the old
Chrome Black PV. N
SCH2CH2NH
DyStar’s Levafix CA dyes are of interest as they are AOX N
free; this range of dyes gives high fixation properties and N
H Cl
excellent light fastness. DYE N N
Cl
For trichromatic dyeing in the paler shade area, DyStar
N
recommend the Procion HE-XL dyes (Amber HE-XL, Red N
Brown HE-XL, and Dark Blue HE-XL). A new range of high- SCH2CH2NH
N
performance reactive dyes for cotton, Remazol SAM, has
recently been launched at Interdye in Istanbul (June 2014). N
DyStar also introduced the first fluorescent reactive dye, Cl
Remazol Luminous Yellow FL, which gives very brilliant
yellows and greens; especially suitable for high-visability Scheme 5 Synthesis of a tetrafunctional chloro-s-triazine dye [47]
clothing.
Clariant have divested their textile dyes into the new
When these dyes were applied to cotton, in medium
company Archroma; Drimarene HF and Drimarene CL dyes
shade depths, by long-liquor processes at 50 °C in the
for application to cellulosic fibres are their flagship reactive
presence of 40 g dm3 of sodium sulphate and fixed with
dye ranges.
sodium carbonate additions, total fixation efficiencies >95%
were obtained; in addition, the large hydrophobic side
Reactive dyes of research interest (not yet chain gave the dyes very good combinability properties in
commercialised) tertiary shades. The dyes were also applicable by pad–batch
Tetrafunctional reactive dyes have been claimed in the processes, but in this case it was preferable to replace the
patent literature; for example, Ciba have covered chromo- cysteamine bridging group with cysteine in order to
gens containing two vinylsulphone/monohalo-s-triazine enhance water solubility of the dyes. The promise of this
residues [46]. A Proctor & Gamble patent [47] describes system was confirmed by Freeman et al. [48], who synthes-
tetrafunctional reactive dyes prepared from the reaction of ised the dyes shown in Structures 4–5.
Cl to give the bis-ethylene-diamine intermediate shown in

Structure 6.
N The above diamine intermediate (1 mol) was reacted
R
with 2 mol of cyanuric chloride at 0–5 °C at pH 10
N
(important to work at this alkalinity in order to deprotonate
SCH2CHNH
N
the aliphatic amino groups and prevent internal salt
N formation with sulphonate residues on the chromophore)
H Cl to give the required tetrachloro-s-triazine (bis-DCT) dye
DYE N N (Structure 7) which was isolated at pH 6.
Cl
The improved efficiency of the tetrachloro-s-triazine dye
N
N
(bis-DCT) versus the starting dichloro-s-triazine dye (DCT),
when applied in long-liquor dyeing (60 °C and fixation at
SCH2CHNH
N pH 10.5) at 2% owf depth, is shown in Fig. 2. The bis-DCT
dye gave a total fixation efficiency value (T) of 93%, whereas
R
N the parent DCT dye gave a T value of 69%.
The differences in the exhaustion/fixation profiles of the
Cl
bis-DCT dye and the DCT dye may be seen further into the
Type 1 (R=CO2H); Type 2 (R=H) fixation phase – post-alkali addition. The bis-DCT dye
underwent rapid fixation during the first 5 min after the
addition of the alkali, after which time the rate of fixation
slowed down but still continued to increase. In comparison,
Cl Cl this was different from the trend seen for the DCT dye,
where no additional increase in the level of absorbed dye
N N
H H
fixation was seen above that already achieved during the
DYE N N N N DYE neutral exhaustion phase.
The DCT and bis-DCT dyes were applied (2% depth) by a
N N
pad–batch technique (20 °C for 24 h) in the presence of
SCH2CHNH various alkalis (20 g dm3). Table 2 shows that the maxi-
mum level of covalent dye fixation (the T value) observed
R with the DCT dye was 74%, whereas with the bis-DCT dye
the corresponding value was 96%.
Type 3 (R=CO2H); Type 4 (R=H)
Dyeings produced from the bis-DCT and DCT dyes were
Structures 4 and 5 Tetrafunctional and bifunctional cysteamine- boiled in dilute acetic acid solution (pH 3); the dye–fibre
triazine dyes synthesised by Freeman et al. [48] bond produced from the DCT reactive dye was very
susceptible to cleavage, as the acid solution became very
coloured, whereas no colour desorbed into the acid solution
The above concept was further developed by replacing in the case of the bis-DCT-dyed samples [49]. The amino
cysteamine with ethylene diamine [49]; the two amine bridging group in the DCT dye is linked directly to the
groups in protonated ethylenediamine show differing pKa aromatic chromophore and thus activates the triazine
values (pKa1 is 6.86 and pKa2 is 9.92 at 25 °C [50]) which system to give a dye–fibre bond prone to acid hydrolysis;
makes possible simple control of its selective substitution the increased dye–fibre bond stability achieved with the
reactions with halo heterocycles. In the following example, new bis-DCT dye is conferred by the aliphatic bridging
1 mol of the starting dichloro-s-triazine (DCT) dye, CI group having no activating effect on the triazine ring
Reactive Red 1, was reacted with 2 mol of ethylene-diamine system.
HN CH2 CH2 NH3
N N
O HN N N CH2 CH2 NH3

H
N
N
H
SO3H
HO3S SO3H
Structure 6 Bis-ethylenediamine intermediate [49]
Cl
N
H
HN CH2 CH2 N N
N
N N Cl
Cl
N
O HN N N CH2 CH2 NH N
H
N N
N
H Cl
SO3H
HO3S SO3H
Structure 7 Tetrachloro-s-triazine dye from CI Reactive Red 1 [49]
100 S 67%, E 85%, F 77%, and T 66%; clearly, the doubling in

90 dye size greatly improves substantivity, yet wash-off per-
80 formance was found to be unaffected as the dye formed after
70 %E DCT b-elimination is the normal vinylsulphone. The first elim-
60 %T DCT
%F DCT ination to vinylsulphone is easy to follow, but the other half
%
50 %E BisDCT
40
of the molecule is a mixed disulphide (HS–S–CH2CH2–SO2–
%T BisDCT
30 %F BisDCT D); protein chemists are well aware that under alkaline
20 conditions unsymmetrical disulphides will reform the
10 symmetrical disulphide or directly b-eliminate; thus, the
0 mixed disulphide dye in Scheme 8 will also form the
0 10 20 30 40 50 60 70 80 90
vinylsulphone.
Time, min
The performance of this type of dye on cellulose was
Figure 2 Exhaustion/fixation profiles of the starting dichlorotri- much improved by preparing heterobifunctional analogues
azine (DCT) dye and the bis-dichlorotriazine (bis-DCT) dye – 20 g [53] using the reactions outlined in Schemes 9–11.
dm3 of sodium carbonate added after 30 min dyeing [49]
When applying the dyes to cotton at 2% owf in the
presence of 50 g dm3 of sodium sulphate, using a 45 min
boil, followed by an aftertreatment at pH 11.5, 60 °C for
Disulphide-ethylsulphone linked dyes 45 min, the following exhaustion and fixation values were
Lewis et al. [51,52] investigated the use of the disulphide- obtained: bis-MCT/DSBES dye – S 65%, E 91%, F 84%, and
bis-ethylsulphone group to link two identical chromo- T 76%; bis-mono-Quat/DSBES dye – S 79%, E 96%, F 93%,
phores and showed that these dyes had good substantivity and T 89%.
and would covalently fix to cotton following elimination to Other workers [54] entered this field using synthesised
two single vinylsulphone moieties. The starting intermedi- disulphide derivatives of vinylsulphone dyes prepared
ate was prepared from the reaction of p-base with sodium in a similar manner from the disulphide-bis-ethylsul-
thiosulphate to form the Bunte salt, which was then phone-diamine intermediate shown in Scheme 10; in
converted to the symmetrical disulphide by reaction with this case the aromatic diamine was bis-diazotised
sodium thioglycollate at 20 °C (Schemes 6–8). and coupled to 2 mol of an MCT derivative of H-acid
The simpler sulphatoethylsulphone analogue of this dye to form the red heterobifunctional dye shown in Struc-
(SES dye) was prepared by diazotisation and coupling of ture 8.
para-base to 1-naphthol-3,6-disulphonate. When dyed (2%
owf) under the recommended conditions, this SES dye gave
Neutral-fixing reactive dyes for cellulosic
a primary exhaustion S value of 35%, a secondary exhaus-
tion E value of 75%, an absorbed dye fixed F value of 75%, fibres
and a total overall fixation T value of 54%. The DSBES dye, Nippon Kayaku introduced the first range of ‘neutral-
applied at 2% owf, gave the following comparative values: fixable’ reactive dyes for cellulosic fibres in 1983; these
Table 2 Total fixation efficiency values from pad–batch application of DCT dye and bis-DCT dye in the presence of various alkalis – dyes
used at 2% owf [49]
TSP 20 g dm3 Na2CO3 20 g dm3 NaHCO3 20 g dm3 Na2HPO4 20 g dm3

DCT bis-DCT DCT bis-DCT DCT bis-DCT DCT bis-DCT
60% 95% 59% 96% 27% 71% 71% 82%
Na2S2O3
H2N SO2CH2CH2OSO3Na H2N SO2CH2CH2SSO3Na
pH 6.5/reflux/4 h
Scheme 6 The synthesis of 1-aminobenzene-4-S-thiosulphatoethylsulphone (Bunte salt)
NaSCH2COONa
H2N SO2CH2CH2SSO3Na H2N SO2CH2CH2SSCOONa
pH 7/2 h
Disulphide
rearrangement
H2N SO2CH2CH2SSCH2CH2SO2 NH2
Scheme 7 The synthesis of the disulphide-bis-ethylsulphone diamine intermediate
H2N SO2 C2H4 S S C2H4 SO2 NH2
temp.< 5 °C NaNO2/H2SO4
O4SH N2 SO2 C2H4 S S C2H4 SO2 N2 HSO4
OH
temp.< 5 °C
2
pH 5–6/2 h
NaO3S SO3Na
O O
N N
N SO2 C2H4 S S C2H4 SO2 N
H H
NaO3S SO3Na NaO3S SO3Na
Scheme 8 The synthesis of a disulphide-bis-ethylsulphone (DSBES) dye
H2N SO2CH2CH2SSCH2CH2SO2 NH2
Cl
N
30 °C
H
pH 4/2 h DYE N N
N
Cl
DYE NH
N
H
N N SO2CH2CH2SSCH2CH2SO2 NH2
N
Cl
Scheme 9 Synthesis of MCT/DSBESA intermediate [53]
DYE NH
N
H
N N SO2CH2CH2SSCH2CH2SO2 NH2
N
Cl
Cl
N
20 °C H
pH 7/3 h DYE N N
N
Cl
DYE NH HN DYE
N N
H H
N N SO2CH2CH2SSCH2CH2SO2 N N
N N
Cl Cl
Scheme 10 Synthesis of bis-MCT/DSBES dyes [53]
DYE NH HN DYE
N N
H H
N N
Cl Cl
N
90–95 °C
pH 6.5/3 h
COOH
DYE NH HN DYE
N N
H H
N N
N N
COOH
COOH
Scheme 11 Preparation of a heteropolyfunctional dye containing a disulphide-ethylsulphone crosslink and two quaternised triazine groups
(bis-monoQuat/DSBES dye) [53]
Cl
N N
NaO3S N NH O
N
H H
N N SO2CH2CH2 S
NaO3S SO3Na
2
Structure 8 Heterobifunctional bis-MCT/disulphidebisethylsulphone dye [54]
dyes were bifunctional bis-nicotinoyl-s-triazines [55]. This as its pKa value, which is the negative logarithm of its Ka
range of dyes was based on an early observation that the value – the smaller the value of pKa, the stronger the acid.
reactivity of monochloro-s-triazine dyes could be greatly Cellulose-OH can be regarded as a very weak acid that has a
enhanced by dyeing in the presence of tertiary amines [56]. pKa value of 14.27, which means that at 25 °C and at the
In 1979, ICI launched Procion Blue HE-G (CI Reactive Blue theoretical pH of 14.27 the concentration of the highly
187), which was prepared by reaction of a bis-monochloro- nucleophilic species, Cell-O, is equal to that of the
s-triazine dye with nicotinic acid; the structure of this dye is extremely weak nucleophilic species, Cell-OH. Thus, in
shown in Structure 9. classical reactive dyeing processes, alkali additions are used
N N NHR
OOC
N N
SO3Na Cl
HNH2CH2CHN O N
N O NHCH2CH2NH
Cl SO3Na
N N
COO
RHN N N
Structure 9 Procion Blue HE-G (CI Reactive Blue 187)
Croft et al. [57] investigated this concept in depth, to increase the concentration of nucleophilic Cell-O
deriving various quaternised dyes from the respective groups. Temperature increases can achieve the same result
reactions of the bis-monochlorotriazine dye, Procion Red because raising temperature from 25 to 100 °C can lower
HE-3B, with nicotinic acid, DABCO, iso-nicotinic acid, the pKa values of conjugate acids by up to 2 units [60], i.e.
nicotinamide, trimethylamine, and pyridine; the reactions increase the concentration of Cell-O 100-fold. Moreover,
were carried out at pH 6.5 for 2–3 h at 80–90 °C. All of these dissociation of acids is also affected by ionic strength; thus,
dyes showed good exhaustion and fixation values after an increase in salt concentration will increase the dissoci-
dyeing at pH 7 at the boil for 1 h (e.g. for 2% shades, 80– ation of the proton from the cotton cellulose hydroxyl
85% exhaustion and 70% relative fixation). residue. The dependence of the rate of reaction on the ion
An interesting paper published in 2007 showed that bis- concentration of the reactive medium is known as the
nicotinoyl-s-triazine dyes applied with disperse dyes to primary salt effect [61]. Sumner [62] also showed that salt
cotton/polyester blends under neutral conditions at 130 °C additions to the cellulose–dye system increased the internal
did not give the good colour yields expected owing to a low pH value of the fibre.
exhaustion level and a low fixation efficiency – MCT dyes Vo et al. [63,64] studied the neutral fixation of a variety of
fixed under alkaline conditions gave significantly better reactive dyes and confirmed that dyeing at a sufficiently
results in this procedure [58]. high temperature would ionise sufficient Cell-OH groups to
The concept of neutral fixation is of great interest because facilitate covalent dye–fibre reactions. Thus, bis-monoflu-
it simplifies the dyeing process – there is no separate oro-s-triazine dyes and vinylsulphone dyes gave very
fixation stage, thus eliminating the need to make additions promising fixation efficiency values when dyed at pH 7
of alkali 30 min into the dyeing cycle. Hydroxyl groups in for 1 h at the boil, whereas with the less reactive mono-
cellulose behave as very weak acids, and thus cellulose has chloro-s-triazines, 1 h at 140 °C was required to achieve
a dissociation constant Ka as shown in the equation. adequate fixation values.
The effects of varying the sodium sulphate concentration
½Cell O ½H3 Oþ
Ka ¼ ð1Þ on the neutral dyeing properties of activated Remazol Black
½Cell OH
B (2% owf, dyed 1 h at the boil) are summarised in Table 3.
. As expected, the amount of absorbed dye fixed (F, %) and
The higher the Ka value, the greater the acid strength; total fixation efficiency (T, %) increased as the concentra-
clearly, the acid strength of cellulose hydroxyl groups is low tion of sodium sulphate increased. When applying free
(according to Neale [59], Ka for Cell-OH is 1.84 9 1014 at vinylsulphone dyes, it was noted that the pH value of the
25 °C). The ease of dissociation of an acid is often expressed dyebaths rose from 7.0 at the start of dyeing to 8.5 at the end
Table 3 Effect of Na2SO4 on dyeing properties [63] cationic dye, impressive exhaustion/fixation values of the
order of 90% were achieved even when applying 4% owf
Na2SO4, g dm3 E, % F, % T, % pure dye.
A very similar approach was taken by Zheng et al. [66].
50 60 71 43 These workers prepared red, green, and blue anthraquinone
80 92 86 80 glycidyl cationic dyes of the structure shown in Struc-
90 93 87 82
ture 10.
100 93 90 83
110 92 94 85 The epoxide group is fibre reactive and reacts efficiently
120 93 94 86 with cotton at 60 °C in the presence of sodium carbonate
(20 g dm3). Even at 10% owf dye, exhaustion fixation values
were very high (of the order of 90%); the blue dye gave a K/S
of dyeing (all pH measurements at 20 °C). Scheme 12 value of 69. It was suggested that the hydroxyl groups from
shows the various vinylsulphone dye–fibre reactions that cellulose and those formed from ring opening of the epoxy
occur under neutral conditions. residue will both react with the dye (Scheme 14).
The nucleophilic cellulosate anion, Cell-O, first reacts
by Michael addition with the electron-poor (d+) carbon on Acid-fixing reactive dyes for cellulosic
the vinylsulphone group to form species 1. The negative fibres
charge on the acidic carbon is first neutralised by a solvated In order to improve the efficiency of cotton/polyester blend
sodium cation, and subsequently a proton is abstracted coloration with mixtures of reactive and disperse dyes,
from water to form a stable methylene group (species 2). In mildly acidic fixation conditions would be desirable, as
this way, NaOH is produced in solution as the vinylsul- many disperse dyes are alkali sensitive.
phone dye reacts; the rise in pH during dyeing a 5% black Early attempts to produce an acid-fixable system resulted
shade of 1.5 units confirms this mechanism. in N-methylol-amino-s-triazine dyes from American Cyan-
amide (USA) (Calcobond dyes) [67], but these were subse-
Cationic reactive dyes for cellulosic fibres quently withdrawn from the market. The above dyes were
Cellulosic fibres carry a negative charge that increases with fixed in the presence of a Lewis acid catalyst such as
alkalinity; it would thus seem entirely logical to synthesise magnesium chloride by a pad–dry-bake procedure.
reactive dyes that carry a positive charge. The advantages The ICI Procion Resin process [5] is reminiscent of the
over existing sulphonated reactive dyes should include: no above. In this case, dichloro-s-triazine dyes were mixed
need for added electrolyte; better build-up properties due to with a cotton durable-press crosslinking agent, such as N,
lack of repulsion from fixed sulphonate residues; high N0 -dimethylol-dihydroxyethylene urea (DMDHEU), and
fixation. magnesium chloride; the mix was padded onto cotton
A paper describing such a dye was published in 2000 fabric, dried, and cured at 170–180 °C for 30 s; excellent
[65]. The dye was prepared as shown in Scheme 13. fixation values were obtained. The procedure still finds
The above dye was applied to cotton without the addition practical use in the printing of cotton/polyester sheeting
of electrolyte. The bath was raised to 85 °C and held for materials. The main problem on 100% cotton fabrics is loss
10 min, then sodium carbonate was added and dyeing was of strength owing to the acidic conditions employed. The
continued for a further 45 min at 85 °C; water rinsing and mechanism for dye–fibre covalent bonding is presumably as
alkaline soaping-off at the boil completed the process. It was shown in Scheme 15 [68].
pointed out that the solubilising pyridinium group was Much effort has been directed at fixing phosphonic
removed by the latter alkaline boil. As anion repulsion does acid containing dyes to cellulosic fibre substrates using a
not occur when dyeing deep shades with this type of high-temperature dry fixation procedure (thermofix) under
δ− δ+
D SO2 CH=CH2 + Cell-O D SO2 CH-CH2-O-Cell (1)
Na
H
O
D SO2 CH2-CH2-O-Cell (2)
+ H-O ....Na
Scheme 12 The reaction between cellulose and vinylsulphone dye, leading to a local rise in pH
Cl
N N
O NH2 Cl O HN N Cl
+ N N Room temp.
Cl N Cl
NO2 O NH2 NO2 O NH2
45–50 °C NH CH CH N
2 2 2
pH 6.5–7.0
Cl
Cl
N N
O HN N NHCH2CH2 N
Cl
NO2 O NH2
Scheme 13 Synthesis of a cationic reactive dye for cellulosics [65]
NHCH2CH2 N
N N
CH3
O HN N NHCH2CH2CH2 N CH2CHCH2
O
R2 CH3
O R1 1 R1 = H; R2 = H
2 R1 = NH2; R2 = H
3 R1 = H; R2 = Br
Structure 10 Cationic reactive dyes for cotton [66]: 1 = red; 2 = green; 3 = blue
mildly acidic conditions. In 1977, ICI introduced the phosphonic acid, supplied by Stauffer. The Procion T dyes
Procion T range of acid-fixable phosphonic acid dyes for were sold, in admixture with alkali-dischargeable disperse
the pad or print thermofix coloration of cellulosic fibres dyes, as Procilene PC dyes for the coloration of cotton/
[69]. The research that formed the basis of this system was polyester blends. The structure of Procion Red T2B
actually carried out at Stamford Research Institute and prepared from simple diazotisation of m-aminobenzene
Burlington Industries (USA) [70,71] and resulted in a range phosphonic acid and coupling this diazo salt to N-acetyl H-
of dyes derived from the intermediate, m-aminobenzene acid is shown in Structure 11.
NHCH2CH2N
N
D N NHCH2CH2N
CH3 CH3 N
N H H2
H2
NHCH2CH2N CH2CH C O Cell + H2C C C NCH2CH2HN N
O N
CH3 OH CH3
D
NHCH2CH2N
N
D N
N CH3
H2
NHCH2CH2N CH2CH C O Cell
NHCH2CH2N
CH3 O OH CH3 N
H2
H2C C C NCH2CH2HN N
H
CH3 N
D
Scheme 14 Reaction of epoxide cationic reactive dyes with cotton and the hydroxyl-propyl residue formed [67]
H H H
DYE N N Cl N N O
DYE
H3O
N N NH
N
Cl O
O OH
HO
Cell-OH
N N
MgCl2
HO OH
Cellulose DMDHEU
HN DYE
N
O N
O
Cell O N
O
N N HN
DYE
Cell O N N
O N O
DMDHEU Cellulose
Scheme 15 Crosslinking hydrolysed triazine dyes to cotton cellulose using DMDHEU [68]
In the above study, cotton fabric was padded with a pad

liquor containing 120 g dm3 of cyanamide, 10 g dm3 of
ammonium dihydrogen phosphate, and 20 g dm3 of pure
H
H2O3P N O NHCOCH3
phosphonate dye (it is important to prepare the dye as the
ammonium salt); after drying and thermofixing at 200 °C for
N 90 s, the alkyl phosphonate dyes gave 95% fixation,
whereas the monofunctional Procion T aryl phosphonate
dye gave only 46% fixation. Thus, the fixation values of the
alkyl phosphonate dyes in thermofixation processes are
HO3S SO3H outstanding; this result was for 2% owf pure dye, which
corresponds to a 3–4% shade of commercial dyes as the
Structure 11 Procion Red T2B latter contain salt, buffers, and dedusting agents. The dye–
fibre phosphonic acid ester bond is remarkably resistant to
In spite of the fact that phosphonate dyes could not treatments in acidic or alkaline media [74].
hydrolyse during the application procedure to form the In a similar vein, polycarboxylic acid containing dyes
phosphonate ester bond with cellulose, only modest fixa- have been synthesised as their ammonium salts and applied
tion efficiencies were recorded. It was important to include to cotton by thermofixation procedures [75] in the presence
a dehydrating catalyst such as cyanamide or preferably of cyanamide as a catalyst. In this case, aspartic acid was
dicyandiamide with the dye in order to promote the above used to make 2,4-diaspartyl-s-triazine dyes according to
esterification reaction. The above catalysts can form carbo- Scheme 18.
diimide tautomers, which are dehydrating agents. The fixation values achieved when the above dye was
Scheme 16 shows the proposed reactions. applied to cotton by a pad–batch thermofix (200 °C, 90 s)
Because of the poor fixation performance of the above procedure from a pad liquor containing 10 g dm3 of pure
phosphonate dyes, aliphatic polyphosphonate dyes were carboxylate dye, 150 g dm3 of cyanamide, and 10 g dm3
studied [72,73]; they were prepared by the simple expedient of ammonium dihydrogen phosphate were of the order of
of condensing aminoethyl phosphonic acid with existing 75%. These results indicate that the system is not as
bis-monochloro-s-triazine reactive dyes according to effective as the phosphonate system; either the carboxylate
Scheme 17. ester dye–fibre bond exhibits lower stability to the alkaline
DYE P OH + H2N C N (HN C NH)
OH
O NH
DYE P O C NH2
OH
DYE-PO3H2
O O O
DYE P O P DYE + H2N C NH2

OH OH
Cell-OH
O O
Cell O P DYE + DYE P OH
OH OH
where DYE = sulphonated chromophore
Scheme 16 Fixation of phosphonate dyes on cotton cellulose
Cl Cl
N N N N
SO3Na O NH O NaO3S
NH N NH N N
N H N
N N
H H
(1) NH2C2H4PO3H2
Cl NHC2H4PO3H2
N N N N
SO3Na O NH NH O NaO3S
N NH N N
N H N
N N
H H
(2) 100 °C/60 min

NH2C2H4PO3H2
NHC2H4PO3H2 NHC2H4PO3H2
N N N N
SO3Na NH O NaO3S
O NH N NH NH N
N N
N N
H H
Scheme 17 The reaction of CI Reactive Red 120 with aminoethyl phosphonic acid [72,73]
(pH 10.5) boiling soaping-off conditions or lower reactivity level-dyeing reactive dye systems for wool occurred in 1966
in the esterification process. with the launch of the Lanasol dyes; these dyes were based
The fixation mechanism is shown in Scheme 19. on the a-bromoacrylamido group [19,20] and were sold with
This area was further developed in a paper describing the the very important level-dyeing amphoteric auxiliary Alb-
pad–dry application of polymaleic acid dyes, followed by a egal B (Structure 12) [79].
pad thermofix process using zinc nitrate and dicyandiamide The launch of the Lanasol dyes coincided with the
as the esterification catalysts [76]. Dye–cellulose fixation marketing of truly machine-washable wool, produced by
values >95% were recorded. the continuous chlorine/Hercosett treatment of wool tops
[80]. Other companies subsequently entered the wool
The application of reactive dyes to natural reactive dye market, Bayer (Germany) and Sandoz
and synthetic polyamide fibres (Switzerland) launching difluoromonochloropyrimidine
dyes (Verofix/Drimalan F) [81] and Hoechst launching a
Brief history of reactive dyes for wool
range of blocked vinylsulphone dyes (Hostalan) [82,83].
The chloroacetylamino reactive group appeared as early as
Dyeings produced on a chlorine/Hercosett-treated sub-
1938 in the IG (Germany) wool dye Supramino Orange R;
strate with acid dyes, acid milling dyes, and premetallised
Ciba put together a small range of bright wool dyes
dyes did not show adequate wash fastness properties, but
containing this grouping in 1954 (Cibalan Brilliant); in
dyeings produced with reactive dyes gave outstanding
1952, Hoechst marketed Remalan and Remalan Fast, 2:1
washing performance [84].
premetallised reactive dyes for wool [77,78] that contained
pendant sulphatoethylsulphone residues capable of b-
Modern usage of reactive dye systems in wool dyeing
elimination to vinylsulphone reactive groups when applied
The chemistry of modern wool reactive dyes has been
from boiling dyebaths above pH 5. These early reactive dyes
reviewed [85,86].
for wool gave unlevel dyeing problems, especially in piece
In light of increasing environmental concerns with heavy
dyeing and yarn hank dyeing, and thus their usage was
metals, it is now usual to use reactive dyes to match deep
mainly in loose stock and top dyeing. The major advance in
shades of black and navy blue in order to offer the dyer a
Cl Cl
N N N N
SO3Na N NH O NaO3S
O NH N NH NH
N N
N N
H H
(1) H2N CH CH2

COOH COOH
HOOC CH2
HOOC CH
Cl NH
N N N N
SO3Na O NH N NH N NH O NaO3S
N
N H N
N N
H H
HOOC CH2 HOOC CH2

HOOC CH HOOC CH
NH NH
N N N N
SO3Na N NH O NaO3S
O NH N NH NH
N H
N N N
H
Scheme 18 The synthesis of a bis-aspartyl-s-triazine dye [75]
real alternative to chrome dyes. In this context, dye The cystine disulphide crosslinked keratin proteins are
manufacturers now offer wool dyers ranges of reactive dyes responsible for most of wool’s physical properties. Cystine
that are attractively priced; examples include Lanasol CE and its reduced form cysteine are particularly sensitive to
dyes from Huntsman, Realan dyes from DyStar, and elimination reactions in water, the extent and nature of
Drimalan dyes from Clariant. which depend especially on the parameters pH, tempera-
Black and navy blue shades are often based on the ture, and time [91–93]. During dyeing, these sulphur-
bifunctional sulphatoethylsulphone CI Reactive Black 5, containing amino acid residues readily undergo a trans-
which slowly activates on boiling at pH 5.5, in situ, to its 1,2-b-elimination reaction to form the dehydroalanine
fibre-reactive vinylsulphone form. residue which contains an activated double bond capable
M€uller [87] studied AOX residues from reactive dyeing of subsequent Michael addition with suitable nucleophiles.
on wool and concluded that there are environmental In general, the thiol form, cysteine, more readily undergoes
advantages in selecting reactive dyes containing only b-elimination than the disulphide form, cystine
sulphatoethylsulphone residues as the reactive group. (Scheme 20).
The hydrogen sulphide or hydrosulphide anion pro-
Developments with reactive dyes for wool and their role as duced in the above reaction is capable of ready reaction
antisetting agents with cystine disulphide residues to produce further cyste-
Permanent setting of wool fibres during dyeing contributes ine thiol residues which will undergo rapid b-elimination to
to loss in wool fibre strength; it is also the main cause of dehydroalanine and hydrogen sulphide in boiling dyebaths
increased hygral expansion of wool fabrics following piece even at pH 3; this is clearly the start of a runaway
dyeing, is the reason for surface marks such as crow’s-feet degradation reaction. The reactive entity, dehydroalanine,
in piece dyeing, and is the source of reduced bulk or yarn will undergo Michael addition with amino nucleophiles
leanness following package dyeing [88–90]. present in histidine and lysine residues and with thiol
H H H H2
DYE N N N C C COOH
COOH
N N
+ H2N C N (HN C NH)
NH
HC COOH
H2C COOH
(Bis-anhydride formation)
H H H
DYE N N N C CH2
O O
N N O
NH O
HC
O
H2C
Cell-OH
O
H H H H2
DYE N N N C C C O Cell
COOH
N N
NH
HC COOH
H2C C O Cell
O
where DYE = sulphonated chromophore
Scheme 19 Fixation mechanism for the reaction of a polycarboxylate dye with cellulose
composition of these new crosslinking amino acids vary

(CH2CH2O)nSO3 greatly with pH and temperature of treatment, as the
nucleophilicities of amino and thiol residues increase with
C18H37 N (CH2CH2O)mSO3 pH and temperature increases. The chemistry of these
crosslinking reactions is exemplified for lysine and cysteine
CH2 residues in Scheme 21.
The above crosslinks will not undergo degradation or
C O m+n=7 elimination reactions under conditions normally encoun-
tered in wool dyeing, and their formation explains the
NH2 permanent setting during wool dyeing. Also of some
importance in setting is the so-called thiol–disulphide
Structure 12 Amphoteric levelling agent for reactive dyeing of interchange reaction [96,97].
wool [79]
The above discussion indicates that inhibition of setting
nucleophiles present in cysteine; in this way, more stable in wool dyeing can be achieved in two ways: inclusion of
crosslinks such as histidino-alanine, lysino-alanine, and oxidants in the dyebath; inclusion of fibre-substantive
lanthionine are formed [94,95]. The extent and exact electrophiles in the dyebath.
C O C O
H2 H2O
HC C SH C CH2 + H2S
NH NH
cysteine
C O O C C O O C
H2 H2 OH H2
HC C S S C CH C CH2 + HS S C CH
NH NH NH NH
cystine dehydroalanine perthiocysteine
O C C O C O
H2 H2O H2 H2O
HS S C CH H2S + HC C SH C CH2 + H2S
NH NH NH
Scheme 20 Elimination reactions of wool cysteine and wool cystine
C O C O C O C O
C CH2 + H
H2N-(H2C)4 CH C C N-(H2C)4 CH
H
NH NH NH NH
lysine lysino-alanine
C O C O C O C O
H2 H2
C CH2 + HS C CH C C S C CH
H
NH NH NH NH
lanthionine
Scheme 21 The formation of lysino-alanine and lanthionine crosslinks
Most of the published research in this area uses Køpke’s mechanism (these dyes include acrylamido dyes and
crease angle method for measuring set [98]. Measuring set is vinylsulphone dyes). The magnitude of this effect increases
a useful indicator of the amount of damage occurring in with increasing amounts of reactive dye applied, being
dyeing – there is a linear relationship. It is important that optimum at ca. 3% owf dye. The importance of this effect
this information is more widely disseminated among wool when dyeing wool fabric at pH 4 with the a-bromoacrylam-
dyers who are not sufficiently aware of its value, and hence ido reactive dye Lanasol Red 6G, 4% owf, is demonstrated
the re-emphasis of this important concept. If an antisetting in Fig. 3.
agent is included in the dyebath when dyeing wool at pH 5 It is interesting to clarify why reactive dyes based on
for 1 h at the boil, it will reduce the measured set value reactive halogenated heterocycles, which react with wool
from ca. 70% to ca. 30%, and hence the amount of fibre fibre nucleophiles by a nucleophilic substitution reaction,
damage. are less effective in controlling wool damage in dyeing than
Selected reactive dyes actively reduce fibre damage in the activated carbon–carbon double bond type of reactive
wool dyeing [99]; particularly effective are those dyes dye. From the above discussions it is clear that successful
that contain activated carbon–carbon double bonds and control of damage and set go hand in hand, and it is thus
thus react with fibre nucleophiles via a Michael addition necessary to look carefully at the reactivity/stability of the
100 H
N N F
D + 2 WOOL-SH
N
90 Cl
80
% Strength retained
H
N N S WOOL
70 D
N
Cl
60 WOOL
S
WOOL-NH2
50
H H
N N N WOOL
40 D
0 0.5 1.0 1.5 2.0
Dyeing time, h N + 2 WOOL-SH
Cl
100 °C 110 °C With reactive dye
105 °C 120 °C Without reactive dye HN WOOL
Figure 3 Effect of time, temperature, and Lanasol reactive dye on Activated carbon–carbon double bond
fabric strength [99]
reactive dye–cysteinyl residue covalent bond. Thioether D-NH-CO-C(Br)=CH2 + 2 WOOL-SH

derivatives of triazine or pyrimidine heterocycles will react
further with amines to form bonds of greater stability, the
leaving group in this reaction being the substituted thiol
[100]. The thioether formed from reaction with an activated
carbon–carbon double bond is, however, resistant to nucle-
ophilic attack or b-elimination under the mildly acidic D-NH-CO-CH(S-WOOL)-CH2S-WOOL
conditions pertaining in wool dyeing [101].
When set was measured from wool fabric dyeings WOOL-NH2
produced at pH 5 from the activated halogenated heterocy-
cle type of reactive dye, Drimalan Red F-2G (Clariant) (3%
owf), a value of 74% was obtained; in contrast, when the NO REACTION
above dye was replaced with a reactive dye containing an Scheme 22 Cysteinyl reactions with active heterocyclic and
activated carbon–carbon double bond, Lanasol Red 6G double bond types of reactive dye
(Ciba) (3% owf), a set value of 41% was obtained [102].
The reactions responsible for these differences are sum-
arises from the reaction of the vinylsulphone with free
marised in Scheme 22.
hydrogen sulphide according to the mechanism shown in
Cho et al. [103] also showed that the trifunctional
Scheme 24.
reactive dye (dye I-1) prepared as shown in Scheme 23
gave excellent overall fixation efficiencies, >95% for a 2%
shade of pure dye, when applied to wool at pH 4 for 1 h at Reactive dyes for silk
the boil; in comparison, the best fixation values obtained Compared with wool, silk has a much lower content of
from existing commercially available reactive wool dyes primary amino residues, 0.150 mol amine kg1 versus
(e.g. Lanasol, Realan, or Drimalan) are around 80%. 0.820 mol amine kg1. Hoechst recommended that silk be
The importance of hydrogen sulphide as a catalyst to dyed with sulphatoethylsulphone dyes (Remazol) at 60 °C
promote setting/wool damage under dyeing conditions was in the presence of Glauber’s salt, adding 2 g dm3 of soda
proven by Lewis and Smith [104] who demonstrated ash to fix the dye after a few minutes [105]. Lewis and Shao
the presence of a bis-(dye-sulphonylethyl)-thioether dye [106] found that better results, in terms of levelness, colour
after dyeing with a model vinylsulphone dye. This dye yield, and fixation, could be achieved by the following
Cl Deepali et al. [108] studied the effect of dyeing temper-

ature/pH and salt content on the exhaustion/fixation param-
CH2CH2SO2CH2CH2Cl eters of heterobifunctional reactive dyes on silk; in general,
N N sodium sulphate additions promoted dye exhaustion under
+
HN
all pH conditions studied.
D N Cl CH2CH2SO2CH2CH2Cl
Reactive dyes for nylon
[P3]
Procion Red MX-8B (Intermediate I) Attempts to dye nylon fibres with reactive dyes have been
frustrated by the paucity of nucleophilic sites available for
pH 5.5, 40 °C reaction; typically, nylon 6,6 from DuPont (USA) contains
only 0.036 mol amine kg1 fibre,which contrasts greatly
with wool (0.820 mol amine kg1) and silk (0.150 mol
Cl amine kg1). This factor alone has meant that achieving
build-up of sulphonated dyes even in moderate depths of
shade is impossible, as every dye molecule covalently fixed
N N means that, depending on the chromophoric component,
CH2CH2SO2CH2CH2Cl one, two or even three strongly anionic sulphonate groups
D N N become fixed at the same time, resulting in a build-up of
negative charge on the fibre that acts as a resist to further
CH2CH2SO2CH2CH2Cl anionic dye uptake.
In light of the above, it is not surprising that the first
Modified dye I-1
range of reactive dyes for nylon was based on disperse dyes
Scheme 23 Preparation of a trifunctional reactive dye suitable for containing a pendant reactive group; these dyes were
wool dyeing [103] marketed as Procinyl dyes by ICI in 1959 and contained a
variety of reactive groups, all but the MCT yellow requiring
alkali activation to form a more reactive residue. The dyes
D-SO2-CH=CH2 + H2S D-SO2-CH2CH2SH were all applied at the boil for 30 min under neutral
conditions, the pH was then raised to 10.5 by the addition of
sodium carbonate, and boiling was continued for a further
D-SO2-CH=CH2 30 min. The alkaline processing step achieved two objec-
tives: firstly, the amino end groups in nylon would not be
significantly protonated, giving maximum nucleophilicity;
D-SO2-CH2CH2-S-CH2CH2-SO2-D
secondly, chlorohydrin groups in Procinyl Blue RS were
Thioether dye converted to the highly reactive epoxide form, or the
chloroethylaminosulphonyl groups in Procinyl Scarlet GS,
Scheme 24 Trapping of hydrogen sulphide by a vinylsulphone dye
Procinyl Orange G, and Procinyl Red GS were converted to
the highly reactive aziridinylsulphone form. Scott and
Vickerstaff [109] described the interesting chemistry behind
Table 4 Fixation values for free vinylsulphone dyes on silk [106]
these dyes and the application process, and demonstrated
that, in full shades of Blue RS or Scarlet GS, more than the
Dye Concentration, % owf E, % F, % T, % theoretical amount of dye, based on an amino end group
content of 0.0426 mol kg1 fibre, could be covalently
CI Reactive Blue 19 2 100 97 97 bonded to the substrate. In particular, results with Scarlet
3 100 96 96
4 98 94 92 GS were very surprising; applying 20% owf dye gave
5 96 92 88 0.1280 mol dye kg1 fibre as covalently bonded dye. To
CI Reactive Black 5 2 99 93 92 explain this excess fixation, given the paucity of amino
3 98 93 91
groups, double addition of the dye at each amino residue is
4 97 92 89
5 96 90 86 clearly possible, as is reaction with ionised hydroxyl
nucleophiles in the dye itself [110].
The use of the vinylsulphone-type dye CI Reactive Blue
method: preactivation of the SES dye to its vinylsulphone 19 for dyeing nylon has been studied in detail [111]. It was
form by treatment in an aqueous solution at pH 8 for 5 min shown that this dye in b-sulphatoethylsulphone form did
at the boil, and then dyeing for 40 min at 80 °C with this not react efficiently with the available amino nucleophiles
solution at pH 4.0–4.5 in the absence of salt. when applied at pH 5; if the dye was preconverted to the
Typical E, F, and T values obtained for CI Reactive Blue vinylsulphone form before dyeing, then much better fixa-
19 and CI Reactive Black 5 are summarised in Table 4. tion efficiencies were observed.
Youssef and Mousa [107] compared exhaustion fixation A cationic reactive dye of the general formula H2C = HC–
values on silk of heterobifunctional monochlorotriazine/ SO2–D–Q+, where D is an azo chromophore and Q is a
disulphide ethylsulphone dyes versus those from simpler quaternary ammonium residue, was prepared by Hinks
bifunctional MCT/sulphatoethylsulphone dyes. The former et al. [112]; this dye coloured nylon efficiently at pH 9.
dyes showed very superior performance. Substantivity of this cationic dye for nylon is high under
alkaline conditions because overall the nylon is negatively When a 2% dyeing (1 h at the boil) was carried out on
charged, and in addition the amino groups are more nylon, from baths buffered at pH 3–10, with the pure
nucleophilic as they will be mainly deprotonated under cationic thio-choline dye, the exhaustion/fixation values
these conditions. shown in Table 5 were obtained.
Lewis and Sun [113,114] published details of the The total efficiency value of 93% with these cationic
synthesis of blocked vinylsulphone dyes using 2-thiol- reactive dyes is impressive, as anionic vinylsulphone dyes
choline; in these dyes, the solubilising group was the give a maximum T value of 85% at 2% owf dye.
trimethylammonium cation. When applied to nylon at pH
10, the dyes showed excellent substantivity, and yet at the Miscellaneous methods for covalent
boil the thiol-choline residue was eliminated to form the bonding of dyes to fibres
vinylsulphone dye which reacted readily with the deprot-
Cellulose modification to enhance dye–fibre covalent
onated amines in nylon. The preparation of this type of dye
bonding
is shown in Scheme 25. The mechanism of its absorption
The fixation of reactive dyes on substrates containing amino
and reaction with the nylon fibre is described in
groups is much higher than on cellulosic substrates. Thus,
Scheme 26.
wool, which contains amino terminal groups on individual
O2
+ H2C C S N N N
(H3C)3N SH H
50 °C pH 8.0
(H3C)3N S O2S N N N
Scheme 25 The reaction of thiol-choline with the VS disperse dye to give a water-soluble cationic dye [114]
NH2
+
D S S N(CH3)3 COO
O2
NH2
COO (H3C)3N S S D
O2
elimination
+
O2S D HS N(CH3)3
HO [O2]
NH O2S D (H3C)3N S S N(CH3)3
COO
Scheme 26 Absorption and reaction of choline-thioether-ethylsulphone dye with nylon under alkaline conditions
Table 5 Exhaustion and fixation values for cationic reactive dyes Thus, the anionic sulphonated reactive dye is initially
on nylon (2% pure dye) [114] absorbed onto the fibre by a powerful ionic attraction to the
quaternary ammonium residue and fixes to the adjacent
(dyebath) E, % F, % T, % ionised (nucleophilic) hydroxyl group. Typical dyeing
conditions that could be employed were pH 7, with no
3 3.5 1.9 0.1 salt, with the bath raised to the boil over 30 min and dyeing
4 13.5 11.5 1.6
continued at the boil for a further 60 min. Dyeing, for
6 48.8 46.6 22.8
7 93.1 89.2 83.0 example, with a 2% owf shade of CI Reactive Red 5
8 94.4 91.3 86.2 (dichloro-s-triazine dye) gave exhaustion values of 85%,
9 95.4 92.4 88.2 and, even more interestingly, 99% of the absorbed dye was
10 97.5 95.2 93.0
apparently covalently fixed; thus, soaping-off of the dyeing
gave rise to hardly any colour removal. Colour yields
compared with the conventional salt/alkali method on
amino acid side chains, can be dyed with reactive dyes from untreated cotton were doubled.
baths set at pH 5–7, to give very high fixation efficiencies. In On account of perceived health and safety problems in
some cases, total overall colour yields (fixation T) of 95– handling the epoxide form, recent efforts to modify cotton
100% are recorded, even in moderate depths of shades. in this manner have concentrated on a pad–batch proce-
These excellent results on wool are achieved without the dure; 3-chloro-2-hydroxy-N,N,N-trimethyl propanaminium
need to add electrolyte. It is therefore not surprising that a chloride (TAHC) is metered into the pad liquor along with
large amount of work has been done to prepare modified sodium hydroxide solution to give a final pad liquor
cellulosic substrates containing amino residues in order to containing 65 g dm3 of TAHC and 50 g dm3 of sodium
improve dyeability. The whole area of cotton modification hydroxide [121]. The high pH converts the above agent,
to improve reactive dyeing was reviewed by Lewis and during the batching procedure, to the corresponding epox-
McIlroy [115]. ide, which then fixes covalently to the fibre. The treated
At one time it was thought that a cheap convenient way cotton can be dyed with selected reactive dyes in the
of modifying cotton to make it readily reactive dyeable was absence of salt; dyebath exhaustion is 99–100%, even in full
to pretreat it, from a long liquor, with a reactive cationic depths of shade, and fixation values also equal or approach
polymer under alkaline conditions [116]. Such treatments 100%. Clark [68] showed that vinylsulphone-containing
imparted a very high neutral substantivity for reactive dyes, reactive dyes gave noticeably duller shades on quaternary-
in the absence of electrolyte, and gave dyeings of good wet amine-pretreated cotton than did reactive dyes based on
fastness. However, such approaches have not met with triazine or pyrimidine; this was attributed to the strong
commercial success, as the treated fabric was dyed to duller electron-withdrawing character of the bonded sulphone
shades than those produced by the conventional salt/alkali group, creating an anionic site that ion paired with the
process, and a significant drop in light fastness of 1–2 points quaternary ammonium residue.
was noted [117]. Lewis and Lei [122] also prepared water-soluble cationic
Bright, light-fast dyeings could, however, be obtained by agents from the reaction of dimethylamine and epichloro-
using a variety of methods to incorporate amino residues on hydrin, and found that they would fix to cotton by an alkali-
cellulosic substrates, and some of the most promising catalysed pad–dry-bake procedure. In an analogous manner
techniques will be discussed. to the glycidyltrimethylammonium chloride (Glytac A)
Rupin et al. [118], Rippon [119], and Lewis and Lei [120] pretreatment, the above agents gave a substrate that was
studied the dyeability of cellulose substrates modified with readily neutral dyeable, at the boil, with reactive dyes, in
glycidyltrimethylammonium chloride (Glytac A from Protex) the absence of electrolyte. Such dyeings exhibited wet and
or its precursor 1-chloro-2-hydroxy-3-trimethyl-ammonium- light fastness properties that mirrored the performance of
propane chloride. This modification may be carried out by an the selected reactive dye applied to untreated cotton by the
alkaline pad–bake (200 °C) or by an alkaline pad–batch normal salt/alkali process.
procedure. Unfortunately, the product has insufficient sub- An alternative method for introducing different aliphatic
stantivity to allow its application by long-liquor methods. The amino groups into cotton involved a pad–bake pretreatment
modified substrate may be considered to have the structure of the fabric with N-methylol acrylamide (NMA), which
shown in Scheme 27, although the possibility of such treat- reacted covalently with cellulose by a Lewis-acid-catalysed
ments leading to the introduction of oligomeric polyether baking reaction [120] (Scheme 28).
chains bearing cationic functionality has not been established. Reaction of the above substrate with appropriate amines
The ease of neutral dyeing of this substrate with reactive gave a series of amino-substituted cellulosic substrates
dyes led Lewis and Lei [120] to speculate that the deprot- (Scheme 29).
onated form II predominates even when dyeing at pH 7.
Cell-OH + HOCH2-NH-CO-CH=CH2
Cell-O-CH2-CH-CH2 -HCl Cell-O-CH2-CH-CH2
OH N(CH3)3Cl O N(CH3)3
I II Cell-O-CH2-NH-CO-CH=CH2
Scheme 27 Different forms of cotton modified with Glytac A Scheme 28 Reaction of NMA with cotton
Cell-O-CH2-NH-CO-CH2-CH2-NH2……………….…..…I
20
Cell-O-CH2-NH-CO-CH2-CH2-NH-CH3……………....…II
Cell-O-CH2-NH-CO-CH2-CH2-N-(CH3)2………………III
Cell-O-CH2-NH-CO-CH2-CH2-N-(CH3)3+X–………..…IV
K/S
Scheme 29 Amino derivatives of NMA-treated cotton 10
AA dye/before soap
AA dye/after soap
Substrates I to IV inclusive were dyed at pH 5 in the P dye/before soap
P dye/after soap
absence of electrolyte, with 2% owf CI Reactive Red 5,
0
raising the bath to the boil and boiling for 1 h. Optimum 0 4 8
exhaustion/fixation values are achieved on substrates I and Dye applied, % owf
II; substrate III containing the tertiary amine gives surpris-
Figure 4 Build-up curves for CI Reactive Red 58 (P dye) on
ingly poor fixation results. untreated cotton and its aminoethyltriazine (AA dye) on NMA
Undoubtedly, the highly reactive dichloro-s-triazine dye cotton
is likely to form a quaternary derivative with the tertiary
amine residues in substrate III, and, failing reaction with a
nearby fibre-bonded nucleophile, this highly reactive spe- The above concept may be reversed by producing dyes
cies will rapidly hydrolyse. containing pendant nucleophiles. Aminoalkyl dyes are
Lewis and McIlroy [123] reacted cotton with nicotinoyl- conveniently prepared from the reaction of aliphatic diam-
thioglycollate (NTG) which was prepared in high yields ines with existing reactive dyes.
from the reaction of sodium thioglycollate with nicotinoyl Reactive cellulosic fibres may be prepared by the follow-
chloride at pH 8 (0–5 °C). NTG was applied to cotton fabric ing methods:
by a pad–dry-bake (typically pH 8, 180 °C for 60 s) (i) Reaction of cotton with N-methylol-acrylamide. It was
procedure to produce the modified cellulose shown in shown [120] that the aminoethylamino-s-triazinyl dye,
Structure 13. prepared from the reaction of CI Reactive Red 58 (Procion
Red H8BN-ICI) with ethylene diamine, gave excellent
colour yields when applied to NMA-activated cotton at pH
10.5 in the presence of 80 g dm3 of salt (dye AA). Typical
Cell-O–(C=O)–Pyridine + H+ Cell-O–(C=O)–Pyridine–H+
results are reproduced in Fig. 4; this figure also shows
Structure 13 NTG-modified cellulose colour yield (K/S) versus dye applied, before and after
soaping, for the unchanged parent monochlorotriazine dye
applied to untreated cotton by the recommended reactive
It was found that a bis-MCT dye (CI Reactive Red 120) dyeing procedure (dye P).
could be dyed at 2% owf dye on this substrate from a boiling This figure demonstrates that practically no dye is
dyebath set at pH 3, in the absence of the usually added removed from the activated cotton, even when soaping at
electrolyte, to give an overall fixation efficiency of 65%; the boil (15 min) in an aqueous solution of nonionic
untreated cotton dyed in this manner gives an efficiency of detergent (5 g dm3) and sodium carbonate (2 g dm3).
zero (the traditional salt/alkali procedure gave a fixation The comparative result, achieved with unmodified CI
efficiency value of 74%). Reactive Red 58 on untreated cotton, indicated that up to
It is important to cite the very early work of Hartmann 30% of non-reacted dye is removable during the soaping
[124], who pretreated cotton with aminoethylsulphate to procedure. Thus, the dyeing of activated cotton with
incorporate aminoethyl residues in the cotton. The objec- aminoalkyl dyes offers significant potential savings
tion raised to this process was the potential to produce because, on the basis of these results, the soaping process
aziridine, although this was subsequently refuted by Her- could be omitted.
linger et al. [125]. (ii) Reaction of 2,4-dichloro-6-(2-pyridino-ethylamino)-s-
A more practical approach to cotton modification is triazine (DCPEAT) with cotton. In an attempt to improve
possible through bioengineering. Workers from the Univer- substantivity in the no-salt dyeing system, a novel
sity of Ghent and Bayer Crop Science NV (Belgium) [126] compound, 2,4-dichloro-6-(2-pyridino-ethyl-amino)-s-tri-
published a paper describing the growing of cotton genet- azine (DCPEAT), has been studied by Lewis and Lei.
ically modified to produce the N-acetyl-glucosamine oligo- If this compound were to be applied and fixed on [122]
saccharide form of cellulose. Some preliminary cellulosic substrates under well-defined conditions, the
investigations of the dyeing properties of this substrate modified substrate shown in Scheme 30 would be
confirmed that amino groups had been incorporated, and produced.
hence efficient reactive dyeing in the absence of salt should This reactive substrate shows excellent dye–fibre fixation
be possible. when it is dyed with aminoalkyl dyes (Scheme 31).
DCPEAT contains two reactive chlorine atoms – when
Reactive fibres rather than reactive dyes applied to cellulosic substrates under weakly alkaline
Existing reactive dye systems depend on two basic ele- conditions, one of the chloro substituents is displaced,
ments: an electron-deficient ‘reactive’ carbon centre in the leading to covalent fixation. The cellulosate substituent
dye; an electron-rich ‘nucleophilic’ centre in the fibre. deactivates the triazinyl ring, ensuring that the product of
Cl 20
As dyed After soaping
N N m=1 m=1 m=2
Cl
N CH2CH2 N N O Cell
H
K/S
10
A simplified representation of this substrate is:
R3H2N N Cl
Reactive centre capable of

Cationic-anionic dye N N reaction with dyes containing
nucleophilic residues 0
attracting centre 1.8 5.4 5.4
DCPEAT, % owf
O
Figure 5 Colour yields of aminoethylamino-s-triazine nucleophilic
Cell dyes applied to DCPEAT-modified cottons
Scheme 30 DCPEAT-activated cotton
containing nucleophilic centres; surprisingly, hydrolysed

O3S CH2CH2 NH
vinylsulphone dyes (hydroxyethylsulphone dyes) could be
D
dyed at 2% depth on tosylated cotton, without salt, from
boiling pH 8 baths, to give fixation efficiencies of 76%.
N N
Covalent bonding of nucleophilic dyes on fibres using
crosslinking systems
R3H2N N N Cl
H The earliest commercial success in this area was achieved
by BASF with the Basazol system [129,130]. In this case,
Scheme 31 Aminoalkyl dye–DCPEAT cotton reaction product dyes containing pendant nucleophilic groups were fixed to
cellulose hydroxyl residues using the trifunctional
the pretreatment reaction contains significant numbers of crosslinking agent 1,3,5-triacroylaminohexahydro-s-triazine
monochloro-s-triazine residues. As aliphatic amino is a (fixing agent P). The dyes employed contained sulphona-
more powerful nucleophile than cellulose hydroxyl, very mide residues, which were sufficiently nucleophilic above
efficient reaction of the dye at the monochlorotriazine pH 10.5 to undergo Michael addition with the activated
residue should be possible during subsequent dyeing with double bonds of the crosslinker. In fact, many of the
aminoalkyl dyes. aminosulphonyl dyes selected as Basazol dyes were already
It was found that the DCPEAT-modified substrate was available as 2:1 premetallised dyes for dyeing wool (Orto-
best prepared by a cold pad–batch (24 h) technique at pH lan; BASF, Germany). The following simplified scheme,
8.5, followed by a thorough cold water wash-off. Although describing the covalent fixation of the sulphonamide dye to
long-liquor applications of DCPEAT were studied, inade- cotton, is relevant, although it should be noted that
quate substantivity of this compound for the fibre gave Baumgarte [129] describes up to nine possible reaction
poorer subsequent dyeings than those obtained on pad– products from such a system (Scheme 32).
batch-prepared substrates.
Two aminoalkyl dyes were employed to dye this modi- H2C=HCOC COCH=CH2
N N
fied substrate in the absence of salt, namely Procion Red + [Dye]-SO2NH2 + [Cell]-O
H8BN (monoaminoethyl-aminotriazine derivative) and Pro- N
cion Red HE3B (CI Reactive Red 120) [bis(aminoethyl- COCH=CH2
aminotriazine) derivative].
The results obtained when dyeing these two nucleophilic
dyes (m = 1, m = 2) on the above substrate are shown in
Fig. 5 (dyeing conditions: no salt, pH 9, dye 2% owf, raise to
H2C=HCOC COCH2CH2NHSO2—[Dye]
the boil, boil 1 h). This figure demonstrates that good N N
substantivity and fixation are achieved at the higher levels
N
of DCPEAT application (5.4% owf); slightly better results
were achieved using the bifunctional aminoethyl dye COCH2CH2O[Cell]
(m = 2) derived from CI Reactive Red 120.
Scheme 32 Fixing agent P/sulphonamido dye/cellulose reaction
Tosylation of cotton is an old method for activating
cotton to make a reactive fibre, developed by Karrer and
Wehrli [127] in 1926. In this case, amination was used to Clearly, the above species contains an unreacted double
displace the tosyl group and thus render the fibre dyeable bond that is capable of undergoing further reaction with
with anionic acid dyes. Arrowsmith and Lewis [128] found either the nucleophilic sulphonamide residue or with the
that tosylated fibres would react very efficiently with dyes nucleophilic cellulosate anion. This system was highly
100 (ICI). Thus, wool could be dyed, from long-liquor baths

set at pH 6, using aminoalkylamino-s-triazine dyes along
Exhaustion/fixation, %
with the above crosslinking agent. Very high exhaustion

values were obtained, and fixation values of 95% were
60
recorded. This system had the advantage of low reactivity
until the boil was reached, giving the dye an excellent
opportunity to level before covalent bonding became
20
significant. Typical exhaustion/fixation results from the
0 aminoethylamino-s-triazine dye/FAP system are shown in
0 40 80 120 160 (min)
Fig. 6.
50 100 100 100 100 (°C)
Lewis et al. also studied the use of a bifunctional
Time/temperature
crosslinking agent, methylene-bis-acrylamide, to fix amin-
Figure 6 Exhaustion/fixation curves from wool dyed by the aminoalkyl dyes on wool [134].
oalkyl dye/FAP method, using 4% owf bisaminoalkyl dye: ϖ If such systems are to be further developed for covalently
exhaustion (E); □ fixation (F); ○ fixation (T)
fixing dyes on cellulosic materials, the Basazol experience
novel, but the dyes were withdrawn from the market place appears to indicate that fibre-substantive crosslinking
because of its restriction to padding and printing processes agents should be developed along with suitably nucleo-
owing to the non-substantive character of the crosslinker philic dyes. Another system [135] has described the
and possible toxicity problems. The clear advantage of such promising covalent fixation to cellulose of sulphonated
a system was that the dyes were not susceptible to chromophores containing pendant aminoalkyl groups by
hydrolysis, and thus, in theory, very high levels of fixation reaction of the dye and the cellulose with the crosslinking
should have been achievable, provided sufficient crosslin- agent disodio-2-chloro-40 ,6-di(aminobenzene-4-sulphato-
ker was present. ethylsulphone)-s-triazine (XLC) (Structure 14).
H H
NaO3SOCH2CH2O2S N N N SO2CH2CH2OSO3Na
N N
Cl
Structure 14 The trifunctional crosslinker XLC
Lewis and Jabbar [131] showed that cotton could be This agent (XLC) has also been investigated as a cross-
efficiently modified with fixing agent P using a pad–batch linking agent for the covalent fixing of amino-nucleophile-
(30 °C, 24 h) application at pH 11.5 (20 g dm3 Na3PO4); containing dyes to nylon [136,137] and wool [138] sub-
this reactive substrate could then be reacted with polyfunc- strates. In the case of wool, a very high degree of covalent
tional amines such as diethylenetriamine to give a substrate fixation was recorded, either by coapplying dye and cross-
containing pendant amino groups; this latter substrate linker at pH 6 (100 °C) or by dyeing first and then adding the
could then be dyed in the absence of added electrolyte by crosslinker to the exhausted bath. Nylon, owing to its paucity
simply boiling at pH 7 in the presence of reactive dye. of nucleophilic amino sites, represented a bigger problem.
Exhaustion/fixation values of 94% were recorded for CI However, promising results were obtained by synthesising
Reactive Red 2 when applied at 2% owf; the recommended the aminoalkyl cationic dye shown (Structure 15) and
long-liquor dyeing process for unmodified cotton (dyeing applying it to nylon at pH 9 at the boil [139]. Subsequent
with 80 g dm3 of salt and using sodium carbonate to fix) aftertreatment with XLC at the boil resulted in promising
gave a comparative value of 55%. levels of dye–fibre covalent bonding, even in deep shades.
O Et
H2N H2CH2C S N N N
O CH2CH2 N
Structure 15 Amino-ethylsulphone cationic dye
It is of interest that the above crosslinking agent has Surprisingly, cyanuric chloride [140] has been proposed
been found efficiently to fix dyes containing pendant as a crosslinking agent for fixing dyes containing pendant
nucleophilic amino groups on both wool and nylon amine groups to cellulosic fibres. Clearly, from a health and
[132,133]. In the former case, very good results safety point of view this approach is flawed; cyanuric
were obtained, providing the crosslinking agent was chloride is a primary skin irritant and is known to cause
predispersed with the anionic dispersant Matexil DA-AC severe allergic reactions in certain individuals.
N quately, giving weaker than desired shades and requiring

CH2 CH2 CH2 intensive washing-off to achieve the required wash fastness.
N 6H2O Furthermore, in long-liquor dyeing, the use of large quan-
CH2 CH2 6HCHO + 4NH3
tities of inorganic electrolytes is increasingly viewed as
N N
environmentally unfriendly, and thus the development of
CH2
new systems using minimal salt without sacrificing level
dyeing properties is desirable. In light of the above, there is
still great scope for further research and development to
D NH2 + HCHO D NH CH2 OH maximise the benefits of reactive dye systems; even so, the
I development and use of reactive dyes have to rate among
1 the most important achievements of colour chemists.
D NH CH2 OH
CH2 OH II
Acknowledgement
The author thanks Dr John Mama for drawing the various
chemical structures.
D NH2 + HCHO + H2N W D NH CH2 NH W 2
III
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244. dyeing materials containing hydroxyl and/or carboxamide
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(2000) 46.
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2003
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135. K N Tapley, The reactive dyeing of cotton to achieve mixtures.
improved fixation efficiency. PhD Thesis, University of DyStar Textil Farben – US6712863(B2) – Black dye
Leeds, Leeds, UK (1992).
mixtures of fibre-reactive azo dyes and the use thereof for
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138. X P Lei, D M Lewis, X M Shen and Y N Wang, Dyes Pigm., 30 materials.
(1996) 271. DyStar Textil Farben – ZA200305261(A1) – piperazine-
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383. derivatives, again crosslinked with piperazine (i.e. four azo
residues per dye molecule).
Appendix: Procter & Gamble – US6518407(B1) – Reactive dye
compounds prepared from halo-s-triazines or halopyrimi-
dines containing at least one substituted thiol residue and
Patent analysis one quaternary residue; these products claim to give very
As the patent literature is extensive, a selection has been good fixation efficiencies on cellulosic and polyamide
made from an Espacenet search of reactive dye patents: substrates.
1999 2004
Ciba SC Holdings – US5892006(A) – Fibre-reactive halo-s- DyStar Textil Farben – US2004049865(A1) – Black dye
triazine dyes; selected dye mixtures for optimised proper- mixtures of fibre-reactive azo dyes and the use thereof for
ties on cotton. dyeing hydroxy- and/or carboxamido-containing fibre mate-
Montforts Textilmaschinen GMBH – US5885305(A) – rials.
Device for fixing dye in reactive dyeing; this is a drying DyStar Textil Farben – ZA 200406380 – Ortho-phenylene-
device that maintains the predetermined moisture content diamine-linked bis-monochloro-s-triazine azo dyes.
to ensure that reactive dye fixation can occur in the hot Everlight USA – US6780204(B2) – Black and navy
drying process. reactive dyes prepared from mixtures of dis-azo dyes.
2001 2005
Ciba SC Holdings – US6307034(B1) – Reactive dyes DyStar Textil Farben – ZA200406381(A1) – Dye mixtures of
containing a formazan dye radical, a process for their fibre-reactive azo dyes and their preparation and use.
preparation and use; in these dyes, the blue copper
formazan chromophore is linked to a halo-s-triazine 2007
attached to an aliphatic diamine, and then the terminal Huntsman – US8066809(B2) – Red reactive dyes, usually
amine is condensed with a different dihalo-s-triazine dye to trifunctional (a variety of reactive groups incorporated, such
give a molecularly mixed dye; an olive green dye is as MCT, MFT, and vinylsulphone), claiming high fixation
exemplified. and excellent light fastness;
DyStar – EP 11364260(A1) – Deep-black dye mixtures of
fibre-reactive azo dyes. 2008
DyStar Textil Farben – US7414129(B2) – Triphendioxazine
2002 dyes containing a variety of reactive groups (for example
Procter & Gamble – US6447554(B1) – Reactive dye com- MCT, MFT, FCP, and VS).
pounds; these dyes were prepared by the reaction of Shanghai Colva Dyestuff Ind. Co. – CN101255282(A) –
substituted thiols with halopyrimidines or haloquinoxa- Reactive dye compound and the use thereof.
lines; surprisingly, the thiols will act as leaving groups in Shanghai Argus Textile Chem. – CN101302355(A) –
subsequent reactions with nucleophilic sites in textile fibres Yellow reactive dye composition and the use thereof.
and human hair.
Shanghai Argus Textile Chem. – CN101302355(A) – Red Everlight Chem. Ind. – TW1381023(B) – Novel bis-
reactive dye composition and the application thereof to fibre reactive dye with N,N-dialkylamino bridging group.
material.
Shanghai Argus Textile Chem. – CN101323710(A) – Red 2011
reactive dye composition and the application thereof. DyStar Colours – PT1789499(E) – Dye mixtures of fibre-
DyStar Textil Farben – TW1294447(B) – Reactive dye reactive azo dyes and the production and use thereof.
mixtures. PMT Chemical Co. Ltd – CN102051068(A) – Brown
DyStar Textil Farben – TW200817479(A) – Dye mixtures reactive dye and the preparation method thereof.
of fibre-reactive dyes and their preparation and use. Everlight Chem. Ind. – TW201107429(A) – Reactive
DyStar Textil Farben – PT1490442(E) – Dye mixtures of printing dye and its aqueous composition.
fibre-reactive azo dyes and the production and use thereof. Sinochem Corp./Shenyang Res. Inst. – CN102250491(B) –
DyStar Textil Farben – PT1397438(E) – Dye mixtures of Disazo reactive dye.
fibre-reactive azo dyes and the use thereof.
Everlight Chem. Ind. Corp. – TW200846420 (A) – Yellow 2012
reactive dye composition. Sinochem Corp./Shenyang Res. Inst. – CN102453349(A) –
Everlight Chem. Ind. Corp. – TW200825142(A) – Reactive Disazo reactive dye.
red dye composition and the application thereof. DyStar Colours – US2012216356(A1) – Fibre-reactive azo
dyes and dye mixtures and the use thereof.
2009 Everlight Chem. Ind. – TW201241102(A) – Reactive dye.
Everlight Chem. Ind. Corp. – TW200902639(A) – Reactive
dye with sulphanyl group and beta-sulphatoethylsulphone 2013
group. Everlight Chem. Ind. – TW201331302(A) – Dark-brown
Shanghai Argus Textile Chem. – CN101440227(A) – reactive dye.
Yellow reactive dye composition and the use thereof. Huntsman – WO201317331(A1) – Mixtures of polyfunc-
Shanghai Argus Textile Chem. – CN101457032(A) – tional MCT/SES containing dis-azo black dyes; applied with
Dark-blue reactive dye composition and the use thereof. a trifunctional SES red dye to produce dark shades.
Shanghai Argus Textile Chem. – CN101463191(A) – Red DyStar Colours – US8349029(B2) – Dis-azo reactive dyes
reactive dye composition and the application thereof. prepared by azo coupling to a sulphonated meta-phenylene
Proctor & Gamble – MX2009010010(A) – Laundry deter- diamine molecule; applied in mixtures with bis-coupled H-
gent with a reactive dye. acid derivatives.
DyStar Textil Farben – WO20090207263(A1) – Continu- DyStar Colours – WO2014063822(A1) – Mixture of fibre-
ous dyeing of cotton/polyester blends from a single bath reactive dyes.
containing reactive and disperse dyes; reactive dye first
fixed by drying at about 130 °C in a defined steam/air 2014
atmosphere, and then the disperse dye thermosol fixed at Everlight Chem. Ind. – TW201400555(A) – Novel reactive
200 °C. dye.
Huntsman – US8740992 – Improved afterclearing reac-
2010 tive dyeings on cotton by washing-off in the presence of a 1-
DyStar Colours – WO2010057830 – Ring-fluorinated reac- ethylenically unsaturated N-heterocycle polymerised with
tive dyes; by using fluorinated aniline sulphonates, the polyethyleneimine.
inventors produced reactive dyes of improved light fastness DyStar Colours – EP2725068(A1) – Reactive dye mixtures
on cotton; a variety of reactive groups claimed. based on bis-coupled H-acid and bis-coupled meta-pheny-
Clariant Finance BV Ltd – JP2010031269(A) – Fibre- lene diamine azo derivatives; improved substantivity, easy
reactive mono-azo dye. wash-off of unfixed dye, and high fixation efficiencies.
Sumitomo Chemical Co. – JP2010013658(A) – Reactive
dye composition and its application.

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Reactive Dye

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doi: 10.1111/cote.

Developments in the chemistry of reactive

Halopyrimidines In the early 1970s, ICI developed homobifunctional dyes

Structure 1 CI Reactive Black 5

Structure 2 Sumiﬁx Supra Brilliant Red 2BF

Structure 3 Remazol Red SBB

2% Remazol Brilliant Blue R (60 °C)

60 E = 88.1% 3% owf 6% owf

DYE–SO2 –CH2 –CH2 –OSO3Na + OH → DYE–SO2 –CH=CH2 + NaHSO4

No dye–fibre reaction possible

Scheme 3 Reaction of monohalo-s-triazine dye with N-methyltaurine [44]

Sulphatoethylsulphone dye Vinylsulphone dye

Scheme 4 Reaction of sulphatoethylsulphone dye with N-methyltaurine [44]

trichromatic combinations of improved levelness and dichloro-s-triazine dyes (or diﬂuoromonochloropyrimidine

Cl to give the bis-ethylene-diamine intermediate shown in

HN CH2 CH2 NH3

O HN N N CH2 CH2 NH3

Structure 6 Bis-ethylenediamine intermediate [49]

Structure 7 Tetrachloro-s-triazine dye from CI Reactive Red 1 [49]

100 S 67%, E 85%, F 77%, and T 66%; clearly, the doubling in

TSP 20 g dm3 Na2CO3 20 g dm3 NaHCO3 20 g dm3 Na2HPO4 20 g dm3

60% 95% 59% 96% 27% 71% 71% 82%

Scheme 6 The synthesis of 1-aminobenzene-4-S-thiosulphatoethylsulphone (Bunte salt)

Scheme 7 The synthesis of the disulphide-bis-ethylsulphone diamine intermediate

H2N SO2 C2H4 S S C2H4 SO2 NH2

O4SH N2 SO2 C2H4 S S C2H4 SO2 N2 HSO4

NaO3S SO3Na NaO3S SO3Na

Scheme 8 The synthesis of a disulphide-bis-ethylsulphone (DSBES) dye

H2N SO2CH2CH2SSCH2CH2SO2 NH2

Scheme 9 Synthesis of MCT/DSBESA intermediate [53]

Scheme 10 Synthesis of bis-MCT/DSBES dyes [53]

Structure 8 Heterobifunctional bis-MCT/disulphidebisethylsulphone dye [54]

Structure 9 Procion Blue HE-G (CI Reactive Blue 187)

D SO2 CH2-CH2-O-Cell (2)

NO2 O NH2 NO2 O NH2

Scheme 13 Synthesis of a cationic reactive dye for cellulosics [65]

In the above study, cotton fabric was padded with a pad

DYE P OH + H2N C N (HN C NH)

DYE P O P DYE + H2N C NH2

Cell O P DYE + DYE P OH

where DYE = sulphonated chromophore

Scheme 16 Fixation of phosphonate dyes on cotton cellulose

(2) 100 °C/60 min

(1) H2N CH CH2

HOOC CH2 HOOC CH2

Scheme 18 The synthesis of a bis-aspartyl-s-triazine dye [75]

composition of these new crosslinking amino acids vary

cystine dehydroalanine perthiocysteine

Scheme 20 Elimination reactions of wool cysteine and wool cystine

Scheme 21 The formation of lysino-alanine and lanthionine crosslinks

reactive dye–cysteinyl residue covalent bond. Thioether D-NH-CO-C(Br)=CH2 + 2 WOOL-SH

Cl Deepali et al. [108] studied the effect of dyeing temper-

NH O2S D (H3C)3N S S N(CH3)3

Reactive centre capable of

Scheme 30 DCPEAT-activated cotton

containing nucleophilic centres; surprisingly, hydrolysed

100 (ICI). Thus, wool could be dyed, from long-liquor baths

with the above crosslinking agent. Very high exhaustion