Chapter 5: Reactive Dyes and Their Application

By J. R. ASPLAND, School of Textiles, Clemson University, Clemson, S.C.

F rom the year 1856,following Perkin’s

discovery of the first synthetic dye,
the growth of organic chemical knowledge
savor to dye research and development,
both continued to be directed primarily
towards cotton and, to a lesser extent,
High Wetfastness
Achieving high wetfastness is intrinsically
more difficult on the cellulosic fibers be-
paralleled that of the dye manufacturing wool. It was not until after the second cause of their extreme hydrophilicity.
industry in particular, and the chemical World War, in the early 195Os, that the They love water, and offer little protection
industry in general. It was explosive! rapid growth of nylon and polyester began against water removal to any soluble
Perkin has even been referred to as “the in earnest, and it was decades later before chemical species which has diffused inside
father of chemical engineering.” anyone thought it possible that King Cot- them. This contrasts with hydrophobic
By contrast, polymer and fiber chemis- ton might one day be dethroned. fibers such as polyester. Polyester fibers
tries were late bloomers. Viscose rayon Duringthefirst 50yearsfollowing 1856, offer water little opportunity to enter until
fibers appeared ca. 1910 and secondary dye research and development had already the temperature is almost up to the atmo-
cellulose acetate fibers ca. 1920. Although discovered members of all but one of the spheric boil (see a later chapter on disperse
both eventually achieved a significant important cellulosic dye application cate- dyes).
market penetration, neither could ever be gories known today. After 49 more years Dyers and dye chemists have known for
called a dominant fiber. The emergence of the numbers of dyes for cellulose had been a long time that there are only three ways
viscose rayon affected dye manufacturers extended, performance had been im- in which dyes can be retained by fibers, and
very little. On theother hand, thearrival of proved, manufacturing and application the first two have been used from time
secondary cellulose acetate created waves, refinements had been put into practice, but immemorial. The three methods are:
and was followed within two or three years no important new dye application cate- 0 Physical sorption: This relies on the
by the forerunners of the disperse dyes gory for cellulose had appeared. same forces which attracted the dyes to the
used today. Although this added a little Thus it was with justifiable pride that fibers initially being strong enough to hold
IC1 introduced, in 1956, the first dyes for onto the dyes through subsequent wet
cellulosics which would actually react treatments-e.g, with direct dyeings on
with the fiber molecules, to form covalent cellulosic fibers-but also acid, basic and
dye-fiber bonds. The introduction of this disperse dyeings on other fibers. The wet-
new dye application category coincided fastness of direct dyes on cellulose is
with the centennial of Perkin’s discovery distinctly limited.
of mauveine. 0 Mechanical retention: This relies on
ABSTRACT the formation of insoluble, pigmentary
The General Nature of Reactive Dyes materials out of the soluble chemicals
This first part of Chapter 5 covers the
background to the development of At this stage, a number of questions may which first diffused into the fibers; e.g.,
reactive dyes, explains the history which spring to mind. For example: what is with vat and sulfur dyeings, those of azoic
led to their belated discovery and gives special about covalent bonds? What are combinations, and also dyeings of mor-
the reasons for their present these reactive dyes? Why did it take so dant and ingrain dyes. Noneof theseoffers
importance. The nature of the dye-fiber long to discover them? Are they impor- either a full color range or a very simple
bond is covered as well as the processes tant? Why are they important? Do they application procedure.
by which it is formed. The overall 0 Fiber reaction: Here the dye mole-
procedure for reactive batch dyeing,
match up to the original expectations?
which involves the three steps of dyeing, These and other such questions will all be cules or ions do not lose all their solubiliz-
fixation and washingoff, is discussed in addressed, directly and indirectly, in the ing groups after diffusion into the fibers,
terms of the chemical and physical following sections. but in the correct conditions they react and
interactions involved. Some of the In all dyeing processes dissolved (sin- attach themselves by covalent chemical
potential problems are indicated, as are gle) organic molecules or ions (dyes, dye bonds to the much larger fiber molecules,
possible means by which they might be derivatives or precursors) are first ad- to form new colored derivatives of the
overcome. sorbed at the surfaces of the fibers (sub- fibers. The small number of dye solubiliz-
strates) and then diffuse into them until ing groups is totally inadequate to cause
they are more or less uniformlydistributed the large new dye-fiber molecules to dis-
KEY TERMS throughout. However, once the dyeing solve in water.
Batch Dyeing process is over, it is necessary that the
colors now within the fibers have some Chemical Bonds
Covalent Bonds
Dye-Fiber Bonds degree of resistance to removal by soi- Attraction between atoms (bonding), to
Dye Hydrolysis vents, such as the water which carried the give molecules or ions, and between the
Exhaustion soluble dyes, dye derivatives or precursors same or different molecules or ions to yield
Fixation out of the dyebath onto and into the fibers different interaction or reaction products,
N ucleophilic,Reactions in the first place. This requirement may be depends on the movement anddistribution
Reactive Dyes of electrical charges, the energy require-
called wetfastness, and dyes for cellulosic
Washingoff
Wetfastness fibers can have a wide range of wetfastness ments of the process and the stabilityof the
properties. Reactive dyes have generally products. The electrical charges represent
high wetfastness. the probability of finding larger or smaller

May 1992 033 31

Reactive Dyes polarization, and makes individual atoms references. Even the author of this chapter
within a molecule more susceptible to was an undergraduate intern in the cotton
electrostatic interaction with atoms of the dyeing laboratories of IC1 during the
opposite characteristic whenever they are summer of 1956.
in close proximity. Many reactions be-
tween different covalently bonded materi- Properties of Reactive Dyeings
als are initiated by polarization, and may These are almost all that the early re-
be completed by formation of products searchers could have wished for. They
with quite different bonding (electron have a full range of bright shades across
distribution) than the original reactants. the spectrum, good to excellent wetfast-
localized excesses (-) or deficiencies (+) The actual outcome of reactions often ness with minimal color loss and excellent
in the distribution of electrons around depends on complex energy consider- ratings for the staining of adjacent white
particular atoms. ations. goods, with moderate to good lightfast-
For the chemist, the different types of ness. They offer all of these advantages,
bonds involved in dyeing processes can be Dye-Fiber Reaction: Historical along with great versatility in choice of
discussed in chemical terms (1). Here the Reactive dyes are those whose ions or application methods.
treatment will be simple and descriptive molecules contain groups which are reac- On the other hand, they have moderate
only. tive with other groups present in fibers to tending to poor fastness to chlorine ( 2 , 4 ) ,
Covalent Bonds: There are two possi- form covalent dye-fiber bonds. It has been relatively long batch processing times and
ble extreme cases when considering bonds known for many years that wool contains high dye and chemical cost. The utiliza-
between atoms. At one extreme lies the mercapto, amino and hydroxy groups, tion of color used to be relatively poor, and
covalent bond; e.g., the carbon-hydrogen -SH, -NH2 and -OH, respectively, listed in the waste color going to drain can be easily
bonds of most organic chemicals, 3 C - H . decreasing order of reactivity, and that 30 to 40%, but this deficiency is undergo-
In this case, both atoms donate an electron cellulosic fibers contain considerable num- ing serious recent improvements (see
to the bond and the resulting pair of bers of the latter. It takes two to tango. It is later) to perhaps 10% or less in the future.
electrons is shared between them. Such not enough to have a reactive dye mole- The salt content of the effluent has also
bonds share a large amount of energy and cule. One must also have a reactive group been very high, but is rapidly falling with
it requires even more energy to tear them in the fiber. the use of lower liquor ratios in dyeing.
apart again. Bonds between reactive dyes As early as 1885, Cross & Bevan made
and cellulose are of this type. yellow and red esters of cellulose by a Importance of Reactive Dyes
Ionic Bonds: A t the other extreme six-step synthesis. In these products, the In 1956, the discovery of reactive dyes was
from the covalent bond lies the ionic bond. dye was covalently bonded to the cellulose considered so important and their poten-
In the simplest case, two adjacent atoms and the fastness to washing was excellent; tial utility was so great that all the major
may both have an available electron to but the reaction conditions were too severe dye manufacturers jumped onto the band-
contribute to a bond, but one atom is able and lengthy to be practical and the fibers wagon as fast as the patent situation would
to gain stability by taking them both for were badly degraded (2,3). allow. By the end of 1961, BASF, Bayer
itself, thereby gaining an extra electron So, in 1885, the principle was clearly (now Miles Laboratories in the US.),
(negative charge). This will leave the other established that chemical, covalent bond- Ciba and Geigy (now Ciba-Geigy), Ho-
atom minus one electron (positive charge), ing between dye and cellulose could result echst (now Hoechst Celanese in the US.),
which makes it more stable as well. Such is in dyeings with outstanding wetfastness. Sandoz and Sumitomo had joined IC1 in
the case with common salt, sodium chlo- But the belief was also reinforced that the the marketplace with no less than 12
ride, which does not exist as covalently hydroxy group of cellulose was of very low different ranges of reactive dyes between
bonded molecules, Na-Cl, but as posi- reactivity and that reactive dyeing might them, representing five different types of
tively charged sodium ions and negatively require to be driven by severe reaction reactive groups.
charged chloride ions, NafC1-. These conditions. (Notice the subjectivity of At least eight more ranges of reactive
oppositely charged ions are attracted to “very low” and “severe”: the meaning is in dyes had been introduced by 1988 ( 3 ) ,and
one another electrostatically but can exist the mind.) now, 25 years after their first introduction,
independently since nothing is shared (like Whether the reasons were conscious or the AATCC Buyers Guide ( 5 ) lists almost
the opposite poles of two different mag- unconscious, for the next 70 years the 200 different reactive dyes by Colour
nets). Such electrostatic attractions are reaction to form covalent bonds between Index name, representing more than 400
involved in dyeing with acid and basic dyes the more reactive thiols and amino groups different commercial products.
(see the appropriate chapter) where fiber in wool and reactive dye species received Currently about one-third of the money
molecules can carry charges opposite to more attention than that between cellulose spent on dyes for cellulose in the U.S. is
those of the dye ions being applied, and hydroxy groups and reactive dyes. The spent on reactive dyes;ca. 30% more than
because of this, attract them. emphasis was placed on reactive dyes for for any other class of dyes for any fiber.
Polarization and Reactivity: It is to wool despite the fact that improving the Several factors might account for some of
be expected that the fairness with which already good wetfastness of the dyeings this value dominance, including high con-
electrons are shared should vary continu- which could be achieved on wool was not a sumption of cotton, consumer demand for
ously between the sharing of the idealized technologically important objective at bright colors, high wetfastness and most
covalent bond and the “winner takes all” that time. importantly, the high relative cost per
of the ionic bond. Some of the other atoms Because the first commercial fiber reac- pound of reactive dyes. But whichever way
in covalently bonded organic carbon com- tive dyes appeared so much more recently you slice it, reactive dyes are very impor-
pounds will always want more than a fair than most other important dye application tant.
share of the available electrons-e.g., categories, it is worthwhile to point out
nitrogen, oxygen, fluorine, chlorine and how complete the scientific and technolog- Reactive Dye Sub-Groups
sulfur-whereby they themselves tend to ical documentation is. Not only that, but The following will be restricted to these
acquire an electronegative character, and many of those who worked with reactive reactive dyes which, when applied to
their carbon neighbors, an electropositive dyes since their commercial inception are cellulosic fibers, react under mildly alka-
character. This tendency does not nor- alive and kicking today, including several line conditions to give covalent bonds
mally lead to ion formation. I t is called of the authors whose work is cited in the between dye and fiber. The restriction is

32 03il Vol. 24,No. 5

not severe but does eliminate the obliga- relatively unreactive. There are actually By the same token, it can be shown that the
tion to discuss the few reactive dyes for three for each repeat unit of the polymer concentrations of hydroxide ions within
other fibers and a few more which were chain. Ignoring the fact that one-third of the fiber [OH-]f and in the dyebath
fixed in other ways. This additional infor- these hydroxy groups are primary and [OH-], (where subscript s means in the
mation is not hard to find for those two-thirds are secondary alcohols, it is solution or dyebath) are also responsible
interested (3). convenient to write as a simple representa- for the rate at which the reactivity of the
There is no other class of dyes which has tion of cellulose: Cell-OH. dye for the fiber is lost, due to the nonfiber
been so fragmented into sub-groups. What is generally not appreciated (even reaction of the dye. This undersirable side
These are based not only on the relative by many polymer chemists) is that, in the reaction is called hydrolysis.
reactivity of the different ranges of reac- presence of even dilute alkalis, cellulose The big surprise to chemists was that it
tive dyes but also on the normal subdivi- behaves as a very weak acid and will ionize does not require extreme alkalinity to
sion of dye ranges into groups with similar according to the normal basic dissociation generate cellulosate ions, and that these
dyeing performance (as opposed to chemi- equation: are many times more reactive than cellu-
lose itself.
cal reactivity) under a particular applica-
Cell-OH + OH-= Since both the cellulosate ions and
tion condition.
The differences in reactivity results, for
Cell-0- + HzO Eq. 1 hydroxide ions are negatively charged, it
the most part, from the incorporation of where makes sense that they would be “on the
chemically different reactive groups in the look-out’’ for areas within molecules
dye molecules. Historically, the most eco- [Cell-OH] X [OH-]f which are electron deficient-i.e., posi-
nomical reactive groups were inaccessible i [Cell-0-1 = KB Eq. 2 tively polarized-with which to react.
to many of the different dye manufactur- Eq. 1 is an equilibrium (two-way ar- These include carbon atoms adjacent to
ers, and they needed to supply alternatives rows) in which cellulose plus hydroxide ion nitrogen in the aromatic heterocyclic rings
without running into patent problems. The (alkali) reacts to give cellulosate anions, which make up many reactive groups (see
chemical nature of individual dye mole- Cell-0-, and water. later). Such negataively charged species
cules also plays a role in determining are called nucleophiles; hydroxide and
Eq. 2 indicates that in such a reaction
reactivity, but it is not a dominant one. cellulosate ions are nucleophilic reagents.
the fraction (cellulose concentration X al-
The number and ranges of reactivity of kali concentration in the fiber + cellulo-
these sub-groups are the reasons this General Dye Features
sate ion concentration), in an excess of
chapter will not attempt to provide much Reactive dyes have been represented as
water, is a constant, Ks, known as the basic
specific information on the type and con- dissociation constant of cellulose. having as many as five different interlock-
centrations of alkali and salt, or the ing features which may be assigned differ-
In work touched on later in this chapter,
preferred application temperatures for ent letters according to the native lan-
Sumner (7) has been able to calculate
individual reactive dye sub-groups. They guage or the personal preference of the
the concentrations of cellulosate anions
are also the reasons dyehouses generally assignor. The features are: the basic part
[Cell-0-1 and hydroxide ions [OH-jf
stick to one supplier, and why it would be of the color molecule (C); solubilizing
within cellulosic fibers (the squared brack-
foolhardy to mix reactive dyes from differ- groups (S); bridging groups linking the
ets indicate concentration, subscript f
ent suppliers unless their compatibility reactive part of the molecule to the soluble
indicates in the fiber and the cellulosate
had been clearly demonstrated under the color portion (B); reactive groups (R) and
ion could be nowhere else) for any given
intended conditions of use and, only then, leaving groups (X). This means reactive
concentration of chloride ion (from com-
if the reactive groups were known to be the dyes may be written: S-C-B-R-X. It can be
mon salt) and hydroxide ion (from alkali)
same. However, since many of the early useful to split up the chemical entities
which might be added to the dyebath.
patents have expired, it is now possible to primarily responsible for fiber reaction (B,
Sumner’s work, using the Donnan
track down comparable competitive dyes. R, X) in this way when it is necessary to
model of the fiber (see later), made it
The question is always whether any small emphasize how they individually affect the
possible to confirm that the chemical
resultant savings justify the large potential reactivity ( 3 ) .
species which reacts with dyes to give Every group, including the bridging,
risks. dye-fiber bonds is the cellulosate anion,
The ranges of available reactivities can reactive and even the leaving groups, has
Cell-0-, because the rates of reaction are
be illustrated graphically ( 3 ) ,but in prac- an effect on the physical properties of the
related to the cellulosate ion concentration total dye molecule. These include color,
tical terms it is better illustrated by the and not to the concentration of cellulose.
results of a batch dyeing study, using molecular size, ability to diffuse into fi-
model compounds with the same dye bers, solubility, substantivity, salt sensitiv-
molecule substituted by different reactive ity, lightfastness, and so on.
groups ( 2 ) . The results indicate that very However, for general purposes, the au-
reactive dyes (with dichlorotriazinyl thor prefers to think of reactive dyes in
groups, see later) may be dyed at 30C simpler terms: as water soluble dye mole-
(85F) with amounts of salt and alkali cules with functional substituents; the
(sodium carbonate) from 25 to 55 and 2 to function being to react with cellulosate
15 grams per liter respectively, depending ions. For simplicity and convenience in
on the liquor ratio and depth of shade. talking about their dyeing reactions, let us
Corresponding figures for dyes of lowest identify reactive dye molecules as Dye-X,
reactivity were 85C (185F), 30 to 100 where the word Dye includes all the
grams per liter salt and 30 to 50 grams per physical, structural components of a water
liter sodium carbonate, although a smaller soluble cellulose reactive dye, except the
amount of a stronger alkali would almost leaving group X. It will be necessary to
certainly be substituted in practice. deal with the bridging, reactive and leav-
ing groups for the purpose of structure
Reactive Groups in Cellulose recognition in Chapter 5, Part 2.
Chapter 1 (6) showed that the cellulose All fiber reactivedyes react with nucleo-
polymer is abundantly supplied with hy- philic reagents, and the overall reactions,
droxy groups, -OH, which are themselves regardless of their mechanisms, can be

May1992 CCO 33
Reactive Dyes However, the next three short sections
Table 1. Solution and Fiber Phases
of Reactive Dyes
I may be of little interest to dyers.
The Donnan Model:
A Research Tool
Solution (3) Fiber (f)
In science, all sorts of model systems are
CI- or SOT CI- or SO4
X-=
used. They do not need to be completely
OH- realistic, although it helps; however, they
represented by the formula below, where Dye-X Dye-Xb need to be useful! The Donnan model of
Dye-OH Dye-OHb fibers is linked with the name of a pioneer
Nu- is any nucleophilic anion, and X is the Na+ Na+c in the area of semi-permeable membranes,
leaving group.
Dye-X + Nu- - Dye-Nu + X-
Eq.3
-
Cell-OH
Cell-0-
Notes:FH-+ the dye leaving groups,
Cell-O-Dyeb
may also be
and it can be used to examine how the
mobile and immobile, reactive and inert,
ionic species will equilibrate in dyebath-
Yes, the reactions are more complicated CI- or SO;.bDyes contain anionic SOggroups, so fiber systems. It is particularly useful for
than this, but the equation represents the these species are anionic. Dye-X is short lived. studying the behavior of alkalis, salts and
CSodiumions from all sources; dyes, salts and al- anionic dyes in cellulose-dyebath systems
beginning and ending state of affairs quite kali.
reliably. Chemists should refer to
so that the concentration of the different
Zollinger ( 3 )for more complete details. ions in the fiber may be calculated from
hydrolysis reaction, by which reactive experimental measurements on the solu-
Batch Dyeing Mechanism
dyes are wasted, to form by-products tions.
which will no longer react with the fiber. The model has been based on a number
Now that the general introduction to the This reaction takes place both in the fiber
unique, reactive dye application category of assumptions, and it has been used along
and in the solution (dyebath) with the with a number of constants some of which
has been made, the actual batch dyeing same rate constant of hydrolysis, kH, but
mechanisms can be discussed. The nature might be labeled empirical. However, they
at different rates, because the concentra- all have a realistic basis, which means that
of the processes involved, both chemical tions of the reactants are different in the
and physical, will be related to the three their use leads to conclusions which make
two locations: good scientific and practical sense. The
steps of conventional reactive batch dye-
ing (exhaustion, fixation and washing- In-Fiber Hydrolysis Rate = assumptions are given below, as are the
off), and the possibility of future technol- [Dye-X]f X [OH-If X kH Eq. 8 nature of the constants used to study
ogy refinements will be explored. cellulose. Their values are given else-
In-Dyebath Hydrolysis Rate = where (7).
Chemical Processes [Dye-XI, X [OH-], X kH Eq. 9
Donnan Assumptions
The chemical equations which follow are The total rate of reaction of the dye, or the
absolutely essential for understanding re- rate at which the dye loses its reactivity, is The following are Donnan assumptions:
active dyeing: given by the sum of the three rates given in Cellulose in (textile) wet processes
can behave as if the external dyebath or
Cell-OH + OH- Cell-0- + H20 Eqs. 7 through 9. Clearly this is larger than
just the rate of fixation (see upcoming solution phase and the internal or fiber
Eq. 4 phase are both aqueous liquids, separated
section, Dyeing, Step 2: Fixation).
by a membrane through which ions but not
Cell-0- + DyeX k_RDye-O-Cell + X- Total Rate of Reaction = cellulose (fiber) derivatives may pass; i.e.,
Eq. 5
Fixation Rate (Eq. 7) + as if the properties of diffusible ions within
In-Fiber Hydrolysis Rate (Eq. 8) + the fibers a t equilibrium can be confined to
In-Dyebath Hydrolysis Rate (Eq. 9) a special reservoir of water intimately
OH- + DyeX k_trDye-OH + X- Eq. I O associated with those outer and inner fiber
Eq. 6 surfaces accessible to water.
Physical Processes 0 Electrical neutrality is achieved in
Compare Eqs. 4,5, and 6 to Eqs. 1 and 3. Exhaust dyeing reactive dyes on cellulose both the external (dyebath) and internal
The reaction represented by Eq. 4 is a involves inorganic and dye ions in two (fiber) phases. This means there are equal
reversible equilibrium reaction between phases, liquid and solid, dyebath and fiber. numbers of positive and negative ionic
cellulose and alkali, to generate the fiber Chemical reactions can take place in the charges in each individual phase. But the
nucleophile with which the dye can react, bath or in the fiber, but the physical two phases may have different numbers of
Cell-0-. This equilibrium is established processes often involve those ions which ions.
almost immediately when the alkali is can move reversibly from dyebath to fiber 0 The conditions of Donnan distribu-
added to the system. and back again. Other ions and molecules, tion of solutes (such as alkali, salt and
The reaction represented by Eq. 5 is the particularly cellulose and cellulose deriva- dyes) across the membrane are applicable.
key to the formation of the covalent tives, are not mobile. The situation can be The most useful condition can be simply
dye-fiber bond and is the reaction, within represented in a simple diagram, Table I, stated. A t equilibrium, the product of the
the fiber, of the dye with the fiber nucleo- which indicates solution and fiber phases, concentrations of each of the ions of a
phile, Cell-0-. This fixation reaction pro- those mobile ions which attempt to equili- solute are equal in both the external and
ceeds a t a rate determined by the product brate between dyebath and fiber (double internal phases. The only caution needed
of the concentrations of the reactants and arrows) and the immobile species. here is that solutes producing more than
their intrinsic reactivity, expressed by the I t is no easy matter to scientifically two ions, even if two or more are the same,
rate constant k R . Squared brackets indi- study all these ion movements and equilib- must be treated as if each ion were
cate concentrations; subscripts f and s ria while studying chemical reaction rates different. For example, sodium sulfate,
mean fiber and solution respectively: as well. The next sections outline a method Na2S04, ionizes to give three ions, two
which is very helpful in such an attempt. sodium ions and one sulfate. The product
Fixation Rate = of the concentrations of these three ions is:
The same general approach has proved
[Dye-X]f X [Cell-0-1 X kR Eq. 7 [Na'] X [Na'] X [SOT] or [Na+12
useful for studying the acid dyeing of
The reaction represented by Eq. 6 is the nylon and the basic dyeing of acrylics (7). X [SO%].The same considerations apply

34 Vol. 24, No. 5

4

to the sodium salts of anionic dyes which Reaction proceeds until no further in- equivalent curve for Dye 11, E 11, indicates
can have four or more sodium ions. crease of color depth takes place on the that the original reactive dye, Dye-X, has
fiber, a t which time there is essentially no very little substantivity under the given
Cellulose Constants free reactive dye left. At the end of this conditions and has achieved its full ex-
For cellulosic fibers (7) these include the stage, Step 2, there might be a total of haustion of about 10%before the addition
ionic product for water Kw; either the anywhere from 75-90% of the color, either of alkali.
acidic dissociation constant for cellulose, exhaustedor fixed, on the fiber; i.e., thereis After the addition of alkali, two new dye
KA,or the basic dissociation constant, KB, 10-25% of hydrolyzed color left in the species begin to form. Curves FI and FII
where KB = KA + Kw;the availability of bath. Of the color on the fiber, 15-25% is represent the increase from zero of-the
Cell-OH (actually glucose residues) for not fixed (reacted with the fiber) but is held covalently bound dyes I and I1 respec-
provision of internal surfaces (41% for by substantivity; Le., only 50-75% of the tively; Dye-0-Cell. The continuation of
cotton, 74% for viscose rayon), which reactive dye added to the bath initially is curves E1 and E11 (beyond the 30 minute
percentages are a function of fiber mor- covalently bonded to the fiber. The re- alkali addition) represent the sum total of
phology, crystallinity and amorphous maining 25-50% of hydrolyzed color will all the colored species associated with the
character; the concentration of Cell-OH probably end up, along with a high concen- fiber. At 30 minutes this color is almost all
residues; the concentration of acidic, car- tration of salt, in thedrain. Dye-X, but Dye-0-Cell and Dye-OH ap-
boxylate groups in cotton and viscose This state of affairs has satisfied no- pear gradually, until a t t = 120 minutes, it
rayon and the volume of the surface phase body, and in many developed countries it is is probably all Dye-0-Cell and Dye-OH.
in liters per kilogram of fiber (for cotton becoming an environmental liability. It is not possible to distinguish from the
and viscose rayon: 0.22 and 0.45). These curves alone what percentages of which
latter values are known as volume terms. Exhaustion and Fixation Graphs species of fiber color E1 and E11 represent.
Steps 1 and 2 can be illustrated graphi- The figures at the right hand side of the
Dyeing cally; e.g., Fig. 1. This shows the changes Fig. 1 indicate:
We are now ready to move on to discuss the in dyebath exhaustion and dye fixation on (i) the percentage of the dyes I and I1
three principle steps of all reactive dyeing: the fiber, with time, in a conventional actuallyfixed: (68%, 66%);
exhaustion, fixation or reaction and wash- dyeing process lasting a nominal two (ii) the percentage of hydrolyzed dyes
ing-off. A section will be devoted to ex- hours, with the alkali addition after 30 dropped with the dyebath: (16%, 25%);
plaining the significance of graphical rep- minutes. The curves represent the behav- (iii) the percentages of hydrolyzed dye
resentations of the process. ior of two commercial dyes from the same exhausted onto the fiber: (16%, 9%);
0 Step 1: Exhaustion: In conventional sub-group, but with no suggestion that +
Together, ii iii indicate the percent-
processes the required amount of dissolved they are suitable for use together. The use ages of wasted color: (32%, 34%).
dye is added to the dyebath at ambient of the word color on they axis obviates the It is apparent that the increased sub-
temperature and circulated through the need to distinguish clearly between Dye-X stantivity of Dye I over that of Dye I1 has
goods. The temperature is gradually and Dye-OH, or reactive and hydrolyzed hardly affected the overall yield of fixed
raised to the recommended dyeing and dye. dye, but has produced 7% (16% minus 9%)
fixation temperature and the required After 30 minutes, just before alkali more of a product on the fiber which is
amount of salt is added in portions, to addition, Dye I, curve EI, is 46% ex- moderately substantive and will have to be
exhaust the bath. hausted, and the majority of the dye at this removed by washing. This is a distinct
This parallels direct dyeing, except in stage will be in its original reactive form, drawback.
one respect: the substantivity of the reac- Dye-X. The shape of the curve seems to But, how does 66% of Dye I1 end up
tive dyes is generally quite low, which indicate that the dye is moderately sub- fixed, when its substantivity is so low
would require the amount of salt to be stantive and could have exhausted to about before the addition of alkali? Certainly the
high, sometimes as high as 200% owg, or, 60% if the alkali had not been added. The added alkali (being an electrolyte, like
a t a 20:l liquor ratio, 100 grams per liter.
The exhaustion might be quite low, re-
gardless; maybe as low as 10%.
In the next few sections we will see why
Key: E1 = Exhaustion of Dye I
E11 = Exhaustion of Dye I1 i
16%
FI = Fixation of Dye I
low exhaustion and high salt concentra- FII = Fixation of Dye I1 E1 1
tions are tolerated. Certainly reactive dyes
could be derivatives of selected direct dye
molecules with high substantivity (al-
though they are not outstandingly bright
in color). Why is this usually not the case? % Color
0 Step 2: Fixation: The required (or on Fiber
recommended) amount of alkali is added
to the goods with good circulation, and
fixation (reaction) proceeds. The hydrox-
ide ion, being a very small ion, enters the
cellulose readily and the equilibrium reac-
tion, Eq. 4, the ionization of cellulose, is 68%
quickly established. This produces a sys-
tem with three possibilities for nucleo-
philic reaction with the dye: two in the
fiber (internal) phase, with the cellulosate
and hydroxide ions, one in the dyebath,
with hydroxide ions. 1 t. mins. (nominal)
The dye is distributed between the
dyebath and the fiber after Step 1, and
reaction proceeds in both phases a t rates
which are given in Eqs. 7 and 8. Fig. 1. Exhaustion and fixation vs. time for two reactive dyes.

Mav 1992 CCO 35

Reactive Dyes to lowered lightfastness and is not prefera- patibility) in mind. In the conditions of
ble to a good washing-off. application they should not only be ad-
sorbed at similar rates and to similar
salt) could drive more dye onto the fiber, Process Improvement extents, but they should also react at
but surely not seven times as much! The What can be done to reduce the amount of similar rates. In general, this means that
answer lies in the diffusion equilibria. Dye hydrolyzed dye and increase the amount of they should come from a set of dyes with
in the bath and dye in the fiber are trying to dye covalently bonded to the fiber? This the same fiber reactive group(s).
establish an equilibrium. But every time a question can be expressed in chemical 0 Once an appropriate dyeing recipe
dye molecule reacts with the fiber, its place terms by examination of Eqs. 7,8 and 9. has been determined, the process variables
has to be taken by a molecule of dye being How can one: (a) increase the ratio of time, temperature, salt, alkali and
transferred out of the bath and into the k R / k H , i.e., make the fixation (reaction) liquor ratio should all be controlled as
fiber, in an attempt to re-establish the rate constant higher relative to the hydrol- carefully as possible to ensure the opti-
equilibrium. Even if equilibrium is never ysis rate constant, Eqs. 7, 8 and 9; (b) mum shade reproducibility and dye fixa-
reached, there is always a driving force to increase the fraction [ Cell-O-If f tion.
attract dye out of solution and into the [OH-],-, also with a view of making the It is safe to say that unless these
fiber as long as dye continues to react. fixation reaction proceed faster relative to conditions are fulfilled, the results will not
Step 3: Washing Off The washing hydrolysis, Eqs. 7 and 8; and (c) reduce the always be up to expectations.
off process is lengthy but unavoidable. To value of [Dye-XI, X [OH-],, Le., reduce The traditional independence of the
achieve the high wetfastness expected the exposure of dye molecules in solution dyer, to be flexible with formulations and
from a fiber reactive dyeing, all the hydro- to hydroxide ions in solution, Eq. 9, by procedures, is seriously challenged by the
lyzed, unfixed dye has to be removed. The reducing either or both? reactive dyes. Many of the tools needed to
more substantive the hydrolyzed dye, the Viewed from these three angles the fine tune the dyeing properties and proce-
more difficult it will be to remove, and it problem looks very difficult. dures for the different groups of reactive
could continue to bleed slowly over time- 0 First, the ratio of kR/kH is a property dyes depend on chemistry, and are in the
c.f. direct dyes-giving unexpectedly poor of individual dye molecules and is out of hands of the dye manufacturers. The
wash- or wetfastness results. the hands of the dyer. market demand for bright colors of high
A batch washing-off sequence might 0 Second, provided the pH is kept wetfastness has put reactive dyes in a
include: acold water wash at 25 to 60C (75 below 1 1, increasing the salt concentration prominent position which seems likely to
to 140F); a hot water wash at approxi- can raise the value of (b) [Cell-O-]~+ be reinforced in the future-so this situa-
mately 60 to 80C (140 to 175F); scouring [OH-]? However, the amount of salt tion is unlikely to go away.
with anionic surfactant at 80 to 90C (175 suggested by the manufacturer is usually There is no virtue in fighting what
to 200F); and all this followed by hot and the optimum for the particular procedure. cannot be changed, so the dyer must learn
then cold water washing. The sequence So there is not much help here either. to accept reactive dyes for what they can
can be critical and manufacturers’ recom- 0 Finally, the traditional batch dyeing do for him, not fight against what they will
mendations should be followed. Some method, of salting of the dye and only then not permit him to do. But first he should
dyes, notably vinyl sulfone derivatives, can adding alkali, should have taken care of carefully select the supplier, or suppliers,
have some of the reactive dye-fiber bonds the hydrolysis of dye in solution, Eq. 9. most likely to be responsive to his present
hydrolyzed if the first process is carried out Certainly the dye in solution could be and future needs.
too hot, with consequent color loss. All reduced to very little before the alkali Many reactive dyes have drawbacks
dye-fiber bonds are capable of being hy- addition if substantive direct dye struc- which will demand the attention of chem-
drolyzed under severe enough conditions tures were used. But the problems of ists. The overall percentage fixation of the
of temperature and at too high or too low wash-off would be a serious drawback. early reactive dyes is low compared with
pH’s. Vinyl sulfone derivatives are more Alternatively, increasing the substantivity that expected from other dye categories.
sensitive on the alkaline side; heterocyclic of existing dyes by increasing the recom- The result is that the effluent is high on
carbon-nitrogen derivatives are more sen- mended salt additions or lowering the both waste (hydrolyzed) dye and salt.
sitive on the acid side. For the structures recommended temperature might be ef- Furthermore, the color yield of many
of those reactive species, see Chapter 5, fective were it not for the adverse possibili- reactive dyes can be quite sensitive to
Part 2. ties. Salt addition may decrease the rate of relatively small changes in the application
Hydrolysis and washing have been dis- dye diffusion and increase the possibility conditions. These problems, lying between
cussed at length (2,3),and the danger of of dye aggregation, even induce precipita- dye manufacture and the dyed goods
too severe washing producing acidic inter- tion, while adding to the effluent problem. market, are waiting to be solved.
nal fiber pH’s and dye hydrolysis is real Lowering the temperature would slow the Research groups of some dye manufac-
(7). The economics of washing have also rate of dyeing. turers are pursuing these problems with
been examined (8). There are some benefits from lowering vigor. m
A good test for whether all the hydro- the liquor ratios, which would increase References
lyzed dye has been removed, or, for the substantivity, although the salt may have
effectiveness of the washing procedure, is to be reduced to avoid aggregation or (1) Giles, C. H., The Theory of Coloration of
the so-called Hot-Wet Press test. A sam- solubility problems. Textiles, Edited by A. Johnson, Society of Dyers and
Colourists, 1989, Chapter 2.
ple of the dyed goods is sandwiched be- Surely lowering the liquor ratio is not (2) Fox, M.R. and H.H. Sumner, The Dyeing of
tween layers of bleached cotton fabric and the only possibility? This question will be CellulosicFibers, Edited by C. Preston, Chapter 4.
heated with a hand iron or a hot head press addressed in the section on Dyestuff Re- (3) Zollinger, H., ref. 1, Chapter 6.
for about 15 seconds. Any loose color in search. (4) Dolby, P. J., Textile Chemist and Colorist,Vol.
12.No.9, September 1980, p74.
water migrates towards the heating sur- ( 5 ) AATCC Buyer’s Guide /or the Textile Wet
faces and is transferred to the white cotton Review Processing Industry, AATCC, published annually as
fabric. A stain generally indicatesunsatis- Some aspects of reactive dyeing should the July issue of Textile Chemist and Colorist.
factory washing-off, although for some be repeatedly emphasized: ( 6 ) Aspland, J. R., Textile Chemist and Colorist,
0 Whenever several dyes are used to- Vol.23,No. 10,October 1991,p14.
heavy shades no process will be adequate. (7) Sumner, H. H.,ref. l,Chapter4.
If the goods are not to be resin finished, gether to match a particular shade they (8) Quebec Section, Canadian Association of Tex-
there may be no alternative other than to should have been selected with similar tile Colourists and Chemists, Textile Chemist and
resort to cationic fixatives. This may lead dyeing and fixation characteristics (com- Colorist, Vol. 23, No. I I , November 199 1, p2 I .