DepartmentofTextileEngineering

Assignmenton:studyonreactivedyes
CourseCode:TEX3021
CourseTitle:wetprocessingtechnology2
SubmittedTo:

Md.SahidulIslam
Lecturer
DepartmentofTextile,SEU
B.Sc.inTextileTech.(DU)

SubmittedBy:

Name:TahmidurRahman

ID:2012200400014

Batch:21st

Section:A
SubmissionDate:22/04/15

History of reactive dyes

From the year 1856, following Perkin's discovery of the first synthetic dye,
Paralleled that of the dye manufacturing industry in particular, and the chemical industry in
general. It was explosive! Perkin has even been referred to as "the father of chemical
engineering."
By contrast, polymer and fiber chemistries were late bloomers. Viscose rayon fibers appeared
ca. 1910 and secondary cellulose acetate fibers ca. 1920. Although both eventually achieved
a significant market penetration, neither could ever be called a dominant fiber. The emergence of
viscose rayon affected dye manufacturers very little. On the other hand, the arrival of secondary
cellulose acetate created waves, and was followed within two or three years by the forerunners
of the disperse dyes used today.
Introduction of reactive dyes such as Procyon Yellow R, Brilliant Red 2B and Blue 3G by ICI in
1956 made its entry into the synthetic dyestuff market in a big way. These dyes chemically
reacted with the fibers with the formation of covalent bond between the dye and the fiber and
therefore their name REACTIVE Dye

The General Nature of Reactive Dyes

At this stage,a number of questions may spring to mind. For example: what is special about
covalent bonds? What are these reactive dyes? Why did it take so long to discover them? Are
they important? Why are they important? Do they match up to the original expectations? These
and other such questions will all be addressed, directly and indirectly, in the following sections.
In all dyeing processes dissolved (single) organic molecules or ions (dyes, dye derivatives or
precursors) are first adsorbed at the surfaces of the fibers (substrates) and then diffuse into them
until they are more or less uniformly distributed throughout. However, once the dyeing process
is over, it is necessary that the colors now within the fibers have some degree of resistance
to removal by solvents, such as the water which carried the soluble dyes, dye derivatives or
precursors out of the dye bath onto and into the fibers in the first place. This requirement may be
called wet fastness, and dyes for cellulosic fibers can have a wide range of wet fastness
properties. Reactive dyes have generally high wet fastness.

Properties of reactive dye:

1. Reactive dyes are anionic dyes, which are used for dyeing cellulose, protein and
polyamide fibres.
2. Reactive dyes are found in power, liquid and print paste form.
3. During dyeing the reactive group of this dye forms covalent bond with fibre polymer and
becomes an integral parts of the fibre.
4. Reactive dyes are soluble in water.
5. They have very good light fastness with rating about 6. The dyes have very stable
electron arrangement and can protect the degrading effect of ultra-violet ray.
6. Textile materials dyed with reactive dyes have very good wash fastness with rating
Reactive dye gives brighter shades and has moderate rubbing fastness.
7. Dyeing method of reactive dyes is easy. It requires less time and low temperature for
dyeing.
8. Reactive dyes are comparatively cheap
9. Reactive dyes have good perspiration fastness with rating 4-5.
10. Reactive dyes have good perspiration fastness.

Trade names:
Trade name

Manufacturer

Country

Procion

I.C.I

U.K

Ciba cron

Ciba

Switzerland

Remazol

Hoechst

Germany

Levafix

Bayer

Germany

Reactone

Geigy

Switzerland

Primazin

BASF

Germany

Drimarine

Sandoz

Switzerland

High Wet fastness

Achieving high wet fastness is intrinsically more difficult on the cellulosic fibers because of their
extreme hydrophobicity. They love water, and offer little protection against water removal to any
soluble chemical species which has diffused inside them. This contrasts with hydrophobic fibers
such as polyester. Polyester fibers offer water little opportunity to enter until the temperature is
almost up to the atmospheric boil.
Dyers and dye chemists have known for a long time that there are only three ways in which dyes
can be retained by fibers, and the first two have been used from time immemorial.

The three methods are:

Physical sorption: This relies on the same forces which attracted the dyes to the fibers initially
being strong enough to hold onto the dyes through subsequent wet treatments-e.g., with direct
dyeings on cellulosic fibers-but also acid, basic and disperse dyeings on other fibers. The wet
fastness of direct dyes on cellulose is distinctly limited.
Mechanical retention: This relies on the formation of insoluble, pigmentary materials out of
the soluble chemicals which first diffused into the fibers; e.g., with vat and sulfur dyeing, those

of azoic combinations, and also dyeing of mordant and ingrain dyes. None of these offers either a
full color range or a very simple application procedure.
Fiber reaction: Here the dye molecules or ions do not lose all their solubilizing groups after
diffusion into the fibers, but in the correct conditions they react and attach themselves by
covalent chemical bonds to the much larger fiber molecules, to form new colored derivatives of
the fibers. The small number of dye solubilizing groups is totally inadequate to cause the large
new dye-fiber molecules to dissolve in water.

Chemical Bonds
Attraction between atoms (bonding), to give molecules or ions, and between the same or
different molecules or ions to yield different interaction or reaction products, depends on the
movement and distribution of electrical charges, the energy require ments of the process and
the stability of the products. The electrical charges represent the probability of finding larger or
smaller localized excesses (-) or deficiencies (+) in the distribution of electrons around
particular atoms. Covalent Bonds:
There are two possible extreme cases when considering bonds between atoms. At one extreme
lies the covalent bond; e.g., the carbon-hydrogen bonds of most organic chemicals, C-H. In this
case, both atoms donate an electron to the bond and the resulting pair of electrons is shared
between them. Such bonds share a large amount of energy and it requires even more energy to
tear them apart again. Bonds between reactive dyes and cellulose are of this type.

Ionic bond
At the other extreme from the covalent bond lies the ionic bond. In the simplest case, two
adjacent atoms may both have an available electron to contribute to a bond, but one atom is
able to gain stability by taking them both for itself, thereby gaining an extra electron (negative
charge). This will leave the other atom minus one electron (positive charge), which makes it
more stable as well. Such is the case with common salt, sodium chloride, which does not exist
as covalently bonded molecules, Na-Cl, but as positively charged sodium ions and
negatively charged chloride ions, Na+c1-. These oppositely charged ions are attracted to
one another electrostatically but can exist independently since nothing is shared (like the
opposite poles of two different mag nets). Such electrostatic attractions are involved in
dyeing with acid and basic dyes (see the appropriate chapter) where fiber molecules can carry
charges opposite to those of the dye ions being applied, and because of this, attract them.

Polarization and Reactivity:

It is to be expected that the fairness with which electrons are shared should vary continuously
between the sharing of the idealized covalent bond and the "winner takes all" of the ionic bond.
Some of the other atoms in covalently bonded organic carbon com pounds will always want
more than a fair share of the available electrons-e.g., nitrogen, oxygen, fluorine, chlorine and
sulfur-whereby they themselves tend to acquire an electronegative character, and their carbon
neighbors, an electropositive character. This tendency does not normally lead to ion formation.
It is called polarization, and makes individual atoms within a molecule more susceptible to
electrostatic interaction with atoms of the opposite characteristic whenever they are in close
proximity. Many reactions between different covalently bonded materials are initiated by
polarization, and may be completed by formation of products with quite different bonding
(electron distribution) than the original reactants. The actual outcome of reactions often depends
on complex energy considerations.

Dye-Fiber Reaction:
Reactive dyes are those whose ions or molecules contain groups which are reactive with other
groups present in fibers to form covalent dye-fiber bonds. It has been known for many years that
wool contains mercator, amino and hydroxyl groups,
-SH, -NH2 and-OH, respectively,
listed in decreasing order of reactivity, and that cellulosic fibers contain considerable numbers
of the latter. It takes two to tango. It is not enough to have a reactive dye molecule. One must
also have a reactive group in the fiber. As early as 1885, Cross & Bevan made yellow and red
esters of cellulose by a six-step synthesis. In these products, the dye was covalently bonded to
the cellulose and the fastness to washing was excellent; but the reaction conditions were too
severe and lengthy to be practical and the fibers were badly degraded.
So, in 1885, the principle was clearly established that chemical, covalent bonding between dye
and cellulose could result in dyeing with outstanding wet fastness. But the belief was also
reinforced that the hydroxyl group of cellulose was of very low reactivity and that reactive

dyeing might require to be driven by severe reaction conditions. Whether the reasons were
conscious or Unconscious, for the next 70 years the reaction to form covalent bonds between the
more reactive and amino groups in wool and reactive dye species received more attention than
that between cellulose hydroxy groups and reactive dyes. The emphasis was placed on reactive
dyes for wool despite the fact that improving the already good wet fastness of the dyeing which
could be achieved on wool was not a technologically important objective at that time.
Because the first commercial fiber reactive dyes appeared so much more recently than most other
important dye application categories, it is worthwhile to point out how complete the scientific
and technological documentation is. Not only that, but many of those who worked with reactive
dyes since their commercial inception are alive and kicking today, including several of the
authors whose work is cited in the references. Even the author of this chapter was an
undergraduate intern in the cotton dyeing laboratories of ICI during the summer of 1956.

Properties of Reactive Dyeing

These are almost all that the early researchers could have wished for. They have a full
range of bright shades across the spectrum, good to excellent wet fastness with minimal color
loss and excellent ratings for the staining of adjacent white goods, with moderate to good
lightfastness. They offer all of these advantages, along with great versatility in choice of
application methods.
On the other hand, they have moderate tending to poor fastness to chlorine, relatively long batch
processing times and high dye and chemical cost. The utilization of color used to be relatively
poor, and the waste color going to drain can be easily 30 to 40%, but this deficiency is
undergoing serious recent
Improvements (see later) to perhaps I 0% or less in the future. The salt content of the effluent has
also been very high, but is rapidly falling with the use of lower liquor ratios in dyeing.

Reactive dyes quality requirements

Should be powder or liquid dyes
Should have excellent stability
Should have good solubility
Low to medium substantively
Good compatibility
Good diffusion and levelling properties
Rapid fixation
High degree of fixation
Excellent washing fastness

Application of Reactive dyestuff

Application of this dyestuff was due to the following facts:
Physical adsorption of the water soluble dyestuffs from an aqueous medium by the fibre by
reversible attachment to active sites present in the fibre
Mechanical retention of the water insoluble dyes in the fibre by application involving temporary
solubilization before applying
Dissolution of the dyestuff in the fibre

Reactivity and affinity of this dye

Reactivity of the dye is related to facts if the reactivity of the dye is increased considerably, the
rate of reaction with the fibre increases, dyeing rate is fast
However, if the rate of hydrolysis of the dye increases, it leads to deactivation of a part of the
dye, resulting in wastage of the dye
If the reactivity of the dye is decreased, the extent of hydrolysis can be reduced considerably,
but this would result in slow rate of reaction with the fibre
However the ultimate objective of dyeing is to react as much o9f the dye as possible with the
fibre and minimise the hydrolysis of the dye.

How it happens
This is achieved in practice in two stages
1. dying should be started in neutral medium when the dye does not react either with the fibre of
with water
2. Glaubers salt or common salt should be added to exhaust the dye onto the fibre as much is
possible
3.Then finally the fixing of the dye is done by the addition of the alkali( soda ash) as the dye is
already exhausted into the fibre, will not be available for reacting with water
4.It is already known that the hydrolysed dye cannot further react with the fibre, but due to
affinity forces, it is absorbed by the fibre and retained in it.

Stripping
During the subsequent washing or soaping the substantial hydrolysed dye gets stripped into the
washing bath thus reducing the wash fastness of the dyed fibre.
If the affinity of the original dye is reduced to a very low value, this problem can be avoided,
however if the affinity is too low, exhaustion of the dye prior to fixation cannot be achieved
substantially.
If the dye affinity is high, then it is very difficult to remove the hydrolysed dye since it is
absorbed and retained in the fibre by fairly strong affinity forces.Thus in actual practice low
affinity dyes are selected
Process applied for dyeing

Dyeing can be carried out by

1. Batch dyeing processes
2. Continuous dyeing process

Batch dyeing processes keeping in mind the following points:

a) The pH of the dye bath
b) The temperature of the dyeing
c) The concentration of the electrolyte
d)The time of dyeing
e) The liquor ratio

Continuous dyeing processes

Reaction of dye with the fibre in the presence of water and alkali in a short time at elevated
temperatures take place
The rate is further increased if the pH is high
This is the basis of continuous dyeing process to be possibly used with reactive dyes
Depending on the reactivity of the dye two processes are possiblesingle padding and double
padding

Single padding
In single padding the pad liquor contains the dye and the alkali, which does not hydrolyse the
dye at room temperature
For example cold brand reactive dyes sodium bicarbonate is the preferred alkali, which on
heating produces strong alkali sodium carbonate
Hot brand reactive dyes sodium carbonate is added to the pad liquor for pad bicarbonate in dry
process
Pad (alkali) dry steam process with bicarbonate or carbonate
Dye solubility in presence of Alkali
Good solubility of the reactive dyes helps in preparation of highly stable and solvent free
solutions of the dyestuff
High solubility at room temperature
No risk of dye being degraded

Easy dyebath preparation

Double padding
In this process the fabric is padded with the dye solution and repadded ( with or without
intermediate drying) with an alkali solution containing a high concentration of salt to minimise
bleeding of the dye from the cloth into alkali bath and then it is steamed
The wastage of the residual liquor at the end of padding is low

Fiber reactive dyes

Fiber reactive dyes are indisputably the best choice for dyeing any cellulose fiber including
cotton, rayon, hemp and flax. They're simpler to use, more fade resistant and generally safer than
direct dyes, vat dyes, napthol dyes and all purpose dyes
Fiber Reactive dyes can also produce exceptional results on silk (when used properly) without
the drawbacks of other dyes traditionally used on silk including acid dyes, natural dyes and vat
dyes.
Fiber reactive dyes offer superior ease of use and vivid, permanent colors yet they still clean up
easily with water. All while being nontoxic, safe for home use and actually fun to work with.

How much reactive dyes are fixed

Mono reactive dye Dye fixation is 75% and dye hydrolysis is 25 %
CIBACRON DYES Pad batch 9099%
Pad dry pad steam 8595%
Pad thermofix 8292%
Pad humidity fix 8292%
Pad steam 7090%

How important is affinity factor

If the reactive dye chosen has low /medium affinity, it will show the following:

1. Good penetration and levelling

2. Excellent wash off and wet fastness properties

3. Low risk of tailing

Pad batch dyeing

Merits
Modest investment layout
Suitable for small and fairly large batches
Very simple working conditions, Limited manpower required
Low energy consumption
Lower water consumption than exhaust dyeing
Good penetration and level dyeing, Good reproducibility
Suitable for dyeing knit goods

Demerits
Batch process
Higher dye consumption than paddrypadsteam

Moderate coverage of dead and immature cotton

Continuous method (Pad steam)

Continuous method mainly used for dyeing fabrics with high liquor retention, such corduroy,
because no intermediated drying is required

Merits
No migration problems
Reduced energy costs
Good appearance of the dyedfabrics
No detrimental influence onfastness

Demerits
Higher amounts of dye are required to produce deep shades compared to the padbatch or pad
drypadsteam processes

Worthwhile for dyeing deep shades when the higher dye costs are at least balanced by savings
in energy and gains in productivity

Pad dry- pad steam process

Merits
Economical process for large production runs
Still economical for fairly small runs (>5000m) on modern equipment
High colour yield
Very good appearance of the dyed fabric
Good reproducibility
No detrimental influence on light and/or chlorine fastness

Demerits
Shade changes are time consuming
Less suitable for dyeing fabrics prone to migration problems or difficult to dry(pile fabrics)

Pad Thermofix process

Merits
Good colour yield on fabric and coverage of dead fabric
Very good lab to bulk reproducibility
Good batch to batch reproducibility
Moderate soiling of machinery
No need for a chemical pad liquor

Demerits
Not recommended for dyeing regenerated cellulose
Possible specky appearance of the dyed fabric
A negative influence on the fabric handle is possible
Danger of yellowing of the substrate
Lower light / chlorine fastness level
The process requires urea

Cotton dyeing with Reactive dyes

Cotton fabric after pretreatments e.g desizing, scouring & bleaching can be dyed using
the following recipe:

Reactive DyesX%
Sequestering agent0.5 G/L
Wetting agent0.10.5 G/L
Antcreasing agent0.52.0G/L
Salt1080 G/L
Soda220G/L
Temperature 6080
Degree Dyeing time 60 minute.

When the cotton fabric dyeing is complete, the dye liquor is drainoff. The fabric is washed with
hot water at 40 degree c & then with cold water. Again wash the dyed fabric with 13 G/L soap
or detergent at 60 degree 80 degree c for at least 10 minutes. Then drain off the washing
liquor. Again wash the dyed fabric with hot water & then with cold water.
Finally, the dyed fabrics is taken out from the machine, hydroextuct the fabric and dry the fabric
passing through any other drying machine