REACTIVE DYE

Reactive dyes were first manufactured by two scientist named Stephen and Ratte in
1955,working at ICI/Zeneca in England..They developed a syes for cotton which under alkaline
condition can react with fibre and become a part of fibre. The fixation of the dyes with fibre by
chemical reaction by formation of covalent bond and so the dye known as reactive dye.

PROPERTIES OF REACTIVE DYE

They are anionic in nature.

They are water soluble.
Molecules of reactive dyes are smaller in size.
They are environmentally friendly.
Cheap in price.
They shows very good fastness properties.
Dyeing process is very easy.
Any shade can be produced.

General Structure of Reactive Dyes:

The general structure of reactive dye is: D-B-G-X.

Chemical structure of reactive dyes
Here,

D= dye part or chromogen (color producing part)

Dyes may be direct, acid, disperse, premetallised dye etc.

B = bridging part.
Bridging part may be –NH- group or –NR- group.

G = reactive group bearing part.

X= reactive group.
SIMPLE REPRESENTATION OF REACTICVE DYE

S C B X

Fig. Simple structure of Reactive dye.

Where, S= Solubilizing group

C= Chromophoric group.

B= Bridging group.

X= Halogen containing reactive group.

Trade Names of Reactive Dye:

Some trade names of this dye are mentioned:

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

Popularity of Reactive Dye:

Reactive are mostly used for dyeing cellulosic fibres. At past cellulosic fibres were dyed with direct and
vat dyes, but after the introduction of reactive dyes there utility has become limited. Reactive dyes are
superior to direct dye in the following aspects:

i) Ability to procedure bright shades of wide range.

ii) High leveling quality.
iii) Good washing fastness.
iv) Good light fastness.
And it is superior to vat dyes in the following aspects:
i) Simple dyeing method therefore one stage dyeing.
ii) Low temperature dyeing (below 1000C)
iii) Lower cost, i.e. cheaper.

Again its dyeing process is fast and gives brighter shades than metallized azo dyes. For the above
reasons reactive dyes are more popular.

Properties of Reactive Dye:

1) Reactive dyes are cationic 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 about 4-5 due to
strong covalent bonds formed between fibre polymer and reactive group of dye.
7) Reactive dye gives brighter shades and has moderate rubbing fastness.
8) Dyeing method of reactive dyes is easy. It requires less time and low temperature for dyeing.
9) Reactive dyes are comparatively cheap
10)Reactive dyes have good perspiration fastness with rating 4-5. Reactive dyes have good perspiration
fastness.
CLASSIFICATION OF REACTIVE DYES

1. According to reactivity:

Three types which are shown bellow with required information-

Reactivity Brand Exhaust Alkali Type Reactive Structure

dyeing Group
Temp.(Co)

High Cold 20o-40o Weak DCT

Medium Medium 40o-60o Mild MFT

Low Hot 60o-80o Strong MCT

2. According to reactive group:

Two types:

Monofunctional Reactive dyes: These dyes contain only one reactive group in their
molecule.
Bi-functional Reactive dyes: These dyes contain more than one reactive group in their
molecule.
Bi-functional Reactive dyes are two types:

Homo functional: Here two reactive group is present and they are similar with
each other.
Example: VS-VS, DCT-DCT.

Hetero functional: Here two reactive group is present and they are dissimilar
with each other.
Example: MCT-MFT,MCT-VS,MFT-VS.

Stages/Steps Involved in Reactive Dyeing

Steps Involved in Reactive Dyeing:

Three basic steps involves in reactive dyeing are as follows:

Exhaustion of the dye from an aqueous bath containing common salt or Gluber’s salt normally under
neutral condition (PH – 7).

Addition of an alkali to promote to further dye uptake and chemical reaction of absorbed dye with the
fiber.

Dyed material is then rinsed and soaped to remove electrolyte, alkali and unfixed dye.

Dissolving the Dyes:

The dyes are in most cases readily water-soluble. They are dissolved either by passing with cold water to
which is then added hot water or by strewing the dye powder into hot water which is stirred at high
speed. Usually a temperature not greater than 80ºC is used for dissolution. In the case of highly reactive
dyes such as Procion MX (ICI) warm (50-60ºC) water is used. Since the dyes are prone to hydrolysis stock
solutions should not be stored for long periods.
Reaction with Cellulosic Fiber:
Reactive dyes formed covalent bond with cellulosic fiber by Nucleophilic substitution and addition
reaction. The reactions are as follows ---

Substitution reaction:

D – R – Cl + HO - Cell ® D – R – O – Cell + HCl

Addition reaction:

D – F – CH2 = CH2 + HO – Cell ® D – F – CH2 – CH2 – O – Cell

Reaction with water:

The cold brand reactive dyes are highly reactive in nature. They react also with water and get
hydrolyzed. The reaction is as follows ----

D – R – Cl + HOH ® D – R – OH + HCl

The hydrolyzed dye is also colored substances and has very low substantivity for the cellulosic fiber. So
they are attached with fiber surface after dyeing. If they do not washed away from the fiber surface the
fastness property of the fiber must be very low.

Salts Used for Reactive Dyeing:

Depends on the substantivity to increase the exhaustion, salt like common salt (NaCl) or Glouber’s salt
(Na2SO4) is used.

Alkalis for Reactive Dyeing:

The common alkalis used for reactive dyeing are sodium bi-carbonate (NaHCO3), sodium carbonate
(NaCO3), sodium hydroxide (NaOH), sodium silicate (Na2SiO3) and sodium phosphate (Na3PO4). Sodium
silicate is very strong alkali and only used for deep dyeing. Sodium carbonate is mostly used alkali in
reactive dyeing.

Eliminating the Hydrolyzed Dye:

The hydrolyzed dye is also colored substances and has very low substantivity for the cellulosic fiber.
They tend to stay on the fiber surface after dyeing for sometimes although there is no bond between
the dye and the fiber. These unfixed dyes come of the fibers when washed or rubbed subsequently.

If they do not washed away from the fiber surface the rubbing and wash fastness property of the fiber
must be very low.

The presence of electrolytes in the washing water causes an increase in the hydrolyzed dye affinity
making it difficult to extract, therefore very saline water must be avoided even if this water conditioned.

Discharging Defective Dyeing:

It cannot be said that dyeing with reactive dyes excessive leveling problems, since the dyes have a low
affinity.

However, it can happen that it is necessary to discharge a dyeing, which can be more or less difficult
depending on the situation of the dye in relation to the fiber.

Thus, in the case of cellulosic fibers dye discharging before the alkalinization of the dye – bath does not
present an difficulty, since hot washing with a detergent with extract the main part of the dye deposited
in the fiber, as it has a low affinity.

When instead the dye has already been covalently fixed to the fiber, it is more difficult to eliminate, as it
is necessary to destroy the molecule chemically by means of oxidizer and or reduction processes.

In the reduction process, the process is started at 50 – 600C the temperature is raised to 980C and held
for 20 minutes, and then the goods are rinsed in hydrogen peroxide before re – dyeing.

Absorption of the Dye:

This is the first dyeing phase, that takes place in the same way as cellulose dyeing with non-reactive
soluble dyes; in this phase the reactive dye does not decompose, but only diffuses towards the interior
of the fiber, when it is absorbed by the cellulosic chains by secondary type forces.

The following parameters influence the absorption:

Nature of the dye.

Liquor ratio.

Electrolyte concentration.

pH.

Temperature.

Type of fiber.
1. Partial stripping:

Partial stripping is obtained by treating the dyed fabric with dilute acetic acid or formic acid. Here
temperature is raised to 70-100°C and treatment is continued until shade is removed by desired
amount. After that a through washing is necessary to remove the product of hydrolysis.

The amount of acid used is as below: -

Glacial acetic acid : 5-10 parts

With water :1000 parts
Or
Formic acid :2.5 to 10 parts
With water :1000 parts
Temperature : 70 - 100°C
Time : until desired shade is obtained.

2. Full stripping:
For complete stripping the goods are first treated with sodium hydrosulphite (hydrose) at boil then
washed off and bleached with 1% sodium hypochlorite (NaOCl) at room temperature. This is carried out
for 30 min.

The recipe is as below: -

Na-hypochlorite : 1% at room temperature

Na-hydrosulpite: at boil.
Time : 30 min

DYEING OF NYLON USING REACTIVE DYES

Reactive dyes can be applied on Nylon 6 or Nylon 66 at weakly acidic condition. The covalent
bond between dye and amino group without an alkaline fixation condition. The dyes contain an
activated double bond and that react by a nucleophilic addition mechanism and capable of
addition at the end of the chain amino group.

NH2 + D NHD + D N(D )D )

The common reactive dye system based on halogenate4d nitrogen hetero cycles(MCT) will not
give even moderate build up since they are capable only single reaction with amino group. A
MCT dye will maximum by gives a fixed dyeing of 1.8% (o.w.f).
Monofunctional reactive dyes can be exhausted to nylon in medium and heavy depth but only a
portion of total exhausted dye form covalent bond and other dyes held by ionic or vander walls
force.

The dyes shows excellent wet fastness up to 0.7 to 1.0% (o.w.f) for regular nylon which is limit
for their reaction and the limit depends on number of free amino group of the substrate.

Bi-functional reactive dyes have higher reaction limit for nylon..The reaction limit is
2%(owm).It is suitable to produce medium to heavy shades by these dyes and amount of linkage
between dye-fibre is also higher.

FASTNESS PROPERTIES OF REACTIVE DYES ON NYLON

Good wet fastness.

Wash fastness is not so good.
Light fastness is not so good.

Better fastness can be achieved if after treatment is done with selected synthetic tanning
agent.