Kaliakor Dye Managers Workshop

Reactive
Dyes
Dr Kelvin N Tapley
Department of Colour Chemistry
University of Leeds, Leeds, UK
September 2003

Outline
History
General Features
Advantages & Disadvantages
Factors influencing performance
Common Types of Reactive Dyes
Reactions of Reactive Dyes
Application Methods
Summary

1
 History
Cyanuric chloride reaction with cotton and then amines
Remazol (vinyl sulphone) chemistry intorduced
1956 Rattee + Stephen (ICI) first reactive dyes
chlorotriazines
Various developments including new chemical types
1980s Mixed bifunctional dyes (esp. Sumitomo Sumifix Supra
dyes)

General Features of a Reactive Dye

Molecule

W = water solubilising group

D = chromophore
B = bridging group
RG = reactive group
X = leaving group

2
 Advantages?
Full Colour Gamut
Brilliant, bright colours
Colvalent fixation high WashFastness (WF)
Varying reactivities
Various temperatures
including low energy (cold dyeing)
Various methods of application
Inexpensive to apply (but dyes expensive)

Disadvantages?
Incomplete fixation (problem with hydrolysis)
Need for wash-off (for high WF)
Need for high concentrations of salt
Affect natural balance of watercourses
High pH
Some dyes are AOX potentially harmful to
the environment

3
Importance of Washing Fastness (WF)

The major issues

Loss of colour fading problems

Transfer of colorants to adjacent fabrics leads
to staining problems

NB some of the WF tests have got tougher!

Laundry washing

Poor wash fastness

4
During the laundry process the fabric is subjected to some
severe conditions and very often dye is beaten from the
fabric.

This results in dye entering the washing liquors.

Once in the washing liquors 3 things can happen to the

dye...

1. Re-adsorb onto original fibre

2. Adsorb to a different substrate
3. Remain in the wash liquor

Degree of staining
=
affinity of dye for original fibre
+
affinity of dye for adjacent fibre
+
affinity for water
(staying in solution)

5
 Factors that affect the dyeing
of cotton with reactive dyes

Auxili
aries
Cotton Pre-treatment

Reactive dye Dyebath (liquor ratio/flow)

Method:
eg.Temperature and duration
of dyeing

Factors Influencing the Performance

of Reactive Dyes
Molecular structure of Dye
Number of reactive groups
Chemical nature of reactive groups
Molecular mass (size)
Number of sulphonic acid groups
Ratio of sulphonic acid groups to aromatic carbons
hydrophobic hydrophilic balance
Linear / planar structure (shape)
Other functional groups present
Realtive positions of functional groups (incl. reactive groups)

Plus characteristics and quantity of impurities / additives

6
Factors Influencing the Performance
of Reactive Dyes
Material being dyed
Chemical type (assume cellulosic)
(Macro) physical structure (yarn, fabric, garment)
(Micro) physical structure (crystallinity vs
amorphous)
Material preparation or damage prior to coloration
Exposure to physical, chemical and biological agents

Pre-
Pre-treatment

It is easy to appreciate that what happens to the fabric before

dyeing will affect dyeing itself !

Pre-
Pre-treatment is crucial to a dyer if he wants to achieve right-
right-
first-
first-time dyeings. After pre-
pre-treatment he can trust his fabric.
fabric.

Pre-
Pre-treatment for cotton
principally involves:
Scouring and bleaching

7
 Scouring
Essentially cleaning!
removal of waxes, fatty acids etc.

Scoured
Exhaustion

Unscoured

Time
Definition of scour: To remove natural impurities, dirt or grease
from (cloth or fibers) by means of a detergent.

Factors Influencing the Performance

of Reactive Dyes
Application conditions
Quality of the water employed
Temperature programme employed
pH programme employed (incl type + conc of alkali)
Electrolyte programme employed
Any other additives/chemicals present (eg. Auxiliaries)
Liquor to materials ratio (LR)
Chemical (incl Dye) addition programme employed
Agitation / liquor circulation method
Time at each stage
[Rinse/Wash/After treatment conditions are also important]

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Factors Influencing the Performance
of Reactive Dyes
Application conditions the Human Factor
You may not be using an optimum method
Do you / your operatives actually do what you say you do?

Try to identify real / potential problem areas, for example:

Volume of water used (LR). Why?

Housekeeping
Use of Chemicals (dyes, electrolyte, alkali, auxiliaries)

Temperature (including storing/dissolving dyes)

Time

Types of Reactive Dyes

[Some examples!]

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Sulphatoethyl sulphone dyes

O NH2
SO3Na

O N
H

SO2CH2CH2OSO3Na

Vinyl sulphone dye (Remazol Brilliant Blue R, C.I. Reactive Blue 19)

Monochloro-s-triazine dyes

Cl

SO3Na N N

OH HN N N
N H
N

NaSO3 SO3Na

Monochloro-s-triazine dye (Procion Red H-3B, C.I. Reactive Red 3)

10
 Bis (monochloro-s-triazine) dyes
Cl Cl

SO3Na N N N N NaSO3

OH HN N N N N NH OH
N H H N
N N

NaSO3 SO3Na NaSO3 SO3Na

Bis(monochloro-s-triazine) dye (Procion Red HE-3B, C.I. Reactive Red 120)

2,4-difluoro-5-chloro-pyrimidine dyes
F

N N

N F
H Cl

H
SO3Na OH N O

N N
SO3Na
NaSO3 SO3Na

2,4-difluoro-5-chloro-pyrimidine dye
(Levafix Brilliant Red E 3BA, C.I. Reactive Red 147)

11
2,4,5-trichloro-pyrimidine dyes

Cl
Cl
SO3Na N
OH
N N HN N Cl

NaSO3

SO3Na

Trichloro pyrimidine dye (Drimarene Red Z 2B, C.I. Reactive Red 17)

Mixed Bifunctional reactive dyes

eg. Cl
N
Dye NH N
N
N
H

SO2CH2CH2OSO3Na

General structure of Sumifix Supra dyes

MCT-SES or MCT-VS
[Reactron Supra F dyes are similar]

12
 Reactions of Reactive Dyes

[Some examples!]

Nucleophilic
addition

Reactive The reactive group is usually the

group vinylsulphone group

SO2 - CH = CH2

Sulphone (SO2) Vinyl (CH = CH2)

13
Nucleophilic addition
H H
O - NaHSO O
4
DYE S C C OSO3Na DYE S CH CH2
O H H O

O H - O
- + Cellulose O +
DYE S CH C O Cellulose DYE S CH CH2
O H O

H2O

O H H
DYE S C C O Cellulose + OH-
O H H

-elimination of -sulphatoethylsulphone to
vinyl sulphone and reaction with cellulose.

Nucleophilic
substitution

Reactive The reactive groups is usually a

group halogenated heterocyclic group

Cl N Cl

N N
e.g.
a dichloro-s-triazine reactive
group

14
Nucleophilic substitution
Cl
N
Dye N N
H
N
Cl Cl
.. O Cellulose
N N
+ X- - Cl-
Dye N N Dye N N OR
H H
N N Cl
Cl X Cl
N
Dye N N
H
N
OH

Competing nucleophilic substitution reactions of s-triazine dyes

Separation of bis-Monochlorotriazinyl Reactive

Dyes and Hydrolysates in Dyehouse Effluent by
Capillary Zone Electrophoresis

0.43

0.33

0.23

0.13

0.03
6 10 14 18 22
Time / minutes

15
 Application Methods
Continuous
eg. Pad - Thermofix
Semi-Continuous
eg. Pad - Batch
Batchwise Exhaustion *
eg. Winch, Jet, Package and Beam Dyeing
Printing
eg. Print - Thermofix

Typical dyeing conditions for a bifunctional

monochlorotriazine dye

16
Typical dyeing conditions for a bifunctional
dichlorotriazine dye

Typical dyeing conditions for a bifunctional

sulphatoethyl sulphone dye

17
 Summary
Dominant dye class for cotton
Importance of nature and number of reactive
groups ( covalent fixation)
Different types/chemistries
many different application methods
Problem of dye hydrolysis
Potential impact on environment

Acknowledgements
Department of
Colour Chemistry,
University of Leeds
DFID

K.Tapley@leeds.ac.uk
www.leeds.ac.uk/ccd Department of Colour Chemistry, University of Leeds, Leeds, LS2 9JT

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Questions ?

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