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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

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

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

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

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)

Factors that affect the dyeing of cotton with reactive dyes


Cotton
Pre-treatment
Auxili aries

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

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-treatment PreIt is easy to appreciate that what happens to the fabric before dyeing will affect dyeing itself ! Pre-treatment is crucial to a dyer if he wants to achieve rightPrerightfirst-time dyeings. After pre-treatment he can trust his fabric. firstprefabric.

Pre-treatment for cotton Preprincipally involves: Scouring and bleaching

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]

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!]

Sulphatoethyl sulphone dyes


O NH2 SO3Na

N H SO2CH2CH2OSO3Na

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

Monochloro-s-triazine dyes
Cl SO3Na N OH HN N N N N N H

NaSO3

SO3Na

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

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Bis (monochloro-s-triazine) dyes


Cl SO3Na N OH HN N N N N N H N H N N Cl N NH OH N SO3Na NaSO3 NaSO3 N

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 H Cl N F

SO3Na N N SO3Na NaSO3

H OH N

SO3Na

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

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2,4,5-trichloro-pyrimidine dyes
Cl SO3Na N N NaSO3 SO3Na
Trichloro pyrimidine dye (Drimarene Red Z 2B, C.I. Reactive Red 17)

Cl OH HN N

N Cl

Mixed Bifunctional reactive dyes eg.


N Dye NH N N H SO2CH2CH2OSO3Na
General structure of Sumifix Supra dyes MCT-SES or MCT-VS [Reactron Supra F dyes are similar]

Cl N

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Reactions of Reactive Dyes


[Some examples!]

Nucleophilic addition

Reactive group

The reactive group is usually the vinylsulphone group

SO2 - CH = CH2

Sulphone (SO2)

Vinyl (CH = CH2)

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

O DYE S O

H CH C H H2O O Cellulose

+ Cellulose

O DYE

O S O CH

+ CH2

O DYE S O

H C H

H C H O Cellulose

OH-

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

Nucleophilic substitution

Reactive group

The reactive groups is usually a halogenated heterocyclic group

Cl N

N N

Cl

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

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Nucleophilic substitution
Cl N Dye Cl N Dye N H N N Cl .. + XN Dye N H N N X N Dye N H N N OH Cl Cl - ClOR Cl N H N N O Cellulose

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 Time / minutes 18 22

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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

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Typical dyeing conditions for a bifunctional dichlorotriazine dye

Typical dyeing conditions for a bifunctional sulphatoethyl sulphone dye

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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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