Chemistry of Colorants & Auxiliaries

Course Outline
Prerequisites: Applied Chemistry
Specific Objectives of the Course:
Introduction to dyes, History of Dyes, and chemical nature of dye molecule, Auxochromes and
Chromophores, Characteristics of Dyes, Physical forms of dyes, organic pigments, Classification of dyes,
Criteria for the selection of dyes, Dye absorption isotherms, Theory of dyeing, Fibre-Dye interactions,
Dye-water interactions, Dye-Dye interaction,
Module 1 Reactive Dyes
Introduction, Chemistry, properties and classification of reactive dyes, Application of reactive dyes .
Auxiliaries uses with reactive dyes, Suitable fibre substrate for reactive dyes, Stripping of Reactive dyes,
Fastness properties of Reactive dyes,
Module 2 Direct Dyes
Introduction, classification, chemical nature and application of Direct dyes. Auxiliaries used in Dyeing
with Direct dyes, After Treatment, Stripping and Fastness properties of Direct dyes. Suitable fibre
substrate for direct dyes.
Module 3 Vat Dyes
Introduction, chemistry and application of vat dyes. Auxiliaries used in dyeing with vat dyes, Stripping
and Fastness properties of vat dyes. Suitable fibre substrate for vat dyes.
Module 4 Sulphur Dyes
Introduction, chemistry and application of sulphur dyes. Stripping and fastness properties of sulphur
dyes. Suitable fibre substrate for Sulphur dyes.
Module 5 Acid Dyes
Introduction, chemistry and application of acid dyes. Mechanism of dyeing protein fibres. Types of acid
dyes. Stripping and Fastness properties of acid dyes,
Module 6 Basic Dyes
Introduction, chemistry and application of basic dyes. Stripping and Fastness properties of basic dyes,
Module 7 Mordant Dyes
Introduction to mordant and mordant dyes, Methods of dyeing with mordant dyes; Chrome-mordant
method, Meta-chrome method, After-chrome method,
Module 8 Disperse Dyes
Dyeing with Disperse dyes, Commercial forms of disperse dyes, Dyeing hydrophobic fibres with disperse
dyes, Chemical characteristics of disperse dyes, Classification of disperse dyes, Use and chemistry of
carriers in dyeing with disperse dyes, Stripping of disperse dyes, Fastness properties of disperse dyes,
Suitable fibre substrate for disperse dyes,
Module 9 Azoic Dyes
Introduction to azoic dyes, Configuration and chemistry of azoic dyes, General properties of azoic dyes,
Application of azoic dyes by various methods of dyeing, Stripping of azoic dyes, fastness properties of
azoic dyes, Suitable fibre substrate for azoic dyes.
Lab Outline
As per course contents
Recommended Books:
1. The Dyeing of Textile Fibres, Theory and Practice by Joseph R.

Class notes
Chapter 1 Introduction
All dyes and pigments are colorants: when present on a substrate they selectively modify the reflection
or transmission of incident light. During application to a substrate, a dye either dissolves or passes
through a state in which its crystal structure is destroyed. It is retained in the substrate by adsorption,
solvation, or by ionic, coordinate or covalent bonding. A pigment, on the other hand, is insoluble in and
unaffected by the substrate in which it is incorporated.
Unlike most organic compounds, dyes possess colour because they;
1) absorb light in the visible spectrum (400700 nm),
2) have at least one chromophore (colour-bearing group),
3) have a conjugated system, i.e. a structure with alternating double and single bonds, and
4) exhibit resonance of electrons, which is a stabilizing force in organic compounds
When any one of these features is lacking from the molecular structure the colour is lost. In addition to
chromophores, most dyes also contain groups known as auxochromes (colour helpers), examples of
which are carboxylic acid, sulfonic acid, amino, and hydroxyl groups. While these are not responsible for
colour, their presence can shift the colour of a colourant and they are most often used to influence dye
solubility. Figure 1 shows the relationships between wavelength of visible and colour observed.

Color Frequency Wavelength
violet 668789 THz 380450 nm
blue 606668 THz 450495 nm
green 526606 THz 495570 nm
yellow 508526 THz 570590 nm
orange 484508 THz 590620 nm
red 400484 THz 620750 nm
Colorant classification system
The earliest comprehensive alphabetical listing of synthetic products used in the coloration industry was
published in 1870. The beginnings of systematic classification based on chemical structure, with
subgrouping according to hue, were first seen in the 1880s. The Society of Dyers and Colourists
embarked on the First Edition of the Colour Index in 1921 as a series of monthly issues that were first
offered as a bound volume in 1924.
Colour Index Classification
The Colour Index uses a dual classification system. The prime descriptor, in that it is the one most
commonly used in discussions by colorant users and is the one easier to remember, is the Colour Index
Generic Name (often abbreviated to CIGN). The other descriptor is the Colour Index Constitution
Number (often abbreviated to CICN) which is chemical-structure related.
Colour Index Generic Name (CIGN)
A C.I. Generic Name describes a commercial product by its recognised usage class, its hue and a serial
number (which simply reflects the chronological order in which related colorant types have been
registered with the Colour Index), e.g. C.I. Acid Blue 52, C.I. Direct Red 122, C.I. Pigment Yellow 176 and
C.I. Solvent Black 34. This definition enables a particular commercial product to be classified along with
other products whose essential colorant is of the same chemical constitution and in which that essential
colorant results from a single chemical reaction or a series of reactions. The definition also includes
multi-constituent substance or products by process.
Colour Index Constitution Numbers (CICN)
Where the chemical constitution of an essential colorant has been disclosed for publication, it has been
classified and allocated a separate five-figure C.I. Constitution Number; since 1997, new disclosures have
been allocated six-figure C.I. Constitution Numbers to alleviate the congestion experienced in certain
areas, notably monoazo colorants. In each category, the various colorants are arranged strictly on the
basis of their chemical structures.
Colon Numbers
Colorants listed under a C.I. Generic Name whose serial number contains a colon differ slightly from
those listed under the parent C.I. Generic Name. This slight difference is usually chemical but may be
due to different crystal modifications in the case of certain pigments.
Thus, for example, C.I. Pigment Red 48 (C.I. 15865) is the sodium salt and C.I. Pigment Red 48:1 (C.I.
15865:1) is the barium salt.
Classification of colorants
Colorants may be classified usefully in two separate ways, either according to their chemical structure or
according to the method of application.
Chemical classes of colorants
In the chemical classification method, colorants are grouped according to certain common chemical
structural features. Thiazole dyes are dealt with immediately after the stilbene class because both of
these, like the polyazo types, contribute notably to the range of direct dyes. The anthraquinone,
indigoid, quinacridone, quinophthalone, benzodifuranone and aminoketone classes form another series
with certain structural similarities and important applications in vat or disperse dyes and pigments.
Phthalocyanine and formazan are stable metal-complex chromogens. The remaining seven categories
included are already less important and still declining in commercial significance. The arylmethane,
xanthene, acridine, azine, oxazine nd thiazine chromogens share a limited degree of resemblance in
structural terms.

Reactive Dyes

Reactive systems
the reactive system, enabling the dye to form a covalent bond with the fibre and often also
contributing some substantivity;
a bridging group that links the reactive system to the chromogen and often exerts important
influences on reactivity, stability and substantivity;
one or more solubilising groups, usually sulphonic acid substituents on the aryl rings of the
chromogen;
The structure of the reactive grouping and substituents attached to it is decisive with regard to the
chemical stability of the dyefibre bond that is formed.
Numerous factors have to be taken into account in designing reactive dyes of commercial interest. Some
of the most important are:
(1) Economy any reactive system selected for a range of dyes must enable them to be produced at
acceptable cost.
(2) Availability the system selected must be free from patent restrictions, health hazards or other
limitations to exploitation.
(3) Versatility it must be possible to attach the reactive system to a variety of dye chromogenic
groupings in manufacture.
(4) Storage stability dyes containing the reactive system must be stable to storage under ambient
conditions worldwide.
(5) Efficiency the manufacturing yield must be economically viable and the dye fixation must be high
under conventional conditions of application.
(6) Bond stability the dyefibre bonds must be reasonably stable to a range of relatively severe
fastness tests.
Only a relatively few reactive systems (Table 1) have met these requirements sufficiently well to become
commercially established in a significant segment of the market for reactive dyes.
Table 1 Important reactive systems for cellulosic dyeing
Monofunctional
Dichlorotriazine
Aminochlorotriazine
Aminofluorotriazine
Trichloropyrimidine
Chlorodifluoropyrimidine
Chlorofluoromethylpyrimidine
Dichloroquinoxaline
Sulphatoethylsulphone
Sulphatoethylsulphonamide
Homobifunctional
Bis(aminochlorotriazine)
Bis(aminofluorotriazine)
Bis(aminonicotinotriazine)
Bis(sulphatoethylsulphone)
Heterobifunctional
Aminochlorotriazine-sulphatoethylsulphone
Aminofluorortriazine-sulphatoethylsulphone
Difluoropyrimidine-sulphatoethylsulphone
Monofunctional dyes
The s-triazine ring is unique amongst the six-membered nitrogen heterocycles in possessing three
electronegative atoms ideally placed to provide the necessary activation of the halogen atoms attached
to the adjacent carbon atoms. Calculations of charge distribution over these various heterocyclic rings
show that the largest possible charge attained in the series is found on the carbon atoms of the s-
triazine ring (Figure). As a result, none of the dyes derived from the alternative chloro-substituted
heterocyclic systems are capable of showing reactivity as high as that of the dichloro-s-triazine
derivatives.

Levels of reactivity of various heterocyclic rings

Presentation on reactive dyes
Presentation on Direct Dyes
Vat dyes
Vat dyes are insoluble in water and are applied to cellulosic fibres, usually with sodium dithionite under
alkaline conditions, by a vatting process involving reduction to produce a water-soluble leuco form
which possesses affinity for the substrate. Air or chemical oxidationthen results in regeneration of the
insoluble form of the colorant trapped within the fibre structure.
Vat dyes based on anthraquinone and related polycyclic systems generally exhibitoutstanding fastness
properties. Most vat dyes contain two carbonyl groups linked by aconjugated (quinonoid) system
(Scheme 6.10). They can be applied as the water-solubledisulphuric esters of the leuco forms; these
have low affinity for cellulose and can beobtained by esterifying the leuco compound with
chlorosulphonic acid.

Classification by Chemical structures
Anthraquinones
Anthraquinone, also called anthracenedione or dioxoanthracene, is an aromatic organic compound with
formula C
14
H
8
O
2
. Several isomers are possible, each of which can be viewed as a quinone derivative. The
term anthraquinone, however, almost invariably refers to one specific isomer, 9,10-anthraquinone
(IUPAC: 9,10-dioxoanthracene) wherein the keto groups are located on the central ring. It is a building
block of many dyes and is used in bleaching pulp for papermaking. It is a yellow highly crystalline solid,
poorly soluble in water but soluble in hot organic solvents. For instance, it is almost completely insoluble
in ethanol near room temperature but 2.25 g will dissolve in 100 g of boiling ethanol

Synthesis
Anthraquinone itself is traditionally available from the anthracene of coal tar by oxidation, often with
chromic acid or nitric acid; a more modern alternative method is that of air oxidation using vanadium(V)
oxide as catalyst. Anthraquinone is also produced in the reaction of benzene with benzene-1,2-
dicarboxylic anhydride (phthalic anhydride) using a Lewis acid catalyst, typically aluminium chloride. This
FriedelCrafts acylation gives obenzoylbenzoic acid (6.5) which undergoes cyclodehydration when
heated in concentrated sulphuric acid. Phthalic anhydride is readily available from naphthalene or from
1,2-dimethylbenzene (o-xylene) by catalytic air oxidation.


Indanthrones
Indanthrone blue, also called indanthrene, is an organic dye made from 2-aminoanthraquinone treated
with potassium hydroxide in the presence of a potassium salt.


Although anthraquinone is the starting point for the preparation of many derivatives, involving
substitution and replacement reactions, certain compounds are obtained directly by varying the
components in the above synthesis. Thus, for example, replacement of benzene with methylbenzene
(toluene) leads to the formation of 2-methylanthraquinone. A particularly important variation on the
phthalic anhydride route is the synthesis of 1,4- dihydroxyanthraquinone (6.6; quinizarin) using 4-
chlorophenol with sulphuric acid and boric acid as catalyst (as below). The absence of aluminium
chloride permits hydrolysis of the chloro substituent to take place.

Benzanthrone derivatives
Benzanthrone (6.73) is the source of various commercially important violet, blue and green vat dyes.
This tetracyclic system can be prepared from a mixture of anthraquinone and propane-1,2,3-triol
(glycerol) by heating with iron powder in concentrated sulphuric acid. The reaction involves reduction of
anthraquinone to anthrone (6.74) followed by condensation (Scheme 6.14) with propenal.

The latter compound being generated from glycerol by dehydration.

Carbazole derivatives
Diphthaloylcarbazole derivatives constitute an important group of vat dyes, possessing good all-round
fastness properties and providing hues ranging from yellow to black.
Synthesis
Two different intermediates were first prepared and then reacted together to form the dye. The
chemical steps are shown below;

Phthalic anhydride and p-chlorophenol were reacted in sulfuric acid to form quinazirin. The quinizarin
was aminated to yield 1,4-diaminoanthraquinone.
The conversion of anthraquinone to 1-anthraquinonesulfonic acid required the use of the catalyst
mercuric sulfate to direct the sulfonation to the number 1 position on the anthraquinone ring.
Chlorination formed 1-chloroanthraquinone.
The next stage was the condensation of the two intermediates in the presence of a copper catalyst to
form the trianthrimid of Brown BR (1,4-(dianthraquinoylamino)-anthraquinone). Carbazolation was
carried out in pyridine and aluminum chloride. The seven step process for Brown BR had an estimated
overall yield of only 19 percent. Low chemical yields and the use of hazardous raw materials and
solvents made vat dyes the most highly polluting class of dyes manufactured.
Some examples


Vatting & oxidation

INDIGOID AND THIOINDIGOID DYES
Indigo dye is an organic compound with a distinctive blue color (see indigo). Historically, indigo was a
natural dye extracted from plants, and this process was important economically because blue dyes were
once rare.

Method of synthesis

After-treatment
The final step consists in after-treating the material in weakly alkaline liquor with a detergent at
boiling temperature.
This soap treatment is not only aimed at removing pigment particles, but also allows the
crystallisation of amorphous dye particles, which gives the material the final shade and the
fastness properties typical of vat dyes.
Classification by method of application
Vat dyeing conditions can vary widely in terms of temperature and the amount of salt and alkali
required, depending on the nature of the dye applied.
Vat dyes are therefore divided into the following groups, according to their affinity for the fibre
and the amount of alkali required for dyeing
Vat dyes are the primary choice where the highest degree of fastness to industrial laundering,
weathering and light are required.
Based on temperature, amount of caustic soda, hydrosulphite and salt, used in dyeing, vat dyes
can be classified into four main groups:
IK dyes (I = Indanthren, K = cold) have low affinity, they are dyed at 20 - 30 C and require little
alkali and salt to increase dye absorption
IW dyes (W = warm) have higher affinity, they are dyed at 40 - 45 C with more alkali and little
or no salt
IN dyes (N = normal) are highly substantive and applied at 60 C and require much alkali, but no
addition of salt.
The leuco form of this solubilized dye can be regenerated by removing the ester group chemically
(with sodium nitrite in dilute sulfuric acid) or by the action of light. The drawbacks of solubilized
leuco esters are their greater expense and their poorer uptake into the fiber, which results in paler
shades.