The Chemistry of Dyes and Dyeing

Not all dyes are suitable for every type of fabric. A dye must have the property of
fastness. It must bond strongly to the fibers of the material and remain there after repeated
washings. It must not fade on exposure to light. Additionally, a dye must dye a fabric evenly if
it is to be of commercial use. Levelness is the term used to refer to the uniformity of the dye
on the fiber. A level dye, therefore, is one that colors the fabric evenly after its application.
Exactly how a dye binds to a particular fiber is a complex subject since there is much variability
possible in both the dye and fiber structure. For example, a dye that is effective in dyeing wool
or silk may not dye cotton well at all. The reverse situation is also observed.
In order to understand the manner by which a dye binds to a fiber, one must know both
the chemical structure of the dye and the fiber. The structures of some common fabric fibers
are illustrated below:
Natural Fibers

R R
H O
H2 N N N OH
n
O H O
R
Wool and Silk (polypeptides)

OH
HO HO OH HO OH
O O
O O O O O
O O
HO OH HO OH
OH OH
Cotton (cellulose)

Synthetic Fibers

OAc
AcO AcO OAc AcO OAc
O O
O O O O O
O O
AcO OAc AcO OAc
OAc OAc O

Rayon Acetate (cellulose acetate) Ac = H C C

3

H
N
HO n
 O
O
HO O
n OH
O
O
Dacron (polyester)

C N C N C N
Orlon (acrylic or polyacrylonitrile)

Two of the natural fibers shown are wool and silk. They are similar in that they are
both polypeptides (polymers made up of amino acid monomer units). The 20 common amino
acids have the same basic chemical structure but differ in the nature of the “side chain” labeled
R. Depending on the amino acid, R may be nonpolar or polar and acidic (e.g. -CO2H), basic
(e.g. -NH2) or neutral (e.g. -CH2OH). In wool and silk, there are many ways in which a dye
can bind to the fiber. It may form covalent or ionic bonds to the -NH2 and/or -CO2H groups on
the ends of the polymer or form similar interactions with the amino acid side chains (R).

Direct Dyes
Dyes that attach themselves to a fiber by direct chemical interaction are called direct
dyes. Picric acid is a direct dye for wool or silk. Since it is a strong acid, it interacts with the
basic end groups and side chains in wool and silk to form a salt linkage or electrostatic
interaction between itself and the fiber. The picric acid gives up its proton to some basic group
on the fiber and becomes an anion, which strongly binds to a cationic group on the fiber by
ionic interaction. This interaction is illustrated below.

Direct Dye
NO2
NO2

O2N NO2
O O2N NO2
H O
..
NH2 + NH3

wool, silk or nylon fiber

Of the synthetic fibers, nylon is most like silk or wool since it is also composed of
peptide or amide linkages and is formed from compounds containing amino groups (e.g. H2N-
(CH2)6-NH2) and carboxylic acid groups (e.g. HO2C-(CH2)4-CO2H). Nylon can be synthesized
 NH2 H2N

N N
N N
+ +
Na -O3S SO3- Na

Congo Red (a disazo dye)

(direct dye for cotton)

OH

N N NO2

Para Red (an azo dye)

Ingrain dye

Cotton, which has only hydroxylic groups in its structure, does not dye well with picric
acid or other anionic or cationic dyes. Simple azo dyes do not bind well to cotton. However,
disazo dyes, such as Congo Red, do act as direct dyes for cotton. A disazo dye has two azo
groups (R-N=N--------N=N-R). When these two azo groups are the correct distance apart
(usually 10.2 to 10.8 angstroms), the disazo dye binds strongly to cotton. Although the nature
of binding is not completely understood, it is likely that this distance positions the nitrogens of
the disazo dye in the correct position for hydrogen bonding with the hydroxyl groups in cotton.
Evidence for this also comes from the observation that cellulose acetate, which does not have
free hydroxyl groups for hydrogen bonding, is not dyed effectively by Congo Red. The
proposed mode of binding of Congo Red to cotton is shown below.
 OH
HO HO OH HO OH
O O
O O O O
O O
HO OH HO OH
OH OH
H-bond R N N R
N N H-bond

spacer
Direct dyeing by the disazo dye Congo Red
Ingrain Dyes
Although simple azo dyes are not direct dyes for cotton, they can be used to dye cotton
as developed or ingrain dyes. Ingrain dyes are synthesized inside the fiber itself. Two smaller
molecules used to synthesize the ingrain dye are allowed to penetrate into the pores within the
fiber. Once there, they react to form the larger ingrain dye which, because of its size, is then
trapped inside (in the grain) of the fiber. Para Red is a typical ingrain dye. It is formed by first
soaking the fabric in a solution of β-naphthol and then in a solution of diazotized p-nitroaniline.
The general scheme is illustrated below.

cotton fiber
OH Cl +N N
pore

NO2

naphthol diazotized p-nitroaniline

cotton fiber
OH

N N NO2
pore

Para Red
Vat Dyes
A third type of dye, which can be used for all fabric types (both natural and synthetic),
is the vat dye. Vat dyes are typically water soluble in their reduced forms but, when oxidized
by air, become insoluble in water. Indigo, the water insoluble blue dye found, for instance, in
blue jeans, is such a vat dye. It can be reduced by sodium dithionite (sodium hydrosulfite) to
leucoindigo, a water soluble, colorless derivative. In the vat process for indigo, the fabric is
impregnated with the soluble leucoindigo in a hot dye bath or vat. Then, the fabric is removed
from the vat, and the leucoindigo is allowed to be oxidized by air to the insoluble indigo. The
indigo precipitates both inside and on the surface of the fabric fibers. Since the indigo is
insoluble in aqueous solution, the dye is fast. The reaction involved is illustrated below.

O
H O
N H
NaOH / Na2S2O4 N

N
H O2 N
O H
O
Indigo (blue, insoluble) Leucoindigo (colorless, soluble)
Disperse Dyes
Fibers such as Dacron (polyester) and acetate Rayon have no groups which would
allow for direct dye-fiber interactions. These fibers are difficult to dye. Disperse dyes are often
times used in these cases. In the disperse dyeing process, a dye that is water insoluble is used.
It is allowed to penetrate the fiber with an organic solvent as “carrier”. Oftentimes, the dye is
suspended in aqueous solution and a small amount of the carrier solvent is added. The carrier
dissolves the dye and carries it into the fiber where it is “dispersed”. The dye becomes trapped
inside the fiber only because of water insolubility. It is not bonded to the fibers but only
dispersed among them.