Synthetic Textile Dyes

What are synthetic textiles?

These are man-made polymers, made up of monomers with specific
characteristics. The polymers most commonly used for clothing are
polyesters, polyamide (nylons), and acrylics2.
Polyesters, and cellulose acetate (a semi-synthetic polymer) are dyed with
disperse dyes. Polyamides have functional groups similar to proteins, so
may be dyed with acid dyes or with disperse dyes. For the dyeing of acrylic
fibres, basic dyes are primarily used2.

Disperse dyes
The general structure of a polyester is shown below:

They tend to be fairly hydrophobic (though this depends on the structure of

R1 and R2), but not as much as, say, a long hydrocarbon would be, since the
-COOC- groups cause some polarity. The polymer chains in a sample of
polyester are highly crystalline (for a polymer) and quite tightly packed
together. The result of this is that polyesters have very little affinity for large
ionic dyes- the dyes simply cannot either distribute between the chains, or
form satisfactory intermolecular interactions. Therefore, acid and direct dye
classes are useless for this polymer2.
Disperse dyes have low solubility in water, but they can interact with the
polyester chains by forming dispersed particles. Their main use is the dyeing
of polyesters, and they find minor use dyeing cellulose acetates and
polyamides. The general structure of disperse dyes is small, planar and nonionic, with attached polar functional groups like -NO2 and -CN. The shape
makes it easier for the dye to slide between the tightly-packed polymer
chains, and the polar groups improve the water solubility, improve the
dipolar bonding between dye and polymer and affect the colour of the dye.
However, their small size means that disperse dyes are quite volatile, and
tend to sublime out of the polymer at sufficiently high temperatures2.

The dye is generally applied under pressure, at temperatures of about

130oC. At this temperature, thermal agitation causes the polymer's structure
to become looser and less crystalline, opening gaps for the dye molecules to
enter. The interactions between dye and polymer are thought to be Van-derWaals and dipole forces2.
The volatility of the dye can cause loss of colour density, and staining of
other materials at high temperatures. This can be counteracted by using
larger molecules, or making the dye more polar (or both). This has a
drawback, however, in that this new larger, more polar molecule will need
more extreme forcing conditions to dye the polymer2.

Classes of disperse dye

The most important class is the azo class. This class of azo disperse dyes
may be further sub-divided into four groups, the most numerous of which is
the aminoazobenzene class. This class of dye can be altered as mentioned
before, to produce bathochromic shifts. A range of heterocyclic
aminoazobenzene dyes are also available. These give bright dyes, and are
bathochromically shifted to give blues. The third class of disperse dye is
based on heterocyclic coupling components, which produce bright yellow
dyes. The fourth class are disazo dyes. These tend to be quite simple in
structure. Other than these, there are disperse dyes of the carbonyl class,
and a few from the nitro and polymethine classes. Below is an example of a
disperse dye2. It is the same as the chime molecule at the top of the page.

Basic dyes
Basic dyes possess cationic functional groups such as -NR3+ or =NR2+. The
name 'basic dye' refers to when these dyes were still used to dye wool in an
alkaline bath. Protein in basic conditions develops a negative charge as the
-COOH groups are deprotonated to give -COO-. Basic dyes perform poorly on
natural fibres, but work very well on acrylics2.
A general structure of an acrylic type polymer is shown below. It is
simplified, and doesn't show any anionic groups which are often present2.

The most common anionic group attached to acrylic polymers is the

sulphonate group, -SO3-, closely followed by the carboxylate group, -CO2-.
These are either introduced as a result of co-polymerisation, or as the
residues of anionic polymerisation inhibitors. It is this anionic property which
makes acrylics suitable for dyeing with cationic dyes, since there will be a
strong ionic interaction between dye and polymer (in effect, the opposite of
the acid dye-protein fibre interaction). An example of a basic dye is shown
below2:

In this case, the charge is delocalised across the molecule, but in some basic
dyes, the charge is located on a single nitrogen atom2.
The structure of nylon 6,6 and nylon 6 are shown below:

It can be seen that there is a distinct similarity between these polymers and
that of keratin (the nylons lack R groups, and have more space between each
amide group). The dyeing of these polymers is quite similar to the acid dye
action on wool2.