Abstract

An aniline hydrochloride, a formaldehyde polymer was synthesised by mixing the solutions

of aniline, hydrochloric acid (HCl) and formaldehyde. During the mixing, when
formaldehyde was added in a solution of aniline and HCl the colour change from red to
white, immediately (within a second), the material froths up to form a solid, porous and a
deep red rubbery mass accompanied by a temperature of 40 – 50 °C. This reaction releases
energy by heat, and therefore this polymerization is regarded as an exothermic. The entire
demonstration was performed in a fume hood. The obtained polymer was removed from the
glass beaker then left over a night in a shelf, at the morning the polymer was weighed and the
obtained mass was found to be 25.66g

Introduction

Aniline formaldehyde resins belong to the family of thermoplastics synthesised by

condensing aniline and formaldehyde in an acidic solution exhibiting high dielectric strength.
Aniline, phenylamine or amino benzene is an organic compound with a chemical formula
C6H5NH2, consisting of a phenyl group attached to an amino group, aniline is the
prototypical aromatic amine. Aniline is a planar molecule, and the amine is nearly planar
owing to conjugation of the lone pair with the aryl group substituent. The C -N distance is
correspondingly shorter in aniline, the C – N and C -C distance is closer to 1.39 Â, indicating
the Л – bond between N and C.

Scheme 1. The chemical structure of an aniline compound

The industrial preparation of aniline involves two steps. The first step, benzene is nitrated
with a concentrated mixture of nitric acid and sulfuric acid at 50 °C to 60 °C to yield
nitrobenzene.

Scheme 2. Nitration of benzene

The nitrobenzene is then hydrogenated (typically at 200 °C to 300 °C) in the presence of a
metal catalyst. The reaction is as follows:

Scheme 3. Hydrogenation of nitrobenzene to produce aniline.

Aniline is commonly used in the manufacture of precursors to polyurethane. Like most

volatile amines, it possesses the somewhat unpleasant odour of rotten fish. It ignites readily,
burning with a Smokey flame.

The largest application of aniline and its polymers such as aniline-hydrochloride is for the
preparation of methylene diphenyl diisocyanato. Aniline is predominantly as a chemical
intermediate for the dye, agricultural polymer and most commonly in rubber industries.
Aniline is also used as a solvent and has been used as antiknock compound for gasoline. The
principal use of aniline in the dye industry is as a precursor to indigo, the blue or blue jeans.
The great value of aniline was due to the readiness with which it yields directly or indirectly.
Aniline is toxic inhalation of the vapour. The early synthesis of aniline resulted in an
increased incident of the cancer in bladder, but these effects are now attributed to
naphthylamines, and not aniline.
Results and discussions

The aniline hydrochloride – formaldehyde was synthesised by the process of condensation

polymerization by mixing the solutions, aniline, hydrochloric acid (HCl) and formaldehyde.
The solid, porous and rubbery mass was formed immediately (not more than 3 seconds) after
the formaldehyde solution was added in a mixture of aniline and hydrochloric acid solutions,
the entire demonstration was done in a fume hood. The obtained polymer appeared in very
deep red colour accompanied by a temperature of 40°C – 50°C. The polymer was allowed to
cool to room temperature in a fume hood, it was then removed in a glass beaker and left over
a night in a shelf. In the morning, the polymer was weighed and it was found to have a mass
of 25.66 g.

In this experiment the aniline hydrochloride – formaldehyde polymer was synthesised by

reacting aniline and formaldehyde in the presence of an acidic catalyst (HCl), and the
chemical reaction is as follows:

Scheme 4: the chemical reaction for the synthesis of the formaldehyde polymer

The above reaction involves condensation of aniline with formaldehyde in the presence of
hydrochloric acid to produce oligomeric di- and polyamines that are phosgenite without
further need of purification. Formaldehyde is a good electrophile that participate in
electrophilic aromatic substitution reaction with an aromatic compound (aniline).
Formaldehyde is also a highly reactive compound that can also undergo an electrophilic
addition with alkenes and aromatic compounds.
Below is the picture of the produced formaldehyde polymer

From left: formaldehyde, aniline and a polymer

Properties

 Deeply red
 Rubbery with pores

Conclusion

The main objection of this experiment was to synthesise a formaldehyde polymer from
aniline and formaldehyde in the presence of hydrochloric acid (catalyst) by condensation
polymerization. The objection was successful since the polymer was produced with a mass of
25.66g and it was porous as it was expected from the procedure.

References

1. Bizzari, Sebastian. N, “Formaldehyde”, Chemical industries Newletter, [Menlo park,

CA]. Mar 2007.
2. The Formaldehyde: Brief history and its contribution to society and the U.S and
Canadian economics. Arlington: The formaldehyde Counsil. Inc Feb 2005.