POLY VINYL CHLORIDE

PREPARATION OF VINYL CHLORIDE

The major method for preparing the monomer commercially since the early 1960s has been the so-called balanced
process from ethylene. In the first stage of the reaction, 1,2-dichloroethane is prepared by reacting ethylene with
chlorine in either the vapour or the liquid phase. In a typical liquid phase process, reaction would be in the range 30-
50°C in the presence of an iron chloride catalyst.

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The crude 1,2-dichloroethane is washed with sodium hydroxide solution and then purified and dried by distillation.
The dry 1,2-dichloroethane is then cracked to give vinyl chloride. This is achieved by vaporizing the 1,2-
dichloroethane and feeding through a series of tubes sited in a furnace.

By adjustment of the temperature (in the range 300-600°C and typically about 530°C) and the residence time
(approx. 20 s) a 40-65%% conversion may be obtained. The reaction product is then quenched and the monomer
isolated by fractional distillation. The particular feature of the balanced process is that the hydrogen chloride formed
during the dehydrochlorination stage and recovered during the purification is then used to generate more 1,2-
dichloroethane by an oxychlorination reaction. In this process ethylene and hydrogen chloride gases are passed, with
air, over a finely divided bed of copper(II) chloride supported on alumina. The reaction may be represented by the
equation

Other Routes
1) The acetylene is usually prepared by addition of water to calcium carbide, which itself is prepared by
heating together coke and lime.

2) Vinyl chloride (a gas boiling at -14°C) is most conveniently prepared in the laboratory by the addition of
ethylene dichloride (1,2-dichIoroethane) in drops on to a warm 10% solution of sodium hydroxide or
potassium hydroxide in a 1 : l ethyl alcohol-water mixture

POLYMERISATION
In commercial practice vinyl chloride is polymerised by free radical mechanisms in bulk, in emulsion and in
suspension, the latter process dominating with about 85% of the market. Today emulsion polymers are mainly used
for paste applications and the bulk polymerised material for UPVC applications.

Bulk Polymerisation
Pechiney-St. Gobain One-Stage Process - Vinyl chloride was polymerised with 0.8% of its own weight of benzoyl
peroxide in a rotating cylinder containing steel balls for 17 hours at 58°C. Bulk polymerisation is heterogeneous
since the polymer is insoluble in the monomer. The reaction is autocatalysed by the presence of solid polymer whilst
the concentration of initiator has little effect on the molecular weight. This is believed to be due to the overriding
effect of monomer transfer reactions on the chain length. As in all vinyl chloride polymerisation oxygen has a
profound inhibiting effect.

Pechiney-St. Gobain (now Rhone-Poulenc) Two-Stage Process - The first stage is carried out as a liquid with up to
about 15% conversion whilst the second stage carried out as a powder takes the conversion to 80-85%. The presence
of two stages allows considerable flexibility for the process, particle characteristics usually being determined by the
operation of the first stage and average molecular weight by the second stage.

Suspension Polymerisations
Suspension polymerisations are generally easier to control and there is little, if any, loss in clarity or electrical
insulation properties. Particle shape, size and size distribution may be controlled by varying the dispersing systems
and the rate of stirring. A typical polymerisation vessel for suspension polymerisation is shown below. It should,
however, be noted that many more modem reactors are fitted with shorter bottom-entry agitators. Autoclave sizes of
40-80m3 are used by most manufacturers although autoclaves as large as 200m3 are in commercial use.