1.

Introduction to Polymers
Definition
Polymers – from the Greek 'poly' (many) and 'meros' (parts) – are a group of chemical products that
share the same training principle. They consist of long chains of molecules called
macromolecules, which consist of a large number of pro-metabolic repeating units. The molecules
formed from a number of monomers less than that are often called 'oligomers', which means 'a few'
parties'.

There are different types of polymers: natural polymers (for example, wool, silk, wood, cotton),
semi-synthetic polymers (chemically modified natural polymers, such as)
casein-based plastics, cellulose-based plastics, and synthetic polymers.

Structure

Macromolecules can exist in linear or branched form (containing side chains)

and be reticulated, linking the chains together. Examples of these three types of macromolecules are
presented in Figure 1.1.

Figure 1.1: Basic structures of polymers

A) linear polymer
B) branched polymer
C) crosslinked polymer

Polymers can be made up of a single type of monomer (homopolymer) or different types.

of monomer (copolymer). In the case of a linear copolymer that contains two distinct monomers
(for example A and B),

Property

The underlying formation principle is very flexible and allows for the production of polymers characterized by
a wide range of properties and property combinations. Polymers in the form of objects, fibers
or flakes can be:
rigid or flexible.
transparent, translucent or opaque.
hard or soft.
resistant to climatic conditions or degradable.
resistant to high or low temperatures.

In addition, it is possible to combine them with filling materials, to mix them with others.
products (for example fiberglass) to form composites or with other polymers to
obtain polymer blends.
A specific polymer is usually not the only material that can be used in a field.
given application. Alternative materials exist and polymers must succeed in
a competitive market.

2. Manufacturing process and application of polystyrene

General manufacturing process of polymers

The manufacture of polymers follows the process shown in Figure 2.1 with the monomers, the Co-
monomers, catalysts, solvents as well as energy and water in input and the product, the effluents
gaseous, wastewater, and waste at the output.

Polystyrene
Generalities
Polystyrene belongs to the group of standard thermoplastics, which also includes polyethylene,
polypropylene and polyvinyl chloride. Polystyrene can, due to its special properties, be
used in an extremely wide range of applications.

Styrene was isolated from the resin of the kauri wood (Agathis australis) for the first time in 1831 by
Bonastre. In 1839, E. Simon, who was also the first to describe the polymer, gave his name to the monomer. The
development of an industrial production process for polystyrene (the molecular structure described at the
Figure 2.1) began around 1925. This research work achieved success in 1930 in Germany. In the United States
Polystyrene began to be produced commercially in 1938.

Figure 2.1: Molecular structure of polystyrene

In practice, three different types of polystyrene can be distinguished. The transparent and brittle polymer.
is called general-purpose polystyrene (GPPS) and the white polystyrene, not shiny but relatively
flexible, modified with rubber is called impact polystyrene (IPS or HIPS). The expandable polystyrene or
Expanded polystyrene (EPS) represents the third type of polystyrene, which must however be differentiated from the
other types due to its different production techniques.
Processes

Figure 2.2: Propagation chain in the polystyrene process

Raw material

Pure styrene is clear and any colored formation is normally due to contamination, such as rust.
metallic. Styrene has exceptional capabilities that allow it to be polymerized
easily by different methods and it can be co-polymerized with a wide range of others
monomers (acrylates, methacrylates, acrylonitrile, butadiene, and maleic anhydride). For this
The most important issue that can be encountered during the storage of styrene is prevention.
of auto-polymerization, which represents an uncontrolled chemical reaction. The main factors
Important factors for giving styrene a long shelf life are: low temperatures, the
appropriate levels of inhibitors, suitable building materials for storage and
handling equipment as well as good basic maintenance.
To inhibit the formation of polymers as well as degradation during transport and successive storage, it
It is necessary to add a TBC inhibitor (4-tert butylcatechol). The TBC prevents polymerization.
reaction with oxidation products (the peroxides forming free radicals) in the presence of a
small amount of oxygen. The level of the inhibitor must be kept above a
minimum concentration of 4 to 5 ppm. The standard level of TBC is 10 to 15 ppm.

General grade polystyrene process (GPPS)

Raw materials, such as styrene (potentially purified) and a processing additive, are
brought into the reactor(s). The reactor train is usually composed of stirred reactors
continue (CSTR) and/or piston flow reactors (PFR).
Styrene itself acts as a reactive solvent. Furthermore, it is possible to add up to 10%.
of ethylbenzene in order to improve the control of the reaction. The temperatures of the reactors are
controlled between 110 and 180°C. The reaction pressure can reach 1 MPa in the case of a REP and a
atmospheric or sub-atmospheric pressure in the case of a CSTR.
Supplementary chemicals are added to the feed stream or in the reactors. In the end
From the reactor chain, the conversion of styrene monomer reaches 60 to 90% solid matter. Then, the flow
The process flows into a devolatilization unit, where it is subjected to one or two purges (one or two
devolatilization units) to separate the polymer from the unaltered species. The devolatilizers operate
at high temperatures (220–260°C) and under high vacuum (< 40 mbar).

Figure 2.3: Schematic diagram of the GPPS process

High Impact Polystyrene (HIPS) Process

In general, the process is very similar to the GPPS process. The main difference lies in the addition of a
rubber component. The polybutadiene rubber received in the form of 35 kg bales is crushed into
small scales. The rubber scales precipitate in the dissolution tank by gravity or by
pneumatic transport. In this tank and thanks to a significant agitation phenomenon, the scales are
dissolved in styrene to obtain a rubbery solution that can contain up to 15% of
rubber.
The antioxidant is generally also added to the dissolution tank. Other chemicals can
to be added to the tank, including white oil, peroxides, recycled styrene, ethylbenzene or the
chain transfer agents. The dissolved mixture is then continuously fed to the reactor train,
in which a bulk polymerization occurs. The chemicals not added to the tank of
dissolutions are added to the feed stream or directly into the reactors.
The reactor train is usually composed of continuously stirred tank reactors (CSTR) and/or reactors with
piston flow (REP). Styrene itself acts as a solvent for the reaction. Furthermore, it is possible
to add up to 10% ethylbenzene in order to improve the control of the reaction. The temperatures
the reactors are controlled between 110 and 180°C. The pressure of a PWR can reach 1 MPa while the
Reactions in a CSTR are carried out under atmospheric or sub-atmospheric pressure.
At the end of the reactor chain train, the conversion of styrene monomer reaches 60 to 90% solid body.
Then, the process stream flows into a devolatilization unit, where it undergoes one or two purges.
(one or two devolatilization tanks) to separate the polymer from the unaltered species. The devolatilizers
operate at high temperatures (220 to 260°C) and under high vacuum (< 40 mbar).

Figure 2.4: Schematic diagram of the HIPS process

Expanded polystyrene (EPS) process

Suspension polymerization is still the most widely used process in the field of production.
to large volumes of expanded polystyrene. This is a batch process that allows for the conversion of styrene.
monomer in expanded polystyrene beads through radical polymerization. In general, styrene is
dispersed under agitation in the aqueous phase containing some suspending agents and/or colloids
protectors as well as some secondary ingredients such as electrolytes. It is possible to use both
Organic suspension agents than minerals. Organic peroxides are mixed with styrene.
before its dispersion in the aqueous phase.
Then, the polymerization follows a process that gradually increases the temperature of the reactive mixture.
towards the almost total conversion of the monomer into polymer. Pentane, which is a mixture of pentane
normal and isopentane is added as a blowing agent during polymerization.
The type and quality of the suspension agent and the reaction temperature profile are two factors
crucial for ensuring proper suspension stability, a grain size distribution of the ball
as well as a high conversion rate. These parameters also affect the properties of the final product.
A brominated aliphatic compound is specifically added for the production of fire-resistant qualities.
At the end of the polymerization, the suspension is cooled, the expanded polystyrene beads are separated by
spinning, they are then washed and dried at a relatively low temperature of 35°C.
After this operation, the beads are then sieved into many granular size fractions to
respond to the numerous applications as well as the various business needs. They are then
coated to improve both processing characteristics and the final product's suitability for use.
Then, a final phase consists of packing and storing these expanded polystyrene beads in
containers or in silos designed for transport.
 3. Polymer and environment
General grade polystyrene

This table indicates the source of emissions and waste during the GPPS production cycle.

High impact polystyrene

This table indicates the source of emissions and waste during the HIPS production cycle.
Expanded polystyrene

This table indicates the source of emissions and waste during the PSE production cycle.