Polystyrene

Polystyrene is a versatile polymer with a broad range

of applications.
40% - packaging and single-use applications (film
and sheet)
About 30% - electronics and appliances
Balance - kitchen, laboratory, office, and medical
goods and furniture and in building and
construction
 Two Main Technologies:

 BP/Lummus Technology –
Robert Stepanian, ABB Lummus Global
Bloomfield, New Jersey

 Polimeri Europa Technology –

Francesco Pasquali and Riccardo
Inglese, "C. Buonerba" Research
Centre Mantova, Italy
BP/LUMMUS TECHNOLOGY FOR THE
PRODUCTION OF EXPANDABLE
POLYSTYRENE
Expandable polystyrene (EPS) beads
- tiny spheres of general-purpose
polystyrene impregnated with a physical
blowing agent (usually pentane).
 Characteristics of EPS Beads:
 good thermal insulation and shock-absorbing
properties
 high compressive strength
 very low density and is resistant to moisture
The Two Major End Uses for EPS
1. Packaging
2. Insulation/
construction — account
for over 85% of EPS
demand.

- Other uses
include shipping
containers, furniture, ice
chests, and helmet
liners.
 Polymerization Steps
Initiation - the double bond on the carbon atom is broken
to form a free radical.

Propagation - the highly unstable free radical combines

with another styrene molecule, forming a new free radical.

Termination - two free radicals

can combine to terminate a
chain, or other chemicals can
be used to terminate a chain.
 Process Description

The BP/Lummus styrene polymerization technology of

expandable polystyrene (EPS) is a batch suspension process
followed by continuous dewatering, drying, and size
classification.
 Characteristics & Advantages

 Consistently high-quality product

 Narrow bead size distribution
 High reactor productivity
 Fines recycle
BP/LUMMUS TECHNOLOGY FOR
THE PRODUCTION OF GENERAL-
PURPOSE AND HIGH-IMPACT
POLYSTYRENES
General-purpose (also known as crystal)
polystyrene (GPPS)
• most efficient process for
producing crystal polystyrene
• styrene homopolymer
• high clarity
• fairly good mechanical
properties
• easy to process into most
types of objects
• relatively brittle
 High-impact polystyrene (HIPS)
• contains an elastomer (usually polybutadiene
rubber)
• tougher than general-purpose polystyrene but
still has good processability

Additives ~ used to impart specific properties

 Process Description

This technology uses a bulk continuous process. GPPS & HIPS

are essentially the same except for the initial rubber-
dissolution for HIPS
 Characteristics
 Large single-train capacity
 Consistently high product quality
 Broad product line
 High reactor productivity, better
plug-flow characteristics with
excellent temperature control
 Chemically initiated
polymerization
 Efficient devolatilization system
 Low capital cost
 Unit flexibility
 Better turndown capability
 Characteristics
 Large single-train capacity
 Consistently high product quality
 Broad product line
 High reactor productivity, better
plug-flow characteristics with
excellent temperature control
 Chemically initiated
polymerization
 Efficient devolatilization system
 Low capital cost
 Unit flexibility
 Better turndown capability
 POLIMERI EUROPA GENERAL-
PURPOSE POLYSTYRENE PROCESS
TECHNOLOGY
 Main Features
• Proprietary, accurate process and mechanical
design of key equipment
• Simple process scheme and easy process control
• Flexible technology
• Minimum quantity of foreign materials
introduced in the process
 Process Chemistry
GPPS process is based on the radical
polymerization of styrene.

4 Distinct Steps:
1. Initiation of Radical Formation
2. Initiation of Chain Formation
3. Propagation
4. Termination
 Thermal Decomposition of
Initiators
 only the peroxides find extensive use as
radical sources
 peroxidic initiator thermally decomposes via
homolytic cleavage of the O—O bond
 Polymer Chain Initiation

 radical formed by peroxide scission can react

with styrene, promoting the formation of a
styrenic radical
 Propagation
 initiated monomer radical propagation

 final polymer monomer units arrangement

 Termination
1. Combination termination or coupling

2. Disproportion termination

At temperatures up to 80°C, termination occurs

almost exclusively by combination
 Side Reactions: Oligomers
 Diels-Alder reaction competes with polymer chain propagation
and leads to the formation of dimers and trimers.
 Residual oligomers in the polymer bulk can have a serious effect
on its final properties and its behavior during processing at the
end user
 Typical thermally initiated commercial polystyrene could contain
up to 0.1 wt % total dimer and 1.0 wt % total trimer
 Process Flow

Polimeri Europa GPPS technology is based on a continuous-

mass, peroxide-initiated polymerization. The mass reaction
occurs in the presence of solvent (ethylbenzene, typically 5 to
10 percent)
 Process Advanced Design
Features
Polymerization Section
 two continuous stirred tank reactors (CSTRs) with
optimized design of the stirrer in such a way as to
ensure the better compromise between thermal
control and polymer production rate

Devolatilization section
 two-stage section with high heat and mass transfer
rates, at very low residence times
 Condensation Section
 allows customization of the balance between product
purification from low-molecular-weight components
(waxes) and specific raw materials consumption

Raw Materials Feed Section

 raw materials are fed to a purification section designed
to selectively remove impurities
 chemical feeding system and mixing facilities provide
the most efficient balance between additive
concentration and their effect on polymer properties
 Plant Layout
 integrated process and the mechanical design of the
equipment around the reaction and devolatilization
sections maximize the efficiency of the plant
 leads to a production unit having the best compromise
between investment cost and
manufacturing/maintenance operability.

Flexibility
 can match any requirements in terms of product
portfolio
POLIMERI EUROPA EXPANDABLE
POLYSTYRENE PROCESS
TECHNOLOGY
 Process Chemistry
based on a batch water suspension
polymerization
styrene is dispersed in small droplets inside the
water phase in an agitated reactor
4 Distinct Steps:
1. Initiation of Radical Formation
2. Initiation of Chain Formation
3. Propagation
4. Termination
 Residual Volatile Content
 important target is to reach a very low amount
of residual volatile content in EPS beads

Coating Technology
 greatly influences final EPS performance
during both processing and final use
 Process Flow

Polimeri Europa EPS technology is a typical batch suspension

polymerization with an inorganic suspending agent.
 Process Advanced Design
Features
Polymerization Section
 impregnation of the beads with a prefoaming agent is
done thus avoiding a further and expensive steeping
phase
Coating Section
 able to fully tailor EPS grades to the desired customer
needs
Flexibility
 can match any possible requirement in terms of
product portfolio, keeping the polymer quality at the
top level
POLIMERI EUROPA HIGH-
IMPACT POLYSTYRENE
PROCESS TECHNOLOGY
 Process Chemistry
most common method for manufacturing HIPS
consists of dissolving polybutadiene rubber
(PBU) in styrene monomer and polymerizing
the mixture in a first reaction step in the
presence of peroxide initiators, chain-transfer
agents, and antioxidants until a conversion of
about 30 percent is reached
 Phase Inversion
Occurs when the volume of the PS-styrene
solution becomes greater than the other phase
solution
PS-styrene solution becomes the continuous
phase, and the PBU-styrene solution becomes the
disperse phase, occurring as droplets suspended in
the continuous phase
Accompanied by a sharp decrease in solution
viscosity
 Grafting Reaction
start with a primary radical attack on the rubber
backbone; most authors describe this reaction
as hydrogen abstraction from the allylic
position in the polybutadiene molecule:

graft copolymer acts as a polymeric emulsifier,

stabilizing the droplets and reducing droplet size.
 Cross-Linking Mechanism
created in the devolatilization step of the
continuous process
prevents particle breakdown during fabrication
processes
 Process Flow

Based on a continuous mass peroxide-initiated polymerization.

HIPS is obtained by polymerization of styrene in a rubber-
styrene solution
 Process Advanced Design
Features
Polymerization Section
 three full plug-flow reactors (PFRs) characterized by
very precise control of the thermal reaction profile

Devolatilization Section
 allows producers to customize the balance between
product purification from low-molecular-weight
components (waxes) and raw materials specific
consumption
 Condensation Section
 allows customization of the balance between product
purification from low-molecular-weight components
(waxes) and specific raw materials consumption

Raw Materials Feed Section

 chemical feeding system and mixing facilities provide
the most efficient balance between additive
concentration and their effect on polymer properties
 Plant Layout
 leads to a production unit having the best compromise
between investment cost and
manufacturing/maintenance operability.

Flexibility
 can match any requirements in terms of product
portfolio, keeping the polymer quality at the top level