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
