PERP Program - Polystyrene

New Report Alert

May 2006

Nexant’s ChemSystems Process Evaluation/Research Planning program has published a new report,
Polystyrene (04/05-4). To view the table of contents or order this report, please click on the link
below:
http://www.nexant.com/products/csreports/index.asp?body=http://www.chemsystems.com/reports/show_cat.cfm?catID=2

Introduction

Polystyrene is a thermoplastic resin that is able to serve many end uses due to its low cost, ease of
processability, and performance properties. 2003 marked the 65th anniversary of Dow Chemical’s
successful commercialization of the polymer in the United States. A number of polystyrene
producers have made their technology available for licensing, including a continuous mass process
from Innovene and ABB Lummus, as well as technology from Shaw/Stone and Webster and Nippon
Steel’s process from Toyo Styrene Company.

Polystyrene is categorized into four fundamental types:

• General Purpose Polystyrene (GPPS)

• High Impact Polystyrene (HIPS)
• Expandable Polystyrene (EPS)
• Syndiotactic Polystyrene (SPS)

Within these broad categories, there are numerous grades, including:

• High Temperature Resistant (HTR)

• Environmental Stress Cracking Resistant (ESCR)
• Flame Retardant (FR)
• Medium Impact Polystyrene (MIPS)
• Super-high Impact Polystyrene (SHIPS)
• Low Residual Monomer (LRM)
• High Gloss

The polystyrene homopolymer is amorphous; it is clear and colorless and exhibits excellent optical
properties, along with high stiffness and good mechanical strength. Above the glass transition
temperature (Tg, around 100ºC), polystyrene is easily molded with less input energy than crystalline
polymers because of its high melt strength and heat of crystallization. Polystyrene also has a low
mold shrinkage rate (0.004 to 0.007 inch per inch) which is less than the shrinkage rate of crystalline
 -2-

thermoplastics (polyethylene and polypropylene), giving it a molding advantage with respect to rates
and scrap.

GPPS resins are generally available with melt flows of 1 to 20. Typical GPPS resin properties are
shown in Table 1.

Table 1
Typical GPPS Resin Properties

Specific gravity 1.04

Melt flow, g/10 min. 1-20
Tensile strength, psi 5,000-7,500(1)
Flexural strengths, psi 17,000-15,000¹
Tensile elongation to break, % 2-3
Flexural modulus, psi 450,000-500,000¹
Vicat softening temperature, °F 195-228

(1) The higher ranges represent high heat (high molecular weight)
resin grades.

High temperature resistant grades of polystyrene are also commercially available for use in
applications that require resistance to high temperature distortion. These are higher molecular
weight resins (lower flow) and they exhibit better mechanical properties than traditional GPPS.

Styrene polymers are nonpolar; they are chemically inert and resistant to water. This gives them
favorable property advantages for use in electronics, food, automotive, and other applications.
Polystyrene homopolymers have good UV stability and resistance to gamma-radiation, allowing
them be used in fabricated products subjected to sterilization.

Overall, polystyrene is a brittle material; however, it also exhibits high stiffness. A type of
polystyrene referred to as oriented polystyrene (OPS) acquires a biaxial orientation during
fabrication. This offers significantly enhanced mechanical properties and toughness (tensile strength
can be doubled and elongation increased twenty fold).

Rubber-modified polystyrene grades were developed in the 1950s to enhance mechanical properties.
They are manufactured by introducing rubber, typically polybutadiene, into the polymerization
system, which creates a two phase polymer system consisting of a dispersed rubber phase and a
continuous polystyrene phase. Impact-resistant grades are known for their rigidity, impact strength,
and good dimensional stability, and typically these grades have less heat, chemical, and UV
resistance than the homopolymer.

Product development in the polystyrene industry has primarily been focused on impact polystyrene
with respect to rubber efficiency and enhanced or improved properties. Typical impact grades
 -3-

include ESCR, FR, SHIPS and high gloss, chemical, and chlorofluorocarbon (CFC) resistant
products. HIPS resins are typically white, but there are specialty clear resins that are commercially
available. Many producers are targeting polystyrene to compete with engineering resin applications
where the conventionally used materials are "over-engineered."

Typical properties of impact polystyrene are shown in Table 2. The impact grades - medium, high
and super high - are generally categorized by Izod impact strength.

Table 2
Typical Properties of Impact Polystyrene (1)

Medium impact, Izod, ft-lb/in 0.5-1.4

High impact 1.5-2.5
Super high impact More than 2.5
Melt flow, g/10 min 2-15
Tensile strength, psi 3,000-7,000
Flexural strength, psi 2,000-8,000
Tensile elongation to break, % 15-65
Flexural modulus, psi 270,000-420,000
Vicat softening temperature, °F 185-225

(1) Properties are dependent on rubber and additive content.

Expandable polystyrene (EPS) is another commercial form of polystyrene, and it is used in

insulating and crush resistant applications (cups, home insulation, packaging). Flame retardant EPS
grades are also available and are used in building and construction. EPS is manufactured by
introducing a blowing agent such as pentane or isopentane in-situ or into the post-process in order to
form polystyrene beads with a typical diameter of 0.01 to 0.10 inches and a density of 1 to 3 pounds
per cubic foot. Foamed sheet can also be produced by extruding solid polystyrene (GPPS) by using
blowing agents in the extrusion step.

Syndiotactic polystyrene (SPS) is a relatively new form of the polymer first synthesized in 1985
according to Idemitsu. The material is particularly interesting because it offers the potential to
overcome one of amorphous polystyrene's primary deficiencies - a low heat distortion temperature.
It is crystalline in nature; its highly regular structure gives the polymer the important feature of a
melting point of 270°C, which is in the range of commonly used engineering polymers such as nylon
or polyacetal. (Normal or "atactic" polystyrene has no order with regard to the side of the chain on
which the phenyl groups are attached). Typical properties of SPS are shown in Table 3.
 -4-

Table 3
Typical Properties of Syndiotactic Polystyrene

Specific gravity 1.02

Mold shrinkage, in/in 0.008-0.010
Tensile yield, psi 6,580
Tensile break, psi 6,580
Tensile elongation, % 30
Tensile modulus, psi 380,000
Flexural strength, psi 11,600
Flexural modulus, psi 465,000
Notched Izod impact , ft-lb/in 1.2

In addition to the polystyrene homopolymer and impact copolymers, other styrenic copolymers and
terpolymers have been commercialized to enhance performance properties. Some of the key resins
include styrene-acrylonitrile (SAN), styrene-butadiene-styrene (SBS), acrylonitrile-butadiene-
styrene (ABS), and styrene maleic anhydride (SMA).

Chemistry

There are three structural forms of polystyrene that can be prepared from styrene: atactic,
syndiotactic, and isotactic.

In atactic polystyrene, the phenyl groups are randomly placed on either side of the extended carbon
chain. Atactic polystyrene is an amorphous material due to the high degree of random placement of
the phenyl groups relative to the backbone. This type of polystyrene is the most common and well-
known polymer, with widespread uses in packaging and durable goods. Consumption has steadily
increased due to the excellent balance between cost and performance. In particular, the two most
important property advantages afforded by polystyrene over similarly priced materials are stiffness
(or rigidity) and processability. Primary weaknesses include brittleness (or low impact strength) and
a low heat distortion temperature. Although brittleness can be improved with the addition of a
rubbery phase, as is done in preparing high impact polystyrene grades, the deficiency related to heat
distortion remains problematic.

In syndiotactic polystyrene (SPS), the phenyl groups alternate regularly from one side of the
extended chain to the other. The highly regular structure of SPS gives it crystalline properties,
similar to engineering polymers such as nylon or polyacetal.

In isotactic polystyrene, all the phenyl groups are on the same side of the stretched chain. Isotactic
polystyrene has been synthesized using Ziegler-Natta catalyst systems. The material is highly
 -5-

crystalline with a high melting point generally accepted to be about 240°C. This form of polystyrene
is not commercially viable due to its slow crystallization rate.

The formation of polystyrene is represented by the following exothermic reaction (with a heat of
polymerization of about 165 calories per gram, 300 Btu per pound):

CH CH2 CH CH2

n
Styrene Polystyrene
G:\2000Q1\IBM\PERP\ITXUW\RP\ITXUW-1.CDX

The molecule acts as both an electron donor and an electron withdrawing center. Styrene and its
substituted derivatives can be polymerized via four different mechanisms; free radical, anionic,
cationic, and Ziegler. However, the free radical mechanism has the most commercial relevance.

When heated to more than 100ºC, styrene is capable of undergoing thermal or spontaneous
polymerization, resulting in high conversion and a suitable molecular weight. In this system, the
temperature typically increases from 100°C to 220°C across three stages of polymerization as the
conversion of styrene increases.

Polymerization can be initiated either thermally or by using chemical initiators such as peroxides.
Both types of initiation are commercially practiced in general purpose polystyrene (GPPS) and high
impact polystyrene (HIPS) manufacturing. The method chosen largely depends on the producers'
choice of operating conditions.

Copolymerization – High Impact Polystyrene (HIPS)

Rubber addition to polystyrene enhances resin impact strength. The system is made up of a
dispersed rubber phase and a continuous polystyrene phase. The rubber initiates crazes in
polystyrene without crack formation during elongation or impact, yielding a tough, impact resistant
resin.

To improve compatibility, rubber is grafted to the polystyrene backbone. Typically, the rubber used
is cis-polybutadiene, although copolymers with styrene and ethylene-propylene copolymers and
terpolymers can also be used. The latter provides impact strength with improved outside aging
resistance.

In bulk polymerization, grafting occurs when styrene free-radicals react with the rubber. Copolymer
grafting is important because it occurs at the interface of the two phases and affects resin
morphology and mechanical properties (impact strength).
 -6-

The mechanism is believed to take place according to the following equations:

R + ( CH2 CH CH CH2 )n ( CH CH CH CH2 )n + RH

CH CH2 CH CH2
( CH CH CH CH2 )n +
( CH CH CH CH2 )n

2001Q1\ITXUW-4.CDX

Process Description

Polystyrene has been commercialized for more than 50 years and is produced by several companies
around the world. The bulk process, also known as the solution or mass process, is by far the most
dominant commercial route, with the suspension process only being used for specialty grades.

While there are more than a dozen different technologies used in commercial operations throughout
the world, they all employ the same fundamental steps. The various processes are distinguished by
the specific hardware and configurations, as well as variations in operating conditions.

Polymerization Reactor Design

A primary feature that characterizes commercial processes is reactor design and configuration. The
key characteristics of the reactors are the method of heat removal, degree of axial mixing (end to
end), degree of radial mixing (side to side), and the number of reactors in series, which includes any
prepolymerizer.

Removal of polymerization heat for temperature control is accomplished by quench with added cold
monomer and diluent, conductive heat removal by transfer surfaces, and reflux cooling.
Commercially, both conductive and reflux cooling systems are employed, as the quench method
alone is insufficient to remove polymerization heat. The cooling method does not affect the quality
of the polymer, and the method chosen is generally up to the producer.

The degree of radial and axial mixing determines product characteristics and properties, regardless
of the heat transfer method. Radial mixing is necessary to prevent temperature and concentration
gradients across the reactor, which can lead to polymer layer formation on the vessel walls, resulting
in poor process control (low heat transfer) and poor product quality (gel formation).
Boiling continuous stirred tank reactors (CSTR) are now commonly used commercially. The reactor
operates at a capacity less than 70 percent or maximum to allow freeboard for foaming and boiling.
These reactors allow for a high degree of redial and axial mixing to be achieved, and the type of
 -7-

agitator used (e.g. turbine, anchor, or helical) depends on the viscosity of the reactor contents. An
external recirculation loop is used to remove heat via condensing and refluxing.

Another reactor system used for polystyrene has a recirculating loop with static mixer reactors
arranged in the loop. In this system, a high degree of heat removal is achieved due to high flow and
multiple tube bundles, which results in good radial and axial mixing.

The second generation tower reactor is also commercially important. This reactor incorporates
alternating rows of heat transfer tubes and agitator blades, allowing for a high degree of radial
mixing and a moderate degree of axial mixing with good heat removal.

A further type of reactor used is horizontal and segmented with an agitation combination that
provides a high degree of radial mixing and moderate axial mixing in each section, simulating plug
flow, with a uniform temperature gradient along the reactor. The plug flow characteristic allows for
faster, more distinct transitions between products and more uniform particle size distribution. Both
latent and conductive heat-based removal systems are used commercially in this type of reactor.

Devolatilization

In the polystyrene industry, an important issue is the product’s level of residual monomer, which
becomes particularly critical in food packaging applications. Typically, 300-400 ppm are permitted
in food applications and 500-600 ppm in non-food applications. Low residual monomer (LRM)
grades containing only about 175 ppm are also commercially available.

Existing techniques for devolatilizing polymers are falling strand devolatilization (FSD),
devolatilizing extrusion, and wiped film evaporation, with FSD being the more commonly used
method. In the FSD method, melt from the reactors is preheated (to about 220ºC to 250ºC) and fed
as strands to a jacketed flash vessel that is operated at a vacuum.

Although it gives producers flexibility of homogeneously incorporating additives into the product
prior to pelletizing, devolatilizing extrusion is costly in terms of investment and operating costs,
mainly power, and is therefore not widely used.

In a wiped film evaporator, a thin film of polymer is deposited on the heated wall of the vessel to
effect devolatilization. A countercurrent stream of inert vapor can be used to enhance monomer
stripping. This technique is rarely used commercially due to the high investment and operating
costs.

Another general technique that is used to improve devolatilization is introduction of a chemical aid
that has some solubility in the molten polymer but can be easily diffused. The aid acts as a stripping
medium, as it lowers the partial pressure of monomers in the melt, and it is also reported to cause
some foaming that enhances the amount of surface area for monomer removal. Typical aids include
water and methanol.
 -8-

Copolymerization

All processes in the production of high impact polystyrene start by grinding the baled rubber and
dissolving it in styrene monomer. As the homogeneous styrene-polybutadiene polymerization
proceeds, a two phase system forms when the conversion to polystyrene exceeds 1.0 percent. A
dispersed phase of polystyrene in styrene droplets separates out of the continuous phase of
polybutadiene in styrene. The droplets are stabilized by the graft copolymer, and larger droplets
form. At this point, agitation is critical and high shear mixers are used to prevent coalescence of the
droplets.

As polymerization proceeds, the polystyrene phase volume increases and the polybutadiene phase
volume decreases. At a conversion of 8 to 12 percent, the phase volumes are approximately equal
and, under intense agitation, phase inversion takes place and polystyrene in styrene becomes the
continuous phase.

Particle size and distribution are controlled by the applied shear rate at phase inversion; factors such
as viscosity and intersurface tension are also important. Once the phase inversion occurs,
subsequent styrene polymerization takes place in both phases, and low speed nonshearing agitation
is used to keep the polystyrene within the rubber particles. Once the required rubber phase is
established, it is important not to have excessive crosslinking.

Economics
Figure 1
Comparison of Polystyrene Production Costs
Cents Per Pound

General Purpose High Impact Expandable

Raw Materials Utilities Fixed Costs Depreciation 10% ROCE

 -9-

Polystyrene Market

United States

Demand for GPPS and HIPS recovered in 2004 and 2005 after a decline in 2003. The packaging
and electronic segments enjoyed the strongest growth, while the construction segment improved due
to a healthy housing industry.

Overall polystyrene growth is mature when compared with other polymers. It is relatively a more
expensive polymer, even more so considering the current high benzene costs for feedstock. As
prices increase, inter-material competition, especially in packaging, will continue to be a threat and
keep demand growth somewhat limited. Polystyrene mainly competes with polypropylene;
however, it also experiences competition from other polyolefins. Over the last five years, the price
of polystyrene has exceeded polypropylene by approximately $200 per ton, and this gap has
hindered the use of polystyrene in applications where the polymers are easily interchangeable.
However, there are end-uses that are specific to each polymer. Crystal polystyrene has better
stiffness and clarity than polypropylene, and is preferred for glass-replacement and cutlery end-uses.
Impact polystyrene extruded sheets are as tough as polypropylene, but are more easily
thermoformed, for applications like refrigerator liners.

Packaging comprises the largest end use application, representing about 58 percent of the
GPPS/HIPS consumption in the United States in 2005. Most packaging grades are used in the food
industry and include both foam and clear, oriented polystyrene single use containers for “take out”
meals. Polystyrene remains an excellent packaging material because of its light weight, strength and
insulation properties. Other packaging applications include DVD and CD-ROM cases. Packaging
will continue to drive the demand for polystyrene.

The consumer electronics and office equipment markets continued to grow in 2005. Polystyrene is
widely used in the components of personal computers, peripherals, printers, electronics products and
small appliances. This market however, remains extremely competitive.

Figure 2 shows the breakdown of U.S. polystyrene consumption by end use for 2005.
 - 10 -

Figure 2
United States Polystyrene Consumption by End Use, 2005

Resellers and
Electronics
compounders
9%
15%

Private
Consumption
10%

Construction
7%

Packaging
59%
C:\missing PS Perp tables section 5.xls\figures pies

Western Europe

In 2005, the polystyrene market suffered from overcapacity and relatively poor margins. Activity in
the packaging sector in Germany has been fairly modest. The strength of the Euro has affected
exports of lower-value finished goods from countries across the region. France and Spain have seen
a more robust growth with healthy increases in domestic consumption, while Italy experienced
lackluster growth.

Historically, polystyrene prices have been higher than many thermoplastics, underpinned by the high
cost of styrene. Despite the higher prices, its use in sectors such as food packaging has grown as a
result of its easy proccessability relative to other thermoplastics. The recent large price premium
over polypropylene has significantly impacted demand in disposable applications.

Packaging remains the largest end-use sector, accounting for 50 percent of consumption. Consumer
products account for the other most significant end use sector, where polystyrene is utilized for
applications such as refrigeration units, television, computer, housing and toys. In these areas,
polystyrene has had some success in substituting for engineering plastics such as ABS.

Polystyrene consumption represents a relatively mature market in Western Europe, and projected
growth rates are expected to be below global economic growth.
 - 11 -

Asia Pacific

Polystyrene demand is growing rapidly due to both local consumption and the manufacture of goods
for export. Polystyrene has had some success in substituting for engineering plastics such as ABS.
Further developments are expected to continue to target markets where ABS and polycarbonate are
in common use. The appliance sector comprises some of the higher specification uses for
polystyrene, and these can offer better margins than typical packaging applications.

The demand from the food packaging and consumer products sectors will continue to grow as a
result of its easy processability and favorable properties relative to other thermoplastics, despite its
frequently higher cost.

China accounts for a large proportion of the growth, and its consumption overtook the United States
to become the largest market for GPPS in 2001. Consumer products such as refrigeration units,
televisions, computers, and housing constitute one major application group, with the other being
disposable housewares and food packaging.

In Japan, polystyrene consumption growth has resumed after a period of decline. Long-term growth
is expected to be minimal.

South Korean polystyrene consumption growth has been relatively buoyant despite the maturity of
some market sectors. South Korea and Japan have focused on supplying higher end polystyrene
goods to China, rather than competing in lower specification applications. Demand growth in
electronics manufacturing is forecast at a lower level in these countries due to their high costs
relative to China.

Demand, supply, and trade estimates are provided for the United States, Western Europe, and Asia
Pacific for the period 2003 to 2010, both for solid and expandable polystyrenes.

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