Polystyrene and

Styrene Copolymers:
Their Manufacture and
Application. II

Ping L. Ku
PLK Consultant
10951 Stepney Road
Chester, Virginia 23831

HIGH IMPACT POLYSTYRENE (HIPS) Manufacture

Bulk Polymerization (Continuous)

Introduction
High impact polystyrene (HIPS) is generally pol-
ystyrene reinforced with a rubbery butadiene polymer.
It may be a blend or a graft copolymer. The former
results in little or no change in the properties of PS;
the latter, based on the amount of PBD incorporated,
shows a great improvement in impact strength and
other properties. The improved properties of rubber-
modified PS lead to a great increase of applications
for HIPS.
(see Flow Diagram, Figure I )
Many blending experiments have shown that the
properties are much inferior in comparison to those
from chemical grafting. The blends of latexes of com-
parable molecular weights are not exceptional. There-
fore, some discussion focusing on the practice of graft-
ing is deemed necessary.
a. Types of Rubber. There are many elastomers
that can be used for grafting. They can generally be
classified into three categories: (1) homopolybuta-
diene, (2) polybutadiene-styrene copolymers, includ-
ing block copolymers, and (3) saturated elastomers
(polyolefinic copolymers).
(1) Among the homopolybutadienes, the cis con-
figuration polybutadiene derived from 1,4 polymeri-
zation of BD is greatly favored. Homopoly BD may
also have pendant vinyl groups from 1,2 polymerized

Advances in Polymer Technology, Vol. 8, No. 3, 201-223 (1988)

8 1988 by John Wiley & Sons, Inc. CCC 0730-6679/88/030201-23$04.00
 POLYSTYRENE AND COPOLYMERS. I1

FIGURE 1
Flow diagram of
continuous bulk
polymerization of

1
PS, SAN, HIPS,
ABS, etc.:
(1) monomer feed
tanks; (2) line
mixer; (3) rubber
grinder; (4) rubber
dissolver;
(5) additive vessel;
(6) cartridge filters;
1
U I
(7) preheating I I
exchangers;
(8) prepolyrnerizer;
(913 (lo), (11)
reactors nos.
1, 2,3;
(12) preheater;
(13) devolatilizer;
(14) cooling trough;
(15) pelletizer;
(16) storage;
(1 7) refrigeration;
(18) condenser;
(19) monorner-
diluent storage.

butadiene. Other homopolymers such as polybutene,
isoprene, and neoprene are also mentioned for graft-
ing. The latter has some slow-burning effects.
In addition to these many types of rubber, there are
high and low molecular weight grades, like Diene 55
and Diene 35, meaning Mooney viscosities of 55 and
35, respectively. These, plus hot and cold polymer-
ization processes, make the selection of elastomers
for graft polymerization very complex.
(2) Polybutadiene-styrene copolymers can be formed
in any proportion. The T,'s of the copolymers vary
in an almost linear manner with the proportion of the
styrene present. High-styrene SBR resins will be dis-
cussed in the section on Styrene-Butadiene Latex, but
in latex form only.
SBR, the world's most important rubber, is mainly
used for automobile tires. The elastomer can also be
used in the same manner as PBD, as a backbone to
be grafted with styrene, and as an impact modifier.
Polyisoprene.is a natural rubber with a high cis con-
tent, which can be used as an impact modifier, but
the quality of rubber varies widely because of low
processing efficiency. The former is generally selected
for use in HIPS.
SBR now has also been developed in the form of
block copolymers, both diblock (SB) and triblock (SBS)
copolymers. They also can be used as backbones for
grafting in HIPS polymerization, or they can be po-
lyblended with PS homopolymer to produce HIPS
directly. These block copolymers will be discussed in
the section on Styrene-Butadiene Block Copoly-
mers-Plastics.
(3) Saturated elastomers are derived from olefinic
monomers. EPDM, for instance, is made by the co-
polymerization of ethylene-propylene, using hetero-
geneous catalysts. Here the grafting of styrene is not
due to the opening of a double bond, but is due to
hydrogen abstraction. The resultant properties are only
moderately high, but costly; the use of these elasto-
mers for HIPS is very limited.
b. Grafting. Graft polymers can be formed by many
techniques. The free radical polymerization technique
is the one most used. The chain transfer agent is in-
volved in the transfer of an atom between a radical
and a molecule, polymer or monomer, saturated or
unsaturated. Transfer to polymer, and transfer to mon-
omer with subsequent polymerization through double
bonds may lead to the formation of branched mole-
cules.
Or, in many instances, the transfer involves abstrac-
tion of a hydrogen atom such as

202 VOL. 8,NO. 3


Ultraviolet, ionizing radiation, and redox initiation are
among the techniques that can also be used to produce
the polymeric radicals leading to graft copolymeri-
zation.
Conventional grafting practice applies primarily to
PBD. If other rubber molecules of different structures
are used, the degree of grafting will be different. The
characteristics of the double bond are different, de-
pending on whether or not it has different groups on
its adjacent carbon atoms. Protons are more or less
labile because of the different structures of these rub-
ber molecules. Furthermore, the type of initiator is
also very influential in the grafting process.
c. Constitution of Graft Copolymers. It appears
that the degree of grafting is crucial. Polybutadiene
is a linear molecule with a double bond at every fourth
bond in the main chain. It is often used as a backbone
for grafting. The question arises as to how many of
the double bonds in PBD are used up. Normally, 5-
10% of rubber is used in HIPS polymerization. Some
data in the literature indicate that a great deal of hom-
opolystyrene is formed as the matrix. The grafted
molecules are discrete particles or domains distributed
in the PS matrix, as evidenced by transmission elec-
tron microscopy (TEM). It seems that the determi-
nation of the degree of grafting or the amount of
grafted polystyrene is crucial. Generally, the Izod test
shows that the more rubber used, the higher the impact
strength is.
d. Raw Materials. Raw materials used in HIPS
are the same as used in crystal PS, plus rubber, often
with additional ethylbenzene, UV stabilizers, pig-
ments, and mineral oil.
Reactors and Auxiliary Equipment.
Rubber grinder-to cut rubber into small pieces
for fast dissolving
Dissolver-to dissolve rubber in styrene
Heat exchangers and condensers-to heat or cool
the prepolymerizer and to condense the vapors
Pumps-various sizes to pump water, steam,
monomer, rubber solution, heating oil, poly-
meric materials, condensates, etc.
Feed tank-to store the rubber solution
(6) Cartridge filters-to filter the rubber solution prior
to polymerization
ADVANCES IN POLYMER TECHNOLOGY
POLYSTYRENE AND COPOLYMERS. II
(7) Motionless line mixers-to mix the additives, if
needed (chain transfer agent, crosslinking agents,
stabilizers, etc.)
(8) Prepolymerization reactor-to start the poly-
merization of the rubber solution
(9) A series of reactors-to react in a continuous
fashion
(10) Devolatilizer-to remove diluent and unreacted
monomers
(1 1) Refrigerator system-to condense vapors
(12) Vacuum system-to vaporize diluent and mon-
omers
(13) Instrument panel-to control all polymerization
conditions
(14) Storage tanks-to store recovered materials
(15) Pressure, temperature, and level gauges-to re-
cord conditions at various points
(16) Other miscellaneous items-to aid the process
f. Procedures and Reaction Conditions. The ma-
jor steps for manufacturing HIPS are as follows:
(1) Styrene and ethylbenzene are charged into the
dissolver
(2) Rubber is ground and dropped into the dissolver.
The dissolver is heated to 50°C
(3) A batch of additive solution is prepared by dis-
solving necessary additives in ethylbenzene in a
small storage tank
(4) The rubber solution and the additive solution are
fed into a line mixer at the calculated rates. The
mixed solution enters the heat exchanger at 70°C
for preheating
( 5 ) The prepolymerizer is filled with a nitrogen blan-
ket
(6) When material starts to enter the prepolymerizer,
the stirrer is started at 50 rpm and the prepoly-
merizer is heated to 80°C
(7) The prepolymerizer is set to run automatically
at the 75% liquid level
(8) Prepolymerization is watched periodically h m g h
the sight glass
(9) At 75% liquid level, the bottom pump starts au-
tomatically at the same rate as the rate of feed
into the prepolymerizer. Pressure is 10 psig. The
pump transfers material into the no. 1 reactor.
Control samples are taken at the exit from the
prepolymerizer. The recycle pump starts
(10) When the no. 1 reactor is filled, the bottom pump
starts feeding to the no. 2 reactor
(11) Reactor no. 2 is set at 105"C, 14 psig, 20 rpm.
Samples are taken to measure conversion
203
 POLYSTYRENE AND COPOLYMERS. II

(12) When the no. 2 reactor is filled, the material
enters zone A and then zone B of the no. 3
reactor, which is set at 11O"C, 15 psig, and 10
rpm (the top sample valves are open, until the
material comes out from the valve, meaning the
reactor is filled)
(13) When the material shows at the top samplevalve,
the pump on the top of the no. 3 reactor is started
to feed to the heat exchanger
(14) The vacuum and cooling systems of the devo-
latilizerareinoperationwith1mmHgand -5T,
ready to receive the highly viscous material
(15) The transfer line from reactor no. 3 to the de-
volatilizer is oil-heated to 250°C and operated at
60 psig. Material enters at the top of the devo-
latilizer and flows down along the wall to the
bottom. Chamber pressure is 1 mm Hg and tem-
perature is 260°C
(16) When the liquid level in the devolatilizerreaches
about 24 in., the bottom pump starts to feed the
material into the strand die, from which strands
flow down and emerge into the water cooling
bath
(17) The rest of the operationis the same as for crystal
PS
(18) After startup, polymerization is allowed to run
4 h, twice the residence time; then samples are
taken and analyzed, and operating conditions are
recorded. These process control checks are re-
peated after another 8 h
(19) After another 16 h, process controls are repeated.
Bottom pumps may need adjustment
(20) If reproducibility is satisfactory, process control
checks are repeated every 12 h
The product is an opaque white pellet. It has a
specific gravity of 1.05. With this new, more eco-
nomical process, the price becomes attractive enough
to compete with polypropylene and ABS.
Suspension Polymerization (Batch Operation)
(See Flow Diagram, Figure 2 )
The following HIPS process, used by most man-
ufacturers throughout the last two decades, is now
being phased out. Its downstream operations after
polymerization are very costly. Practically all man-
ufacturers have switched to the new continuous bulk
process in order to stay in business.
a. Raw Materials. Besides those described in the
continuous bulk process, deionized water, poly(viny1
alcohol), and suspending agents are needed.
b. Reactors and Other Equipment. Suspension
reactor, washing tanks, storage tanks, centrifuge, con-
veyor, and drying tower are needed in addition to the
equipment described previously for bulk HIPS.

FIGURE 2
Flow diagram of
bulk-suspensionfor
HIPS: (1) monomer;
(2) meter;
(3) rubber grinder;
(4) rubber dissolver;
(5) filters;
(6) nitrogen; (7)
prepolymerizer; (8)
suspension reactor;
(9) wash tank;
(10) centrifuge;
(1 1) dryer;
(12) pelletizer;
(13) storage.

204 VOL. 8 , NO. 3


c. Procedures and Processing Conditions.
(1) Prepolymerization is the thermal polymerization
I
described in the continuous process. Samples from
the prepolymerizer are taken frequently. When the
viscosity reaches about 30,000 CP at operating tem-
perature (Brookfield viscosity meter), the batch is ready
for suspension polymerization. It is fed into the sus-
*
pension reactor by gravity.
(2) While prepolymerization is in progress, a sus-
pension kettle is prepared by charging deionized water
and suspending agents; rpm is set at 50, temperature
at 90"C, and it is ready to receive the prepolymer
batch. During prepolymerization, samples are taken
to check their viscosities (Brookfield). When the vis-
cosity of the batch is 30,000 cP, it is dropped into the
suspension kettle and agitated 10 min. The kettle is
purged with nitrogen and then sealed. After poly-
merization at 110°C for 4 h, the temperature is raised
to 130°Cfor 2 h. This is done to minimize the residual
monomer. The batch is then cooled and dumped into
the wash tank. The granular beads are washed, de-
watered, and transferred into the dryer. After drying,
the beads are extruded into strands, and cut into pellets
for packaging.
Emulsion Polymerization (Continuous)
This process is similar to ABS which will be dis-
cussed in the next main section.
Types of HIPS
This is a two-component polymer, with polystyrene
grafted on polybutadiene as a backbone. Polystyrene
homopolymer is a very brittle, rigid plastic matrix;
but when reinforced with the graft copolymer as dis-
crete particles distributed in the matrix phase, the ma-
terial gains considerable impact strength. As more
rubber is incorporated, higher impact strength is
achieved, up to a certain limit. The rubber content
falls in the range of 5-12% for medium to high impact
polystyrene.
In addition, there are injection-molding grades and
extrusion grades. For the former, the molecular weight
of the PS matrix is lower, while the latter has higher
molecular weight. These variables make a total of at
least four grades. If a different type of elastomer is
used, this will give at least eight grades. Since there
are numerous types of elastomers and each has some
unique characteristics, the industry has chosen only a
few for impact modifiers for use in high impact poly-
styrene grades.
Furthermore, there are grades of high impact poly-
ADVANCES IN POLYMER TECHNOLOGY
POLYSTYRENE AND COPOLYMERS. II
styrene reinforced with two levels (normally 20 and
40%) of glass fibers. HIPS incorporated with fire re-
tardant is another type which has gained much market
acceptance.
Phillips Petroleum Co. has developed K-resin BDS
polymers, which are a family of butadiene styrene
thermoplastic block copolymers (styrene ranging 55-
90%), and can be blended with HIPS to give even
more grades. The advantages of the K-resin blends
are: (1) improved impact strength, (2) impact syner-
gistic effect, (3) ease of processability, and (4)lower
cost. The resultant blends thus open wider applica-
tions. The preparation will be discussed in the section
on Styrene-Butadiene Block Copolymers-Plastics,
Manufacturing, Anionic Polymerization subsection.
Manufacture of Various Grades of HIPS at a
given Amount of Rubber (Normally 7%)
1. Injection molding grade is made by increasing
the mercaptan level in the prepolymerization, where
rubber particles are dispersed in the styrene matrix.
As polymerization proceeds, some grafting does OC-
cur.
During thermal polymerization, when viscosity
reaches a certain value (around 30,00040,000 cP),
where agitation becomes strenuous, the batch is dropped
into the suspension kettle where a water suspending
agent, initiator, mineral oil, etc. are precharged and
heated to a desired temperature (around 80°C) for
receiving the batch. When the prepolymerizeris empty,
the suspension vessel is closed. Since this is hot, the
oxygen in the vapor space is mostly expelled through
the vent. After the vent is closed, the vessel pressure
will build up due to temperature rise and exothermic
reaction. The polymerization time is about 4 h, during
which most grafting is accomplished. The kettle pres-
sure drops somewhat when the reaction is completed.
Then the kettle temperature is raised to 125°C for 1
h to minimize the residual monomer. The reactor prod-
ucts are granular beads which are subjected to washing
and drying as described in the subsection under Man-
ufacturing, Suspension Polymerization (Batch Oper-
ation).
2. Injection molding grades of high rubber content
(9-11%) are made similarly. Because of the higher
rubber content, the products have higher impact strength
and elongation. However, other important properties
are generally somewhat sacrificed.
3. The extrusion grades with different levels of
rubber content are made by reducing mercaptan and
lowering polymerization temperature (1O"C), but re-
205
POLYSTYRENE AND COPOLYMERS. ZI

quire longer polymerizationtime. The molecular weight are strong and tough. Flame-retardant grades of im-
of the matrix is almost doubled, and grafting efficiency pact PS broaden the applications for both structural
seems to increase somewhat. These materials are foam and general-purpose HIPS.
tougher than the ones having much lower molecular To summarize the above, Table I contains some
weight. Extruders are used to handle the material, general mechanical, thermal, and physical properties
mainly making articles for food containers. (Ref. 1, 1980-1981, pp. 553-554).
4. Other grades are reinforced with fiber glass. This
is a different type of process consisting of blending
fibers into the HIPS melt. The distribution of glass
- in uses
the polymer is a major concern. The resultant mate-
There are numerous application for HIPS. The larg-
rials certainly yield very unique properties like high
est markets are in packaging, housewares, refrigerator
rigidity, toughness, and dimensional stability; but there
door liners, furniture panels, mirror and picture frames,
is some sacrifice of impact strength due to the presence
appliance housings, business machines, TV housings,
of glass. They are used to mold one-piece bathtubs.
smoke detectors, moldings, toys, tubs, containers and
The incorporation of fiber glass during polymerization
trays and cartons for food.
is not feasible.
In the area of construction, HIPS has been used for
5 . The last grade is fire-retardant HIPS. There are
piping and tubing for drainage, sewers, fittings, dec-
two ways of making it: via polymerization and via
orative articles, and road and advertising signs.
compounding. For the former, the fire retardant is an
Consumer electronics such as cassettes, reels, and
organic material which is miscible with the monomer.
audio-visual equipment components are a fast-grow-
Current research efforts are directed toward attaching
ing market. Now the computer housing and compo-
a vinyl group to fire-retardant materials so that they
nents industry has begun to use HIPS because of its
can be copolymerized with monomer to form discrete
low price and improved properties.
particles which, like the rubber, are distributed in the
Impact PS with flame-retardant additives is used for
polystyrene matrix. In this case, the overall grafting
small appliance housings, electrical socket outlets, fan
seems to increase somewhat, because the vinyl groups
grills, dryers, filters for washing machines, and many
on flame retardant molecules might also be grafted.
other applications.
The compounding method is conventional melt
HIPS has penetrated the automobile interior parts
blending. Normally, the two materials are tumbled
market, which is an exciting prospect. Some prop-
together, and then fed into an extruder for melting
erties of a few popular grades are listed in Table I.
and mixing in the barrel. Then the mixture is forced
through a die to form strands, quenched, and pelle-
tized.
ACRYLONITRILE-BUTADIENESTYRENE
Comparing the two techniques, it appears that the
TERPOLYMER (ABS)
former gives more efficiency but involves complicated
procedures, while the second is simple and econom-
ical.

Properties CN

Adding rubber to PS alters the properties signifi- Graft

cantly. The resulting polymer is less brittle, with im-
pact values of 1 4 ft-lbh. of notch. Elongation in-
creases to 10-50%. Tensile strengths decrease to 2500-
5000 psi. Tensile modulus decreases to about 300,000
psi. Practical toughness, as measured by a falling weight
onto a flat sheet, is high. Toughness values of 25 in.
lb for 0.020-in. sheets are typical.
Impact PS has fair UV stability and chemical re-
sistance properties. The pellets can be used in the
production of structural foam, which has integral skins,
a cellular core, and forms lightweight products which
Introduction
ABS terpolymer has been very successful since the
early 1950s. From its abbreviated name, one can tell
that it is a three-component polymer and is produced
by combining three monomers-acrylonitrile, buta-
diene, and styrene. Each monomer contributes unique
characteristics to the overall property balance. Ac-
rylonitrile is responsible for chemical resistance, heat
and aging stability, and high strength. Butadiene de-

206 VOL. 8. NO.3

 POLYSTYRENE AND COPOLYMERS. II

TABLE I
Some Properties of Various Grades of HIPS
Medium and Heat Flame- 30% Glass-Fiber- Extrusion
High Impact Resistant Retardant Reinforced Grade

Tensile strength 32004900 5000-7800 2800-3606 11,000-13,OOO 34oo4ooo

at break (psi)
Elongation at 13-15 2-60 20-40 1-2 15-100
break (%)
Tensile modulus 260-465 320-460 220-450 760-1200 180-200
( I t ’ psi)
Notched Izod 0.6-3.6 0.4-3.4 0.25-1.8 1.1-2.2 0.4
impact strength
(ft lblin.)
Hardness M10-68 L80-108 LAO-WO M80 -
(Rockwell)
Heat distortion 165-200 200-248 172- 195 210-242 160
(264 psi) (“F)
Specific gravity 1.03-1.06 1.05-1.09 1.08-1.19 1.20-1.22 1.04-1.05

velops impact resistance, toughness, tear resistance
and elongation, and property retention at low tem-
peratures. Styrene contributes rigidity, surface ap-
pearance (gloss), dimensional stability, and process-
ability. The resultant property balance depends on the
ratios and internal structure of the three components.
For this reason, ABS can be developed into many
grades of different properties for specified applica-
tions.
The grades of the ABS family (Ref. 1, 1984-1985,
p. 6) include general purpose, super impact, high heat
resistance, transparency, flame retardancy, chrome
platability, and the capability to be foamed.
The total capacity in the United States is just over
1 billion pounds per annum (Ref. 2, p. 57).
Manufacture (SeeFlow Diagram, Figure 3)
There are many ways of producing ABS resins.
During the early 1950s, ABS was made by physically
blending two copolymers, S A N and butadiene-acry-
lonitrile (nitrile rubber). Even by longer milling and
introducing small amounts of peroxide to effect light
crosslinking, there was little improvement in impact
strength. Even when two latexes of copolymers were
blended together at various compositions before co-
agulation, with the desire to produce more uniform
and better properties, the resultant products were not
satisfactory. Later the development of graft copoly-
merization of styrene and acrylonitrile onto polybu-
tadiene was achieved. These resins showed extremely
high impact strength.
During the past three decades, the technique used
by manufacturers was emulsion polymerization. As
described previously, the emulsion process offers many
advantages. Still, it is costly because of the handling
of process water, the recovery of resins from latex,
plus unit operations such as the drying of fine parti-
cles. The equipment, energy, and labor all involved
heavy costs.
Lower cost processes for making ABS have been
researched for over two decades. Bulk suspension is
a two-step process first using bulk polymerization
(rubber dissolved in styrene and AN mixture) to a
certain conversion point, and then finishing the batch
in a suspension kettle [as described in the subsection
on Bulk Polymerization (Continuous)] of HIPS.
Emulsion suspension is also a two-step process using
an emulsion process first to make PBD latex to be
used as backbones to be grafted with styrene and AN,
which are continuously charged into the kettle. When
the ratio of styrene and AN to PBD latex exceeds a
certain point, the emulsion breaks, becoming heter-
ogeneous. Then more water and suspending agents
are charged to the batch and finished as suspension
polymerization. Some grafting also takes place during
suspension polymerization. In the bulk-in-extruder
process, the rubber solution is fed into an extruder,
which provides four or five temperature zones for
polymerization, similar to bulk process. Furthermore,

ADVANCES IN POLYMER TECHNOLOGY 207

 POLYSTYRENE AND COPOLYMERS.I1

FIGURE 3
Continuous ABS
process vis
emulsion
polymerization: (1)
BD, AN S storage
tanks; (2) BD
polymerizers;
(3) premixer,
(4) continuous
polymerizer;
(5) coagulator;
(6) washing tank;
(7) centrifuge;
(8) dryer;
(9) pelletizer;
(10) storage.

many other ideas were initiated trying to develop a
more economical process, but were not successful.
However, in recent years a continuous bulk poly-
merization process has been developed, and it looks
promising, even though many problems need to be
resolved through research. Nevertheless, today's ABS
is still mostly made by the emulsion process due to
its unique properties, like high gloss and extremely
smooth surface on molded articles. The emulsion pro-
cess seems to produce less or smaller gels, and the
discrete particles are more uniformly distributed in
matrix. The continuous bulk process involves various
types of rubber, monomer ratios, and grafting, and
needs considerable improvement to equal the versa-
tility of emulsion. Therefore, the emulsion ABS pro-
cess will be discussed in more detail.
Emulsion Polymerization (Semicontinuous)
(Ref.3 , p p . 9-14)
This is a semicontinuous process, with PBD as a
backbone for grafting in latex made by batch opera-
tion. It is a continuous emulsion polymerization for
ABS .
a. Raw Materials.
(1) Monomers-butadiene, styrene, and acrylonitrile
(2) Surfactantsand suspendingagents-organic sulfo-
nate, poly(viny1alcohol), and calciumphosphate
(3) Initiaton-cumene hydroperoxide, benzoyl per-
208
oxide, potassium persulfate, hydrogen peroxide,
sodium hydrosulfite, ferrous sulfate, and dextrose
(4) Chain transfer agents-mercaptans and carbon
tetrachloride
( 5 ) Other additives-sodium hydroxide, calcium
chloride, nitrogen, pigments, etc.
b. Reactors and Auxiliary Equipment. Reactors
for making PBD and ABS, pumps, heat exchangers,
condensers, and instruments. Also additional vessels
are: Storage tanks, feed tanks, and coagulators, spare
tanks, washing tanks, and centrifuge, dryers, extru-
ders, pelletizers, blenders, mills, etc.
c. Preparation of PBD. It is used as a substrate
for grafting with AN and styrene, via the batcWemu1-
sion process. Old PBD latex is used to seed each new
polymerization; it is pumped into the reactor to fill
about 3% of the reactor volume. The reactor is purged
with nitrogen and sealed, and nitrogen is continuously
fed to raise the reactor pressure to 20 psig, at a tem-
perature of 5OOC. BD monomer under pressure in liq-
uid form is metered into the bottom (below the liquid
level) of the reactor. Soap solution containing other
additives is simultaneously fed into the reactor. Feed
of the two streams into the reactor continues until it
is full. The pressure will rise to 30 psig, and the
reaction temperature is controlled at 50°C. The feed
time is about 8 h. The batch is polymerized for 30 h;
this has recently been improved to 24 h or even lower.
VOL. 8,NO. 3

The reactor pressure drops to 5 psig, and the final
reactor solids is 50 2 5%.
d. Continuous Graft Polymerization. A 300-gal
reactor with a separate compartment of 10% volume
is used to receive the mixture. The large compartment
(90%) is equipped with an agitator, and an overflow
tube (level controllable) located at the upper edge and
another one at two-thirds of the reactor. Above this
reactor there is a mixer with a stirrer which contin-
uously receives four streams: (1) PBD latex, (2) mon-
omer mixture (with oil-soluble additives), (3) initiator
solution, and (4) soap solution, containing water-sol-
uble additives. The feed rates are precalculated and
held constant. The material in the mixer overflows
into the polymerizer, where the reaction takes place.
The residence time is about 1-2 h. The material in
the polymerizer overflows to the receiving tank,with
agitation, which is fed continuously with 3% calcium
chloride solution for coagulation. The slurry flows to
another tank for treatment if needed; it is then pumped
into the centrifuge for dewatering. The material is
dried and extruded into pellets as product.
It should be pointed out here that the emulsion
polymerization offers an attractive advantage in that
the latices can be blended together. For instance, an
ABS master batch of high rubber content latex, to
which a certain amount of rubber is grafted, can be
blended into many A B S grades containing various
levels of “rubber” for a desired impact property.
Since ABS consists of three components, the com-
position of styrene and of acrylonitrile can also be
varied via a blending technique. If both rubber and
AN levels are higher, the resultant resin will have
significantly improved impact and heat distortion
properties plus oil resistant phenomenon. Therefore,
a number of grades of ABS can be achieved by simply
blending. In addition, it’s possible to taylor a resin
for a specifically desired property. All that is needed
are additional tanks for storing blended materials. Or,
each grade, if not via emulsion polymerization, must
be processed using a specific formula, which is costly
and time consuming.
However, one must bear in mind that before blend-
ing:
a) the solids level of both latexes must be acceptable
to each other and the agitation should not cause co-
agulating
b) the surfactants used in making latexes should be
identical and of the same concentration to avoid co-
agulation difficulties
c) the particle size and the distribution of particle
sizes of blending latexes must be equal
ADVANCES IN POLYMER TECHNOLOGY
POLYSTYRENE AND COPOLYMERS. 11
Multiple ABS (or other resin) grades can also be
obtained by blending dry resins, but this involves ex-
pensive heavy-duty blender, miller, etc. equipment,
and later,also, a cost factor. Furthermom, latex blended
materials produce better uniformity than that of dry
blended resins.
Bulk Polymerization (Continuous)
(See Flow Diagram, Figure 1 )
This process has been discussed three times, for the
manufacture of homopolystyrene, copolymers of sty-
rene-acrylonitrile, and high-impact polystyrene, us-
ing the same equipment. This demonstrates the ver-
satility of such a plant. Here a three-component graft
terpolymer is made in the same series of reactors.
Although it has three components, the procedure and
operational conditions are very similar to those of
HIPS. The rubber solution is made in A N / S monomer
mixture instead of styrene alone. Acrylonitrile is a
poor solvent for dissolving rubber. The solubility var-
ies with the type and quantity of elastomer at constant
temperam. AN dissolves block copolymer much more
readily than pure PBD, especially high molecular weight
rubber. Experience indicates that at high rubber con-
tent, or high ANhtyrene ratio, saturation of the rubber
particles produces a heterogeneous solution.
The presence of acrylonitrile (one of the most dif-
ficult monomers to work with) makes the process more
difficult. Since the prepolymerization plays a very
important role, a more extensive discussion is needed.
In suspension or emulsion polymerization, the very
high solubility of AN in water (8.0%) severely com-
plicates the copolymerizationreaction. The AN in the
aqueous phase may become homopolymer, which would
harm the quality of the product. Aqueous AN mon-
omer must be recovered. This adds to the cost, since
it will pose an environmental problem. In the ABS
process, AN is largely miscible with styrene, although
it is not quite as miscible with rubber. It copolymerizes
with styrene and either is grafted on the rubber or
dispersed as SAN matrix. In samples from the pre-
polymerizer and at its exit, AN is readily determined
by modem analytical instruments. If too much PAN
is formed in subsequent reactors, this may be corrected
by changing its reactivity (AN is only one-tenth that
of styrene). The reactivity of AN can be drastically
increased by introducing a third component, normally
a small amount of ally1 alcohol or trichl~ropropane.~~~
Thus, most of the AN will be reacted in the prepo-
lymerizer, where the removal of heat is more efficient.
It is known that ABS is composed of discrete rubber
particles grafted with S A N , which are dispersed in a
continuous matrix of S A N copolymer. Impact strength,
209
POLYSTYRENE AND COPOLYMERS. 11
toughness, and gloss are closely related to the discrete
rubber particles (or domains) in the whole polymer.
There are three major features of the grafted rubber
particles that would directly affect resin properties:
(1) the size of the discrete particles, which seems to
increase with degree of grafting; (2) the uniformity of
domain sizes, whether they are small or large; (3) the
distribution of particles in the matrix.
If the particle sizes are small (average from 0.1 to
1.O Fm), and uniformly distributed in the “sea” of the
matrix, then impact, gloss, and toughness will all
increase. As the rubber level increases, the impact
increases, but the gloss will generallydecrease. There-
fore, the balance of all three factors must be optimized
at a given rubber level.
To achieve these three factors for rubber particles,
one must study the prepolymerization phenomena and
conditions. Agitation speed is very important. The
degree of phase inversion in the prepolymerizer, which
relates to conversion and the rate of polymerization
(or temperature), must be carefully studied. Especially
in thermal bulk polymerization, the gel effect (reduced
termination) is greater, causing fast reaction and high
viscosity. It is very difficult to detect the point of phase
inversion in the continuous prepolymerization reac-
tion. This may be studied by running a batch poly-
merization to establish the relationships among the
residence time, viscosity, and conversion at constant
temperature and agitation.
It may be postulated that when the residence time
is not long enough and the temperature is not high
enough, both at a given agitation speed, the inversion
period might be delayed and take place in the sub-
sequent reactor. If this happens, it might cause some
particle size or gel problem, because during the in-
version period, a heterogeneous phase does appear at
a given set of conditions. The resultant discrete par-
ticles and/or gels might very well affect resin prop-
erties.
The other procedure and process conditions are sim-
ilar to those described for the HIPS continuous bulk
polymerization.
Grades of ABS
As discussed previously, a two-component copol-
ymer, such as SAN or HIPS,can be produced in many
grades to yield different properties for specific appli-
cations. In a three-component terpolymer like acry-
lonitrile-butadiene-styrene (ABS), it becomes even
more complicated. In this three-component polymer,
by varying the composition and molecular weight of
each component, plus the degree of grafting, one can
210
tailor the structuresto yield a great number of different
types of ABS, with each type offering different prop-
erties for a wide spectrum of applications.
Nevertheless, working with this complicated sys-
tem becomes more an art than science. There is also
an economic aspect; it is costly to process and handle
numerous types of ABS. Today ABS has the largest
number of grades of any commercial plastic. Among
the large ABS producers like Borg-Warner, Mon-
santo, and DOW,each has more than 20 grades for
marketing.
This family of ABS resins is classified based on
two processing methods, injection molding and ex-
trusion.
Injection Molding Grades
Injection molding grades include the following.
a. Medium Impact, Low Viscosity, Low Gloss
and Excellent Processability (Ref. 1, pp. 6, 450).
There are many ways of making medium impact, low
viscosity, low gloss grade. By varying composition,
processing aids, methods of polymerization, and pro-
cessing conditions, one could achieve the purpose,
but these multiple variables make the process design
too complicated and very uneconomical in practice.
The ABS composition is generally fixed, compris-
ing 25% acrylonitrile, 20% rubber (PBD latex), and
55% styrene. The medium-impact, low viscosity, low
gloss grade is simply made by using more t-dodecyl
mercaptan, less surfactant, and no sucrose or ferrous
sulfate.
b. Medi~m-ImpactResistance, High Stiffness and
Strength, and High Gloss. This grade can be pre-
pared by increasing acrylonitrile and slightly lowering
the concentration of chain transfer agent.
C. High-Impact Resistance With Good All-ArOUnd
Balanced Properties. One increases the grafting ef-
ficiency by choosing initiators such as benzoyl per-
oxide, dicumyl peroxide, tert-butyl perpivalate, and
potassium persulfate, all of which are good for graft-
ing. Higher concentration and higher temperatures also
promote grafting efficiency. Using higher levels of
initiator and decreasing or changing the chain transfer
agent would help to produce this grade.
d. Combination of High-Impact and High-Flow
Properties to Yield an Excellent Cost-Performance
Balance. This grade is similar to grade c. High flow
is achieved by introducing some mineral oil during
polymerization.
e. Very High-Impact Resistance with Good Re-
tention of Toughness at Low Temperature. The
rubber content is increased from 20 to 25%, in ad-
dition to slight increase of AN.
VOL. 8 , NO.3

f. High-Impact Resistance with Exceedingly Good
Thermal Properties and Gloss. A high rubber con-
tent formula, similar to that of grade e above, plus
fiberglass reinforcement, will give high impact and
good dimensional stability.
Extrusion Grades
The next seven grades, used for extrusion com-
pounds, are produced similarly to the injection grades,
except that the rubber content in the base formula is
increased from 20 to 30%. Many extrusion grades can
be obtained by varying the other parameters as de-
scribed in the injection molding grades above. The
extrusion compounds include the following grades:
a. High impact resistance with good formability and
high gloss
b. Very high impact resistance with good retention
of toughness at low temperatures and high gloss
C. Medium high impact resistance, maximum strength
and stiffness and high gloss
d. Medium high impact resistance, excellent chemi-
cal resistance, high stiffness, high toughness, low
gloss
e. Very high impact resistance with good balanced
properties at low temperature, sheet extrusion
f. High impact, low gloss, sheet extrusion com-
pounds
g- Very high impact, high gloss for sheet extrusion
Special Grades
In addition to the general-purpose grades, there are
many specialty ABS grades, which are discussed be-
low: (Ref. 1, p. 4).
a. Flame-Retardant Grades. These are obtained
through the use of fire retardants such as halogenated
aliphatic compounds or brominated aromatics or or-
ganophosphorus compounds which can all be used as
described in HIPS. ABS blended with PVC also gives
some fire retardant effect.
b. Electroplating Grades. There are two types of
electroplating materials:
(1) General Purpose Grade. This is used for small
items such as faucets, shower heads, etc.
(2) High Pe$ormance Grades. They meet more
stringent performance demands for larger articles like
automobile grills, exterior decorativetrim, headlights,
etc.
This special grade ABS was the first plastic to be
plated on a commercial scale. It was developed by
Marbon Chemical Division of Borg-Warner in 1960.
The process for making such a grade was patented
ADVANCES IN POLYMER TECHNOLOGY
POLYSTYRENE AND COPOLYMERS. II
and the details are highly confidential. However, the
main principle is to make the plastic conductive. It
was said that a small amount of aluminum dust was
added during polymerization.
The most important step for successful electroplat-
ing is the preparation of the surface to be plated, as
placing in an electroless plating bath. Now universally
used in the industry, such baths contain, basically, a
salt of the metal to be plated, and a reducing agent
that is capable of converting the metal salt to the
metallic form. Other ingredients consist of complex-
ing agents to keep the metal salt dissolved in solution,
and pH buffers.
Besides this important step, the other preparation
steps are just as important as electroless plating:
1. Molding the plastic
2. Etching the material
3. Cleaning and sensitizing
4. Nucleation
5 . Electroless plating
6. Final electroplating.
The development of platable ABS plastics, in place
of solid metal, reduced the cost, increased production
speed, produced weight savings, caused fewer cor-
rosion problems, and added wide design latitude.
Compared to unplated plastics, the plated plastics pro-
vide surface hardness, abrasion resistance, metallic
feel, bright eye-catching appearance, and better me-
chanical properties.
This attractive combination opens a wide range of
applications, especially in the field of electronics by
permitting the use of high packing density and double-
sided wireless circuit boards.
c. High-Heat Grades. They can sustain tempera-
tures up to 230°C without creep problems. High-heat
grades are made by reducing rubber content, adding
more acrylonitrile, and increasing molecular weight
up to twice that of the standard ABS.
d. Structural Foam Grades. The blowing agent
may be added in the extruder or preincorporated in
the pellets. The main advantages are: high strength to
weight ratio, low residual strains in molded parts,
sink-free parts, and large-part molding. There are two
types, (1) standard and (2) flame-retardant. The man-
ufacture of structural foam ABS is similar to that of
structural foam HIPS.
e. TransparentGrades. They offer up to 80%light
transmission. Transparent grade can be made by using
methyl methacrylate (MMA) as the fourth monomer.
The refrslctive indices of the two phases must be closely
matched.
211
 POLYSTYRENE AND COPOLYMERS.ZI

TABLE II
Typical Properties of ABS Alloys (Ref. 6, 1982-1983, p. 128 and 1981-1982, p. 122)
ABSK ABs/Pvc ABSPVC ABSPU ABSPoly sulfone
(Rigid) (Rigid) (Flexible) (Rigid) (Rigid)
~~

Notched Izod impact strength

(ft l b h )
At 73°F 10.3 12.5 15.0 8.0 9.5
At -40°F 1.5 1.3 1.1 2.3 -
Tensile strength at yield, 73°F
(psi) 8200 5450 3000 4450 7365
Tensile modulus at yield, 73°F
(I@ psi) 3.7 3.2 1 .o 2.2 3.5
Hardness, Rockwell R, at 73°F 118 102 50 82 115
Heat deflection temp (3,
unannealed
At 264 psi 246 165 147 182 302
At 66 psi 261 195 161 206 320
Specific gravity at 73°F 1.14 1.21 1.13 1.04 1.13

f. Glass-Fiber-Reinforced Grades. They can be
classified into various types based on long and short
fibers and the amount of fiber used. The manufacture
of ABS reinforced with fibers is similar to that for the
HIPS process. The glass fibers are incorporated in the
melt.
g. Polyblends. They are mixtures of structurally
different polymers. Because polyblending can pro-
duce unique properties, this is a very economical way
of making new materials by simple mixing, instead
of the much more complex and costly development
of new polymer systems.
Commercial polyblends are almost exclusively me-
chanical blends. Recent research also points to chem-
ical blends made by polymerization and crosslinking
of separate polymers in the mixed system, giving an
interpenetrating crosslinked polymer network (IF”)
of structurally different polymers. Numerous new
structures and balance of properties have been devel-
oped by polyblending techniques.
ABS blends well with many thermoplastics, such
as poly(viny1 chloride), polycarbonate, polysulfone,
and polyphenylene oxide to form “alloys” of excellent
properties. Most of these blends result in much higher
impact strength than either material alone.
Blendex 21 1 was developed and patented by Mar-
bon Chemicals for blending purposes. Its components
are ABS (standard grade) and PVC with a composition
of 60/40via the emulsion process. This Blendex 21 1
is specifically made for blending with other thermo-
plastics for desired properties.
Besides melt blending of structurally different ho-
mopolymers or copolymers, the mixture of two latexes
also can form such alloys. Alloys are classified as
either homogeneous or heterogeneous. The former are
single-phasesystems, while the latter have continuous
and dispersed phases in which each retains its own
distinctive T,. Some ABS alloys and their properties
are listed in Table II.
Most properties of such ABS alloys are superior.
Some properties like impact strength are higher than
those of the individual resins. It should be noted here
that both issues (Ref. 6 1981-1982, p. 122 and 1982-
1983, p. 128) show lower deflection temperature for
ABS/PVC (rigid) than those of ABS/PVC (flexible).
The values were switched in this report. Also, the
specific gravity value of 1.04 for ABSPU (rigid) seems
to be low as reported by both issues.
Properties
ABS is amorphous, having a softening range rather
than a sharp melting point. It is viscoelastic, and thus
its properties are time-, ‘emperature-, and load-de-
pendent.
The material has relatively good electrical insulat-
ing properties and is suitable for secondary insulating
applications. It demonstrates good chemical resistance

212 VOL. 8, NO.3

 POLYSTYRENE AND COPOLYMERS. 11

against acids and bases, but poor resistance to esters,

ketones, and aldehydes.
Table III shows some typical property extremes for
TABLE III
available ABS grades. It should be noted that all good
Property Extremes for Available ABS Grades
properties cannot be obtained simultaneously for a
(Ref. 1, 1984-1985, p. 6)
given formulation. Stress-strain behavior of a general- propeay Maximum Minimum
purpose, high-impact ABS is shown in Figure 4 (Ref.
1, 1984-1985, p. 6). ABS has poor resistance to out- Tensile yield smngth at 73°F 8 2.3
(1W3psi)
door ultraviolet light, resulting in significant changes Tensile modulus at 73°F 380 120
in appearance and mechanical properties after expo- ( lW3psi)
sure. Protective coatings can be used to improve UV Flexural strength at 73°F 13 3.8
resistance. The material is available in pellet form, (1W3psi)
natural or precolored. Powder is available for alloying Flexural modulus at 73°F 400 130
(Wpsi)
with other polymers. Rockwell R hardness 117 -
Many specialty grades like flame-retardant, elec- Shore D hardness - 65
mplating, transpamt, heat-resistant, high-gloss, matte- Specific gravity 1.22 0.97
finish, structural foam, and glass-reinforced, are made Notched Izod impact strength 13 2.3
for specific applications. Some typical properties for (ft l b h . )
Heat deflection temp, unannealed, 230 145
these grades are summarized in Table IV. at 264 psi (OF)

uses
The largest single market for ABS is in pipe and
fittings, principally drain, waste, and vent (DWV). In
recent years, pipe! has accounted for approximately
30%of ABS consumption. While DWV is the largest
use, mine pipe and conduit are emerging applications.
Appliances and automotive uses each account for
about 15% of ABS consumption, with business ma-
chines, communications (telephones), and electrical/
electronic applications all accounting for about 10%.
ABS is the material of choice for refrigerator door
and tank liners.

FIGURE 4
10 f 1 Tensile stress/strain
data for general-
purpose, high-
-2OOF impact ABS.

8 -

/-
,
0 1 2 5 5
Strain, X
~~~ ~

ADVANCES IN POLYMER TECHNOLOGY 213

POLYSTYRENE AND COPOLYMERS. II

Other applications include luggage, sporting goods, Electrolyte Lower critical concentration
safety equipment, boats, and camper tops. Flame- Freezing point depressor
retardant and expandable grades are finding increased Increased stability
use in business machines, appliances, building com- Divinylbenzene Crosslinking agent
ponents, and institutional products.
This is a revised formula combined with author’s ex-
perience in this field.
1. A batch of monomeric solution is prepared of
STYRENE-BUTADIENE LATEX S/BD ratio 70/30 containing chain transfer agent and
initiator. A batch is enough for a 3-day feed stock.
The vessel may be jacketed to control temperature at
15°C using a coolant. An emergency concentrated
inhibitor solution (catechol) is located above the mon-
omeric solution tank in case the batch reacts and be-
comes violent. A much smaller vessel contains a con-
Styrene-butadiene 23/77 (SBR) is our leading syn- centrated initiator solution as stream no. 1 for separate
thetic rubber. Its major use is automobile tires, so that feed. Although the calculated boiling p i n t of the mixed
its production in this country alone amounts to 5 MM liquids is 100”C, which is much higher than pure BD
tons annually. SBR can be synthesized in any pro- (-4.4”C),a closed vessel is still necessary. A spare
portion. The more BD used, the more rubbery the vessel is used for continuous operation.
material becomes. As styrene content increases, it 2. A concentrated aqueous batch is prepared con-
becomes leatherlike, while, with 70% styrene, it is a taining emulsifier, FeSO,, N&P20, * 10 H20), and
rigid thermoplastic, with a low softening point. This fructose, as stream no. 2. The third stream is deionized
material has few large applications and suffers in- water.
creasing competition from conventional thermoplas- 3. The deionized water should be available for con-
tics, but, in latex form, it can be used for specialty tinuous operation. When the quality of the deionized
coatings and adhesives. water is off-grade, the flow of raw water is switched
to a stand-by cylinder packed with fresh deionizing
resins and activated carbon. Thus the supply of deion-
Manufacture ized water is not interrupted. The saturated cylinder
Emulsion Polymerization (Continuous)
is then repacked and ready for the next switch.
(See Flow Diagram, Figure 5 )
4.The three streams are fed simultaneously into the
mixing vessel with good agitation. After 15 min resi-
A typical formula may be suggested as follows (Ref. dence time at room temperature, the emulsified mate-
7, p. 276): rial overflows into the small section A of the reactor.
The continuous polymerizer, furnished with a cool-
Styrene 70 parts by weight ing and heating device, is first filled with old latex as
BD 30 “seed” and heated to a polymerization temperature of
Water 100 45-50°C. When the mixed stream enters section A of
Emulsifier 4.0 the vessel, micelles form, and eventually the monomer
n-Dodecyl mercaptan 0.5 will enter them. Due to a redox system at high tem-
NaOH 0.05 perature, polymerization starts in a short period of
Cumene hydroperoxide 0.15 time. Meanwhile the material keeps descending. By
FeSO, 0.015 parts by weight the time the material enters the big section B about
Na4P207 * 10 H20 1.5 5-10% of the monomers are polymerized.
Fructose 0.5 The chain reaction is started in the big section B,
Nitrogen pwe where the redox system produces the free radical in-
itiator. The redox system can be manipulated by with-
Other ingredients may also be used: holding some of the activator from the original feed
and then continuously adding it into the B section of
Na2C03 Buffer the polymerizer. Likewise, control of molecular weight
Polyvinyl Alcohol Protective colloid of the polymer is accomplished by reducing or adding

214 VOL. 8, NO. 3

 POLYSTYRENE AND COPOLYMERS. 11

TABLE IV
Some Properties of ABS Injection Molding and Extrusion Grades (Ref. 1, 1980-1981, pp. 534-535)
ABS Injection Molding Grades

Flame-Retardant
ABS Grades 20%
Extrusion Heat Medium High Platable Glass-
.Properties Grades Resistant Impact Impact ABS ABSlPVC Grades Reinforced

Tensile strength at 2500-8000 6000-7000 6000-7500 4800-6300 500&8000 5800 6ooo-6400 11,000
break (psi)
Elongation at break 20-100 3-20 5-25 5-70 5-25
(%)
Compressive 5200-10,OOO 7200-10,000 1800-12,500 4500-8000 6500-7500 14,000
strength (rupture
or yield) (psi)
Flexural strength 4000-14,000 10,000-13,000 11,000-13,000 8ooO-11 ,000 9000-14,000 9600 10,500-1 1,500 5500
(rupture or yield)
(psi)
Tensile modulus 130-380 300-350 300-400 230-330 320-400 330 330-380 740
(1e3psi)
Compressive 150-390 190-440 220-450 140-300 130-310
modulus
( I t 3 psi)
Flexural modulus 130-420 300-400 350-400 250-350 300-400 340 340-390 710
(lW3 psi), 74°F
Izod impact, ft 2.4-12 2.0-6.5 3.0-6.0 6.5-7.5 3.0-12 10.5 5.0-5.3 1.2
lb/in. of notch
(118 in. thick
specimen)
Hardness Rockwell R74-115 R100-115 R107-115 R85- 105 R100-120 Rl00 R 103- 109 M85
Coef. of linear 60-130 60-93 80-100 95-1 10 65-95 46 47-53 21
thermal
expansion
( lo6 in./in./”C)
Deflection temp 170-220 220-240 200-220 205-215 195-225 204-2 15 210
under flexural annealed annealed annealed annealed annealed annealed
load, 264 psi
(OF)
Specific gravity 1.02-1.06 1.05-1.08 1.03-1.06 1.01-1.04 1.16-1.21 1.21 1.06-1.07 1.22

more mercaptan chain transfer agent during this stage
of reaction.
The residence time is about 2 h depending on other
factors. Since this is an exothermic reaction, the tem-
perature of the vessel rises; therefore, the reactor needs
to be cooled down and controlled at a specific poly-
merization temperature. A steady state condition must
be maintained. Over 90% of the monomers are con-
verted at the exit of the vessel.
5 . From the continuous reactor the latex goes through
a pipe to the second stirred vessel for treatment. At
the required degree of conversion of monomers to
polymer, the reaction is terminated with a “short-stop”
as the material flows continuously to the down-stream
operations.
6. The “short-stop” is actually conducted in the
vessel by continuously feeding a small amount of a
solution of NaOH or alcohol (or even air, with vig-
orous agitation). This is an important step to obtain
balanced and stable properties. If a “short-stop” were
omitted, the polymerization of some reacted mono-
mers would continue, and lead to high branching and
crosslinking.
7. Upon completion of the polymerization process,
the material is ready for the removal of unreacted
styrene and butadiene from the latex. Butadiene is

ADVANCES IN POLYMER TECHNOLOGY 215

 POLYSTYRENE AND COPOLYWERS. 11

flGURE 5
Flow diagram of
styrene-butadiene
latex:
(1) monomers;
(2) mixing tank;
(3) concentrated
soap solution;
(4) premixing
vessel;
(5) polymerizer;
(6) holding tank;
(7) flashing drum;
(8) condenser;
(9) stripper;
(10) water and
styrene condenser;
(1 1) separator;
(12) latex storage.

readily flashed off at a lower pressure. This is followed
by live steam stripping of styrene. While styrene is
being stripped and steam is going off simultaneously,
it is even possible to control solids content of the latex.
Antifoam agent may be needed.
8. At this stage, the collected latex is subject to
antioxidant and antibacterial treatments to prevent
degradation and deterioration. The condensed BD is
stored for re-use. The overhead condensate of styrene
and water will be separated in the tank, and the styrene
can be used again.
9. Before storage or packing for marketing, the pH
is adjusted, and an antifreeze agent is often added as
weather gets cold. In manufacturing latex as an end
product, several manufacturing techniques must be
thoroughly understood and controlled. Among these
techniques, the most important goals are polymer par-
ticle size and molecular weight. They are seriously
affected by the amount of surfactant and initiator, and
by the level of modifiers, agitation, and temperature.
smaller than 1, it is called a rubber latex; higher than
1, it is called a styrene latex. In addition, they may
range from high to low molecular weights. Other vari-
ables, such as particle sizes and hot and cold rubbers
(polymerized at high and low temperatures), also add
to the range of grades.
The section on Grades of High Impact Polystyrene
mentioned K-resins produced by Phillips Petroleum
Co. used for blending. This anionic polymerization
making block copolymers will be elaborated on in the
next main section, the Anionic Polymerization sub-
section under Manufacturing.
Properties
The most important properties for styrene-buta-
diene latex are tackiness, flexibility, curability, water
resistance, abrasion resistance, oxidation resistance,
and aging properties.

Grades USeS
The styrene-butadiene latex are classified into two These latexes can be used for carpet backing, pack-
groups. Since they are copolymers, the composition aging adhesives, fabric adhesives, bonding sheet ma-
can be varied. If the ratio of styrene to butadiene is terials (such as two or more fabric layers, fabric-to-

216 VOL. 8, NO. 3


papers, and fabric-to-leather), coating for papers, and
mixed with clay for paper coatings and laminating.
Styrene-butadiene latexes are also widely used in
the preparation of adhesives for shoe manufacturing,
bonding foam to fabric, bonding nonwoven fabrics,
and in primer formulations and tire cord adhesives.
STYRENE-BUTADIENE BLOCK
COPOLYMERS-PLASTICS
These styrene-butadiene block copolymers are
thermoplastics instead of rubbers because their com-
positions are high in styrene and low in butadiene.
One family of block copolymers is K-resin, which is
available in many grades, developed by Phillips Pe-
troleum Co.
Manufacture
There are many techniques of making block co-
polymers. Several methods are discussed below. Both
diblock and triblock,
S S S S S B B B, SSSBBBSSS
can be prepared by using either one of these methods
(Ref. 8, Vol. 15, p. 508; Ref. 9, p. 916).
Anionic Polymerization (Ref. 10, p . 81)
Producing living polymers via anionic polymeri-
zation is the most useful method of synthesizingblock
copolymers. Although there are four techniques for
producing block copolymers using living polymers,
the sequential monomer addition is the most widely
used. An SB block copolymer is produced by carrying
out the polymerization of monomer S to completion
(not terminated) with an initiator. Monomer B is then
added to the living polyS carbanions. When monomer
B has reacted completely, a terminating agent (H20)
is added, and the SB copolymer is isolated. It is a
diblock polymer, where S is styrene and B is buta-
diene.
A triblock copolymer can be made by the same
method. For instance, styrene-butadiene-styrene (SBS)
block copolymer, containing short styrene blocks on
ADVANCES IN POLYMER TECHNOLOGY
POLYSTYRENE AND COPOLYMERS. II
each side of a relatively long butadieE block (14:72:14),
is now commercially available (Ref. 11, p. 399):
RLi B S
S + R-S SSS-+ R-S S S B B B-+
H20
R-SSSSBBBSSSS- +
R-SSSBBBSSSH
Or a difunctional initiator, such as sodium naph-
thalene or dilithium compounds, can be used to make
ABA (or SBS). Butadiene is initiated by one of the
initiators mentioned above and allowed to react to
completion,
B -
Li, RLi
-LiBBBLi-
Now, monomer S is added and polymerizes on both
sides of LiBBBLi to form SBS block copolymer. The
length of the styrene blocks can be controlled by add-
ing more or less styrene to the difunctional living B
block, which means the molecular weight can be con-
trolled by controlling the lengths of S and B blocks.
It also allows one to make ,a rubbery or more rigid
product.
It should be noted here that in order to produce
efficient living polymers, the system must be ex-
tremely clean-no contamination, such as dust, chem-
icals, moisture, etc.
Mechanochemical Bond Scission (Ref. 11, p . 684)
Mechanochemical bond scission can be used to pro-
duce block copolymers. Radical centers at the ends
of polymer chains can be obtained by breaking a pri-
mary covalent bond in the polymer. If the shearing
forces are sufficiently high during mastication, their
concentration at a single bond in the polymer chain
results in bond rupture. Block copolymers are ob-
tained by the masticating a mixture of two homopol-
ymers, or a mixture of a polymer and a monomer
(Ref. 11, p. 684).
The former gives a mixture of the block copolymer
with the two homopolymers, since the two radicals
217
POLYSTYRENE AND COPOLYMERS. 11

combine randomly; and the latter yields the block
copolymer along with the one homopolymer of M1. (Ref. 12, p. 271) with original polybutadiene blocks
The latter offers more freedom for choosing which
homopolymer will be in the block copolymer mixture.
Condensation (Ref. 11, p . 141;
Ref. 8, Vol. 15, p . 508)
Condensation polymerization is a good way of mak-
ing block copolymers. In condensation polymeriza-
tion, the volume of each monomer can be control-
led, and the functional end group(s) can be selected.
Useful end groups are - O H , - C O O H , -NHz,
and -CONHI. Unfortunately, BD and styrene do
not have such functional end groups, so that this
method does not apply to S/BD block copolymer,
unless such groups are carefully introduced during or this two-component system (styrene-butadiene). The
after telomerization.
Another type of SBS triblock polymer was made
comprising 65% 1,4 and 35% 1,2 centrifugations, and
then hydrogenating the double beads, such that the
center block was equivalent to a high ethylene-butene
rubber. This type of SBS shows good weatherability.
The block polymer shouId be called block copol-
ymer, because a block copolymer contains long blocks
of at least two different monomers. The long chain
of each polymer can be arranged into many types of
blocks. They can be synthesized as SB, SBS, BSB,
and called polyS-polyB , polyS-polyB-polyS, and
polyB-polyS-polyB, respectively (Ref. 11, p. 398).
Combining with other variables, long and short, the
grades could be numerous and complicated, even in
nomenclature system is yet to be determined.

Reactivity Approach (Ref. 4 , p . 36) Preparation of Block Copolymers

The possibility of producing block copolymers by
having both reactivities, y1and yz, greater than unity,
appears impossible for making S/BD block polymers.
The reactivities of styrene and butadiene are 0.78 and
1.39, respectively, unless a third component can be
added to make both y1 and yz larger than 1. This
approach is yet to be experimentally proven.
Grades
Styrene-butadiene block copolymers (Ref. 12, pp.
270-272) can be classified into many grades. Some
grades are due to the formation of structures like di-
block (SB) or triblock (SBS), or even a reverse for-
mation (BSB). The length of block is another variable
for producing additional grades. The mechanism of
polymerization could result in different structures;
however, most block polymers are formed by anionic
polymerization, via living polymers.
There are at least six K-resins (Ref. 1, 1984-1985,
p. 84) produced by Phillips Petroleum Co. This group
of resins is specially made for the purpose of blending
with other polymers, and for making interpenetrating
network (IPN) type of polymers which are potentially
valuable for desirable new properties.
The composition and length of the blocks can form
other grades. In a typical commerical triblock the sty-
rene content is about 30% of the total giving a relative
block size of 14:72:14. The molecular weight of this
commercial triblock polymer is about 80,000, giving
a tensile strength similar to that of a carbon-black-
reinforced SBR elastomer.
Since block copolymers are relatively new and often
offer unique properties, their preparation via anionic
polymerization is described the Anionic Polymeriza-
tion subsection under Manufacturing in this section.
Properties and Uses
Block copolymers often have better impact and ten-
sile strength, tear strength, HDT, modulus, and gloss.
The block copolymers also contribute to processabil-
ity, such as in injection molding, extrusion, and vac-
uum forming.
K-resins, made by Phillips Petroleum Co., as de-
scribed in the HIPS section, the Types of HIPS sub-
section, and the Grades subsection of this section pos-
sess an interesting combination of properties. They
are clear and flexible, but exhibit toughness and strength.
Typical properties are listed in Table V (Ref. 12, p.
409).
Different K-resin grades are used for blending with
other resins to produce improved properties or pro-
cessabilities. HIPS, SAN, PP, and LLDDE have all
been blended with three grades of K-resins (30%).
The reported results showed both advantages and dis-
advantages, but generally favored more advantages,
which matched the needs for specific applications.
In addition to blending, the block copolymers are
used in the areas of electronics, housewares, and ap-
pliances, toys, decorations, and packaging, competing
with other resins.
Some additional interesting characteristics of SBS
and BSB block copolymers are presented in Table VI

218 VOL. 8 , NO. 3

 POLYSTYRENE AND COPOLYMERS. II

(Ref. 13, Vol. 8, p. 629). The SBS segmental block

copolymer showed much superior physical properties.
TABLE V
Some Typical Properties of Styrene-Butadiene Block
STYRENE-ACRYLATE COPOLYMERS Copolymer Thermoplastics (Phillips K-Resins)
~perty Value
CH3
I ASTM deflection temperature under load
(264IbWin.) ("C)
70
[--CHAH-lx- CH2-(2-1,
I I Vicat softening point ("C) 93
Tensile strength ( m a ) 30
c=o Tensile modulus (MPa) 1400
I
0 4 3 3 3
(CH3 could be
written as R or H)
Manufacture

Introduction Acrylic Monomers

Early in the 1870s acrylic acid (CH2 = CHCOOR)
and, more importantly, methacrylate esters
were prepared (Ref. 14, p. 973). But only methyl
methacrylate (MMA)
Fundamentally, the difference between acrylate and
methacrylate is that the hydrogen atom on the a-car-
bon of an acrylic ester (or acrylate) is replaced by a
methyl group. Their structural formulas are:
CH2 = CHCOOR acrylate
CH2 = C-COOR methacrylate
I
CH3

Synthesis of Acrylates and Methyl Methucrylate

a. Methyl Acrylate (Ref. 14, p. 973). There are
many ways of making this monomer; one of the meth-
was manufactured for marketing with sufficient econ-
omy for industrial uses after the turn of the century.
Therefore, this section is devoted mainly to the dis-
cussion of the styrene MMA copolymer.
TABLE VI
In 1927, Rohm and Haas commercialized
Comparison of SBS and BSB Polymers
poly(methy1 acrylate) (Ref. 12, p. 363) which was
mainly used for coating applications. Three years later Composition
R. Hill prepared poly(methy1methacrylate) and found Segmental molecular
it to be a rigid, transparent polymer. Meanwhile, re- weights ( x IC3) 10S-52B-IOS 28B-20.5S-28B
Styrene content (%) 27.5 27
search work led to the copolymerization of methac- Total molecular weight
rylates. Norrish in 1939 developed a styrene-methyl ( X 10-3) 73 76
methacrylate copolymer on a mole to mole basis. Two Mechanical Properties"
years later, Wall pointed out that the chemical com- 100% modulus [MPa (psi)] 1.66 (242) 0.48 (70)
position of the polymer would depend only upon the Extension at break (%) 860 120
Ultimate tensile strength
relative reactivities of two monomers. Hence, the 27.3 (3950) 0.48 (70)
[MPa (psi)]
technique of copolymerizing MMA with styrene was Shore A hardnessb 65 17
much improved. Today, there are several companies
making the copolymer, but mostly for their own in- 'Tensile specimens were cut from compression-molded sheets using a die having a 2.5 cm con-
stricted length. Extension rate was 5 cdmin.
ternal uses. Only the Richardson Co. (Ref. 1, 1984- bASTM 1706-61.
1985, p. 475) produces styrene/methyl methacrylate
copolymer (S-MMA) for marketing.

ADVANCES IN POLYMER TECHNULOGY 219

 POLYSTYRENE AND COPOLYMERS. 11

ods is by pyrolysis of lactic acid, a waste byproduct b. Methyl Methacrylate (Ref. 12, p. 364). This
of the dairy industry. This, therefore, keeps the cost monomer is synthesized from acetone cyanohydrin as
of raw material down. Three steps are involved in follows:
preparing methyl acrylate:
( 1 ) Esterifcation.
OH OH
I CHjOH I
C H d H X O O H + CHdHXOOCH3

+ H2° (3) Copolymerization of MMA and Styrene

(2) Acetylation of the Hydroxyl Group. n CHF C-COOH3+ m C H d H
I I
I
OH CH3
I CH3-
CHdHXOOCH, + CHdH--COOCH3 + HCl
I

(3) Pyrolysis.
475450°C
CHAHXOOCH3 4 CHAHXOOCH3
I Introduction. There are generally more conven-
W 4 H 3 tional methods that can be applied for the preparation
1I of this copolymer. First, it should be mentioned that
0 it was synthesized using various kinds of initiators
+ CH3COOH (5) early in the history of plastics.
Walling and his co-workers (Ref. 15, p. 19) in-
The process is multiple-step and costly; it is there- vestigated the copolymerization behavior of styrene
fore not used today. Another method is the use of and methyl methacrylate charged at 1 : 1 ratio, using
chlorohydrin, which involves higher cost raw mate- a number of different initiators (see Table VII). The
rial: composition showed that the copolymerization prop-
agation was governed by the types of initiators.
NKN CH30H
a. Free Radical Copolymerization.
CHzOHCH2CI + CH2OHCH2CN +
H2S04 1. Copolymerization in Suspension.
( a ) Raw Material: Besides methyl methacrylate,
CHAHCOOCH, (6)
others like styrene, water, and oil-soluble initiators,
chain transfer agents, suspending agents, crosslinking
agents, UV stabilizers, antioxidants, mineral oil, flame
retardants, colorants, and other additives have been
previously mentioned, and their functions discussed
TABLE VII under suspension and emulsion polymerizations in the
Copolymerization Compositional Behavior of Styrene-MMA sections Part I and the first three sections of this paper.
(1:l) Using Different Initiators (Ref. 15, p. 20) (b) Equipment: Suspension kettle and auxiliary
equipment have also been discussed in previous sec-
Initiator Temp (“C) Styrene (a) tions.
( c ) Polymerization: The copolymerization of sty-
Peroxide 60 51.0
SnCI, 30 19.9
rene and methyl methacrylate is similar to the nitrile-
K-metal 30 <1.0 styrene systems (Ref. 16, p. 455). The difficulty in
the suspension copolymerization is that the solubility
of MMA (like AN) is greater than that of styrene in
water, and much higher or AN in water. Therefore,

220 VOL. 8 , NO. 3


the reactivities of two monomers would be different
than those in bulk polymerization. Nevertheless, higher
rates of copolymerization and higher molecular-weight
copolymers can be manipulated.
Unfortunately, the literature carries little or no in-
formation on poly(methy1 methacrylate-styrene) via
free radical suspension polymerization. The Richard-
son Polymer Cop. is the only company manufacturing
and marketing the copolymer, and its technique was
never disclosed. Judging from the literature, it is likely
that a suspension process, using benzoyl peroxide as
a free radical initiator, produces a desired SMMA
copolymer with an appropriate molecular weight and
composition.
2. Copolymerization in Emulsion. A continuous-
emulsion technique is possible, and similar to the
emulsion techniques discussed in the previous sec-
tions. Yamamoto and co-workers of Fukui University,
Fukui, Japan, have developed an emulsion process for
making styrene-MMA copolymer. It is recommended
that a latex seed is initially charged into the reactor
before other ingredients are gradually fed in. The pro-
cess is described in Ref. 17.
3. Copolymerizations in Mass (Ref. 18, p . 450).
Not being a thermally triggered mass copolymeriza-
tion, it is a photosensitized copolymerization of sty-
rene (I) and methyl methacrylate (11) by a 1,l-azo-
biscyclohexane carbonitrile sensitizer carried out by
M. Suzuki and co-workers.'9 It was found that the
rate of initiation of the M M A S system varies with
monomer composition when benzoyl peroxide is used
as an initiator. Another initiator, 2,2-azo-bis-isobu-
tyronitrile, was investigated by Walling" to study the
rate of polymerization at various compositions. It was
found that the addition of a small amount of MMA
to styrene reduces the rate of styrene polymerization
slightly and vice versa. It was concluded that the high
rate of termination might be comparable to the slow
rate of propagation.
b. Ionic Polymerization. Both anionic and cationic
homopolymerizations have been briefly mentioned in
Part I, the first section, in the Manufacturing subsec-
tion, l(e). Here they are further elaborated in copo-
lymerization.
I. Anionic Copolymerization. In 1950, Mayo et al.
(Ref. 18, p. 423), described the well-known study in
which they showed how copolymerization could be
used to differentiate among the three mechanisms of
polymerization. They used sodium metal as a catalyst
to polymerize three pairs of monomers (equal mole):
styrene-MMA, styrene4iethyl fumarate, and AN-
MMA. They concluded that MMA polymerizes al-
ADVANCES IN POLYMER TECHNOLOGY
POLYSTYRENE AND COPOLYMERS. ZZ
most exclusively in the presence of styrene; AN enters
the polymer to the extent of more than 90% in the
presence of MMA, and the second pair does not po-
lymerize at all. The result is unique as evidence of
the presence of AN ionic mechanism.
Another interesting anionic copolymerization ex-
periment, also using alkali metal (n-butyl lithium) in
the same S-MMA system in toluene as solvent at
lower temperature, and when sufficient oxygen was
added to the system, showed turbid reaction mixture
(Ref. 15, p. 179). This oxidation product exhibited a
weak activity toward MMA and styrene; but it would
also initiate both styrene and MMA, resulting in a
copolymer composition of about one-to-one ratio
equivalent to a starting mixture, which indicated that
the oxidized system could act as a radical-type initi-
ator. Other metal alkyls (RM), like boron and cad-
mium to replace lithium (Ref. 15, pp. 4344t9), gave
the same results.
Furukawa and co-workersZ1studied the styrene-
MMA copolymerization with metal halide (MX) sys-
tems. They had shown that the polymerization was a
free-radical mechanism, producing the same copoly-
mer composition as from the ordinary "radical" sys-
tem. It should be stated that the radical mechanism
occurred when the monomer was added to one initiator
component prior to the addition of the other initiator
component.
These two initiators, RM and MX, imparted the
same catalytic function-"free radical" type poly-
merization, differing from anionic in nature. How-
ever, the former needed oxidation steps. The results
on the styrene-MMA copolymerization, using MX as
initiators, were very interesting.
2. Cationic Copolymerization. Copolymerization of
SMMA via cationic polymerization was given much
less investigation in comparison with anionic copo-
lymerization. Since this type of polymerization was
mentioned very little in the literature (Ref. 4, p. 217),
its fundamental concepts for future research and de-
velopment are described as follows.
The cationic polymerization is generally carried out
in solvent, mostly a hydrocarbon medium. Catalysts
used for triggering the reaction are hydrogen halides,
organic acids, and Lewis acid complexes which often
require a cocatalyst, even water, to form a catalyst-
cocatalyst complex. These catalysts are in heteroge-
nous forms, yet they are all strong electron acceptors.
The mechanism of cationic copolymerization (sim-
ilar to homopolymerization) seems to be that of a
cocatalyst donating a proton to form a carbonium-ion
in the system as an initiation step:
22 1
 POLYSTYRENE AND COPOLYMERS. I1

H H H H As in anionic polymerization, the system must be very

I I I I clean, with absolutely no contamination. The solvent
A + Hz0 + H C S +H A - C+ AOH- (9)
must be very dry,so that the cocatalyst, if it is water,
can be controlled.
The description above is homopolymerization; the
S-MMA system is more complicated. However, the
well-known copolymerization Eq. (15) in the second
where A stands for an acid catalyst. section of Part I holds true for cationic copolymeri-
In the propagation step, just as in addition poly- zation. It is believed that no companies today use this
merization, the carbonium ion keeps transposing mon- type of expensive process for manufacturing and mar-
omers and building up molecular weights at a fast keting of the S-MMA copolymer.
pace. In the early 1950s Walling, Briggs, Higashimore,
The termination step is quite complicated, involv- Okamura, and Mayo conducted research studies on
ing various reactions. One of them is the combination this SMMA copolymer via cationic polymerization
of counterion (Ref. 11, p. 352). If A is trifluoroacetic (Ref. 18, pp. 300, 301).
acid, Eq. (10) follows: The SMMA copolymers, today being marketed by
H H Richardson, are basically clear materials, similar to
I I poly(methy1 methacrylate). Some of the grades are
discussed next.

The rate of cationic polymerization is very fast, as
low as a fraction of a second. It is carried out at very
low temperature, - 70°C or even lower. The resultant
molecular weight is very high, up to a few million.
Grades
Two different molecular weights (for a given struc-
ture and MWD) would provide two grades with dif-
ferent physical properties. Different S/MMA ratios
could also provide a range of properties, but they
would have to be quite different ratios because the
properties of PS and PMMA are fairly similar. The
cost plays an important factor since MMA is much
more expensive than styrene.
The five popular grades made by Richardson Poly-
mer Co. are listed below:

1. R-670 acrylic copolymer has excellent clarity and

high gloss
2. NOAN acrylic copolymer needs a polished, chrome
plated mold for optimum clarity and gloss
TABLE VIII
3. NAS Acrylic copolymer has excellent clarity and
Typical Properties of Styrene-MMA Copolymer
high gloss. A warm mold is recommended for best
Tensile strength at break (psi) 10,000 characteristics
Elongation at break (6) 3 4. RSA-2 impact acrylic has high tensile strength and
Tensile modulus (lW3psi) 430 impact strength in addition to clarity and gloss
Compressive strength, yield, (psi) 13,000
Compressive modulus (1W3psi) 270 5 . P-205-UV acrylic copolymer has high UV absorp-
Flexural strength, yield (psi) 17,500 tion characteristics
hod impact (ft Ibf/in.) 0.3
Hardness, Rockwell M75 All the above resins are specialty products for specific
Deflection temperature, 264 psi (OF) 205-2 12 and customized applications. In addition, there are
Thermal conductivity, l(r (cal cm)/s cmz "C) 4.0-5.0
Specific gravity 1.09
fire-retardant and fiber-glass-reinforced grades. The
Water absorption, 24 h (6) 0.15 effect of composition is crucial, because polystyrene
is brittle. The copolymer can be made into sheet and
rod grades. All these grades offer a variety of appli-
cations.

222 VOL. 8, NO. 3


Properties and Uses
Styrene-methyl methacrylate copolymer is a rigid,
transparent amorphous resin. It has a high glass tran-
sition temperature. Generally, its physical, chemical,
and thermal properties are similar to those of SAN.
The properties vary depending on choice of grades
and how they are processed.
Typical properties of styrene-MMA copolymer (Ref.
1, 1980-1981, p. 536) are listed in Table VIII. Some
other properties are low shrinkage, ease of painting,
transparency, excellent UV resistance, color reten-
tion, lower viscosity for ease of injection molding,
and fast mold release. Its major applications include
lighting fixtures, sanitary ware, glazing, automotive
lenses, signs, decorations, optical contact lenses, lamps,
windows, appliance panels, knobs, etc. This copol-
ymer can be blended with nitrile rubber (NBR) to
become a transparent four-component resin by match-
ing their refractive indices. The prices for all grades
are too high; therefore, their market is limited to spe-
cific applications.
CONCLUSIONS
Competitive quality and manufacturing cost are the
two most important factors in developing processes
for producing polymers. Three decades ago, practi-
cally all polystyrene and its derived copolymers (ex-
cept SBR rubber) were manufactured via suspension
polymerization, due to the fact that its capital expen-
diture was low. In recent years, the labor costs have
soared. In order to be competitive, the industry had
to develop an alternative cheaper process to remain
solvent.
The most successful new low-cost process is bulk
continuous polymerization. Therefore, most processes
for manufacturing the polystyrene and its allied co-
polymers discussed in this study emphasized the uti-
lization of the bulk continuous process. This process
does have some disadvantages such as high capital
investment, longer down time for cleaning, and con-
tamination when changing grades. These problems
have been gradually overcome through further re-
search and development.
ADVANCES IN POLYMER TECHNOLOGY
POLYSTYRENE AND COPOLYMERS. II
Certain products still have to rely on suspension
polymerization. Expandable polystyrene, which is
mainly for insulation and packaging applications, is
made into beads from an aqueous medium. Other styr-
enic specialty products, homo- or copolymers having
very high molecular weights for unique properties,
are possible through the versatility of saspension or
emulsion techniques.
The advantages of the bulk continuous process in-
clude: smaller buildings, smaller equipment (no water
in the system), no washing and drying unit operations,
compounding and extrusion equipment are not re-
quired, and, more importantly, the labor is minimal.
Therefore, most producers have now changed from
suspension to the bulk continuous operation.
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