5 Styrenic Plastics
This chapter on styrenic plastics covers a broad
category of polymeric materials of which styrene is
an important part. Styrene, also known as vinyl
benzene, is an organic compound with the chemical
formula C6H5CH¼CH2. Its structure is shown in
Fig. 5.1.
Figure 5.1 Chemical structure of styrene.
It is used as a monomer to make plastics such as
polystyrene (PS), acrylonitrileebutadieneestyrene
(ABS) copolymer, styreneeacrylonitrile (SAN)
copolymer, and the other polymers mentioned in this
chapter.
5.1 AcrylonitrileeButadienee
Styrene Copolymer
Acrylonitrileebutadieneestyrene, or ABS, is
a common thermoplastic used to make light, rigid,
molded products such as pipe, automotive body
parts, wheel covers, enclosures, protective head
gear.
Permeability Properties of Plastics and Elastomers. DOI: 10.1016/B978-1-4377-3469-0.10005-0
Copyright Ó 2012 Elsevier Inc. All rights reserved.
Styreneeacrylonitrile (SAN) copolymers have
been available since the 1940s and while its
increased toughness over PS made it suitable for
many applications, its limitations led to the intro-
duction of a rubber, butadiene, as a third monomer
producing the range of materials popularly referred
to as ABS plastics. These became available in the
1950s and the availability of these plastics and ease
of processing led ABS to become one of the most
popular engineering polymers.
The chemical structures of the monomers are
shown in Fig. 5.2. The proportions of the monomers
typically range from 15 to 35% acrylonitrile, 5 to
30% butadiene, and 40 to 60% styrene. It can be
found as a graft copolymer, in which SAN polymer
is formed in a polymerization system in the presence
of polybutadiene rubber latex; the final product is
a complex mixture consisting of SAN copolymer,
a graft polymer of SAN and polybutadiene, and
some free polybutadiene rubber. The CAS number is
9003-56-9.
Manufacturers and trade names: SABIC Innovative
Polymers CycolacÒ ; INEOS LustranÒ and
NovodurÒ ; Perrite RonfalinÒ ; and BASF AG
TeluranÒ .
Applications: Medical devices, cosmetics, house-
wares, automobiles, business equipment, cabinets
and casings, baths, shower trays, pipes, boat
hulls, and vehicle components (Tables 5.1e5.7
and Figs. 5.3 and 5.4).
Figure 5.2 Chemical structures of ABS
raw materials.
77
78 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS

Table 5.1 Permeation of Oxygen and Water Vapor through Sabic Innovative Plastics
CycolacÒ ABS1

Temperature ( C) 25 24
Relative humidity (%) 90
Penetrant Oxygen Water vapor
Source document units
Permeability coefficient (cc mil/24 h 100 in.2 atm) 100
2
Vapor transmission rate (g mil/24 h 100 in. ) 12
Normalized units
Permeability coefficient (cm3 mm/m2 day atm) 39.3
2
Vapor transmission rate (g mm/m day) 5.88

Table 5.2 Permeation of Oxygen, Nitrogen, and Carbon Dioxide at 24  C through Dow Chemical Low Acrylonitrile
ABS Film2

Permeability Coefficient

Source Document Units Normalized Units

Penetrant Gas (cm3 mil/100 in.2 day) (cm3 mm/m2 day atm)
Oxygen 200e260 79e102
Nitrogen 25e35 9.8e13.8
Carbon dioxide 900e1200 354e472

Table 5.3 Permeation of Oxygen, Nitrogen, and Carbon Dioxide at 24  C through Dow Chemical Medium
Acrylonitrile Content ABS Film2

Permeability Coefficient

Penetrant Source Document Units Normalized Units

Gas (cm3 mil/100 in.2 day) (cm3 mm/m2 day atm)
Oxygen 120e140 47e55
Nitrogen 10e15 3.9e5.9
Carbon 400e600 157e236
dioxide

Table 5.4 Permeation of Water Vapor through Dow Chemical

ABS Film2

Temperature ( C) 24e38
Source document units 5e16
Vapor transmission rate (g mil/100 in.2 day)
Normalized units 2.0e6.3
Vapor transmission rate (g mm/m2 day)
5: S TYRENIC P LASTICS 79

Table 5.5 Permeation of Water Vapor at 23  C through BASF AG TerluranÒ

ABS Films3

TerluranÒ Product Code 997 VE 967 K 887 M

Source document units 27 27 31
Vapor transmission rate (g/m2 day)
Normalized units 2.7 2.7 3.1
Vapor transmission rate (g mm/m2 day)
Sample thickness: 0.1 mm; test method: DIN 53122. Test note: Values for permeability
depend on the conditions under which the film was produced and may differ by as much
as 50% from those given.

Table 5.6 Permeation of Oxygen, Nitrogen, Carbon Dioxide and Water Vapor at 23  C through BASF AG
TerluranÒ ABS Films3

Permeability Coefficient

Source Document Units Normalized Units

Penetrant Gas (cm3 100 mm/m2 day bar) (cm3 mm/m2 day atm)
TerluranÒ Product Code 997 VE 967 K 887 M 997 VE 967 K 887 M
Oxygen 800 500 450 81 50.7 45.6
Nitrogen 200 100 100 20.3 10.1 10.1
Carbon dioxide 3000 2000 2000 304 203 203
Sample thickness: 0.1 mm; test method: DIN 53380. Test note: Values for permeability depend on the conditions under
which the film was produced and may differ by as much as 50% from those given.

Table 5.7 Permeation of Oxygen, Nitrogen, Carbon Dioxide, and Methane

for INEOS ABS LustranÒ 246 ABS Containing 60% Styrene, 27% Acryloni-
trile, and 13% Butadiene4 (see also Figs 5.3 and 5.4)

Source Document Units Permeation Coefficient

Carbon Dioxide Methane Oxygen Nitrogen

T (K) P  10
10 3
(cm (STP)/cm s cm Hg) 2

293 2.97 0.126 0.697 0.103

303 3.57 0.175 0.950 0.162
313 3.97 0.248 1.240 0.210
323 4.95 0.355 1.550 0.264
Normalized Units Permeation Coefficient
Carbon Dioxide Methane Oxygen Nitrogen
T ( C) 3 2
(cm mm/m day atm)
20 195.0 8.3 45.8 6.8
30 234.4 11.5 62.4 10.6
40 260.7 16.3 81.4 13.8
50 325.0 23.3 101.8 17.3
80 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS

Figure 5.3 Temperature dependence of gas permeability coefficients for INEOS ABS LustranÒ 246 ABS con-
taining 60% styrene, 27% acrylonitrile, and 13% butadiene.4

Figure 5.4 Permselectivity vs. temperature for INEOS ABS LustranÒ 246 ABS containing 60% styrene, 27%
acrylonitrile, and 13% butadiene.4

5.2 AcrylonitrileeStyrenee
Acrylate
Acrylonitrileestyreneeacrylate (ASA) is a ter-
polymer that can be produced by either a reaction
process of all three monomers or by a graft process.
The CAS number is 26299-47-8. ASA is usually made
by introducing a grafted acrylic ester elasto-
mer during the copolymerization of styrene and
acrylonitrile, known as SAN. SAN is described in the
next section of this chapter. The finely divided elas-
tomer powder is uniformly distributed and grafted to
the SAN molecular chains. The outstanding weath-
erability of ASA is due to the acrylic ester elastomer.
ASA polymers are amorphous plastics, which have
mechanical properties similar to those of the ABS
resins described in Section 5.1. However, the ASA
properties are far less affected by outdoor weathering.
ASA resins are available in natural, off-white, and
a broad range of standard and custom-matched
5: S TYRENIC P LASTICS 81

Table 5.8 Permeation of Various Gases at 23  C through BASF LuranÒ S 776 S Injection Molding Grade with
Enhanced Toughness and Lower Flowability ASA Film5e7

Permeability Coefficient

Permeant Film Standard Test Source Document Units Normalized Units

Gas Type Method (cm3/m2 day bar) (cm3 mm/m2 day atm)
Hydrogen Blown DIN 53380 5000 507
film
Methane Blown DIN 53380 110 11.1
film
Nitrogen Filma DIN 53380, Part 2 100 10.1
Method N
Nitrogen Blown DIN 53380 70 7.1
film
Oxygen Filma DIN 53380, Part 2 550 55.7
Method N
Oxygen Blown DIN 53380 180 18.2
film
Carbon Filma DIN 53380, Part 2 2300 233
dioxide Method N
Carbon Blown DIN 53380 1400 142
dioxide film
Film thickness: 0.1 mm.
a
Values depend on conditions under which film was produced. Figures may differ by as much as 50%.

colors. ASA resins can be compounded with other
polymers to make alloys and compounds that benefit
from ASA’s weather resistance. ASA is used in many
products including lawn and garden equipment,
sporting goods, automotive exterior parts, safety
helmets, and building materials.
Manufacturers and trade names: BASF LuranÒ S
Applications and uses: Automotive components,
electrical equipment subjected to high tempera-
tures, parabolic reflectors, solar energy systems,
movement sensors, surfboards, and golf cars
(Tables 5.8e5.11).

Table 5.9 Permeation of Nitrogen, Hydrogen, and Methane at 23  C through BASF LuranÒ S 757 R High Stiff-
ness and Medium Flowability ASA Film5,6

Permeability Coefficient

Standard Source Document

Test Units Normalized Units
Permeant Film Type Method (cm3/m2 day bar) (cm3 mm/m2 day atm)
Hydrogen Blown film DIN 53380 5000 507
Methane Blown film DIN 53380 100 10.1
Nitrogen Blown film DIN 53380 60 6.1
Oxygen Blown film DIN 53380 150 15.2
Carbon Blown film DIN 53380 1000 101
dioxide
Film thickness: 0.1 mm.
82 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS

Table 5.10 Permeation of Nitrogen, Hydrogen, and Methane at 23  C through BASF LuranÒ S 797 S Injection
Molding Grade with Very High-Impact Strength ASA Film5,6

Permeability Coefficient

Source Document Normalized Units

Film Standard Test Units (cm3/ (cm3 mm/
Permeant Type Method m2 day bar) m2 day atm)
Nitrogen Filma DIN 53380, Part 2 75 7.6
Method N
Oxygen Filma DIN 53380, Part 2 500 50.7
Method N
Carbon Filma DIN 53380, Part 2 2000 203
dioxide Method N
Film thickness: 0.1 mm.
a
Values depend on conditions under which film was produced. Figures may differ by as much as 50%.

Table 5.11 Permeation of Water Vapor at 23  C through BASF LuranÒ S ASA Films5,6

Vapor Transmission Rate

Film Pressure Gradient Source Document Units Normalized Units

Material Type (Mbar) (g/m2 day) (g mm/m2 day)
LuranÒ S Blown 19.86 30 3
757 R film
LuranÒ S Filma 23.87 35 3.5
776 S
LuranÒ S Filma 23.87 30 3
797 S
Film thickness: 0.1 mm; relative humidity gradient: 85e0%; test method: DIN 53122.
a
Values depend on conditions under which film was produced. Figures may differ by as much as 50%.

5.3 Polystyrene 90e95% PS by weight. The solid plastic beads are

expanded into foam through the use of heat (usually
Polystyrene (PS) is the simplest plastic based on steam). The heating is carried out in a large vessel
styrene. Its structure is shown in Fig. 5.5. Its CAS holding 200e2000 L. An agitator is used to keep the
number is 9003-53-6.
Pure solid PS is a colorless, hard plastic with
limited flexibility. Polystyrene can be transparent or
can be made in various colors. It is economical and is
used for producing plastic model assembly kits,
plastic cutlery, CD “jewel” cases, and many other
objects where a fairly rigid, economical plastic is
desired.
Polystyrene’s most common use, however, is as
expanded polystyrene (EPS). EPS is produced from
a mixture of about 5e10% gaseous blowing agent
(most commonly pentane or carbon dioxide) and Figure 5.5 Chemical structure of PS.
5: S TYRENIC P LASTICS 83

beads from fusing together. The expanded beads are
lighter than unexpanded beads so they are forced to
the top of the vessel and removed. This expansion
process lowers the density of the beads to 3% of
their original value and yields a smooth-skinned,
closed cell structure. Next, the pre-expanded beads
are usually “aged” for at least 24 h in mesh storage
silos. This allows air to diffuse into the beads,
cooling them, and making them harder. These
expanded beads are excellent for detailed molding.
Extruded polystyrene (XPS), which is different
from EPS, is commonly known by the trade name
StyrofoamÔ. All these foams are not of interest in
this book.
Three general forms are:
cakes, croissants, and cookies. Medical and pack-
aging/disposables, bakery packaging, and large
and small appliances, particularly where clarity
is required.
Oriented: OPS films can be printed and laminated
to foams for food service plates and trays
offering improved esthetics. The films can also
be used as a laminate to PS sheet for a high
gloss shine and to prepare bakery, convenience
food items.
High impact: Refrigeration accessories, small appli-
ances, electric lawn and garden equipment, toys,
and remote controls (Tables 5.12e5.15,
Figs. 5.7e5.9).

 General purpose polystyrene (PS or GPPS),

 Oriented polystyrene (OPS),
 High-impact polystyrene (HIPS).

One of the most important plastics is HIPS.

This is a PS matrix that is imbedded with an
impact modifier, which is basically a rubber-like
polymer such as polybutadiene. This is shown in
Fig. 5.6.
Manufacturers and trade names: BASF Polystyrene
and Polystyrol, Dow Chemical TryciteÔ, Styron
StyronÔ
Applications and uses:
General purpose: Yogurt, cream, butter, meat trays,
egg cartons, fruit and vegetable trays, as well as Figure 5.6 The structure of HIPS.

Table 5.12 Permeation of Gases at 24  C through Styron StyronÔ PS8

Permeability Coefficient

Source Document Units (cm3 mil/100 Normalized Units (cm3 mm/

Permeant Gas in.2 day atm) m2 day atm)
Oxygen 300e400 118e157
Nitrogen 40e50 16e20
Carbon dioxide 1000e1500 394e590
Vapor Transmission Rate

Source Document Units

Permeant Vapor (g mil/m2 day) Normalized Units (g mm/m2 day)
Water 2e10 0.8e3.9
84 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS

Table 5.13 Permeation of Oxygen, Nitrogen, Carbon Dioxide, and Water Vapor at 23  C through BASF AG
Polystyrol 168 N GPPS Film9

Permeability Coefficient

Source Document Units Normalized Units

Permeant Gas (cm3/100 in.2 day bar) (cm3 mm/m2 day atm)
Oxygen 1000 101
Nitrogen 250 25.3
Carbon dioxide 5200 527
Vapor Transmission Rate

Permeant Vapor Source Document Units (g/m2 day) Normalized Units (g mm/m2 day)
Water 12 1.2
Thickness: 0.1 mm; test methods: DIN 53380 and DIN 53122.

Table 5.14 Permeation of Oxygen, Nitrogen, Carbon Dioxide, and Water Vapor at 24  C through Dow Chemical
TryciteÔ Oriented PS Film8

Permeability Coefficient

Source Document Units (cm3 mil/100 Normalized Units

Permeant Gas in.2 day bar) (cm3 mm/m2 day atm)
Oxygen 250e350 98e138
Nitrogen 50e60 19.7e23.6
Carbon dioxide 700e1100 276e433
Vapor Transmission Rate

Source Document Units

Permeant Vapor (g mil/m2 day) Normalized Units (g mm/m2 day)
Water 9 3.5

Table 5.15 Permeation of Oxygen, Nitrogen, Carbon Dioxide, and Water Vapor at 23  C through BASF AG
Polystyrol 476L HIPS Film9

Permeability Coefficient

Source Document Units Normalized Units

Permeant Gas (cm3/m2 day bar) (cm3 mm/m2 day atm)
Oxygen 1600 162
Nitrogen 400 40.5
Carbon dioxide 10,000 1013
Vapor Transmission Rate

Permeant Vapor Source Document Units (g/m2 day) Normalized Units (g mm/m2 day)
Water 13 1.3
Thickness: 0.1 mm; test methods: DIN 53380 and DIN 53122; see also Figs 5.7e5.9.
5: S TYRENIC P LASTICS 85

Figure 5.7 Permeation of oxygen vs. temperature through Dow Chemical StyronÔ PS film.8

Figure 5.8 Permeation of water vapor vs. thickness through Dow Chemical StyronÔ PS film.8
86
Figure 5.9 Gas permeation vs. temperature of PS.12
5.4 StyreneeAcrylonitrile
Copolymer
Styrene and acrylonitrile monomers can be copo-
lymerized to form a random, amorphous copolymer
that has good weatherability, stress crack resistance,
and barrier properties. The copolymer is called
styreneeacrylonitrile or SAN copolymer. The SAN
copolymer generally contains 70e80% styrene and
20e30% acrylonitrile. It is a simple random copol-
ymer. This monomer combination provides higher
strength, rigidity, and chemical resistance than PS,
Figure 5.10 Chemical structure of SAN.
P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS
but it is not quite as clear as crystal PS and its
appearance tends to discolor more quickly. The
general structure is shown in Fig. 5.10. Its CAS
number is 9003-54-7.
Manufacturers and trade names: BASF LuranÒ ,
Dow Chemical TYRIL Resins.
Applications and uses: Household: Mixing bowls,
electric mixers, refrigerator inserts, tableware,
vacuum flask casings, food storage containers,
toiletries, cosmetics packaging, writing imple-
ments, and industrial batteries (Tables
5.16e5.18).
5: S TYRENIC P LASTICS 87

Table 5.16 Permeation of Oxygen at 23  C of BASF LuranÒ SAN10

Permeability Coefficient

Source Document Units Normalized Units

LuranÒ Grade (cm3/m2 day bar) (cm3 mm/m2 day atm)
358N 200e500 20.2e50.6
378P 200e300 20.2e30.4
Thickness: 0.100 mm; test method: DIN 53380.

Table 5.17 Permeation of Water Vapor at 23  C of BASF LuranÒ SAN11

Permeability Coefficient

LuranÒ Grade Source Document Units (g2/m2 day) Normalized Units (g mm/m2 day)
358N 20e25 2.0e2.5
378P 20e25 2.0e2.5
Thickness: 0.100 mm; test method: DIN 53122; relative humidity gradient: 85e0%.

Table 5.18 Permeation of Gases at 24  C through Dow Chemical TyrilÒ Low

Acrylonitrile Content SAN11

Permeability Coefficient

Source Document Units Normalized Units

Permeant Gas (cm3 mil/100 in.2 day atm) (cm3 mm/m2 day atm)
Oxygen 80e100 31.5e39.4
Nitrogen 10 3.9
Carbon dioxide 400 157

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1. Oxygen and water permeability, Cycolac Resins.
GE Plastics; 1997e2002.
2. Permeability of polymers to gases and vapors.
Supplier technical report (P302-335-79,
D306-115-79). Dow Chemical Company; 1979.
3. Terluran product line, properties, processing.
Supplier design guide [B 567e/(8109) 9.90].
BASF Aktiengesellschaft; 1990.
4. Marchese J. Gas sorption, permeation and
separation of ABS copolymer membrane.
J Memb Sci 2003;221(1e2):185e97. Available
from, http://linkinghub.elsevier.com/retrieve/pii/
S0376738803002588.
line, properties, processing. Supplier design
guide (B 566e/1 1.90). BASF Aktiengesellschaft;
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6. LuranÒ S Acrylonitrile Styrene Acrylate product
line, properties, processing. Supplier design
guide (B 566e/10.83). BASF Aktiengesellschaft;
1983.
7. LuranÒ S Plastic Plus acrylonitrileestyrenee
acrylate copolymer (ASA and ASA þ PC).
2007.
8. Permeability of polymers to gases and
vapors. Supplier technical report
(P302-335-79, D306-115-79). Dow Chemical
Company; 1979.
88 P ERMEABILITY P ROPERTIES OF P LASTICS AND E LASTOMERS

9. Polystyrol product line, properties, processing.
Supplier design guide (B 564e/2.93). BASF
Aktiengesellschaft; 1993.
10. LuranÒ brochure, LSIL 0701 BE. BASF; 2010.
11. Permeability of polymers to gases and vapors.
Supplier technical report (P302-335-79,
D306-115-79). Dow Chemical Company; 1979.
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gases by means of permeable membranes.
Permeability of plastic membranes to gases. Ind
Eng Chem 1952;44(6):1465e74. Available
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