010

from. 9/2 COMMODITY PLASTICS

T
R IN tern
P n
RE ffe i
o
stst
n
Ku
SBS are found in a
wide variety of applications and are
processed by various methods (photos: BASF)

Styrene-Butadiene-Block Copolymers. By using living anionic polymerization of

rigid styrene and flexible butadiene blocks, it is possible to design SB block
copolymers with customized properties. The spectrum of properties ranges from
soft and elastic for soft-touch applications, to flexible for film and rigid as well as
impact-resistant for transparent injection molded parts. Most applications are
currently found in the packaging sector.

Designer Products Based

on a Modular Approach
DANIEL WAGNER 20 years of Styrolux in Antwerp, Belgium, in Düsseldorf, Germany, only 15 years
KONRAD KNOLL and 15 years of Styroflex. ago.
The SB block copolymer Styrolux was
Modules for a Wide Range of

S
tyrene-butadiene (SB) block copoly- first produced on a commercial scale
mers are a relatively new and inno- about 30 years ago in Ludwigshafen, Ger- Properties
vative field in which many new de- many. In 1990, barely ten years later, a sec-
velopments have recently become ready ond production facility was built in A particular characteristic of the SB block
to market. At the same time – and per- Antwerp. In 2004, an additional produc- copolymers is the intentional creation of
haps for related reasons – BASF is also cel- tion facility was added in in Altamira, block structures through living anionic
ebrating two anniversaries in this field: Mexico. Today, BASF has a production ca- polymerization to yield a sequence of
pacity of 110,000 t/a. hard styrene blocks and soft butadiene or
Translated from Kunststoffe 9/2010, pp. 186–189 A special variant of this product fam- butadiene-rich blocks in clear distinction
Article as PDF-File at www.kunststoffe- ily, the thermoplastic elastomer (TPE) from the elastomers produced from
international.com; Document Number: PE110538 Styroflex, was launched at the K show styrene and butadiene (the SBR synthet-

Kunststoffe international 9/2010 1

 COMMODITY PLASTICS

prene-styrene) and the hydrated, more Developed originally as an alternative

i Contact weather-resistant SEBS (styrene-ethyl- to flexible PVC, Styroflex can, in the
ene-butylene-styrene) as well as the SEPS meantime, be found in many applica-
BASF SE (styrene-ethylene-propylene-styrene) tions, for instance, in stretch and cling
Trade press office Plastics copolymers that were first marketed by films for transparent meat packaging or
D-67056 Ludwigshafen Shell in the mid-1960s under the trade as the soft touch component on baby toys
Germany name Kraton [5, 6]. and razors.
TEL: +49 621 60-43348 The primary characteristics of this
> www.plasticsportal.eu product class include, among others, the High-impact Products with
good elastic recovery (resilience) and the Increasing Styrene Content
low Shore hardness – lowered preferen-
ic rubbers) using the radical technology tially through addition of white oil – mak- SBS block copolymers with a 70 to 80 %
and high-impact polystyrene (HIPS) with ing soft touch applications possible for in- polystyrene hard phase (HS-SBS) belong
grafted, cross-linked polybutadiene par- stance. to the class of tough-rigid, transparent
ticles. The “living”nature of this polymer- Except for polyolefins, however, these thermoplastics. In addition to the trans-
ization with Li alkyls as chain starters was classic styrenic TPEs exhibit only unsat- parency and mechanical strength inher-
discovered and defined in 1956 by Szwarc. isfactory compatibility with other plas- ent to SB block copolymers, good com-
The block structure is achieved through tics. Their low polarity makes printing patibility with general-purpose poly-
sequential addition and complete reac- problematic, and the sometimes very high styrene (GPPS) along with high ductility
tion of the monomers. The reactive chain order-disorder temperature (ODT) caus- and an elongation at break frequently ex-
ends can be terminated by protonization es inhomogeneities in the melt, making ceeding 300 % are particular characteris-
or through addition of multi-functional film extrusion and stable processing dif- tics of these materials. The latter are at-
coupling agents to yield star polymers. ficult [7]. tributable to the deformation mechanism
This yields very monomer-poor styrene
copolymers that are found to be very
rugged thermoplastics.
The creation of statistical SB blocks or
block sequences requires the addition of
specific additives, so-called randomizers,
under closely defined conditions, since
otherwise anionic copolymerization of
styrene and butadiene occurs with pref-
erential incorporation of butadiene into 0.5 µm
the chain [1].
The driving force for phase separation 0% <15 % 15 – 35 % 35 – 65 % 65 – 85 % > 85 % 100 %
Styrene content
and the formation of nanoscale structures
is the incompatibility of the polystyrene Rubber Thermoplastic elastomer „Plastomer”
High-impact
Brittle thermoplastic
thermoplastic
(PS) and polybutadiene (PB) blocks. The
high transparency and mechanical © Kunststoffe
strength of this product class result from
this morphology. The hard-soft-hard (i.e. Fig. 1. Depending on the phase-volume ratio, the thermoplastic or elastomeric character of SBS block
PS-PB-PS) block sequence alone has copolymers predominates
gained technological significance, since it
is responsible for the strength of the ma- Thanks to its considerably more polar under shear, which is distinctly different
terial. Good overviews of the production soft phase, the Styroflex 2G 66 introduced from the “crazing” found in HIPS.
and uses of SBS block copolymers and by BASF in 1995 no longer exhibited these The good compatibility with GPPS is
their blends with other plastics can be drawbacks. Above 145°C (ODT), it yields achieved through an asymmetric
found in the literature references [2] and a homogeneous melt, making it easier to arrangement of the SBS block structures
[3]. The CEH Report [4] analyzes the process and, in addition, is extremely re- with at least one very long PS block. This
worldwide market for this product group. sistant against thermo-oxidative degra- gives the processor a two-fold advantage:
With the symmetrical SBS block dation. This TPE can be printed readily on the one hand, mixing with the consid-
copolymers, the phase volume ratio de- and offers good adhesion and part com- erably lower-cost GPPS brings down ma-
cides whether the thermoplastic or the patibility with a number of transparent terial costs, on the other, the stiffness and
elastomeric character predominates and opaque plastics. This permits its use heat-deflection temperature of the fin-
(Fig. 1). in two-component injection molding and ished product can be increased.
as an adhesion promoter in multi-layer Linear asymmetric SBS block copoly-
High Butadiene Content Yields films, and sealing wax formulations and mers were first marketed by Asahi, and
Thermoplastic Elastomers as a compatibilizer in plastic blends. Fur- star-shaped coupled polymers under the
thermore, as an impact modifier, it im- trade name K-Resin by Phillips 66 (today:
If the soft, elastic component forms the proves the application characteristics of Chevron Phillips Chemical) at the end of
continuous phase, classic thermoplastic HIPS (high-impact polystyrene) and ABS the 1960s [6].
elastomers (TPE) result. These include, in (acrylonitrile-butadiene-styrene copoly- Coupling of long and short block seg-
addition to SBS, the SIS- (styrene-iso- mer) [3]. ments to create star-shaped molecules

2 © Carl Hanser Verlag, Munich Kunststoffe international 9/2010

 COMMODITY PLASTICS

Fig. 2. The long PS the newest grades is the extremely trans-

block in the asym- parent Styrolux 3G 46, which can be
Elastic
Polystyrene
core
Compatible metric SBS block found in high-quality display packages,
Polybutadiene with GPPS structure ensures for instance.
that the polymer is
quite compatible Focus on Memory Effect
with the low-cost
GPPS; coupling of While essentially the basic structure-
long and short seg- property relationships were examined in
ments to form star- the past two decades, today’s research in
shaped structures the field of SBS block copolymers pro-
with good toughness duced using anionic technology is fo-
was already cused increasingly on the synthesis of
achieved in the early “memory” materials and mixtures of dif-
Styrolux grades, also ferent SBS block structure types. The lat-
in mixtures with ter occasionally exhibit unexpected syn-
large amounts of ergistic effects, expanding the property
© Kunststoffe
GPPS spectrum of this product group further.
In 2007, BASF first presented a prod-
uct optimized for production of shrink
leads to a broad molar mass distribution containing styrene and butadiene re- film in the form of Styrolux HS 70. Mod-
as a consequence of the statistical fre- gions, the BASF researchers achieved their eling of the shrink curve, very high final
quency distribution. The average of three objective without having to incorporate shrinkage of over 70 % at temperatures
to five branches per polymer chain im- more butadiene into the polymer chains. near 80°C and little natural shrinkage at
proves processing and reduces the orien- In a further development step, these temperatures below 40 °C was achieved
tation dependence of mechanical prop- smeared transitions were replaced through intentional tuning of different
erties. through the intentional incorporation of glass-transition temperatures. BASF re-
BASF also followed this structure con- defined statistical SB blocks in Styrolux searchers made an additional advance
cept with the Styrolux brands introduced 3G 55. with the two-component Styrolux T/S,
in the early 1980s. In this case, a primary In addition to the hard PS blocks and which allows film producers to achieve
development objective was to further in- the highly elastic PB blocks, the mixed the properties desired in their product by
crease the “toughness efficiency” of these blocks create their own semi-hard and mixing the two components T and S
products in mixtures with GPPS (Fig. 2). pronounced ductile phase (also called an themselves. Styrolux T/S films have the
Here, the expression “toughness efficien- “interphase”) that improves the tough- same optimized shrinkage behavior
cy” stands for the ability of SBS block ness efficiency of products in SBS/PS found in film produced from the HS 70
copolymers to retain a good, useful blends enormously. grade (Figs. 3 and 4). With an even further
toughness even when mixed with relative- The Styrolux grades are characterized improved toughness-stiffness ratio in
ly high amounts of GPPS. The Styrolux by high transparency, surface gloss as combination with exceptional trans-
brands with very high toughness efficien- well as a good ratio of toughness to stiff- parency and brilliance, these materials
cy thus permit economical production of ness. Mixed primarily with GPPS, they differ distinctly from transparent poly-
transparent packaging. are extruded into film and thermo- propylene and in this regard achieve the
With intentional synthesis of mixed, formed to yield a variety of parts, but al- level characteristic of polyesters. The den-
so-called “smeared” block transitions so find use in injection molding. Among sity advantage of up to 30 % compared

Process window
100
% Styrolux T/S
Conventional High final shrinkage
80
SBC/PS blends
Shrinkage

60

40
Gradual,
not too steep
20

0
50 60 70 80 90 °C 100
Temperature © Kunststoffe

Fig. 3. The Styrolux T/S system can be custom-formulated directly at customers Fig. 4. Films made of Styrolux T/S are very well-suited for shrink-labeling
thanks to the newly developed individual components Styrolux T and of complex bottle shapes by means of sleeves (left), but also when using
Styrolux S; film producers and packagers benefit from the uniform shrinkage the ROSO method, which uses a wrap-around adhesive-bonded label
behavior as well as the high final shrinkage of films made from Styrolux T/S (right)

Kunststoffe international 9/2010 3

 COMMODITY PLASTICS

TPE can raise the basic toughness of HIPS REFERENCES

considerably. This converts the general- 1 Knoll, K.: Ionische Polymerisation. In G. W. Becker
purpose plastic into a mechanically very et al. (Hrsg.) Polystyrol, Kunststoff-Handbuch 4,
strong material in a very economical way. Hanser-Verlag, München 1996
Moreover, addition of Styroflex also im- 2 Knoll, K.: Anionische Blockcopolymere. In G. W.
proves adhesion of the film to the foam Becker et al. (Hrsg.) Polystyrol, Kunststoff-Hand-
and creates a non-slip surface. buch 4, Hanser-Verlag, München 1996
3 Styrolux and Styroflex – From Transparent High
Outlook Impact Polystyrene to New Thermoplastic Elas-
tomers. Macromol Symp 132 (1998) pp. 231–243
Development of SBS block copolymer ap- 4 CEH Marketing Research Report: Styrenic Copoly-
plications and markets targeted at growth mers. By Uwe Löchner et al., The Chemical Eco-
segments is accompanying the product nomics Handbook – SRI Consulting, March 2010
innovations. 5 G. Holden et al. (Hrsg.) Thermoplastic Elastomers
While the classic segments – transpar- 2nd Edition, Hanser-Verlag, München 1996
ent food packaging, flexible film and in- 6 Hsieh, H. L.; Quirk, R. P.: Anionic Polymerization:
jection molded items – still represent the Principles and Practical Applications. Marcel
primary areas for sale of SBS polymers, Dekker, New York 1996
Fig. 5. Thanks to high stretchability and elastic special applications such as the above- 7 Hashimoto, T.: Order-Disorder Transition in Block
recovery, goods with a variety of shapes, mentioned shrink and stretch films, im- Polymers. G. Holden et al (Hrsg.) Thermoplastic
including sharp-edged items, can be secured pact modification of other thermoplas- Elastomers 2nd Edition, Hanser-Verlag, München
to a palette by a stretch hood made of tics or elastomers and the compatibiliz- 1996
Styroflex 2G66; in spite of different packaging ing effect in blends are gaining in impor-
tasks and pallet sizes, the packager needs tance. THE AUTHORS
only one film tube size DR. DANIEL WAGNER is responsible for SBS block
copolymer product development at BASF SE, Lud-
to PET-G that is so important for the eco- wigshafen, Germany.
nomics of SBS remains unchanged. DR. KONRAD KNOLL heads the research unit for
The stretch hoods made of the TPE controlled polymerization, with a focus on anionic
Styroflex 2G 66 used to protect goods ef- polymerization, at BASF SE, Ludwigshafen.
fectively during loading and unloading as
well as handling in warehouses are anoth-
er example of a memory product. Films
made of pure Styroflex in multi-layer
structures with polyethylene are also en-
countered in this application. Thanks to
their good elastic recovery, films with Sty-
roflex layers conform closely to the pack-
age goods even after being stretched by
220 %. Here, the high tear strength and
good puncture resistance of the elastic
TPE are beneficial, above all when pack- Fig. 6. At the K2010, BASF will exhibit the new
aging sharp-edged items (Fig. 5). EPS pallettes from the Hirsch company; the film
system that encases the pallets is based on
Impact Modifier, Adhesion several HIPS layers that contain different
Promoter and Slip Preventer amounts of Styroflex (small photo)
in One
Even though the principles of anionic
Another example from the logistics sec- polymerization of styrene and butadiene,
tor is a new application where Styroflex and the SBS block copolymers based on
2G 66 is used as an impact modifier for a this technology have long been known,
two-layer HIPS film (Fig. 6). It protects the dedicated and intense research and mar-
lightweight polystyrene foam core of a ket development efforts together with
plastic pallet against damage. Addition of customers continue to expand the poten-
even small amounts of the highly elastic tial of these products. 

© Carl Hanser Verlag, München 2010. All rights including reprinting,

photographic reproduction and translation reserved by the publishers.

4 © Carl Hanser Verlag, Munich Kunststoffe international 9/2010