ROHSTOFFE UND ANWENDUNGEN
RAW MATERIALS AND APPLICATIONS
Rolling Resistance · Synthetic Rubber
Vulcanizates · Polymer-Filler Interac-
tion · Functionalised Rubber · Chain-
End Functionalisation
Rising oil and fuel prices and the threat
of global warming increase the pres-
sure on both automotive and tire
industries to reduce a vehicle’s fuel
consumption and CO2 emission. An
optimized tire rolling resistance con-
tributes to fuel efficiency. In this
respect, steps of the developmental
work leading to a new modified SSBR
grade are discussed. The new SSBR
enables a significant improvement of
the tire rolling resistance, identified as
37 percent decrease of the tan E @
60 °C. In addition, beneficial heat built
up, abrasion and ice grip characteristics
(measured as tan E @ -10 °C) were
found.
Polymer Modifisierung
Rollwiderstand · Kautschuk
Vulkanisate · Polymer-Füllstoff Wech-
selwirkung · Kautschuckfunktionalisie-
rung · Kettenendfunktionalisierung
Steigende Öl und Treibstoffpreise sowie
das steigende Risiko einer globalen
Erwärmung führen zu immer vehe-
menteren Forderungen die globalen
CO2 Emissionen zu reduzieren. Die
Preisentwicklung bei Benzin und Diesel
sowie erste gesetzlich fixierte Vorgaben
in einigen Industriestaaten fordern
höhere Energieeffizienz in der Automo-
bilindustrie. Eine Möglichkeit der
Treibstoffersparnis besteht in der
Anwendung von Automobilreifen mit
reduziertem Rollwiderstand. Die
Verwendung neuartiger modifizierter
SSBR Typen in der Lauffläche der Reifen
repräsentiert eine Variante der Rollwi-
derstandsoptimierung. Die hier vorge-
stellte SSBR Type ermöglicht eine
Verringerung des Kennwertes für den
Rollwiderstand, tan E @ 60 °C, um 37 %
und führt damit zu einer markanten
Reduktion des Rollwiderstandes.
Weitere vorteilhafte Attribute der
neuen Polymertype sind ein abge-
senkter Wärmeaufbau, ein verbessertes
Haftungsvermögen bei niedrigen
Umgebungstemperaturen, repräsen-
tiert durch einen höheren Wert des
tan E @ -10 °C, und ein verbessertes
Abriebverhalten im
Mischungsvulkanisat.
244 KGK · Mai 2008
Polymer Functionalization
Novel Rubber for Tire Tread Application
With the background of continuously rising
oil prices the pressure on automobile pro-
ducers and tire producers is increasing to
come up with long life, fuel saving and safe
solutions. Accordingly there is the need for
tires with low rolling resistance combined
with excellent wet grip and abrasion per-
formance characteristics.
While silica filled tires have already been
introduced in 1992 to reduce rolling resist-
ance there is still a considerable potential
for further improvement of the rolling re-
sistance and thus for reduction of fuel con-
sumption. Particularly for high performance
automobile tires functionalized solution
butadiene-styrene rubber (SSBR) could of-
fer significant improved rolling resistance
with well balanced wet grip and wear.
The interaction of functionalized rubbers
with carbon black filler has been investi-
gated very intensively in the eighties and
nineties and has led to the development of
chain-end modified polymers. Efficient
chain-end modification was achieved for
carbon black compounds with polymer
chain-end attached amino or cyano groups,
alcohols, epoxides and other functional
groups [1-3].
Chain-end modified SSBR developed for car-
bon black containing compound vulcani-
zates often turned out not to be ideal or
even insufficient for silica containing for-
mulations. Thus, the silica particle distribu-
tion reportedly remained relatively poor
and the improvement of the dynamic vul-
canizate properties was limited. Accord-
ingly, for the application in silica containing
compounds novel polymers based on alter-
native modifiers are required. These modi-
fier molecules have to be linked to polymer
chain ends under mild conditions.
Experimental
Modified and unmodified styrene-butadi-
ene rubbers were compounded with silica
according to test formulations listed in
Table 1 below. A two stage mixing process
was applied.
Tensile strength, elongation at break and
modulus at 300 % elongation (Modulus 300)
were measured according to ASTM D 412-
98A (reapproved 2002) on a Zwick Z010.
Heat build up was measured according to
ASTM D 623, method A, on a Doli ‘Goodrich’-
Flexometer.
Measurement of un-vulcanized rheological
properties according to ASTM D 5289-95
(reapproved 2001) were made using a rotor-
less shear rheometer (MDR 2000 E) to meas-
ure Scorch Time (TS) and Time to Cure (TC).
Tan E (60 °C) was measured using dynamic
spectrometer Eplexor 150N manufactured
by Gabo Qualimeter Testanlagen GmbH
(Germany) applying a compression dynamic
strain of 0.2 % at a frequency of 2 Hz at
60 °C. Tan E (0 °C) & Tan E (-10 °C) were meas-
ured using the same equipment and load
conditions at 0 °C or -10 °C.
DIN abrasion was measured according to
DIN 53516 (1987-06-01).
Results and Discussion
Based on the knowledge derived from typi-
cal model reactions, using alternative mod-
ifier compounds, a number of modified sty-
rene-butadiene copolymers were prepared.
For example styrene-butadiene copolymers
were modified with amines, epoxides, si-
lanes or siloxanes in our Synthetic Rubber
laboratory and investigated with respect to
their affinity to silica filler in rubber com-
pounds.
Novel solution-styrene butadiene copoly-
mers were compounded and vulcanized
and extensively characterized.
Authors
S. Thiele, D. Bellgardt, M. Holzleg,
Schkopau
Corresponding Author
Dr. Sven K.H. Thiele
Dow Olefinverbund GmbH
R&D Synthetic Rubber
PF 1163
06201 Merseburg
Tel.: 03461-49-2711
Fax: 03461-49-3326
E-Mail: ssthiele@dow.com
As one result of our developmental work,
1 1 Rubber-Silica Com-
modified polymers are available which en-
pound Vulcanizate
able an improvement of the tire rolling re- Properties
sistance, identified as e.g. 34 percent de- (The higher the value
crease of the tan E @ 60 °C in silica com- the better the prop-
pound vulcanizates when compared with erty)
non-modified SSBR grade properties
(Ref. B).
Particularly in case of silica based formula-
tions the rolling resistance related tan E @
60 °C of the vulcanizate was decreased by
37 % when compared with Ref A (SE SLR-
4601). Furthermore, the tan @ -10 °C often
referred to tire ice grip properties was im-
proved by 14 %, the DIN abrasion resistance
was reduced by about 10 % and the Goodrich
heat built-up decreased by 18 % (Fig.1 ).
2 2 Benefits of the novel SSBR
grade
Summary (Depicted values relate to
Styrene-butadiene copolymers were appro- absolute values)
priately modified, resulting in an efficient
interaction with silica in silica formulations.
The improved rubber – silica filler interac-
tion is reflected by improved dynamic vul-
canizate properties.
The new modified SSBR grade provides an
excellent balance in the most important
tire properties low tire rolling resistance,
low tire abrasion and grip on a wet road.
The new polymer further improves silica
compound vulcanizate properties, particu-
larly the tan E @ 60 °C by about 37 % 1 Silica Containing Test Formulation*
(Fig.2 ).
Components Amount [phr]
Research efforts are continuing to further
decrease tire rolling resistance, which will SSBR 80.0
help to reduce automobile fuel consump- BR Buna cis 132-Schkopau 20.0
tion and CO2 emission.
Silica U7000GR 80.0

Acknowledgements Silane NXTSilane 9.7

The authors are grateful to The Dow Chem- Stearic acid 1.0
ical Company for granting permission to
Stabiliser system Antilux 1.5
publish this work.
6 PPD 2.0

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KGK · Mai 2008 245