ROHSTOFFE UND ANWENDUNGEN

RAW MATERIALS AND APPLICATIONS

Rolling Resistance · Synthetic Rubber

Vulcanizates · Polymer-Filler Interac-
Polymer Functionalization
tion · Functionalised Rubber · Chain-
End Functionalisation Novel Rubber for Tire Tread Application
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 With the background of continuously rising were measured according to ASTM D 412-
work leading to a new modified SSBR oil prices the pressure on automobile pro- 98A (reapproved 2002) on a Zwick Z010.
grade are discussed. The new SSBR ducers and tire producers is increasing to Heat build up was measured according to
enables a significant improvement of come up with long life, fuel saving and safe ASTM D 623, method A, on a Doli ‘Goodrich’-
the tire rolling resistance, identified as solutions. Accordingly there is the need for Flexometer.
37 percent decrease of the tan E @ tires with low rolling resistance combined Measurement of un-vulcanized rheological
60 °C. In addition, beneficial heat built
with excellent wet grip and abrasion per- properties according to ASTM D 5289-95
up, abrasion and ice grip characteristics
(measured as tan E @ -10 °C) were formance characteristics. (reapproved 2001) were made using a rotor-
found. While silica filled tires have already been less shear rheometer (MDR 2000 E) to meas-
introduced in 1992 to reduce rolling resist- ure Scorch Time (TS) and Time to Cure (TC).
ance there is still a considerable potential Tan E (60 °C) was measured using dynamic
Polymer Modifisierung for further improvement of the rolling re- spectrometer Eplexor 150N manufactured
sistance and thus for reduction of fuel con- by Gabo Qualimeter Testanlagen GmbH
Rollwiderstand · Kautschuk sumption. Particularly for high performance (Germany) applying a compression dynamic
Vulkanisate · Polymer-Füllstoff Wech- automobile tires functionalized solution strain of 0.2 % at a frequency of 2 Hz at
selwirkung · Kautschuckfunktionalisie- butadiene-styrene rubber (SSBR) could of- 60 °C. Tan E (0 °C) & Tan E (-10 °C) were meas-
rung · Kettenendfunktionalisierung fer significant improved rolling resistance ured using the same equipment and load
Steigende Öl und Treibstoffpreise sowie with well balanced wet grip and wear. conditions at 0 °C or -10 °C.
das steigende Risiko einer globalen The interaction of functionalized rubbers DIN abrasion was measured according to
Erwärmung führen zu immer vehe- with carbon black filler has been investi- DIN 53516 (1987-06-01).
menteren Forderungen die globalen gated very intensively in the eighties and
CO2 Emissionen zu reduzieren. Die nineties and has led to the development of Results and Discussion
Preisentwicklung bei Benzin und Diesel chain-end modified polymers. Efficient Based on the knowledge derived from typi-
sowie erste gesetzlich fixierte Vorgaben
chain-end modification was achieved for cal model reactions, using alternative mod-
in einigen Industriestaaten fordern
carbon black compounds with polymer ifier compounds, a number of modified sty-
höhere Energieeffizienz in der Automo-
bilindustrie. Eine Möglichkeit der chain-end attached amino or cyano groups, rene-butadiene copolymers were prepared.
Treibstoffersparnis besteht in der alcohols, epoxides and other functional For example styrene-butadiene copolymers
Anwendung von Automobilreifen mit groups [1-3]. were modified with amines, epoxides, si-
reduziertem Rollwiderstand. Die Chain-end modified SSBR developed for car- lanes or siloxanes in our Synthetic Rubber
Verwendung neuartiger modifizierter bon black containing compound vulcani- laboratory and investigated with respect to
SSBR Typen in der Lauffläche der Reifen zates often turned out not to be ideal or their affinity to silica filler in rubber com-
repräsentiert eine Variante der Rollwi- even insufficient for silica containing for- pounds.
derstandsoptimierung. Die hier vorge-
mulations. Thus, the silica particle distribu- Novel solution-styrene butadiene copoly-
stellte SSBR Type ermöglicht eine
tion reportedly remained relatively poor mers were compounded and vulcanized
Verringerung des Kennwertes für den
Rollwiderstand, tan E @ 60 °C, um 37 % and the improvement of the dynamic vul- and extensively characterized.
und führt damit zu einer markanten canizate properties was limited. Accord-
Reduktion des Rollwiderstandes. ingly, for the application in silica containing
Weitere vorteilhafte Attribute der compounds novel polymers based on alter-
neuen Polymertype sind ein abge- native modifiers are required. These modi- Authors
senkter Wärmeaufbau, ein verbessertes fier molecules have to be linked to polymer
Haftungsvermögen bei niedrigen S. Thiele, D. Bellgardt, M. Holzleg,
chain ends under mild conditions. Schkopau
Umgebungstemperaturen, repräsen-
tiert durch einen höheren Wert des
tan E @ -10 °C, und ein verbessertes
Experimental Corresponding Author
Abriebverhalten im Modified and unmodified styrene-butadi- Dr. Sven K.H. Thiele
ene rubbers were compounded with silica Dow Olefinverbund GmbH
Mischungsvulkanisat.
according to test formulations listed in R&D Synthetic Rubber
PF 1163
Table 1 below. A two stage mixing process
06201 Merseburg
was applied. Tel.: 03461-49-2711
Tensile strength, elongation at break and Fax: 03461-49-3326
modulus at 300 % elongation (Modulus 300) E-Mail: ssthiele@dow.com

244 KGK · Mai 2008

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

References Zinc oxide 2.5

[1] R. P. Quirk, Comprehensive Polymer Science, Oil MES 20.0

First Supplement; Pergamon Press: Oxford, UK,
Sulfur 1.4
1992, page 83.
[2] H. L. Hsieh; R. P. Quirk, Anionic Polymerization: CBS** 1.5
Principles and Practical Applications; Marcel
DPG*** 1.5
Dekker: New York, 1996.
[3] E. J. Goethals, Ed. Telechelic Polymers: Synthesis * 2 stage mixing, Brabender 350S
and Applications; CRC Press: Boca Raton, Fl, ** N-cycloliexyl-2-benzothiazylsulfenamid; Vulcacit CZ/EG , Lanxess AG)
1989. *** Diphenylguanidin, Vulkacit D, Lanxess Deutschland GmbH Bold: Second stage (vulcanization)

KGK · Mai 2008 245