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High performance bio-based elastomers: energy efficient, sustainable

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 Journal of
Materials Chemistry A
COMMUNICATION
Published on 04 August 2016. Downloaded by Beijing University of Chemical Technology on 17/09/2016 13:42:28.
High performance bio-based elastomers: energy
efficient and sustainable materials for tires†
Cite this: J. Mater. Chem. A, 2016, 4,
13058
Weiwei Lei,‡ab Xinxin Zhou,‡ab Thomas P. Russell,*cd Kuo-chih Hua,e Xiaoping Yang,e
Received 15th June 2016 He Qiao,ab Wencai Wang,ab Fanzhu Li,ab Runguo Wang*ab and Liqun Zhang*ab
Accepted 2nd August 2016
DOI: 10.1039/c6ta05001h
www.rsc.org/MaterialsA
Globally, we are faced with a massive growth in the number of urban
vehicles. This growth comes at the cost of enormous fuel consumption,
CO2 emissions and air pollution, commonly seen as a haze. With
a strategy to fabricate low roll-resistance green tire elastomers from
large-scale, bio-based chemicals, specifically itaconic acid, mono-
alcohols and conjugated dienes, each of these problems can be
reduced. By combining a molecular structural design with non-petro-
leum based silica and an in situ process to tune the viscoelastic prop-
erties of the elastomer composites, we have successfully manufactured
silica/poly(di-n-butyl itaconate-co-butadiene) nanocomposite-based
green tires that have very low roll-resistance, excellent wet skid resis-
tance and good wear resistance, promote fuel efficiency and reduce
our dependence on petrochemical resources. The results shown here
open an important avenue for the synthetic rubber and automobile
industry to ameliorate a major problem facing many cities worldwide,
and also provide an effective route for resource sustainability.
Passenger vehicles play a fundamental role in our everyday life.
In 2015, approximately one billion passenger cars were in use
around the world.1 This widespread use of cars has far-reaching
a
State Key Laboratory of Organic–Inorganic Composites, Beijing University of Chemical
Technology, Beijing 100029, China. E-mail: zhanglq@mail.buct.edu.cn; wangrg@
mail.buct.edu.cn
b
Engineering Research Center of Ministry of Education on Energy and Resource Saved
Elastomers, Beijing University of Chemical Technology, Beijing 100029, China. E-mail:
russell@mail.pse.umass.edu
c
Beijing Advanced Innovation Center for So Matter Science and Engineering, Beijing
University of Chemical Technology, Beijing 100029, China
d
Department of Polymer Science and Engineering, University of Massachusetts,
Amherst, Massachusetts 01003, United States
e
Goodyear Innovation Center, Goodyear Tire & Rubber Co., D/463D, P. O. Box 531,
Akron, Ohio 44309-3531, United States
† Electronic supplementary information (ESI) available: Materials and methods;
the structures and properties of di-n-alkyl itaconates, poly(di-n-alkyl
itaconates-co-isoprene) (PDAII) and poly(di-n-butyl itaconate-co-butadiene)
(PDBIB); mechanical properties of silica lled PDAII and silica lled PDBIB;
silica/PDBIB green tire manufacture and roll-resistance test. See DOI:
10.1039/c6ta05001h
‡ These authors contributed equally to this work.
13058 | J. Mater. Chem. A, 2016, 4, 13058–13062
View Article Online
View Journal | View Issue
environmental and health-related consequences, including, but
not limited to, CO2 emission and progressively worsening urban
haze. Tires, an essential component of all urban and rural
vehicles and equipment, account for
20% of fuel used. The
roll resistance of the tire accounts for a startling 4% of world-
wide carbon dioxide emissions from fossil fuels.2,3 It is widely
recognized that fuel consumption will decrease by 2–3%, if the
roll-resistance coefficient decreases by 10%.4 There are indus-
trial guidelines on tire labelling to promote the fuel efficiency of
tires, for example, the EU Tyre Labelling Regulation 1222/2009.
Therefore, developing manufacturable low roll-resistance green
tires is critical.
Usually, elastomers need to be reinforced with llers to
ensure sufficient strength, wear resistance and elastic proper-
ties. However, viscous dissipation, due to the relaxation of
polymer chains, in both lled and unlled systems, under an
applied load results in a great amount of useless fuel
consumption.5–7 Many factors in lled polymeric systems,
including macromolecular structure, aggregate structure,
dispersion and interfacial interaction, can affect the roll resis-
tance of tires. The values of the loss tangent at 60  C for elas-
tomeric materials and the roll-resistance coefficients of tires are
laboratory and industrial benchmarks for fuel consumption.
Tread elastomers, which are the largest elastomeric component
of the tire, are the primary target for fuel saving, wet skid
resistance and wear resistance. Wet skid resistance, determined
by the structure and properties of the tire composites, is of
extreme practical importance and a major concern for safety.
Elastomeric materials with high loss tangents at 0  C will
exhibit good wet skid performance and the energy dissipation of
automobiles will be highly efficient during braking. However,
simultaneously reducing the loss tangent at 60  C and
improving the loss tangent at 0  C of elastomeric materials is
a major challenge. Silica-reinforced anionic solution polymer-
ized styrene-butadiene rubber (SSBR) composites are widely
used in the tire industry and have become the most important
tread material for the present green tires, which have a relatively
high 0  C loss tangent and low 60  C loss tangent. The
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Communication Journal of Materials Chemistry A

molecular structures and properties of SSBR, for example, the

glass transition temperature (Tg) of SSBR increases as the
styrene and vinyl content increases, but SSBR with a high vinyl
content shows less hysteresis heat than SSBR with a high
styrene content even though they possess the same Tg.8
Synthetic elastomers used in tires now are derived mainly
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from petrochemicals, which are not sustainable. In 2014, the

output of synthetic rubber reached 14.2 million tonnes,
consuming
35.5 million tonnes of crude oil9 and emitting
tremendous amounts of CO2. The global problem of climate
change (global warming) and air pollution (smog or haze) strikes
directly at the intersection of societal environmental demands
and economic needs. Environmentally friendly solutions must
be found. New strategies must be developed for the generation of
polymer materials from renewable resources.10,11 Bio-based
polymers such as polylactides,12 polyhydroxyalkanoates,13 and
poly(butylene succinate)14 have been successfully industrialized
on a large scale. Soybean oil based elastomers,15 polyester elas-
tomers,16 and poly(diisoamyl itaconate-co-isoprene) elastomers17
have already been investigated previously, but bio-based
synthetic elastomers designed for tire applications have yet to
emerge. Major tire manufacturers plan to use sustainable
resources for tires in the foreseeable future.18 To meet this target,
renewable elastomers must be developed and non-renewable
carbon black must be replaced with non-petroleum-based llers,
like silica (Fig. 1).
In this study, itaconic acid from renewable resources, one of
the “top 12” bio-based building blocks, was used.19 Aliphatic
alcohols derived from biomass, CnH2n+1OH where n ranged from
1 to 8, commercially available on a large scale for n < 5 (ref. 20),
were used to prepare itaconates. The length of the alkyl side chain
enables some control over the glass transition temperature,
mechanical properties and viscoelastic behaviors of the polymers.
We introduced a conjugated diene—isoprene or butadiene—to
reduce the itaconate pendant side chain hindrance effect and
achieved a high molecular weight. Conjugated dienes play an
essential role in providing unsaturation for subsequent cross-
linking. Bio-isoprene, expected to replace petrochemical isoprene
in the near future,21 and bio-butadiene technologies have been
actively developed over the last decade.21,22 Nanoparticle llers
can also be used to strengthen the targeted elastomers and
improve their physical and mechanical properties.23–25
Fig. 1 The integrated bio-based chemical-synthesis-low roll-resis-
tance green tire pathway for resource sustainability and environmental
protection.
Scheme 1 (a) Synthesis of di-n-alkyl itaconates. (b) Synthesis of poly-
(di-n-alkyl itaconate-co-isoprene) and poly(di-n-butyl itaconate-co-
butadiene). (c) In situ modification and (d) the chemical linking reaction
between bio-based macromolecular chains and nanoparticles during
crosslinking reactions.
Di-n-alkyl itaconates (DAIs) were prepared by the esterica-
tion of itaconic acid using the appropriate alcohols. DAIs were
veried by NMR to ensure that no residual acid groups
remained (Scheme 1a and Fig. S1, ESI†). We initially employed
eight DAIs and isoprene to fabricate a series of elastomers,
designated as poly(di-n-alkyl itaconate-co-isoprene) (PDAII),
through redox-initiated redox emulsion polymerization with
DAI to isoprene with a molar ratio of 2/3 (itaconate mass ratio
ranges from 61% to 80%)17 (Scheme 1b). Sodium hydroxy-
methane sulnate (oxidizing agent) and ferric ethyl-
enediaminetetraacetic acid (reducing agent) were introduced to
decrease the activation energy of tert-butyl hydroperoxide
radical decomposition, which can provide sufficient free radi-
cals at 20  C. The moist PDAII products were washed with
ethanol and deionized water to remove residual monomers and
emulsiers and dried at 60  C under vacuum to a constant
weight. The structures and properties of PDAII are summarized
in the ESI†.
Many engineered elastomers are reinforced by using nano-
scale llers, including carbon black, silica, ber, or clay.25 Silica
was used, since it is not petroleum-based and has been used in
tire applications on a commercial scale. The silanol groups on
the silica surface enable hydrogen-bond interactions with PDAII
and promote uniform dispersion, leading to high performance.
To promote chemical bonding of the elastomer to the ller, VP
Si 363, a silane with a free mercapto group on the rubber-active
site and a combination of an ethoxy substituent and polymeric,
amphiphilic substituent on the silica active site, was used. The
ethoxy substituent is cleaved during the mixing process and the

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Fig. 2 Transmission electron microscopy micrograph of (a) 50 phr (per hundred part of rubber) silica filled PDBII and (b) 50 phr carbon black (CB)
filled ESBR. (c) Loss factor tan d as a function of temperature and (d) signal decay spectra of transverse magnetization relaxation of 50 phr silica
filled PDAII (Si-PDAII). (e) Loss factor tan d of 50 phr silica filled PDBIB (Si-PDBIB) with a butadiene content from 20% to 80% as a function of
temperature. (f) Loss factor tan d versus strain curves of silica/PDBII and silica/PDBIB tread elastomers. The full name and abbreviations of PDAII
and PDBIB samples are as follows: poly(dimethyl itaconate-co-isoprene) (PDMII), poly(diethyl itaconate-co-isoprene) (PDEII), poly(di-n-propyl
itaconate-co-isoprene) (PDPrII), poly(di-n-butyl itaconate-co-isoprene) (PDBII), poly(di-n-pentyl itaconate-co-isoprene) (PDPeII), poly(di-n-
hexyl itaconate-co-isoprene) (PDHxII), poly(di-n-heptyl itaconate-co-isoprene) (PDHpII), poly(di-n-octyl itaconate-co-isoprene) (PDOII), and
poly(di-n-butyl itaconate-co-butadiene) (PDBIB).

silane bonds covalently to the silica surface through an in situ
modication reaction (Scheme 1c). The polymeric chains are
polar, ensuring high silica affinity and a fast adsorption and
reaction on the silica surface. The mercapto group is respon-
sible for the efficient coupling of the silane to the polymer
chains through a click reaction (Scheme 1d). Transmission
electron microscopy results show that the silica particles,
compared to when carbon black was used to ll ESBR (Fig. 2a),
with an average diameter of 30–60 nm, are uniformly dispersed
in the PDAII (Fig. 2b). Tensile testing and dynamic mechanical
analysis were performed to investigate the mechanical proper-
ties of silica/PDAII. The silica/PDBII exhibits the highest tensile
strength of 12.3 MPa followed by silica/PDPeII, silica/PDHxII,
silica/PDHpII, and silica/PDOII (Table S10a, ESI†).

13060 | J. Mater. Chem. A, 2016, 4, 13058–13062 This journal is © The Royal Society of Chemistry 2016

Communication
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Fig. 3 (a) Schematic diagram of energy loss coming from polymer chain–polymer chain friction, nanoparticle–nanoparticle friction and polymer
chain-nanoparticle friction. (b) Different tread elastomer roll-resistance test results: CB/ESBR tread elastomer, silica/SSBR tread elastomer and
silica/PDBIB tread elastomer.
With increasing side chain length, dynamic mechanical
results show that the peak temperatures of silica/PDAIIs
decrease from 35  C to 38  C (Fig. 2c). It is obvious that tan d of
silica/PDAIIs at 60  C decreases slightly from silica/PDEII to
silica/PDOII except for silica/PDMII, which is signicantly
higher than that of the others and not suitable for green tire
applications. The relaxation rate on the short relaxation time
scale, determined by solid-state low-eld NMR, can be used to
characterize the connement of polymer chains on the ller
surface.26,27 The relaxation time increases with the side chain
length from methyl to octyl (Fig. 2d). This increase indicates
that the short side chains of PDAII are restricted and less ex-
ible than the long ones. The tan d value at 0  C correlates with
the wet skid resistance of tires.28 Considering both the roll
resistance and wet skid resistance, silica/PDBII shows strong
potential for use as a tire tread material.
The diene structure is another important factor for visco-
elastic energy dissipation. Therefore, butadiene was further
introduced to copolymerize with di-n-butyl itaconate. We
prepared bio-based elastomeric poly(di-n-butyl itaconate-co-
butadiene) (PDBIB) by redox-initiated copolymerization of di-n-
butyl itaconate and butadiene (Scheme 1b). The structures and
properties of PDBIB with a butadiene content from 20% to 80%
are summarized in the ESI (ESI†). The tan d of silica/PDBIB80
was the lowest at 60  C which indicates a lower roll resistance in
comparison to with that of other silica/PDBIB samples (Fig. 2e).
However, in tire tread applications, the elastomer needs to
combine good wet skid resistance and low roll resistance. From
the mechanical properties, the wet skid resistance, and roll
resistance, PDBIB40 emerged as a potential elastomer to
produce a high-performance bio-based tire tread.
For both silica/PDBII and silica/PDBIB, tan d increases when
the strain is less than 1% which arises from polymer–polymer
friction, polymer–ller friction and ller–ller sliding friction
(Fig. 2f). For strains exceeding 1%, tan d slowly increases and
gradually saturates. At high strains, the silica networks are
broken, in keeping with the decrease in energy dissipation
produced by ller–polymer viscous stress. Usually the value of
tan d at a strain of 7% is closely related to the tire roll resistance.
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Silica/PDBIB shows a lower tan d than silica/PDBII at high
strain, due to the higher content of pendent vinyl groups of
PDBIB40 (6.6%) than PDBII (0.4%). Consequently, silica/
PDBIB40 was used to manufacture tread material for tires.
It is desirable that a tire can transmit the maximum
percentage of engine torque to the road; however, certain energy
losses of elastomeric products undergoing cyclic deformation
are inevitable (Fig. 3a). The energy dissipated in the tire is
ultimately converted into heat,29 which leads to an increase in
the tire operating temperature. The relationship between the
energy loss and dynamic mechanical properties of rubber
materials can be obtained using sinusoidal deformation;
dynamic stress and strain are given by s(t) ¼ sa sin ut and 3(t) ¼
3a sin(ut  d), respectively.29,30 Energy loss per cycle per unit
volume (H) under a controlled energy cycle is given by
ð 2p=u
d3ðtÞ
H¼ sðtÞ dt ¼ psa 3a sin d z psa 3a tan d
0 dt
where sa is the stress amplitude, 3a is the strain amplitude, u is
the angular frequency, t is the time, d is the phase difference
between strain and stress, and tan d is the loss factor. H is
proportional to tan d for equal energy consumption. The rubber
rolling test results showed that the energy loss and temperature
increase of the silica/PDBIB tread elastomer were almost the
same as those of the silica/SSBR tread elastomer, and much
lower than those of the carbon black/ESBR tread elastomer
(Fig. 3b). Akron abrasion of silica/PDBII and silica/PDBIB treads
ranged from 0.08 to 0.20 cm3, which was comparable to that of
traditional treads.
These experiments suggest that the bio-based PDBIB elas-
tomer reinforced with silane-modied silica could be effectively
used in the tire industry as a green tire tread. PDBII and PDBIB
elastomers together with in situ modication technology lead to
the best improvement of roll resistance and wet traction
without any compromise in tread wear. We scaled up the
production of the PDBIB elastomer in a reaction kettle. The
silica/PDBIB tire was manufactured and tested using a MTS tire
roll-resistance measurement system (Fig. S5, ESI†). The roll-
resistance coefficient was 7.7 kg t1 and rated as a ‘B’ level
J. Mater. Chem. A, 2016, 4, 13058–13062 | 13061

Journal of Materials Chemistry A
according to the EU Tyre Labelling Regulation 1222/2009, which
is a high level since class A is few in the European market.
The present approach to create itaconate-based elastomers is
sufficiently general to open the way for bio-based engineering
elastomers that combine the advantages of fast-developing
renewable chemicals with traditional synthesis methods. The
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properties of itaconate-based elastomers can be tuned by using
different aliphatic alcohols or changing isoprene to butadiene.
Silane-modied non-petroleum silica was used to reinforce
PDAII and PDBIB to form uniformly dispersed and strong
silica–polymer interactive nanocomposites which can offer
superior mechanical properties and exhibit low energy
consumption. Combining bio-based chemicals and in situ
modication technology to develop green tires is an important
step in the strategy for sustainable development.
Acknowledgements
This work was supported by the National 973 Basic Research
Program of China 2015CB654700, National Natural Science
Foundation of China (50933001) and the Goodyear Tire &
Rubber Company (S2010-06). T. P. R. acknowledges the support
of Beijing Advanced Innovation Center for So Matter Science
and Engineering.
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