Composites Science and Technology 133 (2016) 136e156

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Composites Science and Technology

journal homepage: http://www.elsevier.com/locate/compscitech

Feature article

Design, preparation and properties of bio-based elastomer composites

aiming at engineering applications
Runguo Wang a, b, Jichuan Zhang a, Hailan Kang a, Liqun Zhang a, c, *
a
Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029,
PR China
b
Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology, Beijing 100029, PR China
c
State Key Laboratory of Organic Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Bio-based polymer products derived from renewable agricultural and biomass feedstock have become
Received 6 May 2016 increasingly important as these sustainable and eco-efficient products bring a significant reduction in
Received in revised form greenhouse gas emissions and saving of fossil energy in comparison with conventional pertrochemical-
18 July 2016
based materials. A series of bio-based elastomers from large-scale produced and petroleum independent
Accepted 21 July 2016
Available online 26 July 2016
monomers such as succinic acid, sebacic acid, itaconic acid, 1,3-propanediol, 1,4-butanediol, soybean oil,
glycerol, citric acid, etc have been developed by authors. Same as conventional elastomers, bio-based
elastomers possess low glass transition temperature, high elasticity and low strength, and this implies
Keywords:
Bio-based elastomers
that they must be reinforced by nano-fillers. However, they also possess particular and novel properties
Composites due to their characteristic macromolecular structures and aggregation structure. For example, the ex-
Engineering istence of abundant ester groups, terminal carboxyl groups, and terminal hydroxyl groups in bio-based
polyester elastomers endow polar fillers like silica disperse homogeneous in the elastomer matrix
without surface modification. Even though, for incorporation of easily agglomerated fillers like graphene
and layered silicates, elaborately dispersion and interfacial tailoring technique is necessary. Combined
with specific structures and relevant effective composite technology, bio-based elastomer composites
exhibit versatile potential applications in tire tread, PLA toughener, thermoplastic vulcanizates, and
dielectric elastomer, etc.
© 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
2. Bio-based chemicals, molecular design, and synthesis of bio-based elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
2.1. Biomass and bio-based chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
2.2. Design and preparation of bio-based elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
2.2.1. Polyester elastomer prepared by condensation polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
2.2.2. Fabricate high molecular weight elastomer from itaconic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
2.2.3. Elastomers based on vegetable oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
2.2.4. Bio-based polyurethane elastomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
2.2.5. Construct conventional elastomer by bio-based monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
2.2.6. Comparison of bio-based elastomers and traditional elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
3. Compounding, interfacial tailoring and applications of bio-based elastomer composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3.1. Compounding and interfacial tailoring of bio-based elastomer composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3.1.1. Reinforced by spherical fillers: silica . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142

* Corresponding author. Key Laboratory of Beijing City on Preparation and Pro-

cessing of Novel Polymer Materials, Beijing University of Chemical Technology,
Beijing 100029, PR China.
E-mail address: zhanglq@mail.buct.edu.cn (L. Zhang).

http://dx.doi.org/10.1016/j.compscitech.2016.07.019
0266-3538/© 2016 Elsevier Ltd. All rights reserved.
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156 137

3.1.2. Reinforced by sheet fillers: montmorillonite and graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142

3.1.3. Reinforced by tubular fillers: carbon nanotube and halloysite nanotube . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.2. Applications of bio-based elastomers and related composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
3.2.1. Tire tread materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
3.2.2. Damping materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.2.3. Oil resistant materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.2.4. Bio-plastic toughener . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
3.2.5. Thermoplastic vulcanizates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.2.6. Shape memory polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
3.2.7. Dielectric elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
4. Summary and conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155

1. Introduction developing various high-performance synthetic elastomers to

replace NR or used in the complicated conditions (NR cannot meet
At the time of great challenge to energy, resource and envi- the requirements) have been the focus in elastomer science and
ronment, with large energy and resource consumption, chemical engineering field. There is no doubt that raw chemicals used in
industry is facing serious problems. It's with great significance to synthetic elastomer production are basically derived from fossil
encourage world economic development by using recyclable resources, including butadiene, styrene, isoprene, chloroprene,
resource and reducing dependence on non-renewable fossil fuels ethylene, and propylene. Compared with bio-based plastics and
[1]. Biomass resource ranks first in the renewable energy and ranks fibers, research and development of bio-based elastomers aiming at
fourth in the world's total energy consumption, preceded only by engineering applications are quite few. Clearly, in order to meet the
coal, oil and natural gas. Countries all over the world are making growing demand for sustainable development, the preparation of
great efforts to support and encourage technological innovation of such elastomers derived from biomass as the next-generation en-
biomass energy and resource. Conversion from fossil energy to gineering elastomers is extremely significant. The objective of
biomass energy will be the greatest challenge and opportunity in present article was to introduce design, preparation, and applica-
the coming fifty years. Polymer materials play irreplaceable role in tions of these bio-based elastomers and related composites.
people's diary life and the volume consumption has already
exceeded steel. Even though, except natural rubber and few other
materials, most polymer materials are highly depended on fossil 2. Bio-based chemicals, molecular design, and synthesis of
resource (mainly oil and coal). Developing bio-based polymers bio-based elastomers
meets the requirements and trend of sustainable development and
circular economy concept. Many efforts have been paid and various 2.1. Biomass and bio-based chemicals
materials have been fabricated from bio-based chemicals, for
example, polylactic acid (PLA) [2], starch based polymers [3], pol- Biomass mainly refers to renewable or recyclable organic sub-
yhydroxyalkanoates (PHAs) [4], 1,3-propanediol based polymers stances including crops, trees, other plants or residues, and animal
[5,6] and polybutylene succinate (PBS) [7], etc. PLA is the most waste, etc. Bio-based chemicals are chemicals produced from
successful bio-based polymer with great potential market by far. renewable bio-resources including grains, legumes, cotton stalks
Dow Chemical has built a 140,000 tons/year PLA plant and is and other biomass as raw materials. Biological fermentation tech-
planning to raise the capacity to 450,000 tons/year. Toyota has nology provides us a low cost and high efficiency method to pro-
made car automobile parts from sugar cane and potato based duce bio-based chemicals in large scale. It is believed that bio-based
plastics [8] and Fujitsu has made computer shells by corn starch- chemicals and renewable energy are the only way to achieve sus-
based plastics [9]. DuPont has developed an engineering thermo- tainable development of mankind. With the depleting of petro-
plastic polymer by PTT which produced from a corn-based PDO. chemical resources and increasing awareness of environmental
Showa Japan and United States Eastman have experienced indus-
trial production of PBS, and the production capacities are 5000
tons/year and 15,000 tons/year, respectively. There is an emergence
of fossil resources replacing by biomass resources to get novel
polymer materials in plastic field, even though bio-based plastics
like PLA still has shortcomings like low heat-resistant temperature
and poor toughness. It's worth noting that the current bio-based
plastic is always aimed at fast biodegradable performance, which
to some extent limits its application and development. We believe
efforts also should be taken to develop environmental stable and
bio-based polymers to meet high-performance demands.
Elastomer is widely used in industry, agriculture, national de-
fense, and our daily life as its unique high elasticity. Natural rubber
(NR) is a valuable elastomer material with excellent comprehensive
properties from hevea brasiliensis. However, hevea brasiliensis need
to be cultivated in the high-temperature and great rainfall envi-
ronment. Therefore, they can only be large-scale cultivated in
certain tropical areas. After years of development, NR production
has been up to the top limit. On this situation, researching and
Scheme 1. Reaction formula of bio-based polyester elastomer.
138 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156

protection, bio-based chemicals play more and more important
role in the industry and people's daily life. With the rapid devel-
opment of processing technology, large scale production of ethanol
from lignin will be realized definitely and at that time, the ethanol
can be used as fuel and chemicals directly. Developing renewable
polymers and resembling existing petroleum dependent polymers
by bio-based chemicals have been a universal consensus. Generally
speaking, there are three major pathways toward synthesis of
renewable monomers including fermentation (such as lactic acid,
and 1,3-propanediol), chemical transformation of natural polymers
(such as glucose, and furfural) and molecular biomass from nature
(such as vegetable oils, terpenes, terpenoids, and resion acids) [10].
In 2004, the US Department of Energy (DOE) announced a group of
top 12 bio-based building block chemicals including succinic acid
(fumaric acid, malic acid), 2,5-furan dicarboxylic acid, 3-
hydroxypropionic acid, aspartic acid, glucaric acid, glutamic acid,
itaconic acid, levulinic acid, 3-hydroxybutyrolactone, glycerol, sor-
bitol and xylitol (arabinitol) [11]. These chemicals can be produced
via microbial fermentation or simple chemical process starting
from sugars and can be further converted to other valuable or
commodity products. After more than ten years developing, ten
chemicals among these top 12 chemicals, excluding the aspartic
acid and 3-hydroxybutyrolactone, have already been commercial-
ized or are close to commercialization [12]. In addition to the top 12
chemicals, several other bio-based platform chemicals such as
methanol, ethanol, isoprene, limonene, vegetable oils etc. are also
highly emphasized and developed.
2.2. Design and preparation of bio-based elastomers
The motivation of our relative research is to prepare new elas-
tomers aiming at engineering applications based on large scale
produced bio-based chemicals. It is believed that following criteria
are required [13]: (i) monomers should be obtained primarily from
readily available and inexpensive renewable biomass feedstock; (ii)
the chemically synthesized or biosynthesized elastomers should
possess excellent environmental stability; (iii) they should be
compatible with traditional rubber processing, such as mixing,
molding and curing; (iv) the prepared elastomers should exhibit
desirable mechanical properties.
2.2.1. Polyester elastomer prepared by condensation polymerization
Polyester elastomers were synthesized by the condensation
polymerization of bio-based diacids and dialcohols [13]. Normally,

Fig. 1. The preparation route of elastomer based on itaconic acid.

Scheme 2. Schematic diagram showing reaction process with an increasing amount of decamethylene diamine.
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156
Scheme 3. The pathway of bio-based polyisoprene.
polyester materials, for example PBS [7], are plastics as they possess
high crystallization degree. In order to suppress the crystallization
of polyester to form elastomer, five bio-based chemicals including
itaconic acid, sebacic acid, succinic acid, 1,4-butanediol, and 1,3-
propanediol were applied to increase the irregularity of the ob-
tained polyester. The use of sebacic acid was to provide high flex-
ibility and the use of itaconic acid was to provide double bonds for
the further crosslinking. The pathway of the design and preparation
of bio-based polyester elastomer was shown in Scheme 1.
The number average molecular weight of synthesized polyester
elastomers was approximately 35,000 g/mol with PDI as 3.2, and
the typical glass transition temperature (Tg) was
56  C. Even
though molecular weight of polyester elastomer was lower than
conventional elastomers, the shortage can be compensated by
further crosslinking. Ideal low Tg was attributed to the long carbon
chain of sebacic acid and the disruption of polymer regularity. This
linear polyester elastomer with double bonds can be processed
smoothly with traditional elastomer processing instruments. Be-
sides, the molecular weights, Tgs, crystallization degrees, and me-
chanical properties of synthesized polyester elastomers can be
tuned by the monomer ratios and reaction conditions.
2.2.2. Fabricate high molecular weight elastomer from itaconic acid
Itaconic acid is a promising organic acid that has been catego-
rized as one of the “top 12” building block molecules in advanced
biorefineries [14]. The output of fermented itaconic acid has ach-
ieved 100 kt and the price was around $1600/ton. Itaconc acid
possesses two carboxyl groups and one double bond, which can
only be polymerized to low molecular weight polymers by radical
initiators as carboxyl groups affect the chain growth during poly-
merization. Usually, high molecular weight polymers can be ob-
tained by the polymerization of itaconates [15e17]. As shown in
Fig. 1, poly (di-alkyl itaconate-co-isoprene) (PDII) type elastomer
was designed and prepared by the copolymerization of itaconates
and isoprene [18]. The use of isoprene was to provide double bonds
for the further crosslinking and increase the macromolecular flex-
ibility of obtained polymer. By calculation of reaction reactivities by
Fineman-Ross method [19] and Kelen-Tüdo €s method [20], reaction
Scheme 4. The pathway of biobasd EPDM.
139
reactivities of itaconate and isoprene are both less than 1, which
means two monomers tend to carry on copolymerization rather
than homopolymerization. The obtained elastomer possesses high
molecular weight (above 3.0  105 g/mol) and low Tg
(below
30  C). Emulsion polymerization was used to carry on the
copolymerization of itaconate and isoprene as it is easy to obtained
high molecular weight polymer and its wide use in elastomer in-
dustry [21,22].
2.2.3. Elastomers based on vegetable oils
Combined with functional double bonds and similar structures
with petroleum-based chemicals, common plant oils including
peanut oil, soybean oil, linseed oil, castor oil, and rapeseed oil, etc.
have been drawn wide attention as their low cost and large output.
The main components of vegetable oils are triglyceride derived
from high fatty acid and glycerol. Most polymers based on vege-
table oils are thermosetting polymers which are not suitable for
further processing and molding [23]. A class of soybean-oil-based,
processable and cross-linkable elastomers poly (epoxidized soy-
bean oil-co-decamethylene daimine) (PESDs) was synthesized
[24,25]. Epoxidized soybean oil was employed to react with
diamine by combining the ring-opening reaction which contributes
to chain growth and the ammonolys was expected to break the
glycerol center (Scheme 2). Decamethylene diamine can be derived
from castor oil. The PESD was cross-linked by succinic anhydride
according to a conventional rubber processing procedure.
2.2.4. Bio-based polyurethane elastomer
PU elastomers were widely applied in medical materials, in-
dustry products, and national defense as their outstanding me-
chanical properties, high elasticity, high abrasion resistance, oil
resistance, and chemical resistance [26]. With the development of
bio-based chemicals and bio-technology, several enterprises and
institutes actively developed the production of soy bean oil and
castor oil based PU materials [27,28]. Actually, using bio-based
polyol to prepare polyurethane is one important trends of the
development of PU materials. Dow, Bayer, DuPont and other
chemical giants have successfully realized the applications of bio-
140 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156
based polyol in the preparation of PU products. Currently, the
research of bio-based polyurethane elastomers is mainly focused in
applying vegetable oils as soft segments to copolymerize with
various isocyanates. The resulting polyurethane based on vegetable
oils not only possesses excellent chemical and physical properties,
but also complies with environment requirements. In many as-
pects, the properties of bio-based polyurethanes are completely
comparable with petroleum-based polyurethanes.
In commercialization, some large companies in the world have
developed bio-based products to meet market demands. US Cargill
has developed soy-based polyol named BiOH and built a plant in
Chicago for this product [29]. Spanish Merquinsa Company devel-
oped a series of bio-based polyurethane elastomers named
Perlthane ECO [30]. Bayer accordingly has launched vegetable oil-
based and foamed polyurethane materials.
2.2.5. Construct conventional elastomer by bio-based monomers
Genencor Company and Goodyear Company announced to carry
on joint research on integrated fermentation, reclaim, and purifi-
cation system to produce bio-isoprene and further isoprene rubber
on March 25th, 2010 [31]. Amyris Company and Michelin Company
also have signed an agreement for developing bio-isoprene. Amyris
Company plan to have commercial production of bio-isoprene for
tires and other special chemicals including adhesives, coatings, and
sealants [32]. The company has already applied mature technology
to produce farnesen and the similar technology can be used to
transfer plant based sugars into isoprene (Scheme 3).
Bio-based EPDM can be prepared by the copolymerization of
bio-ethylene and bio-propylene. Bio-ethylene was derived from
dehydration with catalyst of ethanol, which can be produced in
large scale by the fermentation of biomass resources [33,34]. The
Fig. 2. Strategy for the synthesis and reinforcement of polyester elastomer. Reprinted from Ref. [13] by kind permission of John Wiley & Sons, Inc.
catalyst of dehydration can be alumina, zeolite, heteropoly acid, and
molecular sieve, etc. For now, ethanol was mainly obtained by the
fermentation of sugars (sugar cane, sugar bee etc.) or by the hy-
drolysis of starch (corn, potatoes, cassava, etc.). Bio-based propyl-
ene can be obtained by catalytic dehydration of isopropanol [35].
Then, bio-based EPDM can be obtained by the copolymerization of
bio-ethylene and bio-propylene, the process of synthesis was
showed in Scheme 4.
Currently, Lanxess Company is carrying on industrial attempts.
Its EPDM plant which located in Brazil Triunfo uses bio-ethylene to
prepare EPDM, which is the first bio-EPDM product. The production
has achieved hundreds of tons per year [36].
2.2.6. Comparison of bio-based elastomers and traditional
elastomers
The principle properties of bio-based elastomers and traditional
elastomers are similar. During the last decades, it is generally
considered that the cost of bio-based polymers is higher, and the
mechanical properties are inferior to conventional polymers.
Actually, the phenomenon is changing with the rapid advances of
fermentation technology. Some large scale produced and bio-based
chemicals possess comparable cost with petroleum-based chem-
icals. The comprehensive properties of bio-based elastomers are
comparable or even superior to traditional elastomers, which can
be verified by the following part of present paper. However, the
wide acknowledgement of novel bio-based elastomers is a realistic
problem and need a long period. With the development of
fermentation technology and declining of fossil energy, the pro-
portion of bio-based elastomer will inevitably increase in the near
future.
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156 141

Fig. 3. The formation of hydrogen bonds was simulated through molecular modeling using Materials Studio Software (in a unit cell: red, O; white, H; grey, C; yellow, Si). Reprinted
from Ref. [13] by kind permission of John Wiley & Sons, Inc. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)

Fig. 4. Morphology of polyester/silica composites with 30 phr silica: (a) SEM, (b) TEM,(c) (d) photos of polyester/silica composites.

Table 1
Comprehensive mechanical properties of polyester/silica composites compared with SBR/silica and NBR/silica composites. Reprinted from Ref. [13] by kind permission of John
Wiley & Sons, Inc.

Item Polyester composites silica content/phr SBR1500/50 phr silica NBR-26/50 phr silica

30 40 50

Hardness [Shore A]/ 72 75 81 81 84

Stress at 100% strain/MPa 5.7 7.4 10.1 3.2 3.4
Tensile strength/MPa 14.8 18.9 20.5 23.6 20.7
Elongation at break/% 223 216 189 424 416
Permanent deformation/% 2 2 4 12 14
Tear strength/kN m
1 26.7 25.9 30.3 34.9 42.3
142 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156
3. Compounding, interfacial tailoring and applications of bio-
based elastomer composites
3.1. Compounding and interfacial tailoring of bio-based elastomer
composites
3.1.1. Reinforced by spherical fillers: silica
For engineering applications, amorphous elastomers need to be
reinforced, even for those with strain induced crystallizations [37].
Carbon black was widely used in conventional elastomer applica-
tions like tires as its low cost and significant reinforcement effect.
Without exception, bio-based elastomers also can be reinforced by
carbon black [38]. However, silica was preferred in the reinforce-
ment of bio-based elastomers since silica is petroleum independent
and will not make products black (which is undesirable in certain
applications). Differ from conventional elastomers, typical bio-
based elastomers usually contain polar groups such as hydroxyl
groups, carboxyl groups, or ester groups. As shown in Fig. 2, silica
was incorporated to reinforce bio-based polyester elastomer and
typical elastomer products are prepared in laboratory. It is hy-
pothesized that hydrogen bonds can form between silica and
macromolecular chains, which would contributed to the dispersion
of silica in the elastomer matrix and strengthen interface interac-
tion of filler and elastomer.
Molecular dynamic simulation was adopted to analyze the
hydrogen bonding interaction between silica and polyester elas-
tomer (Fig. 3). The blue dish lines were verified to be hydrogen
bonds formed between polyester macromolecules and silanol
groups. Besides, there is no doubt strong van der Waals interaction
existed between polar groups and silanol groups. Thus, unlike
conventional elastomer, silica doesn't need to be modified by
coupling agent in the reinforcement of bio-based polyester
elastomer.
By SEM and TEM images (Fig. 4), silica has a homogenous
dispersion in polyester elastomer matrix, which also can be verified
by the high transparency of polyester/silica composites (Fig. 4
(c),(d)). Although molecular weight of polyester elastomer was
lower than conventional elastomers, high efficient reinforcing and
crosslinking would contribute to overcome the shortcoming. From
Table 1, with the incorporation of silica, mechanical properties of
polyester elastomer were highly improved. The tensile strength of
Fig. 5. Proposed schematic of green PDBIIVP/MMT composites with ionic bonding interface. Reprinted from Ref. [43] by kind permission of Elseviser.
50 phr silica reinforced elastomer composites was over 20 MPa,
which was comparable with SBR and NBR.
3.1.2. Reinforced by sheet fillers: montmorillonite and graphene
Poly (di-n-butyl itaconate-co-isoprene) (PDBII) elastomer was
synthesized by redox initiated emulsion polymerization. It is found
that silica has significant improvement of mechanical properties of
PDBII elastomer. But the air impermeability of PDBII and PDBII/
silica composites are unsatisfactory. Air impermeability property is
important as the obtained bio-elastomer composites are aimed to
apply in engineering applications including sealing, inner layer of
tires, etc. If we can prepare bio-elastomer composites with high air
impermeability and necessary mechanical properties, the bio-
elastomer composites will be good candidates in these fields. In
order to enhance the air impermeability as well as mechanical
properties of PDBII elastomer for airtight applications, sheet fillers
such as layered silicates and graphene become good candidates
[39e41]. Layered silicates, whose basic building blocks are tetra-
hedral sheets in which silicon is surrounded by four oxygen atoms
and octahedral sheets in which a metal such as aluminum is sur-
rounded by six oxygen atoms [42], are natural resources with a low
cost. Montmorillonite (MMT), a common smectite-type layered
silicate, was used to reinforce PDBII elastomer. The dispersion of
MMT is an important issue as its large aspect ratio and sheet
structure. With the incorporation of negative charge into PDBII
elastomer, we can take the advantage of the positive charge of MMT
surface to form ionic bond between PDBII and MMT. The ionic bond
can greatly improve interface interaction between MMT and PDBII
macromolecules and the dispersion of MMT by reducing filler ag-
gregation. In order to achieve the hypothesis, 4-vinylpyridine (4-
VP) was adopted as the interface modifier to copolymerize with
dibutyl itaconate and isoprene to form the pyridine-included bio-
based poly (dibutyl itaconate-ter-isoprene-ter-4-vinylpyridine)
(PDBIIVP) elastomer [43]. FTIR and NMR spectra confirm the suc-
cessfully incorporation of pyridine groups and the content of pyr-
idine in PDIIVP was relatively higher than the feed ratio. In order to
realize the protonation of pyridine and prepare the nanocomposite
with the designed ionic bonding interfaces, latex co-coagulation
was employed to fabricate PDBIIVP/MMT composites, and hydro-
chloric acid was used as both the proton donor and the flocculant.
The design and preparation route of PDBIIVP/MMT composites was
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156 143

Fig. 6. TEM micrographs of PDBIIVP/MMT composites: (aed) PDBIIVP-0/MMT, PDBIIVP-1/MMT, PDBIIVP-2/MMT, PDBIIVP-4/MMT at low magnification; (eeh) PDBIIVP-0/MMT,
PDBIIVP-1/MMT, PDBIIVP-2/MMT, PDBIIVP-4/MMT at high magnification. Reprinted from Ref. [43] by kind permission of Elseviser.

Fig. 7. (a) Mechanical properties and (b) air impermeability of PDBIIVP/MMT with different 4-VP contents. Reprinted from Ref. [43] by kind permission of Elseviser.

displayed in Fig. 5.
The specific dispersion of MMT in the PDBIIVP matrix is inves-
tigated by TEM micrographs. The dark parts in the images are MMT
layers. Fig. 6 (aed) shows the morphology of PDBIIVP/MMT com-
posites at low magnification. MMT layers stack seriously in
PDBIIVP-0/MMT composites, indicating poor dispersion of MMT
layers. With the increase of 4-VP contents, the dispersion of MMT
layers was highly improved. Fig. 6 (eeh) shows the TEM micro-
graphs of PDBIIVP/MMT composites at higher magnification,
further confirm that the stacking of MMT layers decrease with the
increase of 4-VP content. Fig. 6h indicates that the MMT layers are
completely exfoliated as single layer in the PDBIIVP matrix. The
significant improvement of the dispersion of MMT in PDBIIVP is
due to the formation of ionic bonding interfaces, which is much
stronger than conventional van der Waals force interfaces. With
increasing 4-VP content, the number of ionic bonds at the interface
increases and thus the interfacial interaction is enhanced, effec-
tively preventing the aggregation of MMT layers.
From Fig. 7, tensile strength of PDBIIVP/MMT composites was
significantly higher than pristine PDBIIVP and increased with 4-VP
content. The decrease of elongation at break was due to the in-
crease of crosslinking density. Air impermeability was highly
improved with the incorporation of pyridine groups and ionic
bonding. With the increase of pyridine groups, air permeability
index of neat PDBIIVP gradually decreased with the increase of 4-VP
content, probably due to the reduced free volume after some
replacement of butyl ester side groups with pyridine side groups.
The addition of MMT endowed obvious improvement of air
impermeability and superior result was obtained with high 4-VP
content. For example, air permeability index of PDBIIVP/MMT
composite with 7 wt% 4-VP and 10 phr MMT was only
2.32 m2Pa
1s
1 (71% reduction of neat PDBIIVP). The significant
improvement of air impermeability was attributed to the ionic
bonding interface between MMT and PDBIIVP.
Graphene, the typical layered carbon materials consists of sp2-
hybridized carbon atoms, has been under the spotlight owning to
its unparalleled physical properties. However, due to strong self-
contained van der Waals force and high specific area, graphene
sheets tend to aggregate and stack, leading to poor dispersion in
polymer matrix. Various approaches have been applied to improve
the dispersion of graphene in matrix, oxidizing graphene is one of
the simple and promising methods. Graphene oxide (GO) was
prepared from natural graphite according to a modified Hummers
method and contained multi-functional groups including hydroxyl,
144 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156

Fig. 8. Sketch of the designed PDBIIVP/GO nanocomposite with ionic bonding interfaces. Reprinted from Ref. [45] by kind permission of The Royal Society of Chemistry.

Table 2
Mechanical properties of PDBIIVP/GO composites with different GO contents. Reprinted from Ref. [45] by kind permission of The Royal Society of Chemistry.

Samples Tensile strength/MPa Elongation at break/% Stress at 100% strain/% Hardness/Shore A

PDBIIVP 1.0 ± 0.2 211 ± 17 0.4 ± 0.1 26

PDBIIVP/GO-1 3.7 ± 0.2 216 ± 14 1.3 ± 0.1 35
PDBIIVP/GO-2 5.7 ± 0.2 135 ± 11 4.4 ± 0.3 52
PDBIIVP/GO-4 8.0 ± 0.2 109 ± 3 7.6 ± 0.1 62

Fig. 9. TEM images of MWCNT (3 wt%)/PGSC elastomer composites. Reprinted from Ref. [46] by kind permission of Elseviser.

Table 3
Mechanical properties of PGSC/MWCNT composites.

MWCNT loading (wt%) Tensile strength (MPa) Modulus (MPa) Elongation at break (%) Permanent set (%)

0 2.7 6.9 40 0
0.5 2.8 6.6 44 0
1.0 3.4 8.0 41 0
2.0 4.1 9.2 40 0
3.0 4.4 9.2 42 0

carbonyl and epoxy groups on the surfaces along with carboxyl by the co-coagulation method and was vulcanized under 15 MPa at
groups at the edges [44]. As shown in Fig. 8, it is hypothesized that 150  C. The results showed that the dispersion, mechanical prop-
strong interaction will be formed between GO and PDBIIVP erties, and air impermeability of PDBIIVP were highly improved
macromolecular chains [45]. PDBIIVP/GO composite was prepared after inclusion GO. Tensile strength is highly improved with the
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156 145

Table 4 2 KPa with mechanical agitation. Critic acid monohydrate was

Relationship between cell relative growth rate and cytotoxicity
grade.
RGR (%) Cytotoxicity grade (%)
100 0 (MWCNTs) (0e3 wt%) were added into the moldable mixtures and
75e99 1 were in situ wetted and mixed with moldable mixtures [47]. The in
50e74 2 situ wetting of MWCNTs was effectively contributed to the ho-
25e49 3
1e24 4
0 5
Fig. 10. RGR of the composites with different loadings of MWCNTs at different incu-
bation time. Reprinted from Ref. [46] by kind permission of Elseviser.
incorporation of GO (Table 2). For example, PDBIIVP/GO with 4 phr
of GO, the tensile strength increased by 700% compared to neat
PDBIIVP, respectively. Furthermore, the air impermeability of
PDBIIVP/GO composite was significantly superior to pristine
PDBIIVP.
3.1.3. Reinforced by tubular fillers: carbon nanotube and halloysite
nanotube
Poly (glycerolesebacateecitrate) (PGSC) elastomer was syn-
thesized in laboratory and tensile strength of PGSC was 1.46 MPa
[46]. We plan to further improve mechanical properties of PGSC to
meet high strength requirements. Poly (glycerol-sebacate) PGS
prepolymer was firstly synthesized at 130  C under a pressure of
charged in the prepolymer according to the total molar ratio of 4/4/
1 (glycerol/sebacic acid/critic acid) and kept reacting under 120  C
and 1 KPa for 30 min. Then, multi-walled carbon nanotubes
mogenous dispersion and strong interface interaction. As shown in
Fig. 9, MWCNTs have uniform dispersion in PGSC matrix. Tubular
MWCNTs can be distinguished obviously with diameter as
10e20 nm.
Mechanical properties are always paid much attention and used
to directly reflect the reinforcement effect of the fillers. Mechanical
properties of PGSC composites with different loadings of MWCNTs
are listed in Table 3. Elongation at break of all PGSC composites was
close to that of pure PGSC elastomer, which hinted that the elon-
gation at break should mainly be dependent on the PGSC matrix.
The strength and modulus tended to be greater with the increase of
MWCNT loadings. For example, after filling with 3 wt% MWCNT, the
strength and modulus achieved 4.4 MPa and 9.2 MPa, respectively,
increasing 63% and 33% than that of neat PGSC elastomer. Besides,
the permanent sets of all the composites were 0%, indicating good
elastic recovery.
Elastomers from monomers like glycerol, citrate acid, and se-
bacic acid were expected to be used as biomedical polymers as
these elastomers normally possess high biocompatibility. Cyto-
toxicity is important factor for biomedical applications. Cytotoxicity
testing was carried out to evaluate the biocompatibility of PGSC and
PGSC/MWCNT composites. Based on the cell relative growth rate
(RGR) value, the cytotoxicity of tested sample can be divided into
six grades showed in Table 4. Grade 0 and 1 are accepted as the
qualified and present very weak or no cytotoxicity. Grade 2 should
be further considered by combing with the cell morphology and the
other grades which mean high cytotoxicity are regarded as un-
qualified. From Fig. 10, neat PGSC showed certain cytotoxicity and
become strongest at 7 days. However, with 0.5e3 wt% MWCNTs
added, the cytotoxicity of PGSC/MWCNT composites were grade
0 or grade 1 at every incubation time which means the cytotoxicity
of decreased greatly with the adding of MWCNT and the PGSC/
MWCNT composites were qualified to carry on biomedical
applications.
Chen et al. use melt blending method to prepare poly (glycerol
sebacate) (PGS)/halloysite nanotube (HNT)composites [48]. Hal-
loysite nanotube was employed to balance degradation rate and
strengthen mechanical properties. TEM observations on the PGS/
HNT composites (Fig. 11) revealed that the HNT were uniformly
distributed in the PGS matrix when the filler composition was

Fig. 11. Representative distribution of halloysite nanotubes in the PGS/HNT composites of (a)3, (b)5 and (c)10 wt% concentrations. Reprinted from Ref. [48] by kind permission of
Elseviser.
146 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156

Fig. 12. PDAII sample images, PDAII samples full name and abbreviations: 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).

Fig. 13. Photographs of fabrication and rolling resistance of PDBIB/silica green tires. a, Unfilled elastomer. b, Mixing. c, Tire assembling. d, e, Tire rolling resistance test. f, EU Tyre
Label, rolling resistance grading of bio-based tire. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

1e20 wt%. It was found that the addition of HNT did not compro-
mise extensibility of material. Elongation at break increased from
110% (neat PGS) to 225% (20 wt% composites). Young's modulus and
resilience of 3e5 wt% composites were above 0.8 MPa and 94%,
respectively. In vitro study indicated that PGS/HNT composites can
provide ideal degradation profile in terms of mechanical strength.
3.2. Applications of bio-based elastomers and related composites
3.2.1. Tire tread materials
Tires are the most important application of elastomers and
affect most people's daily life. Tire tread materials are the largest
component of tire elastomer materials. As the only part contacting
road for vehicles, tire tread directly related to car safety and com-
fort. Widely used tire tread materials including styrene butadiene
rubber (SBR) and butadiene rubber (BR) are petroleum-based ma-
terials. It is of great significance if we can replace petroleum-based
tire tread with bio-based elastomers. Wet skidding properties,
rolling resistance properties, and abrasion properties are regarded
as “magic triangle” of tires [49]. With the increasing awareness of
environmental protection and energy saving, the importance of low
rolling resistance of tires was highly valued. EU has carried out the
tire labeling law since 2012, Japan has started the tire labeling since
2011, and China has been preparing to set up tire labeling law. In
order to apply bio-based elastomers as tire tread materials, the
viscoelasticity of bio-based elastomer needs to be tuned elaborately
by structure design and nanoreinforcing technology. In the first
stage, poly (di-n-alkyl itaconate-co-isoprene) (PDAII) elastomers
were selected, and the type of di-n-alkyl itaconates and the content
of isoprene were researched. PDAII elastomers derived from
different di-n-alkyl itaconates and isoprene are displayed in Fig. 12.
By DSC results of PDAII samples, there is no obvious melting
peak, indicating totally amorphous structure. Tg of PDAII samples
decreased with the increase of side chain length as side chain act as
a uniformly distributed plasticizer. Combined by the thermal
properties and dynamic mechanical properties, poly (di-n-butyl
itaconate-co-isoprene) elastomer was chosen to carry on the tire
tread applications and silica was employed to reinforce the PDAII
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156 147

Fig. 14. Molecular structure of (a) AO-80, and (b) PDII, (c) Possible hydrogen bonds in hybrids (dash lines).

elastomer. A batch of tires were manufactured and tested in Ling- tires, butadiene was applied to copolymerize with di-n-butyl itac-
long Tire Company. The rolling resistance index of obtained tire was onate to prepare poly (di-n-butyl itaconate-co-butadiene) (PDBIB)
9.9 kg/t, which rated as E level by the EU Tyre Labelling Regulation. elastomer. PDBIB elastomer with different butadiene contents
In order to further decrease the rolling resistance of bio-based (20e80%) were synthesized. Tan d of PDBIB80 (butadiene content

Fig. 15. Temperature dependence of loss factor (tand) for PDII and PDII/AO80 hybrids Fig. 16. Temperature dependence of loss factor (tand) for PESD elastomer crosslinked
with various mass ratios of PDII to AO80. Reprinted from Ref. [54] by kind permission with different fractions of succinic anhydride. Reprinted from Ref. [24] by kind
of De Gruyter. permission of American Chemical Society.
148 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156

as 80%)/silica was the lowest at 60  C, which indicates lower rolling

resistance than other PDBIB80/silica samples. However, in tire tread
materials, the elastomer needs to combine good wet skidding
properties and rolling resistance. The lowest tand of PDBIB80/silica
at 0  C indicates the worst wet grip resistance. Thus, PDBIB80/silica
was not the appropriate candidate for tire tread. By the overall
evaluating of PDBIB/silica samples, PDBIB40 was selected as po-
tential elastomer to produce high performance bio-based tire tread.
We scaled up the synthesis of PDBIB40 elastomer in a reaction
kettle. The PDBIB40/silica tire (Fig. 13) was manufactured and
tested by Linglong Tire Co., Ltd using a MTS tire rolling resistance
measurement system. The rolling resistance coefficient was 7.7 kg/t
and rated as a B level by the EU Tyre Labelling Regulation 1222/
2009, which achieves high performance since A level tire is quite
few in European market. Akron abrasion of PDBII/silica tread
ranged from 0.08 to 0.20 cm3, which was comparable with tradi-
tional tread.

3.2.2. Damping materials

Vibration and noise often lead to undesirable consequences
such as unpleasant noise, fatigue and failure of structures,
decreased reliability, and degraded performance [50]. Rubber is
commonly used in controlling noise and vibration because of its
high damping property. The viscoelastic properties of rubbers make
them ideally suited for use as effective damping materials because
of their ability to dissipate mechanical energy [51,52]. For rubber
materials, phase lag existed under the alternating stress and vi-
bration energy consumed in the form of heat dissipation at each
cycle. Tan d is important factor predicating damping properties of
rubber material, and the intensity and width of tand at service
temperature was tightly correlated to damping properties. Gener-
ally, the damping property of certain kind of elastomer without
fillers was not satisfactory as the low value or narrow width of tand.
In the previous studies, hindered phenols (AO60, AO80, etc)
with many ester and end hydroxyl groups can form breakable
hydrogen bonds with nitrile butadiene rubber (NBR) macromole-
cules [53]. Under external force, the breakage or weakening of
these hydrogen bonds can consume large amount of energy. By Fig. 17. Mechanical properties retentions of (a) tensile strength (b) elongation at break
above mechanism, the incorporation of hindered phenols can of polyester/CB composite and NBR/CB composite after soaking in ASTM 1# oil at
different temperatures for 24 h.
effectively improve the damping properties. Similar with NBR,
numerous polar groups (ester groups) existed in the PDII elasto-
mers, it is hypothesized that hydrogen bonds can formed between range for effective damping (tand higher than 0.3) is larger than
AO80 and PDII macromolecules (Fig. 14). 50  C and the maximum peak value is higher than 1.4 at all fractions
The PDII/AO80 composites were prepared by the mechanical of succinic anhydride. These properties indicate good damping
kneading at a temperature higher than the melting point of AO-80, properties of PESD elastomer, which can find potential applications
followed by the crosslinking of PDII during the subsequent hot- as damping materials. In addition, the working temperature range
pressing/vulcanization process. The morphology and damping of the bio-based elastomer could be tuned by adjusting the fraction
properties of PDII/AO80 with different AO80 concentration were of crosslinking density.
systematically researched. Damping properties can be effectively
predicted by measuring dynamic mechanical parameters including 3.2.3. Oil resistant materials
loss tangent (tand). From Fig. 15, tand of PDII/AO80 increased Elastomer products often long exposure to oils, thus, high oil
significantly with the increase of AO80 content and the peak point resistant properties are essential for these products. Especially in
of tand curves shifted to higher temperatures, near room temper- aeronautics and aerospace fields, high quality and longtime service
ature (20e40  C). For example, with the incorporation of 100 phr oil-resistant elastomers were highly desired. Polar groups in elas-
AO80, peak value of tand curve of PDII/AO80 composite was 2.6 tomers contributed to the oil resistant. However, high polarity will
times as neat PDII, indicating highly improved damping properties reduce the flexibility of macromolecular chains, which will inevi-
[54]. In the further research, we can incorporate natural molecules tably increase the glass transition temperature. It's with high
with hydroxyl groups like tea polyphenol to prepare full bio-based challenge to provide high oil resistant properties and keep low
composites with ideal damping performance. glass transition temperature at the same time. We hypothesized
Poly (epoxidized soybean oil-co-decamethylene daimine) that bio-based polyester elastomer derived from propanediol,
(PESD) elastomer vulcanizates (crosslined by succinic anhydride) butanediol, itaconic acid, sebacic acid, and succinic acid may
also exhibit excellent potential damping properties. Fig. 16 shows possess excellent oil-resistant properties as large amounts polar
the temperature dependence of the loss factor for PESD elastomer. groups contained and its saturated main chain structure. Besides,
With the increase of succinic anhydride fraction, the peak of tand glass transition temperature of polyester elastomer was
shifts to higher temperatures. It worth noting that, the temperature below
40  C, which was significantly lower than conventional oil-
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156 149

Fig. 18. Typical stress-strain curves of PLA/polyester blends with different amounts of
polyester elastomer . Reprinted from Ref. [59] by kind permission of Elseviser.

resistant elastomers, for example, NBR and acrylate rubber. Nitrile

butadiene rubber (NBR) was widely applied in the sealing products,
rubber rollers, and rubber tubes as its high oil-resistant properties.
Thus, NBR220 (41% acrylonitrile) and NBR240 (26% acrylonitrile)
were employed to carry on the comparison between conventional
elastomer and polyester elastomer on oil-resistant properties.
Comparison experiments were carried out between NBR/CB com-
posite and polyester/CB composite at different temperatures.
Standard oil 1# (Japan Sun Oil) was used in the comparison of oil
resistant properties. Polyester/CB composite with 40 phr CB were Fig. 20. (a)Stress-strain curves of PLA/PLBSI blends and (b) impact strength-mass
prepared in a Haake mixer and crosslinked by 0.16 phr of DCP [55]. fraction curves of PLA/PLBSI blends. Reprinted from Ref. [60] by kind permission of
From Fig. 17, after soaking in oil for 24 h, tensile strength and The Royal Society of Chemistry.
elongation at break were decreased obviously. Tensile strength
retention of polyester/CB was between NBR220/CB and NBR240/CB
inherent brittle of bio-plastics highly restricted the wide applica-
above 100  C, and comparable with NBR 220 when below 100  C. In
tion of these materials. Therefore, toughening of bio-plastics has
general, polyester/CB exhibited high strength retention in wide
attracted many interests [56e58]. Most bio-plastics are polyester
temperature range, which was comparable with the performance
typed materials, for examples, PLA and PHAs. Bio-based polyester
of NBR 220. NBR 240 has obviously lower retention of elongation at
elastomer has similar molecular structure with these bio-plastics
break than NBR 220 and polyester/CB composites. Generally, oil-
[13]. Polylactic acid (PLA) is the most successfully and well-
resistant of polyester elastomer/CB was superior to NBR240 and
known biodegradable plastic. It is hypothesized that polyester
comparable with NBR220.
elastomer should have good toughening effect on PLA. Bio-based
monomers including sebacic acid, itaconic acid, succinic acid, 1,3-
3.2.4. Bio-plastic toughener propanediol, and 1,4-butanediol were chosen to synthesize bio-
Widely used plastic materials facilitate everyone's daily life. based polyester elastomer. The compatibility of PLA and polyester
However, conventional engineering plastics including polystyrene, elastomer was predicted by the calculation of solubility parameter
polyethylene, and polypropylene, etc. are nondegradable, which from Hoftyzer and Van Krevele's method. The calculated solubility
caused serious pollution problem. Thus, developing novel biode- parameters of polyester elastomer and PLA are 9.64 and 8.94 (cal/
gradable plastics become more and more meaningful. However, the cm)0.5, respectively, indicating that PLA/polyester blend is typical

Fig. 19. SEM images of tensile-fractured surface of PLA/polyester blends with (a)0 vol%, (b) 5.8 vol%, (c)11.5 vol% polyester. Reprinted from Ref. [59] by kind permission of Elseviser.
150 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156

Fig. 21. TEM micrographs of bio-based TPVs with different blending ratios of polyester/PLA: (a)60/40, (b)70/30, (c)80/20. Reprinted from Ref. [45] by kind permission of The Royal
Society of Chemistry.

Fig. 22. Phase inversion of bio-based TPVs with different degrees of crosslinking. (BPE: bio-based polyester).

immiscible system. By DSC results, polyester elastomer can greatly
improve the cold crystallization ability of PLA. Brittle-to-ductile
transition can be detected by the mechanical properties of PLA/
polyester blend.
From Fig. 18, with the incorporation of polyester elastomer, the
mechanical properties have undergone significantly changes.
Elongation at break of neat PLA was only 7% without yielding. As
the adding of polyester, PLA/polyester composite displayed obvious
yielding and neck growth. Elongation at break of PLA/polyester was
obviously higher than neat PLA. For instance, elongation at break of
PLA/polyester even achieved 180% with 11.5 vol% polyester con-
tained. By comparison of SEM images, unlike neat PLA's smooth
fracture (Fig. 19), fibril-like morphology was detected in PLA/
polyester fracture, indicating considerable strong interfacial adhe-
sion between PLA and polyester phases [59].
In order to further improve the compatibility of polyester elas-
tomer and PLA, poly (lactate/butanediol/sebacate/itaconate)
(PLBSI) copolyesters were synthesized [60]. By adjusting the con-
tent of lactic acid, PLBSI can vary from rigid plastics to flexible
elastomers. PLBSI elastomer can be used as high efficiency tough-
ener of PLA owing to similar lactate structures of PLA and PLBSI. As
shown in Fig. 20, all the PLA/PLBSI blends showed obvious yielding
and neck growth. Elongation at break of PLA with 15% PLBSI elas-
tomer achieves 300%, which was 30 times higher than that of neat
PLA. Impact strength of PLA/PLBSI blend increased with the in-
crease of elastomer content and reached maximum of 35.3 kJ/m2 at
15 wt%, which was 15 times higher than that of neat PLA.
3.2.5. Thermoplastic vulcanizates
Thermoplastic vulcanizates (TPVs) are very special class of TPEs,
consisting of thermoplastic matrix and a crosslinked elastomer as
the dispersed phase [61]. We prepared bio-based TPV from poly-
ester elastomer and PLA by an in-situ dynamical crosslinking and
mixing method [62]. Considering excellent compatibility with
polyester elastomer and petroleum-independent characteristic,
PLA was chosen as plastic phase. From the morphology during
dynamic crosslinking process, large amount of polyester elastomer
particles (1e4 mm) dispersed homogenously in the continuous PLA
phase, indicating successful occurrence of phase inversion. The
tensile strength and elongation at break of obtained TPV ranged
from 11.4 to 17.8 MPa and 154e184%, respectively. Mechanical
properties of obtained TPV were well kept during reprocessing.
Properties of TPV were highly affected by the elastomer/plastic
ratio. For example, higher elastomer content can ensure high
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156
Fig. 23. (a) Strain-stress curves of biobased TPVs with different blending ratios of BPE/PLA; (b) tensile set at break and hardness at different of BPE contents. Reprinted from Ref. [62]
by kind permission of The Royal Society of Chemistry.
Fig. 24. Variations of tensile strength of biobased TPV (BPE/PLA, 70/30) with number
of reprocessing . Reprinted from Ref. [45] by kind permission of The Royal Society of
Chemistry.
elasticity, but will inevitably cause difficulties in phase inversion
during processing and further affect mechanical properties of
products. Morphology of TPVs with different elastomer/plastic ra-
tios can be seen in Fig. 21. Crosslinked elastomer particles were
broken into PLA matrix with irregular, oval or elongated shape and
ranged 1~4 mm. Some large particles have interconnected with each
other. With high elastomer/PLA ratio (for example 80/20), aggre-
gation of elastomer particles was easily to form.
Crosslinking density was another important factor during the
preparation of polyester/PLA based TPV. Under room temperature,
elastomer was continuous phase and plastic was dispersed phase.
Non-crosslinked elastomer was difficult to occur phase inversion.
As shown in Fig. 22, elastomer particles with low crosslinking
density were easily to flow and deform as its similar viscocity with
plastic phase, which would produce inhomogenous dispersion in
plastic phase. On the contrary, elastomer particles with high
crosslinking density can form homogenous dispersion as high vis-
cocity difference provides strong shearing. However, if crosslinking
density of elastomer is overhigh, the broken of elastomer particle
becomes quite difficult. Phase inversion would not take place. In
summary, appropriate crosslinking density is also an important
factor to concern.
The mechanical properties of the biobsed TPVs with different
blend ratios are shown in Fig. 23. Neat PLA show very high tensile
151
Fig. 25. Preparation of cross-linked BPE and its structure. Reprinted from Ref. [63] by
kind permission of American Chemical Society.
strength and low elongation at break, typical features of brittle
plastic. Compared with that of neat PLA, the stress-strain curves of
biobased TPVs change from plastic (with necking and yielding) to
elastic behavior. Tensile strength and hardness of the biobased TPVs
decreased with increasing BPE content, range from 17.8 MPa to
7.4 MPa and 97 to 86 , respectively, indicating that PLA phase is the
major factor determining the tensile strength and hardness.
An important characteristic of TPVs over conventional thermo-
setting elastomers is that TPVs can be reprocessing without
significantly decreasing of related physical properties. In order to
investigate the reprocessing properties of the biobased TPVs, the
mechanical properties the TPV with a blending elastomer/rubber
ratio of 70/30 were measured after the TPV was reprocessed one,
three, and five times, and the results are shown in Fig. 24. It reveals
that the tensile strength and elongation at break do not change
significantly after it was reprocessed one and three times. These
results indicate that the biobased TPVs can be reprocessing without
significant reduction of mechanical properties. However, the tensile
152 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156

Fig. 26. Transition from the temporary spiral shape to the permanent linear shape for BPE with 20% DEG (upper photos) and without DEG (lower photos). Reprinted from Ref. [63]
by kind permission of American Chemical Society.

Fig. 27. Three-dimensional diagram of stress-controlled programming cycles for (a) D0, (b) D0 with colder cooling step, (c) D50, and(d) D100. (D0: BPE without DEG, D50: BPE with
50% DEG, D100: BPE with 100% DEG). Reprinted from Ref. [63] by kind permission of American Chemical Society.
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156
Fig. 28. (a) Mechanical properties of PPSe and PPSe/BM composites, (b) Weight loss of PPSe/BM composites in phosphate buffer saline at 37  C. Reprinted from Ref. [64] by kind
permission of American Chemical Society.
Fig. 29. Experimental setup for measuring actuated strain.
strength significantly decreases after the TPV was reprocessed five
times because of the breakdown of crosslinked BPE domain from
the strain during the process.
3.2.6. Shape memory polymers
Shape memory polymers (SMPs) are a series of smart materials
which have the ability to respond to external conditions. They can
memory one or more predetermined shapes and then be fixed into
temporary shape. For biomedical applications, bio-based polymers
with excellent biocompatibility have been important resource of
SMPs. Propanediol, sebacic acid, itaconic acid, and diethylene glycol
(DEG) were used to prepare bio-based polyesters (BPEs) [63]. DEG
was incorporated to adjust the macromolecular flexibility and the
prepared BPEs cover from rigid plastics to flexible elastomers. The
contained double bonds in BPEs can be used for further crosslinking
as to form permanent network. Combined with temporary network
which provided by crystallization, the synthesized BPEs meet the
requirements of SMPs. The results revealed that BPEs hold excellent
shape recovery and repeatability and the properties can be easily
tuned by DEG content. The preparation route and schematic map
are displayed in Fig. 25. The shape recovery properties are
researched. The samples were cured with 0.5 phr of DCP, and the
recovery process was recorded after heating the samples to
Tm þ20  C (Fig. 26).
The shape memory behavior was activated by changing the
switching temperature below and above Tm of BPEs with different
compositions. BPEs behave as soft rubber above their Tm in per-
manent shape and could be deformed to a temporary shape under
153
external force. When the deformed samples are cooled below
switching temperature, their temporary shape is fixed without
loading, and the deformed shape can be kept well. However, if the
operation temperature is raised to above the switching tempera-
ture again, then BPEs will quickly return to their initial shapes. The
stress controlled programming cycles (four times) of samples D0,
D50, and D100 are depicted in Fig. 27. It is demonstrated that all
three samples exhibit excellent shape recovery.
Besides, boehmite (BM) nanoplatelets were adopted to fully bio-
based poly (propylene sebacate) (PPSe) to form shape memory
composites [64]. As shown in Fig. 28, the prepared PPSe/BM com-
posites showed stronger shape memory properties and faster
degradation speed than neat polyester material.
3.2.7. Dielectric elastomers
Dielectric elastomers are one kind of electroactive smart mate-
rials, which can be applied in artificial muscles, biomimetics, sen-
sors and robotics, etc. [65,66] When an electric field is applied, an
electrostatic pressure acts on the film, the film will shrink in the
thickness direction and expand in the planar direction. The actu-
ated strain in the thickness direction is given by the following
equation:
 
εε0 U 2
sz ¼ p=Y ¼
Y d
Where p is the electrostatic pressure, Y is the elastic modulus, ε is
the permittivity of the elastomer, ε0 is the permittivity of free space,
U is the applied voltage, and d is the thickness of the film [67]. From
the equation, we can conclude that elastomers with high dielectric
constant and low elastic modulus are ideal candidates for dielectric
elastomers. Various kinds of elastomers are investigated to apply as
dielectric elastomers. Experimental setup for measuring actuated
strain is shown in Fig. 29. Silicone elastomer, acrylic elastomer, and
fluororubber are regarded to exhibit excellent dielectric actuating
properties. One important characteristic of these elastomers was
polar groups contained in above elastomer. Polyester elastomer
derived from sebacic acid, succinic acid, itaconic acid, propanediol,
and butanediol which holds large amount of polar groups was
prepared and investigated. Ester groups provided polymer with
excellent internal rotation capacity, low glass transition tempera-
ture, and high polarity properties. Combined with very low
modulus, polyester elastomer was expected to present high elec-
trostrictive strains. Double bonds contained in the polyester were
used to adjust to appropriate modulus. Tg of polyester elastomer
was below
50  C with number average molecular weight as
154 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156

Fig. 30. TEM micrographs of polyester elastomer composites filled with different contents of TiO2: (a), (d) 3 vol %; (b), (e) 6 vol %; (c), (f) 10 vol %. Reprinted from Ref. [69] by kind
permission of AIP Publishing LLC.

33,000 g/mol, and the polydispersity index as 3.7.

Fig. 31. Dependence of actuated strain (without any prestrain) of polyester elastomer
composites with different contents of TiO2 on electric field. Reprinted from Ref. [69] by
kind permission of AIP Publishing LLC.
With the increase of crosslinking density, tensile strength and
elongation at break differs a lot. Modulus was only 0.097 MPa when
crosslinking density was 3.28  10
5 mol/cm3. However, even at
this density, polyester elastomer also exhibited good elasticity.
Elongation at break achieveed 1000% and permanent set was only
4%. Polyester elastomer had high dielectric constant (5.6e7.8),
which was obviously higher than conventional dielectric materials
(silicone elastomer DC3481 3.25e3.65, arcylic rubber
VHB4910(3M) about 4.7) [68]. It is believed that high dielectric
constant was attributed to numerous ester groups, chained end-
carboxyl groups and hydroxyl groups. Generally, polymers with
more polar groups exhibit higher dielectric constant.
With the increase of crosslinking density, area actuated strain
was decreased at certain electric field. When crosslinking density as
3.28  10
5 mol/cm3, area actuated strain achieved 11.9% at electric
field as 15.6 kv/mm. Besides, titanium dioxide (TiO2) powder was
incorporated to prepare polyester/TiO2 composites for higher
actuated strain [69]. We found that the dielectric constant of
composites increased with increasing TiO2. Nevertheless, elastic
modulus of the composites did not increase with increasing content
of TiO2.
 R. Wang et al. / Composites Science and Technology 133 (2016) 136e156
The TEM micrographs of bio-based polyester elastomer com-
posites filled with different TiO2 contents are shown in Fig. 30. As
high surface energy of TiO2 nano-particles, they are not uniformly
dispersed on nanoscale, with some agglomerations in all the
polyester/TiO2 composites. With the increase of TiO2 contents, the
size of agglomeration increases. If the agglomerations are suffi-
ciently large, the particles will come in contact with each other to
form a filler network [37]. An obvious filler network is formed in
the composites with 10 vol% whereas in the compsite with 6 vol%
TiO2, the agglomerations do not come in contact with one another
although they are larger than those in the composite with 3 vol%
TiO2.
The actuated strains of polyester elastomer composites with
different contents of TiO2 versus electric field are displayed in
Fig. 31. The polyester/TiO2 composite with 6 vol% TiO2 possesses
largest actuated strain at a given electric field. Polyester elastomer
filled with 6 vol% of TiO2 exhibited the lowest elastic modulus,
which led to a high prestrain-free actuated strain of 11.8% at a low
electric field of just 9.8 kV/mm. The actuated strain is better than
other dielectric elastomers reported in the literature. It is believed
that high electromechanical performance was attributed to the
increase in dielectric constant and decrease in elastic modulus of
the composite from those of the pure polyester elastomer. The
polyester elastomer and TiO2 are both environment-friendly,
making possible the composite to be used in biological and medi-
cal devices.
4. Summary and conclusion
With the depleting of fossil energy and fast developing of
biotechnology, bio-based polymers including bio-based elastomers
have attracted wide attention in related fields. It is believed that the
developing of new generation bio-based elastomer from renewable
resources aiming at engineering applications will inevitable to be
hotspot for both academic and industrial fields. Through molecular
design to obtain new bio-based elastomers like polyester type
elastomer, poly (di-alkyl itaconate-co-diene) elastomer, and plant
oil based elastomer have the advantages of low cost, energy saving
and tunable properties. Bio-based monomers such as limonene,
myrcene, etc. are also ideal monomers to fabricate novel bio-based
elastomers. With the rapid development of fermentation technol-
ogy, more and more suitable monomers will emerge. It is believed
that polyester type elastomer and poly (di-alkyl itaconate-co-
diene) elastomer are promising bio-based elastomers and possible
to be produced in large scale, like PLA in bio-plastic field. However,
the wide acknowledge and application development of novel bio-
based elastomers desire a long period. The other method is to
prepare conventional elastomers from bio-based ethylene, pro-
pylene, butadiene, and isoprene, etc. These bio-based elastomers
possess same molecular structure and nearly identical mechanical
properties with conventional elastomers. Thus, these elastomers
are easily to carry on the applications. However, the scale produc-
tion of these monomers is difficult as their high cost. The rein-
forcement of bio-based elastomers and preparation of bio-based
elastomer composites are important process for the development
of bio-based elastomers. Filler selection, interface design, and
elastomer modification are key points to construct bio-based
elastomer composites with satisfied properties. With the devel-
opment of biotechnology, polymer synthesis methods, and high
efficiency fillers, bio-based elastomer composites will definitely
play important role in the rubber industry.
Acknowledgements
This work was supported by the National Natural Science
155
Foundation of China (50933001,51503010) and Fundamental
Research Funds for the Central Universities (JD1511). Thanks for the
financial support of Goodyear Tire & Rubber Company.
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