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Vaysse L, Bonfils F, Sainte-Beuve J, and Cartault M (2012) Natural Rubber.

In: Matyjaszewski K and Möller M (eds.) Polymer Science: A Comprehensive
Reference, Vol 10, pp. 281–293. Amsterdam: Elsevier BV.

© 2012 Elsevier B.V. All rights reserved.

 Author's personal copy

10.17 Natural Rubber

L Vaysse, CIRAD, UMR IATE, Montpellier, France; UMR IATE, Kasetsart University, Bangkok, Thailand
F Bonfils and J Sainte-Beuve, CIRAD, UMR IATE, Montpellier, France
M Cartault, ANVIS SD France S.A.S., Decize, France
© 2012 Elsevier B.V. All rights reserved.

10.17.1 Introduction and History 281

10.17.2 Challenge Facing the Supply Chain 281
10.17.3 The Biosynthesis of Poly(cis-1,4-isoprene) 282
10.17.4 Nonisoprene Components of Natural Rubber (NR) 284
10.17.4.1 Proteins 284
10.17.4.2 Carbohydrates and Cyclitols 285
10.17.4.3 Lipids 286
10.17.4.4 Inorganic Compounds 287
10.17.5 NR Structure 287
10.17.5.1 Introduction 287
10.17.5.2 Microstructure 287
10.17.5.3 Mesostructure 288
10.17.5.3.1 Macromolecular structure 288
10.17.5.3.2 Gel 288
10.17.6 NR in the Manufacture of Antivibration Parts 289
10.17.6.1 The Place of NR in Suspension Joints 289
10.17.6.2 NR/Synthetic Elastomer Competition 289
10.17.6.3 The Main Processes Used 290
10.17.6.3.1 Formulation/mixing 290
10.17.6.3.2 Shaping 290
10.17.6.3.3 Vulcanization 290
10.17.7 General Aspects of NR Applications in Tires 290
10.17.8 Conclusion 291
References 291

10.17.1 Introduction and History
Hevea brasiliensis, a tree indigenous to the tropical forests of the
Amazon basin, is the only major commercial source of natural
rubber (NR). All rubber trees originate from the Hevea seeds,
which were transported by Henry Wickham from Brazil to
British India in 1876, where only 2000 seeds survived.1 As a
consequence, most modern material comes from a narrow base
of a few trees that grew in the Upper Amazon region. A survey
was organized under the aegis of the International Rubber
Research and Development Board (IRRDB) in 1981 in Brazil to
harvest plant material from different regions of the Amazon
basin. Currently, the Asian continent produces 94% of global
production, while the South American region produces only 2%,
mainly due to the presence of South American Leaf Blight (SALB)
that prevents the development of industrial rubber production.
NR from H. brasiliensis is a natural polymer composed of an
association of poly(cis-1,4-isoprene) and some biological ele­
ments, giving its highly specific properties.2
10.17.2 Challenge Facing the Supply Chain
The world elastomer market, and more particularly NR, has
entered an upward phase governed by demand, linked to the
strong growth in demand for tires, particularly in China, which
has overtaken the United States in becoming the world’s
leading motor vehicle market. The production and consump­
tion of elastomers in 2010 exceeded their 2007 levels by 1
million tons, that is, + 4.2% (Table 1). However, the distribu­
tion between the different consumer countries has altered
considerably in 3 years. Between 2007 and 2010, China used
an extra 2 million tons of elastomers, amounting to a 32%
increase, rising from 26.2% to 33% of world elastomer con­
sumption. Over the same period, consumption in Europe fell
by 750 000 tons (− 18.9%, and for NR alone –22.8%), in the
United States by 400 000 tons (− 12.5%, with − 12.2% for NR
alone), and lastly in Japan by 300 000 tons (− 15.4%, with
− 16.8% for NR alone).
World consumption of NR should reach 10.4 million
tons for 2010, outstripping expected production by around
200–300 000 tons, which amounts to roughly 2–3%, depend­
ing on the accuracy of the figures supplied by countries.
Figure 1 reports the different areas where NR is used.
In the tire sector, NR consumption reached around 7.5 million
tons in 2010 and is set to continue growing at an annual rate of
4% on average, reaching 11.4 million tons in 2020. That growth
will be almost exclusively in Asia, and more particularly in China.
The share of NR in total rubber production increased from
41% in 2003 to 44% in 2009. That increase was due to the
development of secondary transformation in producing coun­
tries, which prefer to use a locally produced raw material than
to buy synthetic rubber. That tendency may be reversed with
the new technologies being introduced by the major tire

Polymer Science: A Comprehensive Reference, Volume 10 doi:10.1016/B978-0-444-53349-4.00267-3 281

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282 Sustainable Use of Biomass | Natural Rubber

Table 1 Elastomer market (1000 tons), 2010

NR SR NR SR
Production Production Consumption Consumption
2010 2010 2010 2010

North America 0 2 458 1 054 1 925

South America 262 655 607 889
Europe 0 2 609 1 120 2 254
Russia and others 0 1 177 226 839
Africa 456 72 96 121
Indonesia 2 828 45 421 182
Thailand 3 072 200 420 324
Malaysia 939 86 458 163
China 650 3 137 3 634 4 479
India 851 110 944 404
Japan 0 1 578 739 980
Others Asia 1 189 1 916 951 1 062
Total 10 247 14 043 10 671 13 623

NR, natural rubber; SR, synthetic rubber.

Source: International Rubber Study Group (IRSG).

1%
1% 1% 2% Medium/heavy tires
6%
24 % Car tires
6%
Light car vehicule tires
5%
Others tires

8% Hoses and belts

Non tire automotive
15% Shoes

8% Others GRG
Medical gloves
Threads
Foam
7% Adhesives
16%
Others latex

Figure 1 Fields of natural rubber application. Sources: IRSG and LMC.

makers to meet environmental demands, such as noise reduc­
tion, low roller resistance, and better grip on wet roads. While
each of the major tire makers has started to respond (Goodyear
with BioIsoprene and Michelin with the Helio compound),
securing supplies remains a major challenge. However, it
should be remembered that the aim is to reduce the amount
of NR by 50%, while strengthening certain properties (adher­
ence to wet roads and reduced roller resistance) and reducing
the environmental impact (particularly noise), by replacing
softeners considered toxic today (i.e., highly aromatic (HA)
oil, also called distillate aromatic extract (DAE) oil containing
polycyclic aromatic hydrocarbons (PAHs)).
Due to technological constraints, the degree of substitution
between natural and synthetic rubbers is limited in tire manufac­
ture. For general rubber goods (GRGs), substitution is technically
easier, but is economically governed by the price of petroleum oil
and by the synthetic rubber market (limited C4 and C5 avail­
ability), which directly affects the price of synthetic rubber.
World NR production exceeded 10 million tons for the first
time in 2008, that is, a third higher than the level recorded a
decade earlier. According to the International Rubber Study
Group (IRSG), NR production is expected to reach around
15 million tons in 2020. There are still areas that can expand
rubber cultivation (Figure 2). However, one of the weaknesses of
rubber culture is the long immature period compared to other
cultures and to synthetic rubber production (Table 2).
10.17.3 The Biosynthesis of Poly(cis-1,4-isoprene)
NR has maintained its very competitive share in the elastomer
market for decades, mainly due to the astonishing properties of
poly(cis-1,4-isoprene), which is the polymer stored in so-called
‘rubber particles’ of H. brasiliensis latex. Many studies have been
undertaken to understand the biosynthesis pathway of this very
long-chain polymer, which stands out through having almost
100% cis-double bonds.
Poly(cis-1,4-isoprene) belongs to the polyisoprenoids family,
which contains more than 23 000 compounds derived from
primary or secondary metabolisms. Key biochemical compo­
nents such as sterols, abscisic acid, gibberellins, cytokinins, and
prenylated proteins, belong to the isoprenoids. A central inter­
mediate of the isoprenoid biosynthesis pathway in all organisms
is isopentenyl diphosphate (IPP).3 IPP and its isomer
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NR producing countries with

potential land for rubber cultivation

NR low or nonproducing countries with

potential land for rubber

NR producing countries with low

potential land for rubber cultivation

Figure 2 Map of the rubber growing areas.

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284 Sustainable Use of Biomass | Natural Rubber
Table 2 Immature period for different crops
Immature period
Crops (y)
Perennial crops
Natural rubber (Hevea brasiliensis) 6–7
Oil palm 3–4
Resin of pine 25–35
Eucalyptus 2–3
Jatropha 1–2
Annual crops
Rapeseed 0.5
Beet 0.5
Sugar cane 1 ing phloem zone (young laticifers).21 With regards to the
dimethylallyl diphosphate (DMAPP) are five-carbon units based
on larger molecules such as triterpenes, sterols, squalenes, or
polyisoprenes. It is widely agreed that IPP originates from pyr­
uvate, a glycolysis product. Two pathways are described from
pyruvate to IPP: the cytosolic mevalonate (MVA) pathway and
the plastidial 2-C-methyl-D-erythritol 4-phosphate (MEP) path­
way (Figure 3). The first pathway involves six reactions catalyzed
successively by the pyruvate dehydrogenase complex, thiolase,
HMG-CoA synthase, HMG-CoA reductase, MVA kinase, and
MVAPP decarboxylase. Another pathway leading to IPP has
recently been described by Rohmer.4,5 This plastidial pathway
involves seven enzymes including DXP synthase, DXP reductoi­
somerase, MEP cytidylyltransferase, CDP-ME kinase, cMEPP
synthase, HD synthase, and finally HD reductase. Tracer experi­
ments using 14C HMG-CoA concluded on the involvement of the
MVA pathway in the biosynthesis of IPP for rubber biosynthesis
in H. brasiliensis. Though the expression of the first enzyme of the
MEP pathway (DXP synthase) has been proved in latex and
leaves from Hevea,6 recent work stated that this pathway is not
used for rubber biosynthesis but is most likely involved in car­
otenoid biosynthesis.7
Once IPP is obtained from pyruvate, rubber biosynthesis
continues with an elongation process, which eventually leads
to a long-chain polymer molecule containing more than 5000
isoprenic units. Elongation consists of the sequential conden­
sation of IPP and allylic diphosphate through the action of the
prenyl-chain-elongating enzyme, commonly called prenyl­
transferase, the first allylic diphosphate being DMAPP, an IPP
isomer produced by IPP isomerase. This elongation process
includes two steps: during the first step, short-chain allylic
diphosphates are produced, resulting from the condensation
of DMAAP and 1–3 IPPs. This first step is catalyzed by a trans­
prenyltransferase. This initial step explains the presence of 2–4
trans-isoprene units at the beginning of the NR chain,
farnesyl-PP and geranyl-PP being the most likely prenyldipho­
sphates used as a primer in the case of H. brasiliensis.8–10 The
second step of elongation consists of the sequential cis-
condensation of a few thousand IPPs to the primer. This crucial
step is catalyzed by a ‘rubber transferase complex’, which is for
some authors a cis-prenyltransferase11–13 or a trans­
prenyltransferase associated with cofactors such as the rubber
elongation factor (REF) or the small rubber particle protein
(SRPP).4,9,14 Concerted mechanisms used by a cis­
prenyltransferase, namely undecaprenyl diphosphate synthase
(UPPs), which is able to add through cis condensation eight IPP
units to farnesyl diphosphate, have been proposed recently and
involve the Mg2+ complex.15 Nevertheless, in the case of NR
from Hevea, where the number of condensed IPPs reaches a few
thousand, the mechanisms and the enzyme and cofactors
involved remain unclear. Another uncertainty lies in the cellu­
lar location of rubber biosynthesis. Most authors assume that it
is located at the surface of rubber particles,13,16,17 while others
claim that it could originate in the membrane of nonrubber
particles from the bottom fraction after ultracentrifugation of
latex.18–20 To add to the complexity of NR biosynthesis eluci­
dation, a recent histochemistry study showed that the location
of factors such as REF or SRRP in the laticifers in rubber tree
bark differs: REF being detected in all laticifer layers, while
SRPP was only detected in the laticifers located in the conduct­
termination of the elongation process, although little is
known about the mechanisms, NMR studies led to the identi­
fication of alpha end groups indicating the presence of
phosphate and fatty acid that are attributed to the possible
presence of a phospholipid molecule. Furthermore, once bio­
synthesized, the linear isoprene chain may undergo further
chemical modifications as abnormal groups, such as aldehyde,
epoxy, or lactone, have been detected on the polymer chain.22
Even though NR from H. brasiliensis has been used on a large
industrial scale for a dozen decades, much remains to be
discovered about the details of rubber biosynthesis mechan­
isms. An integrated approach combining proteomics, tree
physiology, and rubber chemistry would certainly lead to a
better understanding in the near future.
10.17.4 Nonisoprene Components of Natural
Rubber (NR)
Around 10% of the dry matter of H. brasiliensis latex comprises
nonisoprene components. Those nonisoprene components
account for about 5% of the raw dry rubber derived from latex
(Table 3). They comprise proteins, carbohydrates, lipids, and
inorganic constituents and represent the main composition dif­
ference between NR and its synthetic counterpart, namely, poly
(cis-1,4-isoprene) synthetic rubber (IR). The nature and quantity
of these nonisoprene components can vary greatly depending on
the clones, the exploitation system, and the environmental con­
ditions.23 Some of these components are either dissolved or
suspended in the aqueous medium of the latex, while the others
are adsorbed on the surface of rubber particles, or contained in
other organelles such as lutoids or Frey-Wyssling particles. It is
worth mentioning that around 50% of nonisoprenes are leached
or degraded during dry rubber processing.
10.17.4.1 Proteins
Fresh latex contains roughly 1.5% of proteins, of which about
25–30% are bound to the rubber phase, another 25% being
associated with the bottom fraction (lutoid) and the remainder
(45–50%) being reported as cytosolic.24,25 Two major particle
surface-bound proteins of 14 kDa (rubber elongation factor)
and 22 kDa (small rubber particle protein) have been identi­
fied. In the bottom fraction, the two major proteins are hevein
(> 50%), an anionic protein, and hevamine. The molecular
weight of the proteins in this fraction is narrow, ranging from
14 to 45 kDa. In C-serum, proteins are numerous and range
from 14 to 133 kDa.25–27 Proteins play an important role in
 Author's personal copy
Sustainable Use of Biomass | Natural Rubber 285

MVA pathway DXP/MEP pathway*

D-glucose

Glycolysis

Isopentenyl diphosphate (IPP)

trans-condensation
trans prenyltransferase

xC

cis-condensation
t=1 “Rubber transferase”
see below
t=2

t=3
Natural rubber long-chain cis -polyisoprene
Short-chain allylic-PP with trans residue (t < 4, c > 5000)

Figure 3 Biosynthesis of poly(cis-1,4-isoprene).

metabolism (glycolysis, biosynthesis, etc.), in the structure of 10.17.4.2 Carbohydrates and Cyclitols
rubber particles (negative charges ensuring colloidal stability),
Quebrachitol or 2-O-methyl-L-inositol is the most important
and in the quality of rubber products (drying,28 stress relaxa­
single component among nonisoprenes, constituting more
tion29 but also allergenicity for a minor, overexposed
than 1.2% of latex (see Box 1). Concerning carbohydrates,
population24).
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286 Sustainable Use of Biomass | Natural Rubber
Table 3 Composition of natural rubber latex and raw dry rubber
Latexa
% w/v
fresh latexa
Rubber hydrocarbon 35.0
Protein 1.5
Carbohydrate 1.5
Lipids 1.3
Organic solutes 0.5
Inorganic substances 0.5
a
Averaged from data published by Wititsuwannakul, D.; Wititsuwannakul, R. In Biopolymers. Vol. 2:
Polyisoprenoids; Koyama, T., Steinbüchel, A., Eds.; Wiley-VCH: Weinheim, 2001; pp 151–201.25
b
Calculated.
c
Sainte-Beuve, J.; Vaysse, L.; Bonfils, F. In La Chimie Verte, Coord. Paul Colonna, Editions
Tec&Doc Lavoisier, Paris, 2006, pp 215–237.47
Approximate values only (they are highly dependent on the clone, season, and physiological
status of the tree).
Box 1 Quebrachitol: A potential high-value added coproduct
among nonisoprenes from latex
Of the nonisoprenes present in Hevea latex, it is worth mentioning queb­
rachitol separately, given the huge amount present in NR latex (more than
1.2% of fresh weight), making this molecule the most important single
component among the nonisoprenes. The chemical structure of quebrachitol,
or 2-O-methyl-L-inositol is shown above. Amazingly, for such a quantita­
tively important component, its physiological function remains unknown.25
Regarding particle diversity in latex (rubber, Frey-Wyssling, and lutoids), an
osmotic stabilizer function in stress-related conditions has been proposed
for quebrachitol.43
In the 1990s, the Rubber Research Institute of Malaysia promoted the
utilization of coproducts to implement a ‘total utilization’ policy to fully
exploit the rubber tree in order to ensure a maximum return on investments.
With regard to the quantity present and the potential applications, quebra­
chitol was found to be the best candidate for such covalorization.44 Being
water soluble, this cyclitol is one of the major organic pollutants in the
processes involving coagulation and release of serum. Extraction and
purification of the molecule would therefore prevent such pollution and
provide new added value for Hevea brasilensis latex.
Quebrachitol, with its levorotary structure can be used as a starting
material to synthesize chiral drugs in an enantiomerically pure form. It
can be used as a versatile building block in the construction of
naturally occurring bioactive compounds.45 Quebrachitol can be simply
transformed to inositol derivatives already known for their medicinal
properties, such as myo-inositol esters (used in hepatology), myo­
inositol hexasulfate (used in chemotherapy), or aminocyclitols (used
as antibiotics in infectiology).44
An international patent for the extraction process has therefore been filed
by a Malaysian–Japanese team proposing the purification of quebrachitol
from Hevea latex serum.46 It is claimed that 9 kg of quebrachitol can be
purified from 1 ton of NR produced. Hence, by extrapolation, a potential
production of 90 000 tons of quebrachitol could have been achieved from
world NR production in 2010 (estimated at about 10 million tons).
Dry rubber
% w/w % w/w
dry matter of latexb dry matterc
87.0 94.0
3.7 2.2
3.7 0.4
3.2 3.4
1.1 0.1
1.2 0.2
latex cytosol contains sucrose (0.3–0.4% of latex weight),
which is the sugar supply for the rubber biosynthesis pathway
as the source of pyruvate (see rubber biosynthesis section).
Sucrose concentration is a key parameter in latex diagnosis
used to assess the physiological status of the rubber tree, mak­
ing it possible to monitor tapping intensity.30–32 In addition to
sucrose, a smaller amount of glucose, fructose and raffinose are
present in latex.
10.17.4.3 Lipids
Lipids are the family of nonisoprenes most retained with the
rubber during processing. Their extraction for analytical purp­
oses has been optimized by Liengprayoon and co-workers.33
Depending on the clone, lipids amount to 2.5–3.8% versus dry
rubber in latex, and 1.8–3.3% in dry NR.34 Phospholipids
account for 18–25% of lipids in fresh latex but only 4–5% of
lipids in dry rubber. The main phospholipid is phosphatidyl
choline, amounting to more than 60% of latex phospholipids.
Considering their amphiphilic character, with their negatively
charged polar head and the apolar lipid moiety, phospholipids
could be involved in the colloidal stabilization of the NR latex
together with charged proteins.35 In concentrated rubber latex
stored for several months, the fatty acid soap, presumably
released by hydrolysis of the ester bonds of phospholipids,
was also described as a major agent of colloidal stabilization.36
Phospholipids were also described as linked to the alpha end of
polyisoprene chains.37
Glycolipids account for 25–35% of lipids in fresh latex and
10–14% of lipids in dry rubber. Like phospholipids, they are
degraded and/or leached during dry rubber processing. The
main two glycolipids are digalactosyldiglyceride (DGDG,
�45% of latex glycolipids) and steryl glucoside (SG, approx.
35%). They also have a structural role in membranes. Neutral
lipids account for 40–60% of lipids in fresh latex but 82–86%
of lipids in dry rubber. Neutral lipids include fatty acids and
unsaponifiables. Linoleic acid (C18:2) is generally the most
important with 40–50% of the fatty acids, followed by oleic
acid (C18:1), stearic acid (C18:0) and furan fatty acid. Fatty
acids have been described as having a technological role in
 Author's personal copy
some properties of rubber, such as green strength38 and tack
property,39 and are known to be activators of vulcanization.
Concerning the unsaponifiable components of lipid extract,
the major one is β-sitosterol (37–45% of unsaponifiables),
followed by γ-tocotrienol (17–22%), Δ5-avenasterol
(16–20%), stigmasterol (6–8%), octadecanol (4–7%) and
α-tocotrienol (4–6%). Some unsaponifiables may have an anti­
oxidant activity, which is of great importance in protecting the
double bonds of isoprenic chains.40,41
10.17.4.4 Inorganic Compounds
About 0.5% of fresh latex is composed of inorganic ions
(K+, Mg2+, Cu2+, Fe2/3+, Na+, Ca2+, and PO43 −).42 Even in
small quantities, they are key cofactors in metabolic pathways,
and are also involved in the technological properties of rubber,
such as susceptibility to thermal oxidation.41
Nonisoprenes of NR are involved in metabolism (carbon
source and enzymes for polyisoprene biosynthesis), in the
structural organization of latex (membranes of rubber, lutoids
or Frey-Wyssling particles, and colloidal stability) and in some
technological properties of rubber, which give NR its unique
properties. Finally, some nonisoprenes, such as quebrachitol,
could be commercially developed as coproducts, which con­
firms that H. brasiliensis is definitively a ‘green chemical factory’
(Box 1).
10.17.5 NR Structure
10.17.5.1 Introduction
As for all materials, a study of NR and the relations existing
between its structure and properties require the knowledge of
the different structural levels. These structural levels are here
defined in terms of microstructure, mesostructure, and macro­
structure. The ‘macrostructure’ of NR concerns the raw material
at the macroscopic scale, where the material is assumed to be
homogeneous with little or no destructuring. The
(a)
CH3
C CHCH2 CH2
CH3 C CH
CH3 CH2
(b)
Protein CH2 CH2
C CH
CH3 CH2
m n
Figure 4 Microstructure of poly(cis-1,4-isoprene) (a) for latex plants other than Hevea and (b) for Hevea.
Sustainable Use of Biomass | Natural Rubber 287
macrostructural properties will not be reviewed in detail in
this chapter, as they primarily involve rheological characteriza­
tions. For a polymer, the definition of the ‘microstructure’
varies depending on the authors. Koenig48 or Sperling49 con­
siders the microstructure to involve the (chemical)
composition, configuration, and conformation of the chain.
Mirau et al.50 propose “the precise way in which monomers
are linked to each other to form a polymer (chemical struc­
ture)”. For NR, the microstructure concerns the chemical
structure of the poly(cis-1,4-isoprene) macromolecules, but
also the composition of nonisoprene constituents (lipids, pro­
teins, etc.), their chemical structure, and their interactions with
poly(cis-1,4-isoprene) macromolecules. These interactions play
a paramount role in the ‘mesostructure’ of NR and its specific
properties. For NR, the mesostructure corresponds to the
macromolecular structure and to the aggregates formed by the
association of poly(cis-1,4-isoprene) molecules (gel).
10.17.5.2 Microstructure
For synthetic rubbers, analysis problems boil down to two
determinations: identification of the constitutive groups and
determination of spatial arrangement. For NR, those two deter­
minations have undergone a great deal of research mentioned
previously.51 The poly(cis-1,4-isoprene) chain in the plants
studied comprises three parts (Figure 4): (1) a (ω) end group
containing one dimethylallyl group and two or three trans
groups, (2) a long chain of cis configuration, and (3) an (α)
end group (Figure 4(a)). For NR from Hevea, the chemical
structure of the two end groups has yet to be completely iden­
tified. So far, neither the hydroxyl group nor the dimethylallyl
group has been revealed. Studies on deproteinized NR from
which ester links had been removed by methanolysis led
Tarachiwin et al.37 and Tanaka52 to suggest the existence of a
protein (or polypeptide) on the (ω) group and a phospholipid
(or fatty acid) on the (α) end group (Figure 4(b)). Those two
nonisoprene compounds attached by covalent bonds to the
polyisoprene chain would seem to lie behind the interactions
CH3
CH3
C CH
CH2 CH2 CH2C CHCH2 OH
m n
CH3
C CH CH3
CH2 CH2 CH2C CHCH2 Lipid
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288 Sustainable Use of Biomass | Natural Rubber
responsible for the associative structure of NR (with regard to
nonisoprene compounds (lipids, proteins, and sugars);
see Section 10.17.3).
10.17.5.3 Mesostructure
The mesostructure covers both the macromolecular scale
(dimension, conformation, and architecture of the macromo­
lecules) and the supramolecular scale (complex aggregates
between macromolecules). This associative mesostructure is
gradually and partly destroyed when dissolved in a conven­
tional solvent of polyisoprene (cyclohexane and
tetrahydrofuran (THF)). However, in many cases, a proportion
of NR remains insoluble in those solvents, a fraction com­
monly referred to as the gel phase or ‘macrogel’. The soluble
fraction contains polyisoprene macromolecules and a variable
quantity of microaggregates making up the ‘microgel’.
10.17.5.3.1 Macromolecular structure
In 1972, Subramaniam53 investigated inherent molar mass dis­
tribution (MMD0) in NR. MMD0 is the MMD of NR on leaving
the tree without undergoing any modification linked to post­
harvest processing (coagulation, maturation, processing, etc.).
The MMD0 of NR is an important criterion for forecasting a
certain number of NR properties that will be obtained after
processing.54 Depending on the clone, MMD0 will lie between
two extreme types: bimodal or unimodal with a shoulder (some­
times also called ‘quasi-unimodal’ in literature) (Figure 5).
MMD evolves after the processing stage depending on the pro­
cess used.54 NR from Hevea is characterized by polyisoprene
chains of very variable size ranging from a few thousand to
some tens of millions of g mol− 1. It is, therefore, characterized
by a very wide molar mass distribution, with a polymolecularity
index (I) sometimes exceeding 8, and a very high average num­
ber molar mass (150 000 < Mn < 300 000 g mol− 1). Amongst
around 20 latex-bearing plants studied by Swanson et al.,55
such long macromolecules are found in rubber from guayule
only. Recently, Kim et al.56,57 analyzed NR samples with
size-exclusion chromatography coupled to a multiangle light
scattering (SEC-MALS) detector. They showed that the soluble
part injected into a SEC system contained very few branched
VM515
GT1 or PB312
RRIC121
PB330
1.E + 03 1.E + 04
Molar mass (g mol
Figure 5 Examples of inherent molar mass distribution for several Hevea clones (size-exclusion chromatography in cyclohexane according to Bonfils et al.).71
macromolecules, contrary to earlier published studies.56–60 Kim
et al.56,57 showed that the soluble part of NR in solution of THF
was made of a mixture of linear chains and assumed compact
microaggregates (radius of gyration or Rg ≈ 110–130 nm).
10.17.5.3.2 Gel
Several studies have covered the mechanisms and involvement
of nonisoprene compounds in gel formation. Prior to the
recent suggestions made by Tarachiwin et al.37 and Tanaka,52
so-called abnormal compounds were incriminated in the inter­
actions responsible for gel. Those compounds (aldehydes,61
epoxy,62 and esters63) were linked to the polyisoprene chain
and assumed to react with some nonisoprene compounds
(amino acids64 or proteins,63 and metal ions65). The involve­
ment of proteins in structuring the gel in NR has been proposed
by several authors,63,66,67 while others assumed that phospho­
lipids are the key parameter.68 It is also worth mentioning the
recent results obtained by Intapun et al.,69 which showed that
the presence of microorganisms in the initial latex had a sig­
nificant influence on gel formation in NR.
Many methods can be used to determine the quantities of
macrogel and microgel in a polymer.70 For NR, the proportion
of macrogel is determined by gravimetry after centrifugation.
The quantity of microgel can be measured by filtration, but that
quite laborious method can be replaced by size-exclusion chro­
matography (SEC).71 Macrogel and microgel exist in both dry
rubber (TSR or RSS) and stabilized latex (field latex or concen­
trate) that has matured.72,73
In the literature, the proportion of macrogel can vary enor­
mously, reaching rates of almost 60% in extreme cases. Allen
and Bristow74 showed that the proportion of gel depended on
the solvent used, and the dissolution time and temperature. It
is, therefore, unlikely that difficulties in dissolving dry rubber
are solely linked to chemical cross-linking problems.
In several studies, the authors settled for measuring the
amount of macrogel, while microgel is clearly preponderant in
many cases.75 The quantity of microgel, determined by filtration,
in an NR sample (5–30%) would seem to vary and depend
greatly on clonal origin.76 Larger quantities can be found
depending on the technique used.77 Campbell and Fuller78
also used the term microgel to describe the cloudy solutions
1.E + 05 1.E + 06 1.E + 07
–1)
 Author's personal copy
obtained when dissolving a sample of NR in dichloromethane.
Allen and Bristow74 presumed that the microgel is due to che­
mical bridges generated inside latex particles. Those bridges
would seem to form between the NR leaving the tree and its
coagulation, maybe even inside the tree. Voznyakovskii et al.79
used dynamic light scattering (DLS) to study NR solutions
(Ribbed Smoked Sheet (RSS), and Deproteinized NR (DPNR),
[NR] ≈ 1–3 mg ml− 1). They showed that microgel displayed two
populations: one centered on 1.1 µm (P1, 0.9 < d < 5 µm), and
the other around 10 µm (P2, 5 < d < 12 µm). The deproteinized
sample (DPNR) only contained small-sized microaggregates
(P1), whereas for smoked sheet (RSS1), they were mostly
around 10 µm (P2). Steam treatment, which eliminates a pro­
portion of the proteins, reduced the quantity of large
microaggregates (P2) to the benefit of small microaggregates
and the soluble portion. Although protein removal did not
eliminate all the microgel, population P1 persisted. They con­
cluded that the interactions lying behind microaggregates
formation were linked to the existence of proteins. They also
discovered the thermo-reversibility of the interactions leading to
microgel. Heating solutions (20– 80 °C) did not eliminate
microgel but reduced the average size (d ≈ 10 µm at 20 °C,
d ≈ 5 µm at 60 °C, for RSS). The concentration and size of micro-
aggregates also depend on the concentration in the solution.
10.17.6 NR in the Manufacture of Antivibration Parts
Aside from tire making, NR is used, among other things, to
make antivibration parts for suspension or ground contact
systems. NR-based parts are also developed to improve the
performance and operational safety of machines and installa­
tions. Indeed, they are used to reduce vibrations, as well as for
sealing and for separating gases and liquids (Figure 6).
A suspension joint consists of a deformable element linked
to several inserts, either metal or plastic, by bonding. Bonding,
called adherization, is carried out when the elastomer is
Steering wheel
Exhaust hangers
Stabilizer bar bushings
Top strut mount Torque strut
Engine mount
Figure 6 Natural rubber antivibration parts.
Sustainable Use of Biomass | Natural Rubber 289
molded, or when rubber is vulcanized. In that way, these
components are used to make elastic links with nonlinear
rigidity, and to reduce or prevent vibrations (from engine to
chassis, from suspension to chassis, etc.) to increase safety and
comfort in motor vehicles.
NR constitutes 60% of the elastomers used for the manu­
facturing of the antivibration parts shown in Figure 6.
10.17.6.1 The Place of NR in Suspension Joints
The main function of a joint is to transmit stresses between two
structural elements while respecting environmental standards
(product/process). To do that, it has to meet the following
criteria between the two elements:
• Relative travel
• A specific stress/displacement law
• Reduction of noises and vibrations
• A life span which is that of the vehicle
• Resistance (hydrocarbons, heat, corrosion, etc.).
These suspension joints are mostly made of NR for reasons
of fatigue resistance. The characteristics of NR make it possible
to meet the demands of the above specifications. This elasto­
mer offers the following range of properties:
• Virtually incompressible
• Nonlinear behavior in terms of strain and speed
• Breaking strain ranging from 300 to 600% with a maximum
strain of 50% in practice (fatigue)
• Damping rate ranging between 4 and 15%
• Possible operating temperature between − 30 and 80 °C
continuous (100 °C at peak).
10.17.6.2 NR/Synthetic Elastomer Competition
NR mainly differs from synthetic rubbers through its ability to
crystallize, which helps to strengthen mechanical properties with
dampers
Decouplings
Transmission mount
Chassis parts
 Author's personal copy
290 Sustainable Use of Biomass | Natural Rubber
regard to rigidity and fatigue. The ability of NR to crystallize at
high strain rates (involved in antivibration applications) imparts
its good tensile strength and slower crack propagation compared
to synthetic rubbers. This unique performance makes it possible
to meet the specifications defined by motor vehicle manufac­
turers for antivibration applications.
For equivalent antivibratoire applications, a formulation
based on NR and another on ethylene propylene diene mono­
mer (EPDM) gave very different results in terms of fatigue. The
tests were carried out on laboratory test-pieces prepared using
the same molding process, under identical test conditions with
monoaxial sinusoidal strain (traction-compression) and at the
same stress level. The results shown in Figure 7 reveal differ­
ences of around 50% between the basic NR compound and an
EPDM-based compound.
For specifications in which strains remain within very small
ranges, the use of NR is not necessary and the choice must then
be made according to the prices of competing elastomers.
For stricter specifications in terms of temperature resistance
(as much for low as for high temperatures) and/or resistance to
fluids and/or ozone/oxygen, NR has its limitations and has to
be replaced by or blended with synthetic elastomers (EPDM,
NBR, SBR, etc.).
10.17.6.3 The Main Processes Used
10.17.6.3.1 Formulation/mixing
For a given part, it is possible to vary numerous parameters
merely by the mix: static rigidity, dynamic rigidity, phase angle,
flow, endurance, resistance to temperature, resistance to ozone,
processing parameters, and so on. Some of these properties are
antagonistic and one must bear in mind that formulation is a
matter of compromise.
Formulation alone is not enough to achieve the properties
sought in a rubber compound. Just like the choice of raw
materials, definition of the mixing process is a guarantee of
obtaining the required characteristics.
Good knowledge of the raw materials used in the manufac­
ture of rubber compounds is, therefore, essential if the mixing
stage, during which interactions occur between the different
ingredients, is to be correctly defined. Thus, a compound
25 000
Life span of samples (number of cycles])
20 000
15 000
10 000
5 000
0
NR compound
Figure 7 Fatigue results for parts made of natural rubber and EPDM.
made on the basis of a clearly defined formulation and process
will meet the demands of precise specifications.
10.17.6.3.2 Shaping
There are several shaping techniques. The ones most frequently
used at the moment are extrusion, molding by transfer or
compression, or injection.
Molding is frequently used to make antivibration parts. It
consists in pressing and curing the rubber compound between
the dies of a heated mold. This allows the insertion of metallic
supports or strengtheners in the rubber. Injection molding is
used to make complex parts. This consists of using a piston to
transfer the plastified hot compound warmed in an extruder in
the mold, filling the mold cavities.
10.17.6.3.3 Vulcanization
This key stage brings the rubber from its raw state to its finished
state. It can conserve its elastic properties and its definitive
shape. Vulcanization reactions help to improve other proper­
ties of raw rubber, such as hardness, resistance to abrasion, and
resistance to aging. Vulcanization is the result of a series of
complex chemical reactions between sulfur and the raw rubber.
A three-dimensional network is thus formed. At ambient tem­
perature, the chemical reaction between sulfur and NR is slow,
so vulcanization is commonly carried out at between 150 and
180 °C. Vulcanization activators may also be added, such as
stearic acid and zinc oxide, which facilitate the combination
between the sulfur and the rubber.
10.17.7 General Aspects of NR Applications in Tires
NR is mainly used in tire making – around 75%. Today, tires
require:
• good grip, even on wet roads, for safety,
• the lowest rolling resistance to use as little energy as possible,
• greater endurance for a longer life span, and
• a damping capacity and minimum noise for personal comfort.
EPDM compound
 Author's personal copy
Tread
Breaker
belt
Bracing
plies
Inner liner
Bead
Bead core
Figure 8 Details of a truck tire.
Table 4 Estimates of average natural rubber (NR) use for
different tires
Rubber weight
(kg)
Passenger car tires 4 34
Light vehicle tires 6 50
Medium/heavy commercial tires 25
Off the road 2 25
Source: Landell Mills Development Consultants, Trowbridge, UK.
All these constraints, some of which are contradictory,
require tire makers to make compromises, hence to use numer­
ous components, each having highly specific properties, so as
to provide an optimum combination in terms of characteristics.
Generally speaking, for radial tires on a passenger car
(Figure 8), NR is only used in the casing and bead, blended
with styrene-butadiene rubber (SBR), the tread being made of
SBR and silica, which improves grip on wet roads. However, for
heavy/medium truck tires, NR remains unavoidable in the
tread and other parts of the tire.
This is why the rubber proportions are very different depend­
ing on the different types of tires, as can be seen in Table 4. NR is
mainly used in tires – around 75% – but in different proportions
depending on the type of tire. As shown in Table 4, the propor­
tion of NR is greater in truck tires than in car tires.
10.17.8 Conclusion
NR remains an essential biological material for complex appli­
cations such as tires or antivibratory parts. Its very positive
carbon balance and the character as a renewable, industrially
available biopolymer may open up new fields of application. It
may also help some emerging economies to cover part of their
Sustainable Use of Biomass | Natural Rubber 291
Truck tire
Wedge
inserts
Sidewall
Rim
cushion
rubber demand by national NR production (see Figure 2)
instead of investing in naphtha or light-feed liquefied petro­
leum gas (LPG) crackers or importing butadiene for SBR. The
NR increasing pressure toward fuel economy, however, will push
(%) the trend toward lightweight cars with an increasing demand
for high-performance automobile parts on the one side and
their weight reduction on the other side. Moreover, it is to be
66 mentioned that the potential of H. brasiliensis tree as a source
for plant-based active ingredients is not yet fully exploited.
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Sustainable Use of Biomass | Natural Rubber 293

Biographical Sketches
Laurent Vaysse obtained his ‘Ingénieur Agronome’ degree in 1995 and a PhD degree in lipid biochemistry and biocatalysis
in 2000 from Montpellier SupAgro, France. In 2001, he started working as a researcher for CIRAD and was posted in 2002
to Kasetsart University, Bangkok, Thailand to start a joint project on the analysis of lipids from natural rubber and their
involvement in quality variability. Since 2008, he has been the coordinator of the ‘Hevea Research Platform in Partnership
(HRPP)’, a research platform which gathers 16 higher education and research institutes working on the scientific challenges
faced by the natural rubber commodity chain.

Frédéric Bonfils was born in Arles, France, on April 24, 1963. He obtained an MSc in chemistry in 1985 and a PhD degree in
material chemistry in 1990, both from the University of Montpellier. After spending 1 year as a research scientist at the
University of Manchester, working with Professor Phil Hodge, he joined CIRAD in 1992 and was posted for 2 years to the
University du Maine (Le Mans) and then to Montpellier in 1994. From 1992, he devoted his research activities to natural
rubber in the framework of finding new quality criteria for a better forecasting of Natural Rubber properties. His research
topics include mesostructure of Natural Rubber, oxidation mechanisms, vulcanization, and rheological characterization.

Jérôme Sainte-Beuve obtained his MSc degree in fluid mechanics in 1981 from the University Paris VI. After 2 years as a
researcher for CEA (Atomic Energy Commission), he joined CIRAD in 1984, as a project manager of a liquid natural rubber
pilot plant in Ivory Coast for 2 years. From 1986 to 1999, in France, he was involved as researcher, coordinator, advisor, or
expert in many international research and development projects dealing with processing improvement and natural rubber
quality. In 1997, he received his PhD in material and structural mechanics, process engineering (University of Montpellier
II) on a study focusing on a crucial step of natural rubber primary processing: the drying. From 2000 to 2004, he was the
head of CIRAD Rubber Programme, involving 25 researchers. He is currently an expert advisor on Rubber at CIRAD, where
he is carrying out research activities related to the environmental impact of natural rubber production as well as the impact
of postharvest processes on natural rubber quality.

Marie Cartault obtained an MSc in polymer sciences from Bordeaux University in 1998. In 2003, she obtained a PhD degree
in macromolecular chemistry from the University of Paris VI under the supervision of Professor J.L. Leblanc. She joined the
R&D department of ANVIS Cie in 2004, working on the development of new formula and laboratory tools for a better
characterization of natural rubber compounds.

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