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JOURNAL OF
COMPOSITE
Article M AT E R I A L S
Journal of Composite Materials
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carboxylated styrene butadiene rubber DOI: 10.1177/0021998314533363
jcm.sagepub.com
latex in polymer composites and blends:
review from structure to future
prospective
Mohammad Alimardani and Foroud Abbassi-Sourki
Abstract
The present review focuses on the properties and developing applications of carboxylated styrene butadiene rubber
(XSBR) as a modified grade of styrene butadiene rubber (SBR). Carboxylated polymers, and particularly carboxylated
rubbers, are regarded as a new class of polymers with superior physical and mechanical properties over non-carboxy-
lated counterparts. Upon introducing carboxyl groups, the properties such as elasticity range, strength, compatibility
towards functional fillers and polymers, resistance to hydrocarbon solvents enhance and cross-linking by non-sulfur
reagents becomes possible. The XSBR latex benefits from excellent mechanical and chemical stability, excellent liquidity,
high bond and conjunction strength, high toughness and the strength after molding, low water absorption and air
shrinkage, excellent durability, abrasion, oil and corrosion resistance of cement products. Due to the polarity offered
by carboxyl groups, fiber, and particulate composites of XSBR exhibit improved physical and mechanical properties. The
stable interface created between carboxyl group and the second polymer phase generally results in an enhancement for
the host polymer.
Keywords
Carboxylated styrene butadiene rubber (XSBR), blends, composites, latex
between the polymer and the second polar constituent,

Introduction
which in turn deteriorates the physicomechanical prop-
During the last decades, the use of functional polymers erties of the materials. There exist many practical exam-
has rapidly increased due to their intrinsic ability in the ples in which the interfacial interactions play a major
formation of strong interactions with the second polar role in the ultimate properties of the systems. For
phases which by consequence modify the mechanical, instance, the conventional natural fiber composites
rheological, and electrical properties.1–7 When carboxyl have weak adhesion and mechanical properties result-
groups are laid along the main chain of elastomers, they ing from the incompatibility and non-uniform disper-
bring an elevated elasticity range, impart higher sion of the hydrophilic natural fibers in the
strength to the rubber, increase the hydrocarbon solv- hydrophobic polymer matrices. This weak mechanical
ent resistance and also provide a vulnerability to be strength is due to the poor stress transfer between the
cross-linked by the non-sulfur reagents.8 Nowadays polymer matrix and load bearing natural fibers.10,11 To
many polymers are commercially produced carboxy-
lated such as carboxylated acrylonitrile butadiene Department of Polymer Processing, Iran Polymer and Petrochemical
rubber (XNBR), carboxylated polystyrene (PS), car- Institute, Tehran, Iran
boxylated poly (butyl acrylate), etc.9
Corresponding author:
In preparing polymer composites and polymer Foroud Abbassi-Sourki, Department of polymer processing, Iran Polymer
blends, the lack of such polar groups in non-functional and Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran.
polymers leads to a weak interfacial interaction Email: F.Abbasi@ippi.ac.ir
Downloaded from jcm.sagepub.com at PENNSYLVANIA STATE UNIV on September 12, 2016

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2 Journal of Composite Materials 0(0)
overcome this challenge, the functionalization of and XSBR; however XSBR is the most common
hydrophobic polymers using maleic anhydride (MAH) terminology used.
as a high performance coupling agent has been sug-
gested.12–15 Experimental studies show that the pres-
Structure–property relationship
ence of such polar groups increases the thickness of
the interphase region between the polymer and the Prior to commencing with the unique properties of
second phase.16 The importance of the polymer func- XSBR, it seems vital to briefly address and distinguish
tionality is by no means limited to the examples men- three different commercial grades of SBR including
tioned. It is quite well known that in tire industry, the cold SBR, hot SBR and carboxylated SBR.
use of carbon black is extensively being substituted with Polymerized at temperatures below 15 C, the cold
silica so as to reduce the rolling resistance of tire treads SBR has high molecular weight with a styrene content
and enhance wet grip. This is while silica is not a rein- of 20–35 wt% and nearly linear chains. The films made
forcing agent (RA) in the proper sense and it deterior- from cold SBR latices have low modulus and high
ates the mechanical properties of the compound in the elongation. In order to improve physical and mechan-
absence of appropriate coupling agents.17 The arising ical properties of these latices, curing with sulfur/accel-
difficulty is attributed to the strong filler–filler inter- erator system is mandatory. Hot SBR has a styrene
actions between the hydrophilic hydroxyl groups of content of about 45% and is polymerized at tempera-
silica and the weak filler–polymer (styrene butadiene tures above 35 C. Because of the relatively higher tem-
rubber (SBR)) interactions between the hydroxyl perature of polymerization, lesser linear chains along
groups of silica and hydrocarbonic SBR chain.18 The with a lower molecular weight compared with cold
problem is commonly settled by modifying the chemis- SBR is obtained. From the mechanical properties
try of either silica or polymer. Lei et al.19 modified the point of view, this kind of latex has a higher modulus
structure of SBR using a thiol-containing ionic liquid to and lower elongation than cold one. Similar to the cold
enable it to react with the functionalized silica effi- SBR, the system of sulfur/accelerator is generally used
ciently. Pourhossaini and Razzaghi-Kashani20 used an to cure the hot SBR.27 XSBR is a terpolymer prepared
intermediate of isocyanate and hydroxyl terminated by the emulsion polymerization of butadiene, styrene,
polybutadiene to make a chemical bond between the and one or more unsaturated acids such as acrylic acid,
silica and SBR. This modification was led to an incred- methacrylic acid, crotonic acid, maleic acid, fumaric
ible improvement in both ultimate tensile strength and acid, tectonic acid, and 3-butene-1,2,3-tricarboxylic
elongation at break. Similarly, in blend preparation an acid. In some cases, substituted monocarboxylic acid
important issue is to reach a satisfactory compatibility and substituted polycarboxylic acids can also be
between blend components. For instance, the presence used.28 Since XSBR is completely unique in its struc-
of compatibilizer is necessary when SBR is blended ture and properties, it is considered as a new type of
with polar polymers such as acrylonitrile butadiene polymer. The chemical structure of XSBR has been
rubber (NBR), polyvinyl chloride (PVC), and chloro- shown in Figure 1.
prene rubber (CR).21–26 Although the percentage of styrene is usually varied
Despite the versatile application of XSBR in the pro- over a wide range, XSBR composition typically consists
duction of gloves, water based paints, membranes as of about 65% styrene and less than 3% of a monomer
well as blends and composites, due to the lack of thor- having carboxyl group, notably acrylic acid or meth-
ough and comprehensive knowledge in this field, acrylic acid, and the rest is butadiene.27,29 XSBR latices
reporting a study has always necessitated giving have a solid content of about 52%, a pH between 7.5
detailed information concerning the structure, prop- and 9.0 and a monomodal particle size distribution
erty, and characteristics of this polymer. Therefore, with an average diameter of about 150 nm. Owing to
the aim of this study is to fill this important gap by this small particle size, the instantaneous conversion
collecting outspread works published concerning this
polymer. In the coming sections, first a concise study
of structure–property relationship of XSBR will be
given. Subsequently, XSBR micro- and nanocompo-
sites and blends will be reviewed and the main indus-
trial and miscellaneous applications of XSBR will be
presented. Then, the subject is followed by introducing
the rheological and mechanical properties of XSBR.
Finally the conclusion will be drawn. It is worthwhile Figure 1. Chemical structure of XSBR; X, Y, and Z show
to note that XSBR has been denoted in the literature by different concentration of monomers in the structure of XSBR.
various abbreviations such as SSBR, XSB, SB, SBR, XSBR: carboxylated styrene butadiene rubber.

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Alimardani and Abbassi-Sourki 3
during the emulsion polymerization is high, which leads form.27 In general, the films of carboxylated latices pre-
to low concentrations of by-products, such as 4-phenyl- sent honeycomb-like structures because the hydrophilic
cyclohexene (4-PCH) and 4-vinyl-cyclohexene (4-VCH) carboxylic acid groups accumulate near the surface of
generated by the Diels–Alder reaction of styrene and latex particle.33
butadiene.30 In principle, the latices of carboxylated
copolymers have an outstanding mechanical and chem-
ical stability compared to those of non-carboxylated XSBR composites
copolymers. This is partly due to the type of stabilizer
used in the production of such latices and mainly
General considerations
results from the presence of hydrophilic carboxyl Most of polymers in the original form have no ade-
group which has high affinity with the water mol- quate properties and need to be reinforced with the
ecules.31 The presence of carboxyl group also enables active fillers or fibers to suit the increasing demands
the latex to react with new and additional reagents of today’s world. Moreover, fillers are incorporated
which is certainly of great importance in achieving into polymers to reduce the cost, modify the viscosity,
desirable adhesion to polar substrates such as textile, impart the color to final product, and also to reinforce
paper, etc. It also lets the latex be cured without any the matrix.34 The most common used fillers in the latex
restriction with the ordinary vulcanizing agents such as industry are clay, whiting, silica, and carbon black. In
sulfur but with epoxies, polyamines and metal oxides.31 the preparation of latex articles like gloves, one of the
The polarity of the carboxyl group offers significant important goals of using fillers is to reach the highest
mechanical properties to the latex even in the uncured possible mechanical properties. This necessitates the
form and thus there would be no much need for vul- proper transfer of the external loads applied to com-
canization. On the other hand, the carboxyl group may posites to the RAs, allowing them to sustain the major
result in high absorption of water in films derived from share of the load.35 The effectiveness of the load trans-
their latices which is considered as the principal disad- fer is mainly determined by the strength of the inter-
vantage of this functional group. The synthesis of facial bond between the filler and the matrix. The
XSBR latices is performed in a quite different way stronger the interfacial adhesion, the greater is
than that of SBR. It is conducted under acidic condi- the mechanical properties of composite. The dispersion
tions to encourage the carboxylic acid monomer to be of active fillers in non-polar polymers is another serious
copolymerized.32 In comparison with the SBR, the challenge which may deteriorate the final properties of
XSBR shows a higher glass transition temperature composites. It is worth noting that more than 90% of
because of the polarity and self-cross linking nature. the present used fillers have hydrophilic characteristics
Contrary to SBR, XSBR is a highly branched and phy- which have no adequate tendency to hydrophobic poly-
sically cross-linked polymer which is related to the com- mers.36 Difficulties associated with the dispersion of
plete degree of conversion achieved during the polymer polar fillers in non-polar matrices become more signifi-
synthesis.32 Infrared spectrum of XSBR shows some cant when the size of filler is in the nanometer range. In
distinctive characteristics including the peaks at fact, the increased surface area of such particles induces
699 cm1 due to styrene units, 757 cm1 related to 1,4 agglomeration. Accordingly, the preparation of com-
cis, 909 cm1 corresponding to 1,2 vinyl and 967 cm1 posites by the use of functional polymers such as
characterizing 1,4 trans of butadiene units. A peak also XSBR and XNBR has become well documented in lit-
appears at 1694 cm1 attributed to C¼O stretching. erature.37–40 In particular, XSBR is capable of reacting
The broadness of peak C¼O suggests that most – with the functional fillers and therefore presents good
COOH groups in XSBR are hydrogen bonded. H- mechanical properties. As it will be seen in the next
NMR spectrum of XSBR shows intensive peaks over sections, the superior compatibility of XSBR with
0.5–2.8 ppm attributed to aliphatic protons. The signals polar fillers like silica has led to a vast substitution of
of olefinic protons due to 1,4 unsaturation are located SBR latices with XSBR ones in preparing composites.
at 5.3 ppm, while those of 1,2 unsaturation appears at Various fillers such as multiwall carbon nanotube
4.9 ppm. There are also aromatic peaks in the region of (MWCNT),41,42 halloysite nanotube (HNT),43 silica,34
6.8–7.2 ppm related to the styrene group. Further infor- cellulose nanocrystals,44 organically modified boeh-
mation regarding the microstructure of this polymer mite,45 layered silicates,46 crab chitin,47 soy protein,48,49
may be found elsewhere.8 The films made from XSBR wheat flours,50 PS-encapsulated nanosilica,51 and dual
latex usually have higher modulus and lesser elongation fillers such as silica/carbon black,52 defatted soy flour
than two other grades, i.e. cold and hot SBR. The most (DSF)/carbon black,53 and MWCNT/carbon black54
of SBRs made by emulsion or solution polymerization are used to improve the physical and mechanical prop-
methods are commonly coagulated to corresponding erties of XSBR. Having a look at the above-mentioned
solid SBRs, while XSBR is only used in the latex fillers it is found that many of them benefit from being

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the most abundant biorenewable material in the world

as well as having low density, low energy consumption
in manufacturing, the ease of being recycled by com-
bustion, high sound attenuation, and comparatively
nonabrasive nature which allows the ease of processing,
large filling percentage, and consequently significant
cost savings.44 Nowadays there is a growing interest
in the use of natural based fillers and polymers in pre-
paring composites. Since the media of latex is aqueous
and environmentally friendly, using natural fillers pave
the way of preparing sustainable materials.55
Moreover, most of these fillers possess hydroxyl
groups on their structures enabling them to react with
the carboxyl groups of the polymer.
Notice that carboxyl and hydroxyl groups are
simply associated with the esterification reaction, how-
ever; this reaction is quite difficult to proceed in the
aqueous media of latex and also at room temperature,
where the reversed reaction (hydrolysis of ester) may
strongly occur.56 By consequence, the hydrogen bond-
ing will be the prominent way of the interactions
between the carboxyl and hydroxyl functional
groups.41,43 Regarding the higher mechanical proper-
ties resulting from chemical coupling of XSBR and
fillers, efforts have been made to stimulate the possible
esterification between the fillers and the XSBR func-
tional groups.43 Although there are a few approaches
for efficient activating of carboxyl groups to react with
hydroxyl groups in an aqueous media,56,57 the risk of
latex coagulation has strongly impeded such an ideol-
ogy. For instance, using Bronested acids is highly
accepted for this purpose but this would adversely
result in the latex coagulation. Due to a rapid and
explosive reaction with water, using some strong
Lewis acids such as AlCl3 is also forbidden. As a
result we are involved with a very special ester manu-
facturing system. Water-soluble carbodiimide agent
known as 1-ethyl-3-3-dimethylaminopropyl carbodii-
mide hydrochloride (EDC) is commonly used in aque- Figure 2. Interaction of XSBR chains with hydroxyl functiona-
ous media to activate carboxyl group to react with lized reinforcing agent in the presence of ZnO as a Lewis acid.
amines or alcohols.57 However, EDC needs an acidic XSBR: carboxylated styrene butadiene rubber; ZnO: zinc oxide.42
media to apply its role and providing such a circum-
stance leads to the coagulation of latex. It is also ZnO in carboxylated latices because it can act as a
reported that zinc oxide (ZnO) can improve the effect- cross-linking agent and links carboxylated polymer
iveness of the hydrogen bonding of XSBR towards the chains.31,58
hydroxyl functionalized fillers which in turn improves In cases where fillers do not have such functional
the eventual properties. The corresponding possible groups, the modification of filler is mandatory. For
mechanism for the case where hydroxyl functionalized instance, prior to incorporating Boehmite into
MWCNT has been used as RA for XSBR in the pres- XSBR, Florjanczyk and his coworkers modified par-
ence of zinc oxide is illustrated in Figure 2.42 ticles with organic ligands through a reaction of
It is interpreted that ZnO is a Lewis acid with the Boehmite with acrylic acid and diethylphosphoric
vacant d orbitals which can catalyze and ease the delo- acid.45 This modification led to the preparation of a
calization of electrons through the involved bonds and stable aqueous suspension of nanoparticle which in
therefore use of it may lead to a good filler–polymer turn resulted in a homogenous composite when
interaction. However, care should be taken when using added to the latex.

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Preparation of XSBR micro- and nanocomposites compounded with micro- or nanoparticles as well as
The methods used for the preparation of XSBR com- curing agents and then the resulting mixture is pre-
posites are fundamentally similar to those of other latex vulcanized. The process of pre-vulcanization is usually
systems and are mainly based on the so-called latex carried out by heating the compounded latex in a
technology. Unlike the in situ polymerization method, water bath at the temperature of 70–80 C for nearly
in the latex technique, the polymer is first prepared and 2 h. During this process, the vulcanization is taken
then the RAs are added to the resulting polymer latex. place in each of the individual latex particles without
This method, in principal, begins with dispersing RAs noticeably altering their state of dispersion. The pre-
in an aqueous surfactant solution by means of ultraso- vulcanized latex can then be cooled to room tempera-
nication for instance followed by incorporating this dis- ture and stored for later use. The pre-vulcanized
persion to the polymer latex. The resulting aqueous latices are very similar in appearance to unvulcanized
nanocomposite may be solidified using freeze- ones and, particularly the original fluidity is chiefly
drying,59 casting,41 spray-drying,60 etc. to a solid film maintained. In addition, the effective control of the
containing dispersed RAs. The coagulation of latex is physical properties can be implemented prior to man-
another drying method which is usually performed by ufacturing of articles. The pre-vulcanized latex is a
adding the aqueous solution of a salt such as calcium convenient form of the latex used widely for manufac-
chloride into the latex dispersion.61,62 In the case of turing adhesives, coating, carpet backings, dips,
rubber lattices such as natural rubber (NR), SBR, threads, tapes, and foams. The articles made from
XSBR, NBR, and XNBR, however, curing agents pre-vulcanized latex are then completely vulcanized
may also be added into the system to enhance the mech- at relatively high temperatures which is associated
anical properties through vulcanization, even though with drying of the product.74–76
nanocomposites of carboxylated latices show fair mech- The preparation of latex–MWCNT nanocomposites
anical properties in gum form.63 The curing agents may commences with either dry milling or ultrasonication of
directly be added to solidified nanocomposites on two MWCNT. However, both methods may lead to the
roll mill or as water slurry to the stirring latex nano- breakup of MWCNT imparting inferior properties to
composites prior to drying.64–66 To cure the master- the resulting nanocomposite as a consequence of strong
batch compound prepared on two roll mill, it is compression and shear forces of ball milling or high
subjected to heat and pressure for a given time. The power of ultrasonicating.68,77,78 Alimardani et al.42
process of curing for the latex compounds is generally placed the XSBR together with the MWCNT in a
carried out in a high temperature oven. ball-mill and obtained a better dispersion for the
The preparation of composites from polymer lattices MWCNT. The type of the ball-mill employed was a
benefits from many advantages; the whole process is low energy one which allowed decreasing the aspect
reproducible and easy since it is basically implemented ratio of MWCNT in a controlled manner and thus
by a simple mixing of two aqueous components, more- minimizing their excessive breakup. Evidently, this
over, since the system is aqueous, the process is safe, approach could not be simply implemented for conven-
environmentally friendly and less-costly.67,68 tional latices due to the risk of latex coagulation. The
Ball milling may also be performed on RAs to results of particle size determination performed on con-
obtain a proper dispersion by breaking down the initial ventional and carboxylated SBR latices before and
bundles and agglomerates.69–71 As a result of high shear after being ball milled also confirmed the stability of
and compressive forces existing inside the ball-mill, the XSBR latex, Figures 3 and 4.
experimental investigations show that an excellent dis- It can be deduced that for both samples ball milling
persion of difficult material can be achieved using this has had an influence on the particle size of latices by
method.72 For instance, Ma et al.73 put Na-montmor- shifting the particle size distribution toward larger
illonite (Naþ-MMT), dispersing agent, emulsifier, values indicating the aggregation of the latex particles.
potassium hydroxide (electrolyte), and deionized However, compared to the SBR latex, this aggregation
water in a ball-mill to reach a homogeneous and inter- is rather minor for the XSBR on account of higher
calated layered silicate dispersion. At the same time, stability against ball-mill mechanical and dynamic
they prepared a slurry of curing agents including stresses. In other words, the higher stability of
sulfur, accelerator, zinc oxide, oleic acid, dispersing XSBR allows short time milling to be conducted in
agent, emulsifier, and potassium hydroxide by means a low energy ball-mill. The use of potassium hydrox-
of the ball-mill. ide (KOH) can further maintain the stability of XSBR
It will be seen later that RAs are occasionally added by enhancing electrostatic repulsion between the par-
to the blend of NR/XSBR latices in order to take ticles. The assessment of dispersion using rheological
advantages of both NR desirable properties and investigations confirmed the effectiveness of the
XSBR ones. In such cases, the latex blend is first method.

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blend of 38% solid content NR latex and 22% solid

content SBR latex indicates a very good processability.
This blend also takes the benefits of better crack resist-
ance, wet grip, and the weather resistance of SBR along
with superior strength and low temperature properties
of NR.74 XSBR can be advantageous over SBR by shar-
ing high resistance to hydrocarbon oils, high colloid sta-
bility, and high tolerance with the addition of large
quantities of mineral fillers, which in turn further sim-
plifies its processability. Accordingly, the blending of
NR with XSBR has attracted great attention in litera-
ture.34,51,82–84 The high polarity of XSBR leads to a
better adhesion of the blend to polar substrates such
as textile fibers and papers. The mechanical and rheo-
Figure 3. Particle size distribution of XSBR latex before and logical behavior of an immiscible blend depends on the
after being milled with and without stabilizer.42 shape, size, interparticle distance, and the orientation of
XSBR: carboxylated styrene butadiene rubber. dispersed phase which is governed by interfacial tension
between two polymers. For many practical purposes,
blending of SBR with polar polymers is inevitable.
The lack of compatibility in such cases inspired some
researchers to graft the MAH to the structure of SBR
prior to blending with polar polymers such as polyethyl-
ene terephthalate (PET).85,86 This is while XSBR is
intrinsically hydrophilic and does not need such a modi-
fication. For example, Peng et al.87 prepared a blend of
XSBR with nylon 6. In this study cross-linked ultrafine
XSBR powders were prepared through gamma irradi-
ation and subsequent spray-drying.88 The prepared
rubber powders with a diameter of about 150 nm were
uniformly dispersed in nylon matrix by classical pro-
cessing techniques without any compatibilizers.
Microstructural characterization of the blend with IR
(Infrared spectroscopy) indicated that the carboxyl
group of XSBR can effectively react with the amine
Figure 4. Particle size distribution of SBR latex before and after end group of nylon 6 during the melt blending and
being milled.42
therefore improves the miscibility. In addition to the
SBR: styrene butadiene rubber.
acid–base interaction existing between the primary
amine end group of nylon 6 and the carboxyl group of
XSBR, strong hydrogen bonding could also be created
XSBR blends at the interface of two polymers. While blending of
The latex blending of two polymers is a simple way to XSBR with nylon 6 decreased the tensile strength, flex-
obtain a good degree of dispersion and reinforcement.79 ural strength, and flexural modulus, it considerably
Since most of the polymers are nowadays available also increased Izod impact strength and elongation at
in their latex form, the method is becoming a common break. According to the authors, nylon–XSBR blend
practice to improve the processability and also mech- presented higher toughness compared with nylon 6/
anical properties of a single polymer.80,81 For two poly- MAH grafted polyethylene octane (POE-g-MAH).
mers which are partially miscible, the latex blending These superior properties were attributed to the appro-
may assist in improving the compatibility of the com- priate interface, fine dispersion, and shear yielding of
ponents. Latex blending can be carried out without XSBR–nylon 6 blend.
much phase separation or flocculating. When dealing with a blend, the morphology is
Blending the SBR and NR latices offers many advan- another determining factor. The morphology of blends
tages. NR is generally characterized by its excellent has strong impact on mechanical and dynamic proper-
mechanical properties, elastic behavior, resilience, and ties and therefore, on its end-use application.89,90 Blend
damping behavior, however; it has poor oil and chemi- morphology depends on many factors such as the com-
cal resistance and processability. For instance, a 70/30 position, interfacial tension between constituting

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Figure 5. Optical images of XSBR–NR blend, (a) XSBR is minor; (b) co-continuous blend; (c) NR is minor.84
NR: natural rubber; XSBR: carboxylated styrene butadiene rubber.
phases, and the viscosity of the individual components.

The higher the viscosity of the minor phase, the larger is
its particle size on account of the coalescence of the par-
ticles. Figure 5 shows the optical micrographs obtained
from the blends of NR/XSBR for (a) XSBR as the dis-
persed phase, (b) co-continuous blend having equal
volume of two phases, and (c) NR as the minor phase.
Accordingly, having the knowledge of latex viscosity
is compulsory to predict the morphology and mechan-
ical properties of blends.
XSBR blends have also been used in polymer mod-
ified cement to achieve and compromise required prop-
erties.91,92 Although mortars modified by a single
polymer may exhibit good properties, they also have
few shortcomings. XSBR and chloroprene rubber mod-
ified mortars show high chloride diffusivity. On the
other hand, mortars modified by poly vinylidene chlor-
ide (PVDC) provide unsatisfied workability when the
polymer-cement ratio was higher than 0.1. Results have
revealed that blends of XSBR–PVDC can resolve the
challenges of both XSBR and PVDC.91 Figure 6. A comparison between mechanical properties of
XSBR and HXSBR.8
XSBR can even be blended with non-polar polymers
XSBR: carboxylated styrene butadiene rubber; HXSBR: hydro-
to increase the accommodation of polar nanofillers. genated XSBR.
Recently, in order to introduce nanoclay into ethylene
propylene diene monomer (EPDM) rubber/carbon
black, XSBR was used during the preparation of nano- for the hydrogenation of polymers including catalytic
composites to improve the compatibility. Primarily the and non-catalytic ones, the diimide reduction has a
nanoclay was dispersed in XSBR by the solution unique feature of being performed in the latex systems.
mixing followed by ultrasonication.93 The method has been successfully applied for the latices
of NBR, polybutadiene rubber (BR), SBR as well as
XSBR.94–96 In Figure 6, a comparison has been made
Hydrogenated XSBR between the mechanical properties of XSBR and 80%
In addition to XSBR blends and composites, it is pos- hydrogenated counterpart denoted as HXSBR.8
sible to chemically modify XSBR through hydrogen- It is seen that while hydrogenation has led to an
ation and introduce a novel monomer sequence along increase in tensile strength and also modulus, it has
with new chemical and physical properties to the result- decreased the elongation at break. Similar study on the
ing hydrogenated XSBR (HXSBR) polymer. Such hydrogenation of SBR showed a remarkable increase in
changes in molecular architecture cannot be simply the tensile strength from 0.5 to 5.4 MPa and elongation
obtained by the conventional polymerization methods at break from 170% to 991% which was explained by
or blending. Among various methods being available the crystallinity of HSBR.97 However, the crystallinity

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cannot take place in the case of HXSBR. Surprisingly, water and dissolved salts. This reduced permeability to
the above-mentioned hydrogenation reaction is one of salts (e.g. chloride) provides a protection against the
the few chemical reaction implemented so far in the corrosion of underlying steel reinforcing elements.
XSBR latex. With a reduced water ingress, the polymer modification
also promotes improved freeze–thaw resistance of the
mortar; a feature which is particularly important in
XSBR applications exterior or cold climate applications. Improved tensile,
compressive, and flexural strength are generally realized
Industrial applications in polymer modified cement mortars.99,100 A typical
The main industrial applications of XSBR are paper formulation of the polymer latex used in this applica-
coating, carpet backing, and polymer modified mortars. tion has been shown in Table 1.29
Traditionally, SBR was used in nearly all these appli- The reason why XSBR has found such a role can be
cations due to its elastic and versatile properties. In explained by a three stage mechanism involved between
addition, the molecular weight and cross-linking of polymer and cement. In the first step when XSBR is
SBR could be adjusted widely by choosing the degree mixed with the fresh cement mortar or concrete, the
of conversion and also the amount of chain transfer polymer particles are uniformly dispersed in the
agents. However, XSBR which benefits from a high cement paste phase. Then, because of the drainage due
degree of stability and also compatibility with fillers to the development of the cement gel structure, the poly-
has fully hold new markets.29,63 mer particles are gradually confined in the capillary
pores. Since the cement paste mainly has an agglomer-
Carpet backing. Carpet backing industry is number four ated structure of calcium silicate hydrates and calcium
in the ranking of the largest user of synthetic dispersions hydroxide, in this step some chemical reactions may also
in North America. Starches and NR were traditionally take place between the carboxyl group of polymer and
used as binders for improved tuft bind in carpet back- calcium ion, calcium hydroxide, and other agents which
ing.29,30 Few years later these polymers were substituted are available in the mixture as illustrated in Figure 7.
by hot and cold SBR dispersion and eventually, devel- Ultimately, with water withdrawal owing to the
opment of XSBR latex hold the major share of this cement hydration, the close-packed polymer particles
business until today with an estimated 95% of the on the cement hydrates coalesce into continuous films
volume sold in 1999. The remaining part is contributed or membranes, and the films or membranes bind the
by ethylene-vinyl acetate, polyvinyl chloride, and poly- cement hydrates together to form a monolithic network
urethane dispersions. In this application, the XSBR dis- in which the polymer phase interpenetrates throughout
persions provide many advantages including less costly the cement hydrate phase.99
compounding, fast drying rate, and improved perform-
ance in terms of specific adhesion to the fabric sub-
strates. The dispersions of this polymer have since
Miscellaneous applications
become the workhorse of the carpet backing industry.98 Glove production. Although NR dominates the dipping
articles industry, there are also two commercially
Polymer modified mortars. Polymer cement mortar (PCM) important water-borne polymers extensively used in
and concrete (PCC) are a category of concrete–polymer the production of gloves: nitrile gloves which are made
composites made by partially substituting the cement of NBR or its carboxylated counterpart (XNBR) and
hydrate binders of conventional cement mortar or con- chloroprene gloves.29 The main objectives pursued from
crete with polymers.99 Polymers are added to the the production of synthetic gloves are as follow:
mortar systems for a number of reasons. Firstly, poly-
mers improve the key properties of the fresh, non har- Table 1. A typical formulation for preparation of polymer
dened mortar, i.e. adhesion, workability, and open modified mortar.29
time. Polymer additives also have a plasticizing effect
Part A: Liquid components Wet parts
on the cementation of mortars, thereby reducing the
amount of added water required to achieve workability Dispersion XSBR 54
and mortar flow properties. Minimizing the added Diluent Hydration water 83
water results in fewer capillary pores, lower porosity, Part B: Dry components
and stronger cements. In addition, the properties of a Filler 1 Silica sand 721
hardened cement mortar are improved. Properly Cement Portland cement 273
selected polymers, i.e. those with Tg lower than 15 C, Filler 2 Microsilica 6
form a film within the mortar matrix thereby filling
XSBR: carboxylated styrene butadiene rubber.
voids, pores, and reducing the potential for ingress of

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(1) increasing the resistance to non-polar organic solv- and the adhesion properties of conventional adhesives
ents, (2) producing completely protein-free skin-contact such as acrylic emulsions or solvent based SBR, they
articles; allergic reactions and anaphylactic shock have are either costly or environmentally unfriendly. The
been experienced by some users of NR gloves which aim of all patents has been replacing the solvent based
attributed to the presence of protein in these latices, SBR and emulsion acrylic adhesives with those of XSBR
(3) obtaining the gloves with lower electrical resistance latex which is environmentally friendlier (than SBR) and
being capable of using in applications where presence of rather inexpensive (than acrylic dispersion).
the static charge may be a challenge. Although synthetic
NBR, XNBR, and chloroprene gloves may fulfill these
challenges, they suffer from the lack of excellent feeling XSBR as an excellent binder for water based paints. In the
and mechanical properties of NR. As a result they need area of coatings, film-forming agents or volatile solv-
to be blended with other rubber latices. Taneja and ents are traditionally used to obtain film formation
Sekaran101 prepared and patented a medical glove com- property. However, environmental concerns are grow-
posed of an elastomeric blend of chloroprene rubber ing increasingly and consequently the use of volatile
and XSBR. Table 2 compares the mechanical properties organic compound (VOC) is more and more being
of this blend with those made of NR, NBR, and also a restricted. Polymer latices play a major role in develop-
blend of chloroprene with XNBR. It is seen that the ing VOC-free coatings. Despite the widespread applica-
newly designed glove offers superior mechanical proper- tion of water based paints, due to water absorption
ties over others. there are also challenges regarding the binders used.
Permeation of water into the dry film leads to some
phenomena like swelling, distortion, and formation of
Pressure sensitive adhesive. There are patents describing raised areas which in turn results in the buildup of the
the extensive use of XSBR as pressure sensitive adhe- puddles of rainwater. The problem becomes more ser-
sives.102–104 Despite the excellent mechanical stability ious where the paints are used in exterior applications,
such as roof coatings. This behavior is known as the
‘‘ponding effect’’ in the roofing industry. In general,
the absorption of water induces detrimental effects on
the performance of a composite material, like disrupt-
ing the filler–matrix interfacial region, debonding the
matrix from the filler surface and reducing the mechan-
ical properties of the composite. Surfactants and sus-
pending aids used in the preparation of latices make the
problem of water uptake more pronounced.105,106
A study on the extent of water uptake for a variety of
commercial latices namely Primal EC 2848 P, Primal
EC 1791 E, Revacryl 123, Texicryl 13 002, Primal LT
2949, (acrylic latices), Texicryl 13 031 (styrene and
acrylic copolymer), Alberdingk UC90 (polyacrylate
polyurethane dispersions), and Synthomer 47B40
(XSBR) has been conducted. Figure 8 shows the
increase of the mass as a function of immersion time
Figure 7. Mechanism of XSBR performance in polymer modi-
fied mortar.99 in water for the above-mentioned latices. It is observed
XSBR: carboxylated styrene butadiene rubber. that XSBR is the best in terms of water absorption with
Table 2. Mechanical properties of three types of gloves.101
Tensile strength Modulus at Modulus at

Type of medical gloves (MPa) 300% (MPa) 500% (MPa)
70:30 blend of chloroprene and XSBR 20 4.5 8

60:40 blend of chloroprene and XNBR 14.49 1.95 4
Natural rubber 24 1.75 2
NBR 12 2.1 4.3
NBR: acrylonitrile butadiene rubber; XNBR: carboxylated acrylonitrile butadiene rubber; XSBR: carboxylated styrene butadiene rubber.

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Figure 9. Solvent uptake of membranes of filled XSBR, filled

NR, and their filled blend.83
Figure 8. Water uptake of several types of commercial
NR: natural rubber; XSBR: carboxylated styrene butadiene
latices.107
rubber.
only 15% (w/w) absorbed water after being immersed

for more than 150 h. required for the gust materials to diffuse in composite
This was explained by minimal amount of surfactant material. Since most of fillers have hydrophilic character-
used during synthesis and also lesser polarity of the istics,36 the presence of carboxyl functional groups in
hydrocarbon nature of XSBR. The behavior for XSBR can alter the permeability and selectivity of a
Alberdingk UC is eccentric showing a decrease in membrane by improving the accommodation of polar
mass which was related to the initial cracks made in fillers, thereby twists and elongates the path of diffused
the film and falling off the fragments.107,108 gas.82 The permeability of the NR to various gases has
similarly been reduced by blending with other polar poly-
XSBR in membrane technology. Polymer membranes are mers such as epoxidized natural rubber (ENR).113 The
widely used in many applications such as gas and permeability of such a membrane to solvents such as
liquid separations and barriers for packaging. They are benzene, toluene, and p-xylene has been also studied by
also used as materials for cable coating, food packaging, Stephen et al.83 In Figure 9, the equilibrium uptake of
electronic circuits, petrochemical process, etc. hence, the benzene solvent as a function of weight percentage of
transport properties of organic solvents through poly- filler has been depicted. It is observed that in the case
mers are of great technological importance.109–111 of NR and XSBR, increasing the filler concentration
Elastomers and in particular NR blends play a major can lead to a decrease in solvent uptake. This behavior
role in this regard due to low permeability coefficient of follows a fully declined trend for XSBR with increasing
these polymers. For instance, NR has an oxygen perme- the filler content which is due to the polymer/filler inter-
ability of 2 109 cm3 cm=ðs cm2 cm HgÞ which is action induced by the carboxyl polar groups of XSBR. It
much lower than other elastomers such as nitrile and is also due to the restricted chain mobility of XSBR
silicone (polydimethylsiloxane) rubbers.112 Moreover, because of its high cohesive energy density. However,
NR membranes have the advantage of excellent mechan- for NR the rate of decrease in uptake becomes nearly
ical properties. In particular, the use of XSBR–NR constant at higher loadings owing to its poor rubber/
blends filled by micro- and nano RAs has become a filler interaction. A rather complex behavior is observed
common way of developing gas barrier and solvent resist- for 70/30 NR/XSBR blend when the filler is distributed
ant products. The reason for the use of NR in this appli- unevenly between the phases.83
cation is self-evident; however, the permeability of
unfilled NR is still a concern. For the membrane appli-
cations, the polymer should be accompanied by proper
Rheological properties of XSBR
fillers to benefit from the mechanical as well as barrier The knowledge of latex rheology is industrially import-
properties induced by the filler. These agents make diffi- ant for polymer processing and also designing the end
culties in the outgoing of gases and solvents through the products.34 It can also be applied to establish predictions
membrane by twisting and meandering the pathway for the mechanical behavior based on the micro- or

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nanostructure of the materials.114 Moreover, the rhe-

ology can be used to evaluate the polymer–filler inter-
action and the state of filler dispersion.115–117 Early
studies on the rheology of synthetic latices date back
to the work of Maron et al., where the effects of concen-
tration, temperature of preparation, etc. on the flow
behavior of latices in different conditions were compre-
hensively studied.118–122 In recent reports, the frequency
dependence of viscosity and storage modulus are two
commonly used techniques to characterize the rheo-
logical properties of latex systems. The rheological prop-
erties of pure XSBR as well as its corresponding
composites and blends have been investigated in detail
in literature. For instance, the rheology of MWCNT/
XSBR nanocomposites was investigated as a tool for Figure 10. Variations of storage modulus as a function of fre-
the microstructure assessment of the composite.41,42 quency for pristine and also nanocomposites of XSBR–MWCNT
The rheology of such systems depends on numerous par- and SBR–MWCNT.42
ameters such as the filler characteristics, filler loading, MWCNT: multiwall carbon nanotube; SBR: styrene butadiene
the aspect ratio, the state of filler dispersion, the polymer rubber; XSBR: carboxylated styrene butadiene rubber.
molecular weight, and the interfacial interaction between
the polymer and filler. Having eliminated the effects of The effect of temperature on the viscosity of XSBR
MWCNT loading, its aspect ratio, and the polymer latex may be given by the Arrhenius equation;
molecular weight, changes in the rheological properties
were attributed to the state of dispersion and the ¼ 0 eEa =RT ð1Þ
improvement of interfacial interactions. Figure 10
clearly shows this method of microstructural character- where 0 is the zero shear viscosity and Ea is the acti-
ization where identical concentrations of hydroxyl func- vation energy. Ea shows the temperature sensitivity of
tionalized MWCNT have led to a significant discrepancy the latex viscosity. Some rheological parameters of
in the storage modulus of resulting SBR and XSBR XSBR and NR/XSBR blend are shown in Table 3.34
nanocomposites. The rheological properties can also be regarded as a
The rheological experiments on latex systems can be measure of the miscibility of two phase systems. In par-
either conducted on the liquid form of the latex or the ticular, the Cole–Cole diagrams have been employed to
corresponding dried film. Similar to most polymers, evaluate the miscibility of NR–XSBR blend. Generally,
XSBR latices show a non-Newtonian behavior, i.e. a a homogeneous system is characterized by a semicircle
pseudo-plastic behavior, having an index of 0.72. This in the Cole–Cole diagrams, while a two-phase system
index decreases as the filler content increases indicating shows two modified semicircles. Such graphs are simply
that the shear thinning behavior becomes predominant constructed by plotting the values of loss modulus (G00
by raising the filler loading.34 Traditionally, the forma- or E00 ) versus storage one (G0 or E0 ). In Figure 11, the
tion and destruction of filler networks at different shear Cole–Cole plot of a 50/50 unvulcanized XSBR–NR
rates were explained as the main reason of shear thin- blend has been shown in three different frequencies.
ning behavior; however, recently the theory of rubber Two modified semicircles observed can be attributed
immobilization at filler surface has also been accounted to the immiscibility of two components.84,124
for this behavior in XSBR composites.123 In other Despite the importance of latex rheology, such stu-
words, polymer chains that become immobilized in dies in XSBR are still in its infancy and most of
the filler surface can contribute to the dispersed phase reported works are limited to those of Stephen et al.34,84
and lead to a rise in the effective filler volume fraction.
Accordingly, at each shear rate there would be a struc-
tural equilibrium between the immobilized and mobi-
Mechanical properties of XSBR
lized parts and therefore the effective volume fraction Filled latex products generally show inferior properties
will change with shear rate. Interestingly, Stephen compared to those obtained from the filled dry rubbers.
et al.34 reported a dilatants behavior for the unfilled This behavior is explained by the hypothesis34 that
blend of NR/XSBR at low shear rate. This was attrib- during the compounding of dry rubbers, due to both
uted to the network formation in the blend system upon the high viscosity of rubber and large applied shear,
applying force that disappears by increasing shear rates free radicals are created as a result of the breakup of
and destroying the networks. polymer molecules, and since the resulting radicals are

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Table 3. Rheological parameters of pristine XSBR, XSBR filled by 2.5 phr sodium bentonite, and a blend of 70:30 NR–XSBR.34
Nano-reinforced Unreinforced blend

XSBR XSBR (70:30 NR–XSBR)
Type of behavior Pseudo-plastic Pseudo-plastic Dilatants at low shear rate

Zero shear viscosity (0) (MPa) at 25 C 13 46 8.87
Activation energy (kJ/mol) 13.98 26.6 37.63
Pseudoplasticity index 0.72 0.32 1.06
NR: natural rubber; XSBR: carboxylated styrene butadiene rubber.
Figure 11. Cole–Cole diagram of a 50/50 unvulcanized XSBR–

NR blend.84
Figure 12. Effect of blending of NR with XSBR on the mech-
anical behavior.84
rubber.
rubber.
very susceptible to interact with the active sites of fil-
lers, a polymer–filler link may be generated. This chem- reinforced with different varieties of fillers to acquire
ical bond can contribute to the transfer of load from the improved properties.
matrix to the filler and thus ensures improved mechan- Blending of XSBR with NR shows an intriguing
ical properties. In a completely contradictory state- mechanical behavior as depicted in Figure 12.
ment,125 a superior quality for polymer latices has Increasing the amount of XSBR in XSBR/NR blend
also been reported and attributed to the lack of masti- leads to the enhancement of the modulus (modulus at
cation step and high temperature vulcanization com- 300% elongation) in a linear manner. However, the
pared to dry rubbers. tensile strength exhibits a maximum at the blend ratio
The films prepared from XSBR latex usually have a of 50/50 (wt/wt). In fact XSBR has a reinforcing effect
higher stiffness and rigidity compared to those prepared on the ultimate properties of NR which was previously
from dry SBR or its related latex. Naturally, such films observed by other polar latices such as polyvinyl
have a lower elongation and flexibility. The higher stiff- chloride. Certain synthetic polymer latices play a rein-
ness of XSBR compared with SBR is partly due to its forcing action when blended with NR and improve
elevated cohesion energy resulting from the presence of properties such as tensile strength, tear strength, and
polar carboxyl groups on its main chain; and partly due puncture resistance. According to Blackley, structuring
to the higher amount of styrene used during the syn- and networking of the particles is likely to be conducive
thesis of this polymer. The gum vulcanizates of car- towards the reinforcement. In the present case, the self-
boxylated polymers exhibit relatively good mechanical curing nature of XSBR latex is responsible for impart-
properties; however, these polymers have also been ing a higher tensile strength to NR latex.84,126

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Conclusion 7. Prochoń M, Przepiórkowska A and Zaborski M. Keratin

The results presented in this review article disclose the as a filler for carboxylated acrylonitrile-butadiene rubber
great potential of XSBR for various applications either XNBR. J Appl Polym Sci 2007; 106: 3674–3687.
as a single polymer or as a blend constituent with or 8. De Sarkar M, De PP and Bhowmick AK. Diimide reduc-
tion of carboxylated styrene–butadiene rubber in latex
without reinforcing micro- or nano-fillers. Various stu-
stage. Polymer 2000; 41: 907–915.
dies have focused on the unique chemical and mechan- 9. Huang T. Colloidal and rheological properties of carboxy-
ical properties which carboxyl groups bring to XSBR. lated latices. Britain: University of Bristol, 1993, p.98.
As a single polymer it is a good candidate for the prep- 10. Mohanty AK, Drzal LT and Misra M. Novel hybrid
aration of polymer nanocomposites as most RAs nat- coupling agent as an adhesion promoter in natural fiber
urally characterize with one or some polar groups in reinforced powder polypropylene composites. J Mater
their structure. The prepared nanocomposites generally Sci Lett 2002; 21: 1885–1888.
present improved properties due to the possibility of 11. Li Q and Matuana LM. Surface of cellulosic materials
developing different bonding between the polymer modified with functionalized polyethylene coupling
matrix functional groups and reinforcing filler. agents. J Appl Polym Sci 2003; 88: 278–286.
Blending is another aspect of the XSBR capability 12. Keener TJ, Stuart RK and Brown TK. Maleated cou-
pling agents for natural fibre composites. Compos Part
and leads to a significant expansion of the already
A Appl Sci 2004; 35: 357–362.
broad scope of its applications. Through blending
13. Pickering KL and Ji C. The effect of poly[methy-
with hydrophobic or hydrophilic polymers, XSBR lene(polyphenyl isocyanate)] and maleated polypropylene
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as NR, nylon, polyvinyl chloride, etc. Membrane tech- polypropylene composites. J Reinf Plast Compos 2004;
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Funding posites. Polymer 2001; 42: 9819–9826.
This research received no specific grant from any funding 16. Nair SS, Hurley DC, Wang S, et al. Nanoscale charac-
agency in the public, commercial, or not-for-profit sectors. terization of interphase properties in maleated polypro-
pylene-treated natural fiber-reinforced polymer
composites. Polym Eng Sci, Epub ahead of print 2012.
Conflict of interest 17. Mark JE, Erman B and Eirich FR. Science end technology
of rubber. Amsterdam: Elsevier Academic Press, 1994,
None declared.
p.245.
18. Ansarifar A, Nijhawan R, Nanapoolsin T, et al.
Reinforcing effect of silica and silane fillers on the prop-
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Mohammad Alimardani and Foroud Abbassi-Sourki

between the polymer and the second polar constituent,

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2 Journal of Composite Materials 0(0)

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Alimardani and Abbassi-Sourki 3

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the most abundant biorenewable material in the world

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blend of 38% solid content NR latex and 22% solid

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Alimardani and Abbassi-Sourki 7

phases, and the viscosity of the individual components.

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Alimardani and Abbassi-Sourki 9

Table 2. Mechanical properties of three types of gloves.101

Tensile strength Modulus at Modulus at

70:30 blend of chloroprene and XSBR 20 4.5 8

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Figure 9. Solvent uptake of membranes of filled XSBR, filled

only 15% (w/w) absorbed water after being immersed

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Alimardani and Abbassi-Sourki 11

nanostructure of the materials.114 Moreover, the rhe-

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Nano-reinforced Unreinforced blend

Type of behavior Pseudo-plastic Pseudo-plastic Dilatants at low shear rate

Figure 11. Cole–Cole diagram of a 50/50 unvulcanized XSBR–

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Alimardani and Abbassi-Sourki 13

Conclusion 7. Prochoń M, Przepiórkowska A and Zaborski M. Keratin

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Alimardani and Abbassi-Sourki 15

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