BUTADIENE-STYRENE RUBBER

(SBR)
 Introduction
• The butadiene-styrene rubbers whose abbreviation is
SBR (Styrene Butadiene Rubber), are today the most
consumed elastomers in the world.
• The first butadiene-styrene copolymers were produced
in Germany in 1937, in the laboratories of the company
IG Farbenindustrie, using the emulsion process.
Researchers Bock and Tschunker named this product
Buna S. This same process later resulted in the
butadiene-acrylonitrile copolymer, which became
commercially known as Buna N.
 Introduction
• The product produced in Germany had poor
properties when compared to natural rubber.
During the 2nd world war, the United States
improved the technology and arrived, in 1942,
to the production of the so-called rubber GR-S
(styrene), later called SBR. At the end of the
2nd war, the United States had 15 SBR plants,
16 butadiene plants and 5 styrene plants, later
sold to the private sector, between 1946-
1955.
 Introduction
• The first butadiene-styrene copolymers were produced by
emulsion polymerization, with persulfate polymerization
initiators, at a temperature of 50°C. With the introduction
of redox polymerization catalysts , the production
temperature became 5ºC; to differentiate the types
produced at one temperature or another, the first ones are
called hot SBR (hot SBR) and those obtained at 5ºC, cold
SBR (cold SBR). The application of ionic polymerization
techniques allowed the production of styrene-butadiene
rubbers in solution; to differentiate them from the previous
ones, the abbreviations E-SBR and S-SBR were proposed for
SBR polymerized in emulsion and solution, respectively.
Introduction
E-SBR. Structure and commercial types
• Among the E-SBR, the cold polymerized types are
practically the only ones used in the rubber
industry today. The main reason for this is that,
with redox-type polymerization at 5°C, the
tendency to branching during polymer chain
formation is considerably reduced; This trend is
very much observed in polymerizations at 50ºC,
which can even lead to chain cross-linking and
consequent gel formation, limiting its molecular
weight to 90,000.
E-SBR. Structure and commercial types
• In polymerization at 5°C, the chains maintain a predominantly linear
structure, allowing molecular weights of around 250,000 to be
obtained; this process can lead to obtaining molecular weights of
800,000, corresponding to vulcanized rubbers with better
mechanical resistance, but which, due to their high molecular
weight, are practically unprocessable in conventional rubber
equipment. This problem is solved by introducing extender oils
during the polymerization process, when an oil emulsion is added
mineral, naphthenic or aromatic, in the proportions of 25, 37.5 or
50 parts (phr). In these oilextended SBRs (OESBR - extended SBR),
the presence of the plasticizer makes mixing in conventional rubber
equipment possible, however, there is a decrease in mechanical
strength; but, as it starts from a very high level, the end result is a
rubber with resistance comparable to that of non-extended types
and with a lower price, as the plasticiser is cheaper than the rubber.
E-SBR. Structure and commercial types
• To obtain an optimal dispersion of fillers, a
dispersion of carbon black is introduced into
the latex phase of some SBRs and then
coagulation is carried out. These SBRs, known
as masterbatches, reduce or avoid carbon
black handling, which also increases
production capacity by ensuring correct and
uniform carbon black dispersion.
E-SBR. Structure and commercial types
• Regardless of the trade name of each product,
the International Institute of Synthetic Rubber
Producers (IISRP) assigns a number to each type
of SBR. The hundred from 1000 to 1099 are
reserved for hot cured SBRs; from 1100 to 1199
to masterbatches of these with carbon black
(whose commercial production does not
currently exist); from 1500 to 1599 the cold SBRs;
from 1600 to 1699 with masterbatches of these
with carbon black; from 1700 to 1799 SBRs
extended in oil and from 1800 to 1899 OESBR
masterbatches with carbon black.
E-SBR. Structure and commercial types
• Within each group, the characteristics that differentiate one type from the other and those
that we must consider to select the most suitable SBR for a given application are:
• Staining or non-staining factor of the antioxidant incorporated into the rubber during its
manufacturing process. This is the only difference between an SBR 1500 (with staining
antioxidant) and an SBR 1502 (with non-staining antioxidant);
• The type of soap used as an emulsifier: we basically use two types of soap - fatty acid soap
and rosin soap (also known as rosin soap). SBRs made in fatty acid soap have better
vulcanization speed; however, those made with rosin soap have better stickiness; although
there are some types with combinations of the two soaps, their effects can easily be
compensated in the formulation;
• The combined styrene content: most types of SBR have 23.5% styrene, however, there are
types with a different content - from 9.5% in SBR 1505 to 40% in SBR 1513, 1519 and 1516.
E-SBR. Structure and commercial types
• Mooney viscosity: is related to molecular
mass and molecular weight distribution; in
most types it is 50 ± 5 Mooney units, but there
are also types with lower viscosity, such as
SBR 1510 (viscosity 32), suitable for the
production of expanded artifacts; there are
others with higher viscosity, such as SBR 1570
(viscosity 117), especially indicated for
formulations with a large amount of fillers and
plasticizers.
E-SBR. Structure and commercial types
• The type of coagulation system, with acid or
salts. This characteristic only affects electrical
insulation; for example, SBR 1509 coagulated
with aluminum sulphate, is especially suitable
for cable insulation.
 Formulation and Processing
• Like natural rubber, SBR can be vulcanized by sulfur and accelerators, by
peroxides and by other special vulcanizing agents, the first system being the
most used.
• Because it has less unsaturation, it needs smaller doses of sulfur, around 1.5-
2.0 phr; on the other hand, the lower chemical reactivity of the double bond,
derived from butadiene, when compared to isoprene from NR or IR, requires
higher activation energy, which means the use of faster accelerators or higher
doses of conventional accelerators. In the case of OESBR, the proportion of
vulcanizing agents is calculated on the rubber portion, excluding the
incorporated oil. The lower reactivity of the double bond reduces the
pre_x0002_vulcanization tendency, but as this is related to the accelerator
system, in some cases it is advisable to use a retarder.
 Formulation and Processing
• Compared to NR, SBR is less prone to oxidation, partly
because it has an antioxidant incorporated into the
manufacturing process, and partly because of the lower
reactivity of the double bond. It is recommended to add
1-2 parts of an antioxidant to the compound, as well as
to use EV and semi-EV vulcanization systems. The use of
peroxides or special systems, such as isocyanates, are
also indicated to obtain better heat resistance. The
double bond in SBR makes it sensitive to ozone;
therefore, if the SBR must be exposed to ozone, the use
of a chemical antiozonant or waxes is recommended.
 Formulation and Processing
• The differences between SBR and natural rubbers
are predominantely in load acceptance.As with all
rubbers that do not crystallize under stress (the
rule for most synthetic rubbers), unfilled SBR has
very low mechanical strength, but with the
addition of reinforcing or semi_x0002_reinforcing
fillers, a level of mechanical strength is achieved.
acceptable. Inert fillers can be used to reduce the
cost of the compost, but they should always be
added as a complement to a reinforcing filler, not in
its place.
 Formulation and Processing
• The SBR is not as sensitive to hot mechanical chewing in
the presence of peptizers as is the NR; thus, plasticizers
play an important role in adjusting the viscosity of
compounds; but, fortunately, as most synthetic rubbers
have a standardized viscosity, a standardized viscosity can
be used to make a compound. SBR does not have
particular compatibility problems with plasticizers. As it
does not have natural tackiness, it is recommended to
use tack agents, such as rosin resins, coumarone-indene,
pine tar, etc., to increase tackiness, for example, in tire
covers.
 Formulation and Processing
• The preparation of the compounds can be done either in a cylinder mixer or in an
internal mixer. For mixing in cylinders, a temperature of 45-55ºC is used, and the
addition of fillers must be done quickly so that the compound is smooth and
homogeneous. During the mixing generates more heat than NR, which requires
good cooling to maintain shear forces that ensure good dispersion of ingredients.
In closed mixers, the cycles must be shorter compared to the NR, and the power
consumption is about 20% higher. In the case of mixers with tangential motors,
with the OESBR it is recommended to carry out the mixing in two stages:
• - 1st. Step: high-speed preparation - 150-165ºC discharge - of the masterbatch
with rubber, fillers and plasticizers;
• - 2nd. Step: after the compost has cooled down, it is finished preparing at a lower
speed.
• With the new interpenetrating mixers the compost can be prepared in a single
step
 Formulation and Processing
• In the remaining operations, such as molding,
extrusion, etc., we must follow the same
procedures used in NR. These steps must be taken
into account:
• The lower resistance to tearing can damage the
parts when removed from the mold;
• In extrusion and calendering, generally the
processing temperatures are lower than those of
NR.
 Formulation and Processing
• Hot polymerized SBRs provide higher extrusion speed, followed by
cold polymerized SBR and equal to NR in OESBR.
• Swelling at the extruder nozzle is minimal with cold cured SBRs; it is
medium with OESBR and maximum with hot cured SBRs.
• For complicated profiles with sharp edges, the most recommended
types are cold polymerized SBRs, which give smoother and more
regular surfaces; hot cured SBRs give brighter, more irregular
surfaces. OESBR have opaque and rough surfaces.
 E-SBR Properties and Applications
• With the use of reinforcing fillers, SBR have
superior abrasion resistance than NR, with a
more competitive price. Due to this, the SBRs
replaced the NR in the manufacture of small
tread parts (bicycles, motorcycles, passenger
cars and light trucks), in conveyor belts, in
footwear and many technical artifacts.
 E-SBR Properties and Applications
• SBR rubber is inferior to NR rubber in terms of resilience and
hysteresis, absorbing (and transforming into heat) a greater amount
of imposed energy. The need to use greater amounts of reinforcing
loads makes this difference more pronounced. Therefore, in larger
tires (trucks, tractors, etc.), where the tread is thicker, it is more
difficult to dissipate the heat generated; in particularly severe
services (airplanes and competition cars), due to the heat
generated by their higher speed, NR also continues to be used. NR
generates less heat and maintains a better level of mechanical
properties at moderately high temperatures.
 E-SBR Properties and Applications
• With regard to behavior against dynamic
fatigue, in the appearance of cracks due to
fatigue or mechanical laceration, SBRs are
better than NR; however, once the crack is
generated, it propagates quickly. Its resistance
to heat and oxidation is better than NR.
 E-SBR Properties and Applications
• As for your applications;
• 70% is used in the tire sector, 13% is
consumed in the form of latex (mainly for
foams) and the rest is used in a wide variety of
applications, including: conveyor belts, shoes,
hoses, moldings, etc.
 Solution Polymerized SBR (S-SBR)
• The polymerization of this type of SBR occurs
with the monomers dissolved in an organic
solvent, which in turn dissolves the polymer
produced; polymerization occurs with the use
of butyl-lithium type catalysts. Unlike
emulsion polymerization, latex is not
obtained, but rubber dissolved in a solvent,
which, after evaporation, separates the rubber
from the residual monomers.
 Solution Polymerized SBR (S-SBR)
• Its main advantage is to allow certain control
of the resulting polymer, varying the
polymerization conditions, such as catalyst
concentration, type of solvent, presence or
absence of polar compounds, the order of
addition of monomers, etc.; within certain
limits, it is possible to easily modify the
molecular characteristics of the resulting
rubber, and, as a consequence, its technical
properties
 Solution Polymerized SBR (S-SBR)
• In the SBR emulsion synthesis and due to the reactivity ratio of
styrene and butadiene being close to unity, the entry of both in the
chain is random; as a consequence, the structure of the copolymer
is also random in terms of the distribution of monomers. On the
contrary, in ionic solution polymerization, the reactivity of
butadiene is greater than that of styrene to the point that, if we
load a mixture of the two monomers in equal parts, the
polymerization of butadiene will continue to grow in a linear chain
until all the monomer is exhausted. ; only then will the
polymerization of the styrene begin, which will give rise to a
polystyrene block; this process taken to the extreme is the basis of
styrenic thermoplastic elastomers (SBS). One
 Solution Polymerized SBR (S-SBR)
• Another peculiarity is that the growing chain acts
like a living polymer, that is, it is capable of
continuing to grow when more monomer is added.
The addition of a polar compound, such as diethyl
ether, tetrahydrofuran or tertiary amines at the
beginning of polymerization, tends to equalize the
reactivity of the monomers in the
btyllithium_x0002_induced polymerization, leading
to an S-SBR with a random structure.
 Solution Polymerized SBR (S-SBR)
• It is also possible to regulate the molecular weight of the
chains, the distribution of molecular weights, the
proportion of cis-1,4, trans-1,4 and 1,2 (vinyl) additions
of the butadiene molecules that enter the chain, the
degree branching, etc
• It is also possible to regulate the molecular weight of the
chains, the distribution of molecular weights, the
proportion of cis-1,4, trans-1,4 and 1,2 (vinyl) additions
of the butadiene molecules that enter the chain, the
degree branching, etc
Solution Polymerized SBR (S-SBR)
 Solution Polymerized SBR (S-SBR)
• As the initial problem was not having enough
knowledge of how these molecular characteristics
would translate into technological properties;
numerous studies have been done in order to:
• 1st: improve process control to obtain the desired
characteristics;
• 1st: improve process control to obtain the desired
characteristics;
• 2nd: to improve the understanding of the influence
of these characteristics on the properties of
vulcanizates.
 Solution Polymerized SBR (S-SBR)
• Solution polymerization provides a molecular
weight distribution and structure
predominantly linear, with few branches; thus,
the S-SBR have greater resistance to abrasion
and tearing, compared to E-SBR, as well as
better dynamic properties, in favors less
fatigue cracking and less hysteresis heat
generation
 Solution Polymerized SBR (S-SBR)
• The absence of low molecular weight fractions, which in E-
SBR and other emulsion-polymerized synthetic rubbers, which
act as internal plasticizers and which do not have “nerves”,
makes mixing in a cylinder mixer difficult, as the band tends to
detach and the compound, to be glued to the rear cylinder.
When using this equipment, a low friction ratio, smaller
volume and greater cooling must be used in the front cylinder,
keeping it at a temperature of 45-55ºC and in the rear
cylinder at 70-80ºC. In internal mixers, increase the load
factor by 10-15%, compared to NR or E-SBR, as the power
consumed is lower and the increase in the mixture size
increases the machine's performance.
 Solution Polymerized SBR (S-SBR)
• The second important group of solution-
polymerized SBRs are those with a block structure.
The grouping of styrene units in blocks increases
thermoplasticity, especially useful in extrusion and
calendering operations with higher speeds and
smaller deformations (swelling at the extruder
nozzle or at the exit of the cylinders and their
subsequent contraction). Another effect of
polystyrene blocks is to provide vulcanizates with
higher hardness, when compared to a random SBR;
this is important in the manufacture of high
hardness artifacts, such as shoes.
 Solution Polymerized SBR (S-SBR)

• On the other hand, polybutadiene blocks improve low temperature resistance,

as well as resistance to abrasion and bending, when compared to vulcanizates
of similar hardness based on random SBR.
• With regard to the preparation of SBR compounds with a block structure, the
same recommendations made for the random types are valid: it is advisable to
add stearic acid quickly as it acts more as a peptizer than as an activator, and
to increase the load factor on internal mixer. When preparing in cylinder
mixers, it is only recommended to raise 10ºC at the recommended
temperatures.
• S-SBR with block structure are used in the footwear industry and in the
manufacture of extruded and calendered artifacts. They are widely used in
blends with natural and synthetic rubber to improve extrusion and
calendering characteristics.
 Referências
• HOFMANN, W, Rubber Technology Handbook,
Hanser Publishers, Munich, 1989.
• M. Morton, Rubber Technology (3d ed. 1987)
• Plioflex Literature, Goodyear