Nippon Gomu Kyokaishi, No. 5, 2015, pp.
178–183
Industrial Synthetic Method of the Rubbers.
1. Butadiene rubber
Takuo Sone
Polymer Materials Laboratory, Performance Polymer Research Laboratories, JSR Corporation (100 Kawajiri-cho,
Yokkaichi, Mie 510-8552, Japan
Selected from International Polymer Science and Technology, 42, No. 9, 2015, reference NG 15/05/178; transl. serial no. 17421
INTRODUCTION
Products making use of rubber materials, typified by
automotive tyres, occupy a key supporting role in daily
life. Rubber may be natural rubber from plants, or synthetic
rubber, a man-made product derived from petroleum.
According to the Japanese Rubber Manufacturers
Association, the (estimated) consumption of new rubber
in Japan in 2014 was 689 kt of natural rubber and
about the same amount, 703 kt, of synthetics. It is clear
from the large amount used that synthetic rubber is a
raw material of some industrial importance. Numerous
synthetic rubbers have been developed for industrial
application since Hofmann [1] obtained the first synthetic
rubber patent for methyl rubber (polydimethyl­butadiene)
in 1909. The properties of synthetic rubbers vary
with the nature of the monomer starting material and
manufacturing process. For future technological and
product development, it is useful for rubber technologists
to have a broad understanding of how the various
rubbers are synthesised, and what their properties are.
This Keynote Review focuses on prominent examples of
synthetic rubbers still in commercial use today in diverse
applications; aspects ranging from synthetic technology
to structural characteristics, properties and applications
will be covered in a series of articles. This first review
looks at butadiene rubber, familiar as a general-purpose
rubber.
BUTADIENE RUBBER BASICS
Butadiene rubber, a polymer of 1,3-butadiene, is classed
as a general-purpose rubber. The abbreviation used is
© 2016 Smithers Information Ltd.
Translated by K. Halpin
BR. As a general-purpose rubber, BR has a high output
and high consumption, second only to SBR. The structural
formula is shown in Figure 1. BR is an addition polymer
of the conjugated diene monomer 1,3-butadiene,
and depending on how the monomer units combine,
therefore, three different geometric isomers are formed
in the polymer chain, namely the cis-1,4 linked chain
(cis-), trans-1,4 linked chain (trans-) and 1,2-linked chain
(vinyl-). Furthermore, as 1,2-linkages contain a chiral
carbon atom, the differences in absolute configuration
when a 1,2-linked chain is formed give rise to three
kinds of stereo­regularity (tacticity): isotactic (iso), syndio­
tactic (syn) and atactic (ata). The mode of linkage in
the butadiene rubber chain is generally referred to as
the polymer microstructure. The microstructure and the
tacticity can be controlled by selecting the method of
polymerisation [2, 3].
BR is generally classed according to polymerisation
process (microstructure). BR of cis content 90% or above
produced by anionic coordination polymerisation is called
high cis-BR, while BR with a low cis content of not more
than 40% produced by anionic polymerisation is called
low cis-BR. These two products together make up the bulk
of commercial BR. Another type of BR is synthesised by
emulsion polymerisation. It is used mainly as the starting
material for ABS resins and is generally supplied as latex.
This article reviews high cis-BR and low cis-BR.
BR ANNUAL PRODUCTION AND
MANUFACTURERS
Production of BR has increased worldwide following the
recent growth in output of vehicles. Figure 2 shows global
T/49

Figure 1. Structure of butadiene rubber (BR)
Figure 2. Growth in global BR production capacity
Figure 3. BR production capacity by region
BR production capacity as reported by the IISRP [4]. The
production capacity of 2,914 kt recorded in 2005 has
increased year-on-year, reaching 4,788 kt in 2013. In
2013 the worldwide capacity for synthetic rubber stood
at 18,626 kt, of which 25% was accounted for by BR.
Figure 3 shows the regional breakdown of capacity in
T/50
2013. Production capacity decreases in the order China,
Asia (excluding China), and North America, the whole
of Asia inclusive of China accounting for roughly 63%
of total capacity. Capacity in China in particular has
risen sharply since 2011.
According to the IIRSP report [4], there are four
domestic manufacturers of BR in Japan: Ube Industries
Co., JSR Corporation, Zeon Corporation and Asahi
Kasei Chemicals Corp. (including Japan Elastomer Co.).
Ube Industries and JSR produce high cis-BR only, while
Asahi Kasei Chemicals produces low cis-BR only. Zeon
is the only domestic manufacturer producing both high
cis-BR and low cis-BR. As of 2013, the four corporations
had a combined production capacity of 298 kt. Since
the low cis-BR part of output is produced along with
solution polymerised SBR at a multipurpose living anion
polymerisation plant, etc, the overall production capacity
inclusive of all such products has been indicated in
the footnotes to Table 1. In addition to the above four
corporations, Bridgestone Corporation has a subsidiary
Firestone Polymers LLC manufacturing synthetic rubber;
this produces high cis-BR and low cis-BR in the USA, and
has a capacity of 160 kt (319 kt as multipurpose plant
capacity including solution polymerised SSBR).
With recent growth in demand for synthetic rubber in
the Asian region, press releases from all manufacturers
are announcing strengthened BR capacity. Ube Industries
strengthened BR plant capacity at its Chiba Factory
in 2014, increasing production by 16 kt to a total of
126 kt; the corporation is also operating high cis-BR
plants established as overseas bases in Thailand (72 kt),
China (72 kt) and Malaysia (50 kt).
In Singapore, both Asahi Kasei Chemicals and Zeon
have set up multipurpose plants of respective capacity
50 kt and 30-40 kt producing BR with solution polymerised
SBR; the plants began producing low cis-BR in 2013.
With increasing demand for fuel economy tyres, both
corporations are engaged in doubling the capacity of
their production facilities.
The price of BR fluctuates with market conditions and
the price of naphtha; according to the “16514 Chemical
Table 1. Japanese BR manufacturers and production
capacity (2013)
Domestic manufacturer Capacity
Ube Industries *1 110 kt
JSR Corporation * 2
72 kt
Zeon Corporation *3 65 kt
Asahi Kasei Chemicals Corp.* 4
51 kt
(including Japan Elastomer Co.)
*1 Co catalyst *2 Ni and Nd catalyst
*3 Co catalyst: also has Li catalyst SSBR multipurpose plant;
total output 120 kt
*4 Li catalyst: also has Li catalyst SSBR and SBC multipurpose
plant; total output 225 kt
International Polymer Science and Technology, Vol. 43, No. 1, 2016
Products, 2014 Edition” published by the Chemical within the system increases markedly as polymerisation
Daily Co. in Japan, the price per kg was ¥380-¥420 proceeds; appropriate pre­cautions must therefore be
as of October 2013. devised in production of BR. An example of production
process flow is shown in Figure 4.

SYNTHESIS AND STRUCTURE-DEPENDENT

CHARAC­TERISTICS High cis-BR
High cis-BR is synthesised by anionic coordination
polymerisation and has high stereoregularity with a
1,3-Butadiene chain structure of more than 90% cis content. To realise
this level of stereoregularity, a specific Ziegler catalyst
BR is obtained by the addition polymerisation of
has to be chosen. The Ziegler catalysts used for high
1,3-butadiene. The 1,3-butadiene monomer is produced
cis-BR are prepared by reacting an organo-aluminium
industrially from a petroleum feedstock using either
compound with a metal compound. High cis-BR can
extraction or dehydrogenation [5]. The extraction process
be produced by reacting 1,3-butadiene with such a
uses solvent, etc, to extract and purify the monomer from
catalyst in an organic solvent. Table 2 lists examples
the C4 fraction formed as a by-product in the production
of the catalysts used industrially [8] and the properties
of ethylene by naphtha cracking. The dehydrogenation
of the BR obtained. The metal compounds deployed as
process produces the monomer by dehydrogenating a
catalysts may be transition metal compounds making
feed of butane or butene. The butane, butene and other
use of titanium, cobalt and nickel, or rare earth metal
C4 compounds are extracted and purified from the C4
compounds using neodymium. The choice of catalyst
fraction after butadiene extraction, or are produced by
the dimerisation of ethylene [6].

Methods of production
As noted in Section 2 above, commercial BR generally
denotes high cis-BR and low cis-BR, which require
different methods of polymerisation. Organic solvent
is used in production (polymerisation) for both kinds of
BR. Another general feature is that, in order to conduct
polymerisation with a catalyst (or initiator) comprising
organometallic compounds, production steers clear of
oxygen and moisture and is carried out under nitrogen.
The polymerisation solvent used is non-polar dehydrated
toluene, hexane or cyclohexane. Although there are
some differences in production flowchart between
manufacturers, process flow follows the sequence (1)
purification of monomer and polymerisation solvent,
(2) polymerisation reaction, (3) recovery of unreacted
monomer and solvent, (4) finishing [7]. Polymerisation
is an exothermic reaction, and the solution viscosity Figure 4. BR production process flow (example)

Table 2. Industrial processes for BR polymerisation in relation to BR structure

BR Process Catalyst Microstructure (%) Mooney viscosity*1
(initiator) cis trans vinyl ML1+4,100°C
High cis BR Anionic coordination TiX4/A1Et3 90-93 4-2 6-5 45
(catalyst) Co(OCOR)2/A1Et2Cl 96-98 2-1 2-1 30-50
Ni(OCOR)2/A1Et3/ 96-98 2-1 2-1 35-50
BF3(OEt2)
Nd(OCOR)3/A1R'3/ 97-99 2-1 1-0 35-60
Et2Al3Cl2
Bu-Li 32-36 53-58 8-11 30-70
*1 Manufacturer’s catalogue data

© 2016 Smithers Information Ltd. T/51

affects the micro­structure of the BR, the cis content BR PROPERTIES AND APPLICATIONS
increasing in the order Ti-BR 90-93%, Co-BR and Ni-BR
The characteristics of high cis-BR and low cis-BR are
96-98%, and Nd-BR 97-99%. The metal used for the
summarised in Figure 5. Both BRs have a low Tg and
catalyst also affects the molecular weight distribution
therefore have outstanding low temperature properties.
and degree of branching. High cis­-BR production in
Viewed as a general-purpose rubber, BR has character­
Japan has used chiefly catalysts based on Co, Ni and
istics of high resilience, low hysteresis loss, and excellent
Nd. It is known that, of the different catalysts, the Nd
wear resistance. However, processability is poor
compounds allow insertion of functional groups at the
compared with natural rubber and styrene-butadiene
polymer chain ends, a characteristic not shared by
rubber; in applications such as tyres, therefore, it is
the Ti, Co or Ni compounds [9]. However, because of
commonly blended with other rubbers instead of being
the different polymerisation mechanism, the fraction of
used alone.
terminal group inserted at the chain end is low compared
Table 3 shows the results from evaluation of the
with solution-polymerised styrene-butadiene rubber
polymer properties and compound properties of high
synthesised by living anion polymerisation.
cis-BR variously polymerised with Nd, Co and Ni based
Because the polymer backbone is predominantly catalysts [11]. The properties correlate with cis content,
cis-1,4 linked, high cis-BR has a low glass transition a high cis content giving better properties. BR of high
point (Tg) of -95°C to -100°C. However, despite the cis content synthesised with Nd-catalyst exhibited
high stereoregularity, it differs from natural rubber (NR) superior tensile strength, hysteresis loss (tan d) and wear
in resisting stretch crystallisation in the vicinity of room resistance. As noted in Section 4, functional groups
temperature. The double bonds in the polymer chain can be introduced at the polymer chain ends when
originating from butadiene are highly reactive and react Nd-catalyst is used. A reaction scheme for introducing
with sulphur, peroxides and various other crosslinking terminal functional groups with Nd-catalyst is shown in
agents to give a crosslinked polymer. At the same time, Figure 6. End-functionalised BR is reported to improve in
the double bonds are susceptible to degradation by heat resilience and wear resistance through interaction with
and oxidation; and unlike NR, degradation behaviour the reinforcing agent [9].
is of the hardening type. The chief application of high cis-BR is automotive tyres.
The BR is generally blended with styrene-butadiene rubber
or natural rubber and widely used as tread rubber, side
Low cis-BR wall rubber, bead filler, etc, for passenger vehicle tyres,
Low cis-BR is synthesised by anionic polymerisation using goods vehicle tyres and bus tyres. Apart from its use in
an organolithium compound as initiator. The term low tyres, it is also used in footwear, golf ball cores, rubberised
fabrics, gaskets and O-rings. Like high cis-BR, low cis-BR is
cis-BR generally denotes a low vinyl type BR of cis content
used in automotive tyres and various industrial products.
around 35% and vinyl content close to 10% (see Table 2)
It also has resin modifying applications, especially as
[10]. Unlike high cis-BR, it has a low cis content; and as
an ingredient of high impact polystyrene (HIPS). Ube
the polymer is synthesised by anionic polymerisation, the
Industries recently developed a butadiene rubber “MBR”
vinyl content can be controlled within the approximate
suitable for enhancing the impact resistance of HIPS
range 10-90% and BR of high vinyl content can be
and ABS [12]. Polymerisation of 1,3-butadiene using
synthesised. The vinyl content can be controlled by the
a catalyst of vanadium metallocene complex enables
addition of a Lewis base such as an amine compound to
the synthesis of BR of cis content around 90% and vinyl
the polymerisation system. Synthesis by anionic polymer­
isation means that, compared with high cis-BR, there is
a narrow molecular weight distribution, little branching,
and almost no gel fraction. Because the polymerisation
process is anionic, living polymers are possible and BRs
have been developed that have been functionalised by
star branching and insertion of functional groups.
The Tg of low cis-BR is dependent on vinyl content and
lies in the approximate range -85°C to -30°C, rising the
higher the vinyl content. The usual low vinyl type BR has
a low Tg of about -85°C, somewhat higher than that of
high cis-BR. On the other hand, since the vinyl content is
higher, low cis-BR is highly reactive toward crosslinking
agents like peroxides, and compared with high cis-BR, Figure 5. Structure and characteristics of high cis-BR and
there is a sharper rise in the cure curve. low cis-BR

T/52 International Polymer Science and Technology, Vol. 43, No. 1, 2016
Table 3. Results from properties evaluation of high cis-BR synthesised with different catalysts
(Recipe: BR/CB (N339)/oil/stearic acid/ZnO/IPPD/BBS/S = 100/50/10/2/31/1/1.5 parts)
BR/catalyst BR-A/Nd BR-B/Co BR01/Ni
Polymer properties
Cis-1,4 mol% 96 94 94
Vinyl-1,2 mol% 1.3 3.2 2.9
Mw/x104 53 52 63
Mw/Mn 2.8 3.3 4.2
ML1 + 4, 100°C 43 44 43
Compound properties
ML1+4, 100°c 74 62 64
Roll processability - factory good unsatis good
Mill shrinkage % 29 44 43
Appearance of sheet excellent poor good
Vulcanised properties
300% Modulus MPa 9.1 9.3 7.5
Tensile strength MPa 20.0 16.1 18.2
Elongation at break % 550 450 580
Wear resistance/index*1 122 98 100
tan d at 50°C*2 0.144 0.173 0.188
*1 Lambourn wear (slip ratio 60%, temperature 50°C)
*2 Frequency 15.9 Hz, strain 3%

a vulcanisable rubber
material because of
the crystallinity of the
polymer chains. It is used
for industrial products
ranging from automotive
sound-deadening material
and meltable bags to
film and various types of
footwear. Blending with
SB based thermoplastic
elastomers typified by
styrene-butadiene-styrene
copolymer (SBS) improves
polymer flow and the
Figure 6. Inferred reaction mechanism in terminal functionalisation with Nd-catalyst appearance of the moulded
articles; it is for this reason
also used as a modifier.
content around 10% which has the special feature that,
Ube Industries produces “VCR”, a BR in which syn-
because of its characteristic micro­structure, styrene graft
1,2-polybutadiene resin (SPB) of higher crystallinity than
reactivity can be combined with graft polymer elasticity.
RB is combined with high cis-BR to form a composite
[14]. VCR is produced by high cis-BR polymerisation
with Co/Al catalyst, adding SPB catalyst (Co catalyst)
FUNCTIONALISED BR
to the reaction mixture and then polymerising SPB in
A number of examples will be given of purely 1,3-butadiene- the reaction vessel. As a composite with SPB resin, it
based materials produced commercially in Japan. The first has high green strength and superior processability to
is syn(syndiotactic)-1,2-polybutadiene [13]. This polymer conventional BR. Again, owing to reinforcement with
was developed independently by JSR and is marketed resin, the hardness and elasticity modulus are high and
as “RB”. RB uses cobalt/organo­aluminium/H2O catalyst tensile strength improves. VCR is used in a wide range
to control the stereoregularity of the 1,2-linkages in of industrial products including automotive tyres and
the polymer chain. Its special feature is that it shares vibration insulators, hoses and belts.
the properties of both a thermoplastic elastomer and Zeon Corporation has developed the industrial

© 2016 Smithers Information Ltd. T/53

production of a terminally modified low cis-BR in which
a functional group reactive toward carbon black has
been added to the chain end of BR made by anionic
living polymerisation. It is used for the tread rubber of
fuel economy tyres and in rubber vibration insulators.
JSR produces a hydrogenated BR synthesised by
anionic living polymerisation followed by hydrogenation
[15]. The hydrogenated BR is obtained by hydrogenating
a triblock polymer in which both ends of a polybutadiene
chain of high vinyl content have been terminated with
polybutadiene blocks of low vinyl content. The blocks
introduced at the chain ends are primarily ethylene
chains, and because of the crystallinity of these blocks,
the product is a thermoplastic elastomer. Its unusual
structure it exploited by using it as a compatibiliser for
polypropylene (PP), polyethylene (PE) and ethylenic
resins such as ethylene-ethyl acrylate copolymer (EAA)
and ethylene-vinyl acetate copolymer (EVA), and for the
softening (resin modification) of high density polyethylene
(HDPE).
CONCLUSIONs
This review of butadiene rubbers in industrial production
has focused on high cis-BR and low cis-BR. As a general-
purpose rubber, BR is used primarily in the manufacture
of automotive tyres and demand is likely to increase
with growth in the output of vehicles. That said, the
characteristics and properties of BR are dependent
on the polymerisation recipe. Although BR is a simple
polymer using only 1,3-butadiene, design of the polymer
skeletal structure, including control of microstructure and
stereoregularity, and functionalisation of the chain ends
can realise diverse functionality. As greater performance
is imparted to automotive tyres, the development of
polymerisation processes affording a high degree of
control over butadiene chain structure continues. The
near future should see the development and commercial
production of new forms of BR.
T/54 International Polymer Science and Technology, Vol. 43, No. 1, 2016
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