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POLYBUTADIENE (BR)
PROPERTIES AND APPLICATIONS
Polybutadiene (BR) is the second largest volume synthetic rubber produced, next to styrene-butadiene rubber (SBR).
Consumption was about 1,953,000 metric tons worldwide in 1999. The major use of BR is in tires with over 70% of
the polymer produced going into treads and sidewalls. Cured BR imparts excellent abrasion resistance (good tread
wear), and low rolling resistance (good fuel economy) due to its low glass transition temperature (Tg). The low Tg ,
typically <90C, is a result of the low vinyl content of BR, which will be discussed below. However, low Tg also
leads to poor wet traction properties, so BR is usually blended with other elastomers like natural rubber or SBR for
tread compounds. BR also has a major application as an impact modifier for polystyrene and acrylonitrile-butadiene-
styrene resin (ABS) with about 25% of the total volume going into these applications. Typically about 7% BR is
added to the polymerization process to make these rubber-toughened resins (see picture below). Also, about 20,000
metric tons worldwide of high cis polybutadiene is used each year in golf ball cores due to its outstanding
resiliency. This application is growing since the golf ball industry seems to be moving away from the traditional
wound ball technology to the two-piece, solid core construction.
CHEMISTRY AND MANUFACTURING PROCESS
Polybutadiene is a homopolymer (only one monomer) of 1, 3 butadiene, a monomer containing four carbon atoms,
and six hydrogen atoms (C4H6). The four carbon atoms are in a straight chain containing two double bonds as
follows:
CH2=CH-CH=CH2
1,3 butadiene
It is the double bonds that are the key to polymer formation. They are attacked by catalysts to maintain a repetitive
chain growth process which continues unti
l something is added to terminate the reaction at the desired molecular weight. Molecular weight can become quite
high. For a typical BR, molecular weight (Mn =number average) is usually >100,000 grams per mole. This
represents a chain that contains over 2,000 butadiene units. Most BRs are made by a solution process, using either a
transition metal (Nd, Ni, or Co) complex or an alkyl metal, like butyllithium, as catalyst. Since the reaction is very
exothermic, and can be explosive, particularly with alkyllithium catalysts, the reaction is normally carried out in
solvents like hexane, cyclohexane, benzene or toluene. The solvents are used to reduce the rate of reaction, control
the heat generated by the polymerization and to lower the viscosity of the polymer solution in the reactor. A typical
BR polymerization would be run at about 20% monomer and 80% solvent. The polymerization can either be a batch
process or a continuous process. In batch mode, monomer, solvent and catalyst are charged to the reactor, heated to
initiate the process, and then allowed to continue to completion. The polymer solution is then transferred to another
vessel or process unit to remove the solvent. In continuous mode, monomer, solvent and catalyst are continuously
fed into the bottom of the first of a series of reactors at a temperature suitable for polymerization. The
polymerization progresses as the solution flows through the reactors and polymer solution is taken off at the top of
the last reactor without stopping the process. The continuous process is the most economical. In both processes, the
finished product is usually in the form of bales which weigh from 50 to 75 pounds each.
HIGH CIS POLYBUTADIENE
The alkyl lithium and transition metal catalysts make very different products. The transition metal, or so called
Ziegler catalysts produce very stereo-regular BRs with one type having the main polymer chain on the same side
of the carbon=carbon double bond contained in the polybutadiene backbone. This is called the cis configuration.
High cis BR will usually have cis content >95% which gives rise to better green strength and
increased cut growth resistance in the cured product. Green strength, which is the strength of the
uncured rubber compound, is important for the tire building process and cut growth resistance is
Figure 2 cis 1,4
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necessary for tire performance. Cut growth resistance is the resistance to the propagation of a tearor crack during a
dynamic operation like the flexing of a tire in use. High cis BR also shows lower Tg compared to alkyllithium-based
BR because it has almost no vinyl structure. As mentioned earlier, vinyl tends to increase the Tg of the polymer. The
low vinyl content and low Tg makes high cis BR ideal for golf ball cores. Golf ball cores are cured with peroxides,
which tend to over cure the vinyl units making a very hard and slow golf ball. The neodymium catalyst system
produces the highest cis content of about 99% and also makes the most linear chain structure (no branching)
producing a polymer with the best tensile and hysteresis (low heat build-up)
properties of all the high cis types. The cobalt system produces a highly branched
BR with a low solution viscosity that makes a good polystyrene and ABS
modifier. The nickel catalyst makes BR with an intermediate level of branching.
The neodymium (Nd) catalyst system gives a polymer structure enabling marked
improvements in vulcanizate performance. The Nd-BR grades have the highest
cis-1,4 content, a relatively low molecular weight distribution and a low degree of branching. The use of Nd-BR will
continue to grow to produce high performance tires offering high fuel economy and improved wet grip capability.
LITHIUMBASED POLYBUTADIENE
The alkyllithium or anionic catalyst system produces a polymer with about 40% cis, 50% trans and 10% vinyl
when no special polar modifiers are used in the process. The alkyllithium process is probably the most versatile,
because the growing chain end contains a living anion (negative charge) which can be further reacted with
coupling agents or functional groups to make a variety of modified BRs. It also produces gel-free BR making it ideal
for plastics modification. Vinyl increases the Tg of the polybutadiene by creating a stiffer chain structure. Vinyl also
tends to crosslink or cure under high heat conditions so the high vinyl polymers are less thermally stable than low
vinyl. Note above, that in vinyl units the double bonds are pendent to the main chain, giving rise to the
special properties of high vinyl polymers. Vinyl units can be increased in lithium-based anionic
polymerization through the use of polar modifiers, which are usually nitrogen or oxygen-containing compounds.
The modifiers direct the attack of the propagating anion on the living chain end to give a 1,2 addition to the
butadiene monomer.
CH3 CH==CH CH2 (CH2 CH==CH CH2)n CH2 CH==CH CH2 Li
Growing living anion (negative charge) on end of live polybutadiene chain with Lithium counterion (positive
charge).
HIGH TRANS POLYBUTADIENE
High- trans BR is a crystalline plastic material similar to high trans polyisoprene or balata, which was used in golf
ball covers. Note below, that in the trans configuration the main polymer chain is on opposite sides of the internal
carbon-carbon double bond. Trans BR has a melting point of about 80C. It is made with transition metal catalysts
similar to the high cis process (La, Nd, and Ni). These catalysts can make polymers with >90% trans again using the
solution process.
