INDUSTRIAL POLYMER CHEMISTRY I

SID2002

POLYBUTADIENE (PB)

NAME : NAZIRAH BINTI ARBAIN (SEW 150034)

AZSVINY A/P NADARAJAH (SID160003)

LECTURE NAMA : DR. NORAZILAWATI BINTI MUHAMAD

SARIH

DATE COMPLETION : 13 OCTOBER 2017

 1. INTRODUCTION
Polybutadiene is an example of synthetic rubber. Polybutadiene was one of the first type of
synthetic rubber to be invented. Polybutadiene has high resistance towards wear and tear.
Manufacture of tires, elastic objects golf balls, belts, hoses, gaskets, automobile parts and to coat
electronic assemblies used the raw material of polybutadiene. Tires treads are also made of
polybutadiene copolymers. Polybutadiene had become so useful as it has high electrical resistivity.
Other many polymers become brittle at low temperatures, but not polybutadiene. It is also good
for uses which require exposure to low temperatures as it can resist to cold temperatures.
According to Interne search, polybutadiene rubber accounted for about a quarter of total global
consumption of synthetic rubbers in 2012. Polybutadiene is like natural rubber, polyisoprene. A
stiff rubber called poly(styrene-butadiene-styrene), or SBS rubber is a copolymer containing
polybutadiene.

POLYBUTADIENE
 2. RAW MATERIALS/ MONOMERS

Polymerization of monomer 1,3-butadiene produces a polymer named polybutadiene rubber. 1,3-

Butadiene is an organic compound, It is simple conjugated diene hydrocarbon, which has two
carbon-carbon double bonds. Polybutadiene is formed by linking many 1,3-butadiene monomers
to join and make a longer polymer chain molecule., Butadiene can polymerize in three separate
ways in terms of the connectivity of the polymer chain, which are called cis, trans and vinyl. The
cis and trans forms are formed by connecting the butadiene molecules end-to-end, and this process
is called 1,4-polymerisation. The properties of the products, isomeric forms of polybutadiene differ
from each other in terms of their molecular weights and branching. During polymerization, the
trans double bonds formed allows the polymer chain to stay straight, and thus allows sections of
polymer chains to align to form microcrystalline regions in the material. The cis double bonds
cause the polymer chain to bend. This prevents the polymer chains from aligning to form
crystalline regions, which results in larger regions of amorphous polymer. A crucial percentage of
cis double bond configurations in the polymer will result in a material with flexible elastomer
(rubber-like) qualities. Both cis and trans double bonds would form in percentages that depends
on temperature in free radical polymerization. The catalysts have an influence on the cis vs trans
ratio.

3. TYPES OF POLYBUTADIENE

Typical composition of
polybutadiene based on the
catalyst used
cis (%) trans (%)
Neodymium 98 1
Cobalt 96 2
Nickel 96 3
Titanium 93 3
Lithium 10 to 30 20 to 60

The catalyst used in the production determines the type of polybutadiene product.
 a) High vinyl polybutadiene

The researchers from Zeon, a Japanese company found that high-vinyl polybutadiene (70%), is
having a high liquid-glass transition. This transition could be advantageous as it can be used in
combination with high cis in tires, in 1980. An alkyl lithium catalyst is used to produce with this
material. Moreover, Zeon, the Japanese company, with the American company named Firestone
produces high-vinyl polybutadiene.
A type of polybutadiene where it contains 90% vinyl is being marketed by JSR Corporation, which
it gives the properties of an elastomeric thermoplastic: a fluid at high temperatures but, elastic at
room temperature which makes it usable to process it using injection molding.
b) High trans polybutadiene

Using catalysts, polybutadiene with more than 90% trans can be produced like those of high cis:
neodymium, lanthanum, nickel. This material is known as plastic crystal (not an elastomer) that
melts at about 80 C. The outer layer of golf balls was formerly made by this kind of polybutadiene.
But today it is only used industrially. Since then companies like Ube are determining other possible
applications.
c) High cis polybutadiene

High cis polybutadiene has high proportion of cis (over 92%) and a small proportion of vinyl (not
more than 4%). Ziegler-Natta catalysts is used to manufacture it based on transition metals. The
properties vary slightly depending on the metal used.
High cis polybutadiene gives branched molecules using cobalt, which enables it to become a low
viscosity material that is easy to use. Its mechanical strength is relatively low. The material that
gives the most linear structure is Neodymium (in result higher mechanical strength) and a higher
percentage of 98% cis. Nickel and titanium are examples of other less used catalysts.
d) Low cis polybutadiene

Alkyl lithium (e.g. butyllithium) is used as the catalyst to produce a polybutadiene called "low cis"
which contains 36% cis, 54% trans and 10% vinyl.
Other than its high liquid-glass transition, tires are also manufactured using low cis polybutadiene.
It is mixed with other tire polymers, and it can be advantageous as it can be used as an additive in
plastics because it has low contents of gels.
4. CHEMISTRY AND MANUFACTURING PROCESS
Polybutadiene is produced by solution polymerization, and one important feature governing
the performance of the resultant polymer is the cis-1,4 and cis-1,2 vinyl content. High cis-1,4
polymers (90%) have a Tg around -90C, hence exhibit excellent low temperature flexibility,
exceeded only by the phenyl silicones. They also exhibit excellent resilience and abrasion
resistance. Since, however, the high resilience gives poor wet grip in tire treads, this rubber
finds limited use as the sole base for such compounds.
As the 1,4 content decreases, and 1,2-vinyl content increases, the low temperature properties,
abrasion resistance, and resilience become inferior.
The polymerization of butadiene results in a polymer with a narrow molecular weight
distribution which can be difficult to process. Indeed, commercially available grades present a
compromise between processibility and performance. Most polybutadiene rubbers are
inherently difficult to break down during mixing and milling and have low inherent tack;
moreover, the inherent elasticity of the polymer gives poor extrudability. Peptizers can be used
to facilitate breakdown, hence aiding in processing.
The unsaturation present in the main chain necessitates protection against oxygen, UV light,
and ozone. Oil resistance is poor, and the polymer is not resistant to aromatic, aliphatic, and
halogenated hydrocarbons.
Polybutadiene-based compounds can be cured by sulfur, sulfur donor systems, and peroxides.
Less sulfur and higher level of accelerators are required than for natural rubber. The cure of
polybutadiene by peroxides is highly efficient in that many crosslinks are produced per free
radical. Thus, the resultant highly crosslinked rubber exhibits high resilience; this factor is
utilized in the manufacture of superballs.
Compounds based on polybutadiene give optimum properties only at high filler and oil
loadings. Most polybutadiene is used in tire applications, and most of this use is in blends with
other polymers such as natural rubber and SBR, where polybutadiene reduces heat buildup and
improves the abrasion resistance of the blend. The coefficient of friction on ice of snow tires
is also improved by using higher levels of polybutadiene in the tread blend.
When polybutadiene is used in blends for other application, the improved abrasion and low
temperature flexibility conferred on the blend offer advantage, for example, in shoes and
conveyor and transmission belts.
 5. PRODUCTION USING BATCH AND CONTINOUS PROCESSING
Polybutadiene can be prepared by several processes including bulk, solution, suspension,
emulsion, and gas-phase polymerizations. Of the commercially significant polymerization
processes, production of polybutadiene by solution technologies is predominant. Solution
polymerization processes are often used when polymerization are largely thermodynamics are
largely exothermic, as in the case of polybutadiene. The solvent not only acts as a diluent, but also
allows for efficient transfer of the heat of polymerization to a heat sink. Polybutadiene
polymerization can be carried out in aliphatic, cycloaliphatic, or aromatic solvents. Solution
polymerization systems may be either batch or continuous in operation, with the broadness of the
molecular weight distribution dependent on the configuration used. High vinyl elastomeric
materials are typically produced via anionic solution polymerization.
The polymerization of polybutadiene can be both batch process or a continuous process. In
batch method, the monomer, solvent and catalyst are introduced to the reactor. After that, they are
heated to initiate the process until the process of completion. The polymer solution is then assigned
to another vessel or process unit to eliminate the solvent.
In continuous method, the monomer, solvent, and catalyst are run continuously into the bottom
of the first series of reactor at the optimum temperature for polymerization. The polymerization
continuous as the solution runs through the reactors and polymer solution is removed at the top of
the last reactor without ending the process. The continuous method is the most preferable in the
economical aspect.
 6. PROPERTIES AND APPLICATION
Polybutadiene (PB) is the second largest synthetic rubber produced after styrene-butadiene
(SBR). It was the first types of synthetic rubber to be invented. Its properties are almost same as
the natural rubber which is polyisoprene. Due to its high resistance, PB is highly used in
manufacturer of car parts like tires, belts, hoses, and gaskets. It is also used to produce golf balls,
various elastic objects and to coat or encapsulate electronic devices.

A. TIRES

Polybutadiene has a varied function mostly in automobile tires with it dominancy almost
70% of world production of polybutadiene.
The tire is made up from tire treads which from stiff rubber known as poly(styrene-
butadiene-styrene) or SBS rubber. SBS is a copolymer that contains polybutadiene.
Diagram below show the structure of SBS:

Polybutadiene with high content of cis-1,4 structural units have the super quality of elastic
properties. Pure poly-cis-1,4-butadiene has Tg below 100 C while pure polybutadiene 1.2
is about 15C. But, low transition temperature (Tg) tends to have poor grip especially
during raining. So, polybutadiene is merged with other elastomers like natural rubber or
SBR to improve it treads properties.
Lower liquid-glass Tg give more advantages to polybutadiene compared to SBR and
natural rubber as it offers high resistance to wear and have a low rolling resistance. Thus,
the tires have more longer durability and good fuel economy (less consumption).
The major parts of tires that produced from polybutadiene is treads and sidewalls. They are
also used mostly in the sidewall of truck tires to recover exhaustion due to the continuous
flexing during run. Therefore, the tires will endure in extreme conditions. They also give
benefits in the tread portion of massive truck tires to recover the scratch.
 Others car component such as belts, hoses, and gaskets are produced from polybutadiene
because it withstands the cold temperatures better than other elastomers.

B. GOLF BALLS

About 20,000 metric tons of high cis polybutadiene is used each year in golf ball cores
due to its outstanding demands. Today innovation of golf balls consists the inner core and
a cover having at least one layer liable on the core.
The inner core includes:
i. 50% - 95% by weight of a non-metallocene catalyzed polybutadiene rubber;
ii. 5 - 50% by weight of a metallocene-catalyzed polybutadiene rubber.
The center of the inner core and outer surface of the inner core layer each has a hardness.
But, the hardness of outer surface is greater than the center hardness of the inner core.
In each embodiment, the non-metallocene catalyzed polybutadiene rubber has a Mooney
viscosity in the range of 40 to 75 and the metallocene catalyzed polybutadiene rubber has
a Mooney viscosity in the range of 30 to 130.
Non-metallocene catalysts that can be used to catalyze the polybutadiene rubber such as
catalysts selected from the group consisting of neodymium, nickel, cobalt, titanium,
aluminum, boron, and alkyl lithium-based catalysts, and combinations thereof.
In another embodiment, the golf ball comprises a dual-core having an inner core and outer
core layer; along with a cover having at least one layer disposed about the dual-core.
The inner core has an outer surface and geometric center and the outer core layer has an
outer surface and inner surface.
The center of the inner core and surface of the outer core layer each has a hardness, and the
surface hardness of the outer core layer is greater than the center hardness of the inner core.
The inner core comprises:
i. 50% - 95% by weight of a non-metallocene catalyzed polybutadiene rubber;
ii. 5% - 50% by weight of a metallocene-catalyzed polybutadiene rubber.
Preferably, the outer core layer comprises metallocene-catalyzed polybutadiene rubber
with no metallocene-catalyzed polybutadiene rubber being present in the outer core layer.
C. POLYBUTADIENE AS AN IMPACT MODIFIER IN OTHER POLYMERS

In general, polybutadiene is a poorer-processing polymer than SBR, but this is not a

problem as it is blended with other polymers in use. The very high cis polymers have the
potential for strain-induced crystallization, which can lead to improved green strength and
increased cut growth resistance in the cured product. High cis polybutadiene is reported to
have a melting point of 6C.
The other major use for polybutadiene is as an impact modifier in plastics. The quality of
the process is more important in the use in plastics than in tires, especially when it comes
to color and content of gels which must be as low as possible. In addition, the products
need to meet a list of health requirements due to its use in the food industry.
Polybutadiene 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% polybutadiene is added to the polymerization
process to make these rubber-toughened resins (see figure 1).

Figure 1. Electron micrograph of a polybutadiene modified or rubber toughened

polystyrene resin. Polybutadiene domains are shown in black.
REFERENCES
1. Yoshioka, A.; et al. (1986), "Structure and Physical Properties of High-Vinyl
Polybutadiene Rubbers and Their Blends", IUPAC
2. Arlie, Jean-Pierre (1992), Synthetic rubbers: processes and economic data, Editions
TECHNIP, p. 34, ISBN 978-2-7108-0619-6
3. "Polybutadiene, technical paper" (PDF). International Institute of Synthetic Rubber
Producers. Archived from the original (PDF) on October 1st, 2017.
4. Encyclopedia of Polymer Science and Technology, Concise by Herman F. Mark
5. Handbook of Vinyl Polymers: Radical Polymerization, Process, and Technology edited
by Munmaya Mishra, Yusuf Yagci
6. Kent and Riegel's Handbook of Industrial Chemistry and Biotechnology edited by James
A. Kent
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11. https://en.wikipedia.org/wiki/Polybutadiene