AL-FARABI UNIVERSITY

COLLEGE
Oil and Gas Refining Engineering
Department

Polybutadiene

Report done by

Huthyfa Ahmed Shakir

Supervisor
Assist. Lecturer Hamza A Lafta
Introduction
Polybutadiene rubber is a polymer formed from the polymerization of the monomer
1,3-butadiene. Polybutadiene has a high resistance to wear and is used especially in
the manufacture of tires, which consumes about 70% of the production. Another
25% is used as an additive to improve the toughness (impact resistance) of plastics
such as polystyrene and acrylonitrile butadiene styrene (ABS). Polybutadiene rubber
accounted for about a quarter of total global consumption of synthetic rubbers in
2012 [1]. It is also used to manufacture golf balls, various elastic objects and to coat
or encapsulate electronic assemblies, offering high electrical resistivity [2].
Polybutadiene was first prepared in the early years of the 20th century by such
methods as sodium-catalysed polymerisation of butadiene. However, the polymers
produced by these methods and also by the later free-radical emulsion
polymerisation techniques did not possess the properties which made them desirable
rubbers. With the development of the Ziegler–Natta catalyst systems in the 1950s, it
was possible to produce polymers with a controlled stereo regularity, some of which
had useful properties as elastomers.
Polymers containing 90–98% of a cis-1,4-structure can be produced using Ziegler–
Natta catalyst systems based on titanium, cobalt or nickel compounds in conjunction
with reducing agents such as aluminum alkyls or alkyl halides. Useful rubbers may
also be obtained by using lithium alkyl catalysts but in which the cis content is as
low as 44% [3].
Stricture

The structure of cis-1,4-polybutadiene is very similar to that of the natural rubber

molecule. Both materials are unsaturated hydrocarbons but, whereas with the natural
rubber molecule, the double bond is activated by the presence of a methyl group, the
polybutadiene molecule, which contains no such group, is generally somewhat less
reactive. Furthermore, since the methyl side group tends to stiffen the polymer chain,
the glass transition temperature of polybutadiene is consequently less than that of
natural rubber molecules [3].

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 (C 4H6). The four carbon
atoms are in a straight chain containing two “double bonds” as follows:

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 until
something is added to terminate the reaction at the desired molecular weight [4].

Molecular Weight of Polybutadiene

Molecular weight can become quite high. For a typical polybutadiene, molecular
weight (Mn = number average) is usually >100,000 grams per mole. This represents
a chain that contains over 2,000 butadiene units [4].

Process for producing polybutadiene rubber

A process for producing a polybutadiene rubber having a cis-1,4 content of 94% or
more. A ratio of weight average molecular weight to number average molecular
weight of 2.5 to 3.5 as measured by a gel permeation chromatography, and a Mooney
viscosity (ML1+4, 100° C.) of 20 to 100, which process comprises polymerizing 1,3-
butadiene in an inert organic solvent with a catalyst comprising as the main
components (a) a nickel compound; (b) a specific fluorine compound; (c) a
trialkylaluminum, and (d) a halogenated aldehyde and/or a quinone compound. The
use of the specific catalyst enables the production in a high yield of a polybutadiene
rubber which maintains the abrasion resistance, high impact resilience and low heat
buildup which are the characteristics of polybutadiene rubber and has a small die
swell when extruded in the form of a blend with a natural rubber and is excellent in
physical properties of vulcanizate [5].

PROCESS FLOW DIAGRAMS AND MATERIAL BALANCES

This process is divided into four sections as stated below: Section 100: Metathesis
Section 200: Distillation Section 300: Oxidative Dehydrogenation Section 400:
Extractive Distillation Each section is explained in the following pages using stream
tables and process diagrams. A

Depiction of Overall process

: Diagram of Metathesis Process
Types

High cis polybutadiene

This type is characterized by a high proportion of cis (typically over 92%) and a
small proportion of vinyl (less than 4%). It is manufactured using Ziegler–Natta
catalysts based on transition metals. Depending on the metal used, the properties
vary slightly.
Using cobalt gives branched molecules, resulting in a low viscosity material that is
easy to use, but its mechanical strength is relatively low. Neodymium gives the most
linear structure (and therefore higher mechanical strength) and a higher percentage
of 98% cis. Other less-used catalysts include nickel and titanium.
Low cis polybutadiene
Using an alkyllithium (e.g. butyllithium) as the catalyst produces a polybutadiene
called "low cis" which typically contains 36% cis, 59% trans and 10% vinyl.
Despite its high liquid-glass transition, low cis polybutadiene is used in tire
manufacturing and is blended with other tire polymers, also it can be advantageously
used as an additive in plastics due to its low contents of gels [7]
High vinyl polybutadiene
In 1980, researchers from the Japanese company Zeon discovered that high-vinyl
polybutadiene (over 70%), despite having a high liquid-glass transition, could be
advantageously used in combination with high cis in tires. This material is produced
with an alkyllithium catalyst [8] and there are many other types.
Uses
The annual production of polybutadiene is 2.1 million tons (2000). This makes it the
second most produced synthetic rubber by volume, behind styrene-butadiene rubber
(SBR).
Tires
Racing tire
Polybutadiene is largely used in various parts of automobile tires; the manufacture
of tires consumes about 70% of the world production of polybutadiene, with a
majority of it being high cis. The polybutadiene is used primarily in the sidewall of
truck tires, this helps to improve fatigue to failure life due to the continuous flexing
during run. As a result, tires will not blow out in extreme service conditions. It is
also used in the tread portion of giant truck tires to improve the abrasion, i.e. less
wearing, and to run the tire comparatively cool, since the internal heat comes out
quickly. Both parts are formed by extrusion.
Its main competitors in this application are styrene-butadiene rubber (SBR) and
natural rubber. Polybutadiene has the advantage compared to SBR in its lower
liquid-glass transition temperature, which gives it a high resistance to wear and a
low rolling resistance. This gives the tires a long life and low fuel consumption.
However, the lower transition temperature also lowers the friction on wet surfaces,
which is why polybutadiene almost always is used in combination with any of the
other two elastomers. About 1 kg of polybutadiene is used per tire in automobiles,
and 3.3 kg in utility vehicles.
Plastics
About 25% of the produced polybutadiene is used to improve the mechanical
properties of plastics, in particular of high-impact polystyrene (HIPS) and to a lesser
extent acrylonitrile butadiene styrene (ABS). The addition of between 4 and 12%
polybutadiene to polystyrene transforms it from a fragile and delicate material to a
ductile and resistant one.
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 have to 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.
Golf balls
A cross section of a golf ball; its core consists of polybutadiene
Most golf balls are made of an elastic core of polybutadiene surrounded by a layer
of a harder material. Polybutadiene is preferred to other elastomers due to its high
resilience [9]
The core of the balls are formed by compression molding with chemical reactions.
First, polybutadiene is mixed with additives, then extruded, pressed using a calendar
and cut into pieces which are placed in a mold. The mold is subjected to high
pressure and high temperature for about 30 minutes, enough time to vulcanize the
material.
The golf ball production consumes about 20,000 tones of polybutadiene per year
(1999).

Conclusion
Polybutadiene is and will continue to be a high volume rubber for use in tyres,
toughened plastics, and golf balls due to its low cost, availability and unique
properties. As new markets develop, there will be a need to develop new, higher
performance grades of polybutadiene using both the alkyllithium and Ziegler
systems.
References

1. "Market Study Synthetic Rubber". Ceresana. June 2013. Archived from the
original on 2015-03-18.
2. Heinz-Dieter Brandt, Wolfgang Nentwig, Nicola Rooney, Ronald T. LaFlair,
Ute U. Wolf, John Duffy, Judit E. Puskas, Gabor Kaszas, Mark Drewitt and
Stephan Glander in "Rubber, 5. Solution Rubbers" Ullmann's Encyclopedia
of Industrial Chemistry, 2011, Wiley-VCH, Weinheim.
doi:10.1002/14356007.o23_o02
3. Aliphatic Polyolefins other than Polyethylene, and Diene Rubbers J.A.
Brydson, in Plastics Materials (Seventh Edition), 1999.
4. AZoMOct 23 2002.Polybutadiene - Properties, Applications, Processing and
Types of Polybutadiene (BR).
5. Process for producing polybutadiene rubber United States Patent 5686543
6. ChemSystems (2004). New York: Nexant (ed.). Styrene Butadiene Rubber /
Butadiene Rubber.
7. "Polybutadiene, technical paper" (PDF). International Institute of Synthetic
Rubber Producers. Archived from the original (PDF) on December 9, 2006.
8. ^ Yoshioka, A.; et al. (1986), "Structure and Physical Properties of High-
Vinyl Polybutadiene Rubbers and Their Blends", IUPAC
9. Ube website Archived 2005-12-15 at the Wayback Machine (page retrieved
28 April 2006)