Polybutadiene

Yasir Abbas

OUTLINE

Introduction
Synthesis
Morphological properties
Application
Limitations

INTRODUCTION
Polybutadiene was one of the first types of synthetic
elastomer, or rubber, to be invented.

Polybutadiene is a homopolymer (only one monomer)

of 1,3 butadiene.

Polybutadiene (BR) is the second largest synthetic

rubber produced, next to styrene-butadiene rubber
(SBR).

Polybutadiene rubber accounted for approx. a quarter

of total global consumption of synthetic rubbers in
2012.

GEOMETRIC ISOMERS
1,3-butadiene can be polymerized to give poly(1,2butadiene) or either of two geometric isomers of poly(1,4butadiene). These two isomers are
calledcisandtranspoly(1,4-butadiene).

SYNTHESIS
Synthetic approaches applied for butadiene
polymerization.

Anionic polymerization.
Insertion polymerization
ZieglerNatta polymerization.
Metallocene polymerization

ANIONIC POLYMERIZATION
The alkyllithium catalyst system produces a polymer with
about 40% cis, 50% trans and 10% vinyl

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 BR.

ANIONIC POLYMERIZATION

ANIONIC POLYMERIZATION
An alternative method for initiation involves a oneelectron reduction of the monomer by Li or Na to form a
radical anion which is either reduced or dimerized to a
dianion. Li +
Li +
Butadiene

A radical anion

radical coupling
to form a dimer
Li

Li
A dimer dianion

Li

Li

Li
A dianion

ANIONIC POLYMERIZATION

INSERTION POLYMERIZATION
Coordination polymerization: Monomer adds to growing
macromolecule through an organometallic active center.

ZIEGLERNATTA
POLYMERIZATION
With a ZieglerNatta catalyst, a polymer of 1,3-butadiene
can be produced, in which all the additions are 1,4 and
the remaining double bonds are all cis.

ZIEGLERNATTA
POLYMERIZATION
Ziegler natta catalysts- titanium tetrachloride+aluminium
cocatalyst.

ZIEGLERNATTA
POLYMERIZATION

METALLOCENE
Well-defined molecular structure, Single-site catalyst
(polymerization occurs at one position in the molecule, the
transition metal atom)

Formation of active site

Polymerization mechanism

COBALT-BASED CATALYST
The proposed polymerization mechanism for butadiene
polymerization with (a) traditional cobalt-based catalyst
and (b) cationic cobalt-based catalyst.

MORPHOLIGICAL PROPERTIES
The polymer withtransdouble bonds forms straight rigid
rods, which align together making the material behave a
bit like a crystal, with a sharp melting point and with
stiffer, harder properties.

MORPHOLIGICAL PROPERTIES
The polymer withcisdouble bonds causes bends in the
chain, preventing the chains aligning, resulting in a much
more amorphous material.

The morecisbonds in the polymer, the more flexible and

elastic it becomes.

MORPHOLIGICAL PROPERTIES
Vinyl polybutadienes occur when using an alkyllithium
catalyst. The dangling side groups also prevent the chains
aligning, so make the polymer more flexible.

MORPHOLIGICAL PROPERTIES
On heating or cooling most polymers undergo thermal
transitions that provide insight into their morphology. These are
defined as themelt transition, Tm, and theglass transition,
Tg.

Tmis the temperature at which crystalline domains lose their

structure, or melt. As crystallinity increases, so does T m.
Tgis the temperature below which amorphous domains lose the
structural mobility of the polymer chains and become rigid
glasses.

MORPHOLIGICAL PROPERTIES
Tg = 80C, Tm = 140C

Tg = -100C, Tm = 0C

APPLICATION
About 70% of the worlds production of over 2 million tons of
polybutadiene per year goes towards making tires.

Pure polybutadiene is too soft and elastic for most tires, which need to be
harder and more wear resistant.

The properties of butadiene can be altered by using different catalysts to

change the way it polymerizes.

The other major use for polybutadiene is as an impact modifier in

plastics, in particular high impact polystyrene (HIPS) and acrylonitrilebutadiene-styrene resin (ABS).

About 20,000 metric tons worldwide of high cis polybutadiene is used

each year in golf ball cores due to its outstanding resiliency.

LIMITATIONS
Polybutadiene has excellent low-temperature properties, high
resiliency, and good abrasion resistance due to its low glass
transition temperature. However, this same fundamental
property also leads to very poor wet skid resistance.

For this reason tire manufacturers mix the polybutadiene with

another polymer made from butadiene and styrene. So-called
styrene-butadiene-rubber (SBR) is used in 50% of car tires, with
the styrene content being used to control the hardness of the
rubber.

REFERENCES

George Odin, Principles of Polymerization, Fourth edition, a John Wiley & sons, Inc., Publication, (2004).

Monodisperse macromolecules A stepping stone to understanding industrial polymers,Richard et.al. European Polymer Journal, 47, 447
464 (2011)

Hotani, G. K., Dodge, T. C. & Arbige, M. V. Industrial Chemistry and Biotechnology. Springer, (2012).

Aminova, G. A. et al. Mechanism of Butadiene Polymerization on Cobalt-Containing Catalyst. 75, 11461150 (2002).

Korthals, B., Berkefeid, A., Ahlmann, M. & Mecking, S. Catalytic polymerization of butadiene in aqueous systems with cationic nickel(II)
complexes. Macromolecules 41, 83328338 (2008).

Shamiri, A. et al. The influence of Ziegler-Natta and metallocene catalysts on polyolefin structure, properties, and processing ability. Materials
(Basel). 7, 50695108 (2014).

Lisa, S. Baugh, Stereoselective Polymerization with Single-Site Catalysts. CRC Press, Taylor and Francis group, (2007).

http://polymerdatabase.com/polymer%20physics/Cis-Trans.html

Li Liu et.al Synthesis and butadiene polymerization behaviors of cationic cobalt-based catalyst, Journal of Saudi Chemical Society, 82-95
(2014)
http://www.chm.bris.ac.uk/motm/butadiene/butadieneh.htm
http://iisrp.com/WebPolymers/01FinalPolybutadieneVer2.pdf

THANK YOU