Engineering Chemistry MODULE-4
CHES102/202 Polymers
Mahendra kumar H S
Assistant professor,
Dept. of Chemistry,
ATMECE, Mysuru
<Chemistry>
<Chemistry> Dr. Kiran Kumar P<Mahendra Kumar<Mahendra
H S> Kumar H S>
• Polymers are macromolecules, formed by the combination of many
smaller repeating molecules. These smaller molecules are termed as
monomers.
• The word "polymer" is derived from Greek language poly means many,
meros means part. "Deoxyribonucleic acid (DNA), ribonucleic acid (RNA)
and proteins are macromolecules and are essential forms of life and hence
polymers are linked to life.
• Cellulose, lignin, starch and natural rubber are other examples of natural
polymers. Polypropylene, PVC, Polyester, PTFE, Polyethylene are the well-
known synthetic polymers.
• They find applications in every possible field of human activity from personal
care products like clothing, shoes to electrical and electronic appliances,
packaging, utensils, automobile parts, coatings, paints, adhesives, tyres and so
on. Hence the synthetic polymers are more important to modern society in
terms of their utility and the economic value that they signify.
<Chemistry> <Mahendra Kumar H S>
• The first synthetic organic polymer
polyvinylchloride was synthesized in 1838 by
accidentally. Later, polystyrene was discovered in
1839.
• The process of linking the repeating molecules is
called polymerisation
• If a polymer is made of one type of monomer, it is
called homopolymer. Ex- Polyethylene.
• If the polymer is made of different types of
monomers, it is called copolymer, Ex- Phenol
formaldehyde resin.
• Number of times the monomer unit is repeated in a
polymer is called degree of polymerisation. Higher
the degree of polymerisation, higher will be the
molecular mass.
<Chemistry> <Mahendra Kumar H S>
Molecular weights of Polymers
The substances like water, ammonia, benzene, etc., are monodispersed in nature i.e., their molecules
have same size whereas polymers contain molecules of different size depending on their chain length.
Therefore, polymers supposed to have average molecular mass. The average molecular mass can be
calculated in two ways:
1. Number Average Molecular Weight/Molar mass (Mn)
2. Weight Average Molecular Weight/ Molar mass (Mw)
<Chemistry> <Mahendra Kumar H S>
1. Number Average Molecular weight [Mn]:
The number average molecular weight is the total weight of the sample divided by the total number of molecules in sample.
• n1, n2, n3, - Number of different molecules present in the polymer sample
• M1, M2, M3, - Mass of different molecules present in the polymer sample
The above equation may also be written as,
• ni, = number of monomer molecules
• Mi = masses of simple monomer molecules.
<Chemistry>
<Chemistry> Dr. Kiran Kumar P<Mahendra Kumar<Mahendra
H S> Kumar H S>
2. Weight Average Molecular weight [Mn]:
The sum of the products of each molecule's mass divided by the total sum of all molecular masses
• n1, n2, n3, denotes the number of molecules having masses M1, M2, M3…,
Then m1= n1M1, m2 = n2M2, m3 = n3M3……
• The above equation may also be written as,
<Chemistry>
<Chemistry> Dr. Kiran Kumar P<Mahendra Kumar<Mahendra
H S> Kumar H S>
Conducting Polymers
Introduction:
Conducting polymers are organic polymers that conduct electricity.
In polymer, electrons are localized and do not take part in conduction and there is a wide
energy gap between valence band and conduction band. This makes polymer exhibit poor
conductivity. But doping can delocalize the electrons responsible for conduction. The
polymer with conjugated backbone consisting of alternative double and single carbon-carbon
bonds, can be converted into a conductor by doping it with either an electron acceptor such as
I2, FeCl3 (oxidative dopant) or an electron donor such as sodium naphthalide (reductive
Examples:
dopant). Polyacetylene, Polypyrrole, Polyaniline, etc
<Chemistry> <Mahendra Kumar H S>
i) Oxidative dopant takes away electrons from the π-backbone of polymer
and creates holes in the chain, resulting in the increase of conductivity of
polymer.
ii) Reductive dopant donates electrons to π-backbone of the polymer. These
electrons are free to move along c-chain, resulting in the increase of
conductivity of polymer.
<Chemistry> <Mahendra Kumar H S>
Conducting polymers – synthesis and conducting mechanism of polyacetylene.
In 1977, Hideki Shirakawa, Alan J. Heeger, and Alan G. MacDiarmid discovered doped
polymer polyacetylene.
Polyacetylene is one of the polymers in the study that resulted in the Chemistry Nobel
Prize in 2000.
Synthesis: Several methods have been developed to synthesize polyacetylene from pure
acetylene and other monomers. One of the most common methods uses Ziegler-Natta
catalyst, such as TiCl4/Al(C2H5)3, with gaseous acetylene. Acetylene undergoes
polymerization in the presence of Ziegler-Natta catalyst to give polyacetylene.
<Chemistry> <Mahendra Kumar H S>
• Polymers are doped with Oxidative dopant Ex:
I2/[Link] partial oxidation in the
polymer takes place results in which
dopant accepts one electron, and the
polymer forms a radical cation(Hole)
called polaron.
• Another dopant accepts one more electron
creating one more positive charge called
bipolaron.
• As dopants are inserted in the polymer, the
chains of polymers contain charges. The
delocalisation or movement of positive
charge causes electrical conduction i.e.,
Soliton, when a potential is applied, gives
rise to the conductivity of the material.
<Chemistry> <Mahendra Kumar H S>
The conductivity of polyacetylene is 4.4 X 10 -3 S/cm. But the doped polyacetylene shows the conductivity of 4 X 10 4 S/cm
<Chemistry> <Mahendra Kumar H S>
Applications of polyacetylene
• Doped polyacetylene offers a particularly high electrical
conductivity therefore it can be used in electric wiring or electrode
material in lightweight rechargeable batteries.
• Used as a sensor to measure glucose concentration.
• Used in biosensors, and even as a component in light-emitting
diodes (LEDs) and solar cells
<Chemistry> <Mahendra Kumar H S>
GRAPHENE
• Graphene is an allotrope of carbon consisting of a single layer of atoms arranged in a honeycomb planar nanostructure
• The name "graphene" is derived from "graphite" and the suffix "-ene", indicating the presence of double bonds within the
carbon structure
• Each carbon atom is covalently bonded (sp2 hybridized) to three other carbon atoms in a hexagonal array, leaving one free
electron per each carbon atom
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<Chemistry> <Mahendra
<Mahendra Kumar H S> Kumar H S>
Introduction to Graphene
• Andre Geim and Kostya Novoselov discovered graphene in 2004.
• The first 2-Dimensional material ever discovered.
• Found in graphite, coal. Graphene is also found in meteorites.
• Hard to manufacture in large quantities, just about all graphene produced is
used for R&D within companies and universities.
• The strongest, lightest, and most conductive material known to man.
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<Chemistry> <Mahendra
<Mahendra Kumar H S> Kumar H S>
Properties of Graphene oxide
• Strength: It is 100-300 times stronger than steel.
• Conductivity: It has high thermal conductivity.
• Transparency: It is optically transparent.
• Dispersibility: It can disperse in water, organic solvents, and different
matrices.
• Surface area: It has a large surface area.
• Chemical stability: It is chemically stable.
• Weight: It is remarkably lightweight.
<Chemistry> <Mahendra Kumar H S>
Synthesis
• They are generally prepared by Hummer's method.
• Hummers process
• The method is named after its developers, Hummers and
Offeman, who created it in 1958. Strong oxidizing agent
KMnO4 and acids like H2SO4 and HNO3 are used to convert
graphite to Graphene Oxide(GO).
<Chemistry> <Mahendra Kumar H S>
• Take 2g graphene and 2g of NaNO3 (catalyst) in 50 ml of H2SO4 in 1000 ml
beaker kept in an ice bath (0-5 °C) with continuous stirring for 2 hours.
• Then add 6g KMnO4 (oxidizing agent) very slowly at temperature kept below 15
°C.
• After some time, remove the ice bath and allow the mixture for stirring at 35 °C for
3 hours.
• Then dilute it with slow addition of 200 ml of water.
• Finally, treat the solution with 10 ml H2O2 to terminate the reaction and filter. Wash
with HCl and water.
• After filtration, dry it in vacuum at room temperature to get powdered graphene
oxide.
• Essentially
<Chemistry> creating single-layer graphene<Mahendra
oxide flakes.
Kumar H S>
<Chemistry> <Mahendra Kumar H S>
<Chemistry> <Mahendra Kumar H S>
Applications of Graphene oxide
► Graphene oxide can be used in coating technology.
► Graphene oxide papers can be used in desalination technique to get pure water from saline water.
► GO can be used in the biomedical fields such as drug delivery, cancer therapy and biosensor because of its
biocompatibility nature.
► Nanocomposite of GO and silver (Ag) ions used for bacteria detection.
► GO can be as a bio-imaging tool for cancer cells.
► Reduced GO that can be produced from GO is used as a transparent electrode in polymer, solar cells and LED.
► Reduced GO can be used as energy storage material in supercapacitors and in a lithiumion batteries.
► Graphene Oxide-gold nanocomposites are good absorbents used for the removal of industrial dyes and
aromatic pollutants from aqueous atmosphere.
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<Chemistry> <Mahendra
<Mahendra Kumar H S> Kumar H S>
Kevlar fiber
Kevlar, a high-strength, lightweight synthetic fiber and it is produced with a reaction of 1,4-phenylene-diamine (para-
phenylenediamine) and terephthaloyl chloride in a condensation reaction yielding hydrochloric acid as a by-product and
Kevlar
<Chemistry> <Mahendra Kumar H S>
<Chemistry> <Mahendra Kumar H S>
<Chemistry> <Mahendra Kumar H S>
Mahendra Kumar H S
Assistant professor,
THANK YOU Dept. of Chemistry,
ATMECE, Mysuru
<Chemistry> <Mahendra Kumar H S>