Unit-3 (CS cluster)

CF section
Polymers for Engineering Applications
Introduction:
A polymer is a large molecule, or macromolecule, composed of many repeated subunits. The term
"polymer" derived from the ancient Greek word polus, meaning "many, much “and meros, meaning
"parts, and refers to a molecule whose structure is composed of multiple repeating units, from which
originates a characteristic of high relative molecular mass and attendant properties. The term was coined
in 1833 by Jöns Jacob Berzelius. Because of their broad range of properties, both synthetic and natural
polymers play an essential and ubiquitous role in everyday life. Polymers range from familiar synthetic
plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to
biological structure and function. Polymers, both natural and synthetic, are created via polymerization
of many small molecules, known as monomers. Their consequently large molecular mass relative to
small molecule compounds produces unique physical properties, including toughness, viscoelasticity,
and a tendency to form glasses and semi crystalline structures rather than crystals.
Definition of polymers: A polymer is a large molecule of high molecular weight obtained by the
chemical interaction of many small molecules of low molecular weight of one or more type. The process
of manufacture of a polymer is called the polymerization.

Monomers: Small molecules of low molecular weight, which combine to give a polymer, are called
monomers.

Degree of polymerization: The number of monomers used in the process is called degree of
polymerization.

Functionality: The total number of functional groups or bonding sites present in a monomer molecule
is called the functionality of the monomer.

Polymerization: Is the process of conversion of low molecular weight substances into high molecular
weight substances with or without the elimination of by products such as HCl, H2O, NH3 etc.

Molecular Weight Determination

Techniques to determine Molecular Weight of polymers include Gel permeation chromatography,
osmometry, light scattering, viscometry, cryoscopy, ebulliometry, ultracentrifugation, mass
spectrometry, and end-group analysis.

Number average molecular weight (Mn¯):

The number average molecular weight is defined as the total weight of polymer divided by the total
number of molecules.
Polydispersion Index

Polydispersity index (PDI) is used as a measure of broadness of molecular weight

distribution.
The larger the PDI, the broader the molecular weight or width or spread of the particle
size distribution.
In order to have an idea about the homogeneity of a polymer, we define the term
polydispersity index or heterogeneity index. It is the ratio of mass average molecular
mass to the number average molecular mass.

For natural polymers, PDI is usually equal to one which means that they are
monodisperse. Such polymers are more homogeneous.
Synthetic polymers on the contrary generally have PDI > 1 which means that they were
less homogeneous.
4.

The weight average molecular mass of the polymer is given by

5.
Glass transition temperature (Tg)
Definition: The glass transition is the temperature at which a polymer abruptly transforms form the
glassy state (hard) to rubbery state (soft).
Factors affecting Tg:
1.Flexibility: The flexibility of the polymer chain is determined by the degree of freedom. Linear
polymers with single bonds have high degree of freedom of rotation. The presence of inherently rigid
structures in the polymer chain such as aromatics, cyclic structures or bulky groups on backbone hinder
this rotation and increase in Tg.
For example: Polyethylene, Tg = -110oC.
Polystyrene, Tg = 100oC (Presence of Benzene ring)
2.Intermolecular forces: Presence of large number of polar groups in the molecular chain lead to strong
intermolecular cohesive forces which restrict the molecular mobility. This leads to an increase in Tg.
For example: polypropylene has lower Tg compared to nylon 6,6.
3. Presence of branching and cross-linking: Increase in branching and cross-linking restrict the chain
rotation and therefore Tg increases.
For example Polyethylene (No branching and cross linking), Tg = -110oC
Bakelite (Cross linking), Tg = 97oC

4. Molecular weight: As molecular mass increases Tg also increases but Tg is not affected by
molecular masses if degree of polymerization is above 250.

5. Presence of stereo regularity of the polymer: Syndiotactic polymer has a higher Tg than atactic
stereoisomer compare to isotactic polymer.
Significance of glass transition temperature
 Tg gives us idea of the thermal expansion, heat capacity, electrical and mechanical properties of
the polymer.
 The use of any polymer at any temperature is decided by its Tg value.
 Stiffness and flexibility of the polymer can be studied with the help of Tg.
 Many polymer show an abrupt change in their properties at their glass transition temperature,
like coefficient of thermal expansion, modulus of elasticity, heat capacity, refractive index,
mechanical dampening, and electrical properties.Tg also determines usefulness of a polymer
over a temperature range.
 Tg provides an appropriate temperature range for processing operations such as moulding,
calendaring and extrusion.
Kevlar (fibre)
5 to 10 micrometers (0.00020–0.00039 in) in diameter composed mostly of carbon
atoms.
Synthesis of Polyacetylene
Poly(acetylene) is the simplest conjugated polymer and the first conducting polymer to
be synthesised.
Polyacetylene or Polyethyne having a repeating unit (C₂H₂)ₙ, is a rigid, rod-like polymer
that consists of long carbon chains with alternating single and double bonds between the
carbon atoms.
There are two types of structure of Polyacetylene that is cis- and trans-polyacetylenes.
Synthesis of polyacetylene
Polyacetylene films are synthesized using the Zeigler-Natta catalyst, The catalyst
tetrabutoxytitanium and triethylaluminum suspended in silicone oil through which
acetylene is passed, is stirred for two hours at 120° C, and then cooled slowly to room
temperature resulting in thin sheets of polyacetylene.

Example - Mixed catalyst of alkyl aluminium and titanium tetraalkoxides

Bonding in Polyacetylene
The poly unsaturated hydrocarbons consist of hydrogen atoms and sp2 hybridized carbon
atoms that share two pairs in a double bond.
This molecule is linear: all four atoms lie in a straight line. The carbon-carbon triple bond
is only 1.20Å long. In the hybrid orbital picture of acetylene, both carbons are sp-
hybridized. In an sp-hybridized carbon, the 2s orbital combines with the 2px orbital to
form two sp hybrid orbitals that are oriented at an angle of 180°with respect to each other
(eg. along the x axis). The 2py and 2pz orbitals remain unhybridized, and are oriented
perpendicularly along the y and z axes, respectively.
It is the second pair of electrons in the double bonds, which becomes delocalized. One
pair of electrons, which holds two atoms together, is denoted as the sigma-bond and
additional pairs are denoted as п-bond.
Conduction mechanism of Polyacetylene
The localized electrons in the s bond form the backbone of the polymer chain and
electrons in the pi bond are delocalized and hence responsible for electrical properties of
the conjugated polymer. Any two adjacent atoms can then share their lone electron to
form a double bond, are able to transport charges effectively within the system therefore,
the energy of such systems would be very low. The charged species transported in
conjugated double bond polymers with spin ± ½ is referred to as polaron.
Doping: In addition to alternative single and double bonds giving rise to mobile
electrons, doping enhances the conductivity of the polyacetylene.
There are two types of doping oxidative doping and reductive doping.
(i) Oxidation with halogen (p-doping)

Polyacetylene now is positively charged and termed as “radical cation” or “Polaron”.

As a consequence, double bond successively moves along the molecule.
Similarly, on second oxidation, another free radical-cation is formed which is called as
bipolaron. If the polyacetylene is heavily doped, polarons condense and form “solitons”
which become responsible for the transport of charges along the polymeric chain.
The radicals migrate towards each other and combine to form one double bond. The chain
now has two positive charges (holes). Positive charges are compensated by I-3
ions and thus the polymer is electrically neutral. As positive charges are mobile, on
applying potential they move and thus making a conductive polymer.
 OR

(ii) Reduction with alkali metal (n doping)

Here the polymer is treated with a reducing agent like sodium or lithium naphthalides.
These reducing agents supply electrons to back bone of the chain. Thus polymer
becomes n-type conductor as it conducts by free mobile electrons.
Applications
 In corrosion inhibitor and antistatic coating
 In electromagnetic shielding
 In solar cells, capacitors and LEDs
 In solution-processing for film-forming conductive polymers.
Synthesis of Poly-glycolic acid
Polyglycolide or poly glycolic acid (PGA), is a biodegradable, thermoplastic polymer
and the simplest linear, aliphatic polyester. It can be prepared starting from glycolic acid
by means of polycondensation or ring-opening polymerization. PGA has a glass
transition temperature between 35 and 40 °C and its melting point is reported to be in the
range of 225-230 °C. The polymer degrades due to hydrolysis in presence of a catalyst
such as Tin octanoate.
 Question Bank
1. Define: (a) monomer(b) polymer (c) polymerisation(d) degree of polymerisation
2. Compare addition and condensation polymerisation reactions with suitable examples.
3. Distinguish between number average and weight average molecular weights of a polymer.
4. Solve for Mn and Mw of a polymer which consists of 35% molecules having molecular mass 25000, 35%
molecules having molecular mass 20000 and the remaining molecules havingmolecular mass 10000.

5. Solve for number average and weight average molecular weights of a polymer consisting of 150
molecules with molecular mass 1000, 200 molecules with molecular mass 10000 and 350 molecules
with molecular mass 100000.
6. A polymer sample contains 2, 3 and 4 molecules having molecular weights 2 x 10 3, 3 x 103 and 4 x 103
respectively. Solve for the number average and weight average molecular weights of the polymer.
7. Solve for the number average and weight average molecular weights of two polymers of molecular
weights 10000 and 100000 when they are mixed: (a) in equal parts by weight,
8. A polymer sample has population as follows: 5 molecules of molecular mass each = 25000; 10 molecules
of molecular mass each = 5000; 20 molecules of molecular mass each = 10000; 25 molecules of
molecular mass each = 15000. Solve for its number average and weight average molecular weights.
9. Illustrate the significance of glass transition temperature.
10. Clarify the role of Tg on (a) molecular mass (b) branching & cross linking (c) stereoregularity
11. Illustrate the influence of the following on Tg (a) flexibility (b) intermolecular forces (c) branching and
cross linking (d) intermolecular forces (e) increase in molecular weight (f) addition of plasticizers (g)
stereo regularity of repeating units
12. Define: (a) glass transition temperature (Tg) (b) elastomer (c) polymer composite(d) conducting polymer
(e) Plastics
13. Illustrate the structure and property relationship in polymers based on strength, crystallinity and
chemical resistance with suitable examples
14. Distinguish between Plastics and Resins with examples.
15. Summarize the mechanism of conduction of polyacetylene with relevant structures.
16. Outline the synthesis, properties and applications of PMMA, UF resin, butyl rubber, nitrile rubber,
Kevlar, carbon fibre, and polyglycolic acid.
17. Define biodegradable polymers. Ouline the synthesis and properties of polylglycolic acid along with its
applications
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