Department of Chemistry
Engineering Chemistry
Module-3 Engineering Materials
Polymers:
Introduction:The word polymer is derived from two Greek words: Poly means many, meros
means units. Polymers have become the integral part of our day-to-day life; it may be tooth
brush, a wrapper on an ice cream candy, an artificial heart valve, contact lens etc. To put in one
sentence – it is a plastic age. Polymers are extremely large molecules that are essential to our
daily life. They are a main constituent of our food. Ex: starch, protein, etc. our clothes
polyester, nylons, etc., and our body made up of nucleic acids, proteins
Basic definitions;
Polymer;
A polymer is a large molecule formed by the repeated covalent linkage of small units
called monomers.
Ex: Starch, Polyvinyl chloride, Polyethylene, Nylon 6, 6 and etc.
Monomer;
Monomer is defined as a simple molecule or single unit representing in a polymer with two or
more binding sites either unsaturation or having two or more than two functional groups
through which it forms covalent linkages with other monomeric units to form the
macromolecule.
Polymerization: Polymerization is the process of formation of a polymer by the repeated
covalent linkage of monomeric units.
Classification of polymers.
Polymers are classified into two types as follows:
i) Natural Polymers.
ii) Synthetic (artificial) polymers.
i) Natural polymers: These are the polymers obtained naturally by plants and animals.
Ex: Silk, wool, natural rubber, protein, starch, cellulose, etc.
ii) Synthetic Polymers: These are artificially prepared polymers also known as
manmade polymers.
Ex: PVC, Nylon 6.6, Polythene, Phenol, Formaldehyde, Resin etc.,
Homo Polymers: If all the monomeric units are same in a polymer called Homo Polymer
Ex:Poly Ethylene
Hetero Polymer :If the Monomeric units are different in a polymer chain called hetero
polymer Ex: Nylon 6,6
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Polymerization : it is classified into two types as follows.
i) Addition Polymerization
ii) Condensation Polymerization
i) Addition Polymerization: It is process in which the monomers undergo simple
addition reactions to give raise to a polymer without eliminating by products. Alkenes and
substituted alkenes readily undergo addition polymerization reactions.
Ex: When large number of ethene molecules undergoes addition polymerization reactions,
polyethylene polymer is obtained.
n CH2=CH2 → (CH2-CH2) n
ii) Condensation Polymerization:- It is a process in which the monomers undergoes
intermolecular condensation reactions to form a polymer with the elimination of simple
molecules like water, HCl, ammonia, phenol etc.
Ex: When adepic acid and hexamethylene diamine undergoes condensation polymerization
reaction forms Nylon 6,6 polymer.
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n. NH2–(CH2)6-NH2 + n. HOOC–(CH2)4–COOH →
Hexa methylene di amine Adipic acid
(NH – (CH2)6- NH -OC – (CH2)4 – CO-)n + n H2O
Nylon 6,6
Synthesis ,Properties and applications of Polyurethane:
Polyurethanes are important and most versatile family of polymers. Characterized by Urethane
linkage HN-C=o-O in their polymer chain. They have linear structure and formed by addition
polymerization.
SYNTHESIS: Prepared by Poly addition Polymerization of disocyanate and diol or triol.
Mechanism: During addition the H atom of OH group migrates to and adds to nitrogen atom
without elimination of any biproducts .Polyurethanes (-N−𝐻-C=o-O ) linkage resembles Amide
(-N-H-C=O ) but the presence of extra oxygen atom in urethane linkage offers flexibility to the
chain and lowers melting point.
Applications:
i.)Used in Elastomers: Because of their resistance to oil & grease & corrosive chemicals,
used for tyre heads & in industrial wheels.
ii.) Coatings: Used for floor coating for gymnasium and dance floors because of high
abrasion resistance required.
iii.) Used as foams: Used for cushions of furniture & automobiles.
iv.) Fibres: Polyurethane fibre used for light wight swimming suits and garments because
of stretching property.
Polymer Composite- Introduction, Synthesis, Properties & applications of
Kevlar Fibre
INTRODUCTION: Composites are materials composed of at least two distinct dissimilar
materials having different physical and chemical properties. But the properties of the composite
system are different with respect to the materials combined.
In one of the component used is polymer in the composite called polymer composite Ex. Kelvar
Fibre( Fibre reinforced polymer resin matrix)
The addition of polymer to the composite provides unique properties to the materials like
• Have higher strength per unit weight
• Light weight
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• Resistance to corrosion
• Low cost of fabrication
• Low coefficient of thermal expansion
• High chemical inertness.
Synthesis of Kevlar fibre: prepared by condensation polymerization para-phenylenediamine
and terephthaloyl chloride or Tere Phathallic acid
Properties of Kevlar
1. High tensile strength at low weight
2. Low elongation to break
3. High modulus of elasticity (structural rigidity)
[Link] electrical conductivity.
5. High chemical resistance
6. Low thermal shrinkage
7. High toughness (work-to-break)
8. Excellent dimensional stability
9. High cut resistance
10. Have Flame resistant.
Application: has many application
1. Used from Bicycle tyres to racing cars and to bullet proof vests because high tensile
strength to weight ratio.
2. Can also be used to replace heavier materials in aeroplanes for fuel saving.
3. Can withstand heavy load without plastic deformation.
4. Modern racing cars containing Kevlar reinforced fuel tanks used,.( high tensile strength
of Kevlar makes the fuel tank difficult to break even in case of accident.)
5. Used in aircraft structural parts.
Conducting Polymers:
Organic polymers are normally used in electrical and electronic applications as insulators.
However these are one class of polymers showing unique unusual electric and electronic
properties such polymers are called conducting polymers.
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Factors influencing conductivity of organic polymers:
These polymers will have
i. Linear structure
ii. Extensive conjugation in polymeric backbone(pi-back bone)
such polymers showing the property of conductivity on doping with an oxidizing or reducing
agent or protonic acid doping
Definition: an organic polymer with highly delocalised pi-electron system having electrical
conductance of the order of a conductor is called conducting polymer.
Conducting polymers are promising materials for various applications because of flexibility,
stability, ease of fabrications and ease of processability, low cost.
Conducting polymers are better than conventional conducting inorganic polymers.
Synthesis: Prepared by Oxidation of aniline hydrochloride with ammonium peroxy disulphate
yields polyaniline.
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Mechanism of conduction : The Congugated polymers in their pure state are insulators or
semi [Link] pi electrons are normally localized and do not take part in conductivity
.But,these electrons delocalize on doping and conduct electricity. The dopant may be Oxidiging
agent or reducing agent or protonic acid
Protonic acid doping
Step 1: Polyaniline is partially oxidized in presence of 𝑁𝐻4 𝑆2 𝑂8a suitable oxidizing agent, into
a base form of aniline which contains alternating reduced and oxidized forms of polyaniline (
base form of Aniline has imine nitrogen ) .
Step 2: This base form of aniline when treated with aqueous HCl (1M), undergoes protonation
of imine nitrogen atom, creating current carrying charged sites (+ve) in the polymer back bone.
Step 3: These charges are compensated by the anions (Cl) of the doping agent, giving the
corresponding salt
Reactions of protonic acid doping in polyaniline.
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Biodegradable polymers:
These are the polymers which get decomposed under aerobic or anaerobic condition as a result
of the action of microorganisms/enzymes into natural by-products such as 𝐶𝑂2 ,𝑁2 , 𝐻2 𝑂,
biomass and inorganic salts.
Classification of Biodegradable Polymers: can be broadly classified as
1. Natural biodegradable polymers.
2. Synthetic biodegradable polymers.
Natural Biodegradable Polymers:
Natural biodegradable polymers are produced in nature by all living organisms.
Polysaccharides such as starch is the most prevalent natural biodegradable polymers in
commercial use. Aliphatic polyesters has poly hydroxyl alkanoates (PHA) are also a family of
easily biodegradable polymers found in nature .
In these polymers, the biodegradation reactions are typically enzyme-catalyzed and occur in
aqueous media. Natural macromolecules containing hydrolyzable linkages, such as protein,
cellulose and starch, are, generally susceptible to biodegradation by the hydrolytic enzymes of
microorganisms. Thus the hydrophilic/hydrophobic character of polymers greatly affects their
biodegradability. It also has a great impact on their performance and durability in humid
conditions.
Synthetic Biodegradable Polymers:
While natural polymers are produced by living organisms, synthetic biodegradable polymers
are produced by mankind. The major category of synthetic biodegradable polymers consists of
aliphatic polyesters with a hydrolyzable linkage along the polymer chain such as polylactic acid
(PLA). Other widely available synthetic types include aliphatic/aromatic co-polyesters. The
biodegradation reactions of synthetic biodegradable polymers is same as that of natural
polymers. These are enzyme catalyzed proceed in aqueous media. Over the last 30 years or so,
many attempts have been made to improve the biodegradability of synthetic polymers by
incorporating polysaccharide-derived materials.
Properties of biodegradable polymers/ requirements:
1. Biodegradable polymers are hydrophilic
2. Non toxic
3. Have extremely strong carbon backbone that are difficult to crack but degradation
usually begins at the end groups.
4. Degradation rate can be controlled.
5. Can retain good mechanical integrity.
Advantages of biodegradable polymers:
1. Easy to recycle polymers.
2. Amount of waste generated can be reduced.
3. Reduced carbon emission.
4. Green house gas emission can be reduced.
5. Reduced use of petroleum.
6. Needs less energy during their manufacture.
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Synthesis, properties and applications of polylactic acid:
PLA is a biodegradable thermoplastic aliphatic polyester derived from renewable resources
such as corn starch or sugar canes. Lactic acid is produced by bacterial fermentation of
sugarcane or from the conversion of starch from corn. The lactic acid is oligomerized and then
catalytically distracted to make the lactide monomer. High molecular weight PLA is produced
from the lactide monomer by ring opening polymerization using a stannous octoate catalyst.
Condensation of lactic acid in to dimeric lactide followed by ring opening polymerization
to form polylactic acid
Properties:
1. Polylactic acid PLA is a thermoplastic polymer.
2. It is biodegradable.
3. Environmental friendly.
4. Non toxic.
Applications:
1. Used as feed stock material in desktop fused filament fabrication 3D printers.
2. Used to carry anti-cancer drugs – encapsulating the therapeutic drugs in a polymer and
adding targeting agents decreases the toxicity of the drug to healthy cells.
3. Used for production of plastic films, plastic bottles, and medical devices ( Bio
degradable in nature).
4. Has lot of industrial application.
