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Unit V Functional materials and Green chemistry

FUNCTIONAL MATERIALS
CONTENTS
• Polymers: Introduction and classification

• Definition of Glass transition temperature, Structure - property relationship,

• Commercial Polymers: Synthesis, properties and applications of Butyl rubber,

biodegradable polymers, and epoxy resin,

• Polymer Composites: Synthesis, properties and applications of Kevlar and

Carbon fibres.

• Conducting polymers-examples, types of doping, applications of conducting

polymers.

• Number average molecular weight; Weight average molecular weight; Viscosity

average molecular weight

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A polymer is a large molecule or a macromolecule which essentially is a combination

of many monomeric units.

• Monomer: A simple molecule, having two or more binding sites, which can be
linked together to form a giant molecule.

• Polymerization: The process by which monomers of low molecular weight are

converted to polymers of high molecular weight.

• Functionality: The total number of functional groups or bonding sites present in

a monomer.

• Degree of polymerization (DP): The total number of repeat units in a polymer

chain. It can be used to determine length of the polymer chain and molecular
weight of the polymer.

CLASSIFICATION OF POLYMERS
Polymers cannot be classified under one category because of their complex
structures, different behaviours, and vast applications. We can, therefore, classify
polymers based on the following considerations.
1. Based on the Origin
Natural Polymers:
They occur naturally and are found in plants and animals. For example- proteins,
starch, cellulose, and natural rubber.
Synthetic Polymers:
These are man-made polymers. For example- nylon-6, 6, polyester etc.
Semi-synthetic polymers:
These polymers are mostly derived from naturally occurring polymers by chemical
modifications. Cellulose derivatives as cellulose acetate (rayon) and cellulose nitrate,
etc. are the usual examples of this category.
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2. Types of polymerization reaction

Addition Polymerization:
These are polymers formed by the addition together of the molecules of the
monomers to form a large molecule without elimination of anything. The process of
the formation of addition polymers is called addition polymerization.
For example- Polymerization of ethene in the presence of Peroxides, PVC,
Polypropylene

Types of addition polymers:

Homomer: In this type, a single type of monomer unit is present. For example,
Polyethene

Heteropolymer or co-polymer: It consists of different type of monomer units. For

example, nylon –6, 6, phenol- formaldehyde resin etc.

Condensation Polymerization:
Condensation polymers are formed by the combination of monomers with the
elimination of simple molecules such as water or alcohol. This process is called

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condensation polymerisation. Proteins, starch, cellulose etc. are the example of

natural condensation polymers
For example - Preparation of nylon -6, 6, polyester etc.

Addition Polymerization Condensation Polymerization

It takes place only in monomers having It takes place in monomers having
multiple bonds. reactive functional groups
It takes place without elimination of It takes place with elimination of simple
simple molecule. molecule like H2O, NH3, HCl
It is also known as chain growth It is also known as step growth
polymerization polymerization
Molecular weight of polymer is an Molecular weight is not integral multiple
integral multiple of the molecular of that of the monomer.
weight of the monomer.

Linear or branched polymers are formed Linear, branched or cross-linked

polymers are formed
A thermoplastic polymer is formed. A thermoplastic or thermosetting
polymer is formed.
Initiators are required Catalyst is required.

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3. Classification of Polymers based on the arrangement of polymeric chain:

Linear Polymers:
The structure of polymers containing long and straight chains fall into this category.
PVC, i.e. poly-vinyl chloride is largely used for making pipes and electric cables are an
example of a linear polymer.
Branched-chain Polymers:
When linear chains of a polymer forms branches, then, such polymers are categorized
as branched chain polymers. For example, Low-density polythene.
Cross-linked Polymers:
They are composed of mostly trifunctional monomers. Cross linked polymers have
three-dimensional network of polymers. They have a stronger covalent bond existing
between the polymeric chains. Bakelite and melamine are examples.

4. Classification of Polymers based on Stereoregularity of Polymer:

The special orientation of groups in a polymer molecule can be in an order (or)
disorder with respect to main chain and this is known as Tacticity. The three types of
stereo - regular polymers are
Isotactic polymer: If the side groups attached to the polymeric chain are arranged on
the same side of the main chain, the polymer is called Isotactic polymer.
Syndiotactic polymer: If the side groups attached to the polymeric chain are arranged
in an alternating fashion along the main chain, the polymer is called Syndiotactic
polymer.

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Atactic polymer: If the side groups are arranged randomly to the polymeric chain, the
polymer is called atactic polymer.

5. Classification of Polymers based on response to heating:

Thermoplastic - A thermo plastic polymer is one which softens on heating and
becomes hard on cooling. They can remoulded into new shapes. Polyethylene,
polypropylene, polystyrene is the example of thermoplastics.
Thermosetting - A thermo setting polymer becomes hard on heating. They cannot be
remoulded, their structure instead undergoes a total degradation on heating.
Bakelite, Aniline aldehyde resin, urea formaldehyde polymer.

6. Classification of Polymers based on molecular forces:

Elastomers:
These are the polymers having very weak intermolecular forces of attraction between
polymer chains. Elastomers possess elastic character. For example, Neoprene, Buna-S,
Buna-N etc.

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Fibres:
These are solids having thread like structure possessing strong intermolecular force.
Due to this strong force of attraction, they have high tensile strength. For example,
Nylon - 6, 6 is obtained by condensation polymerisation of hexamethylene diamine
and adipic acid. Nylon-6, 10 is obtained by condensation polymerisation of
hexamethylene diamine (6C) and sebasic acid (10C).
STRUCTURE PROPERTY RELATIONSHIP OF POLYMERS
Polymers are extremely versatile when it comes to their properties. Some are hard
while others are soft and flexible. Some are insoluble and resistant to heat while a few
others are soluble and fusible. The important properties of polymers that are
influenced by their structure are-
• Crystallinity
• Tensile strength
• Elasticity
• Chemical resistance
• Plastic deformation
CRYSTALLINITY
The degree of cystallinity of a polymer depends on its structure. Polymers contain
both crystalline and amorphous regions. Crystalline regions occur when linear
polymer chains without branching and carrying no bulky groups, are orderly arranged
parallel and close to each other. A close packing between polymeric chains because of
strong secondary forces like hydrogen bonding imparts a high degree of crystallinity.
Therefore, the polymers containing polar groups are more crystalline.
Crystallinity also depends on the stereoregularity of the polymer

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Isotactic polymers are found to be most crystalline while atactic are found to be least
crystalline.
High crystallinity leads to sharper melting point, higher density, greater rigidity,
strength, and density.
TENSILE STRENGTH

Tensile strength is one of the most useful properties of polymers of commercially

useful polymers. It directly depends on the molecular weight of the polymer. By
increasing molecular mass, the tensile strength increases to a certain extent and then
becomes constant. Melt viscosity initially shows gradual increase then increases
steeply with high molecular weight. Cross linking in a polymer also increases its
molecular weight.

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ELASTICITY OF POLYMERS
The property of a polymer by which it deforms on applying force and regains original
shape on release of force is called elasticity. Elastomers have long coiled and
entangled chains which straighten and orient themselves on stretching. When stress is
removed, they go back to coiled form.
Presence of polar groups in the polymer chain results in strong secondary force of
attraction between the chains making them stiff and inflexible. Nonpolar groups have
weak van der Waal’s attraction between them and hence they are more elastic.
Presence of bulky, aromatic, and cyclic groups in the polymer decreases the elasticity
of the polymer.
Introducing cross linking at suitable molecular positions like in vulcanisation helps in
improving the elasticity of rubber.
Using plasticizers, for example (Ph3PO4), which penetrates between the polymer
chains and make a polymer more flexible.
CHEMICAL RESISTANCE OF POLYMERS
Resistance to swell, dissolve and get degraded in the presence of a solvent or
chemical. Chemical resistance of a polymer depends on the chemical nature of
monomeric units and their molecular arrangement.
Presence of polar and non-polar groups: Like dissolves like - A polymer is more soluble
in a solvent of similar chemical structure. Polymers having polar groups (–OH or –
COOH groups) are usually attacked or dissolved by polar liquids such as water or
alcohols. (e.g. PVA dissolves in water). Polymers with non-polar groups (such as –CH3
and –C6H5) are not easily attacked by polar solvents but they easily swell and
sometimes dissolve in non-polar solvents such as petrol, benzene and carbon
tetrachloride.
• Residual unsaturation leads to oxidative degradation: polymers with residual
double bonds get attacked and degraded in air and UV light for example
Natural rubber.
• Molecular mass: For a given polymer, the swelling character decreases with the
increase in the molecular mass.
• Degree of cross linking: Greater the degree of cross linking lesser is the
solubility.

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• Packing: Dense packing does not allow the solvent to penetrate between the
layers hence resistance increases, for example Teflon.
PLASTIC DEFORMATION
Property of a polymer by which on application of heat it becomes soft and flexible and
on cooling returns to its original shape is called plasticity or plastic deformation. Based
on their response to heat two kinds of polymers are:
Thermoplastic - A thermo plastic polymer is one which softens on heating and
becomes hard on cooling. They can be remoulded into new shapes. Polyethylene,
polypropylene, polystyrene is the example of thermo plastics.
Thermosetting - A thermo setting polymer becomes hard on heating. They cannot be
remoulded, their structure instead undergoes a total degradation on heating.
Bakelite, Aniline aldehyde resin, urea formaldehyde polymer
The reason for the difference in this thermal behaviour is that thermoplastics have
relatively weak forces of attraction like van der Waals forces, dipole-dipole attraction
or H-bonding between the chains, which are overcome when the material is heated,
unlike thermosetting plastics, where the cross-linking between the chains is by strong
covalent bonds cannot be broken easily. On strong heating will result in charring and
degradation.

GLASS TRANSITION TEMPERATURE

All amorphous polymers, when cooled below a certain temperature, become stiff,
hard, brittle, and glassy but above this temperature they are soft, flexible, and
rubbery. This transition temperature of a polymer is called its glass transition
temperature. It is denoted by Tg.

The Tg values of some polymers are listed:

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The glass transition temperature is not the same as melting temperature. Melting is
something that happens to a crystalline polymer, while the glass transition happens
only to polymers in the amorphous state. A given polymer will often have both
amorphous and crystalline domains within it, so the same sample can often show a
melting point and a Tg. But the chains that melt are not the chains that undergo the
glass transition.
• The value of Tg is a measure of flexibility of a polymer and predicts its response
to Mechanical stress.
• Knowledge of Tg and Tm is useful in choosing right temperature range for
fabrication.
• The Tg value gives an idea of thermal expansion, heat capacity, refractive index,
electrical and mechanical properties of a polymer.
ELASTOMER/ BUTYL RUBBER
The property of a polymer by which it deforms on applying force and regains original
shape on release of force is called elasticity. Elastomers have long coiled and
entangled chains which straighten and orient themselves on stretching. When stress is
removed, they go back to coiled form. Introducing cross linking at suitable molecular
positions like in vulcanisation helps in improving the elasticity of rubber.

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BUTYL RUBBER
Monomer: Isobutylene mixed with 1.5 to 4.5% isoprene
• Isobutylene is dissolved in methyl chloride. Anhydrous AlCl3 dissolved in methyl
chloride is added and the reaction carried out at -95oC. A finely powdered butyl
rubber is obtained.
• Isoprene introduces of unsaturation to chain and helps in vulcanization
• Copolymerization

Properties:
• Butyl rubber has exceptional resistance to gas and moisture (water and steam)
permeation.
• Butyl rubber also has excellent resistance to oxygenated solvents (ketones and
alcohols), alkalis, flexing, and abrasion.
• Butyl rubber has good resistance to sunlight, ozone, heat aging, animal and
vegetable oils, oxidizing chemicals, silicone fluids and greases.
• It has excellent electrical isolation performance.

Applications:
• Butyl rubber’s excellent impermeability to gas makes it very useful in seals for
vacuum applications.
• Butyl rubber’s gas impermeability coupled with its air retention capabilities
makes it popular for use in tyre inner liners and inner tubes.
• It is also used in hydraulics applications where synthetic fluids are used.

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Adhesives/ Epoxy Resin

Substances used to bind two or more materials firmly by surface attachment due to
penetration of adhesive into material and solidification leading to interfacial locking.
Natural- example Gum, Glue, starch etc & Synthetic example PF, UF, epoxides etc.
Synthesis: It is synthesized from the monomer units of epichlorohydrin and
bisphenol A.

Condensation of the monomeric units gives rise to Epoxy resin

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• Excess of epichlorohydrin is used so that the end groups are epoxy groups
which are very active. When curing agents are added immediately three -
dimensional crosslinked structure is formed.
• Curing agents are diamines, dicarboxylic acids or acid anhydrides
PROPERTIES:
• Epoxy also has excellent resistance to chemicals. After setting, there is no
worry of a chemical reaction that will weaken the seal.
• It has very high mechanical strength
• They absorb less moisture.
• The resins are relatively high in viscosity, so that they are usually moulded at
temperatures in the region of 50-100°C, or dissolved in an inert solvent to
reduce viscosity to a point at which lamination at room temperature becomes
possible.
• Good insulation properties.
APPLICATIONS:
• Cured epoxies are frequently used in aerospace and defence.
• They can used to bind metal, leather, wood, ceramic etc.
• Coated on floor to give it an antiskid layer.
• Crease and shrinkage resistance fabrics
POLYMER COMPOSITES
Materials made from two or more constituent materials and their properties are not
attainable by any individual component alone are called composites and when one or
more of the components are polymers, they are called polymer composites.
• Two components are fibre and matrix.
• Polymer composite are produced by suitably bonding a fiber material with a
polymer resin matrix and curing the same under pressure and heat. The
reinforcements could be in different forms such as short, chopped fibers, continuous
filaments, twisted stands, mats, woven fabrics, etc.,
• Example: resin: - polyester, epoxy, phenolic, silicone, melamine, vinyl derivatives
and polyimide.

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• Example: fibers: - glass fiber, boron filaments, carbon/graphite fibers, aramid

(aromatic polyamide), aluminum fiber, polycrystalline metal oxide fibers, silicon
carbide fibers, etc.,
• Composites have high strength / unit weight.
KEVLAR
It is an aramid fibre - Aromatic polyamide
It’s chemical name is Poly-paraphenyleneterepthalamide:[–CO-C6H4 -CO-NH-C6H4 -NH-
]n
Synthesised by condensation of 1,4 phenylene diamine and 1,4 benzenedicarbonyl
chloride

Intermolecular Hydrogen Bonding in Kevlar

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PROPERTIES:
High tensile strength, high strength to weight ratio, high chemical inertness, low co-
efficient of thermal expansion, flame resistance, High impact, cut resistance, Textile
processibility, High modulus of elasticity
APPLICATIONS:
• Kevlar can be used by itself or as part of a composite material (one material
combined with others) to give added strength
• bulletproof vests and knifeproof body armor
• It is used as reinforcement in car tires, in car brakes.
• in the strings of archery bows, and in car, boat, and even aircraft bodies
CARBON FIBRE
Carbon fibers or carbon fibres (alternatively CF, graphite fiber or graphite fibre)
are fibers about 5–10 micrometers in diameter and composed mostly
of carbon atoms. Several thousand Carbon fibres are twisted together to form a yarn
which is used as such or woven into fabric.
SYNTHESIS:
It is synthesised from polyacrylonitrile (PAN). Its synthesis can be divided into four
stages-
(i) polymerization
(ii) cyclization
(iii)Dehydrogenation
(iv)graphitization

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PROPERTIES:
• Carbon Fiber has High Strength to Weight Ratio (also known as specific
strength)
• Rigidity or stiffness of a material is measured by its Young Modulus and
measures how much a material deflects under stress. Carbon fiber reinforced
plastic is over 4 times stiffer than Glass reinforced plastic
• Carbon fiber is Corrosion Resistant and Chemically Stable.
• Carbon Fiber has good Tensile Strength.
• Non-Poisonous, Biologically Inert, X-Ray Permeable
• Low Coefficient of Thermal Expansion
APPLICATIONS:
• Aerospace, road and marine transport, sporting goods
• Medical applications in prostheses, surgery and x-ray equipment, implants,
tendon/ligament repair

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• Automobile hoods, novel tooling, casings, and bases for electronic equipments,
EMI and RF shielding, brushes
• Audio equipment, loudspeakers for Hi-fi equipment, pickup arms, robot arms
CONDUCTING POLYMERS
• Polymers are generally insulators because the organic molecules of which they
are composed have no free electrons to carry current; all the electrons are held
firmly by atoms forming the molecules.
• Polymers in which the carbon atoms in the backbone are linked by double
bonds have the potential to conduct electricity, especially when several such
bonds occur in vicinity of each other.
• Conducting polymers are those polymers which Conduct electricity due to
delocalization of π electrons. An organic polymer can be converted into
conducting polymer–
• If it has linear structure
• Has extensive conjugation in its polymeric back bone
• E.g. - Polyacetylene, Polythiophene, Polyaniline, Polypyrrole etc.
• Discovered in the late seventies (1977) by Alan Heegar, Dr. Hideki Shirakawa
and Alan Macdiarmid. Prior to this polymer were used only as insulators.

Some Important conducting Polymers

• Conducting polymers are synthesized by doping (introduction of charged

chemical species) having pi-backbone. Doping reactions are:
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1. OXIDATIVE DOPING (p-doping)

2. REDUCTIVE DOPING (n-doping)
3. PROTONIC DOPING
1. OXIDATIVE DOPING (p type doping)
• OXIDATIVE DOPING (p-doping) - In this process, pi-backbone of a polymer is
partially oxidized using a suitable oxidizing agent.
• This creates positively charged sites on the polymer backbone which are the
current carriers for conduction.
• The oxidizing agents used are Iodine in CCl4, HBF4 etc.

2. REDUCTIVE DOPING (n-doping)

• In this process, pi-backbone of a polymer is partially reduced using a suitable
reducing agent.
• This creates negatively charged sites on the polymer backbone which are the
current carriers for conduction.
• The reducing agent used is sodium naphthalide in THF

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3. PROTONIC ACID DOPING

• Doping of polyaniline is a typical example of this type of doping.

• In this technique, current carrying charged species (+ve and –ve) are created by
protonation of imine nitrogen.
• Polyaniline is partially oxidized using a suitable oxidizing agent (ammonium
peroxy disulfate) and a base polyaniline is formed.
• The base polyaniline is treated with HCl (1M) when protonation of imine
nitrogen takes place creating +ve charged sites (which carry current); and the
+ve charges are compensated by Cl- of HCl.

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Polyaniline exists in different forms, oxidized form consists of only imines, it is known
as pernigraniline, and the reduced form consists of only amine groups and is called
leucoemeraldine. In the case of a mix of 50% imine and 50% amine group in the
polymeric chain of PANI, it called emeraldine base. None of these forms of PANI are
conducting. The only conducting form of PANI is emeraldine salt.

APPLICATIONS OF CONDUCTING POLYMERS

• Conducting polymers such as polyaniline is used as a electrode material for

commercial rechargeable batteries, biosensor, electrochromic display window,
printed circuit boards etc.
• Polypyrrole is used as neural biosensor, bioactuators, antioxidant, in drug
delivery, neural prosthetics and has cardiovascular applications.
• They are used as supercapacitors and Light emitting diodes (LEDs)
• Conducting polymers have been considered for important materials in
microelectronics applications, electrocatalysis, fuel cell electrodes, reinforced
composites etc.

MOLECULAR MASS OF POLYMERS

The average molecular weight is an important characteristic of a polymer sample.
Almost the entire range of mechanical properties like thermal properties, stress-strain
properties, impact, fracture, fatigue, creep, stress relaxation and cracking are
influenced by average molecular weight and molecular weight distribution. Electrical
properties like conductivity, dielectric constant, dielectric loss and breakdown are also
significantly dependent on molecular weight.

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Polymer molecular weight is expressed as an average molecular weight. Molecular

weight of polymers can be given as:
1. Number average molecular weight
2. Weight average molecular weight
3. Viscosity average molecular weight
NUMBER AVERAGE MOLECULAR WEIGHT (Mn)
Number average molecular mass of a polymer is obtained by dividing the total mass of
the dispersed material with the total number of polymer units present i.e.,

Where n1, n2, n3------- are number of polymer units having masses M1, M2, M3
respectively.

Where ni is the number of polymer units of molecular mass Mi

1. MASS AVERAGE MOLECULAR WEIGHT (Mw)

It gives representation to various molecular species in proportion to their masses in
the given material. Hence, in the averaging process, the molecular weight of each
individual species is multiplied by the mass

Where n1, n2, n3------- are number of polymer units having masses M1, M2, M3
respectively. Then m1 = n1M1, m2 = n2 M2---

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• The ratio Mw/Mn is called the polydispersity index (PDI) or heterogeneity index.
• It is a measure for the broadness of a molecular weight distribution of a
polymer, that is, the larger the polydispersity index, the broader the molecular
weight distribution.
• The larger the polydispersity index, the broader the molecular weight.
• A monodisperse polymer where all the chain lengths are equal (such as a
protein) has a PDI =1
• PDI > 1, shows that the polymeric sample is less homogeneous and
polydisperse.
2. VISCOSITY AVERAGE MOLECULAR WEIGHT (Mv)

a is the Mark- Houwink parameter, its value depends on the polymer- solvent system,
value of a is 0.5≤ a ≤ 0.9. The viscosity average molecular is usually larger than the
number average but smaller than the mass average molecular mass.

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REFERENCES
• Engineering Chemistry, Gadag, R.V. and Nityananda Shetty A, I. K. International
Publishing House,3rd edition, 2015.
• Engineering Chemistry, Jain P.C. and Monica Jain., Dhanpat Rai Publishing
Company (P)Ltd., 6thedition, 2017
• Ates, M., Karazehir, T. and Sezai Sarac, A., 2012. Conducting polymers and their
applications. Current Physical Chemistry, 2(3), pp.224-240.
• Yi, N. and Abidian, M.R., 2016. Conducting polymers and their biomedical
applications. In Biosynthetic Polymers for Medical Applications (pp. 243-276).
Woodhead Publishing.
• https://www.conserve-energy-future.com/
• https://www.plasticseurope.org/
• https://youmatter.world/
• https://en.wikipedia.org/

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