UCB009-CHEMISTRY

Polymers
2024-2025 ODD Semester
UCB009 (Chemistry)
 A brief outline:
➢ Introduction and Definition of Polymers, Polymerization and Degree of Polymerization
➢ Polymers vs Macromolecules and Classification of Polymers
➢ Classification based on Origin
➢ Classification based on Monomer: Homopolymer and Copolymer
➢ Classification on the basis of chain structure
➢ Classification based on Type of Polymerization Reaction
➢ Addition Polymerization vs Condensation Polymerization
➢ Classification based on Polymer Behavior w.r.t. Temperature
➢ Average Molecular Weights of Polymers
➢ Tacticity in Polymers
➢ Dispersity of Polymers
➢ Thermoplastics vs Thermosetting Polymers
➢ Polydispersity Index and Average Molecular Weights of Polymers
➢ Conducting Polymers
➢ Inorganic Polymers
➢ Biodegradable Polymers
Polymers, Polymerization and Degree of Polymerization
Definition: A polymer is defined as a large molecule or a macromolecule which is a
combination of many monomers or subunits that are linked together via covalent bonds.
The monomers can have identical and/or non-identical chemical structures.

“Poly” means “many” and “mer” means “unit”

Polymerization: It is defined as a process wherein small molecules or monomers

undergo chemical reactions and give rise to long-chain molecules or three-dimensional
networks known as polymers.

Degree of Polymerization:

The number of repeating units in a polymeric chain is called ‘degree of polymerization (DP)

The molecular weight of the polymer can be calculated by knowing the value of DP.
Molecular wt of the polymer = DP × Molecular wt of each monomer.

Exercise 1: Calculate the molecular weight of the polyethylene polymer whose DP value is 100.

Solution: Molecular weight of the polyethylene = DP × Molecular weight of Ethylene

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= 100 × 28 = 2800. UCB009 (Chemistry)
Polymers vs Macromolecules
Polymers and Macromolecules are often used synonymously but on a strict basis,

Polymers
➢ A polymer is a long-chain molecule which
contains covalently-linked repeating units i.e.
monomers
➢ For example: DNA is a polymer formed from all
nucleotides as monomers
➢ Similarly, Polythene, Poly-vinylchloride, Nylon-
6,6 etc. are polymers

Macromolecules
➢ A macromolecule is a giant molecule that may
or may not contain repetitive monomer units.
➢ For example, triglycerides (fat) are
macromolecules which are made up of glycerol
backbone and several long-chain fatty acids.
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So, all polymers are macromolecules but not all macromolecules are polymers
UCB009 (Chemistry)
Classification of Polymers
Typically, polymers can be classified based on several parameters.
Here, we have shown a broad classification of polymers

Classification of Polymers

Thermal Behavior
Origin ➢ Thermoplastic
➢ Thermosetting
➢ Natural
➢ Synthetic
Monomer Composition Polymerization Reaction
➢ Homopolymer ➢ Addition
➢ Copolymer ➢ Condensation

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Polymers: Classification based on Origin
Natural Polymers: Naturally occurring polymers existing in plants and animals

Polymer Monomer Chemical Structure (Extra Info)

Cotton

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Starch Glucose Units
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Natural Polymers Monomer Chemical Structure (Extra Info)
Polymer

DNA (the genetic material)

Protein

Amino acids: Monomers

Amide bond linkages:

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ODD Semester
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Wool (made from cross-linked proteins called keratin)
Polymers: Classification based on Origin
Synthetic Polymers: These are prepared in the lab artificially.
Examples: polyethylene, polyvinylchloride, Nylon, Bakelite etc.

2024-2025
Synthetic polymers can be further classified into Organic and ODDpolymers
Inorganic Semester
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Synthetic Polymers: Classification

Organic Polymers: Contain carbon atom in the polymer backbone

polyethylene polystyrene polyvinyl chloride

Inorganic Polymers: Do not contain carbon atom in the polymer backbone

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Will be discussed later
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Polymers: Classification based on Monomer Composition
Monomer Composition

Identical Monomers Non-identical Monomers

 Homopolymer  More than 1 type of Monomer
 Heteropolymer / Copolymer
e.g. Poly-ethene,
Poly-vinyl chloride e.g. Nylon-6,6; Dacron polyester

Arrangement of Monomeric Units

A-A-A-A-A-A-A-A-A-A-  Homopolymer

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Types of Copolymers: Arrangement of Monomer Units

:Two different Monomers

A-A-A-A-B-A-B-B-A-B-A-B-B-A-

Monomeric units Random copolymer

arranged randomly
A-B-A-B-A-B-A-B-A-B-A-B-A-B-

Monomeric units Alternating copolymer

arranged alternatively
A-A-A-A-A-A-B-B-B-B-B-
Monomeric units Block copolymer
arranged in blocks

Main Chain Graft copolymer

The backbone is formed
from one type of monomer Branch
A-A-A-A-A-A-A-A-A-A-A-A-A-A- The branches are formed
B B B from other types of monomer
B B B 2024-2025 ODD Semester
Note: Either alphabetical or schematic B B B
representation can be used UCB009 (Chemistry)
B
 Polymers: Classification on the basis of chain structure

Cross-linked

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Note: Either alphabetical or schematic representation can be used UCB009 (Chemistry)
Polymers: Classification based on Type of Polymerization Reaction

Polymerization Reaction

Addition (Chain) Polymerization Condensation Polymerization

e.g. Poly-ethene, e.g. Nylon-6,6; Dacron

Poly-vinyl chloride

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 Addition Polymerization: Sequence of Steps
➢ Addition polymerization, also known as chain polymerization, is a chemical process that joins
small-chain monomers into long-chain polymers.

➢ This process is initiated by a chemical catalyst, also known as an initiator e.g. Benzoyl
peroxide, Azo-bis-isobutyronitrile (AIBN)

1. Initiation

2. Propagation

3. Termination

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Real-life examples of Addition Polymers: Extra Info

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How does the Degree of Polymerization affect Addition Polymers?

Low Density Poly-Ethylene (LDPE)

n = 1000 - 2000

High Density Poly-Ethylene (HDPE)

n = 10,000 – 100,000

Ultra High Molecular Weight Poly-Ethylene (UHMWPE)

n = 2 – 3 million
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Joint Replacement Gears
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Addition Polymers/Homopolymer: Examples and their applications

S. No. Names of Polymers Names of Monomer Applications

1 Polyethylene Ethylene Bottles, plastic bags, toys

Membrane filters, electronics,

2 Polypropylene (PP) Propylene
construction
3 Polyvinylchloride (PVC) Vinylchloride Pipes, flooring
Packaging foams, disposable
4 Polystyrene Styrene
medical
Polytetrafluoroethylene Non-sticky surfaces,
5 Tetrafluoroethylene
(PTFE i.e. Teflon) electrical insulation
6 Polyacrylonitrile Acrylonitrile Blankets, clothing, rugs

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Condensation Polymerization:

Involves two different types of di/tri-functional monomers or end groups that react with
one another, forming a chain and also producing a small molecular by-product (water,
HCl, etc.)

Synthesis of Nylon-6,6:

➢ As the chain grows, the short-chain molecules are called oligomers.

➢ This reaction can, theoretically, continue until no further monomers and reactive
end groups are available.
➢ The process, however, is relatively slow and can take up to several hours or
days. 2024-2025 ODD Semester
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Condensation Polymers: Examples

Ester linkage

Amide linkage 2024-2025 ODD Semester

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Real-life examples of Condensation Polymers: Extra Info

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Real-life examples of Condensation Polymers: Extra Info

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Addition Polymerization vs Condensation Polymerization

S. No. Addition polymerization Condensation polymerization

The method involves the repeated The method involves a series of
addition of monomers to produce long condensation reactions, generally involving
1.
chains without elimination of any by- two monomers with the elimination of small
products molecules like H2O, NH3, or HCl
Monomers must have double or triple Monomers must have two similar or different
2.
bonds functional groups
3. The reaction is very fast The reaction is very slow
The molecular weight of the resultant The molecular weight of the resultant
4. polymers is a multiple of the monomer’s polymer is not a multiple of monomer’s
molecular weight molecular weight
Lewis acids or bases, radical initiators
5. No such catalysts are required
are catalysts in addition polymerization
High molecular mass polymers are Polymer molecular mass rises steadily
6.
formed at once throughout the reaction
Example: Polyethylene, Teflon, Polyvinyl
7. Example: Nylon -6, 6, polyesters.
chloride (PVC)

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Polymers: Classification based on Polymer Behavior w.r.t. Temperature
Thermoplastic Polymers
➢ A thermoplastic is a polymer that softens when
heated and freezes to a very glassy state when Lego bricks
cooled sufficiently.
➢ Can be molded into another shape when it is
softened upon heating
➢ Most thermoplastics are high-molecular-weight
polymers whose chains are associated with weak
van der Waals forces (polyethylene), stronger
dipole-dipole interactions, and hydrogen bonding
(nylon).
➢ More examples: Polystyrene and cellulose
acetate

Thermosetting Polymers
Electrical Plugs
➢ Thermosetting polymers, when heated, will
chemically decompose, so they can not be
recycled. Yet, once a thermoset is cured, it tends to
be stronger than a thermoplastic because the
chains within these polymers are cross-linked.
➢ Typically, linear polymers with minor branched
structures (and flexible chains) are thermoplastics.
The networked structures are thermosets. For
example, Phenol-formaldehyde (Bakelite) and
urea-formaldehyde 2024-2025 ODD Semester
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Thermoplastics vs Thermosetting Polymers: Differences

S. No. Thermoplastic Polymers Thermosetting Polymers

Thermoplastic polymers are Thermosetting polymers are those
those which can be softened which cannot be softened upon
1
upon heating and remolded heating. Rather, they decompose
repeatedly upon heating
It consists of linear long chain It consists of three-dimensional
2
structure network structure
The chains in the polymer are The chains in the polymers are held
3 held together by weak van der together by strong covalent bonds i.e.
Waals forces they are cross-linked
They are soft, weak and less They are hard, strong and more brittle
4
brittle
5 They are amorphous in nature They are crystalline in nature
Example: Polyethylene, Example: Vulcanized rubber, phenol-
6
polypropylene, polystyrene formaldehyde resin (Bakelite)

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Tacticity in Polymers:
Tacticity: It is defined as the spatial arrangement of the functional/pendant groups with
respect to the polymeric backbone.

❖ Isotactic: spatial arrangement of functional/pendant groups on the same side

❖ Syndiotactic: spatial arrangement of functional/pendant groups in an alternate manner
❖ Atactic: spatial arrangement of functional/pendant groups in a random manner

Fischer Projections

Isotactic Syndiotactic Atactic

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Note the positions of the “R” groups with respect to everyUCB009
carbon centre
(Chemistry)
Tacticity in Polymers: Representations of Fischer Projections

Propylene (monomer) Polypropylene (polymer)

Fischer projection of
Isotactic Polypropylene

R = -CH3

Which one is correct??

Incorrect Representation Correct Representation

(Every carbon centre (Every alternate
2024-2025 ODD carbon
Semester
contains “R” group) contains
centre UCB009 “R” group)
(Chemistry)
Importance of Tacticity:

• Tacticity affects the physical properties of polymers

• Atactic polymers will generally be amorphous, soft, flexible materials
• Isotactic and syndiotactic polymers will be more crystalline, thus
harder and less flexible

• Polypropylene (PP) is a good example

• Atactic PP is a low-melting, soft/gummy material
• Isotactic PP is a high melting (176º), crystalline, tough material that
is industrially useful
• Syndiotactic PP has similar properties as that of isotactic PP

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Dispersity of Polymers
It is defined as the measure of the heterogeneity in terms of the size of particles in a mixture.

Monodisperse polymers are uniform in Polydisperse polymer is non-uniform and

that all molecules have the same degree contains polymer chains of unequal length, so
of polymerization molecular or relative the molecular weight is not a single value – the
mass. Many biopolymers, especially polymer exists as a distribution of chain lengths
proteins, are monodisperse. and molecular weights.

Monodisperse sample Polydisperse sample

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How do we calculate the molecular weight of a polydisperseUCB009
polymer??
(Chemistry)
Average Molecular Weights of Polymers
Different types of average molecular weights can be obtained such as,
Number Average (𝑀𝑛) and Weight Average (𝑀𝑤 )

𝑁1𝑀1 + 𝑁2𝑀2 + 𝑁3𝑀3 + … … … . ∑𝑁𝑖𝑀𝑖

𝑀𝑛 = = … . (𝑒𝑞𝑛. 1)
𝑁1 + 𝑁2 + 𝑁3 + … … … … ∑𝑁𝑖
where, N1, N2, N3, etc. denote no. of polymer chains
M1, M2, M3, etc. denote mol. wt. of each polymer chain

𝑤1𝑀1 + 𝑤2𝑀2 + 𝑤3𝑀3 + … … … . ∑𝑤𝑖𝑀𝑖 … . (𝑒𝑞𝑛. 2)

𝑀𝑤 = =
𝑤1 + 𝑤2 + 𝑤3 + … … … … ∑𝑤𝑖
where, w1, w2, w3, etc. denote weights of polymer chains

𝑆𝑖𝑛𝑐𝑒 𝑤𝑖 = 𝑁𝑖𝑀𝑖 Therefore, substituting 𝑤𝑖 = 𝑁𝑖𝑀𝑖 in eqn. 2, we obtain

𝑁1𝑀12 + 𝑁2𝑀22 + 𝑁3𝑀32 + … … … . ∑𝑁𝑖𝑀𝑖2
𝑀𝑤 = = … . (𝑒𝑞𝑛. 3)
𝑁1𝑀1 + 𝑁2𝑀2 + 𝑁3𝑀3 + … … … … ∑𝑁𝑖𝑀𝑖

For a monodisperse system: 𝑀𝑛 = 𝑀𝑤

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For a polydisperse system: 𝑀𝑛 < 𝑀 𝑤 UCB009 (Chemistry)
Exercise 2: In a polymer sample, 30% of molecules have a molecular mass of
20000, 40% have a molecular mass of 30000, and the rest have 60000. Calculate
mass average and number average molecular masses.

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Polydispersity Index and Average Molecular Weights of Polymers
Polydispersity Index (PDI): It is defined as the ratio of weight-averaged
molecular weight to the number-averaged molecular weight
𝑀𝑤
 It gives an idea about homogeneity of the polymers 𝑃𝐷𝐼 =
𝑀𝑛
For a monodisperse system: 𝑀𝑛 = 𝑀𝑤
For a polydisperse system: 𝑀𝑤 > 𝑀𝑛

Exercise 3:
In a polymer, there are 150 molecules of molecular weight 100, 200 molecules of
molecular weight 1000 and 300 molecules of molecular weight 10000. Find the
number and weight average molecular mass of the polymer and PDI.

Number average molecular weight = Mn = NiMi/Ni

= [150 x 100 + 200 x 1000 + 300 x 10000] / [150 + 200 + 300]
= [15000 + 200000 + 3000000]/650 = 3215000/650 = 4946.15

Weight average molecular weight = Mw = WiMi/Wi = NiMi2/NiMi

= [150 x (100)2 + 200 x (1000)2 + 300 x (10000)]2 / [150 x 100 + 200 x 1000 + 300 x 10000]
= [1.5 x 106 + 200 x 106 + 30000 x 106] / [3.2 x 106] = [30201.5 x 106] / [3.2 x 106] = 9437.96.
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Polydispersity index (PDI) = Mw / Mn = 9437.96 / 4946.15 = 1.91 UCB009 (Chemistry)
Conducting Polymers
Development of polymers from electrical insulators to electrical conductors

Nobel Prize in Chemistry (2000)

For the discovery and development of conducting polymers
Conducting Polymers: Why do they conduct ?

Generally, polymers e.g.

polyethylene, PVC, Teflon etc., are
poor conductors as these are held
by single covalent bonds. The sigma-
bonds in such polymers have low
mobility of electrons and does not electrons
contribute to the electrical
conductivity of the material. Thus,
these are good insulators.

Some polymers, under certain

conditions, have electrical
conductivities comparable to that of
metallic conductors due to delocalized
π-electrons. Such polymers are
called CONDUCTING POLYMERS. electrons
Conducting Polymers: Why do they conduct ?

➢ However, conjugated bonds do not

render polymeric materials to be
highly conductive.

➢ To enhance their conductivity, a

dopant needs to be added that either
generates a free electron or a hole,
as in the case of semiconductors.

➢ Thus, depending on which dopant

has been added, conducting
polymers can be either p-type or n-
type.
 p-type Conducting Polymers: Formation and Mechanism of Conduction
➢ p-Doping: Any electron-deficient Lewis acid, e.g., FeCl3, I2 vapors, or I2/CCl4, is
added in the conjugated system to induce oxidation and thus generate a positive
charge (cation).
➢ A cation or a hole is generated, which, when it moves through the doped
conjugated system, causes electrical conduction.

Mechanism of Conduction in p-Doped Polymers

Conjugated Polymer

p-Doped Polymer
with Radical Cation

Polyacetylene Lewis Acid p-Doped Polymer

Movement of Hole
or
Radical Cation

Movement of Hole / Radical Cation

 n-type Conducting Polymers: Formation and Mechanism of Conduction

➢ n-Doping: Any electron-rich Lewis base, e.g., naphthyl radical anion, is added in
the conjugated system to induce reduction and thus generate an anion.
➢ Thus, an anion or an electron is generated, which, when it moves through the
doped conjugated system, causes electrical conduction.

Mechanism of Conduction in n-Doped Polymers

Conjugated Polymer

n-Doped Polymer with

Radical Anion

Polyacetylene Lewis Base n-Doped Polymer

Movement of Electron
or
Radical Anion

Movement of Electron / Radical Anion

Applications of Conducting Polymers

➢ Replacement of Metal Conductor: Conducting Polymers have replaced

conventional metallic conductors due to their lightweight and comparable
conductivities in electronic devices.

➢ Chemical Sensors: Conducting polymers, such as polypyrrole, polyaniline,

polythiophene, and their derivatives, have applications as gas sensors.

➢ Light Emitting Diodes (LEDs), in Display Devices

➢ Rechargeable Batteries: The capability of repeated oxidation and reduction of

CPs make them eligible for rechargeable batteries as compared to conventional
Ni-Cd Cells.
Inorganic Polymers
• Most of the polymers have a backbone of carbon
e.g. organic polymers

• Polymers in which the backbone of the carbon is replaced by silicon, phosphorous

or any other inorganic atom are called Inorganic Polymers.

R R R
Si Si O P N
R n R n R n
Polysilanes Polysiloxanes Polyphospazenes

• Inorganic Polymers offer properties different from Organic Polymers

➢ Non-flammability

➢ Low Temperature Flexibility

➢ Electrical Conductivity
Examples of Inorganic Polymers

Poly-thiazyl
(used in LEDs, transistors)

Poly-dimethyl siloxane
(commonly known as “Silicone Rubber”)
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Daily Applications of Silicone polymers (Extra info)

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Biodegradable Polymers

All natural polymers are biodegradable

Polymers produced by nature are called Natural Polymers

➢ Proteins - have Amino Acids as monomer unit.

➢ Starch & Cellulose - have Glucose as a monomer unit.

➢ DNAs – have Nucleic acids as monomer units.

Why natural polymers are biodegradable?

All natural polymers are biodegradable because nature has all the enzymes to
degrade them. The enzymes, also called biocatalysts, are present in soil, water, and
all living organisms.
Biodegradable Polymers: Natural and Synthetic
Naturally Biodegradable:
Examples: Starch, Cellulose, Proteins, DNA Polyhydroxyalkanoates (PHA)
Synthetic Biodegradable:
Examples: Nylon-2-nylon-6, PHBV, Poly-lactic acid

Do synthetic polymers get degraded by biocatalysts (enzymes)?

Yes, this may be possible only if a synthetic polymer also has the same chemical
linkage as that of natural polymers like ester, amide bond or a glycosidic bond.

H H2 H H2
O C C C O C C C

CH3 O CH2 O

CH3
n

PHBV
This synthetic polymer has a Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
peptide linkage that can be
hydrolyzed by same enzymes The synthetic polymer has an ester
that degrade a protein in the linkage that can be hydrolyzed by
nature. living organisms & the products of
hydrolysis further metabolized by soil
microbes.
Real-life examples of Biodegradable Plastics: Extra Info

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Biodegradable Polymers: Applications
Food Packing, Single serve cups, or other
disposable food service items
Foam for industrial packaging, film wrapping,
jute bags, etc.
Slow release device or hygiene products,
Medical: as bone plates and surgical sutures
Adhesives, paints, and coatings.
Eco-friendly / Disposable cutlery

Surgical Sutures
Bone-plates 2024-2025jute
Eco-friendly ODDbags
Semester
Clips and Rods UCB009 (Chemistry)
 Department of Chemistry and Biochemistry, TIET, Patiala

Solutions to the Polymer Assignment

1. What is polymerization and degree of polymerization? How polymers are classified?

Ans: The chemical reaction in which high molecular mass molecules are formed from
monomers is known as polymerization or the fundamental process by which low molecular
weight compounds are converted into high molecular weight compounds.
The degree of polymerization (DP) refers to the number of repeat units in the chain, and gives
a measure of molecular weight.
Polymers can be classified as;
A. Classification on the basis of source:
i. Natural polymers – Polymers which are found in nature in plants and animals e.g. Starch,
cellulose, proteins, natural rubber etc.
ii. Synthetic polymers- These are man-made polymers like polyethylene, polypropylene,
polyvinylchloride, nylon etc.
B. Classification on the basis of structure:
i. Linear polymers – Monomeric units in these polymers are joined in form of long straight
chains e.g. nylons, polyester etc. They have high M.P, density and tensile strength due to
close packing of chains.
ii. Branched polymers - have a chain structure that consists of one main chain of molecules
with smaller molecular chains branching from it.

iii. Cross linked Polymers- In cross-linked polymers, adjacent linear chains of polymer are
joined one to another at various positions by covalent bonds e.g. Vulcanized natural rubber,
where sulfur joins the chains of natural rubber, Bakelite etc. Due to cross links, they are hard
and rigid.
 Other Ways to Classify Polymers
Classification Based on Polymerization
i. Addition Polymerization: Example, polyethylene, Teflon, Polyvinyl chloride (PVC)
ii. Condensation Polymerization: Example, Nylon -6, 6, perylene, polyesters.

Classification Based on Monomers

i. Homomer: In this type, a single type of monomer unit is present. For example, Polyethene
ii. Heteropolymer or co-polymer: It consists of different type of monomer units. For
example, nylon -6, 6
Classification Based on Molecular Forces
i. Elastomers: These are rubber-like solids weak interaction forces are present. For example,
Rubber.
ii. Fibres: Strong, tough, high tensile strength and strong forces of interaction are present. For
example, nylon -6, 6.
iii. Thermoplastics: These have intermediate forces of attraction. For example, polyvinyl
chloride.
iv. Thermosetting polymers: These polymers greatly improve the material’s mechanical
properties. It provides enhanced chemical and heat resistance. For example, phenolics,
epoxies, and silicones.
2. Differentiate the following with examples:
i. Addition and condensation polymerisation
Addition polymerisation Condensation polymerisation
1. The method involves the repeated addition 1. The method involves series ofcondensation
of monomers to produce long chains without reactions, generally involving two monomers
elimination of any by-products with the elimination small molecules like
H2O, NH3 or HCl
2. Monomers must have a double or triple 2. Monomers must have two similar or
bond different functional groups
3. The molecular weight of the resultant 3. The molecular weight of the resultant
polymers is a multiple of monomer’s polymer is not a multiple of monomer’s
molecular weight molecular weight
4. Lewis acids or bases, radical initiators are 4. No such catalysts are required
catalysts in addition polymerization
5. High molecular mass polymers are formed 5. Polymer molecular mass rises steadily
at once throughout the reaction
6. Example-polyethylene, Teflon, Polyvinyl 6. Example-Nylon -6, 6, perylene, polyesters.
chloride (PVC)

ii. Homopolymer and copolymer

Homopolymer Copolymer
 1. Homopolymers are produced by using a 1. Copolymers are formed by polymerisation
single type of monomer or single species of of mixture of two or more monomers/two or
repeating units more types of repeating units.
2. Homopolymers are formed through 2. Copolymers are formed through
addition polymerisation condensation polymerisation
3. They often have a simple structure 3. They usually have complex structure
4. Example-polyethylene, Teflon, Polyvinyl 4. Example-polyethylene-vinyl acetate
chloride (PVC) (PEVA), nitrile rubber, and acrylonitrile
butadiene styrene (ABS)

iii. Thermoplastic and thermosetting polymer

Thermoplastic polymer Thermosetting polymer

1. They soften on heating readily and once 1. They do not soften on heating, hence once
moulded they can be resoftened and reused moulded, they set permanently
2. They are softer and less strong; the 2. They are strong and hard, there are cross
polymeric chains are held together by weak linkages and covalent bond formation
vander Waals forces between the adjacent polymeric chains
3. They are generally formed by addition 3. These are formed by condensation
polymerisation reaction polymerisation reaction
4. As they soften again and again, they can be 4. They cannot be recycled, reused or
recycled, reused and reclaimed from waste. reclaimed from waste.
6. Example-polyethylene, Teflon, Polyvinyl 6. Example-Bakelite, melamine
chloride (PVC) formaldehyde.

3. Why polymers are expressed in terms of average molecular weights? For a polymeric
sample, discuss the number average and weight average type of molecular mass.
Ans: In the process of polymerisation, the chain termination is a random process, all the
polymeric chains formed are of different lengths, hence it becomes difficult to express the
molecular weight of the polymer. Therefore, the molecular weight can be expressed as average
of the molecular weights contributed by individual molecules in the sample. In other words,
polymers are mixtures of molecules of different molecular masses (polydisperse and
heterogeneous).
The molecular weight of a polymer is expressed in two ways:
i. Number average molecular weight M n. - If N1, N2, N3, … are the numbers of molecules with
molecular masses M1, M2, M3, …, respectively, then the number average molecular weight is:
 Mn = [N1M1 + N2M2 + N3M3 + ----- ] = S NiMi/ S Ni
N1 + N2 + N3 + ----

Where N1, N2, N3 -number of molecules, M1, M2, M3 – Mol. wts

Total mass of the polymer sample / Total number of molecules present in the sample
ii. Weight average molecular weight Mw - If m1, m2, m3 ,... are the weights of species with
molecular masses M1 , M2 , M3 , …, respectively, then the weight average molecular weight is:
Mw = m1M1 + m2M3 + m3M3+---------

m1+ m2 + m3 + -----------
Mw = ∑mi Mi
∑ mi
But

Hence,
Mw = [N1M 2 + N M 2 + N M 2 + ----- ]
1 2 2 3 3 = S N M 2/ S N M
N1M1 + N2M2 + N3M3
 where ni = number of molecules of mass Midispersion of molecules in a sample narrows, Mw
approaches Mn, and in the unlikely case that all the polymer molecules have identical
weights (a pure mono-disperse sample), the ratio Mw/ Mn (i.e PDI) becomes unity.

4. In a polymer sample, 30% molecules have a molecular mass 20000, 40% have molecular
mass 30000 and rest have 60000. Calculate mass average and number average molecular
masses.

Mn = [N1M1 + N2M2 + N3M3 + ----- ]

= S N i M i / S Ni
N1 + N2 + N3 + ----
Ans:

(30 × 20,000) + (40 × 30,000) + (30 × 60,000)

=
30 + 40 + 30
= 36000
Mw = [N1M 2 + N M 2 + N M 2 + ----- ]
1 2 2 3 3 = S N M 2/ S N M
i i i i
N1M1 + N2M2 + N3M3 +--

30(20,000)2 + 30(20,000)2 + 30(20,000)2

=
(30 × 20,000) + (40 × 30,000) + (30 × 60,000)

= 43333

5. In a polymer there are 150 molecules of molecular weight 100, 200 molecules of molecular
weight 1000 and 300 molecules of molecular weight 10000. Find the number and weight
average molecular mass of the polymer and PDI.

Mn = [N1M1 + N2M2 + N3M3 + ---- ]

= S NiMi/ S Ni
N1 + N2 + N3 + ----
Ans:

(150 × 100) + (200 × 1000) + (300 × 10000)

=
150 + 200 + 300
= 4946.15
Mw = [N1 M1 2 + N2 M22 + N3 M32 + ----- ]
= S N i M i 2 / S Ni M i
N1 M1 + N2 M2 + N3 M3 +--

150(100)2 + 200(1000)2 + 300(10,000)2

=
(150 × 100) + (200 × 1000) + (300 × 10,000)

= 9393.93

PDI =
 9393.93
=
4946.15
= 1.89
6. Calculate the degree of polymerization of vinyl chloride if the number average weight of
polymer is 1.31× 105 g/mol.
Ans: Mn̅ = D.P (molar mass of monomer)
1.31× 105 g/mol = D.P (62.5 g/mol), hence D.P = 2096

7. When 52 g of styrene was polymerized, average degree of polymerization was found to be

1.5× 105. Calculate the number of styrene molecules in the original sample and number
of molecules of polystyrene produced.
Ans: (i) No. of molecules of styrene in 52g = 52 × (6.023 ×1023/ 104.15) = 12.07 ×1023 molecules
(ii) No. of molecules of polystyrene formed
No. of styrene molecules
=
Degree of polymerisation
12.07 × 1023
=
1.5 × 105
= 8.04 ×1018 molecules
8. What is tacticity? Draw and differentiate syndiotactic and isotactic forms of polyvinyl
chloride.
Ans: Tacticity is defined as the way pendant groups (side groups/functional groups) are arranged
along the backbone chain of polymer. This refers to different atomic configurations for the same
composition. Based on the orientation of the side groups polymers can be classified as isotactic,
syndiotactic or atactic polymers:
Isotactic polymers: When the orientation of the side groups on alternate asymmetric carbon
atoms is the same, the polymer is termed as a syndiotactic polymer.
Syndiotactic polymers: When the orientation of the side groups on alternate asymmetric
carbon atoms is the same, the polymer is termed as a syndiotactic polymer.
 .
9. What are inorganic polymers? How are their properties different from organic polymers?
Ans: The polymers in which backbone of the carbon (as in organic polymers) is replaced by
silicon, phosphorous or any other inorganic atom are called Inorganic Polymers.

In contrast to organic polymers, inorganic polymers exhibit following properties:

• Nonflammability
• Low temperature flexibility
• Electrical conductivity
10. What are biodegradable polymers? Give two examples each of natural and synthetic
biodegradable polymers
Ans: The polymers that can be degraded into small segments after their intended purpose by
bacterial decomposition process to result in natural byproducts such as gases (CO2, N2), water,
biomass and inorganic salts are called “Biodegradable polymers”.
i. Natural - Starch, Cellulose, Proteins, DNA, Polyhydroxyalkanoates (PHA)
ii. Synthetic - Nylon-2-nylon-6, PHBV, Polylactic acid
11. Which functional groups are generally present in the biodegradable polymers? With the
help of suitable examples, explain how the synthetic polymers are also being degraded by
biocatalysts (enzymes)?
Ans: Biodegradable polymers tend to consist of ester, amide or ether functional groups.
Synthetic polymers can be biodegraded only if they possess same chemical linkage as that
present in natural polymers.

Nylon-2-nylon-6 has a peptide linkage that can be hydrolysed by same enzymes that degrade a
protein in nature while PHBV has an ester linkage that can be hydrolysed by living organisms
and the products of hydrolysis are further metabolized by soil microbes.

12. What are conducting polymers? Give examples. Write their applications
Ans: Some polymers, under certain conditions, have electrical conductivities comparable to that
of metallic conductors due to delocalized π electrons. Such polymers are called conducting
polymers. Examples of conducting polymers are given as below:

Polyphenylene

Polythiophene

S S

Polyphenylvinylene

Applications of conducting polymers

• Replacement of Metal Conductor: Conducting polymers have replaced conventional metallic
conductors due to their light weight and comparable conductivities in electronic devices.
• Chemical Sensors: Conducting polymers, such as polypyrrole, polyaniline, polythiophene and
their derivatives, have application as gas sensors.
• Printed Circuit Boards (PCBs): Conducting Polymer coated polymer sheets for PCBs are
inexpensive and have better adhesive properties compared to metallic conductors coated with
epoxy resins.
• Rechargeable Batteries: The capability of repeated oxidation and reduction of CPs make them
eligible for rechargeable batteries as compared to conventional Ni-Cd Cells.
• Numerous other applications such as Light Emitting Diodes (LEDs), in Display Device

13. Why doping is required in conducting polymers? Explain the mechanism of conduction
in n-doped polymers
Ans: The conductivity in conducting polymers is due to presence of conjugated system in the
backbone or delocalized π electrons but conjugated bonds do not render polymeric materials to
be highly conductive. Therefore, to enhance their conductivity a dopant needs to be added that
either generates a free electron or a hole, as in case of semiconductors.
Mechanism of Conduction in n-Doped Polym

Polyme

Na

Na

Na

Na

n-Doping: An electron-rich species (Lewis bases) like napthyl radical anion is added in the
conjugated system to induce reduction and thus generate a radical anion. Thus, a radical anion or
an electron is generated that when moves through the doped conjugated system causes electrical
conduction.
 School of Chemistry and Biochemistry, TIET, Patiala Applied Chemistry (UCB008)
Tutorial Sheet (Chemistry of Polymers)

1. What is polymerization and degree of polymerization? How polymers are classified?

2. Differentiate the following with examples:
(a) Addition and condensation polymerization
(b) Homopolymer and co-polymer
(c) Thermoplastic and thermosetting polymer
3. Why polymers are expressed in terms of average molecular weights? For a polymeric sample, discuss the
number average and weight average type of molecular mass.
4. In a polymer sample, 30% molecules have a molecular mass 20000, 40% have molecular mass 30000 and
rest have 60000. Calculate mass average and number average molecular masses.
5. In a polymer there are 150 molecules of molecular weight 100, 200 molecules of molecular weight 1000 and
300 molecules of molecular weight 10000. Find the number and weight average molecular mass of the
polymer and PDI.
6. Calculate the degree of polymerization of vinyl chloride if the number average weight of polymer is 1.31×
105 g/mol.
7. When 52 g of styrene was polymerized, average degree of polymerization was found to be 1.5× 105. Calculate
the number of styrene molecules in the original sample and number of molecules of polystyrene produced.
8. What is tacticity? Draw and differentiate syndiotactic and isotactic forms of polyvinyl chloride
9. What are inorganic polymers? How are their properties different from organic polymers?
10. What are biodegradable polymers? Give two examples each of natural and synthetic biodegradable
polymers
11. Which functional groups are generally present in the biodegradable polymers? With the help of suitable
examples, explain how the synthetic polymers are also being degraded by biocatalysts (enzymes)?
12. What are conducting polymers? Give examples and their applications
13. Why doping is required in conducting polymers? Explain the mechanism of conduction in n-doped polymers