Here are some short notes on polymers, drawing from the provided sources, for you to

study:

What are Polymers?

•Polymers are high molecular mass substances consisting of large numbers of repeating
structural units derived from simple molecules1 ....

•They are also called macromolecules1 ....

•The repeating structural units are formed from simple reactive molecules called
monomers1 ....

•The process by which simple molecules (monomers) are converted into polymers is called
polymerisation1 ....

Classification of Polymers

Polymers can be classified in several ways:

1.Based on Source of Availability2 ...

◦Natural polymers: Obtained from nature (plants and animals)2 .... Examples: starch,
cellulose, proteins, nucleic acids, natural rubber2 ....

◦Synthetic polymers: Prepared in laboratories2 .... Also called man-made polymers3 .

Examples: polythene, PVC, nylon, teflon, bakelite, terylene, synthetic rubber2 ....

◦Semisynthetic polymers: Mostly derived from naturally occurring polymers by chemical

modifications2 .... Example: cellulose acetate, cellulose nitrate2 ....

2 Based on Structure2 ...

◦Linear polymers: Monomers are joined together to form straight chains2 .... They are
packed closely and have high density, high tensile strength, and high melting points4 .
Examples: polythene, nylons, polyesters, PVC2 ....

◦Branched chain polymers: Monomers are joined to form long chains with side chains or
branches irregularly2 .... They are not packed well and have lower density, tensile strength,
and melting points than linear polymers4 . Examples: low density polythene, glycogen,
starch2 ....

◦Cross-linked or network polymers: Monomer units are cross-linked together to form a

three-dimensional network structure2 .... These are hard, rigid, and brittle4 . Examples:
bakelite, melamine formaldehyde resin2 ....

3.Based on Molecular Forces2 ...

◦Elastomers: Polymers with the weakest intermolecular forces2 .... They have elastic
character, meaning they can be stretched and regain their original shape when the stress is
removed2 .... Examples: natural rubber, Buna-S, Buna-N, Neoprene2 ....

◦Fibres: Polymers with strong intermolecular forces, such as hydrogen bonding or dipole-
dipole interactions2 .... These forces lead to close packing of chains, imparting high tensile
strength and less elasticity5 . Examples: nylons, polyesters (terylene)2 ....

◦Thermoplastics: Polymers with intermolecular forces intermediate between those of

elastomers and fibres2 .... They can be softened easily upon heating and molded into desired
shapes, and can be processed again and again2 .... Examples: polythene, polystyrene,
polyvinyl chloride (PVC), teflon2 ....

◦Thermosetting polymers: Polymers that undergo permanent change on heating, becoming

hard, infusible, and insoluble2 .... Heating causes cross-linking between polymer chains to
form a three-dimensional network2 .... Examples: bakelite, melamine formaldehyde
resin2 ....

4.Based on Mode of Synthesis2 ...

◦Addition polymers: Formed by direct addition of repeated monomers without the

elimination of byproduct molecules2 .... Monomers are generally unsaturated compounds8 .
The molecular formula of the repeating unit is the same as that of the starting monomer8 .
Examples: polythene, PVC, polystyrene2 ....

◦Condensation polymers: Formed by the condensation of two or more monomers with the
elimination of simple molecules like water, ammonia, hydrogen chloride, alcohol, etc.2 ....
The repeating structural unit is different from the starting monomers8 . Examples: nylon-6,6,
nylon-6, polyesters, bakelite2 ....

Polymerisation Reactions8

The polymerisation process occurs mainly via two types:

1.Addition Polymerisation (or Chain Growth Polymerisation): Occurs by addition of

monomers (unsaturated compounds). It can proceed via free radical, cationic, or anionic
mechanisms8 .

◦Free Radical Addition Polymerisation: Initiated by substances like peroxides which

generate free radicals8 .... The process involves Chain initiation, Chain propagation
(monomer units add to the growing chain), and Chain termination (radicals combine to end
the growth)9 . Example: Polymerisation of ethene in the presence of benzoyl peroxide9 .

◦Cationic Polymerisation: Initiated by acids, forming a carbocation intermediate10 ....

◦Anionic Polymerisation: Initiated by bases or nucleophiles, forming a carbanion

intermediate11 .
2.Condensation Polymerisation (or Step Growth Polymerisation): Monomers with
functional groups react, eliminating small molecules8 .... The polymer is formed step by
step12 .

Important Polymers and their Monomers/Uses

•Polythene: Monomer is ethene. Produced as Low Density Polythene (LDP) (branched, low
density, used in packaging, insulation, toys) or High Density Polythene (HDP) (linear, high
density, used for buckets, pipes)13 ....

•Teflon (Polytetrafluoroethene): Monomer is tetrafluoroethene14 . Very tough and

chemically inert, used in non-stick utensils, gaskets14 .

•PAN (Polyacrylonitrile) or Orlon: Monomer is vinyl cyanide (acrylonitrile)14 . Used as a

substitute for wool, making carpets14 .

•Terylene (Polyester): Monomers are ethylene glycol and terephthalic acid12 . Used in
blending with cotton, wool, and for making magnetic recording tapes12 .

•Glyptal (Polyester): Monomers are ethylene glycol and phthalic acid12 . Used in paints and
lacquers12 .

•Nylon-6,6 (Polyamide): Monomers are hexamethylenediamine and adipic acid15 . Used in

bristles for brushes, textiles, sheets, ropes15 .

•Nylon-6 (Polyamide): Monomer is caprolactam15 . Used in manufacture of tyre cords,

fabrics15 .

•Bakelite (Phenol formaldehyde resin): Monomers are phenol and formaldehyde15 ....
Cross-linked polymer. Used for making electrical switches, handles of utensils, phonograph
records16 .

•Melamine formaldehyde resin: Monomers are melamine and formaldehyde16 . Used in

making unbreakable crockery16 .

•Buna-S (Butadiene-styrene co-polymer): Monomers are buta-1,3-diene and styrene17 ....

A synthetic rubber used in making automobile tyres, footwear components18 .

•Buna-N (Nitrile rubber): Monomers are buta-1,3-diene and acrylonitrile18 . A synthetic

rubber resistant to action of oil, petrol, and organic solvents18 . Used for making oil seals,
tank linings18 .

•Natural Rubber: Polymer of isoprene (2-methylbuta-1,3-diene)17 . It is cis-polyisoprene19 .

Soft and sticky at high temperatures19 ....

◦Vulcanisation: Process of heating natural rubber with sulfur to improve its properties19 ....
Sulfur forms cross-links between polymer chains, making it harder, stronger, more elastic,
and resistant to solvents19 .... Typical amount of sulfur is 3-5% for tyre rubber19 .
Molecular Mass18 ...

•Polymers have a range of molecular masses. Average values are used:

◦Number average molecular mass (Mn)18 ...

◦Weight average molecular mass (Mw)18 ...

•Polydispersity index (PDI): Ratio of Mw to Mn (PDI = Mw / Mn)21 .

◦For homodisperse polymers (where all molecules have nearly the same mass), PDI is 121 .

◦For polydisperse polymers (wide range of masses), PDI is greater than 121 .

◦Natural polymers are generally more homogeneous (PDI usually unity) than synthetic
polymers21 .

Biodegradable Polymers22

•Polymers degraded by micro-organisms within a suitable period22 . They do not cause

serious environmental problems22 .

•Examples: Poly-β-hydroxybutyrate-co-β-hydroxyvalerate (PHBV), Polyglycolic acid (PGA),

Polylactic acid (PLA), Poly (ε-caprolactone) (PCL), Nylon-2-Nylon-622 ....

•PHBV is a copolymer of 3-hydroxybutanoic acid and 3-hydroxypentanoic acid, linked by

ester linkages22 . Used in specialty packaging, orthopedic devices, drug capsules22 .

Other Notes

•Copolymers: Polymers made from two or more different monomers2 .... Example: Nylon-
6,6, Buna-S2 .... Homopolymers are made from one type of monomer2 ....

•Plasticizers: Certain organic compounds added to polymers (like PVC) to make them soft
and flexible7 . Example: Dibutyl phthalate7 .

•Super glue: A polymer of methyl α-cyanoacrylate12 . Very strong fast-acting adhesive12 .