POLYMERS

Unit 15 | Class 12 NCERT Chemistry

1. Basic Definitions
• Polymer: from Greek poly (many) + mer (unit/part); very large molecules with high molecular mass (10³–10⁷
u); also called macromolecules
• Formed by joining repeating structural units (monomers) linked by covalent bonds on a large scale
• Monomer: simple, reactive molecule that is the repeating structural unit of a polymer
• Polymerisation: process of formation of polymers from their respective monomers
• Polymers are the backbone of four major industries: plastics, elastomers, fibres, paints and varnishes
• Polymer molecular mass always expressed as an average because chains of varying lengths are
produced; can be determined by chemical and physical methods

2. Classification of Polymers
2.1 Based on Source
• Natural polymers: found in plants and animals; e.g., proteins, cellulose, starch, some resins, rubber
• Semi-synthetic polymers: cellulose derivatives; e.g., cellulose acetate (rayon), cellulose nitrate
• Synthetic polymers: man-made; e.g., polythene (plastic), nylon 6,6 (synthetic fibre), Buna-S (synthetic
rubber)

2.2 Based on Structure

• Linear polymers: long straight chains; e.g., HDP, nylon, PVC — high tensile strength, high density due to
close packing
• Branched chain polymers: linear chains with side branches; e.g., LDP — lower density, lower tensile
strength
• Cross-linked (network) polymers: 3D network via covalent bonds between chains; e.g., bakelite,
melamine — hard, rigid, thermosetting

2.3 Based on Molecular Forces

Type Intermolecular Properties Examples
Forces
Elastomers Weakest (van der Can be stretched; retract Rubber, Buna-S, Buna-N,
Waals) on release; few Neoprene
crosslinks added to
retract
Fibres Strong H-bonding or High tensile strength, Nylon 6,6, Terylene, silk, wool
dipole-dipole crystalline, low elasticity
Thermoplastics Intermediate; no Soften on heating, Polythene, PVC, polystyrene,
crosslinks harden on cooling; can polypropene
be remoulded
Thermosetting Extensive crosslinks; Permanently hard; Bakelite, melamine-formaldehyde
3D network cannot be
reused/remoulded;
infusible
2.4 Homopolymer vs Copolymer
• Homopolymer: addition polymer from a single monomeric species; e.g., polythene (from ethene),
polyacrylonitrile (from acrylonitrile)
• Copolymer: polymer from two or more different monomers; contains multiple units of each monomer in the
same chain; e.g., Buna-S (1,3-butadiene + styrene)
• Copolymers have properties quite different from homopolymers

3. Types of Polymerisation Reactions

3.1 Addition (Chain Growth) Polymerisation
• Molecules of same or different monomers add together on a large scale
• Monomers used: unsaturated compounds — alkenes, alkadienes and their derivatives
• Chain growth via free radicals (most common) or ionic species
• Chain length increases continuously; no small molecule eliminated

Free Radical Mechanism (e.g., polythene from ethene)

• Initiator (catalyst): benzoyl peroxide, acetyl peroxide, tert-butyl peroxide (free radical generating)
• Heating or exposing to light → initiator generates free radicals

Step 1 — Chain Initiation

Benzoyl peroxide decomposes → 2 phenyloxy radicals → CO₂ lost → phenyl radical (Ċ₆H₅)
(C₆H₅CO-O-)₂ → 2 C₆H₅COO• → 2 Ċ₆H₅ + 2CO₂
Phenyl radical adds to ethene double bond:
Ċ₆H₅ + CH₂=CH₂ → C₆H₅-CH₂-ĊH₂

Step 2 — Chain Propagation

The new radical adds to another ethene molecule → bigger radical → repeats:
C₆H₅-CH₂-ĊH₂ + CH₂=CH₂ → C₆H₅-CH₂-CH₂-CH₂-ĊH₂
C₆H₅-(CH₂-CH₂)ₙ-CH₂-ĊH₂ (growing chain radical)

Step 3 — Chain Termination

Two chain radicals combine to form polythene:
C₆H₅-(CH₂-CH₂)ₙ-CH₂-ĊH₂ + ĊH₂-CH₂-(CH₂-CH₂)ₙ-C₆H₅
→ C₆H₅-(CH₂-CH₂)ₘ-CH₂-CH₂-CH₂-CH₂-(CH₂-CH₂)ₙ-C₆H₅
Polythene
⚠ Termination can occur in different ways — two radicals can combine or disproportionate

3.2 Condensation (Step Growth) Polymerisation

• Repetitive condensation reactions between bi-functional or tri-functional monomers
• Monomers contain groups: –NH₂, –OH, –COOH
• Each step eliminates a small molecule (H₂O, HCl, alcohol, etc.)
• Product of each step is again a bi-functional species → condensation continues
• Each step is independent of the others → step growth polymerisation
3.3 Copolymerisation
• Mixture of more than one monomeric species polymerised together
• Can occur via chain growth OR step growth
• Product contains multiple units of each monomer in the same polymeric chain
• Copolymers have properties different from corresponding homopolymers

4. Important Addition Polymers

4.1 Polythene (Polyethylene)
• Linear or slightly branched long chain molecules; thermoplastic
• Can repeatedly soften on heating and harden on cooling

(i) Low Density Polythene (LDP)

• Monomer: ethene (CH₂=CH₂)
• Conditions: 1000–2000 atm pressure; 350–570 K; traces of O₂ or peroxide initiator
• Mechanism: free radical addition + H-atom abstraction → highly branched structure
LDP structure (branched):

~~~CH₂-CH₂-CH₂-CH₂-CH₂-CH₂~~~
| |
(CH₂)ₙ (CH₂)ₘ
| |
CH₃ CH₃
• Properties: chemically inert, tough but flexible, poor conductor of electricity
• Uses: insulation of electricity-carrying wires; squeeze bottles, toys, flexible pipes

(ii) High Density Polythene (HDP)

• Monomer: ethene (CH₂=CH₂)
• Conditions: hydrocarbon solvent; Ziegler-Natta catalyst (triethylaluminium + TiCl₄); 333–343 K; 6–7 atm
• Structure: linear molecules (no branches) → close packing → high density; also called linear polymers
HDP structure (linear):

~~~CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂~~~
~~~CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂~~~
~~~CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂~~~
• Properties: chemically inert, more tough and hard than LDP
• Uses: buckets, dustbins, bottles, pipes

4.2 Polytetrafluoroethene (Teflon)

• Monomer: tetrafluoroethene (CF₂=CF₂)
• Conditions: free radical or persulphate catalyst; high pressure; heating
n CF₂=CF₂ →[catalyst, high P]→ -(CF₂-CF₂)ₙ-
Teflon repeating unit:

~~~-CF₂-CF₂-CF₂-CF₂-CF₂-CF₂-~~~
(all H replaced by F)
• Properties: chemically inert; resistant to attack by corrosive reagents
• Uses: oil seals and gaskets; non-stick surface coated utensils
4.3 Polyacrylonitrile (Orlon / Acrilan)
• Monomer: acrylonitrile (CH₂=CHCN)
• Conditions: peroxide catalyst; addition polymerisation
n CH₂=CHCN →[peroxide catalyst]→ -(CH₂-CH(CN))ₙ-
Polyacrylonitrile repeating unit:

CN CN CN CN
| | | |
~~~-CH₂-CH-CH₂-CH-CH₂-CH-CH₂-CH-~~~
• Uses: substitute for wool in commercial fibres — orlon or acrilan

5. Important Condensation Polymers

5.1 Polyamides (Nylons)
• Possess amide linkages (–CO–NH–); important synthetic fibres
• General preparation: condensation of diamines + dicarboxylic acids OR condensation of amino acids or
lactams

(i) Nylon 6,6

• Monomers: hexamethylenediamine [H₂N(CH₂)₆NH₂] + adipic acid [HOOC(CH₂)₄COOH]
• Conditions: 553 K; high pressure; condensation releases H₂O
n HOOC-(CH₂)₄-COOH + n H₂N-(CH₂)₆-NH₂
→[553K, high P]→ -[NH-(CH₂)₆-NH-CO-(CH₂)₄-CO]ₙ- + nH₂O
Nylon 6,6 — amide linkage shown:

H O O H
| || || |
~~~-N-(CH₂)₆-N-C-(CH₂)₄-C-N-(CH₂)₆-N-~~~
↑
amide (-CO-NH-) linkage
• Properties: fibre-forming solid; high tensile strength due to strong H-bonding between chains → close
packing → crystalline nature
• Uses: sheets, bristles for brushes, textile industry
• Intermolecular forces order: Buna-S < Polythene < Nylon 6,6 (increasing)

(ii) Nylon 6
• Monomer: caprolactam (a lactam/cyclic amide)
• Conditions: 533–543 K with water (H₂O opens the ring)
n [Caprolactam] →[533-543K, H₂O]→ -[CO-(CH₂)₅-NH]ₙ-
Caprolactam ring opening:

H₂C-CH₂
| |
H₂C C=O → -(CO-(CH₂)₅-NH)ₙ-
| |
H₂C-NH
Caprolactam Nylon 6
• Uses: tyre cords, fabrics, ropes

5.2 Polyesters — Dacron / Terylene

• Type: polycondensation products of dicarboxylic acids and diols
 • Monomers: ethylene glycol (ethane-1,2-diol, HOCH₂CH₂OH) + terephthalic acid (benzene-1,4-dicarboxylic
acid, HOOC-C₆H₄-COOH)
• Conditions: 420–460 K; zinc acetate–antimony trioxide catalyst
n HOCH₂CH₂OH + n HOOC-C₆H₄-COOH
→[420-460K, ZnOAc/Sb₂O₃]→ -[OCH₂CH₂-OC-C₆H₄-CO]ₙ- + nH₂O
Terylene / Dacron — ester linkage:

O O
|| ||
~~~-O-CH₂CH₂-O-C-[C₆H₄]-C-O-CH₂CH₂-O-~~~
↑
ester (-C(=O)-O-) linkage
• Properties: crease resistant
• Uses: blending with cotton and wool fibres; glass reinforcing material in safety helmets

5.3 Phenol–Formaldehyde Polymer (Bakelite and Novolac)

• Oldest synthetic polymers
• Monomers: phenol (C₆H₅OH) + formaldehyde (HCHO)
• Catalyst: acid (H⁺) or base (OH⁻)
• Step 1: phenol + HCHO → o- and/or p-hydroxymethylphenol derivatives
C₆H₅OH + HCHO →[H⁺ or OH⁻]→ o-/p-HOCH₂-C₆H₄-OH (mixture)
• Step 2: hydroxymethylphenol reacts with more phenol → chains joined by –CH₂– groups → Novolac
(linear, used in paints)
Novolac (linear):

OH OH OH OH
| | | |
~~~-[Ph]-CH₂-[Ph]-CH₂-[Ph]-CH₂-[Ph]-~~~

where [Ph] = phenyl ring (Ph = C₆H₃)

• Step 3: Novolac + more HCHO → crosslinking at reactive sites → infusible solid Bakelite
Bakelite (crosslinked):

~~~CH₂-[Ph(OH)]-CH₂-[Ph(OH)]-CH₂~~~
| |
CH₂ CH₂
| |
~~~CH₂-[Ph(OH)]-CH₂-[Ph(OH)]-CH₂~~~
(3D network — thermosetting)
• Bakelite properties: thermosetting — cannot be reused or remoulded
• Uses: combs, phonograph records, electrical switches, handles of utensils, computer discs

5.4 Melamine–Formaldehyde Polymer

• Monomers: melamine (C₃H₆N₆, a triamine) + formaldehyde (HCHO)
• Type: condensation polymerisation
Melamine structure: Melamine polymer:

H₂N NH₂ HN NH
\ / \ /
N=< N=<
/ \ / \
N N N N
| |
NH₂ NH-CH₂-
Melamine Melamine polymer unit
 • Uses: manufacture of unbreakable crockery

5.5 Glyptal (Alkyd Resin)

• Monomers: ethylene glycol + phthalic acid
• Type: condensation polymerisation (polyester type)
HOCH₂CH₂OH + HOOC-C₆H₄-COOH → -[OCH₂CH₂-OOC-C₆H₄-CO]ₙ-
• Uses: manufacture of paints and lacquers

5.6 Urea–Formaldehyde Resin

• Monomers: urea (NH₂CONH₂) + formaldehyde (HCHO)
-[NH-CO-NH-CH₂]ₙ-
• Uses: making unbreakable cups; laminated sheets

6. Rubber
6.1 Natural Rubber
• Natural polymer with elastic properties → classified as elastomeric polymer
• In elastomers: chains held by weak intermolecular forces → can be stretched
• Few crosslinks introduced between chains → help polymer retract to original position after force released
• Manufactured from rubber latex = colloidal dispersion of rubber in water
• Obtained from the rubber tree found in India, Sri Lanka, Indonesia, Malaysia and South America
• Chemical identity: linear polymer of isoprene (2-methyl-1,3-butadiene); also called cis-1,4-polyisoprene
Isoprene (monomer): Natural Rubber:

CH₃ CH₃ H
| | |
H₂C=C-CH=CH₂ ~~~C=C~~~
/ \
2-methyl-1,3-butadiene CH₂ CH₂
cis configuration
(same side of C=C)
• Cis-polyisoprene: chains held by weak van der Waals interactions; coiled structure → can be stretched
like a spring → elastic properties

Limitations of Natural Rubber (Why Vulcanisation is Needed)

• Soft at high temperature (>335 K)
• Brittle at low temperatures (<283 K)
• High water absorption capacity
• Soluble in non-polar solvents
• Non-resistant to attack by oxidising agents

Vulcanisation of Rubber
• Process: heating raw rubber with sulphur and appropriate additive at 373–415 K
• Sulphur forms cross links at reactive sites of double bonds → rubber gets stiffened
• Tyre rubber: uses 5% sulphur as crosslinking agent
Vulcanised rubber — S crosslinks between chains:

CH₃ CH₃
| |
 ~~~CH₂-C=CH-CH₂~~~ ~~~CH₂-C=CH-CH₂~~~
| |
S S
| |
~~~CH₂-C-CH-CH₂~~~ ~~~CH-CH=CH-CH₂~~~
| | |
S S S
(S crosslinks stiffen and strengthen the rubber)
• Result: improved elasticity, strength, resistance to oxidation and solvents, less temperature sensitive

6.2 Synthetic Rubbers

• Any vulcanisable rubber-like polymer capable of being stretched to twice its length and returning to
original shape when force released
• Synthetic rubbers = homopolymers of 1,3-butadiene derivatives OR copolymers of
1,3-butadiene/derivatives with another unsaturated monomer

(i) Neoprene (Polychloroprene)

• Monomer: chloroprene (2-chloro-1,3-butadiene, CH₂=CCl-CH=CH₂)
• Mechanism: free radical polymerisation
n CH₂=CCl-CH=CH₂ →[free radical]→ -(CH₂-CCl=CH-CH₂)ₙ-
Chloroprene: Neoprene:

Cl Cl
| |
CH₂=C-CH=CH₂ -(CH₂-C=CH-CH₂)ₙ-
2-chloro-1,3-butadiene (polychloroprene)
• Properties: superior resistance to vegetable and mineral oils
• Uses: conveyor belts, gaskets, hoses

(ii) Buna-S (Styrene-Butadiene Rubber, SBR)

• Monomers: 1,3-butadiene (CH₂=CH-CH=CH₂) + styrene (C₆H₅CH=CH₂)
• Type: addition copolymerisation
n CH₂=CH-CH=CH₂ + n C₆H₅CH=CH₂
→ -(CH₂-CH=CH-CH₂-CH(C₆H₅)-CH₂)ₙ-
Buna-S copolymer unit:

C₆H₅
|
~~~-CH₂-CH=CH-CH₂-CH-CH₂-~~~
[butadiene unit] [styrene unit]
• Properties: tough; good substitute for natural rubber
• Uses: auto tyres, floor tiles, footwear components, cable insulation

(iii) Buna-N (Nitrile Rubber, NBR)

• Monomers: 1,3-butadiene (CH₂=CH-CH=CH₂) + acrylonitrile (CH₂=CHCN)
• Conditions: peroxide catalyst; copolymerisation
n CH₂=CH-CH=CH₂ + n CH₂=CHCN
→[peroxide]→ -(CH₂-CH=CH-CH₂-CH₂-CH(CN))ₙ-
Buna-N copolymer unit:

CN
|
~~~-CH₂-CH=CH-CH₂-CH₂-CH-~~~
 [butadiene unit] [acrylonitrile unit]
• Properties: resistant to petrol, lubricating oil and organic solvents
• Uses: oil seals, tank lining
⚠ Buna-S vs Buna-N: both are copolymers of 1,3-butadiene but Buna-S uses styrene while Buna-N uses
acrylonitrile as the second monomer

7. Biodegradable Polymers
• Large number of synthetic polymers resist environmental degradation → accumulate as solid waste →
acute environmental problems
• Solution: biodegradable polymers designed with functional groups similar to biopolymers
• Aliphatic polyesters = one of the most important classes of biodegradable polymers

7.1 PHBV — Poly β-hydroxybutyrate-co-β-hydroxy valerate

• Monomers: 3-hydroxybutanoic acid (CH₃-CH(OH)-CH₂-COOH) + 3-hydroxypentanoic acid (CH₃CH₂-
CH(OH)-CH₂-COOH)
• Type: copolymerisation (polyester type)
CH₃-CH(OH)-CH₂-COOH + CH₃CH₂-CH(OH)-CH₂-COOH
→ -(O-CH(CH₃)-CH₂-C(=O)-O-CH(CH₂CH₃)-CH₂-C(=O))ₙ-
PHBV structure:

OH O OH O
| || | ||
-O-CH-CH₂-C-O-CH-CH₂-C-
| |
CH₃ CH₂CH₃
[β-OH butyrate unit] [β-OH valerate unit]
• Degradation: undergoes bacterial degradation in the environment
• Uses: speciality packaging; orthopaedic devices; controlled release of drugs

7.2 Nylon 2 – Nylon 6

• Type: alternating polyamide copolymer
• Monomers: glycine (H₂N-CH₂-COOH) + amino caproic acid [H₂N-(CH₂)₅-COOH]
• Contains amide linkages; is biodegradable
-(NH-CH₂-CO-NH-(CH₂)₅-CO)ₙ-
Nylon 2 – Nylon 6 structure:

O O
|| ||
~~~-NH-CH₂-C-NH-(CH₂)₅-C-NH-CH₂-C-~~~
[Nylon-2 unit] [Nylon-6 unit]
(glycine) (amino caproic acid)
8. All Polymers — Quick Reference Master Table
Polymer Monomer(s) Type Conditions / Properties Uses
Linkage
LDP (Low Ethene Addition / 1000–2000 atm; Inert, tough, Wire insulation,
Density (CH₂=CH₂) chain 350–570 K; O₂ flexible, poor squeeze bottles, toys,
Polythene) growth or peroxide; conductor flexible pipes
branched
HDP (High Ethene Addition / 6–7 atm; 333– Inert, tougher Buckets, dustbins,
Density (CH₂=CH₂) chain 343 K; Ziegler- and harder bottles, pipes
Polythene) growth Natta catalyst; than LDP
linear
Teflon Tetrafluoroeth Addition / Free radical or Chemically Oil seals, gaskets,
(PTFE) ene chain persulphate inert; non-stick utensils
(CF₂=CF₂) growth catalyst; high corrosion
pressure resistant
Polyacrylonitr Acrylonitrile Addition / Peroxide Substitute for Commercial fibres
ile (CH₂=CHCN) chain catalyst wool (orlon, acrilan)
(Orlon/Acrila growth
n)
Polypropene Propene Addition / Ziegler-Natta Hard, Ropes, toys, pipes,
(CH₂=CHCH chain catalyst thermoplastic fibres
₃) growth
Polystyrene Styrene Addition / Free radical Insulator, Insulator, wrapping,
(C₆H₅CH=C chain transparent toys, radio/TV
H₂) growth cabinets
PVC Vinyl chloride Addition / Free radical Rigid or Rain coats, handbags,
(Polyvinyl (CH₂=CHCl) chain flexible vinyl flooring, water
chloride) growth depending on pipes
plasticiser
Nylon 6,6 Hexamethyle Condensat 553 K; high High tensile Sheets, bristles,
nediamine + ion; step pressure; –CO– strength; textiles
adipic acid growth NH– linkage; crystalline; H-
releases H₂O bonding
Nylon 6 Caprolactam Condensat 533–543 K; Strong, tough Tyre cords, fabrics,
ion; step H₂O; –CO–NH– fibres ropes
growth linkage
(ring
opening)
Dacron / Ethylene Condensat 420–460 K; Crease Blending with
Terylene glycol + ion; step ZnOAc/Sb₂O₃; resistant cotton/wool; safety
terephthalic growth –CO–O– ester helmets
acid linkage; releases
H₂O
Bakelite Phenol + Condensat H⁺ or OH⁻ Hard, Combs, electrical
formaldehyde ion; step catalyst; infusible, switches, handles,
growth crosslinked 3D thermosetting; computer discs
network; cannot be
thermosetting remoulded
Novolac Phenol + Condensat H⁺ catalyst; Thermoplastic Paints
formaldehyde ion; step linear polymer linear polymer
growth
Melamine- Melamine + Condensat Crosslinked; Hard, Unbreakable crockery
 formaldehyde formaldehyde ion; step thermosetting unbreakable
growth
Urea- Urea + Condensat Crosslinked; Hard, brittle Unbreakable cups,
formaldehyde formaldehyde ion; step thermosetting laminated sheets
resin growth
Glyptal Ethylene Condensat Ester linkage Film-forming Paints and lacquers
glycol + ion; step
phthalic acid growth
(polyester)
Natural Isoprene (2- Natural cis configuration; Elastic; soft After vulcanisation:
rubber (cis- methyl-1,3- addition van der Waals >335K; brittle tyres, tubes, footwear
1,4- butadiene) polymer forces; coiled <283K;
polyisoprene) structure soluble in non-
polar solvents
Vulcanised Isoprene Crosslinke 373–415 K + Hard, elastic, Tyres, mechanical
rubber (natural d natural sulphur; 5% S resistant to goods
rubber + S) polymer for tyre rubber heat/cold/solv
ents/oxidation
Neoprene Chloroprene Addition Free radical; cis Resistant to Conveyor belts,
(polychloropr (CH₂=CCl- homopoly structure vegetable and gaskets, hoses
ene) CH=CH₂) mer mineral oils
Buna-S 1,3-Butadiene Addition Peroxide Tough; Auto tyres, floor tiles,
(SBR) + styrene copolymer catalyst substitute for footwear, cable
natural rubber insulation
Buna-N 1,3-Butadiene Addition Peroxide Resistant to Oil seals, tank lining
(NBR) + acrylonitrile copolymer catalyst petrol,
lubricating oil,
organic
solvents
PHBV 3- Condensat Bacterial Biodegradable Speciality packaging,
Hydroxybutan ion degradation in orthopaedic devices,
oic acid + 3- copolymer environment; drug release
hydroxypenta (aliphatic biodegradable
noic acid polyester)
Nylon 2– Glycine + Condensat Alternating; Biodegradable Biodegradable
Nylon 6 amino caproic ion amide linkage; polyamide applications
acid copolymer biodegradable
(polyamide
)

9. Classification Quick Reference

9.1 Addition vs Condensation
Feature Addition Polymerisation Condensation Polymerisation
Monomers Unsaturated (alkenes, alkadienes) Bifunctional: –NH₂, –OH, –COOH groups
Small molecule No — atoms of monomer fully Yes — H₂O, HCl, alcohol, etc.
eliminated? incorporated
Mechanism Chain growth via free radicals or ions Step growth — each step independent
Also called Chain growth polymerisation Step growth polymerisation
Examples Polythene, PVC, Teflon, Nylon 6,6, Nylon 6, Dacron/Terylene,
polyacrylonitrile, Buna-S, Buna-N, Bakelite, Novolac, Melamine polymer, PHBV
 Neoprene

9.2 Thermoplastic vs Thermosetting

Property Thermoplastics Thermosetting
On heating Soften repeatedly Permanently harden (infusible)
Crosslinks None (linear/branched) Extensive 3D crosslinks
Remoulding Can be remoulded Cannot be remoulded or reused
Structure Linear or branched Network / crosslinked
Examples Polythene (LDP, HDP), PVC, polystyrene, Bakelite, melamine-formaldehyde, urea-
polypropene, nylon, dacron formaldehyde

9.3 Intermolecular Forces — Increasing Order

Elastomers < Thermoplastics < Fibres
Buna-S < Polythene < Nylon 6,6 (NCERT answer to intext Q 15.5)