Unit 14: POLYMERS

BY SHIVANGANI RAWAT
 POLYMERS AND POLYMERIZATION
POLYMERS
• Large molecules formed by smaller repeating units (Monomers).
• Process of forming polymers from monomers- Polymerization.
 CLASSIFICATION OF POLYMERS
(A) BASED ON SOURCE
 NATURAL POLYMERS
• (derived from plants and animals)
• E.g. Proteins, cellulose
 SEMI- SYNTHETIC POLYMERS
• (derived from natural polymers)
• E.g. Rayon, cellulose nitrate
SYNTHETIC POLYMERS
• (derived from chemicals- Man made)
• E.g. Polythene, Nylon-6,6
 CLASSIFICATION OF POLYMERS
(B) BASED ON STRUCTURE
 LINEAR POLYMERS
• Long and straight chain
• E.g. High density polythene, PVC
BRANCHED POLYMERS
• Linear chain with some branches
• E.g. Low density polythene
CROSS-LINKED POLYMERS
•Formed by bifunctional or trifunctional monomers.
•E.g. Bakelite, melamine
 CLASSIFICATION OF POLYMERS
(C) BASED ON MODE OF POLYMERIZATION
ADDITION POLYMERS
formed by the repeated addition of monomer molecules containing multiple bonds
HOMOPOLYMER: Formed by one kind (same) monomers.
E.g.

COPOLYMER : obtained by the polymerisation of two or more kind of monomers.

E.g.
 CLASSIFICATION OF POLYMERS
(C) BASED ON MODE OF POLYMERIZATION
 CONDENSATION POLYMERS
• formed by the repeated condensation reaction of different bifunctional or trifunctional
monomers.
• elimination of small molecules like H2O,HCl, CH3OH takes place.
e.g. NYLON 6,6
 CLASSIFICATION OF POLYMERS
(D) BASED ON MOLECULAR FORCES
 ELASTOMERS
• held together by weak van der Waals forces.
• low elasticity.
• For example: Buna-S, buna-N, neoprene.
 FIBRES
• held together by strong hydrogen bonds.
• high tensile strength.
• sharp melting point.
• For example: Nylon, polyster, silk, wool, orlon, rayon.
 CLASSIFICATION OF POLYMERS
(D) BASED ON MOLECULAR FORCES
 THERMOPLASTIC POLYMER
• intermolecular forces of attraction intermediate between elastomers and fibers.
• Soft and remoulded by heating.
• For example: Polythene, PVC, polystrene, polypropene.
 THERMOSETTING POLYMER
• hard, rigid, cross-linked polymers.
• cannot be remoulded.
• For example: Melamine, bakelite.
TYPES OF POLYMERIZATION REACTIONS
1. ADDITION POLYMERISATION
(CHAIN GROWTH POLYMERIZATION)

2. CONDENSATION POLYMERIZATION or
(STEP GROWTH POLYMERIZATION)
 ADDITION POLYMERISATION
(CHAIN GROWTH POLYMERISATION)
• Monomers - unsaturated compounds ( same or different)
• takes place through free radical mechanism.

Free radical
mechanism

Chain Chain Chain

Initiation Propagation Termination
 FREE RADICAL POLYMERISATION OF
ETHENE
ETHENE is converted to POLYTHENE by free radical polymerization as follows:
Chain initiating step:

Chain propagating step:

 FREE RADICAL POLYMERISATION OF
ETHENE
 Chain terminating step:
SOME IMPORTANT ADDITION POLYMERS
 POLYTHENE
 Low density polythene (LDPE):
• obtained by polymerization of ethene at 350 to 750 K and 1000 to 2000 atm pressure.
• chemically inert.
• tough but flexible.
• poor conductor of electricity.
• used in the insulation of electricity carrying wires and manufacture of squeeze bottles, toys and
flexible pipes.
SOME IMPORTANT ADDITION POLYMERS
 High density polythene (HDPE):
• obtained by the addition polymerisation of ethene at 330 to 350 K at atmospheric pressure.
• tough and hard.
• high tensile strength.
• used in the manufacture of plastic containers, house wares, pipes.
SOME IMPORTANT ADDITION POLYMERS
 POLYACRYLONITRILE

• used in the formation of substitute for wool as orlon or acrilan.

SOME IMPORTANT ADDITION POLYMERS
 POLYTETRAFLUOROETHENE (TEFLON)

• chemically inert.
• resistant to attack by corrosive reagents.
• used in the manufacture of oil seals and gasket and non-stick kitchen wares.
 CONDENSATION POLYMERISATION
(STEP GROWTH POLYMERISATION)
• repetitive condensation reaction between two bi-functional monomers.
• elimination of some smaller molecules like H2O, NH3, HCI, ROH, etc., therefore it is also named as
step Growth Polymerisation.
• For example: Dacron
 SOME IMPORTANT CONDENSATION
POLYMERS
 POLYAMIDES
• polymers possessing amide linkages (-NH-CO-).
• These polyamides are known as nylons.
 Nylon 6:
Monomer : Caprolactum

• used for the manufacture of tyre cords, fabrics and ropes.

 Nylon 6,6
• Monomers: hexamethylenediamine , adipic acid

• used in making stocking, socks, ropes, Parachutes, fabrics, bristles of tooth brush.
 Melamine – Formaldehyde Polymer
• Monomers: Melamine and formaldehyde

• used in the manufacture of unbreakable crockery.

 COPOLYMERISATION
• Two different monomers are involved in polymerization.
• E.g. Buna- S ( Butadiene-Styrene copolymer)
• Monomer: 1,3-butadiene and Styrene
RUBBER

Rubber

Synthetic Natural
Rubber Rubber

Neoprene Buna-N
 NATURAL RUBBER
• Monomer: Isoprene
• elastic properties.

• soft at high temperature and brittle at low temperatures.

• non-resistant to the attack of oxidizing agents.
 VULCANISATION OF RUBBER
• The process of adding sulphur to rubber to improve its physical properties is called
vulcanisation of rubber.

• Vulcanisatlon is carried out by adding sulphur (3-5%) to the rubber.

• Sulphur forms cross links at the reactive sites of double bonds and thus the rubber gets
stiffened.
 VULCANISATION OF RUBBER
Vulcanised rubber has:
• High elasticity
• Low water-absorption tendency
• Resistance to oxidation.
 SYNTHETIC RUBBER
 Neoprene
• Monomer: Chloroprene

• used for manufacturing conveyor belts, gaskets and hoses.

 SYNTHETIC RUBBER
 Buna-N
• Monomers: 1,3-butadiene and acrylonitrile

• used in making conveyor belts and printing rollers.

 BIODEGRADABLE POLYMERS
 Poly-hydroxybutyrate- co-β-hydroxy valerate (PHBV):
• Monomers: 3-hydroxy butanoic acid and 3-hydroxy pentanoic acid.

• used in packaging, orthopaedic devices.

 BIODEGRADABLE POLYMERS
 Nylon-2-Nylon-6:
• Monomers: glycine and amino caproic acid.
POLYMERS OF COMMERCIAL IMPORTANCE
Polymer Monomer Uses

CH2=CHCl Manufacture of rain coats, hand bags, vinyl

Polyvinyl chloride (PVC)
Vinyl Chloride flooring, and water pipes.

CH2=CH2 Manufacture of wire insulators, bags, used in

Polyethylene
Ethylene packaging.

CH2=CH‒C6H5 As insulator, wrapping material, manufacture of

Polystyrene
Vinylbenzene (Styrene) toys, radio and television cabinets

CH2=CH‒OCOCH3
Polyvinyl acetate (PVA) Making latex, paint
Vinylacetate

CH2=CH‒CH=CH2
BUNA rubber Manufacture of tyres and hoses
1,3-Butadiene