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Lecture 2

Classification of Polymers
Classification of Polymers
Thermal response
Mode of formation/Polymer mechanism
Line structure
Application and Physical properties
Natural Polymer : Renewable resources such
as Natural rubber, starch, silk, cellulose,
Semisynthetic Polymer: chemical Modification
of natural polymers ethers and esters of
cellulose, cellulose nitrate, methyl cellulose
Synthetic Polymers: Obtained from
polymerization of petroleum based products
Polyethylene, Polystyrene
Application and Physical properties

Rubber: tensile strength 300-3000 psi, elongation

at break 300-1000 %, natural and synthetic
rubber, elastomers.
Plastic : tensile strength 4000-15000 psi,
elongation at break 20-200 %, polyethylene,
polypropylene etc
Fiber : tensile strength 2000-150000 psi strongest
used in industries, textiles, warmth, flexible,
thermal insulation, cotton, cellulose, silk,
synthetic polyamide, polyester fiber and acrylic
Thermal Response
Thermoplastics (resins): Thermoplastics soften
when heated and subsequently melt. When
cooled they become hard and rigid once again.
Example: Polyethylene, PVC, Nylon Uses: Bags,
Mugs, Toys
Thermosetting plastics (resins): Thermosetting
resins do not become softy on heating & they
never melt once set. Example: Phenolic resin,
diene rubber ,Bakelite Uses: Electric switches,
Telephone parts, Cooker handles
Difference between TP & TS
Formed by addition Polymerization
Long chain linear polymers
Soften on heating and stiffen on cooling
Can be remoulded
Usually soft, weak & less brittle
Can be reclaimed from wastes
Soluble in organic solvents Insoluble in organic

1. Formed by condensation Polymerization
2. Three dimensional network structure joined by
strong covalent bonds
3. Do not soften on heating
4. Cannot be remoulded
5. Usually hard, strong & more brittle
6. Cannot be reclaimed from wastes
7. Insoluble in organic solvents
Polymerization mechanisms

Chain Growth/addition Step Growth/condensation

Monomer with carbon carbon Monomer with different functional
unsaturated group OH, COOH, NH2,
The only growth reaction is addition Reaction can occur independently
of monomer to a growing chain between any pair of molecular
with a reactive monomer species
The reaction mixture consists of high
polymer and unreacted The reaction mixture consists of
monomers with very few oligomers of many sizes in a
actively growing chain statically calculable distribution
Monomer concentration decreases
steadily as reaction time Monomer disappear early in favor of
increases low oligomer
Polymerization mechanisms

Chain growth Step Growth

Examples Examples are Polyesters,
Benzoyl peroxide Polyamide, Polyurethane,
Acetyle peroxide
Line structure
Linear chains :a polymer consisting of a single continuous chain of
repeat units
Branched chains :a polymer that includes side chains of repeat
units connecting onto the main chain of repeat units
Cross linked polymer :a polymer that includes interconnections
between chains
Net work polymer :a cross linked polymer that includes numerous
interconnections between chains

Linear Branched Cross-linked Network

Direction of increasing strength

Microstructure - Tacticity

atactic syndiotactic isotactic

Side groups on random Side groups on alternating Side groups on the same
Sides of the backbone sides of the backbone side of the backbone
Polyolefins with side chains have stereocenters on every other carbon


With so many stereocenters, the stereochemistry can be complex.

There are three main stereochemical classifications for polymers.
Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

1. Tacticity affects the physical properties
1. Atactic polymers will generally be amorphous, soft, flexible
2. Isotactic and syndiotactic polymers will be more crystalline, thus
harder and less flexible
2. Polypropylene (PP) is a good example
1. Atactic PP is a low melting, gooey material
2. Isoatactic PP is high melting (176), crystalline, tough material
that is industrially useful
3. Syndiotactic PP has similar properties, but is very clear. It is
harder to synthesize
3-Crystalline polymer : solid polymers with a high degree of
structural order and rigidity
4- Amorphous polymers : polymers with a low degree of
structural order
5-Semi crystalline polymer : most polymers actually consist of
both crystalline domains and amorphous domains with properties
between that expected for a purely crystalline or purely
amorphous polymer

Amorphous Crystalline