• Subject Name: Applied Chemistry

• Subject Code: 202

• Unit IV Polymers & Corosion

Faculty Name : Dr Vibha Gajbe

Unit No: 4 Unit name: Polymers & Corrosion

Polymers
 Polymers
• The word polymer is derived from two Greek words; Poly-
many & mer- unit.
• Large molecules having large molecular mass (103- 107μ ).
• Also called macromolecules.
• Polymerization is the process of
chemically bonding monomer building
blocks to form large molecules.
– Commercial polymer molecule contains
Polymerization
thousands of repeat units.
Ethene Repeating Unit Polythene Polymer
nCH2=CH2 n-[CH2-CH2] [-
CH2-CH2]n

polymerization
Hexamethylene diamine Adipic acid

nNH2 ( CH2)6 NH2 + nHOOC

Nylon 6,6
(CH2)4COOH
 Classification of Polymers

Protein,
cellulose,
Natural Polymers
starch, rubber
etc.

Cellulose
Classification based Semi synthetic
acetate,
on source polymers
cellulose nitrate

Polyethene,
nylon 6,6;
Synthetic polymers
synthetic
rubber
Classification based on structure of polymers

Linear chain
Polymers

Classification
Branched chain
based on
Polymers
structure

Cross Linkage
Polymers
 Linear Polymers
Monomers linked together to form straight
chain polymers.

Well packed.

High magnitude of intermolecular forces of

attraction.

High density, high tensile strength.

High melting points.

PVC, HDP, Nylon, Polyester.

Linear Polymers
 Branched Chain Polymers
Branches connected to main ones.

Branches have repeating unit as the main polymer

chain.
Branches result from side reactions during
polymerization.
Irregular packing of polymer chains.

Less crystalline & less dense.

Low density, low tensile strength, low melting point.

Weak intermolecular forces.

Branching affects the physical properties such as

viscosity & elasticity.
Copolymer
 Graft Copolymers
Consisting of long sequence of one monomer (the backbone)

Represent material combining the property of two or more polymers in one

entity.
Characterized by low density of grafts.

Backbone & the branches may differ in chemical nature.

Same in chemical nature are called comb shaped copolymers.

 Branched Chain Polymers
Examples: Low Density Polyethene, Glycogen, Starch,
Amylopectin etc.

HDPE – High Density PolyEthylene is a linear polymer with

minor branching.
LDPE – Low Density PolyEthylene contains short chain
branches.

Greater chain linearity and chain length:

• Increases the melting point.
• Improves the physical and mechanical properties of the
polymer.
Effect of branching on density of a
polymer
LDPE & HDPE
 Cross-linked polymers

Cross links
between chains

• Adjacent polymer chains are connected in a 3D network structure.

• Monomers are cross linked together to form 3D network polymer.
• Cross links between polymer chain makes the polymer more elastic.
• Cross linking decreases the viscosity of polymers.
• They are hard, rigid ,less viscous, less elastic & brittle.
• Do not melt, but burn on strong heating.
 Cross-Linked Polymers
• Strong covalent bonds.
• Giant molecules.
• Insoluble in solvents.
• The movement of monomeric unit is prevented by cross-
links.
• Bakelite, Melamine Formaldehyde, Urea Formaldehyde
etc.
Cross-Linked Polymer

Stretch

Relax
The cross-links hold the chains together.
When released, the polymer will return to it's
original form.
Linear Polymer

Stretch

The chains can be stretched, which causes

them to flow past each other. When released,
the polymer will not return to its original form.
 Classification based on mode of
polymerization
• Addition polymers
– Repeated addition of monomers
– Molecules grows by the addition of one
new monomer at-a- time via a chain
reaction.
– Each new monomer unit creates an active
site for the next attachment.
Polymerization
nCH2=CH2 n-[CH2-CH2] (homopolymer)
Ethene Polyethene
 Addition Polymers
A + A + A+ A A A A A
monomers polymer

+ + +

ethylene (ethene) polyethylene linear

+ + +
branched
propylene (propene) polypropylene
Preparation of some important addition polymers
 Polythene
– Low Density Polythene (LDP) [Branched Chain Polymer]:

350K-570K
nCH2=CH Low Density Polythene
1000-2000
Ethene atm pressure
Dioxide/ peroxide

 LDP obtained is chemically inert, flexible.

 Poor conductor of electricity.
 Hence LDP is used in the insulation of electricity carrying wires.
Polyethylene
Preparation of Low-density polythene
Preparation of Polythene
Preparation of Low-density polythene
 High Density Polythene [Linear
chain polymer]

333K-343K, 6-7 atm Pressure

nCH2=CH
(C H ) Al
2 – TiCl High Density
Ethene 2 5 4
(Zeigler-Natta catalyst)

Polythene

 HDP consists of linear molecules.

 High density & tensile strength.
 Chemically inert, tough and hard.
 Used in manufacture of buckets, dustbins,
Preparation of High-density polythene
Polyvinyl Chloride
 Polytetrafluroethene (Teflon)

[CF 2-CF2]n
Persulphate Catalyst
High pressure
Tetrafluroethene Teflon

 Teflon is tough and chemically inert.

High softening point 350°C. (Can be moulded at high temperature by
applying high pressure)
 High chemical resistance (resistant to attack by corrosive reagents).
Good mechanical & electrical properties.
 Used in making oil seals and gaskets, for non-stick surface coated utensils.
Uses of Teflon
 Polyacrylonitrile
CN
Polymerization
n CH2=CHCN -[CH2-CH]n-
Peroxide catalyst
Acrylonitrile
Polyacrylonitrile

 Polyacrylonitrile is used as a substitute for wool in

making commercial fibres as acrilin.
 SOME COMMON ADDITION POLYMERS
Example Monomer Polymer Uses
most common polymer
polyethylene CH2 CH2 CH2 CH2
bags, wire insulation,
squeeze bottles
polypropylene CH2 CH CH2 CH
fibers, bottles,
CH3 CH3 indoor-outdoor carpet

polystyrene CH2 CH CH2 CH

styrofoam,
inexpensive molded
objects: household items,
toys

polyvinyl chloride CH2 CH CH2 CH synthetic leather, clear

(PVC) Cl bottles, floor coverings,
Cl
water pipe
Teflon CF 2 CF 2 CF 2 CF 2 non-stick surfaces,
chemically resistant items
polyacrylonitrile CH2 CH CH2 CH fiber used in sweaters,
(Orlon, Acrilan) C N C N blankets, carpets
 Condensation Polymers

 Formed by repeated condensation reaction between

two different monomeric units.
 Polymerization occur via the elimination of small
molecules such as water, alcohol etc.
 Dacron(Terylene), nylon-6, nylon 6,6.
 Condensation Polymers
O O
420-460 K
HO C C OH H O CH2CH2 OH
ZnSbO3

Terephthalic acid Ethylene glycol

O O
C C O CH2CH2 O + H2O

Dacron polymer (Terylene)

Condensation polymerization reactions characterized by
their linking units

Polyamides
– Polymers possessing amide linkages.
• Nylon 6
• Nylon 6,6
Polyesters
– Polycondensation products of dicarboxylic acids and
diols.
– Dacron, melamine formaldehyde.
 Preparation of nylon 6

High temperature

 Nylon 6 is used for the manufacture of tyre cords, fabrics and

ropes.
 Preparation of nylon 6,6

 Nylon 6,6 is also a co-polymer since it is made from two

different monomers.
Properties and uses of Nylon-66
Nylon-66
Preparation of Nylon 6,6
Properties & Uses of Nylon 6,6
Polyester
Polyester
Polyester
Preparation of Melamine-Formaldehyde Polymer
 CoPolymerization
 Polymers which are formed by combining two different
monomers in alternating fashion are called copolymers.

A + B + A + B A B A B

Butadiene

Styrene

styrene-butadiene
rubber (SBR)
• Addition of two different monomers are termed
co-polymers.
• Buna-S, Buna-N

nCH2=CH-CH=CH2 + nC6H5CH=CH2
1,3 butadiene Styrene

-(CH2-CH=CH-CH2-CH2-CHC6H5-)n
Butadiene-styrene copolymer (Buna-S)
 Addition & Condensation Polymerization
Addition Polymerization Condensation Polymerization

Formed by repeated addition of Formed by repeated

monomers. condensation reaction two
different monomeric units.

Number of units decreases Monomer disappear early in the

steadily through the reaction. reaction.

Single units of monomer Polymerization occur via

polymerizes to form eliminationnof small molecules.
homopolymer.
 Addition Polymerization Condensation Polymerization

High molecular mass Polymer molecular mass rises

polymer is formed. steadily throughout the
reaction.

Longer reaction times have a To obtain polymer of high

little effect on molecular molecular weight longer
weight, gives higher yield. reaction time is essential.

The reaction mixture

All types of molecular species
contains only monomers &
are present at any stage.
high polymers.
Classification Based on Molecular Forces

Based on
molecular forces

Thermoplastic Thermosetting
Elastomers Fibers
Polymers polymers
 Elastomers
Loosely cross -linked polymers.

Rubber like solids with elastic properties.

Amorphous polymers.

Weak intermolecular forces.

Weak intermolecular forces stretch the polymer.

Cross links help the polymer to regain its original position.

Natural rubber, Buna-S, Buna-N, neoprene.

Examples of elastomers
 Fibers
Thread forming solids.

Strong intermolecular forces.

Close packing of chains.

High tensile strength, less

elasticity.
Nylon 6,6, Dacron, Silk, Polyester
etc.
 Thermoplastic Polymers

Long chain molecules

 Thermoplastic Polymers
Linear, slightly branched long chain molecules.
Softened on heating and hardened on cooling.
Possess intermolecular forces of attraction.
No cross linkage between the chain.
Polymer chain move freely, softens easily.
Polythene, polystyrene, polyvinyl etc.
 Thermoplastic Polymers
The word
What does
‘plastic’ the
means
word ‘plastic’
‘easily shaped
or mean?
moulded’.
Formed by heat

Soften when heated

Made of long
polymer chains
with few cross links

Can be reheated
and reshaped
Mostly recyclable
 Thermosetting polymers
On heating undergo permanent change.

Heavily branched cross linkage polymers.

Can not be recycled or reprocessed.

On heating form cross linkage, become hard & infusible.

Cross-linked molecules
Cross link does not allow molecule to move freely.

Permanently rigid.

Bakelite, Urea formaldehyde resins.

 Thermosetting polymers
Thermosets are formed when two or more components chemically react with
each other under ambient conditions to form highly cross linked network.

Hard & rigid.

High temperature resistance when exposed to heat-High heat Stability.

Exchange electrons/ cross links to form new chemical bonds during cross
linking.

Formed by condensation polymers.

Examples: Silicones, polyurethanes, polyesters

 Thermosetting polymers
Initially set by heat

Consist of polymer Cannot be

chains with strong reshaped once set
bonds between
each chain

Strong and durable Common in powder

or resin forms
 Thermoplastic Polymers Thermosetting Polymers

• Long chain macromolecules. • 3D network structure joined by

• Formed by addition covalent bond.
polymerization. • Formed by condensation
• Soften on heating readily. polymerization.

• Can be reshaped & reused. • Do not soften on heating.

• Retain their structure on heating.
Hence cannot be reshaped &
reused.
 Thermoplastic Polymers Thermosetting Polymers

• Soft, weak & less brittle. • Hard, strong & more brittle.
• Can be reclaimed from • They cannot be reclaimed.
waste. • Insoluble due to strong
• Soluble in some of the bond & cross linking.
organic solvents.
 Rubber
Rubber

Natural Rubber Synthetic Rubber

Linear polymer of Any vulcanised

isoprene rubber

Isoprene unit Natural rubber

2-methyl-1,3-butadiene Cis-1,4-polyisoprene
 Vulcanization Of Rubber
Charles Goodyear in 1839

100°-140°C

Raw rubber (isoprene)

Vulcanized Rubber

Structure of vulcanized rubber molecule

 Benefits of Vulcanization
Good tensile strength Can bear load of 200 kg/cm2
Low water absorption tendency

High resistance to oxidation and to abrasion.

Very high resistance to wear & tear

Resistance to organic solvents

Low elasticity
Property Raw Rubber Vulcanized Rubber
Tensile Strength 200 kg/cm2 2000 kg/cm2
Synthetic rubbers
 Synthetic Rubbers
Preparation of neoprene
 Neoprene is formed by free radical polymerization
of chloroprene.

Cl Cl
Polymerization
nCH2=C-CH=CH2 -[CH2-C=CH-CH2]n
Chloroprene Neoprene
2-Chloro-1,3-butadiene

 Superior resistance to vegetable & mineral oil.

 Used for the manufacture of conveyor belts & gaskets.
Neoprene
 Preparation of Buna-N
CN
Copolymerization
nCH2=CH-CH=CH2 + nCH2=CH
Peroxide
1,3-Butadiene Acrylonitrile
CN

[ CH2-CH=CH-CH2-CH2-CH]n
Buna-N

 Resistant to the action of petrol, lubricating oil & organic solvents.

 Used in making oil seals, tank lining.
Glass Transition Temperature
 Glass Transition
Temperature
• Glass transition occurs in amorphous polymers.
• HDPE -125°C
• LDPE -130 °C

Effect of heat on polymers

Temperature controls behaviour of ploymers.

Amorphous polymers have softening point (do not have melting point).

At very low temperature both amorphous and crystalline polymers behave like glass.

On heating Tg is reached after which they soften.

Amorphous polymers become rubbery, and then gummy and liquifies on further heating.

Crystalline polymer on heating above Tg exhibit thermoplastic behaviour and finally liquifies.
Biodegradable Polymers
 Aliphatic Polyesters
Poly β-hydroxybutyrate-co- β-hydroxy valerate
(PHBV)
OH OH
Copolymerization
CH3-CH-CH2-COOH + CH3-CH2-CH-CH2-COOH
3-Hydroxybutanoic acid 3-Hydroxypentanoic acid

(O-CH-CH2-C-O-CH-CH2-C)n
O
O
 Used in packaging, orthopaedic devices. PHBV
 Undergoes bacterial degradation in the environment.
 Nylon 2-nylon 6

Copolymerization
NH2-CH2-COOH + [NH2-(CH2)5-COOH] ?
Glycine Amino caproic acid
 Explain the difference between Buna-N and
Buna-S.
 Arrange the following polymers in the order
of their intermolecular forces.
 Nylon 6,6; Buna-S, Polythene.
 Nylon 6, Neoprene, Polyvinyl chloride.
 Classify the following as addition and
condensation polymers:
– Terylene, Bakelite, Polyvinyl chloride, Polythene
Thank
You