Polymer

POLYMER-

Small molecule(monomer) joining together to

form long molecule (polymer)

Degree of Polymerization

DP

Degree of Polymerization

no. of repeating units

3CH2 = CH2

( n= 3)

Degree of Polymerization-the
number of monomeric units
contained in the polymer

high polymers-

Polymers with high

degree of
polymerization

low polymers

-Polymers with low

degree of
polymerization

Functionality

Functionality
monomer - at least 2 reactive
sites / bonding sites
Reactive sites
1.Functional group
2. = / triple bond

Types of Functionality

Bifuctional
monomer
(2 reactive
site)

Trifuctional
monomer
(3 reactive site

Tetrafuctional

monomer

(4 reactive site)

1. Bifuctional monomer ( 2 reactive site )

1.CH2 = CH2
2. CH2

= CH- Cl

3. NH2- CH2 - COOH

4. CH2 = CH
C6H5

2.Trifuctional monomer ( 3 reactive site )

HO -CH2 -CH CH2-OH

OH
Glycerol

3. Tetrafuctional monomer( 4 reactive site )

CH2=CH-CH=CH2
1,3 - Butadiene

Classification
of polymer

1.On the
basis of

5.On the
basis of

source

2.On the
basis of

structure

Tacticity
Classification
of polymer

3.On the
basis of

5.On the
basis of

molecular
force

4.On the
basis of

growth
polymer
chain

method of
synthesis

Natural polymerfound in nature

silk, cotton, jute ,
proteins ,rubber , Wool

Starch- D gluose
Cellulose- -D
gluose
Proteins-polypeptides,
polyamides
Nucleic acid Cis isoprene,
natural rubber

Synthetic polymerman made

PE (polyethylene)
PP (polypropylene)

PS (polystyrene)
PVC (polyvinyl
chloride)
Nylon
Terylene
Bakelite

a) LinearHDPE
Nylon
polyester

c) 3 D network
polymerBakelite
UF
Melamine
formaldehyde

2.On the
basis of
structure

b)Branched
LDPE
Glycogen
amylopectin

Difference between linear, branched & 3D polymer

Linear polymer
3D polymer
Branched polymer
1.All monomeric units
are joined in the

long
straight
chains.
form of

2.Polymer possesi) high M.P.

ii)Density
iii)Tensile strength
due to close
packing of polymer
chain.
3.EX. HDPE
Nylon
polyester

1.All monomeric units

are joined in the
form of long

branches chains.
2.Polymer possesi) low M.P.
ii)Density
iii)Tensile strength

due to poor packing

of polymer chain in
presence of
branches.
3.EX. LDPE
Glycogen
Amylopectin

1.All monomeric
units connected to
each other by only

covalent bonds
with strong
cross-link.

2.Polymer possesi) hard

ii)rigid
iii)Brittle
iv) Do not melt but
burn on strong
heating.
3.EX. Bakelite
UF

Melamine formaldehyde

1. Homopolymer

1.
2.

Linear
Branched

3. Crossed Link

2.

Hetero/copolymer

1.
2.
3.
4.
5.
6.
7.

Linear
Branched
Crossed link
Regular
Irregular
Block
Graft

1.HomopolymerLinear

Same monomer

Branched

Crossed Link

2.Heteropolymer- Different monomer

Linear
Branched

Crossed Link

REGULAR
IRREGULAR

BLOCK

GRAFT

Main chain

Branched
chain

Main chain

Branched
chain

GRAFT copolymer

3.On the basis

of their
method of
synthesis

ADDITION
POLYMER

CONDENSATION
POLYMER

ADDITION POLYMER

CONDENSATION POLYMER

additional polymerization

Two different monomers

having functional group

Example-

Example-

Are obtained by

(repeated addition of same

monomeric unit to yield
long chain)

1.PE
2.PP
3.PS
4.PVC

joined with loss of small

molecules (like-H2O,
NH3,HCl ) to form product

1.nylon
2.Bakelite
3.polyester

4.On the
basis of
growth
polymer chain

1 -STEP
GROWTH
POLYMER

2-STEP GROWTH
POLYMER

1-STEP GROWTH POLYMER

(Addition polymerization)

Are obtained by successive

additional

of
monomeric units to the
growing chain.

Example-

1.PE
2.PP
3.PS
4.PVC

2-STEP GROWTH POLYMER

(Condensation polymerization)

formed bond formation

(condensation) between
two different monomers with loss
of small molecules (like-H2O,
NH3,HCl )

Example-

1.nylon
2.Bakelite
3.polyester

Heating & cooling cycle of

thermosoftening & thermosetting plastic

THERMOSOFTENING

THERMOSETTING

THERMOSOFTENING

THERMOSETTING

Long chain -linear

Cross-linked

THERMOSOFTENING

THERMOSETTING

Can be melted &

reshaped many
times
EXAMPLE
BUCKETS, BOWLS

Do not soften when

heated so can be
moulded only once.
ExampleUTENSILS HANDLES,
ELETRICAL FITTINGS

1. THERMOPLASTICS (TP)
1.

Soften

on

heating

&

stiffen

cooling,.

2. THERMOSETTING (TS)
on 1. On heating they are converted into an
infusible mass & once set, cant be reshaped.

2. formed by addition polymerization. 2.formed by the condensation polymerization.

3.3- dimensional cross linked network.

3.long linear chains

4.,

reshaped & thus reused.

4.

cannot be reshaped & reused.

5.

soft, weak & less brittle.

5.

hard, strong & more brittle.

6. Can be reclaimed from the wastes.

7.

physical change

6. Cannot be reclaimed from the wastes.

are involved on 7.

Chemical changes

occur on heating.

heating.
8.

low

9.

soluble

molecular weight.

8.

in organic solvents due to 9.

high

molecular weight.

Insoluble

in organic solvents due to strong

weak forces holding the chains.

bonds & cross links.

Eg. PVC, Teflon etc.

Eg. Phenol formaldehyde, polyurethane etc.

3. Elastomer (Synthetic Rubber)

4. Fibers

3. Elastomer

(Synthetic Rubber)

4. Fibers

1. Elastomer is any rubberlike polymer, which can be

stretched to at least thrice its
length, but it returns back to
its original shape & dimensions
as soon as release the force.

1.
Fibers
are
those
polymers whose chains are
held
by
strong

2. Elastomer molecular chain is

coil

in the form of
& hence it
can be stretched like a spring.
3.Example-Silicon rubber, polyurethane

intermolecular
forces
like H-bonding.
2. Crystalline in nature.
3. High tensile strength
4. Example- nylon, polyester

6. On the basis of
TACTICITY
ISOTACTIC
(Same side)

SYNDIOTACTIC
(Alternate fashion)

ATACTIC
(Random fashion)

Same side

Alternate fashion

Random fashion

Types of Polymerization

Addition
Polymerization

Condensation
polymerizations

EXAMPLE

EXAMPLE NYLON 6,6 ,

TERYLENE , PF

-PE,PP,PS,

PVC

Copolymerisation
EXAMPLE -

Buna S
Buna N

Addition polymerization

1. PE TYPES HDPE & LDPE

2. PP
3. PS
4. PVC
5. TEFLON
6. PAN

PE

Types of PE

HDPE

LDPE

1000-5000atm

250c in presence of O2

Low

LDPE

HDPE

LDPE

HDPE

LDPE

Polypropylene (PP)

POLYSTYRENE ( PS )

Poly vinyl chloride (PVC)

PTFE

Polyacrylnitril (PAN)

CONDENSATION POLYMERIZATION

1.Nylon 6,6
2. TERYLENE
3.PF

NYLON

6,6

Terylene

TERYLENE

Phenol formaldehyde

Phenol

formaldehyde

Monomethylol Phenol
Dimethylol Phenol

Monomethylol Phenol

Novolac

Trimethylol Phenol

PROPERTIES
1.Hard , rigid infusible solid
2.Excellent electrical insulator
3.Very
low
thermal
conductivity. Do not melt
with exposed to flame

Switches , plugs , heater handles

Telephone , radio, TV

Co polymerisation

1. BUNA S
2.BUNA -N

BUNA -S
Reactant

1,3- butadiene
&
styrene

BUNA -S

BUNA -N
Reactant
1,3- butadiene
&
Acrylonitrile

BUNA -N

Sr.
No

ADDITION POLYMERIZATION

CONDENSATION POLYMERIZATION

.
1. Requires unsaturated monomer

Any

two molecule having two different

functional groups
2. Monomers containing

C=C

Monomers possessing OH, -COOH, -NH2

3.

Exothermic reaction

Endothermic reaction

4.

Linear polymers obtained

3-D cross-linked network obtained.

5. Requires free radical or ions as Does not require an initiator but may require
an initiator
6.

Molecular weight is

catalyst to speed up the reaction.

low.

Molecular weight of is

high.

7. No by products

Simple-H2O,NH3,CH3OH by products

8.

Soluble in organic solvent.

Insoluble in organic solvent.

9.

One step reaction.

Stepwise reaction.

10

Rate of reaction faster.

Rate of reaction slower.

Compounding of Plastics

Binders
or

resins

Filler

Pigment

Catalyst

Plasticizer

Lubricant

Stabilizer

PIGMENT
LUBRICANT

BINDER
COMPOUNDING

STABILIZER

CATALYST
FILLER

BINDER

hold

the other
constituents of
the plastic
together

BINDER
Example
1. Natural resins
2. synthetic resins
3. cellulosic derivatives

low molecular
weight, the
plastic gets
moulded very
easily.

FILLER

Reduces
shrinkage &
brittleness.

Reduces
the cost
of plastic
per unit
weight

Fillers
Impart better
tensile strength,
hardness, &
workability

improving
the
mechanical
strength

Carbon black

paper pulp

Lubricants

Impart glossy

& elegant
finish to the
product

Eg. Waxes,
oils,
oleates,sterat
es, soap

Lubricants

prevent
sticking of
the plastic to
the mould

help in easy
moulding of
the plastic

Lower
moulding &
remoulding
temperature

Lower
softening
temperature

Plasticizer

Increase
workability
during
moulding

to improve
the
plasticity &
flexibility

Decrease
brittleness

Cyclic Organic
plasticizers

Acyclic
plasticizers

Tricresyl phosphate

Adipic acid ester

Triphenyl phosphate

Epoxidised esters

Butyl phosphate

Esters of oleic,
steric

Diethyl phthalate

STABILIZER

Improves thermal
stability during
processing

Stabilizers
eg. White lead,
red lead,
lead chromate

Vinyl chloride
Vinylidene
chloride

CATALYST

accelerate
the speed
polymerisation
reaction

Eg. hydrogen
peroxide,
benzoyl
peroxides

TiO2

Dyes or Pigments

CrO

AtS

PbCr

FeO

White
Green

TiO2
CrO

Red
Crimson
yellow

FeO
AtS
PbCr

Moulding
Or
Fabrication
Of Plastics

Fabrication means giving

the desired shape

to the plastic

with
the help of a mould

1)Compression
1)Compression
moulding
moulding

4) Extrusion
4) Extrusion

moulding
moulding

Types
Types

3) Transfer
3) Transfer

moulding
moulding

2) Injection
2) Injection

moulding
moulding

Curing of plastic

Curing

Compression moulding
Applied to both TS & TP.

Raw materials - two halves of mould

Moulding temp - 130-180o C and

moulding pressures 100-500 kg/cm2

plastic gets fluidized and fills the

cavity of the mould.

Curing- (TS)-heating

& (TP)- cooling

Compression moulding

Products -Radio / TV Cabinets ,

Electric Switch

Box

Injection mouldingApplied to TP

Injection moulding

Products - Bottle Caps , Dustbins , Buckets

Transfer moulding
Applied to TS

Transfer moulding

Products Fine Wires and Glass Fibres

can be fabricated

Extrusion moulding
Applied to TS

Articles

of uniform cross section

tubes , rods , strips

insulated electric cable
1. Horizontal Extrusion Moulding
2. Vertical Extrusion Moulding

Horizontal Extrusion Moulding

Articles of uniform cross section -

tubes , rods

Vertical Extrusion Moulding

Articles of uniform cross section - strips
insulated electric cable

Extrusion moulding

Articles of uniform cross section tubes , rods , strips , insulated

electric cable

Synthesis , properties & uses of PF(Phenol Formaldehyde)

PMMA (polymethyl metha acrylate)
kevlar

(Phenol Formaldehyde) PF
Step 1: Methylolation
1:1
heat/catalyst
Phenol

formaldehyde

1:2
heat/catalyst
Phenol

Monomethylolphenol

Dimethylolphenol

formaldehyde

Trimethylolphenol
Phenol

formaldehyde

Step 2: Novolac formation

Step 3 :Phenolic resin (Bakelite) formation

Properties
Hard,
heat resistance

Uses
electric insulator parts like
switches, plugs, switching
board, heater handles

Scratch resistant,
water resistant

missile parts

Resistant
to
nonoxidising acids, salts
and
many
organic
solvents

paints, varnishes,
enamels
and
protective coating

excellent electrical
insulating character

propeller shaft

PMMA

Properties
amorphous, polar

colorless,
transparent

Hard,
Tg(>65oc)

Uses
Wash basins

fibers
higher

weather
ability,softening
point 30-140oC

Optical

Solar heater

Motorcycle
windscreen.

Skylights

TV SCREENS

Contact lenses

Windscreen

KEVLAR
1,4- diaminobenzene

2,4 dichloro terpethalate

Bullet proof vest & helmet

Automotive parts

Glass transition
temperature
(Tg)

Glass transition temperature (Tg)

Hard, brittle,
glassy state

Soft, rubbery,
flexible, viscous

Rubbery ball

below temperature

Above temperature

Amorphous
solid

Melting state

AMORPHOUS
1.
2.
3.
4.

Random str.
Broad M.P.
Low shrinkage
Lower mechanical
properties
5. Ex. PS

CRYSTALLINE
1.
2.
3.
4.

Orderly str.
Narrow M.P.
Higher shrinkage
Higher mechanical
properties
5. Ex. Nylon

AMORPHOUS

CRYSTALLINE

Polymer
chain
tangled
up

Polymer
chain
folded
regularly

CRYSTALLINE

AMORPHOUS

SEMICRYSTALLINE

CRYSTALLINE

AMORPHOUS

Tg

- used as a measured of evaluating the

flexibility of a polymer molecule.

The glass transition temperature occurs in

.
K.E.

viscoelastic state
( rubbery)
low K.E.
lower region

Hard,
Tg
brittle Glass

High
higher region

Tm Melt
soft, viscous

Highly crystalline
polymer
Amorphous
polymer
Partially or
semi- crystalline
polymer

Determine-Tm
Determine-Tg
Determine- the lower
temperature range
representing the Tg region &
the higher one the Tm region.

Viscofluid state

1.Crystallinity
7. Force of
attraction
between
chains

6. Coiled
polymer
chain

2. Molecular
weight
Factors
affecting
Tg

5.Plasticizer
effect

3. Side
groups on
chain
4. Crosslinking of
polymer
chain

Factors affecting Tg
1.Crystallinity

2.Molecular
weight

Higher the crystallinity

higher is the Tg value
(Crystalline >amorphous)

Higher the molecular

weight, higher is the
Tg value.

(PS > PE )

3.Side groups
on chain

4.Cross-linking
of polymer
chain

bulky group in side chain,

increase Tg value.

(PS > PE )

higher extent of cross-linking

of polymer chains with
increases Tg value.

(PF > PE )

5.Plasticizer
effect

6.Coiled
polymer
chain

presence of plasticizer in
polymer, lower is the Tg
value.

coiled or spring-like structure,

lower is the Tg value.

( RUBBER < PLASTIC)

7.Force of
attraction
between
chains

stronger force of
attraction, higher
is the Tg value.

Conducting
Polymers (CP)
Intrinsically
conducting polymers
(ICP)

Conducting
polymers having
conjugated
electrons in the
back bone.

Extrinsically
conducting
polymers (ECP)

Doped
conducting
polymers (DCP)

P
doping

n
doping

Conductive
Element
Filled
Polymer
(CEFP)

Blended
Conduct
ing
Polymer
s (BCP)

Intrinsically conducting polymers

(ICP)

These polymers have extensive

conjugation in the backbone which is
responsible for conductance.

Conducting polymers
having conjugated
electrons in the
back bone.

Doped conducting
polymers (DCP)

POLYACETYLENE

POLYPYRROLE

POLYANILINE

Doped Conducting Polymers (DCP)

P doping
oxidation process

Conducting polymer of type (a)

is treated with Lewis acid (A)

(CH)

+ A

(CH) x + A- ( oxidation)

n doping
reduction process

The conducting polymer of type

(a) is treated with Lewis bases (B)
(CH) x +B
(CH) x-B+
(reduction)

 Example of p-doped (CH) x + 2 FeCl3

2 (CH) x + 3I2

(CH) x FeCl4 + FeCl2

+

2 (CH) x I3

Example of n-doped (CH) x + Na (C10H8)

Na

(CH) x + C10H8

Extrinsically Conducting Polymers (ECP):

Conductive element
filled polymer (CEFP)

Blended conducting
polymer (BCP)

Conductive Element Filled Polymer (CEFP)

polymer acts
as binder

to hold the conducting

elements
metallic
C-black
fibers

metallic
oxides

Mechanically durable
polymer possess
conductivity

light in weight
strong

Blended Conducting Polymers (BCP)

polymers are
obtained by
blending

conventional polymer with

a conducting polymer
physical

polymer possess

chemical
mechanical properties

Example Polypyrrole

rechargeable
batteries

making ion
exchangers

Analytical
sensors
Application
of
Conducting
Polymers

photo voltaic
devices

Electronics
electro chromic
displays and
optical filters

 RUBBER Or ELASTOMERS

Rubber-latex(milky colloidal liquid)

Compositon of latex:
i) Rubber hydrocarbon -90-95%
ii) proteins - 2-4%
iii) Resins- 1-2%

STRUCTURE

Cis-polyisoprene

Treatment of latex
Dilution
latex + water

Filtration

smoke rubber

Crepe rubber

Coagulation
acetic acid

Crude rubber

RUBBER Or ELASTOMERS

Natural rubber

Synthetic rubber

Vulcanization

Vulcanization - Plastic state

Elastic state

Process :To improve the properties of rubber it is

compounded with some chemicals like sulphur,

benzoyl chloride.

The process consists in heating raw rubber with S at 100

140oC. The added sulphur combines chemically at the
double bonds of rubber springs and forms three
dimensional structures.

UNVULCANISED RUBBER

VULCANISED RUBBER

VULCANISED RUBBER

Natural
rubber

Vulcanized
rubber

Branched structure

Crossed linked structure

Low molecular weight

High molecular weight

Soluble in organic solvent

Insoluble in organic solvent

can be reshaped & reused

can not be reshaped & reused

Plastic in nature

Elastic in nature

Tacky or sticky

Non-tacky or non- sticky

Properties & Drawbacks of Natural Rubber

useful
temperature
range 10-50oC
only

it
becomes
brittle below
10oC

and
soft
after 50oC.

excessively
elastic
and
has low tensile
strength

easily attacked
by
oxidizing
agents
like
HNO3
con.
H2SO4

Less
durability and
poor abrasion
resistance

decays due
to oxidation
in air

swells
in
many
organic
solvents.

large
water
absorption

Synthetic Rubber

Silicone Rubber

Polyurethane Rubber

Silicone Rubber

Synthesis 1 step
Cu Catalyst
2

Chloromethane

Si
Dichlorodimethyl
silane

2 step
Hydrolysis
2H2O

Dichlorodimethyl
silane

Dihydroxydimethyl
silane

3 step
Dehydration
-H2O

Dihydroxydimethyl
silane

Unstable silane

4 step

polymerisation

n
Unstable silane

SILCONE RUBBER

Tensile
strength is
lower than
natural rubber
Stable over a
temperature
range of 70o C
Properties-

Silicone
Rubber

Good water
repellency
Unaffected
by UV light

Non toxic &

insulating
characteristics
to 250oC

Chemical
inertness,
flexible at 952500 o C

Sealing
material in
search light
& aircraft
engines

Making
lubricants,
paints

Uses

1.insulating wires,
2.cables,
3.tyre for fighter
aircrafts

Making
1.artificial heart
valves,
2. transfusion
tubing's
3.padding for plastic
surgery

Adhesive

Artificial Heart Valve

Transfusion tubing

Polyurethane

they are highly

resistance to
oxidation.

Polyurethanes
Properties
less stable
at elevated
temperatures

good resistance
to acids and
organic solvents

adhesives,foams
,coatings,films

Uses
foundation
garment and
swim suits

produce
gasket and
seals

substitute
for leather

Urethane foam

Urethane Gasket

BUNA- S

Properties
High abrasion
resistance
High load bearing
capacity

resilience
Easily oxidised

Uses
Motor- Tyres
Floor tiles, shoe soles
Gaskets,
foot wear components
Wire & cable
insulations,
adhesive

Industrial & Engineering

Applications

SR
NO

SUBSTANCE

PROPERTIES

1.Easily mouldable
2.Strong chemical
1.

Polyamides or
Nylons

resistant
3.low coefficient of
friction

Automobile Tyres
High Tensile Ropes

SR.
NO

SUBSTANCE

PROPERTIES

1.Stiffer
2. High tensile strength

3.high tear strength

2.

Polyethylene

4. extreme
flexibility
5.Chemical and
breakage resistant

Packing and wrapping frozen food

squeeze bottles

textile products

SR.
NO

SUBSTANCE

PROPERTIES

1.Transparent
2. acids and
3. Polystyrene

alkalis
resistant

Making of moulded containers, lids, jars & foamed plastic

SR
NO

SUBSTANCE

PROPERTIES

1.High strength
2. Resistant to
4. Polycarbonate

water & many

organic
compounds

Solar Collector

Camera

Goggles

SR
NO

SUBSTANCE

PROPERTIES

High chemical
5.

Polyvinyl

resistant, high

Chloride

dielectric
constant

Lining of reactor pipes,

SR.
NO

SUBSTANCE

PROPERTIES

1.Nonstick
2.possess extreme
toughness
Teflon
6.

3.high softening
points
4.good electrical

Pump valves and pipes

Filter Cloth

Non Stick Cookware's

Polymers in
medicine and surgery

No. Polymers

Application

Polyethylene

Disposable syrings

Polypropylene

Heart valves ,blood filters

Polyvinylchloride

Disposable syrings

Acrylic Hydrogels

Grafting

PMMA

Contact lenses

Polyalkyl sulphone

Memberane oxygenerator

Silicone rubber

Heart valves,drain tubes

polyurethane

Heart

valves,

artificial heart

blood

filters,

BIOMATERIALS FOR APPLICATIONS

Cardiovascular system
Blood vessel
Polyurethane

Teflon,

Heart
valve
Reprocessed
Stainless steel, carbon

tissue,

Catheter polyurethane
LECTURE 1

prosthesis

Silicone rubber, Teflon,

BIOMATERIALS

232

Blood vessel prosthesis - Teflon,

Polyurethane

Catheter - Silicone rubber, Teflon,

polyurethane

Heart valve Reprocessed tissue,

Stainless steel, carbon

Organs

Artificial Heart

Artificial Kidney

Heart Lung Machine -

LECTURE 1

BIOMATERIALS

Polyurethane
Cellulose, PAN

Silicone rubber

236

Heart Lung Machine -

Silicone rubber

Artificial Kidney - Cellulose, PAN

Senses
Cochlear replacement -Platinum
(cavity of the inner ear)
Intraocular lens (within the eye)
Contact Lens -

PMMA

Silicone

Corneal bandage
LECTURE 1

electrodes

Collagen,hydrogel

BIOMATERIALS

240

Cochlear replacement -Platinum electrodes

(cavity of the inner ear)

PVC - Disposable needle syringe

Polyurethane heart valve, blood filter

PMMA: contact lenses

Thank you