polymers

Definition:
 Polymerization is a chemical reaction that
can unite two or more molecules of similar or
different types resulting in the formation of
giant molecule.
 Polymers are 2 types
1.Homo polymers
2.Co polymers
 Homo polymer is combination of identical
monomer units.
Eg: (-A-A-A-A-A-)
 Co polymer is combination of different
monomer units.
Eg: (-A-B-A-B-A-B-)
Types of Polymerization mechanisms:
1. Addition polymerization.
2. Condensation polymerization.

1) Addition polymerization :
 This kind of polymerization is typified by the presence of
a carbon – carbon double bond in the monomer.
 This reaction takes place in presence of catalyst or light,
heat.
 A monomer is a small molecule that makes
up a polymer.
 The monomer molecules usually contain
one or two doubles bonds
 During addition of polymerization the double
bond breaks and becomes a single bond.
Ex : polymerization of ethylene, pvc, poly
styrene, poly acrylonitrile.
Polymerization of PVC
Mechanism of addition polymerization :
Chain growth polymerization:
 It involves the linking together of molecules
incorporating double or triple. These unsaturated
monomers have extra internal bonds that are able to
break and link up with other monomers to form the
repeating chain.
 It involves 3 steps:
1. Chain initiation step
2. Chain propagation step
3. Chain termination step
1.Chain Initiation step :
 Initiators are chemicals that produce the
chain initiating species, the chain
initiators under go homolytic cleavage
when excited.
 E.g.: acetyl peroxide, benzoyl peroxide.
2.Chain propagation step :
 Free radicals combines with another
monomer to give a new radical and this
radical will again with a monomer to give
a longer chain radicals.
 This process goes on continuing
producing a high polymer.
3.Chain termination step :
 Termination of the propagation of polymer
chain can happen either by coupling reaction
or disproportionation.
hv/ heat
R O O R 2 R * + O2

PROPAGATION STEP
R* + CH2=CH2 R-CH2-CH2*

R-CH2-CH2* + CH2 = CH2 R-CH2-CH2-CH2-CH2*

.............. R- (CH2 -CH2)n- CH2-CH2*

TERMINATION STEP

2 R- (CH2 -CH2)n- CH2-CH2* + CH2-CH2* R-(CH2-CH2)n-R

2) Condensation polymerization:
 A condensation polymer generally involves 2
monomers that have different functional
groups.
 They also involve the elimination of water or
another small molecule. Hence the term
condensation polymer

 E.g.: formation of urea formaldehyde, nylon 6,6.

 Polymerization of polyester
Mechanism in condensation polymerization
Step growth polymerization:
 Step-growth polymers are defined as
polymers formed by the stepwise reaction
between functional groups of monomers.
Most step-growth polymers are also
classified as condensation polymers.
 This rate is lower than chain growth
polymerization.
3) Co
polymerization:
 Is a reaction that
yields a polymer
made of different
monomer units
 E.g.: Bunna-s
rubber, poly
acrylo nitril-co-
vinyl chloride
polymer
 Plastics and Resins :
 Plastics are the basic materials, those
show property of plasticity and can be
moulded by applying heat /pressure.

 Resins are the binding materials of

polymers which form major part of
polymer.
 Plastic have advantages over metals and other
materials, because they have :
1. Light weight and high strength.
2. good thermal and electrical insulation
3. high corrosion resistance
4. easy coorkability (casting, molding etc.)
5. High chemical intertness
6. Decorative
7. Law maintenance cost.
Classification :
a) Thermo plastic Resins
b) Thermo setting Resins
Thermo Plastics resins:
 The polymers which are softened on heating and
hardened on cooling.,
 Repeated heating or cooling do not alter any chemical
change.
 These are prepared by addition reaction.
 These are made of long chains attached by weak vander
waal’s fames of attraction.
 These are soft, weak and less brittle.
 These are reclaimed from waste.
 These solvable in some organic solvents.
 Resins and plastics are synonomous in this case.
Ex : PVC, PE, PS, etc.,
Thermo setting Resins :
 The polymers which are hardened during their molding
process.
 Once they are hardened they cannot be softened. Hence
these are called permanent setting resins.
 These acquire cross – linked, 3D, Network structure.
 The bonds retain their structure.
 Prolongated heating causes charring of the polymer.
 These are produced by condensation polymerization.
 These are hard, strong and more brittle.
 These cannot be reclaimed from waste.
 These don't solvable in organic solvents.
Ex : Becalite, Novalac, etc.,
PVC (poly vinyl chloride ) :
Preparation:
n[ H2C=CHCl]  [-CH2-CHCl-]n
vinyl chloride poly vinyl chloride
Properties:
 Colour less, odour less, non-inflammable,
chemically inert,
 resistant to light, atmospheric oxygen, inorganic
acids and alkalis but soluble in hot chlorinated
hydro carbons
 Greater rigidity and stiffness compared to P.E
USES:
 unplasticized PVC have superior chemical
resistance and high rigidity but brittle
 used for making sheets, light fittings, safety
helmets, tires, refrigerator components etc,….
 Plasticized PVC used for making continuous
sheets, rain coats, electrical insulation, chemical
containers,
 Radio components, thermal insulating foam,
conveyor belts etc..,
Poly tetra fluoro ethylene or TEFLON:
(PTFE):
Preparation:
n[F2C=CF2]  [-CF2-CF2-]n
Properties:
 Due to high E.N atoms strong attractive
forces b/w different chains.
 Extreme toughness, high softening point,
high density, waxy tough, high density.
 Good electrical and mechanical properties.
USES:
 An insulating material and for making gaskets,
packings, pump parts, tank linings, chemical carrying
pipes, tubings and tanks etc…,
 For coating and impregnating glass fibers, asbestos
fibers and clothes.
 Non- lubricating and non- sticking stop clocks.

BAKALITE or PHENOL FORMALDEHYDE resin:

Preparation:
 Novolac is prepared by condensing phenol with
formaldehyde in presence of acidic/ alkaline catalyst.
 The addition of hexa methylene tetramine to novolac it
is into a hard, insoluble and infusible solid.
 OH OH
OH
CH2OH

+ HCHO +

polymarization

OH OH
OH
OH
CH2
CH2 CH2 CH2

NOVOLAC

OH OH
OH
CH2 CH2
H2C
CH2

CH2
CH2

CH2 CH2
H2C CH2
OH OH
OH
Properties:
 Set to rigid, hard, scratch resistant, in soluble,
water resistant.
 They posses excellent electrical insulating
character.
Uses:
 For making electric insulator parts like switcher
plugs, switch boards, heater handles etc..,
 For impregnating fabrics, wood and paper,
adenines for grinding wheels.
 For making bearings, used in propeller shafts
for paper industry and rolling mills.
Nylon:
 Among the poly amides the most widely
known are the nylons, in which nylon 6,6 is
the most common.
Preparation:
 It is prepared by condensation reaction of
hexa methylene diamine with adipic acid.

n[(CH2)6(NH2)2 + (CH2)6(COOH)2]
adipic acid
 polymerization

H H O H O

N C N C C C + 2n H20
6 4
H H H H n

NYLON 6,6
Properties:
 It has remarkably low efficient of friction against many
metals
 Self extinguishing when it comes in contact with a
flame.
 Low water absorption and good strength which does
not deteriorate even when used for a long period.
Conducting polymers
Conducting
Polymers

Intrinsically C.P Extrinsically C.P

C.P having Conductive Element

conjugation Doped C.P Filled polymers Blended C.P

  e-s increases the conductivity to a large extent because
of conjugation results formation of valence bands &
conduction bands over entire back bone.
Ex: poly acetylene, poly anilene
H3C-CH=CH-(CH=CH)n-CH=CH-CH3

N N N *

poly anilene
Doping:
the conductivity of a polymer can be increased
by creating either +ve or -ve charges on polymer
back bone oxi’n or red’n is called doping. it is
two types
1)P-DOPING:
 Treating an intrinsically conducting polymer
with a lewis acid there by oxi’n process takes
place and +ve charges on polymer are
created.
 Comon p-dopants are I2,Br2,AsF5,PF6 etc…
 Ex:(C2H2)n + 2FeCl3  (C2H2)n+FeCl4- + FeCl2
2) N-DOPING:
 Treating an intrinsically conducting polymer with a
lewis base there by red’n process takes place and
-ve charges on polymer are created.
 Common N-dopants are Li, Na, Ca etc..,
 Ex:(C2H2)n + NH3  (C2H2)n-NH3+

Applications:
• Increase use b’cos they are light weight use to
process and have good mechanical properties.
• In rechargeable light weight batteries, optically
display devices, wiring air crafts and air space
components, telecommunication systems and
antistatic coatings for clothing.
2) The group of specialty polymers include in
organic polymers such as poly
organophophazenes, polysilastyrene
Characteristics:
 Exhibit superior creep resistance , chemical
resistance, dimensional stability, high rigidity,
tensile strength and thermal properties
USES:
 In electronic components, housings of light wave
conductors, aero space applications,
 Separation of polymers, bio medical devices,
electronics and encapsulation.
 Rubber:
 High polymers with elastic properties in excess of
300%
 Is not straight chained but in form of a coil and
stretched like a spring.
Natural rubber:
 Consist of a basic material latex which is a
dispersion of isoprene
 M.Wt is around 10,000 – 1,50,000
H
CH3
CH3 H
H
C
C
H C C
C C
C H
H
H H H
H
Vulcanization:
 To improve the properties of rubber it is
compounded with some chemicals like sulphur,
H2S, Benzoyl chloride etc..,
 Most imp is addition of sulphur
 The process consist in heating the raw rubber
with sulphur at 100-140oc
 The sulphur is added on double bonds
 Thus serves to stiffen the material by a sort of
anchoring and consequently, preventing inter
molecular movement of rubber springs.
 CH3 CH3

CH2 C CH CH2 CH CH2

C

+
CH3 CH3

CH2 C CH CH2 CH CH2

C

CH3 CH3
H
CH2 C C CH2 CH2
C CH

S S S S

CH2 C C CH2 CH2

C CH
H

CH3 CH3

VULCANIZATION OF RUBBER WITH SULPHUR

ELASTOMERS:
 An elastomer / artificial rubber is any
vulcanisable man made rubber like polymer,
stretched to at least twice its length but it
returns to its original shape and dimensions as
soon as stretching force is released.
BUNNA-S / STYRENE RUBBER / GR-S :
 Which is produced by copolymerization of
butadiene & styrene.
USES:
 Manufacture motor tires, floor tiles, shoe-soles,
gaskets, adhesives etc..,
 H H
H H H H
nx + n C C
C C C C
H
H H

butadiene 75 parts styrene 25 parts

co polymerization

H H H H H H

C C C C C CH

H H H
x

styrene-butadiene rubber
BUTYL RUBBER: (GR-I)
 Produced by copolymerization of isobutene with
small amounts of isoprene.
USES:
 For making cycle & auto mobile tubes,
 Auto mobile parts
 Conveyor belts for food
 Tank linings etc.,
 CH2 C CH3
m + n CH2 C CH CH2
CH3
CH3
isobutene isoprene

CH3

CH2 C CH2 C CH CH2 *

CH3 n
m

butyl rubber
 Thicol rubber or GR-P:
 Produced by the reaction b/w sodium
polysulphide & ethylene dichloride.

H2 H2
Na S
* C C S S * + 2n NaCl
Cl CH2
n + n S S
Na S
Cl CH2 n
S
sod. tetra sulphide thiokol
ethylene di chloride
Uses:
 They are cheap & can easily be shaped but have
an un pleasant smell.
 Making hose pipe and tank linings
FIBERS:
 These are a class of materials that are
continuous filaments are discrete elongated
pieces
 They highly crystalline form of polymers and imp
in both plants and animals
 These are two types 1) natural fibers
2)synthetic fibers
Polyester:
 Have ester linkages in main chain
 Used exclusively for making textiles
 Synthesis of polyesters by poly condensation of
purified terephlthalic acid and mono ethylene glycols

COOH

2HC OH
+ * O H2C OOC COO * + 2 H2O
2
H2C OH

COOH