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POLYMERS  Rayon : Rayon is a man made material which
consists of purified cellulose in the form of long fibres.
Polymers are compound of very high molecular masses Cellulose is treated with cold NaOH solution to purify it
formed by the combination of a large number of simple and then treated with CS2 to form a viscose solution. This
molecules. is why rayon is sometimes called viscose rayon. This
Classification of polymers solution is allowed to pass through fine pores in metal
cylinder, into a dilute solution of H2SO4. This results in
(1) Classification based on source of
the formation of long fibres. Rayon fibre is chemically
availability : They are classified as
identical to cotton but has a shine like silk. As such rayon
(i) Natural polymers (ii) Synthetic polymers is also known as artificial silk. Rayon is used on a large
(iii) Semi-synthetic polymers scale for making textiles, tyre-chord, carpets and surgical
(i) Natural polymers : The polymers obtained dressings. Unlike fully synthetic polymers, it absorbs
from nature (plants and animals) are called natural moisture and is bio-degradable.
polymers. These polymers are very essential for life. (2) Classification based upon structure : On
They are as under. the basis of structure of polymers these can be classified
(a) Starch : It is polymer of glucose and it is food as
reserve of plant. (i) Linear polymers (ii) Branched chain polymer
(b) Cellulose : It is also a polymer of glucose. It is a (iii) Cross linked polymers
chief structural material of the plant both starch and
(i) Linear polymers : These are polymers in which
cellulose are made by plants from glucose produced
monomeric units are linked together to form linear chain.
during photosynthesis.
These linear polymers are well packed and have high
(c) Proteins : These are polymers of -amino acids, magnitude of intermolecular forces of attraction and
they have generally 20 to 1000  amino acid joined therefore have high densities, high tensil (pulling)
together in a highly organized arrangement. These are strength and high melting points. Some common
building blocks of animal body and constitute an example of linear polymers are high density polyethylene
essential part of our food. nylon, polyester, PVC, PAN etc.
(ii) Branched chain polymers : These are
(d) Nucleic acids : These are polymers of various polymers in which the monomers are joined to form long
nucleotides. For example RNA and DNA are common chains with side chains or branches of different lengths.
nucleotides. These branched chain polymers are irregularly packed
 It may be noted that polymers such as and therefore, they have low tensile strength, low
polysaccharides (starch, cellulose), proteins and nucleic density, boiling point and melting points than linear
acids etc. which control various life processes in plants polymers. Some common examples are low density
and animals are also called biopolymers. polythene, glycogen, starch etc. (Amylopectin).
(iii) Cross linked polymers : These are polymers
(ii) Synthetic polymers : The polymers which are in which monomers unit are crosslinked together to form
prepared in the laboratories are called synthetic a three dimensional network polymers. These polymers
polymers. These are also called man made polymers. For are hard, rigid and brittle because of network structure
example polyethene, PVC nylon, teflon, bakelite terylene, e.g., Bakelite, malamine formaldehyde resin etc.
synthetic rubber etc. (3) Classification based upon molecular forces
(iii) Semisynthetic polymers : These polymers : Depending upon the intermolecular forces, the
are mostly derived from naturally occurring polymers by polymers have been classified into four type.
chemical modifications. For example cellulose is (i) Elastomers (ii) Fibres
naturally occurring polymers, cellulose on acetylation (iii) Thermoplastics (iv)Thermosetting polymers
with acetic anhydride in the presence of sulphuric acid (i) Elastomers : The polymers that have elastic
forms cellulose diacetate polymers. It is used in making character like rubber (a material that can return to its
thread and materials like films glasses etc. Vulcanized original shape after stretching is said to be elastic) are
called elastomers. In elastomers the polymers chains are
rubber is also an example of semisynthetic polymers
held together by weak intermolecular forces. Because of
used in making tyres etc. gun cotton which is cellulose
the presence of weak forces, the polymers can be easily
nitrate used in making explosive.
stretched by applying small stress and regains their
 Semi-synthetic polymers : Rayon and other original shape when the stress is removed. The most
cellulose derivatives like cellulose nitrate, cellulose important example of elastomers is natural rubber.
acetate etc., are semi-synthetic polymers. These are (ii) Fibres : These are the polymers which have
thermoplastic polymers. Viscose rayon in the form of a strong intermolecular forces between the chain. These
thin transparent film is known as cellophane. forces are either hydrogen bonds or dipole-dipole
interaction. Because of strong forces, the chains are
closely packed giving them high tensil strength and less
elasticity. Therefore, these polymers have sharp melting
Cellophane is softened with glycerol. Unlike plastic points. These polymers are long, thin and thread like and
sheets it absorbs water.
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can be woven in fabric. Therefore, these are used for (5) These have usually These have three
making fibres. linear structures. dimensional cross linked
Example : Nylon 66, dacron, silk etc. Ex. Polyethylene, PVC, structures.
(iii) Thermoplastics : These are the polymers teflon. Ex. Bakelite, urea,
which can be easily softened repeatedly when heated formaldehyde, resin.
and hardened when cooled with little change in their
properties. The intermolecular forces in these polymers (4) Classification based upon mode of
are intermediate between those of elastomers and fibres. synthesis : They are of two types on the basis of their
There is no cross linking between the chain. The synthesis.
softening occurs as the polymer chain move more and (i) Addition polymers (ii)Condensation polymers
more freely because of absence of cross link. When (i) Addition polymers : A polymer formed by
heated, they melt and form a fluid which can be moulded direct addition of repeated monomers without the
into any desired shapes and then cooled to get the elimination of by product molecule is called addition
desired product. polymers. For example,
Example : Polythene, polystyrene, PVC, teflon etc. nCH2  CH 2  (CH 2  CH 2 )n
(iv) Thermosetting polymers : These are the Ethene Polyethene
polymers which undergo permanent change on heating.
They become hard and infusible on heating. They are  
 
generally prepared from low molecular mass semifluid nCH 3  CH  CH 2    CH 2  CH  
|
substances. When heated they get highly cross linked to
Propylene
 CH 3  n

form hard infusible and insoluble products. The cross Polypropyl
ene

links hold the molecule in place so that heating does not (ii) Condensation polymers : A polymer formed
allow them to move freely. Therefore a thermosetting by the condensation of two or more than two monomers
plastic is cross linked and is permanently rigid. with the elimination of simple molecule like water,
Example : Bakelite, melamine formaldehyde resin ammonia, HCl, alcohol etc. is called condensation
etc. polymers. For example,
 Plasticizers do lower the softening point (so
called melting point) of a polymer. A plasticizer cannot
convert a thermosetting polymer into thermoplastic one. nH2 N  (CH 2)6  NH 2  nHOOC  (CH 2)4  COOH
In fact plasticizers can convert a hard and brittle plastic Hexamethyl
enediamine Adipicacid
into soft and easily pliable. Plasticizers reduce the
interparticle forces between polymer molecules.  O 
Plasticizers are generally high-boiling esters or high-
 ||

 nH 2O  
boiling haloalkanes. They are added to plastics to make    NH  (CH 2)6  NH  C  (CH 2)4  C  
them soft and rubber-like. For example, polyvinyl ||
chloride as such is hard, stiff and glass-like, but the  O 
addition of plasticizers like dioctylphthalate (DOP) or  Nylon- 66 n
dibutylphthalate (DBP) can make it soft and rubber like. Difference between addition and
Similarly, chlorinated paraffin wax (CPW) is used as a
plasticizer in polythene. On long exposure to air and condensation polymers
sunlight, these plasticizers evaporate and the plastic Addition polymers Condensation
articles become hard and brittle. polymers
Difference between thermoplastic and Formed by addition Formed by condensation
thermosetting polymers reaction. process with elimination
Thermoplastic Thermosetting of small molecules like
polymers polymers H2O.
(1) These soften and melt These do not soften on Molecular mass is a Molecular mass is not
on heating. heating but rather whole number multiple of whole number multiple of
become hard in case the monomer. the monomer units.
prolonged heating is Generally involve one Generally involve more
done these start burning. monomer unit. than one monomer unit.
(2) These can be These can not be Monomers are Monomer units must
remoulded recast and remoulded or reshaped. unsaturated molecules. have two active
reshaped. functional groups.
(3) These are less brittle These are more brittle They are generally chain They are generally step
and soluble in some and insoluble in organic growth polymers. growth polymers.
organic solvents. solvents.
(4) These are formed by These are formed by (5) Classification based upon the nature of
addition polymerisation. condensation monomer : On the basis of nature of monomer. Polymer
polymerisation. are of two types
(i) Homopolymers (ii) Copolymers
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(i) Homopolymers : A polymer formed from one (1) Chain growth or addition polymerisation : It
type of monomers is called homopolymer. For example, involve a series of reaction each of which consumes a
polythene is a homopolymer of monomer ethene. reactive particle and produces another similar one. The
nH2C  CH 2 Polymerisa
tion
( CH 2  CH 2 )n Homopolyme rreactive particle may be free radicals or ion (cation or
Ethene Polythene anion) to which monomers get added by a chain
(ii) Copolymers : A polymer formed from two or reaction. The polymers thus formed are known as chain
more different monomers is called copolymer or mixed growth polymers. Chain growth polymerisation is an
polymer. For example, nylon-66 is a polymer of two important reaction of alkenes and conjugated dienes or
types of monomers : hexamethylenediamine and adipic indeed of all kinds of compounds that contain carbon-
acid. carbon double bond polythene, polypropylene,
polybutadiene, teflon PVC, polystyrene are some of chain
growth polymers. It is based on Free radical mechanism
nH 2 N  (CH 2 )6  NH 2  nHOOC  (CH 2 )4  COOH Free-radical mechanism : Free-radical polymerisation
enediamine monome
Hexamethyl Adipicacid
rs is initiated by organic peroxide or other reagents which
Polymerisati
on decompose to give free radicals. Following steps are
(–NH – (CH2)6 – NH – CO – (CH2)4 – CO –)n involved.
+nH2O (a) Chain initiation : Organic peroxides undergo
Nylon-66 (Copolymer) homolytic fission to form free radicals.
Copolymer are commercially more important.
For example copolymerisation of vinyl chloride with O O  O 
vinylidene chloride (1, 1 dichloroethane) in a 1 : 4 ratio
forms a copolymer known as saran.
| |
heat
|    
Polymerisa
mH2C  CH  nCH 2  C Cl 2   tion

R  C  O   O  C R  R  C O   R  CO2
 
| Vinylidenechloride
Cl
Vinylchloride
 


Cl  
|  
Cl 
|  Peroxide Unstable
  CH 2  CH   CH 2  C  
   |  (b) Chain propagation : Free radical adds to an
   Cl 
  m n alkene molecule to form a new free radical.
Saranpolymer

Copolymerisation of monomer mixtures often leads  


to the formation of polymers which have quite different
properties than those of either corresponding R  CH 2  CH 2  R  CH 2  CH 2
homopolymer. For example, a mixture of styrene and
methyl methacrylate can form a copolymer. The free radical formed attacks another alkene
molecule and the process continues in building a long

CH3 CH3 chain.


 
| |
RCH2 CH 2  CH 2  CH 2  RCH2CH 2CH 2CH 2
CH 2  CH  H2C  C  ~ CH2  CH  CH2  C ~ (c) Chain termination : The chain reaction comes to
| | | | halt when two free radical chains combine.

C6H5 COOCH3 C6H5 COOCH3 

2R(CH 2CH 2 )n CH 2CH 2  R(CH 2CH 2
Styrene Methyl Copolymer
methacryltea : CH 2CH 2 (CH 2CH 2 )n R
 Benzoyl or t-Butyl peroxide are common
The composition of the copolymer depends on the initiators, used.
proportion of the monomers and their reactivity. It may Free radical polymerisation can also be initiated by a
be noted that some monomers do not polymerise at all mixture of ferrous sulphate and hydrogen peroxide
but copolymerize. For example, maleic anhydride does
(FeSO4  H 2O2) .
not polymerise as such. However, it copolymerises with
styrene in a highly symmetrical manner to form styrene (2) Step growth or condensation
maleic anhydride copolymer. polymerisation : In this type of polymerisation
General methods and mechanism of polymerisation monomers generally contain two functional groups, i.e.,
difunctional monomers. In this process no initiator is
needed and each step is the same type of chemical
reaction. Since in this polymerisation reaction the
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polymer is formed in a stepwise manner. It is called step  CH 3 

growth polymer and the process is called step growth  | 
 CH 2  C  CH  CH 2  
polymerisation. The process for two monomer A and B  
may be expressed as. 
 
n
Naturalrubber
Condense
A  B    A  B (2) Synthetic rubber : The synthetic rubber is
Monomers Dimer
Condense obtained by polymerising certain organic compounds
A  B  A 
 A  B  A which may have properties similar to rubber and some
Trimer
A  B  A  B  A  B  A  B desirable properties. Most of these are derived from
Alternatively, step growth can proceed as butadiene derivatives and contain carbon-carbon double
A B A B bonds. The synthetic rubbers are either homopolymers of
1, 3 butadiene or copolymer in which one of the
A  B  A  B  A  B  A  B or (A  B)2
monomers is 1, 3 butadiene or its derivative so that the
A  B  A  B  A  B  A  B  (A  B)n
Polymer polymer has the availability of double bonds for its
vulcanization. Some important examples are Neoprene,
Some common examples of step growth
styrene, butadiene rubber (SBR) thiokol, silicones,
polymers are polyurethane, rubber etc.
Polymers Monomers Vulcanization of rubber : The process of heating
Nylon-66 Hexamethylenediamine and adipic natural rubber with sulphur to improve its properties is
acid called vulcanization. Vulcanization was introduced by
Charles Goodyear.
Bakelite Phenol and formaldehyde
Although natural rubber is thermoplastic substance
Dacron Terephthalic acid and ethylene
in which there are no cross link between the polymer
(polyester) glycol chain and it on vulcanization set into a given shape
Rubber which is retained.
It is a polymer which is capable of returning to its CH3 CH3
original length, shape or size after being stretched or | |
deformed. It is the example of elastomer. Rubber are of ~CH2 – C – CH – CH2~ ~CH – C = CH – CH2~
two types. | | |
S S S
(1) Natural rubber (2) Synthetic rubber
| | |
(1) Natural rubber : It is obtained as latex from ~CH2 – C – CH – CH2~ ~CH – CH = C – CH2~
rubber trees. The latex is coagulated with acetic acid or | |
formic acid. The coagulated mass is then squeezed. CH3 CH3
The raw natural rubber is a soft gummy and sticky
mass. It is insoluble in water, dil. Acids and alkalies but Natural rubber Vulcanized rubber
soluble in benzene, chloroform, ether, petrol and carbon (1) Natural rubber is Vulcanized rubber is hard and
disulphide. It absorb a large amount of water. It has low soft and sticky non-sticky.
elasticity and tensile strength. (2) It has low tensile It has high tensile strength.
strength.
Destructive distillation of natural rubber gives
mainly isoprene (2-methyl butadiene). (3) It has low It has high elasticity.
elasticity.
Thus isoprene is a monomer of natural rubber the (4) It can be used It can be used over a wide
no. of isoprene unit are 11,000 to 20,000 which linked over a narrow range range of temperature (–40° to
together in a chain. of temperature 100°C).
(from 10° to 60°C).
CH 3
| (5) It has low wear It has high wear and tear
Polymerisa
tion and tear resistance. resistance.
nCH2  C  CH  CH 2 
Isopreme (6) It is soluble in It is insoluble in all the
solvents like ether, common solvents.
carbon,
tetrachloride,
petrol, etc.
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Some important polymer and their uses
Rubber
Rubber Monomers Formula Applications
(i) CH 2  C  CH  CH 2 



Making
Neoprene |   CH 2  C  CH  CH 2   automobile,
rubber Cl 

|
Cl

n refrigerator parts
Chloropren
e
and electric wire.
CH 2  CH  CH  CH 2 CH = CH2

  CH 2  CH  CH  CH 2  CH  CH 2  
(ii) Styrene and Making of tyre and
Butadiene
(75%)
Butadiene other mechanical
Rubber
(SBR) or Styrene  
rubber goods.

 
Buna-S (25%)

 
 n
(iii) Butyl CH 3 Making of toys,
 CH 3 CH 3  tyre, tube etc.
rubber |  | | 
CH 2  C and   CH 2  C  CH  CH 2  C  CH 2  
|  | 
CH 3  CH 
Isobutylen
e (98%)  3 n

CH 2  C  CH  CH 2
|
CH 3
Isoprene
(2- 3 %)
(iv) Nitrile CH 2  CH  CH  CH 2 and  Used for make of
 
rubber or Butadiene
(75%)   CH 2  C H  CH 2  CH  CH  CH fuel
2  tank.
Buna N or  |

 CN n
GRA CH 2  CH  CN
Acrylonitr
ile(25%)
(v) Cl  CH 2  CH 2  Cl (CH 2  CH 2  S  S  S  S)n Used in the
Polysulphid Ethylene
dichloride manufacture of
e rubber hoses and tank
(Thiokol) and
Na2S4 lining, engine
Sodiumtetrasulp
hide
gasket and rocket
fuel.
(vi) Silicone CH 3 Silicon rubber
 CH 3 
rubber |  | 
Cl  Si  CH 3   O  Si  
|
 | 
Cl  CH 
Chlorosila
nes  3
n
(vii) HOCH 2  CH 2OH In the manufacture
Polyurethan Ethylene
glycol of fibre. Paints and
e rubber and heat insulator.
O
||
C  N  CH  CH  N  C  O
Ethylene
di-isocyanate
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Plastics and resin

Fibre
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