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Polymers

used in making tyres etc. gun cotton which is cellulose


nitrate used in making explosive.

Polymers are compound of very high molecular  Semi-synthetic polymers : Rayon and other
masses formed by the combination of a large number of cellulose derivatives like cellulose nitrate, cellulose
simple molecules. acetate etc., are semi-synthetic polymers. These are
thermoplastic polymers. Viscose rayon in the form of a
The simple molecules which combine to give polymers
thin transparent film is known as cellophane.
are called monomers. The process by which the simple
Cellophane is softened with glycerol. Unlike plastic
molecule (i.e. monomers) are converted into polymers
sheets it absorbs water.
is called polymerisation.
Example : Polyethylene  Rayon : Rayon is a man made material which
consists of purified cellulose in the form of long fibres.
 All polymers are macromolecule but all Cellulose is treated with cold NaOH solution to purify it
macromolecules are not polymers because polymer and then treated with CS2 to form a viscose solution.
consist repeating unit of monomer e.g., chlorophyll is a This is why rayon is sometimes called viscose rayon.
macromolecule but not a polymer. This solution is allowed to pass through fine pores in
Classification of polymers metal cylinder, into a dilute solution of H2SO4. This
(1) Classification based on source of results in the formation of long fibres. Rayon fibre is
availability : They are classified as chemically identical to cotton but has a shine like silk.
As such rayon is also known as artificial silk. Rayon is
(i) Natural polymers (ii) Synthetic polymers
used on a large scale for making textiles, tyre-chord,
(iii) Semi-synthetic polymers
carpets and surgical dressings. Unlike fully synthetic
(i) Natural polymers : The polymers obtained polymers, it absorbs moisture and is bio-degradable.
from nature (plants and animals) are called natural
(2) Classification based upon structure : On
polymers. These polymers are very essential for life.
the basis of structure of polymers these can be
They are as under.
classified as
(a) Starch : It is polymer of glucose and it is food
(i) Linear polymers (ii) Branched chain
reserve of plant.
polymers (iii) Cross linked polymers
(b) Cellulose : It is also a polymer of glucose. It is (i) Linear polymers : These are polymers in
a chief structural material of the plant both starch and which monomeric units are linked together to form
cellulose are made by plants from glucose produced linear chain. These linear polymers are well packed and
during photosynthesis. have high magnitude of intermolecular forces of
(c) Proteins : These are polymers of α -amino attraction and therefore have high densities, high tensil
acids, they have generally 20 to 1000 α amino acid (pulling) strength and high melting points. Some
joined together in a highly organized arrangement. common example of linear polymers are high density
polyethylene nylon, polyester, PVC, PAN etc.
These are building blocks of animal body and constitute
(ii) Branched chain polymers : These are
an essential part of our food.
polymers in which the monomers are joined to form
(d) Nucleic acids : These are polymers of various long chains with side chains or branches of different
nucleotides. For example RNA and DNA are common lengths. These branched chain polymers are irregularly
nucleotides. packed and therefore, they have low tensile strength,
low density, boiling point and melting points than linear
 It may be noted that polymers such as
polymers. Some common examples are low density
polysaccharides (starch, cellulose), proteins and nucleic
polythene, glycogen, starch etc. (Amylopectin).
acids etc. which control various life processes in plants
(iii) Cross linked polymers : These are polymers
and animals are also called biopolymers.
in which monomers unit are crosslinked together to
(ii) Synthetic polymers : The polymers which form a three dimensional network polymers. These
are prepared in the laboratories are called synthetic polymers are hard, rigid and brittle because of network
polymers. These are also called man made polymers. structure e.g., Bakelite, malamine formaldehyde resin
For example polyethene, PVC nylon, teflon, bakelite etc.
terylene, synthetic rubber etc. (3) Classification based upon molecular
forces : Depending upon the intermolecular forces, the
(iii) Semisynthetic polymers : These polymers
polymers have been classified into four type.
are mostly derived from naturally occurring polymers by
(i) Elastomers (ii) Fibres
chemical modifications. For example cellulose is
(iii) Thermoplastics (iv)
naturally occurring polymers, cellulose on acetylation
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
rubber is also an example of semisynthetic polymers

1
called elastomers. In elastomers the polymers chains on heating. heating but rather
are held together by weak intermolecular forces. become hard in case
Because of the presence of weak forces, the polymers prolonged heating is
can be easily stretched by applying small stress and done these start burning.
regains their original shape when the stress is removed. (2) These can be These can not be
The most important example of elastomers is natural remoulded recast and remoulded or reshaped.
rubber.
reshaped.
(ii) Fibres : These are the polymers which have
(3) These are less brittle These are more brittle
strong intermolecular forces between the chain. These
and soluble in some and insoluble in organic
forces are either hydrogen bonds or dipole-dipole
organic solvents. solvents.
interaction. Because of strong forces, the chains are
closely packed giving them high tensil strength and less (4) These are formed by These are formed by
elasticity. Therefore, these polymers have sharp melting addition polymerisation. condensation
points. These polymers are long, thin and thread like polymerisation.
and 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
(4) Classification based upon mode of
properties. The intermolecular forces in these polymers
synthesis : They are of two types on the basis of their
are intermediate between those of elastomers and
synthesis.
fibres. There is no cross linking between the chain. The
(i) Addition polymers (ii)
softening occurs as the polymer chain move more and
Condensation polymers
more freely because of absence of cross link. When
heated, they melt and form a fluid which can be (i) Addition polymers : A polymer formed by
moulded into any desired shapes and then cooled to get direct addition of repeated monomers without the
the desired product. elimination of by product molecule is called addition
Example : Polythene, polystyrene, PVC, teflon etc. polymers. For example,
(iv) Thermosetting polymers : These are the nCH 2 = CH 2 → (−CH 2 − CH 2 −)n
polymers which undergo permanent change on heating. Ethene Polyethene
They become hard and infusible on heating. They are
 
generally prepared from low molecular mass semifluid  
nCH − CH = CH →− CH − CH −
substances. When heated they get highly cross linked to 3 2 2
|
Propylene  CH 3 
form hard infusible and insoluble products. The cross  n
Polypropyl ene
links hold the molecule in place so that heating does not
allow them to move freely. Therefore a thermosetting (ii) Condensation polymers : A polymer formed
plastic is cross linked and is permanently rigid. by the condensation of two or more than two monomers
Example : Bakelite, melamine formaldehyde resin with the elimination of simple molecule like water,
etc. ammonia, HCl, alcohol etc. is called condensation
 Plasticizers do lower the softening point (so polymers. For example,
called melting point) of a polymer. A plasticizer cannot
convert a thermosetting polymer into thermoplastic
one. In fact plasticizers can convert a hard and brittle nH 2 N − (CH 2)6 − NH 2 + nHOOC − (CH 2)4 − COOH
Hexamethylenediamine Adipic acid
plastic into soft and easily pliable. Plasticizers reduce
the interparticle forces between polymer molecules.
 O 
Plasticizers are generally high-boiling esters or high-  ||

boiling haloalkanes. They are added to plastics to make − nH2O  
them soft and rubber-like. For example, polyvinyl   →  − NH − (CH 2)6 − NH − C − (CH 2)4 − C − 
||
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.
Similarly, chlorinated paraffin wax (CPW) is used as a Difference between addition and
plasticizer in polythene. On long exposure to air and condensation polymers
sunlight, these plasticizers evaporate and the plastic
articles become hard and brittle. Addition polymers Condensation
Difference between thermoplastic and polymers
thermosetting polymers Formed by addition Formed by condensation
reaction. process with elimination
Thermoplastic Thermosetting of small molecules like
polymers polymers H2O.
(1) These soften and melt These do not soften on

2
Molecular mass is a Molecular mass is not
whole number multiple of
the monomer.
whole number multiple of
the monomer units.
C3H C3H
Generally involve one Generally involve more | |
C 2 =HCH + H2C = C → ~ C 2 − HCH − C 2 − HC ~
monomer unit. than one monomer unit.
Monomers are Monomer units must
unsaturated molecules. have two
functional groups.
active
| | | |
They are generally chain
growth polymers.
They are generally step
growth polymers.
C6H5 C O 3 OC6H5C HC O 3 O C
(5) Classification based upon the nature of S t y r e n Me e t h y l C o p o l y m e
monomer : On the basis of nature of monomer. Polymer
are of two types
m e t te h a c r y l a
(i) Homopolymers (ii) Copolymers
The composition of the copolymer depends on the
(i) Homopolymers : A polymer formed from one proportion of the monomers and their reactivity. It may
type of monomers is called homopolymer. For be noted that some monomers do not polymerise at all
example, polythene is a homopolymer of monomer but copolymerize. For example, maleic anhydride does
ethene. not polymerise as such. However, it copolymerises with
Polymerisation
nH 2C = CH 2   →(− CH 2 − CH 2 −)n Homopolymer
styrene in a highly symmetrical manner to form styrene
Ethene Polythene maleic anhydride copolymer.
(ii) Copolymers : A polymer formed from two or It may be noted that many types of copolymers
more different monomers is called copolymer or can be obtained depending upon the distribution of
mixed polymer. For example, nylon-66 is a polymer of monomer units in the chain. Two monomers can
two types of monomers : hexamethylenediamine and combine in either regular fashion (although this is rare)
adipic acid. or random fashion. For example, if monomer A is
copolymerised with monomer B, the resultant product
nH 2 N − (CH 2 )6 − NHmonome
2 + nHOOC − (CH 2 )4 − COOH
may have a random distribution of the two units
Hexamethyl
enediamine rs Adipicacid throughout the chain or it might have alternating
Polymerisati
on
distribution.
(–NH – (CH2)6 – NH – CO – (CH2)4 – CO –)n (– A – B – A – B – A – B – A – B –) Alternating
+nH2O copolymer
Nylon-66 (Copolymer) (– A – A – A – B – A – B – B – A – B –) Random
Copolymer are commercially more important. copolymer
For example copolymerisation of vinyl chloride The exact distribution of monomer units depends
with vinylidene chloride (1, 1 dichloroethane) in a 1 : 4 on the initial proportion of the two-reactant monomers
ratio forms a copolymer known as saran. and their reactivities. Most copolymers have varying
Polymerisa
mH2C = CH + nCH 2 = C Cl 2   tion
→ distributions. Two other types of copolymers that can be
| Vinylidenechloride prepared under certain conditions are called block
Cl copolymers and graft copolymers.
Vinyl chloride
(a) Block copolymers are those in which different
 Cl   Cl 
 |   |  blocks of identical monomer units alternate with each
− CH 2 − CH  CH 2 − C − other as
   | 
   Cl  (–A–A–A–A–B–B–B–B–A–A–A–A–B–B–B–B–)n
 m  n
Saran polymer
These are prepared by initiating the
Copolymerisation of monomer mixtures often polymerisation of one monomer as if growing a
leads to the formation of polymers which have quite homopolymer and then adding an excess of second
different properties than those of either corresponding
monomer to the active reaction mixture.
homopolymer. For example, a mixture of styrene and
methyl methacrylate can form a copolymer. (b) Graft polymers are those in which
homopolymer branches of one monomer units are
grafted on the homopolymer chains of another
monomer units as :

3
(− A − A− A − A − A − A − A− A − A − A − A− A−)n •• •

|
B
|
B
|

|
|
B
|
R + C 2H− C 2H→ R − C 2H− CH 2
B B B
| | | The free radical formed attacks another alkene
B B B molecule and the process continues in building a long
|n |n |n chain.
These are prepared by radiation of γ -rays on a
completed homopolymer chain in the presence of the • •• •
second monomer. The high energy radiation knocks
hydrogen atoms of the homopolymer chain at random R C2 CHH 2 + C H2 − C H2 → R C2CH 2HC 2HCH 2
points resulting radical sites for initiation of the added
monomer. By careful control of the polymerisation (c) Chain termination : The chain reaction comes
reaction, we can produce copolymers of desired to halt when two free radical chains combine.
properties by combination of different monomers in
various ratios and geometric arrangements. •
General methods and mechanism of polymerisation 2R(CH 2CH 2 )n CH 2CH 2 →R(CH 2CH
(1) Chain growth or addition polymerisation : : CH 2CH 2 (CH 2CH 2 )n R
It involve a series of reaction each of which consumes a
reactive particle and produces another similar one. The  Benzoyl or t-Butyl peroxide are common
reactive particle may be free radicals or ion (cation or initiators, used.
anion) to which monomers get added by a chain Free radical polymerisation can also be initiated by a
reaction. The polymers thus formed are known as chain mixture of ferrous sulphate and hydrogen peroxide
growth polymers. Chain growth polymerisation is an
(FeSO 4 + H 2O2) .
important reaction of alkenes and conjugated dienes or
indeed of all kinds of compounds that contain carbon- (ii) Cationic mechanism : Cationic
carbon double bond polythene, polypropylene, polymerisation is initiated by use of acids such as
polybutadiene, teflon PVC, polystyrene are some of H 2 SO 4 , HF or BF 3 in H 2O . The following steps
chain growth polymers. It is based on three mechanism
are involved :
(i) Free radical mechanism (ii) Cation
(a) Chain initiation : The acid furnishes proton.
mechanism (iii) Anion mechanism
Each mechanism of polymerisation reaction H 2 SO 4 ⇌ H + + HSO 4−
involves an initiator of their corresponding nature. The
HF ⇌ H + + F −
addition polymerisation reaction is very rapid and is also
characterized by three steps i.e. chain initiation, chain BF 3 + H 2O ⇌ H + + BF 3 (OH )−
propogation and chain termination step.
The proton adds to the carbon of the double bond
(i) Free-radical mechanism : Free-radical
of the alkene to form a carbonium ion.
polymerisation is initiated by organic peroxide or other
reagents which decompose to give free radicals. +
Following steps are involved. H + + CH 2 = CH 2 → CH 3 C H 2
(a) Chain initiation : Organic peroxides undergo (b) Chain propagation : The carbonium ion
homolytic fission to form free radicals. combines with another molecule of alkene to form a
new carbonium ion and the process continues to form a
O O  O  long chain.

h e a t  •
| | | •
R − C− O − − O − C− R    →  R − C− O  → R + C 2O +
CH 3 CH 2 + CH 2 = CH 2 → CH 3 CH 2CH 2CH 2
+

 
  +
P e ro x id e U n s t a b le C
H 3C
H 2C
H 2CH 2 +n
CH
= CH2
(b) Chain propagation : Free radical adds to an
alkene molecule to form a new free radical.
(c) Chain termination : The chain may be halted
by combination with negative ion or loss of a proton.

4
+ 

H 
| 
C 3HC 2H(C 2HC 2H)n C H − CH 2   → Styrene
   →  C l3C − CH2 − C H − CH2 − C − 
 | | 
|  C H
6 5 C 6H 5  n

H H S− O Chain transfer agents determinate chain reaction


4 and inhibit further polymerisation and are also called
inhibitors.
CH 3CH 2(CH 2CH 2)n CH = CH 2 + H 2SO 4 (2) Step growth or condensation
Polymer polymerisation : In this type of polymerisation
(iii) Anionic polymerisation : This type of monomers generally contain two functional groups, i.e.,
polymerisation is initiated by anion (Bases nucleophiles) difunctional monomers. In this process no initiator is
it proceeds through the formation of carbanion. The needed and each step is the same type of chemical
reaction. Since in this polymerisation reaction the
initiation may be brought about by K + NH 2 of polymer is formed in a stepwise manner. It is called step
L+NH 2 . growth polymer and the process is called step growth
polymerisation. The process for two monomer A and B
The following steps are involved may be expressed as.
(a) Chain initiation : Conden se
A + B  → A − B

Nu + CH 2 = C H → Nu − CH 2 − C H  M onom ers Dim er
| | Condense
A − B + A   
→ A − B − A
W W Trim er
(b) Chain propagation : A − B − A + B → A − B − A − B
Alternatively, step growth can proceed as
Nu − CH 2 − C H 2 + CH 2 = C H → Nu − CH 2 − C H − CH 2 − C H A + B → A − B
| | | |
W W W W A − B + A − B → A − B − A − B or (A − B)2
  A − B − A − B + A − B − A − B  →(A − B)n
Repeat   Polymer
  →Nu −CH 2 − C H − CH 2 −
 |
 Some common examples of step growth polymers
 W n
(c) Termination : are

    Polymers Monomers
  
+  
Nu −  CH 2 − C H  − CH 2 + H → Nu − CH 2 − C H − Nylon-66
CH 3 Hexamethylenediamine and adipic
 |   |  acid
 W n  W n
Polymer
Bakelite Phenol and formaldehyde
Chain transfer agents : In Vinylic Dacron Terephthalic acid and ethylene
polymerisation various other molecules react with main
(polyester) glycol
growing chain to interrupt the further growth of the
original chain. This leads to lowering of average Rubber
molecular mass of the polymer such reagents are called It is a polymer which is capable of returning to its
chain transfer agents. The common example original length, shape or size after being stretched or
CCl 4 ,CBr 4 etc. deformed. It is the example of elastomer. Rubber are of
two types.
For example in the presence of CCl 4 styrene
(1) Natural rubber (2) Synthetic rubber
polymerizes to form a polymer of lower average
molecular mass which also contains some chlorine. (1) Natural rubber : It is obtained as latex from
rubber trees. The latex is coagulated with acetic acid or
• • • •
Initiator formic acid. The coagulated mass is then squeezed.
CH2 = CH   → CH 2 − CH → CH 2 − CH − Cl + CCl3
| | | The raw natural rubber is a soft gummy and sticky
C6 H 5 C6 H 5 C6 H 5 mass. It is insoluble in water, dil. Acids and alkalies but
soluble in benzene, chloroform, ether, petrol and carbon
disulphide. It absorb a large amount of water. It has low
• elasticity and tensile strength.

CCl 3
CH 2 = CH →Cl 3C −CH − CH
Destructive distillation of natural rubber gives
2
mainly isoprene (2-methyl butadiene).
| |
C6H 5 C6H 5

5
Thus isoprene is a monomer of natural rubber the molecule acts as reactive sites. The allylic −CH 2,
no. of isoprene unit are 11,000 to 20,000 which linked
alpha to double bond is also very reactive. During
together in a chain.
vulcanization, sulphur forms cross links at these
CH3 reactive sites. As a result, rubber gets stiffened and
| intermolecular movement of rubber springs is
P olym erisa
tion
nCH2 = C − CH = CH2    → prevented resulting in physical character of rubber. The
Isopre m e extent of stiffness of vulcanized rubber depend upon
 CH  the amount of sulphur added. For example about 5%
3
 |  sulphur is used for making tyre rubber while 30% of the
−CH 2 −C = CH −CH 2 −
sulphur is used for making battery case rubber.
 

 n
 In a polymer, the chains are normally tangled up
Natural rubber
with each other. When the rubber is stretched, the
(2) Synthetic rubber : The synthetic rubber is chains straighten out to some extent. The chains cannot
obtained by polymerising certain organic compounds slip past each other because of the polysulphide
which may have properties similar to rubber and some bridges. Thus, rubber can be stretched only to a limited
desirable properties. Most of these are derived from extent. When the tension is removed, the chains try to
butadiene derivatives and contain carbon-carbon double coil up again and the rubber resumes its original shape.
bonds. The synthetic rubbers are either homopolymers CH3 H
CH3
H
of 1, 3 butadiene or copolymer in which one of the
CH2 CH2
monomers is 1, 3 butadiene or its derivative so that the C=C C=C
polymer has the availability of double bonds for its
vulcanization. Some important examples are Neoprene, CH2 C=C CH2
~CH2 CH2~
styrene, butadiene rubber (SBR) thiokol, silicones,
CH3 H
polyurethane, rubber etc.
Natural rubber
Vulcanization of rubber : The process of All cis
heating natural rubber with sulphur to improve its configuration
The comparison of the main properties of natural
properties is called vulcanization. Vulcanization was rubber and vulcanized rubber are given below in the
introduced by Charles Goodyear. table,
Although natural rubber is thermoplastic Natural rubber Vulcanized rubber
substance in which there are no cross link between the (1) Natural rubber is Vulcanized rubber is hard and
polymer chain and it on vulcanization set into a given soft and sticky non-sticky.
CH3 CH3 (2) It has low tensile It has high tensile strength.
shape which is retained.
| | strength.
~CH2 – C – CH – CH2~ ~CH – C = CH – CH2~ (3) It has low It has high elasticity.
| | | elasticity.
S S S (4) It can be used It can be used over a wide
| | | over a narrow range range of temperature (–40° to
~CH2 – C – CH – CH2~ ~CH – CH = C – CH2~ of temperature 100°C).
| | (from 10° to 60°C).
CH3 CH3 (5) It has low wear It has high wear and tear
and tear resistance. resistance.
The vulcanization process performed originally
was slow. Now a days, some additives such as zinc (6) It is soluble in It is insoluble in all the
solvents like ether, common solvents.
oxide etc. are used to accelerate the rate of
carbon,
vulcanization. During vulcanization, sulphur cross links tetrachloride,
are formed (figure) the double bonds in the rubber petrol, etc.
Some important polymer and their uses

Rubber
Rubber Monomers Formula Applications
(i) CH 2 = C − CH = CH 2 



Making automobile,
Neoprene | −CH 2 −C =CH −CH 2 − refrigerator parts
rubber Cl 

|
Cl

n and electric wire.
Chloroprene

6
CH = CH2
CH 2 = CH − CH = CH 2 and

 − C 2 H− C = HC − HC 2 H− C − HC 2 H− 
(ii) Styrene Making of tyre and
Butadiene(75%)
Butadiene other mechanical

 
Rubber rubber goods.
Styrene
(SBR) or (25%)
Buna-S

 
 
 n
(iii) Butyl CH 3 Making of toys,
 CH3 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 −CH −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 Ethylenedichloride manufacture of
e rubber hoses and tank
(Thiokol) and
Na2S4 lining, engine
Sodium tetrasulp
hide
gasket and rocket
fuel.
(vi) Silicone CH 3 Silicon rubber
 CH 3 
rubber |  | 
Cl − Si − CH 3  − O − Si − 
|
 | 
Cl  CH 
Chlorosilanes  3
n

2 − CH 2OH
(vii) HOCH In the manufacture
Polyurethan Ethyleneglycol of fibre. Paints and
e rubber and heat insulator.
O
||
C = N − CH = CH − N = C = O
Ethylenedi- isocyanate

Plastics and resin


Name of polymer Abbreviat Starting materials Nature of Properties Applications
-ion (monomers) polymer
(i) Polyolefines
(a) Polyethylene or LDPE (Low CH 2 = CH 2 Low density Transparent, Packing material
polyethene density homopolymer moderate carry bags,
polyethen (branched) tensile insulation for
e) chain growth. strength, high electrical wires
toughness. and cables.
HDPE CH 2 = CH 2 High density Transluscent, Manufacture of
(high homopolymer chemically buckets, tubs,
(linear) chain inert, greater house ware,

7
density growth. tensile pipes, bottles and
polyethen strength, toys.
e) toughness.

Packing of
(b) Polypropylene or PP CH 3CH = CH 2 Homopolymer Harder and
polypropene , linear, chain stronger than textiles and
foods, liners for
growth. polyethene.
bags, heat
shrinkage wraps,
carpet fibres,
ropes,
automobile
mouldings,
stronger pipes
and bottles.
(c) Polystyrene or C 6 H 5 CH = CH 2 Homopolymer Transparent Plastic toys,
Styron or styrofoam , linear, chain house hold
growth wares, radio and
television bodies,
refrigerator
linings.
(ii) Polyhaloolefines

(a) Polyvinyl chloride PVC CH 2 = CH − Cl Homopolymer Thermoplastic (i) Plasticised


Vinylchloride chains growth with high boiling
esters PVC used
in rain coats,
hand bags,
shower curtains,
fabrics, shoe
soles, vinyl
flooring (ii) Good
electrical
insulator (iii)
Hose pipes.
(b) Polytetrafluoroet- PTFE F2C = CF 2 Homopolymer Flexible and (i) For nonstick
hylene or Teflon , high melting inert to utensiles coating
point solvents (ii) Making
boiling acids gaskets, pump
even aqua packings valves,
regia. Stable seals, non
upto 598 K. lubricated
bearings.
(c) PCTFE ClFC = CF 2 Homopolymer Less resistant Similar to those
Polymonochlorotri- to heat and of teflon.
fluroroethylene chemicals due
to presence of
chlorine
atoms.
(iii) Formaldehyde
resins
(a) Phenol Phenol and Copolymer, Thermosettin (i) With low
formaldehyde resin formaldehyde step growth g polymer, degree
or Bakelite hard and polymerisation as
brittle bindings glue for
wood varnishes,
lacquers.
(ii) With high
degree

8
polymerisation
for combs, for
mica table tops,
fountain pen
barrels electrical
goods (switches
and plugs).
(b) Melamine Melamine and Copolymer, Thermosettin Non-breakable
formaldehyde resin formaldehyde step growth g polymer, crockery.
hard but not
so breakable.
(iv) Polyacrylates
(a) Polymethacrylate PMMA CH 3 Copolymer Hard Lenses light
(lucite, acrylite and | transparent, covers lights,
plexiglass and CH 2 = C − C OOCH 3 excellent light shades
perspex) transmission, signboards
optical clarity transparent
better than domes skylight
glass takes up aircraft window,
colours. dentures and
plastic jewellery.
(b) Polyethylacrylate CH 2 = CH − COOC 2 H Copolymer
5
Tough, rubber
like product

Fibre
Name of Abbreviatio Starting materials Nature of Properties Applications
polymer n polymer
(i) Polysters PET HO − CH 2 − CH 2 − OH Copolymer, Fibre crease For wash and
(a) Terylene or (Polyethylene Ethyleneglycolor Ethane-1, 2-diol step growth resistant, low wear fabrics,
Dacron or mylar terephthalate and linear moisture tyre cords
) O condensation absorption, not seat belts and
O ||
||
C – OH polymer damaged by sails.
HO – C pests like
moths etc.
Terephthalic
acid

(b) Glyptal or HO − CH 2 − CH 2 − OH Copolymer, Thermoplastic, Paints and


alkyd resin Ethyleneglycol linear step dissolves in lacquers.
and COOH growth suitable
condensation solvents and
COOH polymer solutions on
Phthalic
acid evaporation
leaves a tough
but not flexible

9
film.
(ii) Polyamides
(a) Nylon-66 O O Copolymer, Thermoplastic Textile fabrics,
|| || linear, step high tensile bristles for
HO − C[CH 2 ]4 C − OH growth strength brushes etc.
Adipic acid
condensation abrasion
and polymer resistant.
H 2 N − [CH 2 ]6 − NH 2
Hexamethyl
lenediamin
e

(b) Nylon-610 H 2 N − [CH 2 ]6 − NH 2 Copolymer, Thermoplastic, (i) Textile


Hexamethyllene diamine linear, step high tensile fabrics,
and growth strength, carpets,
abrasion bristles for
HOOC [CH 2 ]8 COOH resistant brushes etc.
Sebacicacid
(ii) Substitute
of metals in
bearings.
(iii) Gears
elastic
hosiery.
(c) Nylon-6 or H Homopolymer Thermoplastic Mountaineerin
Perlon N O , linear high tensile g ropes, tyre
strength cords, fabrics.
Caprolactum or
abrasion
H2N – [CH2]5 – COOH
resistant.
∈-Aminocaproic acid
(iii) Polyacryloni- PAN CH 2 = CH − CN Copolymer Hard, horney Orlon, arcrilon
trile or orlon or and high used for
acrilon melting making
materials. clothes,
carpets
blankets and
preparation of
other
polymers.

 Copolymer of acrylonitrile (40%) and vinyl safe uses in human systems, attempts have been made
chloride (60%) is called dynel it is used in hair wigs. to develop biodegradable synthetic polymers. These
 Artificial silk is the term given to fibres derived synthetic polymers mostly have functional groups which
from cellulose. The most important process for the are normally present in biopolymers and lipids.
production of artificial silk is viscose process. The Among these aliphatic polyesters are one
difference between natural and artificial silk is natural important class of biodegradable polymers which are
silk contain nitrogen while artificial silk may not have commercially potential biomaterials. The common
nitrogen. Natural silk on burning gives a smell of examples of biodegradable polymers are polyhydroxy
burning hair and shrinks into a ball of cinder while butyrate (PHB), polyhydroxy butyrate –co-β -hydroxy
artificial silk gives a thread of ash. valerate (PHBV), polyglycolic acid (PGA), polylactic acid
Biodegradable polymers (PLA), poly (∈-caprolactone) (PCL), etc.
These are the polymers which are degraded by Uses : Biodegradable polymers are used mainly
micro-organisms within a suitable period so that for medical goods such as surgical sutures, tissue in
biodegradable polymers and their degraded products growth materials or for controlled drug release devices,
do not cause any serious affects on the environment. plasma substitutes etc. The decomposition reactions
In biological systems, biopolymers degrade mainly usually involve hydrolysis (either enzymatically induced
by enzymatic hydrolysis and to some extent by or by non-enzymatic mechanisms) to non-toxic small
oxidation. Therefore, in view of the disposal problems of molecules which can be metabolized by or excreted
polymer waste and for developing polymers for other from the body. These are also finding use in agriculture

10
materials (such as films, seed coatings), fast food  O 
 || 
wrappers, personal hygiene products, etc. −O −(CH 2 )2 − C −

 

(i) Polyhydroxy butyrate (PHB)  n
PCL
Polyhydroxy butyrate (PHB) is obtained from
hydroxy butyric acid (3-hydroxy butanoic acid) Uses : PGA and PLA (90 : 10) is used to make
absorbable structure to close an internal of external
wound and has replaced cat gut these are completely
degraded and absorbed by the body within 15 days to
O  O  one month of the surgery.
||
 ||

Condensati
on
nHOCHCH 2C OH     
→ − O − CHCH 2C −  Polyhydroxybutyrate (PHB) and (PHBV) have been
| |
  used for making films for packaging and into moulded
CH3  CH3 n items.
3-Hydroxybutanoic
acid Polyhydrox
ybutyrate
(PHB)
Molecular masses of polymers
(ii) Poly-Hydroxybutyrate-co-β -Hydroxy
valerate (PHBV) : It is copolymer of 3-hydroxy A polymer sample contains chain of varying
butanoic acid and 3-hydroxy pentanoic acid, in which lengths and therefore its molecular mass is always
the monomer units are joined by ester linkages. expressed as an average on the other hand natural
polymer such as proteins contain chain of identical
nCH 3 − CH − CH 2COOH + nCH 3 − CH 2 − CH − CH 2 length
− COOHand therefore they have definite molecular mass.
| |
OH OH The molecular mass of a polymer can be
3-Hydroxy butanoicacid 3-Hydroxy pentanoicacid
expressed in two ways.
  (1) Number average molecular mass (M N )
 
→−O −CH −CH 2 −CO − ,
 | ||

 R O n (2) Weight average molecular mass (M W ) .
PHBV

R = CH 3 , C 2 H 5 (1) Number average molecular mass (M N ) :

The properties of PHBV vary according to the ratio If N1 , N 2 , N 3 ….. are the number of molecules with
of both the acids. 3-Hydroxy butanoic acid provides molecular masses M 1 , M 2 , M 3 …… respectively,
stiffness while 3-Hydroxypentanoic acid gives flexibility then the number average molecular mass is
to the copolymer.
(iii) Polyglycolic acid (PGA) : Polyglycolic acid
N 1 M 1 + N 2 M 2 + N 3 M 3 + ...
MN =
(PGA) is obtained by the chain polymerisation of cyclic N 1 + N 2 + N 3 ...
dimer of glycolic acid, HO − CH 2 − COOH .
∑ Ni M i
 O  This may be expressed as : MN =
Heat

→− OCH
||  ∑ Ni
nHO − CH 2COOH   2 C −
Glycolic acid 
 

 n Where N i is the number of molecules of the ith
Polyglycol ic acid (PGA)

(iv) Polylactic acid (PLA) : Polylactic acid (PLA) type with molecular mass M i .
is obtained by polymerisation of the cyclic dimer of
(2) Weight average molecular mass (MW ) :
lactic acid (HO − CH (CH 3 )COOH ) or by
If m1, m2, m3 …. are the masses of species with
microbiological synthesis of lactic acid followed by the
polycondensation and removal of water by evaporation. molecular masses M1, M 2, M 3 ….. respectively,
then the weight average molecular mass is
m1M 1 + m2 M 2 + m3 M 3 ....
O  O  MW = or
||
Condensati
on
 ||  m1 + m2 + m3 + ...
nHOCH C − OH   →  − OCH − C − 
|  |  ∑ mi M i
CH3  CH n
=
Lacticacid
3
Polylactic
acid(PLA)
∑ mi

(v) Poly (∈ -caprolactone) (PCL) : It is obtained


by chain polymerisation of the lactone of 6-hydroxy
hexanoic acid.

11
But mi = N i M i , so that with free radical intermediate to form a non reactive
radical which is highly stabilized by resonance because
∑ N i M i2 of the lack of reactivity of the new radical formed, it
MW = inhibit the further progress of the chain reaction.
∑ Ni M i Therefore the reaction stops.
O OR
where N i is the number of molecules of mass

Mi . R• +
Free radical
 Polydispersity index : The ratio of weight
average molecular mass to the number average O O•
molecular mass is called polydispersity index, PDI. Resonance
Benzoquinone
stabilized
OR OR OR OR
MW
PDI = •
Mn
This gives an idea about the homogeneity of a •
polymer.
O• O O O
(i) The polymers whose molecules have nearly
same molecular masses are called monodisperse
(6) A thin film of polyester is known as Mylar film.
polymers. For these molecules, MW = M N and
(7) PET plastic commonly used for soft drink
therefore, PDI is one. bottles, transparent jars and bottles for use in kitchen
(ii) The polymers whose molecules have wide are made up of polyethylene terephthalate.
range of molecular masses are called polydisperse (8) Glyptal resins or Alkyd resins obtained from
polymers. For these polymers, MW > M N and ethylene glycol and phthalic acid are thermoplastic.
However, resins obtained from glycerol and phthalic
therefore, their PDI is greater than one. acid are thermosetting polymers, due to the formation
Thus, it may be concluded that in general, natural of cross-links by the third –OH group present in glycerol.
polymers are more homogeneous than synthetic (9) Thermosetting plastics are also called heat setting
polymers. plastics whereas thermoplastics are called cold setting
plastics.
For natural polymers, PDI is usually unity and
therefore, natural polymers are monodisperse. (10) Latex is a colloidal dispersion of rubber in
water. It is not a colloidal solution of isoprene in water
For synthetic polymers, the PDI is greater than or any other solvent.
one and therefore M W is always greater than M N . (11) Polymerisation of isoprene by free radical
mechanism (in the presence of Na and heat) gives a
MN is always determined by employing methods
product which is different from natural rubber (Natural
which depend upon the number of molecules present in rubber is a polymer of isoprene). The synthetic product
the polymer sample. For example, colligative property so obtained is a mixture of cis and trans configurations
such as osmotic pressure is used. On the other hand, and resembled Gutta percha. Gutta percha is a
weight average molecular mass is measured by using naturally occurring polymer in plants. It is all trans-
the methods such as light scattering and stereoisomer and is non-elastic.
ultracentrifugation, sedimentation, etc. which depend (12) Terylene is a British name of Dacron.
upon the mass of individual molecules. (13) Co-polymer of vinyl chloride 90% and vinyl
(3) Polymer in increasing order of their acetate 10% is called VINYON.
intermolecular forces are polythene < Buna S < Nylon- (14) Co-polymer of acrylonitrile 40% and vinyl
66. chloride 60% is called DYNEL.
(4) We always use purest monomer in free radical (15) Co-polymer of vinyl chloride and vinyledene
polymerisation reaction because the impurities can act chloride is called SARAN.
as chain transfer agent and may combine with the free (16) Plasticizers cannot convert a thermosetting
radical to slow down the reaction or even stop the polymer into thermoplastic one. It converts a hard and
reaction. brittle plastic into soft and easily pliable one at room
temperature.
(5) Benzoquinone inhibit the free radical
polymerisation of vinyl derivative because it combine

12
(17) Free radical polymerisation of isoprene do not (6) Epoxy resins : These are obtained by
give Gutta percha (Gutta percha is a natural polymer). copolymerisation of epichlorohydrin and bisphenol-A.
The synthetic product so obtained resembles Gutta These resins have good adhesive strength. These are
percha. used for making adhesives (Araldite, M-seal etc.) for
(18) Co-ordination polymerisation of isoprene making glass reinforced plastic (fibre glass), for
gives a product similar to natural rubber. lamination, to impart crease resistance and shrinkage
control to cotton, rayon and for making anti-skid surface
(19) Latex is not a colloidal dispersion of isoprene
for highways.
in water.
(7) Polycarbonates : These are obtained by
Other polymers in day to day use copolymerisation of diphenyl carbonate and bisphenol-
A. It has very high optical transparency, high impact
(1) Thermocol is polystyrene foamed with vapour strength over wide range of temperature. It is used for
of pentane. making bullet-proof glass, baby-feed bottles, fridge
(2) Cups used for hot drinks are made up of containers, mixi jars etc.
polystyrene. It does not become soft like other plastics (8) Thermoplastics are also called cold setting
at temperatures near boiling point of water. polymers. They are moulded when hot but set into the
required shape only on cooling. Thermosetting polymers
(3) A major development of co-ordination
are also called heat setting polymers. Such polymers
polymerisation is stereochemical control. For example
are supplied in the partially polymerised form.
Propene could polymerise to any of the three different
(9) On long exposure to air and sun-light thermo-
arrangements.
plastics becomes brittle. It is due to the evaporation of
(i) Isotactic (Same order) : When groups are plasticizer with time. The faint smell associated with
arranged on one side of the chain. All y group i.e. on various thermoplastics is due to slow evaporation of this
one side and all Z groups on the opposite side of the plasticizer.
chain. (10) High density polyethene is a linear polymer.
Y Y Y Carry bags made out of it are not so soft and make a
crackling sound when crushed in hands. You can easily
tear them in one direction, but not at right angle to it.
Z Z Z Plastic twine is made out of such a polymer. They have
(ii) Syndiotactic (Alternating order) : The Y very high tensile strength in one direction (along the
and Z groups lie alternately on each side of the chain. polymer chain) and a low tensile strength at right angle
to it. Such carry bags are used to carry clothes, note-
Y Z Y
books etc. Carry bags made of low density polyethene
are soft, make no noise when crushed with hands, have
same tensile strength in all directions. Such carry bags
Z Y Z
are used to carry heavy objects (vegetables, fruits etc.)
(iii) Atactic (Random order) : The Y and Z (11) Kevlar is a nylon-polymer and is obtained by
groups are arranged in a random fashion. condensation copolymerization of terephthalic acid with
Y Z Z 1, 4-diaminobenzene (p-phenylenediamine). The fibres
of this polymer are so strong that they are used to make
bullet-proof vests.
Z Z Y (12) Lexan is a polycarbonate(polyester) and is
(4) Addition polymers, generally, have only carbon prepared by condensation copolymerization of diethyl
atoms in their main chain. On the other hand, carbonate and bisphenol A. It has unusually high impact
condensation polymers, generally, have atoms other strength and hence is used in making bullet-proof
than carbon atoms, in their main chain. windows and safety or crash helmits.
(5) Polyurethanes : Polyurethanes are polymers (13) Nomex is a polyamide made from m-phthalic
obtained by the polymerisation of a urethane. acid and m-diaminobenzene. It is known for its fire-
It is used for heat and sound insulation in the form resistant properties and is used in protective clothing
of polyurethane foam. Mattresses, cushions and pillows for firefighters, astronauts and race car drivers.
made out of polyurethane foam are washable and long (14) Ebonite is high sulphur (20-30 %S) rubber
lasting. and is obtained by vulcanization of natural rubber.
(15) Rayon was originally called artificial silk but
H
| now the name rayon is given to all fibres obtained by
R − N − C − OR′ chemical treatment of cellulose. Thus, artificial silk is
||
polysaccharide, i.e., cellulose derivative.
O
A urethane

13
14