Chapter 6

POLYMER CHEMISTRY
Lecture/Lession Plan -5

POLYMER CHEMISTRY

6.1 Conducting polymer:

Polymer made from natural sources or from artificially they are normally bad conductor or poor
conductor of electricity. Conducting polymer are those which conduct electricity. We know all metals
are good conductor of electricity but when a polymer conduct electricity we called it conducting
polymer or intrinsic conducting polymer or simply synthetic metal. We know metals have free
electron which moves and current flows but how does the electricity or current flows through some
polymers. The main cause of conducting current by a polymer is presence of conjugated Π electrons
in the backbone chain. Here the conduction takes place by overlapping of orbital of conjugated Π
electrons in the polymer chain., due to high coordination number, valence shell electrons are not
sufficient for pairing with all surrounding atoms to form covalent bonding. Hence, the lower bands
are filled up first but the upper band are farthest from from the nucleolus and they are empty or
partially filled due to insufficient electrons.

11
12 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -5

Band theory (valence band and conduction band)

The lower energy band is called valence band and the upper energy band is called conduction band.
The band theory explains the position of these mobile electrons and the process of electrical conduc-
tion. In polymer, when they occupy a definite positions, the electrons are subjected to a non-uniform
electric field. The electrons may now take position in the band. The band however non-continuous,
but separated by forbidden zones.

Molecular orbital picture of H2

If the energy gap between the valence band and conduction band(band gap) are large then the
polymer is called electrically insulator.
6.1. CONDUCTING POLYMER: 13

Band theory in case of insulator

In case of semiconductor a small amount of electric current can flow at room temperature and
the normal value of conductivity of semiconductors are in the order 102 to10−10 ohm−1 .m−1 .

6.1.1 Semiconductor

Semi-conducting polymers are having the energy gap between the valence band and conduction
band(band gap) are not so large and not so small. They have low conductivity.
14 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -5

Band theory in case of semiconductor

Examples are poly acetylene1.7 × 10−9 ohm−1 .m−1 and polyaniline10−10 ohm−1 .m−1 .

Delocalisation of electron in a conjugated system)

The normal Due to this low conductivity these are not used in practical field. The conductivity
of these semiconductor however enhance by many ways-
1. Doping
2. Filled with conducting polymer
3. Blending with conducting polymer
6.1. CONDUCTING POLYMER: 15

6.1.2 Doping

The conduction power of semiconductor can be enhanced by input some foreign material or impu-
rities. These impurities are called doping agent or dopant. Appropriate doping agent increase the
conductivity of semiconductors upto 104 times. Doping enhances the conductivity of semiconductor
and called extrinsic semiconductor. The increase in conduction is due to participation of impurity
elements in between the valence band and conduction band and thus making a bridge through which
electrons can jump easily from the valence band to the conduction band.Actually the conjugated Π
electrons have very low ionisation potential and high electron affinities the foreign materials develop
positive or negative charge through oxidation or reduction of the semiconductor. Doping are mainly
two type.
i) p-type doping through oxidation of materials: In this type of doping some electrons from
the conjugated Π bonds are removes through oxidation creating a positive hole called polaron inside
the polymer. The positive hole or polaron can move throughout the polymeric chain and make it
conducting polymer.

p-type doping creates positive hole

Lewis acids(FeCl3 , AlCl3 are generally use as doping agent.

ii) n-type through reduction of materials: In this type of doping some electrons are introduced
to the conjugated Π bonds through reduction creating a negative hole or charge inside the polymer.
The negative hole or charge can move throughout the polymeric chain and make it conducting
polymer.
16 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -5

n-type doping creates positive hole

Lewis bases(Na+ C10 H− + −

8 , K C10 H8 are generally use as doping agent.

2. Filled with conducting polymer:The conduction power of semiconductor can be enhanced by

input some foreign conducting material or good conductor in powder(carbon dust) form or granule
from(metallic fibers). The role of polymer is to bind the conducting materials. The minimum con-
centration of conducting filler required to start the conduction is called percolation threshold.
3. Blending with conducting polymer:The conduction power of semiconductor can be enhanced
by input some foreign conducting polymer material. During such type of blending we should alert
about the compatibility of those polymer. In such cases the strength properties of the blend polymer
also enhanced.
Another application of conducting polymer Due to light weight low cost than metal semi-
conductor and easy to preparation conducting polymers have diversified application.
a. Rechargeable light weight batteries
b. Optical display device
c. Solar cell
d. telecommunication system
e. electronic toys
f. As analytical sensor.

6.2 Glass transition temperature (TG )

The glass is said to be a supercooled, liuid, hard, brittle, amorphous substance having variable
melting point and very high viscosity(1013 Poise or more). The glass transition temperature of any
amorphous polymer is the temperature where it undergo transition from rubbery (soft and called
viscoelastic state) to glassy (hard and rigid) solid or vice-versa. This can be done by heating the
solid polymer to melt and allow to cool gradually. The viscosity of liqid gradually increses and it will
converted to rubber like material. On farther cooling at a particular temperature the rubber form
6.3. CRYSTALLIZATION TEMPERATURE(TC ) 17

transformed to rigid form. This temperature is called glass transition temperature. The term glass
transition temperature is only applicable for thermoplastic polymer not for thermosetting polymer.
The molecular force of polymer very much depend on glass transition temperature. Glass transition
temperature of few amorphous polymers are-

Amorphous polymer T0G C

Polyvinyl Chloride(PVC) 80
Polytetrafluoroethylene(Teflon) 115
Polypropylene(PP) 5
Polyethylene(PE) -20

Glass transition temperature depends on following factor:

1) It increases with increase in molecular weight of polymer.
2) It increases with increase in branch in polymeric backbone chain.
3)It increase with increase in large group in polymeric backbone chain.

6.3 Crystallization temperature(TC )

Specific volume Vs temperature

Glass transition temperature(TG ),
Crystallization temperature(TC )
Melting temperature(TM )
18 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -5

Heat flow Vs temperature

Glass transition temperature(TG ),
Crystallization temperature(TC )
Melting temperature(TM )
In case of crystalline polymer and amorphous polymer, above the glass transition a state will arrive
where molecules moved into ordered arrangement with a very stable crystalline structure by gaining
of energy and there by given off energy called crystalline temperature (TC ). TC can be measured
by differential calorimetry(DSC)
Crystallization temperature depends on following factor:
1) It increase with increase in molecular weight of polymer.
2) It increase with decrease the branch in polymeric backbone chain.
3)It increase with decrease the large group in polymeric backbone chain.

6.4 Melting temperature(TM )

In case of both amorphous and crystalline polymer a point above crystallization temperature another
thermal transition state will arrive where by gaining of energy the molecules moved into a disor-
dered arrangement with a very unstable structure and get melts called melting temperature(TM ).
Reaching this temperature(TM ) where melting starts the the temperature remain unchanged until
whole polymer get melts. Melting temperature of few polymers are-

Amorphous polymer T0M C

Polyvinyl Chloride(PVC) 212

Polystyrene(PS) 240
Polypropylene(PP) 175
High density polyethylene(HDPE) 115
Low density polyethylene(LDPE) 135
6.5. CRYSTALLINE, SEMICRYSTALLINE AND AMORPHOUS POLYMER 19

Melting temperature depends on following factor:

1) It increase with in crease in aromatic part in polymer.
2) It increase with in crease in molecular weight of polymer.
3)It increase with in crease the large group and polar in polymeric backbone chain.

6.5 Crystalline, semicrystalline and amorphous polymer

The polymer is made of large number of repeating monomer unit varying from 100 to lacks or
more and consequently their respective molecular weights are also high. In polymer the molecules
are held together by van der Waals force or by hydrogen bonding. In polymer the molecules are
arranged in well packed form or haphazardly oriented in one dimensional or linear, two dimension
or sheet, three dimensional or cross linked network structure. Due to presence of giant structure
and curing conditions the molecules of polymers are arrange in different fashion called crystalline,
semi-crystalline or amorphous polymer. and their crystallinity may vary from 0 to 99%.

6.5.1 Crystalline polymer

In polymer the molecules are arranged in regular fashion and thereby well packed in the form of
crystal having a thickness about 10 to 18 nm with parallel long backbone chain perpendicular to
the surface of the polymer plate is called crystalline polymer. The crystallinity about 95 to 99%.
Example of crystalline polymers are Polyethylene, polyester, polyethylene terephthalate etc.
Properties of crystalline polymer:
Crystalline polymers have the following properties-
1. Rigid and strong
2.having high melting point
3.high molecular forces
4.less effected by solvents

6.5.2 Semi-crystalline polymer

In polymer the molecules are arranged in regular closed pack as well as haphazard fashion and
thereby polymer have both crystalline and amorphous portion is called semi-crystalline polymer.
The crystallinity in semi-crystalline polymer about 50 to 75%. Example of crystalline polymers are
Polyvinyl alcohol(both PVA hot and PVA cold), polyester, polyethylene terephthalate etc.
Properties of crystalline polymer:
Crystalline polymers have the following properties-
1. soft and weak
2.having low melting point
3.low molecular forces
4.highly sensitive towards solvents

6.5.3 Amorphous polymer

In polymer the molecules are arranged in irregular and disorder fashion and thereby polymer have
low molecular force, melting point is called semi-crystalline polymer. The crystallinity in semi-
crystalline polymer about 20 to 50%. Example of amorphous polymers are Polyvinyl acetate(fevicol),
polystyrene, poly methyl methacrylate (PMMA) etc.
Properties of crystalline polymer:
20 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -5

Crystalline polymers have the following properties-

1. very soft and weak
2.having low melting point
3.low molecular forces
4.highly sensitive towards solvents

6.6 Degree of crystallinity:

Polymer having different strength due to presence of different percentage of crystallinity. Polymer
crystallinity is also called degree of crystallinity is the ratio of polymer of the crystalline part of the
polymer to the rest amorphous polymer.
Mathematically represented as-

ρPolymer − ρAmorphous
ρCrystalline − ρAmorphous

Where, ρPolymer, ρAmorphous and ρCrystalline are densities of whole polymer, amorphous part
and crystalline part of polymer respectively.
6.6. DEGREE OF CRYSTALLINITY: 21

Table 6.1: Some common important monomer and polymer of addition polymer:
Sl. Name of structure Name of polymer structure commercial Uses
No. monomer of monomer Name of polymer of polymer Name Uses

1. Ethylene CH2 = CH2 Polythene −[CH2 − CH2 ]− Polythene Bag,

/Ethene Packing
materials
2. Propene CH(CH3 ) = CH2 Polypropene −[CH(CH3 )− PP Seat covers,
Polypropene CH2 ]− ropes,
carpet
fiber
3. 1,3-Butadiene CH2 = CH Polybutadiene −[CH2 − CH Polybutadiene Tyres,
−CH = CH2 = CH − CH2 ]− shoe
soles
4. Styrene CH(C6 H5 ) = CH2 Polystryne −[CH(C6 H5 ) − CH2 ]− Polystryne Refrizerator
linings,
toy, cup
5. Vinyl chloride CH(Cl) = CH2 Polyvinyl −[CH(Cl) − CH2 ]− PVC Gramaphone
chloride records,
electrical
insulator
6. Isoprene CH2 = C(CH3 ) Cis −[CH2 − C(CH3 ) Natural Tyres,
−CH = CH2 Polyisoprene = CH − CH2 ]− rubber tubes
7. Chloroprene CH2 = C(Cl) Neoprene −[CH2 − C(Cl) Synthetic Container
−CH = CH2 rubber = CH − CH2 ]− Rubber for oil,
Pipe for
petrol
8. Acrylonitrile CH(CN) = CH2 polyacrylo −[CH(CN) PAN Blankets,
CH(CN) = CH2 nitrile −CH2 ]− Carpets,
sweater
9. Methyl C(COOCH3 ) Polymethyle −[C(COOCH3 ) PMMA Lenses,
methacrylate (CH3 ) = CH2 methacrylate (CH3 ) − CH2 ]− Aircraft
window
10. Tetrafluoro CF2 = CF2 Polytetra −[CF2 − CF2 ]− Teflon Non stick
ethylene fluoroethylene Teflon frying
pan,
gaskaets
11. Monochloro CClF = CF2 PolyMonochloro −[CClF − CF2 ]− PCTFE Valves,
trifloroethylene trifloroethylene gaskaets
12. Ethyl CH(COOCH3 ) Polyethyle −[CH(COOCH3 ) PEA Blankets,
acrylate = CH2 methacrylate −CH2 ]− Cloths
13. Butadiene CH(C6 H5 ) = CH2 Styrene −[CH(C6 H5 ) SBR Shoes sole,
styrene + CH2 = CH butadiene −CH2 − CH2 SBR Tyres
−CH = CH2 rubber −CH = CH − CH2 ]−
14. Butadiene CH2 = CH − CH Polybutadiene −[CH2 − CH = Polybutadiene Carpets,
acrylonitrile = CH2 + CH acrylonitrile CH − CH2 ]− acrylonitrile sweater
(CN) = CH2 −CH(CN) − CH2 ]−
15. Vinyledene CH2 = CCl2 + Polyvinyl −[CH2 − CCl2− Swaran electrical
chloride CH2 = CH(Cl) chloride CH2 − CH(Cl)]− Warp insulator
+ Vinyl
chloride
22 CHAPTER 6. POLYMER CHEMISTRY LECTURE/LESSION PLAN -5

Table 6.2: Some common important monomers and polymer of condensation polymer:
Sl. Name of structure of Name of structure commercial Uses
No. monomer monomer polymer of polymer Name Uses

1. Ethylene HOCH2 − CH2 OH + Polyethylene −[OCH2 − CH2 OOC Terylene Seat belts,
glycol + HOOC − C6 H4 − COOH terephthalate −C6 H4 − CO]− or Decron ropes,
Terephthalic (PET) nets,
acid magnetic
tapes
2. Ethylene HOCH2 − CH2 OH Polyethylene −[OCH2 − CH2 OOC Glyptal Paints,
glycol + + C6 H4 − (COOH)2 terephthalate −C6 H4 − CO]− lacquers
Phthalic + (PET)
acid +
3. Caprolactum (−CH2 )5 CONH− Polyamide −[NH Nylon-6 Ropes,
(CH2 )5 CO]− tyre cords
thrade,
fabris
4. ε-Amino NH2 − (CH2 )5 − NH2 Polyamide −[NH(CH2 )5 CO]− Nylon-6 Ropes,
caproic tyre cords,
acid thrade,
fabris
5. Hexamethylene NH2 − (CH2 )6 NH2 + Polyamide −[NH − (CH2 )6 Nylon-6,6 Fabrics
diamine + HOOC− NHOC − (CH2 )4 for textile,
Adipic (CH2 )4 − COOH −CO]− bristles
acid for brushes
6. Ethylene HOCH2 − CH2 OH + Polyethylene −[OCH2 − CH2 O Terylene Seat
glycol + CH3 O − OC − C6 H4 terephthalate −OC − C6 H4 or belts,
Dimethyl −CO − OCH3 −CO − O]− Decron ropes, nets,
terephthalic magnetic
acid tapes
7. Phenol + C6 H5 − OH Poly Three Novoloc or Wood adhesive,
Formaldehyde + HCHO phenol dimensional resol Electrical
formaldehyde cross linking (Phenoplast) equipments
network PF (PO box)
structure resin pressure
(see p.-) cooker
handle
8. Melamine + C 3 N6 H6 Poly Three dimensional (Aminoplast) plywood
Formaldehyde + HCHO melamine cross linking network MF adhesive,Cup
formaldehyde structure(see p.-) resin plate, dish
structure(see page-) plate, dish
9. Urea + NH2 − CO − NH2 Poly Three dimensional (Aminoplast) MR grade
Formaldehyde + HCHO urea crosslinking network UF plywood
formaldehyde structure(see p.-) resin adhesive
structure(see p.-) adhesive