UNIT 1: POLYMER CHEMISTRY

Polymers can be defined as the large molecules (macro molecules) formed by the linking together
of large number of smaller molecules called monomers. (In Greek language ‘poly’ means “many”
& ‘mer’ means “units”).
Number of monomer units (low molecular weight compounds) undergoes the polymerization gives
polymers (high molecular weight compounds), the whole process is called as polymerization.

Example: - polyethylene is a polymer formed by linking together of monomer units of ethylene

molecules.
n CH2 = CH2 (-CH2−CH2-) n
Ethylene (Monomer) Polyethene (Polymer)

Functionality of monomers:
The functionality of a monomer means the number of bonding sites presents in it, example. The
functionality of ethylene glycol, Adipic acid, and Hexamethylene Diamine is two.
Bifunctional polymers: The functionality of monomer is two. Here linear and straight chain
polymers are formed, for example, all vinyl polymers, Adipic acid, and amino acid.
Ethylene glycol – HO – CH2- CH2- OH,
Adipic acid – HOOC – (CH2) 4 – COOH
Hexa Methylene Diamine - H2N- (CH2)6- NH2
Trifunctional polymers: functionality of monomers is three. Here three-dimensional network
polymers are formed. For example, Phenol, Melamine and Glycerol etc
Glycerol - HO- CH2- CH-CH2-OH
OH
- Bi-functional monomers containing two functional groups give linear polymers.
- Certain Trifunctional monomers may react and produces ring or cyclic polymers.
- Poly-functional compounds with more than two functional groups per molecule of the
monomer give branched or cross-linked polymers.
Degree of polymerization
The degree of polymerization, or DP, is the number of monomeric units in
a macromolecule or polymer or oligomer molecule.
For a homo polymer, there is only one type of monomeric unit and the number-average degree of
polymerization is given by
DPn = Xn = Mn / Mo
Where Mn is the number-average molecular weight and
Mo is the molecular weight of the monomer unit.
Ex: Calculating Degree of Polymerization

Aditya College of Engineering & Technology (A), Surampalem

 Classification of Polymers:
Classification Based upon source:
(1) Natural polymers: Polymers which are found in nature.
Ex. Starch, cellulose and natural rubber, Silk, Proteins, Nucleic acid etc.
(2) Semi synthetic polymers It is obtained from naturally occurring polymers by chemical treatment.
Most of the semi synthetic polymers are prepared from cellulose.
Ex. Cellulose acetate, cellulose nitrate, cellulose xanthate and rayon
(3) Synthetic polymers Man maid polymers are known as synthetic polymer.
Ex. PVC, polyethylene, polystyrene, nylon-6, nylon-6, 6, Terylene, synthetic rubbers etc
Classification Based upon structure
1. Linear polymers: Monomers are joined together to form long straight chains. The various linear
polymeric chains are stacked over one another to give a well packed structure close packed in nature,
having high densities, high melting point and high tensile (pulling) strength. Note: All fibers are
linear polymers. Ex. cellulose, silk, nylon, Terylene etc
2. Branched chain polymers: Polymers in which the monomeric units constitute a branched chain.
Branched chain polymers have lower melting point low densities and tensile strength as compared to
linear polymers. Examples are amylopectine, glycogen, low density polyethylene and all vulcanized
rubbers.
3. Cross linked or Three-Dimensional network polymers: When linear polymeric chains are
joined together to form a three-dimensional network structure. These polymers are hard rigid and
brittle. Cross linked polymers are always condensation polymers. Resins are cross linked polymers.

Classification Based upon molecular force (End Use)

1. Elastomers: Polymers in which the intermolecular forces of attraction between the polymer chains
are the weakest (weak van der Waals forces of attraction) these polymers consist of randomly coiled
molecular chains of irregular shape having a few cross links. Examples are natural rubber, Buna-S,
Buna-N etc.
2. Fibres: Those polymers in which the intermolecular forces of attraction are the strongest are called
fibers. These polymers held together by H-bonding or dipole-dipole interaction. Fibres have high
tensile strength, least elasticity having high melting point and low solubility.
3. Thermoplastics: In thermoplastics intermolecular forces of attraction are in between those of
Elastomers and fibres. Thermoplastics become soft and viscous on heating and rigid on cooling.
Examples are polythene, nylon-6, nylon-6,6 etc.
4. Thermosetting polymers: these polymers have low molecular masses and are semi-fluid
substances. These polymers are hard and infusible. Examples are melamine-formaldehyde, Bakelite
(phenol-formaldehyde) etc.

Aditya College of Engineering & Technology (A), Surampalem

Based on Tacticity:
TACTICITY OF POLYMER: The orientation of monomer units in a polymer molecule can takes
place in an orderly or discordantly fashion with respect to the main chain. This difference in the
configuration is known as tactility which affects the physical properties of the polymers. On the basis
of tacticity, the structure of the polymer may be divided into the following categories
(i) Isotactic (ii) Syndiotactic (iii) Atactic

(i) Isotactic Polymer: These polymers consist of chain segments which display a regular repetition
of the monomer units with teat C atoms of the same satiric configuration. In this polymer the
substituent group (R) on the polymer lies above or below the plant of the main polymer chain.

(ii) Syndiotactic polymers: The chains of these polymers consist of regular species of monomer
units in which even second C-atoms of the chain possesses opposed steric configuration.
In this polymer the substituent groups (R) lies alternatively above and below the plane of the main
chain

Aditya College of Engineering & Technology (A), Surampalem

(iii) Atactic polymers: The polymeric chain lacks regularity in the distribution of steric configuration
of the monomer units. In these polymers there is a random arrangement of substituent groups (R) in
the polymer chain.

Polymerization:
The process of formation of large molecule by repeated combination of many small and simple
molecules or the chemical reaction that involves the fomation of polymer from the monomer
The polymerisation can be achieved by Four methods.
 Addition
 Condensation
 Co-polymerization
 Co-ordination
Addition or chain polymerization:
Addition polymerization involves the self addition of n- saturated molecule to form a large
molecule without elimination of any by product by rapid chain reaction
Condensation or step wise polymerization:
The condensation polymerization proceeds by a stepwise inter molecular condensation of
monomers into a polymer with the elimination of smaller molecules called by product like water
alcohol,ammonia etc

Mechanism of Polymerization:
Addition Polymerization or Chain Growth Polymerization
Polymers formed by chain wise addition reaction. An addition reaction is two or more molecules
combine to form large molecule with no elimination of small molecules. Molecules need a double
or triple bond. Total molecular weight of polymer chain segment is an exact integer multiple of
molecular weight of monomers.
Example: n CH2 = CH2 (-CH2−CH2-) n
Ethylene (Monomer) Polyethene (Polymer)
Chain-growth polymerization is a reaction in which the high-molecular-weight polymer is produced
early in the polymerization process and the polymer yield (the percentage conversion of the monomer
into the polymer) gradually increases with time. In this polymerization, unsaturated monomer
molecules add onto the active site on a growing polymer chain one at a time.
It is useful to distinguish four polymerization procedures fitting this general description.
A) Radical Polymerization: The initiator is a radical and the propagating site of reactivity
(*) is a carbon radical.
B) Cationic Polymerization: The initiator is an acid and the propagating site of reactivity
(*) is a carbocation
C) Anionic Polymerization: The initiator is a nucleophile and the propagating site of
reactivity (*) is a carbanion.
D) Coordination Catalytic Polymerization: The initiator is a transition metal complex and
the propagating site of reactivity (*) is a terminal catalytic complex.
Aditya College of Engineering & Technology (A), Surampalem
In chain-growth polymerization, a polymer is synthesized from monomers in four steps.
(i) Chain initiation step is the reaction to generate a chain carrier (intermediates such as
radicals and ions in the chain propagation) in chain polymerizations.
(ii) Chain propagation step is a step in which an active center on the developing polymer
molecules adds one monomer compound forming a new polymer molecule that is one
repeat unit longer with a new active center.
(iii) Chain transfer step is a key step in which the active center of polymer A receives an atom
from B compound and gets terminated. Then the B molecule forms an active center. In
this step the active point only shifts to another molecule and does not disappear. This step
may occur in coordination, ionic, and free radical polymerizations.
(iv) Chain termination means that the active center disappears in chain polymerization,
causing the termination of chain propagation.

Radical Chain-Growth Polymerization

Virtually all of the monomers described above are subject to radical polymerization. Since this can
be initiated by traces of oxygen or other minor impurities, pure samples of these compounds are often
"stabilized" by small amounts of radical inhibitors to avoid unwanted reaction. When radical
polymerization is desired, it must be started by using a radical initiator, such as a peroxide or certain
azo compounds.
In this polymer formation is an addition to an alkene. The mechanism is in most cases a free
radical addition. In free radical reactions the pi pair of electrons separates. One of these electrons
pairs with an electron from the attacking reagent to form a sigma bond with one of the alkene carbons,
and the other electron remains attached to the other alkene carbon. (Curved arrows with only one
"barb" on a point are used to follow the path of a single electron in the same way that "double-headed"
arrows follow the path of an electron pair.) Intermediates with an unpaired electron are called free
radicals, so this step can be described as adding a free radical to an alkene to lengthen the chain by
two carbons and generate a new free radical. In its turn this new free radical can add to another
molecule of monomer and continue the process.

Aditya College of Engineering & Technology (A), Surampalem

The most common termination processes are Radical Combination and Disproportionation. These
reactions are illustrated by the following equations. The growing polymer chains are colored blue
and red, and the hydrogen atom transferred in disproportionation is colored green. Note that in both
types of termination two reactive radical sites are removed by simultaneous conversion to stable
product(s). Since the concentration of radical species in a polymerization reaction is small relative to
other reactants (e.g. monomers, solvents and terminated chains), the rate at which these radical-
radical termination reactions occurs is very small, and most growing chains achieve moderate length
before termination.

A) Cationic Chain-Growth Polymerization

Cationic polymerizations are typically acid-catalyzed. Electrophilic addition of H + to a double bond
forms a carbocation which is propagated by repeated reactions with addition alkene monomers.

Aditya College of Engineering & Technology (A), Surampalem

Alkene monomers bearing cation stabilizing groups, such as alkyl, phenyl or vinyl can be
polymerized by cationic processes.

Polymerization of isobutylene (2-methylpropene) by traces of strong acids is an example of cationic

polymerization. The initiation reagent cationic polymerization is commonly the Lewis acid, boron
triFluoroboride (BF3), along with traces of water to form the acidic BF3OH-H+ catalyst. The poly
isobutylene product is a soft rubbery solid, which is used for inner tubes. This process is similar to
radical polymerization, as demonstrated by the following equations. Chain growth ceases when the
terminal carbocation combines with a nucleophile or loses a proton, giving a terminal alkene.

Anionic Chain-Growth Polymerization

Only monomers having anion stabilizing electron-withdrawing groups (EWG) substituents, such as
phenyl, cyano or carbonyl can undergo anionic polymerization.

Species that have been used to initiate anionic polymerization include alkali metals, alkali amides,
alkyl lithium’s and various electron sources. The fundamental reaction for anion polymerization is a
conjugate nucleophilic addition. Treatment of a cold THF solution of styrene with 0.001 equivalents
of n-butyl lithium causes an immediate polymerization. This is an example of anionic polymerization,
the course of which is described by the following equations. Chain growth may be terminated by
water or carbon dioxide, and chain transfer seldom occurs.

Aditya College of Engineering & Technology (A), Surampalem

Coordination polymerization:
Organometallic compound has a great role in many chemical reactions as well as polymerization
reaction also. When Organometallic compound act as initiator in Polymerization reaction is called
coordination polymerization reaction.
Ziegler and Natta first prepared polymer by coordination polymerization halide of Ti, V, Zr, Cr, W
and Mo. The coordination polymerization can be done by the combination of halide of different
transition metal like TiCl2, TiCl3, TiCl4 etc. and Organometallic compound such as trialkyl
(Trimethyl, Triethyl) aluminium.
The most common and useful catalyst is the combination of triethyl aluminium with titanium
trichloride. These catalysts are heterogeneous catalyst. The monomer catalyst complex involves
coordination between a carbon atom of a monomer and a metal atom of the catalyst. In this
polymerization the triethyl aluminium act as electron donor and metal halide acts as an electron
acceptor.
Mechanism of coordination polymerization:
1) Chain initiation: This is the first step of coordination polymerization reaction where complex
catalyst is added to the monomer unit resulting in the formation of metal-carbon bond in monomer
unit.
2) Chain propagation: This is the second rapid step of coordination polymerization reaction where
second third fourth ...... monomer units are added with generated metal-carbon bond in monomer
unit, consecutively resulting in the formation of large chain metal-carbon bond.
3) Chain termination: This is the third and final step of coordination polymerization reaction where
termination of large chain metal-carbon is terminated by the transfer of hydrogen atom from
monomer or from active hydrogen containing compound.

Aditya College of Engineering & Technology (A), Surampalem

Importance of coordination polymerization:
1) Normal free radical polymerization involves Atactic polymer whereas coordination
polymerization Isotactic polymer. That means stereo specific polymer can be prepared by this
coordination polymerization. Using this process (Zeigler-Natta catalyst) of polymerization isoprene
produces only stereo specific Cis-1, 4-polyisoprene
2) Coordination polymerization always involves mainly linear polymer hence highly crystalline in
nature.

Step Growth Polymerization or Condensation Polymerization:

Polymers formed by step wise condensation reaction. A condensation reaction is, two or more
monomer molecules combine to form large polymer molecule with elimination of small molecules
like water, ammonia etc.

Step Growth Polymerization, in this type of polymerization method, monomers with di or multi-
function groups are necessary at least to form a polymer. A Bifunctional monomer or equal molar
amounts of two different bifunctional monomers can form a linear high molecular weight polymer.
In a step-growth polymerization, the molecular weight of the polymer chain builds up slowly and
there is only one reaction mechanism for the formation of polymer. The distinct initiation,
propagation, and termination steps of chain-growth polymerization are meaningless in step-growth
polymerization. The polymerization reaction proceeds by individual reactions of the functional
groups on the monomers. Thus, two monomers react to form a dimer.
Monomer + Monomer …………. Dimer + H2O
The dimer may now react with another dimer to produce a tetramer, or the dimer may react with
more monomer to form a trimer.
Monomer + Dimer………………….Trimer + H 2O
Dimer + Dimer………………………..Tetramer + H 2O
This process continues, each reaction of the functional groups proceeding essentially at the same
reaction rate until over a relatively long period of time, a high molecular weight polymer is
obtained.
Mono functional condensation reaction: you can recall that making an ester requires a Carboxylic
Acid, an Alcohol and an Acid catalyst.

Aditya College of Engineering & Technology (A), Surampalem

 Bifunctional condensation polymerization: If we started with a diols (a molecule with two alcohol
groups HO-ROH instead of a normal alcohol ROH), and reacted it with a diCarboxylic acid
(HOOC-R-COOH) then the esterification could happen at either end of the molecule forming a
long molecule containing multiple ester linkages.

Methods of Polymerization:
Heterogeneous Polymerization:
In such a process more than one phase is involved. Two types: Viz. Emulsion and Suspension
Polymerization.
Emulsion Polymerization:
The monomer is dispersed in aqueous phase as fine droplets which is stabilized by addingsurfactant
[Fatty acids (Stearic acids), Sodium Lauryl sulfate].
The surfactants lead to the formation of micelles when their concentration exceeds Critical
Micelle Concentration.
Addition of water- s o l u b l e initiator [Potassium persulphate K2S2O8] at this stage initiates
the polymerization reaction in themicelles which ultimately increase the micelle size.
For the continuation of the reaction, monomers diffuse from its droplets to the micelle.

Aditya College of Engineering & Technology (A), Surampalem

The process continues till the size of polymer is big enough to come out the micelles, thus high
molecular weight polymers can be formed.
Suspension Polymerization:
The monomer is dispersed as large droplets in water and kept in suspension using stabilizers
such as Gelatin or water-soluble cellulose derivatives.
The initiators used remains soluble in monomer which initiates polymerization in each droplet.
The polymer is obtained as spherical beads.
This technique is cheap as it involves water instead of solvent.
The method is limited to water insoluble monomers such as vinyl chlorides, vinyl acetates, and
Styrene

PLASTICS:
Definition: Plastic is an organic polymer; it can be desired into any shape by applying heat
and pressure in the presence of a catalyst is called Plastic.
Properties of Plastics:
 They are light in weight.
 Easily molded into different shapes and sizes.
 Good insulation and low thermal conductivity.
 Good impact resistance and they do not rust.
 Chemically inert compounds.
 They are non-biodegradable and are not degraded by microbial action.
 Low processing cost.
Preparations, properties and applications of Plastics:

Poly Vinyl Chloride: (PVC)

Preparation: Vinyl chloride is prepared by treating acetylene with hydrogen chloride at 60 o –
80oC, and presence of a metal oxide catalyst.

Aditya College of Engineering & Technology (A), Surampalem

Number of monomer units of vinyl chlorides undergoes the addition polymerization in the
presence of benzoyl peroxide gives poly vinyl chlorides.

Properties:
 PVC is a colorless compound
 Chemically inert compounds and non - inflammable.
 PVC is strong and brittle.
 It has specific gravity 1.33
 Resistant to atmospheric conditions like
Oxygen, Carbon dioxide and moisture.
Applications:
 PVC is used for electrical insulations.
 Prepare injection molding articles like radio,
camera and telephone components, chemical
containers.
 PVC is used for making safety helmets refrigerator components.
 PVC is used to prepare tyres, cycle and motor mudguards.
Teflon:
Teflon is a synthetic fluoropolymer made up of tetrafluoroethylene monomer. The chemical name of
Teflon is poly (1, 1, 2, 2 tetrafluoroethylene). It is a thermoplastic polymer. Teflon chemical formula
is (C2F4)n. The Teflon formula shows repetitive or n numbers of C 2F4 units. It has an ability to
maintain high strength, toughness, and self-lubrication at low temperatures (around 5 K), and good
flexibility at temperatures above 194 K.
Teflon is produced by a free radical mechanism. The net reaction for the production of Teflon is
given below:
To aid this reaction, a sulphate catalyst is used with high-pressure heating. During the reaction of the
production of the Teflon or Polytetrafluoroethylene (PTTE), the polymer tetrafluoroethylene
decomposes into tetrafluoromethane and a carbon atom

Properties of Teflon
 It is a white solid compound at room temperature.
 Its density is about 2200 kg/m3 2.2 g/cm3
 Its melting point is 600 K.
 It is a chemical resistance compound; the only chemicals that can affect these compounds are
alkali metals.
 It shows good resistance towards heat and low temperature.
 It has a low water absorption capacity.
 It has an anti-adhesion ability due to which it is used as non-stick kitchen utensils.

Aditya College of Engineering & Technology (A), Surampalem

Applications of Teflon
 It is used in making waterproof fabric.
 It is used in making non-stick cookware.
 It is used in making an anti-friction device.
 It is used for coating medical appliances (surgical devices).
 Due to its high resistance to corrosion, it is used for coating the lining of laboratory
appliances.
Bakelite: Thermosetting resin
These are obtained by condensation of phenol with formaldehyde in the presence of either an acid
or a base catalyst. The preparation of Bakelite involves 3 steps
Step 1: formation of methylol derivatives
Step 2: Formation of Novolac
Step 3: Formation of Crosslinked Bakelitr
The reaction starts with the initial formation of ortho and para hydroxyl methyl phenol or its
derivatives, which further reacts with phenol to form compounds through methylene bridges (CH 2
groups) in ortho, para or both ortho and para positions. The initial product could be a linear product
called as Novolac. Which on heating with hexamine forms an infusible solid mass called Bakelite
(cross linked structure)

Aditya College of Engineering & Technology (A), Surampalem

 Properties:
 These are very hard, rigid and strong
 Water resistant polymer
 Good adhesive
 It is an excellent electrical insulator
 Good chemical resistant
 It is an ion exchange resin, exchanges alcohol groups with any other anion.
 Corrosion resistance.
 Resistance to atmospheric conditions
Applications:
 These polymers used in paints and varnishes.
 Used for making electrical insulator parts like switches, switch boards, heater handlers
 Used for making molded articles like telephone parts, cabinets for radio and television.
As an adhesive for grinding wheels making bearing used in propeller shafts, paper industry
and rolling mills

Nylon-6, 6 (Poly amide Polymer)

Nylon-6, 6 is prepared by condensation polymerization of Hexamethylene Diamine with Adipic acid
at high temperature and pressure.

Properties:
 Nylon 6, 6 pursues excellent abrasion resistance and a high melting point.
 Nylon 6, 6 is an amorphous solid so it has a large elastic property
 It is slightly soluble in boiling water.
 Nylon 6, 6 is very stable in nature and has high tensile strength
 It also provides a very good resistance to photo degradation.
 Nylon 6, 6 resistant towards heat
 Nylon 6, 6 has long molecular chains resulting in more hydrogen bonds, creating chemical
springs and making it very resilient (Flexible or Elastics),
 Its chemical properties don’t allow it to be affected by solvents such as water, alcohol etc.

Aditya College of Engineering & Technology (A), Surampalem

Applications:
 Nylon is a light material; it is used in parachutes.
 Nylon 6, 6 is waterproof in nature so it is also used to
make swimwear.
 Nylon 6, 6 having a high melting point make it more
resistant to heat and friction so it is suitable to be used
in airports, offices and other places which are more
liable to wear and tear.
 Nylon 6, 6 being waterproof in nature is used to make
machine parts. It is also used in the following like
airbags, carpets, and ropes. Hoses etc.

ELASTOMERS:
The organic polymer which can stretched to twice or more than that to its original size as soon as
the stretching force released it returns to its original strength is called Elastomers or Rubber.
Characteristics of Natural Rubber:
 It becomes soft at high temperatures and brittle at low temperatures
 Low tensile strength, High water absorption capacity.
 It is soluble in non-polar solvents like benzene and carbon tetra chlorides
 It has less durability
 When stretched to great extent it suffers permanent deformation.
 Elasticity is low. Depends upon extent of Sulphur added.
Preparations, properties and applications of Elastomers:
Buna – S – Rubber: (Styrene Rubber):
Buna-S- Rubber is produced by the copolymerization of butadiene with styrene using sodium as
a catalyst.

Butadiene is produced form acetaldehyde and ethyl alcohol.

Styrene is produced from benzene and ethylene in presence of acid catalyst (anhydrous
aluminum chloride).

Aditya College of Engineering & Technology (A), Surampalem

 Properties:
 Strong and tough polymer.
 Vulcanized by Sulphur monochloride or Sulphur.
 It is good electrical insulators.
 Resistant to chemicals
 Buna – S – rubbers possess excellent abrasion
resistance.
Applications:
 These used in the manufacture of tyres.
 Used in the footwear industry
 Used for making wires and cable insulations.
 Used for the production of floor files, tank
linings in chemical industries and as anadhesive.
Buna-N Rubber: (Nitrile rubber)
It is commonly used Elastomers. Buna-N is also known as, NBR or Perbunan. It is synthetic rubber
copolymer of Acrylonitrile (ACN) and butadiene.
Acrylonitrile monomer used to prepare Buna-N gives hardness, tensile strength and abrasion, fuel
and oil resistance. It usually contains 34% ACN. Butadiene monomer used to make Buna-N gives
elasticity and low temperature flexibility.

Properties:
 Buna-N is resistant to oil, fuel and other chemicals
 It is resistant to aliphatic hydrocarbons.
 It has tensile strength as well as excellent abrasion and compression set resistance.
 It is not resistant to solvents.
 Buna-N should not be stored near ozone generating electric motors, welding equipment or in
UV light.
 Buna-N performs well in petroleum oils and fuels, silicone oils and greases, ethylene glycol,
dilute acids and water below 212oF.

Aditya College of Engineering & Technology (A), Surampalem

Applications:
 Buna-N is used in the automotive.
 Used in aeronautical industry to make fuel and oil
handling hoses, seals and grommets
 It is used to make protective gloves in the nuclear
industry.
 It is ideal material for aeronautical application
 It is useful material for disposable lab, cleaning and
examination gloves.
 Buna-N, is used for hoses, rubber belts, sealing parts,
special purpose article in oil well, reciprocating oil
seal, rubber seal, gaskets, roll covers, shoe soles, varieties molded part for shoe heels and O-
rings.

Conducting Polymers:
Organic polymers that conduct electricity are known as conducting polymers.Examples:
Polyacetylene, Polypyrrole, Polyaniline, etc
Conducting polymers classified in the following way:

Intrinsic Conducting Polymers: ICPs have extensive conjugation in the backbone which is
responsible for conduction. These are further divided into two types;
With Conjugation 𝝅 - electrons in the backbone:
Overlapping of orbital’s having conjugated PI electrons over the entire backbone forms the valency
bands as well as conduction bands. The valence band is filled band and conduction band is empty.
When the energy gap is low, the electrons from the valence band are excited to the conduction band
and become mobile throughout the polymer show conductivity. Conduction occurs only after
Aditya College of Engineering & Technology (A), Surampalem
thermal or photolytic activation of electrons.
Examples: Polyacetylene, Polyaniline, Polypyrrole and Polybutadienylene polymers etc.

Polyacetylene,

Doped Conducting Polymers:

These polymers can be easily oxidized or reduced on account of their ionization energy and high
electron affinities. The conductivity of such polymers can be increased by creating either positive
(+ve) or negative (-ve) charges on the polymer backbone by oxidation or reduction. These are two
types’ viz., p-type and n-type.
i) p - Type doping: It is achieved by oxidation. Intrinsic polymer is treated with suitable oxidizing
agent such as a Lewis acid or with I2 vapor or I2 / CCl4 so as to generate positive charge. These
delocalized positive charges help in conduction by forming an acceptor band between valence
band and conduction bands.

(ii) n - Type doping: It is achieved by reduction. Intrinsic polymer is treated with suitable reducing
agent such as a Lewis base (naphthylamine, sodium naphthalide etc.) so as to generate negative
charge. These delocalized positive charges help in conduction by forming a donor band
between valence band and conduction bands.

Aditya College of Engineering & Technology (A), Surampalem

Extrinsic Conducting Polymers: ECPs. The polymers in which conductivity is attributed to the
presence of externally added ingredient to them are known as extrinsic conducting polymers. These
are further divided into two types;

Conductive element filled polymers:

In this case, polymer acts as a binder to hold the conducting elements such as carbon black, metal
oxides and metallic fibres together in the solid matrix. The minimum concentration of conducting
filler which should be added to the polymer so that it starts conducting is known as percolation
threshold.
These polymers possess good conductivity, light in weight, mechanically durable, can easily
molded and are low of cost.
Blended conducting Polymer:
These are obtained by blending a conventional polymer with a conducting polymer. Suchpolymers
possess better physical chemical, electrical and mechanical properties.
Applications of conducting polymers:
 These are used in rechargeable batteries.
 Also used for making ion exchangers
 Used for making analytical sensors for pH, oxygen, Sulphur dioxide, ammonia and
glucose.
 Conducting polymers used in making electronic displays and optical fibers.
 These are applicable in photovoltaic devices.
 They are used for electron beam lithography.

Aditya College of Engineering & Technology (A), Surampalem

Biodegradable polymers:
Biodegradable polymers are defined as the degradable polymers in which degradation is caused by
the action of naturally occurring microorganisms such as algae, fungi and bacteria. They are easily
compostable. During composting they yield CO 2, H2O, inorganic compounds and biomass at a rate
constant with other compostable material without leaving toxic residues. They decompose through
enzymatic hydrolysis and oxidation processes.

Natural polymers are biodegradable, but synthetic polymers and plastics are not prone to
biodegradation and cause pollution of the environment.
Biodegradable polymers may be naturally occurring or may be synthesized by chemical methods.
Naturally Occurring Biodegradable Polymers: These are Bio Polymers Ex; Polysaccharides,
proteins, nucleic acids and natural rubbers. Polysaccharides include starch and cellulose. Proteins
are amino carboxylic acids; Nucleic acids are Nucleotides (DNA, RNA).
Biosynthetic Polymers, they are produced by the fermentation process by microorganisms. Ex:
polyhydroxy alkanoates are the polyesters of biodegradable type. The rate of degradation and
formation of metabolites depends on the structural complexity of the material and environment
selected for degradation.
Synthetic Biodegradable Polymers: These polymers are derived from biological sources or
photochemical reactions. Examples: Polylactic acids, Polyvinyl Alcohol, Polyvinyl esters,
polyamide esters, and these polymers undergo degradation by microorganisms and also by chemical
and mechanical methods.
POLYLACTIC ACID:
Biodegradable aliphatic thermoplastic Polymers, It is derived from Corn, starch, sugar cane etc.
Lactic acid is produced by the bacterial fermentation of sugarcane or from the starch obtained from
corn.

Lactic acid undergoes the dimerization gives Lactide monomer. The Lactide monomer undergoes
polymerization in the presence of stannous octate catalyst to give Polylactic acid.
The Lactide may be LL or DL,

The racemic mixture of L and D leads to the synthesis of poly DL Lactide. The D-isomer of
Aditya College of Engineering & Technology (A), Surampalem
polylactide is crystalline and L-isomer is amorphous. The biodegradation of the D- isomer is also
slower than the L- isomer.
Properties:
 The glass transition temperature of PLA is 60oC- 65oC.
 PLA possess melting point 173oC- 178oC
 It is a chiral compound
 It possesses good biocompatibility,
 It contains high strength.
Applications:
 These are widely used for making medical implants like anchors, screws, pins, mesh etc.
 For making compostable packing material, disposable garments, diapers, food packing
3D printings.
 Used in the biomedical applications such as sutures, stents, and drug delivery devices.
Polyglycolide (or) Poly Glycolic Acid (PGA),
It is a biodegradable, thermoplastic polymer and the simplest linear, aliphatic polyester. It can be
prepared starting from glycolic acid by means of polycondensation or ring-opening polymerization.
PGA is a tough fiber-forming polymer.
Polyglycolide and its copolymers (poly (lactic-co-glycolic acid) with lactic acid,
Poly (glycolide-co-caprolactone) with ε-caprolactone
Poly (glycolide-co-trimethylene carbonate) with trimethylene carbonate) are widely used for
synthesis.

Properties:
 Polyglycolide has a glass transition temperature between 35 and 40 °C
 Melting point range of 225 to 230 °C
 It is also the simplest linear, aliphatic polyester.
 PGA is insolubility in water.
 Polyglycolide is soluble in highly fluorinated solvents like hexafluoro isopropanol (HFIP)
and hexafluoroacetone sesquihydrate,
 Fibers of PGA exhibit high strength and modulus (7 GPa) and are particularly stiff
Applications:
 Used for the absorbable sutures and are being evaluated in the biomedical field.
 Implantable medical devices have been produced with PGA, including rings, pins, rods, plates
and screws.
 It has also been explored for tissue engineering or controlled drug delivery.
 PGA as a filler material integrated into other degradable polymers.
 PGA resins are known for their excellent gas barrier properties, high strength, and excellent
biodegradability.

Aditya College of Engineering & Technology (A), Surampalem

 Biodegradation rate similar to cellulose and decompose under composting conditions into
CO2 and water within one month.
 It has the advantages of high tensile strength, smooth passage through tissue, easy handling,
excellent knotting ability, and secure knot tying.
 It is commonly used for subcutaneous sutures, abdominal and thoracic surgeries.

Aditya College of Engineering & Technology (A), Surampalem