Module 7 Polymers Hours SLO

1. Thermoplastic & Thermo setting resins – comparative 6 2,11, 15

properties
2. Properties and engineering applications of ABS, PVC,
Teflon and Bakelite
3. Compression, injection, extrusion, Transfer moulding
methods of plastics
4. Conducting polymers: Intrinsic, extrinsic and doped
polymers - Polyacetylene-mechanism of conduction-
Applications of conducting polymers in LEDs, Mobile
phones
 What are Monomers and Polymers?
MONOMERS are basic units from which MACROMOLECULES are built upon!
Polymerization : The process by which the monomer molecules are
linked to form a big polymer molecule is called polymerization.

Ethylene Polyethylene or Polythene

Degree of Polymerization is termed as the number of repeating units
(n) in a polymer chain. The molecular weight increases with increase
in the number of monomer units; denoted as ‘n’ in -[CH2]n-
Most of the polymers possess 5,000 to 200,000 molecular mass range.
1. Polymer Classification based on their origin
polymers are classified into natural and synthetic polymers.
Natural polymers include starch, cellulose, nucleic acids, natural rubber and proteins
Synthetic polymers include PE, PVC, PS, Nylon, etc.
2. Polymer Classification based on Structure
• Homopolymer: Polymers consisting of identical monomers as repeating units.
A + A  -A-A- Eg. PE from -[CH2-CH2]n- and PVC from -[CH2-CHCl]n-
• Heteropolymer or Copolymer: Polymers consisting of two different monomers or different
chemical structure.
A + B  -A-B- There are 5 types of Copolymers.
(a) Alternating copolymers: two monomers incorporated sequentially/alternately
in the main chain ABABABABABABABAB
poly(styrene-alt-acrylonitrile)

(b) Graft copolymers: different

monomers in main-chain and side-
chain.
poly(isobutylene-graft-butadiene)
(a) (c) Graft terpolymer: a combination of
(a) and (b).
(b) (d) Random copolymers: Two different
monomers randomly distributed in the
back-bone chain.
(c) AABAAABBABAABBA
poly(acrylonitrile-co-butadiene)
(e) Block copolymers: linear/alternate
arrangement of blocks of high molecular
weight species
(d) AAAABBBBAAAA
poly(styrene-b-butadiene-b-styrene)
3. Polymer Classification based on the Chain Architecture
Linear: A linear polymer chain is one without branches. They exhibit high melting point and
density.
Branched: Chains with an appreciable number of side-chains are classified as branched. If these
side chains differ in composition from that of the main chain, then they are classified as Branched
chain copolymer. If both branched and main chain contain same monomer, then they are
classified as Branched chain homopolymer. They exhibit low melting point and density compared
to linear polymers due to their poor packing of polymer chains (due to the side chain).

Cross-linked: A continuous 3-D network of

polymer chains gives a cross-linked
structure. They are hard, rigid and brittle.
They do not melt but burn on strong
heating. Chain architecture results in high
viscosity and temperature stability.
Give examples for each type!
4. Polymer Classification based on the Atoms present in the chain
Depending on the different types of atoms forming the main chain of the polymer, they are
classified as homo-chain polymer and hetero-chain polymer.
A polymer in which main chain consist of only one kind of atom is called homo chain polymer.
Homochain polymers: PE, PP, PS, PVC, etc. (-C-C-C-).
Hetero chain polymers consist of more than one kind of atoms in their main chain.
Heterochain polymers: polyamide (-C-N-), polyester ((-C-O-), polyurethane (-N-C-O-), etc.
 5. Polymer Classification based on the Tacticity

Polyethylene is used as a
reference material

Syndiotactic: Gutta percha

Isotactic: PE Latex is a stable dispersion (emulsion) of polymer
microparticles

Atactic: PP

The orientation of the monomeric units in a polymer molecule can take place in a orderly or
random fashion with respect to the main chain. The difference in configuration (Tacticity) affect
their physical properties.
Isotactic: Functional side groups are all on the same direction.
Syndiotactic: Functional side groups are all in alternating direction.
Atactic: Functional side groups are arranged randomly around the main chain.
6. Polymer Classification based on functionality

The number of bonding sites in a monomer is referred to as its functionality. In

the case of vinyl bond, the double bond is considered as a site for two free
valences. Eg. Ethylene is bi-functional.
Depending upon the functionality of the monomer units, different types of
structures can be formed.

Bifunctional: Linear or straight-chained polymer is formed. Monomer units are

linked together by covalent bonds (chemical links) to form a linear chain.
Eg. HDPE [High-density polyethylene (Swimming pool installation, Food storage
containers, fuel tanks for vehicles etc.)], nylon, etc. HDPE has ID code 2

Trifunctional: A trifunctional monomer mixed with small amounts of

bifunctional monomer gives a branched structure or semi-cross linked structure.
Eg. LDPE [Low-density polyethylene (Corrosion-resistant work surfaces, Plastic
wraps)] LDPE has ID code 4

Polyfunctional: results in the formation a highly cross linked 3-D network.

Eg. Bakelite, urea-formaldehyde.
7. Polymer Classification based on the kind of atoms constituting
backbone of the polymer

Organic back bone: backbone chain is made of carbon atoms

Inorganic back bone: Inorganic atoms like Si in their backbone chain.

Eg. siloxanes or silicone resins.
 8. Polymer Classification based on the method of synthesis
(i) Addition/Chain Polymerization:
Monomers of only one type (homo-monomers) having multiple double bonds undergo
addition polymerization by the application of heat, light, pressure or catalyst to give
polymers. No other by-products are formed. Eg. PE, PP, PS, PVC, etc.

• Monomers contain C=C bonds; Double bond opens to (link) bond to next monomer molecule;
Chain forms when same basic unit is repeated over and over.
(ii) Copolymerization:
Similar to addition polymerization; reaction occurs between two or more monomer types
without the loss of any by-products. High molecular weight polymers are obtained by this
method. Eg. Butadiene-co-Styrene rubber, SBR.
(iii) Condensation or stepwise polymerization
• The polymerization proceeds by stepwise reaction between the reactive functional groups,
and small molecules (H2O, HCl, NH3, etc) are eliminated. Eg. Nylon, Bakelite, Polyester, etc.
nH2N–R-NH2 + nHOOC-R’-COOH  -(-HN-R-NH-OC-R’-CO-)n + H2O
Diamine Dicarboxylic acid Nylon
1. What are the main differences between Addition and Copolymerization?
2. What are the main differences between Addition and Condensation Polymerization?
 9. Polymer Classification based on its applications
1. Elastomers: static uses: gaskets, hoses; dynamic uses: tires, sports equipment
2. Adhesives: structural: epoxy resins; non-structural: pressure-sensitive tapes, hot-melt
adhesives
3. Coatings: lacquers, paints
4. Plastics: semi-crystalline: automobile exterior; amorphous: packaging films, plexi-glass
5. Fibers: natural/modified: cotton, rayon; synthetic: carpeting, apparel

10. Polymer Classification based on Molecular Forces

(a) Thermoplastic polymers: Polymers that are linear, long chain which can be softened on
heating and hardened on cooling reversibly. They can be recycled and reused many times by
heating and cooling process. Eg. PS, PE, PVC, PTFE, recyclable food containers.
(b) Thermoset polymers: Polymers whose individual chains have been chemically cross linked
by covalent bonds and form a 3-D cross linked structure. Therefore, they resist heat softening
and solvent attack. Thermoset polymers are hardened during the molding process and once
they are cured, they cannot be softened and they cannot be recycled and reused. Eg. Phenol-
formaldehyde resins, urea-formaldehyde paints.
(c) Elastomers: Can be stretched at least thrice its length but returns to its original shape and
dimensions as soon as the stretching force is released. In normal state, they exist in the form
of a coil and hence they can be stretched like a spring. Thus elasticity is caused by
lengthening and shortening of their polymeric chain springs.
(d) Fibers: Due to the strong intermolecular forces of attraction (hydrogen bonding) between
neighboring chains, these polymers exhibit high tensile strength and crystallinity. Eg. Nylon.
 Thermoplastics

• No cross links between chains. Thermoset

• Weak attractive forces between chains broken by • Extensive cross-linking
warming. formed by covalent bonds.
• Change shape - can be remoulded. • Bonds prevent chains
• Weak forces reform in new shape when cold. moving relative to each
other.
Distinguish between Thermoplastic and Thermosetting Polymers
Thermoplastic polymers Thermosetting polymers
Consists of long-chain linear polymers Have 3-Dimensional network structures
with negligible cross-links. joined by strong covalent bonds.

Soften on heating readily because Do not soften on heating; On prolonged

secondary forces between the individual heating, they are charred.
chain can break easily by heat or pressure.
By re-heating to a suitable temperature, Retain their shape and structure even on
they can be softened, reshaped and thus heating. Hence, cannot be reshaped.
reused.

Usually soft, weak and less brittle. Usually, hard, strong and brittle.

Can be reclaimed from wastes. Cannot be reclaimed from wastes.

Usually soluble in some organic solvents. Due to strong bonds and cross-linking,
they are insoluble in almost all organic
solvents.
Molding of Plastics into Articles
1. Compression Molding
 This method is applied to both
thermoplastic and thermosetting
resins.
 Pre determined quantity of Raw
materials (Resin + Filler + other
additives) are placed between the two
half- pieces of the mold which are
capable of being moved relative to
each other.
 The mould is closed carefully. Mold is
heated to 100°C to 200°C and high
pressure is applied (100–500
Kg/Cm2).
 Thermosetting plastics are cured by
applying heat and pressure.
 Thermoplastics are cured by cooling.
 Curing of article takes place in the
mold itself.
 2. Injection Molding

 This method is applicable mainly to thermoplastic resins.

 The molding plastic powder is fed into a heated cylinder, gets softened by the applied
heat, and then injected into a tightly-locked mold under high pressure by means of a
screw arrangement or by a piston plunger.
 The mold is kept in cold condition to allow the hot plastic to cure and become rigid.
 Once cured completely, half of the mold is opened to allow the molded object to be
ejected without any deformation.
Advantages: High speed production, 2. Low mold cost (fewer cavities are needed), 3. Low
loss of materials, and 4. Low finishing cost.
Disadvantage: Large number of cavities cannot be filled simultaneously, there is a limitation
in the design of articles to be molded.
Applications: Objects can be made by this method are buckets, dustbins, etc.
 3. Extrusion Molding

 Used mainly for continuous molding of thermoplastic materials into articles of

uniform cross-section like tubes, rods, insulated electric cables, etc.
 The molding powder is softened by heating in a heated chamber and then pushed by
means of a screw extruder into a die.
 The material coming out of the die is cooled by atmospheric exposure or by
spraying water.
 A long conveyor carries away the cooled product continuously.
 Uses: Thermoplastics only: sheets, tubes, rods etc.
4. Transfer Molding

Mainly used for the injection

molding of thermosetting
resins.
Transfer molding is a process in
which the molding material is
preheated and loaded into a
chamber known as the pot.
A plunger is used to force the
material from the pot into the
mold cavities.
The mold walls are heated to a
temperature above the melting
point of the mold material; this
allows a faster flow of material
through the cavities.
The mold remains closed as the
material is inserted and is
opened to release.
 Important thermoplastic and thermosetting resins
Types of Thermoplastic resins: Types of Thermosetting resins:
(a) Vinyl resins (a) Phenolic resins or phenoplasts
(i) PVC (i) Novolac
(ii) TEFLON or FLUON (ii) Bakelite
(iii) ABS

Polyvinyl Chloride (PVC)

Acetylene is treated with HCl at 1 to 1.5 atm at 60 to 80 oC in the presence of metal chloride as
catalyst.

Vinyl chloride treated with benzoyl peroxide or hydroxyl peroxide under high pressure and
temperature undergoes polymerization to produce PVC.

Properties: Colorless, odorless, non-inflammable.

Resistant to light, atmospheric oxygen, inorganic acids and alkalis but soluble in hot chlorinated
hydrocarbons such as ethyl chloride.
High softening point (148 oC), greater stiffness, rigidity and brittle compared to PE.
Uses: for making sheets, tank linings, safety helmets, motor cycle mud guards, pipes, etc.
What is plasticized PVC? Obtained by adding plasticizers like dibutyl phthalate, dioctyl
phthalate, etc. Used for making toys, radio-components, conveyer belts, covering of electric
cables, tool – handles, etc.
(ii) TEFLON or FLUON

Teflon is obtained by polymerization of tetrafluoro ethylene under pressure in the presence of

BPO as catalyst.
(iii) Acrylonitrile butadiene styrene (ABS)
ABS is a terpolymer, and polymerized from three different monomers
(acrylonitrile, butadiene and styrene).

It is an amorphous and thermoplastic polymer

Properties:
• Cost effective
• Good Impact Strength
• Good Chemical Resistance
• High Gloss Surface Finish
• Good Flexural Properties
• ABS can be recycled
Applications
• musical instruments
• automotive bumper bars
• buffer edging for furniture and joinery panels
• luggage and protective carrying cases
• small kitchen appliances
• Keyboard keycaps
• golf club heads (because of its good shock
absorbance) 18
Thermosetting Plastics: (a) Phenolic resins or Phenoplasts
(Novolac & Bakelite)
Phenolic resins are condensation polymerization products of phenol derivatives and aldehydes.
At first, Phenol reacts with
Formaldehyde in presence of acidic
/ alkaline catalyst to form
Monomethylol phenol.

Monomethylol phenol further

reacts with Phenol to form a
linear polymer “Novolac”. Water
is removed as the by-product.

Novolac
Further addition of HCHO at
high temperature and pressure
converts Novolac (soft and
soluble) into cross-linked
“Bakelite” (hard and
insoluble).

Bakelite
 Conducting Polymers
Introduction
Polymers are typically insulators due to their very high resistivity. Insulators have
tightly bound electrons so that nearly no electron flow occurs, and they offer high
resistance to charge flow.
For conductance, free electrons are needed. Conductivity in polymers can be
induced by delocalizing their orbitals with conjugated p-electron backbones.

Alan J. Heeger, Alan

G. MacDiarmid and
Hideki Shirakawa
discovered that
Polyacetylene can be
made conductive
almost like a metal
(Nobel Prize for
Chemistry in 2000).
What are the two conditions for a insulating polymer to
become a conducting polymer?
1st Condition: The polymer should consist of alternating
single and double bonds, called conjugated double bonds.

2nd Condition: The polymer structure has to be disturbed by

removing electrons (oxidation), or inserting them (reduction).
This process is known as Doping.

Conducting polymers are of three major types:

1. Intrinsically Conducting Polymer (ICP)
2. Doped Conducting Polymer (DCP) and
3. Extrinsically Conducting Polymer (ECP).
2. Doped Conducting Polymer (DCP): is obtained by exposing a polymer to a charge
transfer agent in gas or solution phase. This technique is of two types:

Conductivity Mechanism in Polyacetylene:

Polyacetylene upon doping with halogens exhibit conductivity upto 105 S/cm.
When doped with Iodine, polyacetylene undergoes oxidation causing electrons to be removed
from the polymer, leaving "holes" in the form of positive charges that can move along the
polymer chain.
 Polyacetylene

The mechanism followed by polyacetylene for the transfer of charge from one chain to
another is called intersoliton hopping.
What is a soliton? The soliton is a charged or a neutral defect in the polyacetylene chain
that propagates down the chain, thereby reducing the barrier for interconversion.

In p-type doping, The dopant (Iodine, I2) attracts an e- from the polyacetylene chain to form
(I3-) leaving a +ve soliton in the polymer chain that can move along its length.
The lonely e- of the double bond, from which an electron was removed, can move easily.
As a consequence, the double bond successively moves along the molecule.
The polymer is stabilized by having the charge spread over the polymer chain.
P-type doping

Conductive Polymer Fibers from Thermoplastic trans-1,4-Polyisoprene

Langmuir, 2016, 32 (19), pp 4904–4908

In n-type doping (This can be done by dipping the film in THF solution of an alkali metal)
soliton is a resonance-stabilized polyenyl anion of approximately 29-31 CH units in length,
with highest amplitude at the centre of the defect.
The solitons (anions) transfer electrons to a neutral soliton (radical) in a neighboring chain
through an isoenergetic process.
The charged solitons are responsible for making polyacetylene a conductor.

Applications of Conducting Polymers

As light weight rechargeable
batteries.
In electrochemical actuators, the
anode and cathode strip changes its
size at different rates during
charging and discharging.
As smart structures like smart skis
which do not vibrate during skiing.
Biocompatible conducting polymers
may be used to transport small
electrical signals through the body.
i.e., act as artificial nerves.
By coating aircraft with a conducting
polymer the electricity can be
directed away from the vulnerable
internals of the aircraft.
Constituents in solar cells and
semiconductor devices.
 (ii) Blended conducting polymer: obtained by blending a conventional polymer with a
conducting polymer by physical or chemical methods.
POLYANILINE (PANi):
When Polyaniline (PANi) is doped with charge transfer or charge carrier
agents, it exhibits electrical conductivity as high as 1.5x107 ohm-1m-1.
But its practical applications are limited due to the poor mechanical
properties.
Hence, PANi is blended with a conventional polymer, Polycaprolactone
(PCL) using a bi-functional cross linker, p-hydroxybenzenesulphonic acid
(PHBSA) to improve its mechanical properties.
 Ammonium persulfate
1. Polyaniline
synthesis
from aniline

2. PHBSA

3. PCL
 Structure of
doped PANi -
Polycaprolactum (PCL)
blend system

What is the role of PHBSA in conducting polymers? A bifunctional linkage such as

PHBSA increases the force of attraction between two polymeric components (PANi and
PCL) and acts as a charge transfer agent to increase the system’s conductivity.
Hydrogen bond formation between OH-group in PHBSA and the C=O group in PCL:
PHBSA anion has one hydroxyl functional group. This functional group can be used to
establish hydrogen bonding (physical forces of attraction) between doped PANi and
carbonyl functional groups of PCL.
Structure of doped PANi:
Polyaniline can be found in one of three idealized oxidation states:
Leucoemeraldine (LB): white & colorless (fully reduced or only Benzenoid amine
structures)
Emeraldine (EB): green for emeraldine salt; blue for emeraldine base (neutral or partially
reduced/oxidized)
Pernigraniline (PB): blue/violet (fully oxidized or only Quinonoid imine structure).

Benzenoid amine Quinonoid imine

Structure of undoped polyaniline (PANi): n + m = 1, x = degree of polym. By varying the “n and
m” concentration (where n = 1, 0.5 or 0), three different oxidation states are obtained.
Why EB form is preferred over LB and PB forms?
The emeraldine based (EB) form of PANi is the most preferred as it is fully conductive and stable
compared to Leucoemeraldine base (LB) which is easily oxidized when exposed to air and
Pernigraniline base (PB) which is easily degraded.

Bipolaron structure of Polaron structure of

doped EB-PANi doped EB-PANi
Bipolaron and Polaron structure of EB type PANi:
Formation of bipolaron structure: Doping PANi with acid such as PHBSA can
increase conductivity because doping forms a polaron/bipolaron structure that will
increase PANi’s charge due to increased delocalization.
The hydrogen ions from PHBSA attach to the quinonoid imine nitrogen atoms to form an
unstable structure because of its high energy. Geometrical relaxation quickly occurs
resulting in the breakage of C=N bond of the quinonoid imine structure to form the more
stable benzenoid ring (having lower energy) by aromatization, thereby creating the
bipolaron structure of doped polyaniline.

Formation of polaron structure: Although the new benzenoid ring is more stable than
before, it still has high energy because of the repulsive force from the adjacent positive
charges. To stabilize the structure, the positive charge of one of the hydrogen ions will
attract electrons from the neighboring benzene ring, neutralizing the charge. This will
create new positively charged nitrogen with a neutral nitrogen atom in between the
positive ones. The increased distance between the two positive charges will result in the
polaron structure which has a lower energy level than the bipolaron structure.

Since the ionic interactions between PANi and PHBSA anions are weak, the PHBSA
anions are able to migrate to the newly formed positively charged nitrogen atom as the
doped polyaniline complex stabilizes itself by transforming into the polaron structure.
The migration of PHBSA is easier in the solution form.
Electrically Conducting Polymer (ECP): How does doping process improve the
electrical conductivity in polymers?
Though the undoped PANi possesses relatively large number of delocalized π-
electrons, a large energy gap (band gap) exists between the valence band and the
conducting band, and hence PANi is considered to be a semi-conductor with
conductivity of about 10-8 S/cm.
But once it is doped (altering the number of π-electrons) by adding charge transfer
agents like p-hydroxybenzenesulphonic acid (PHBSA) in the ratio of 1:2 (PANi:
PHBSA) in the gas or solution phase, new donor or acceptor states were created
within the existing band gap, and thermodynamically accessible by the π-electrons,
resulting in significant increases in conductivity by a factor of 10 or more.
Doping forms a polaron/bipolaron structure in PANi in which the polaron structure is
more stable and conducting than the bipolaron structure.
Mechanism of Conductivity in PANi:
After doping with the charge transfer agent such as PHBSA, the polyaniline (PANi)
is able to conduct electricity due to the presence of conjugated π-bonding system
and alternating carbon-carbon bond lengths (C-C and C=C) in the backbone of the
polymer chain.
The conjugated double bonds permit easy electron mobility throughout the molecule
because the electrons are delocalized (Delocalization is the condition in which the
π-bonding electrons are spread over a number of atoms rather than localized
between two atoms). This condition allows electrons to move more easily thereby
making the polymer electrically conductive.
Introduction to Biodegradable Polymers:
Conventional synthetic polymers such as PE, PP, etc. are non-biodegradable, and their
recycled products exhibit reduced mechanical and thermal properties. “Biodegradable
polymers” relate to the polymeric materials that disintegrate under environmental
conditions in a reasonable period of time.
What are the four types of polymer degradation processes?
(a). Biodegradation: It is promoted by aerobic or anaerobic enzymes and provides for the
complete removal of the polymer from the environment.
(b). Photo degradation: It is promoted by irradiation e.g. sunlight and it rarely leads to complete
removal though small fragments may be produced for subsequent degradation.
(c). Environmental erosion: This is promoted by the elements of weather such as wind, rain and
temperature. This method also cannot remove the polymer completely.
(d). Chemical degradation: This is promoted by chemical reactions through additives, e.g. metals
and functional groups, which produces smaller fragments of the polymer.
Why biodegradation is the best method for recycling polymers?
Compared to (b) photo degradation, (c) environmental erosion and (d) chemical degradation,
the (a) biodegradation method completely removes the polymer from the environment without
leaving any residue. The biodegradation process is promoted by aerobic or anaerobic enzymes.
Biodegradation process:
The biodegradation of polymer proceeds due to:
(i) The presence of hydrolysable and oxidisable linkages in the polymer main chain,
(ii) the presence of suitable substituent,
(iii) correct stereo configuration,
(iv) balance of hydrophobicity and hydrophilicity and
(v) conformational flexibility contribute to the biodegradability of the polymer.