Module 4

Classification based on polymerization

 Addition Polymers

Addition polymers are formed by linking together simple unsaturated molecules.

Self-addition of monomer

Example: polymerization of ethylene to polyethylene

 Addition Polymerization
Also called chain growth polymerization

Driving force : conversion of weak carbon-carbon π-bonds into strong carbon-carbon σ-bonds

There are two types of addition polymers .

 1,2- addition
 1,4- addition.
Addition polymerization is brought about by adding a small amount of substance
called initiators.
They form free radicals, cations or anions, which are added to monomer units and
chain growth takes place.
 1,2-addition

In 1,2 addition each monomer consists of a π-bond, during polymerisation it is

converted to a σ-bonds, joining positions of each monomer unit.

Example: polymerization of ethylene to polyethylene

 1,4-addition In 1-4 addition, each monomer unit consists of two
π-bonds, during polymerisation one new π-bond and
σ-bond is formed

Example:
Polymerisation of butadiene
to polybutadiene
 Condensation Polymerization
Also called step growth polymerization

Condensation polymerization taken place by linking together monomer

molecule, and is accompanied by elimination of simple molecules like water,
ammonia, HCl etc.

• In condensation polymerisation, monomer units used are generally

different.
• The condensation polymerization is called step growth polymerization as
the process of chain growth taking place from all parts in a step by step
manner.
Eg: condensation of terephthalic acid with ethylene glycol gives
polyethylene terephthalate(PET)

PET (polyethylene terephthalate

• Co-polymerization is the polymerization of two or more
different monomeric species together.

Example : KEVLAR
• Aromatic polyamide

• It is a fiber that woven together

has the five times stronger than steel.
Preparation
• Condensation polymer with HCl as by-product.

Additional strength is derived from aromatic

stacking interactions between adjacent strands.
Properties of Kevlar
• The polymer owes its high strength to the many inter-chain bonds.
• These inter-molecular hydrogen bonds form between the carbonyl groups and NH
centers.
• Additional strength is derived from aromatic stacking interactions between adjacent
strands.
• These interactions have a greater influence on Kevlar than the van der Waals
interactions and chain length that typically influence the properties of other synthetic
polymers and fibers.
• Kevlar's structure consists of relatively rigid molecules which tend to form mostly planar
sheet-like structures.
• Kevlar maintains its strength and resilience down to cryogenic temperatures (-1960 C): in
fact it is slightly stronger at low temperatures.
• At higher temperatures the tensile strength is immediately reduced by about 10-20
percentage, and after some hours the strength progressively reduces further.
• For example at 1600C about 10 percentage reduction in strength occurs after 500 hours.
At 2600C ,50 percentage strength reduction after 70 hours.
19
Applications
1. Conjugated π-electron conducting Polymers:
• The presence of conjugated double bonds along the backbone of the polymer.

• The orbitals of conjugated π-electrons overlap over the entire backbone of the
polymer, resulting in the formation of valence bands and conduction bands, which
extends over the entire polymer molecule.
Electrical conduction occur when electron from valence band are
excited to conduction band either thermally or photolytically

Eg: Polyacetylene and Polyaniline

In comparison to conventional polymers the conducting
polymers with conjugated pi electrons in their backbone can be
easily oxidized or reduced as they have low ionization
potentials and high electron affinities. i.e., their conductivities
can be increased by creating positive or negative charge on
polymer backbone by oxidation or reduction. This process is
referred to as doping and are of two types
a) P-doping:
Some electrons from pi-bond of the conjugated double bonds are
removed and forming holes (+ve charge) are moving along the
molecule. The oxidation process is generally brought about by
Lewis acids such as FeCl3

b) n-doping:
Some electrons are introduced into the polymer having conjugated
double bonds forming –ve charge by reduction with Lewis base like
lithium, sodium naphthalide etc
These polymers are:
• Low in cost
• Light in weight
• Easily processable in different forms, shapes and sizes.
• Used in making computer key boards.
• These polymers posses better physical, chemical and mechanical properties.
Preparation :
 Methods of synthesis:
1. Chemical Method (Oxidative Polymerization): To a solution of aniline

dissolved in dilute HCl, aqueous solution of ammonium per sulphate is added

and agitated. The formed precipitate is filtered, washed with ammonium

hydroxide solution and dried.

2. Electro-chemical method: It is done by dipping platinum foil electrodes on

acidified aqueous solution of aniline and a potential of 0.7 V is applied. Thin

film of polyaniline formed on the surface of the electrode.

 Properties of PANI
 Among various conducting polymers, polyaniline (PANI) is a unique and promising candidate
for potential applications because of its stability in air and solubility in some organic solvents.

 It also exhibits dramatic changes in its structure and physical properties on protonation.

The colour change associated with polyaniline in different oxidation states can be used in
sensors and electrochromic devices.

 Polyaniline is more noble than copper and slightly less noble than silver which is the basis
for its broad use in printed circuit board manufacturing and in corrosion protection

.Doped poly aniline is a good conductor comparable to copper, whereas the original form is a
semiconductor.
 BIODEGRADABLE POLYMERS

• Polymers which are found in nature or the synthetic polymers which are
biodegradable or biocompatible are grouped in this class of polymers.

• Biodegradable polymers are materials that can break down into natural
substances like water, carbon dioxide,
dioxide and biomass with the help of
microorganisms.

• These polymers are environmentally friendly and play a crucial role in

reducing plastic waste and pollution.
 Mechanism of Biodegradable action

• Biodegradable plastics suffer degradation from the action of naturally occurring microorganisms
such as bacteria, fungi and algae.
• The enzymatic degradation of plastics by hydrolysis occurs by a two-step process.

• The 1) adherence of microorganisms on the surface of plastic followed by 2) the

occupation of the exposed surface.

In the first step, the enzyme binds to the polymer substrate and then catalyses a hydrolytic cleavage of

the polymer. Polymers get degraded into low molecular weight oligomers, dimers and monomers and

lastly to CO2 and H2O. The degradation potential of various microorganisms towards a polymer is

different.
 Mechanism of Biodegradable action

The microbial degradation occurs in two ways: aerobic biodegradation (in the presence of O2) and anaerobic
degradation (in the absence of O2). The former results in the formation of CO2, water, and biomass, while
the latter forms methane, biomass, water, and CO2.
Biodegradable polymers and their applications
Preparation of PLA (Polylactic Acid)

PLA is prepared using agricultural resources like corn, sugarcane, or cassava. The steps involved are:

[Link] of Starch:
1. Corn or similar crops are used to extract starch, which is hydrolyzed into glucose (simple sugar).

[Link] to Produce Lactic Acid:

1. Glucose is fermented by microorganisms (e.g., Lactobacillus bacteria) to produce lactic acid.

[Link] of Lactic Acid:

There are two primary methods:
1. Direct Condensation Polymerization: Lactic acid is heated under controlled conditions to
remove water, forming PLA.
2. Ring-Opening Polymerization: Lactic acid is converted to lactide (a cyclic dimer), followed by
polymerization using catalysts like tin compounds to produce high-molecular-weight PLA.

4. Decomposition:
Lactic acid is metabolized by microorganisms into carbon dioxide (aerobic conditions), methane
(anaerobic conditions), and water.
Properties of PLA

[Link] Properties:
1. Thermoplastic material
2. Glass transition temperature of 60–65°C
3. Melting point around 150–160°C.
4. Transparent and glossy appearance.

[Link] Properties:
1. High tensile strength and stiffness but lower toughness compared to conventional plastics like
polyethylene.

[Link]:
1. Breaks down into non-toxic byproducts (CO₂, H₂O, and organic matter) under industrial
composting conditions.

[Link]:
1. Safe for use in biomedical and food packaging applications.
Applications of PLA
 Applications of PLA
1. Packaging Industry: Used for making food containers, trays, bottles, and
biodegradable films.

2. Biomedical Field: Sutures, tissue scaffolds, drug delivery systems, and

biodegradable implants.

3. 3D Printing: A popular filament material for 3D printers due to its ease of use
and low shrinkage during printing.

4. Agriculture: Biodegradable mulch films and planting pots.

 Applications of PLA
4. Textiles: Production of PLA-based fibers for sustainable clothing and home
furnishings.

5. Automotive Industry: Used in interior components for cars to reduce environmental

impact.

6. Electronics: Biodegradable casings for electronic devices.

7. Compostable Products: Disposable cutlery, plates, and other eco-friendly products.

Shape--memory polymers (SMPs)
Shape

• Shape-memory polymers are polymeric smart materials that have the ability to
return from a deformed state (temporary shape) to their original (permanent)
shape when induced by an external stimulus (trigger). Thermal energy is probably
the most common stimulus.
• Example: PTFE (Polytetrafluoroethylene)
Thermal-responsive shape memory polymer (I) PTFE (II) PLA (III) Ethylene –vinyl acetate
Thermo-responsive shape memory effect
Shape Memory Polymers: Classification

Based on the type of Stimuli induced, SMPs are primarily classified into:

• Temperature (Thermo-responsive)

• Chemicals (Chemo- responsive)

• Light (Photo-responsive)

• Mechanical force (Mechano-responsive)

Design and Mechanism of SMPs

The Shape Memory Cycle consists of 3 steps

Programming Storage Recovery

Step 1: ‘Programming’: the polymer sample is deformed and fixed into a
temporary shape. This step occurs by two consecutive processes.

The SMP is heated above its melting temperature (Tm), the

crystalline region is transformed into the amorphous state and becomes soft,
flexible and extendable (Fig. 1a).
Then, a load is applied and the specimen of SMP extends, while it is
under heat, into a temporary shape (path 1).

Step 2: ‘Storage’: The specimen is then cooled when it is deformed to a

temperature under its Tm (path 2) and the amorphous region then changes
back to the crystalline state.

Step 3: ‘Recovery’: If the specimen is then heated again to a temperature

above its Tm with no load on, the specimen will then recover its initial
permanent shape (path 3). The speed at which this polymer returns to its
original structure is limited by the friction generated within the molecular
structure.
1. Heat shrinkable tubes

2. Self repairing structural components

3. Sports wear, building industry, automobiles

Self tightening sutures and vascular stents

They have low density and can

be used in aircrafts.
 Tetrafluoroethylene PTFE

Structure of PTFE
The presence of stable C-F bonds leads to
PTFE with outstanding,
•Heat resistance
•Chemical resistance
•Electrical insulation characteristics
•Low coefficient of friction

PTFE is a linear polymer and free from branching.

 Why PTFE in twisted ZIG-ZAG shape?
The fluorine atoms is larger than those of hydrogen,
• As a consequence the molecule takes up a twisted

zigzag shape, with the fluorine atoms packing tightly

in a spiral around the carbon-carbon skeleton.

• This compact interlocking of the fluorine atoms

leads to a molecule of

•Great stiffness
•High crystalline melting point
•Thermal stability
 Why PTFE has high heat stability ?

• The carbon-fluorine bond is very stable.

• Further, when two fluorine atoms are attached
to a single carbon atom, there is a reduction in
the C-F bond distance, as a result, bond
strength is very high and thus PTFE has a very
high heat stability, even when heated above its
crystalline melting point of 327 °C.
 Other Properties

•Its mechanical strength remains unchanged over a

wide range of temperatures (-100 to 300°C).

•Unlike other thermoplastics, PTFE cannot be processed

by melt extrusion.
Applications of PTFE
Applications of PTFE
• Metamaterials are artificial structures engineered to have properties
not found in naturally occurring materials.

• Metamaterials are not commonly found in nature.

• They are designed to achieve specific electromagnetic, acoustic, or

mechanical properties through their structure (geometry) rather than
their chemical composition.

• These materials gain their unique properties from their precise, often
periodic, arrangement of unit cells or "meta-atoms."
 All “natural” materials, such as glass and diamond, have positive
electrical permittivity and magnetic permeability. As a result,
they possess a positive refractive index.

 In contrast, metamaterials exhibit negative values for both

electrical permittivity and magnetic permeability.
 Consequently, the refractive index of metamaterials is negative.

 Because these material parameters are negative, metamaterials

are also referred to as negative index materials (NIMs).
Backward Wave Propagation:

• Waves in metamaterials can propagate backward (energy flow in

opposite directions). This property is seen in left-handed materials
(LHM). So Metamaterials are also known as left-handed
materials.
 a)

b) c)
1. Metamaterial antennas are highly efficient.
2. Cloaking Devices:
a. Create the illusion of invisibility by guiding light around an
object.
b. Acoustic Cloaking: Make objects undetectable by sound
waves.
3. Superlens: Achieving resolutions beyond the diffraction
limit in imaging.
4. Metamaterials are used in solar cells and enhancing their
efficiency.
 Create the illusion of invisibility

Metamaterial Superlens

metamaterial antenna

[Link]
Liquid crystals (LCs) is a fourth state of matter that
has properties between conventional liquid and solid.
Examples: Liquid crystal form of Kevlar
p-cholesteryl benzoate
• Molecules in the liquid state are mobile in three directions &

can rotate freely about three axes perpendicular to one

another.

• On the other hand, solids are immobile & rotations are not as

readily possible.

• There is a mesomorphic state (intermediate state) of mobility

& rotation should exist, & these are called Liquid crystals.
I. Depending on the arrangement, mobility and rotation

1. Smetic Liquid Crystals

(Meaning soap like)

• These are more solid like and less liquid like.

• These are Two-D crystals.
• They do not flow as normal liquids.
• They have limited mobility.
• They flow in layers as if different sheets are
gliding over one another.
Smetic Liquid Crystals

• They have both positional and orientational order.

• They are always uniaxial and are not affected by magnetic field.

• There is no overlap of molecules.

• These are of most pharmaceutical significance, because, they can
help with drug delivery.
2. Nematic Liquid Crystals
(Meaning thread like)

• These are more liquid like, but turbid.

• Flow behavior is as normal liquids.

• mobile in 3 d’s and rotate about one axis

• Flow more readily than smectic phase.

• Low viscosity compared to normal liquids.

• They have no positional order, but they have long range oriental
order.

• There may be overlap of molecules, molecules are arranged parallel.

• Less temperature sensitive.

3. Cholesteric Liquid Crystals

• Also known as Chiral Nematic.

• Much thicker than smectic layer.

• Arrangement and behaviour are to some extent combination of

smectic and nematic LCs.

• Structure is helical, twisting repetition of nematic phase.

4. Columnar Liquid Crystals

• These are disc shaped.

• Consists of discs stacked one on top of the other to form

stacked columns of molecules.

II. Depending on their formation,

1. Thermotropic LCs

• Formed by heating of solids up to a particular

temperature.

Eg: Cholesteryl benzoate at 145 oC.

2. Lyotropic LCs

• Two component system, by dissolving amphiphilic

compound in a solvent
• Eg: Kevlar dissolved in sulphuric acid act as a liquid
crystal
• They have properties of solid as well as liquids.
• They are mobile.
• They possess birefringent property.
• They show anisotropy in various properties like
refractive index, conductivity etc.
• They are sensitive to electrical and magnetic field.
• They show electro-optical properties.
• There are used in display devices (Liquid crystal display (LCD’s)).

They are used in the screen of TV, computer… because they

consume very little power.

• In drug delivery system.

• Found applications in food and dermal products

• Some LCs show colour changes with temperature. Hence it is

used to detect areas of increased temperature under skin.

• Smectic liquid crystals are present in Emulsions