MODULE V : ADVANCED POLYMERS

(No. of hours – 03, Weightage of marks with option – 11)

• Course Objective: To study the different types of

advanced polymers with their applications.

• Course Outcome: Recognize different advanced

polymers for specific engineering applications.

1
 MODULE V : ADVANCED POLYMERS
Sr. No. TOPIC REMARKS

1. A) Conducting polymers Basic concepts of conducting polymers, Types of

conducting polymers: a) Intrinsic conducting
polymers b) Extrinsically conducting polymers c)
Doped Conducting Polymers d) Blended Conducting
Polymers. Applications of Conductive Polymers.
2. B) Biopolymers Definition, Classification- Natural biopolymers (ie.
Carbohydrates, Proteins, Nucleic acids) and
Synthetic biopolymers (i.e. Microbial and Chemical
synthesis), Advantages, Disadvantages and
Applications.

2
Sr. No. TOPIC REMARKS

3. C) Liquid crystal polymers Definition, Types of LCP’s (i.e.

Thermotropic and Lyotropic LCP’s),
Structural Features of LCP’s,
Applications of LCP’s.
4. D) Intelligent (smart) polymers Types of Smart Polymers:
Thermoresponsive Polymers, pH-
Responsive Polymers, Light -Responsive
(Photo-Responsive) Polymers,
Applications in various fields.

3
 Conducting Polymers
• Conducting polymers are finding increased use due to their light weight,
easy to process, and good mechanical properties.
• Polymers are poor conductors of electricity, due to the non-availability of a
large number of free electrons
• Polymers with polyconjugated structures are insulators in the pure state but
can be converted into polymers with electrical conductivities comparable to
metals.
• In non-conjugated polymers like polyethylene, the valence electrons are
present in sp3 hybridized covalent bonds. Such electrons involved in a
sigma-bond have low mobility and do not contribute to the electrical
conductivity of the material.

Dr. Megha Arya

POLYACETYLENE
2. Doped conducting polymer
Polymer matrix has to be disturbed –
This is obtained by exposing a polymer to a charged transfer agent in
either gas or in solution.
ICP possess low conductivity, but these possess low ionization
potential and high electron affinities, so these can be easily oxidized
or reduced.
• Removing electrons (oxidation) by electron acceptors(lewis acid) like
AsF5, Iodine, etc
• Inserting electrons(reduction) by electron donors(lewis donor) like alkali-
metal ion Li, Na, Ca

• This technique is called doping, is of two types

Dr. Megha Arya
(C2H2)n + 2 FeCl3 → (C2H2)+ FeCl4- + FeCl2

Dr. Megha Arya

(ii) N-doping: treating an ICP with a lewis base, thereby reduction process takes place and
negative charge created on polymer backbone

Dr. Megha Arya

 Applications of conducting polymers
1. Batteries: Conducting polymers are used as electrodes in
rechargeable batteries, improving their performance and lifespan.

1. Organic Light-Emitting Diodes (OLEDs): Conducting polymers are

used as hole-injecting materials in OLEDs, improving their brightness
and lifespan.
2. Sensors: Conducting polymers are used in various sensors, such as
gas sensors, biosensors, and pressure sensors.
3. Tissue Engineering: Conducting polymers are used as scaffolds for
tissue engineering, providing electrical stimulation for cell growth.
4. Corrosion Protection: Conducting polymers are used as coatings for
corrosion protection of metals.
5. Water Treatment: They are used in water treatment technologies,
such as electrochemical water treatment.

13
 Applications of conducting polymers

14
 Liquid Crystalline Polymers
Introduction:
• Liquid crystalline polymers (LCPs) are a special type of thermoplastic that
exhibits properties between highly ordered solid crystalline materials and
amorphous disordered liquids over a well-defined temperature range.
• The term liquid crystal originates from the fact that the crystal structure of the
polymer is partly maintained in the liquid phase above the melting point.

15
 Liquid Crystalline Polymers
• This is because the polymer consists of ordered, rigid rods, or mesogens
either along the polymer backbone or on the polymer’s side chains (Fig.).

• Thus, LCPs exhibit a highly ordered structure in both the melt and solid
states. This results in their properties being in between those of liquids and
crystalline solids. For example, they can have liquid-like flow properties
and solid-like tensile strength and stiffness.

16
 Structural Features of Liquid Crystalline Polymers
• Liquid Crystalline Polymers (LCPs) have unique structural features
that enable their exceptional properties. Here are some key
structural features of LCPs:
1. Mesogenic Groups- LCPs contain mesogenic groups, which are
rigid, rod-like structures that exhibit liquid crystalline behavior.
These groups can be composed of aromatic rings, heterocyclic
rings, or other rigid structures.
2. Flexible Spacers- Flexible spacers, such as alkyl chains or ether
linkages, connect the mesogenic groups. These spacers provide
flexibility and help to reduce the melting point of the polymer.

17
 Structural Features of Liquid Crystalline Polymers
3. Main Chain or Side Chain Architecture- LCPs can have either a main
chain or side chain architecture. Main chain LCPs have the mesogenic
groups incorporated into the polymer backbone. Side chain LCPs have
the mesogenic groups attached to the polymer backbone as side chains.
4. Molecular Weight and Polydispersity- LCPs typically have high
molecular weights, which contribute to their exceptional mechanical
properties. The polydispersity index (PDI) of LCPs can affect their
processing and properties.
5. Crystallinity and Liquid Crystallinity- LCPs can exhibit crystallinity,
liquid crystallinity, or a combination of both. The degree of crystallinity
and liquid crystallinity can impact the properties of LCPs.

18
Structural Features of Liquid Crystalline Polymers
These structural features enable LCPs to exhibit
unique properties, such as:
- High mechanical strength and stiffness
- High thermal stability
- Low melt viscosity
- Anisotropic properties
- Self-reinforcement

19
 Liquid Crystalline Polymers
• LCPs may be divided into two main categories, depending on how
they achieve their liquid-crystalline characteristics.
• Lyotropic LCPs are obtained from solutions; that is, when
polymers are dissolved in solvents. E.g. Poly(p-phenylene
terephthalamide) (PPTA), Poly(2,5-benzoxazole) (ABPBO).
• Thermotropic LCPs are produced via heat; that is, when polymers
are heated to a molten state. They are more commercially viable
and are the materials used in medical device applications. E.g.
Polyesters, Polyamides, Polyimides.

20
 Applications of Liquid Crystalline Polymers
1. High-Performance Composites
- LCPs are used as matrices in high-performance composites for
aerospace, automotive, and sports equipment applications.
- They provide exceptional mechanical properties, thermal stability,
and resistance to chemicals and abrasion.
2. Electrical and Electronic Components
- LCPs are used in electrical and electronic components, such as
connectors, sockets, and switches.
- They provide high thermal stability, chemical resistance, and
electrical insulation.

21
 Applications of Liquid Crystalline Polymers
3. Medical Devices and Implants
- LCPs are used in medical devices and implants, such as surgical
instruments, catheters, and bone screws.
- They provide biocompatibility, high mechanical strength, and
resistance to sterilization methods.
4. Packaging and Barrier Films
- LCPs are used in packaging and barrier films for food,
pharmaceutical, and cosmetic applications.
- They provide high barrier properties, thermal stability, and
chemical resistance.

22
 Applications of Liquid Crystalline Polymers
5. Membranes and Separations
- LCPs are used in membranes and separations, such as filtration,
separation, and purification applications.
- They provide high selectivity, thermal stability, and chemical
resistance.
6. 3D Printing and Additive Manufacturing
- LCPs are used in 3D printing and additive manufacturing,
providing high thermal stability, mechanical strength, and
chemical resistance.

23
 Applications of Liquid Crystalline Polymers
7. Optical Components and Displays
- LCPs are used in optical components and displays, such as
lenses, prisms, and liquid crystal displays (LCDs).
- They provide high optical clarity, thermal stability, and chemical
resistance

24
 Biopolymers
Definition:
‘Biopolymers’ are naturally occurring long-chain molecules which
are involved in biological changes important for our lives.
e.g. polysaccharides (carbohydrates), lipids (fats), proteins, nucleic
acids (DNA, RNA), and natural rubber. These polymers are present
in living matter (animals and plants).

25
 Natural Biopolymers
• CARBOHYDRATES:
1. General formula- Cx(H2O)y
2. Carbohydrates are divided into Monosaccharides (e.g. ribose,
glucose), oligosaccharides (maltose, sucrose) and
polysaccharides (starch, cellulose, glycogen) with general
formula (C6H10O5)n where n=1000-3000.
Functions:
1. They form structural components of cells. For example,
cellulose is present in the cell walls of all plant cells.
2. They function as bio-fuels to provide energy for the functioning
of living system and doing work.

26
 CARBOHYDRATES
• Functions:
3. They act as storage of chemical energy in the form of glycogen
in liver. In case of emergency (such as illness or fasting), glycogen
hydrolysis to glucose, which then supplies the necessary energy.
Similarly, starch is the main energy storage polysaccharide in
plants.
4. Cellulose present in grass and plants acts as food for various
grazing animals because they contain in their body specific
enzymes which can hydrolyze cellulose into glucose next point.
5. Some carbohydrates acts as food e.g. cane sugar, glucose and
starch.
27
 Natural Biopolymers
• PROTEINS:
1. Proteins are nitrogenous organic compounds of high molecular
masses, synthesized by plants and animals, which on hydrolysis
(by enzymes) yield amino acids.
2. Thus, proteins are polymeric amides, composed of long chains
of numerous amino acids, linked by peptide bonds. Chemically,
proteins yield alpha-amino acids on hydrolysis.
Functions:
1. They serve as fuel to yield energy.
2. They serve as the structural component of the living
organisms.

28
 PROTEINS
• Functions:
3. They are responsible for the functional characteristics.
4. They serve as enzymes, which catalyze biochemical reactions.
5. They help in the formation of haemoglobin, chromosomes, etc.
6. They form hormones and antibodies (protective agent), which are
highly essential for animals.
7. They act as mode of transport e.g. haemoglobin (present in
blood) acts as carrier of oxygen and carbon dioxide.
8. They take part in genetics.

29
 NUCLEIC ACIDS
Nucleic acids polynucleotides (a nucleotide consist of sugar, a
phosphate group and a nitrogen base residue). Thus, nucleic acids are
high polymers of nucleotide. In other words, nucleotides are the
repeating are the repeating of nucleic acids.
Structure of nucleic acid: It consists of three parts, namely, (i) nitrogen-
containing base, (ii) pentose sugar, (iii) phosphate group.
Types of nucleic acid:
(i) DNA: It is responsible for the inheritance of genetic character of a
particular species of living cell.
(ii) RNA: r-RNA – This forms the site for protein synthesis. m-RNA – It
carries the genetic information from DNA to ribosomes, where
protein is synthesized. t-RNA: It acts as carriers of amino acids.

30
 SYNTHETIC BIOPOLYMERS
• Production methods:
1. Microbial Synthesis: Microorganisms such as bacteria and yeast
are used to produce biopolymers through fermentation.
Examples include polyhydroxyalkanoates (PHA) and poly(lactic
acid) (PLA).
2. Chemical Synthesis: Chemical reactions are used to produce
biopolymers from renewable resources such as starch,
cellulose, and proteins. Examples include polylactic acid (PLA)
and polybutylene succinate (PBS).

31
 SYNTHETIC BIOPOLYMERS
• Advantages:
1. Biodegradable: Synthetic biopolymers are biodegradable,
reducing plastic waste and environmental pollution.
2. Renewable Resources: Many synthetic biopolymers are
produced from renewable resources, reducing dependence on
fossil fuels.
3. Customizable: Synthetic biopolymers can be tailored to have
specific properties, such as tensile strength, elasticity, and
biodegradability.
4. Competitive Pricing: Synthetic biopolymers can be produced at
competitive prices, making them a viable alternative to
traditional plastics.
32
 SYNTHETIC BIOPOLYMERS
• Advantages:
1. Biodegradable: Synthetic biopolymers are biodegradable,
reducing plastic waste and environmental pollution.
2. Renewable Resources: Many synthetic biopolymers are
produced from renewable resources, reducing dependence on
fossil fuels.
3. Customizable: Synthetic biopolymers can be tailored to have
specific properties, such as tensile strength, elasticity, and
biodegradability.
4. Competitive Pricing: Synthetic biopolymers can be produced at
competitive prices, making them a viable alternative to
traditional plastics.
33
 SYNTHETIC BIOPOLYMERS
• Disadvantages:
1. Higher Production Costs: While prices are decreasing, synthetic
biopolymers can still be more expensive to produce than traditional
plastics.
2. Limited Availability: Synthetic biopolymers are not yet widely
available, limiting their adoption in various industries.
3. Performance Limitations: Synthetic biopolymers may not have the
same performance characteristics as traditional plastics, such as
durability and shelf life.
4. End-of-Life Management: While biodegradable, synthetic
biopolymers require specific end-of-life management practices to
ensure proper decomposition.

34
 SYNTHETIC BIOPOLYMERS
• Applications:
1. Packaging: Synthetic biopolymers are used in packaging
applications, such as food containers, bags, and wraps.
2. Textiles: Synthetic biopolymers are used in textile applications, such
as clothing, carpets, and upholstery.
3. Medical Devices: Synthetic biopolymers are used in medical device
applications, such as implants, sutures, and wound dressings.
4. Agriculture: Synthetic biopolymers are used in agricultural
applications, such as mulch films, greenhouse films, and
biodegradable pesticides.
5. Consumer Goods: Synthetic biopolymers are used in various
consumer goods, such as disposable cutlery, straws, and bags.

35
 Intelligent (smart) polymers
• Smart polymers are a class of advanced polymers that
exhibit a change in their properties in response to external
stimuli.
• These stimuli can include electrical, mechanical (stress
or strain), thermal, light, magnetic, biological, or chemical
influences.

36
 Types of Intelligent (smart) polymers
1. Thermoresponsive Polymers,
2. pH-Responsive Polymers,
3. Light -Responsive (Photo-Responsive) Polymers

37
 Thermoresponsive Polymers
• Thermoresponsive polymers are a class of smart
materials that change their properties or behavior in
response to changes in temperature. These polymers are
also known as temperature-sensitive or thermo-
responsive polymers.
• Some common characteristics of thermoresponsive
polymers include:
1. Reversible phase transitions
2. Temperature-dependent solubility
3. Changes in shape, size, or color

38
 Types of Thermoresponsive Polymers
1. Lower Critical Solution Temperature (LCST) Polymers:
These polymers are soluble in water below a certain
temperature (LCST) and become insoluble above it.
Examples include PNIPAAM and PVME.
2. Upper Critical Solution Temperature (UCST) Polymers:
These polymers are insoluble in water below a certain
temperature (UCST) and become soluble above it.
Examples include poly(acrylic acid) and
poly(methacrylic acid).

39
 Thermoresponsive polymers
• Examples:
1. Poly(N-isopropylacrylamide) (PNIPAM)
2. Poly(vinyl methyl ether) (PVME)
3. Poly(ethylene oxide) (PEO)
• Applications:
1. Biomedical devices (e.g., drug delivery, tissue engineering)
2. Sensors and actuators
3. Smart textiles and fabrics
4. Separation and purification technologies

40
 pH-responsive polymers
• pH-responsive polymers are a class of smart materials
that change their properties or behavior in response to
changes in pH levels. These polymers are also known as
pH-sensitive or acid-responsive polymers.
• Examples of pH-Responsive Polymers:
1. Poly(acrylic acid) (PAA): PAA is a pH-responsive
polymer that contains carboxylic acid groups
2. Poly(methacrylic acid) (PMAA): PMAA is a pH-
responsive polymer that contains carboxylic acid groups

41
 Properties of pH-responsive polymers
1. pH-Dependent Solubility: pH-responsive polymers can
change their solubility in response to changes in pH
levels.
2. Conformational Changes: pH-responsive polymers can
undergo conformational changes, such as unfolding or
folding, in response to changes in pH levels.
3. Changes in Swelling Behavior: pH-responsive polymers
can change their swelling behavior in response to
changes in pH levels.

42
 Types of pH-Responsive Polymers
1. Weak Polyelectrolytes: Weak polyelectrolytes are pH-
responsive polymers that contain weakly acidic or basic
groups, such as carboxylic acid or amine groups.
2. Strong Polyelectrolytes: Strong polyelectrolytes are pH-
responsive polymers that contain strongly acidic or
basic groups, such as sulfonic acid or quaternary
ammonium groups.

43
 Applications of pH-Responsive Polymers
1. Drug Delivery Systems: pH-responsive polymers are being
explored for use in drug delivery systems, where they can release
drugs in response to changes in pH levels.
2. Biomedical Devices: pH-responsive polymers are being used to
develop biomedical devices, such as biosensors and implantable
devices.
3. Tissue Engineering: pH-responsive polymers are being used to
develop tissue engineering scaffolds that can respond to changes
in pH levels.
4. Environmental Applications: pH-responsive polymers are being
explored for use in environmental applications, such as water
treatment and pollution remediation.

44
 Light-responsive (photo-responsive) polymers
• Light-responsive (photo-responsive) polymers are a class
of smart materials that change their properties or
behavior in response to light. These polymers are also
known as photo-reactive or photo-sensitive polymers.

45
 Examples of Light-responsive Polymers:
1. Poly(ethylene glycol) (PEG) Derivatives: PEG
derivatives can be made photo-responsive by
incorporating photo-cleavable or photo-cross-linkable
groups.
2. Poly(acrylamide) (PAM) Derivatives: PAM derivatives
can be made photo-responsive by incorporating photo-
cleavable or photo-cross-linkable groups.
3. Spiropyran-Containing Polymers: Spiropyran-
containing polymers are photo-chromic polymers that
change color in response to light.
46
 Properties of Light-responsive Polymers
1. Photo-Induced Conformational Changes: Light-
responsive polymers can undergo conformational
changes, such as folding or unfolding, in response to
light.
2. Photo-Induced Solubility Changes: Light-responsive
polymers can change their solubility in response to light.
3. Photo-Induced Cross-Linking: Light-responsive
polymers can undergo cross-linking reactions in
response to light.

47
 Types of Light-Responsive Polymers
1. Photo-Cleavable Polymers: Photo-cleavable polymers
contain groups that can be cleaved by light, leading to
changes in the polymer's properties.
2. Photo-Cross-Linkable Polymers: Photo-cross-linkable
polymers contain groups that can be cross-linked by
light, leading to changes in the polymer's properties.
3. Photo-Chromic Polymers: Photo-chromic polymers
change color in response to light.

48
 Applications of Light-Responsive Polymers
1. Optical Data Storage: Light-responsive polymers are being
explored for use in optical data storage applications.
2. Biomedical Devices: Light-responsive polymers are being used
to develop biomedical devices, such as photo-controlled drug
delivery systems.
3. Soft Robotics: Light-responsive polymers are being used to
develop soft robots that can change shape in response to light.
4. Smart Coatings: Light-responsive polymers are being used to
develop smart coatings that can change color or properties in
response to light.

49