POLYMER

Polymers are large molecules made by bonding (chemically linking) a

series of building blocks.

The word polymer comes from the Greek words for “many parts.” Each
of those parts is scientists call a monomer (which in Greek means “one
part”).

Think of a polymer as a chain, with each of its links a monomer. Those

monomers can be simple — just an atom or two or three — or they might
be complicated ring-shaped structures containing a dozen or more atoms.
 In some cases, polymers form branching networks rather
than single chains, classified as macromolecules due to their
significant size.
Polymer chains can consist of hundreds of thousands to
millions of atoms, with longer chains resulting in heavier
molecules. Typically, materials derived from longer polymers
exhibit elevated melting and boiling points. Additionally, longer
polymer chains tend to possess higher viscosity, primarily
because of their increased surface area, which promotes
stronger interactions with neighboring molecules, impeding
their flow as a liquid.
ANATOMY OF
POLYMERS
 The backbone of these long molecules is the
carbon, C, atom. From valence theory it is known that
carbon has 4 electrons in its outer shell. It can
therefore share a further 4 electrons to complete its
atomic structure. In order to achieve this it must
covalently bond with other atoms around it.
 One of the more common atoms that carbon is likely to
bond with is hydrogen, H.

It is known that hydrogen will share 1 electron to complete

its outer shell, therefore carbon will bond with 4 hydrogen
atoms
 Polymers, whether artificial (such as the plastic
shown) or natural, are made of repeating chains of
smaller chemical units. Here, carbon atoms are shown
as black, oxygen as red and hydrogen as white.
 A chemical bond is what holds atoms together in a
molecule and some crystals. In theory, any atom that can form
two chemical bonds can make a chain; it’s like needing two
hands to link with other people to make a circle. (Hydrogen
wouldn’t work because it can form only one bond.)

Monomer
CHARACTERISTICS
AND
PROPERTIES
Characteristics
- Low Density
- Good Corrosion Resistance
- Good mold ability
- Excellent surface finish can be obtained
- Can be produces with close dimensional tolerances
- Economical
- Poor tensile strength
- Low mechanical properties
- Poor temperature resistance
- Can be produced transparent or in different colors.
 Properties
The physical properties of a polymer, such as its strength and
flexibility depend on:
Chain length - in general, the longer the chains the stronger the
polymer;
Side groups - polar side groups give stronger attraction between
polymer chains, making the polymer stronger;
Branching - straight, un branched chains can pack
together more closely than highly branched chains, giving
polymers that are more crystalline and therefore stronger;
Cross-linking - if polymer chains are linked together
extensively by covalent bonds, the polymer is
harder and more difficult to melt.
CLASSIFICATION
OF POLYMERS
 Since Polymers are numerous in
number with different behaviors and
can be naturally found or
synthetically created, they can be
classified in various ways. The
following below are some basic ways
in which we classify polymers:
Natural polymers
The easiest way to classify polymers is their
source of origin. Natural polymers are polymers
which occur in nature and are existing in natural
sources like plants and animals. Some common
examples are Proteins (which are found in humans
and animals alike), Cellulose and Starch (which are
found in plants) or Rubber (which we harvest from
the latex of a tropical plant ).
Synthetic polymers
Synthetic polymers are polymers which humans
can artificially create/synthesize in a lab. These are
commercially produced by industries for human
necessities. Some commonly produced polymers
which we use day to day are Polyethylene (a mass-
produced plastic which we use in packaging) or
Nylon Fibers (commonly used in our clothes, fishing
nets etc.)
Semi-Synthetic polymers
Semi-Synthetic polymers are
polymers obtained by making
modification in natural polymers
artificially in a lab. These polymers
formed by chemical reaction (in
a controlled environment) and
are of commercial importance.
Example: Vulcanized Rubber
(Sulphur is used in cross bonding
the polymer chains found in
natural rubber) Cellulose acetate
(rayon) etc.
Linear polymers
These polymers are similar in structure to a long
straight chain which identical links connected to
each other. The monomers in these are linked
together to form a long chain. These polymers have
high melting points and are of higher density. A
common example of this is PVC (Poly-vinyl chloride).
This polymer is largely used for making electric
cables and pipes.
Branch chain polymers
As the title describes, the structure of these polymers is
like branches originating at random points from a single
linear chain. Monomers join together to form a long
straight chain with some branched chains of different
lengths. As a result of these branches, the polymers are
not closely packed together. They are of low density
having low melting points. Low-density polyethene (LDPE)
used in plastic bags and general purpose containers is a
common example.
Crosslinked or Network polymers
In this type of polymers, monomers are linked
together to form a three-dimensional network. The
monomers contain strong covalent bonds as they
are composed of bi-functional and tri-functional in
nature. These polymers are brittle and hard. Ex:-
Bakelite (used in electrical insulators), Melamine
etc.
Addition polymers
These type of polymers are formed by the
repeated addition of monomer molecules. The
polymer is formed by polymerization of monomers
with double or triple bonds (unsaturated
compounds). Note, in this process, there is no
elimination of small molecules like water or alcohol
etc (no by-product of the process). Addition
polymers always have their empirical formulas
same as their monomers. Example: ethene
n(CH2=CH2) to polyethene -(CH2-CH2)n-.
Condensation polymers
These polymers are formed by the combination of
monomers, with the elimination of small molecules like
water, alcohol etc. The monomers in these types of
condensation reactions are bi-functional or tri-functional
in nature. A common example is the polymerization of
Hexamethylenediamine and adipic acid. to give Nylon –
66, where molecules of water are eliminated in the
process.
Elastomers
Elastomers are rubber-like solid polymers, that
are elastic in nature. When we say elastic, we
basically mean that the polymer can be easily
stretched by applying a little force.
 Thermoplastics
Thermoplastic polymers are long-
chain polymers in which inter-molecules
forces (Van der Waal’s forces) hold the
polymer chains together. These
polymers when heated are softened
(thick fluid like) and hardened when
they are allowed to cool down, forming
a hard mass. They do not contain any
cross bond and can easily be shaped
by heating and using molds. A common
example is Polystyrene or PVC (which is
used in making pipes).
Thermosetting
Thermosetting plastics are
polymers which are semi-fluid in
nature with low molecular masses.
When heated, they start cross-
linking between polymer chains,
hence becoming hard and
infusible. They form a three-
dimensional structure on the
application of heat. This reaction is
irreversible in nature. The most
common example of a
thermosetting polymer is that of
Bakelite, which is used in making
electrical insulation.
 Fibres
In the classification of polymers,
these are a class of polymers which are
a thread like in nature, and can easily
be woven. They have strong inter-
molecules forces between the chains
giving them less elasticity and high
tensile strength. The intermolecular
forces may be hydrogen bonds or
dipole-dipole interaction. Fibres have
sharp and high melting points. A
common example is that of Nylon-66,
which is used in carpets and apparels
TWO MAIN
TYPES OF
POLYMER
SYNTHETIC POLYMERS
These are man-made polymers
produced through chemical reactions.
Synthetic polymers are extensively used
in various industries due to their
versatility, durability, and tailored
properties.
 EXAMPLES

Polyethylene Polyvinyl chloride (PVC) Polystyrene

Nylon Polyester
NATURAL POLYMERS
These occur naturally and are
often found in biological systems.
Natural polymers are derived from
renewable resources and are
biodegradable in many cases.
 EXAMPLES

Carbohydrates
Proteins

Rubber Silk Nucleic acids

POLYMERIZATION
POLYMERIZATION
Polymerization is a chemical process in
which small molecules, called monomers,
are combined to form larger molecules
known as polymers. This process can
occur through various mechanisms,
including addition polymerization,
condensation polymerization, and ring-
opening polymerization.
Addition Polymerization
In this process, monomers with
unsaturated double or triple bonds
react with each other to form a
polymer without the generation of
any byproducts. Examples include the
polymerization of ethylene to form
polyethylene and the polymerization
of styrene to form polystyrene.
 Condensation
Polymerization
This type of polymerization involves the
formation of a polymer along with the
elimination of a small molecule, such as water
or alcohol, as a byproduct. Common
examples include the polymerization of
dicarboxylic acids with diamines to form
nylon and the reaction of diols with diacids to
produce polyester.
 Ring-Opening
Polymerization
In this process, cyclic monomers open up and
link together to form linear polymers or networks.
Examples include the polymerization of lactide to
form polylactic acid (PLA) and the polymerization
of ε-caprolactam to produce nylon-6.
TYPES OF
MONOMERS
 Vinyl Monomers
Vinyl monomers contain a vinyl group (–CH=CH2)
and can undergo addition polymerization to form vinyl
polymers. Examples include:
• Ethylene (C2H4): Used in the production of
polyethylene (PE).
• Styrene (C8H8): Used in the production of
polystyrene (PS) and acrylonitrile butadiene styrene
(ABS).
Acrylic Monomers
Acrylic monomers contain the acrylic or
methacrylic group and are widely used in
the production of synthetic polymers and
copolymers. Examples include:
• Methyl methacrylate (MMA): Used in the
production of polymethyl methacrylate
(PMMA), commonly known as acrylic glass
or Plexiglas.
• Acrylonitrile (AN): Used in the production
of acrylonitrile butadiene styrene (ABS) and
synthetic fibers such as acrylic.
Diene Monomers
Diene monomers contain two double
bonds in their structure and are used in the
production of elastomers through
polymerization. Examples include:
• Butadiene: Used in the production of
synthetic rubbers such as styrene-
butadiene rubber (SBR) and polybutadiene
rubber (BR).
• Isoprene: Used in the production of
natural rubber and synthetic rubber
polymers.
Aromatic Monomers
Aromatic monomers contain aromatic
rings in their structure and are used in the
production of aromatic polymers. Examples
include:
• Terephthalic acid: Used in the production
of polyethylene terephthalate (PET),
commonly used in beverage bottles and
synthetic fibers.
• Bisphenol A: Used in the production of
polycarbonate (PC), a durable and
transparent thermoplastic.
 Heterocyclic
Monomers
Heterocyclic monomers contain one or more
heteroatoms (such as oxygen, nitrogen, or sulfur) in
their ring structure. Examples include:
• Caprolactam: Used in the production of nylon-6,
a versatile engineering thermoplastic.
• Tetrahydrofuran (THF): Used in the production of
polytetramethylene ether glycol (PTMEG), a
precursor to elastomers and polyurethanes.
 Silicone Monomers
Silicone monomers contain silicon-oxygen (Si-
O) bonds and are known for their heat resistance,
flexibility, and water repellency. Examples
include:
• Dimethylsiloxane: Used in the production of
silicone elastomers, sealants, and lubricants.
• Methyltrichlorosilane: Used as a precursor in
the synthesis of various silicone polymers.
CHOICE OF
MONOMER
 Chemical Structure
The chemical structure of monomers
affects the properties of the resulting
polymer. Monomers with different functional
groups, side chains, or backbone structures
can lead to polymers with varied properties
such as stiffness, flexibility, thermal stability,
and chemical resistance.
Monomer Reactivity
The reactivity of monomers influences
the polymerization kinetics and control
over the polymerization process. Highly
reactive monomers may polymerize
rapidly, leading to higher molecular
weight polymers, while less reactive
monomers may require catalysts or
specialized reaction conditions.
Monomer Purity
The purity of monomers is crucial to
ensure the quality and reproducibility
of the polymerization process.
Impurities in monomers can lead to
defects in the polymer structure,
affecting its properties and
performance.
Monomer Cost and
Availability
The cost and availability of
monomers are important
considerations, especially for large-
scale industrial applications.
Monomers that are readily available
and cost-effective are preferred for
commercial production.
 Polymer End Use
The intended applications of the polymer
guide the selection of monomers. For
example, monomers with high heat resistance
may be chosen for engineering plastics, while
monomers with flexibility and elasticity may be
preferred for elastomers and rubber-like
materials.
Environmental and
Regulatory Considerations
Monomers should be chosen considering their
environmental impact and compliance with
regulatory standards. Sustainable monomers
derived from renewable resources or monomers
with minimal environmental impact are
increasingly preferred in polymer synthesis.
 Compatibility with
Polymerization Method
The choice of monomers should be
compatible with the selected
polymerization method (e.g., bulk, solution,
suspension, emulsion). Some monomers may
polymerize more efficiently in specific
reaction conditions or require certain
catalysts or initiators.
POLYMERIZATION
METHOD
Bulk Polymerization
In this method, monomers are
polymerized in their pure form, without the
presence of a solvent or diluent. Bulk
polymerization is often used for monomers
that are liquid at room temperature or
can be melted easily. It offers simplicity
and high reaction rates but may suffer
from heat buildup and poor heat transfer.
Solution Polymerization
Monomers are dissolved in a suitable
solvent, and polymerization occurs in the
solution phase. Solution polymerization
offers better temperature control, easier
handling of viscous reaction mixtures, and
the ability to achieve higher molecular
weights compared to bulk polymerization.
Common solvents include organic solvents
like toluene or hexane.
Suspension
Polymerization
Monomers are dispersed in a continuous
phase (usually water) with the aid of
surfactants or stabilizers to form droplets or
particles. Polymerization takes place within
these dispersed droplets, forming polymer
beads or particles. Suspension polymerization is
suitable for monomers insoluble in water and
allows for the production of polymer particles
with controlled size and morphology.
 Emulsion
Polymerization
Similar to suspension polymerization, but
monomers are dispersed as droplets in water with
the aid of surfactants or emulsifiers. Polymerization
occurs within these emulsified droplets, resulting in
the formation of polymer latex particles. Emulsion
polymerization offers advantages such as high
conversion rates, good control over particle size,
and the ability to produce latex with varying
properties.
Bulk Solution
Polymerization
A combination of bulk and solution
polymerization, where monomers are dissolved in
a suitable solvent, but the polymerization
reaction occurs without the presence of a
dispersing agent. This method allows for better
control over reaction conditions and polymer
properties compared to traditional bulk
or solution polymerization alone.
 Gas-Phase
Polymerization
Monomers are vaporized and polymerized in the
gas phase under controlled conditions, often in the
presence of a catalyst. Gas-phase polymerization offers
advantages such as high purity of the resulting polymer,
ease of product recovery, and scalability for industrial
production. It is commonly used for the production of
polyolefins like polyethylene and polypropylene.
What are the main
factors that can be
empirically adjusted
to modify polymers
Monomer Selection
The choice of monomers determines
the chemical structure, composition, and
properties of the resulting polymer.
Different monomers can be selected
based on their functional groups,
reactivity, and compatibility with the
desired polymerization method.
Monomer Ratio and
Copolymerization
Adjusting the ratio of different monomers
in copolymerization reactions allows for the
synthesis of copolymers with specific
properties. By varying the monomer
composition, copolymers can be tailored to
exhibit desired characteristics such as
flexibility, stiffness, or chemical resistance.
Polymerization
Conditions
Parameters such as temperature,
pressure, reaction time, and the presence
of catalysts or initiators can be adjusted
to control the polymerization process and
influence the molecular weight, degree
of branching, and polymer
microstructure.
 Polymerization
Technique
Different polymerization techniques (e.g.,
bulk, solution, suspension, emulsion, or gas-
phase polymerization) offer varying degrees of
control over polymer properties. The selection
of the appropriate polymerization method
depends on factors such as monomer
reactivity, solubility, and desired
polymer morphology.
 Additives and Fillers
Incorporating additives, fillers, or
reinforcing agents into polymers can modify
their mechanical, thermal, electrical, or
optical properties. Common additives
include plasticizers, flame retardants,
antioxidants, UV stabilizers, and reinforcing
fibers or nanoparticles.
 Post-Polymerization
Modifications
Polymers can undergo post-
polymerization modifications, such as
crosslinking, grafting, blending, or surface
functionalization, to further tailor their
properties. These modifications can
enhance polymer stability, adhesion,
compatibility, or processability.
Processing Conditions
Parameters during polymer processing,
such as temperature, pressure, shear rate,
and cooling rate, can significantly impact
the final properties of the polymer.
Optimization of processing conditions is
crucial to achieving desired mechanical,
rheological, and morphological
characteristics in the finished product.
 CRUCIAL
ROLE OF
POLYMERS
- Materials Engineering
- Manufacturing
- Packaging
- Electronics and Electrical Engineering
- Automotive Industry
- Healthcare and Biotechnology
- Energy and Environment
- Consumer Goods
APPLICATION OF
POLYMERS
Packaging
Polyethylene , polypropylene , polyethylene
terephthalate , and polystyrene are widely
used in packaging materials for food,
beverages, pharmaceuticals, and consumer
goods due to their lightweight, durability, and
barrier properties.
CONSTRUCTION
Polymers such as polyvinyl chloride
(PVC), polyethylene (PE), and polystyrene
(PS) are used in pipes, insulation, flooring,
roofing materials, and adhesives due to
their strength, weather resistance, and
insulation properties.
 AUTOMOTIVE
Polymers are used in
various automotive
components such as
bumpers, dashboards,
interior trim, tires, seals,
and adhesives due to
their lightweight,
durability, and ability to
reduce vibrations and
noise.
 ELECTRONICS
Polymers are used in electronics for
insulation, encapsulation, and as substrates
for flexible displays and printed circuit
boards.
 MEDICAL
Polymers are used in medical devices, implants,
drug delivery systems, and packaging for
pharmaceuticals and medical devices. Biocompatible
polymers like polyethylene glycol (PEG), poly(lactic-co-
glycolic acid) (PLGA), and polyvinyl chloride (PVC) are
commonly used in medical applications.
 AGRICULTURE
Polymers are used in agricultural films,
mulches, irrigation systems, and crop
protection products to improve soil quality,
conserve water, and enhance crop yield.
ADVANTAGES
OF
POLYMERS
Versatility: Polymers can be engineered to have a wide
range of properties, making them suitable for diverse
applications in various industries.
Lightweight: Many polymers are lightweight, which is
advantageous for applications where weight reduction is
desirable, such as automotive and aerospace industries.
Durability: Polymers can be highly durable and resistant
to wear, corrosion, and chemical attack, increasing the
longevity of products and reducing maintenance
requirements.
Flexibility: Some polymers are flexible and can be easily
molded or shaped into complex forms, offering design
flexibility and enabling innovative product designs.
Cost-Effectiveness: Polymers are often more cost-effective
compared to traditional materials like metals and ceramics,
resulting in lower manufacturing costs and overall product
costs.
Insulating Properties: Polymers exhibit good electrical and
thermal insulating properties, making them suitable for
electrical and electronic applications as well as thermal
insulation.
Biocompatibility: Certain polymers are biocompatible and can
be safely used in medical and healthcare applications, such as
implants, drug delivery systems, and medical devices.
Recyclability: Many polymers are recyclable, allowing them to
be reused or repurposed to reduce waste and environmental
impact. Recycling programs help divert polymer waste from
landfills and conserve resources.
DISADVANTAGES
OF POLYMERS
Environmental Impact: Some polymers, especially
those derived from non-renewable fossil fuels, contribute
to environmental pollution, litter, and plastic waste
accumulation, posing environmental challenges.
Degradation: Polymers can degrade over time due to
exposure to environmental factors like sunlight, heat, moisture,
and chemicals, leading to loss of mechanical properties and
product deterioration.
Low Melting Point: Many thermoplastic polymers
have relatively low melting points, limiting their use
in high-temperature applications where thermal
stability is required.
Brittleness: Some polymers may be brittle at low
temperatures or under certain conditions, increasing
the risk of fracture or failure, especially in applications
subject to impact or stress.
Creep: Polymers can experience creep, which is the
gradual deformation or flow of the material under
constant load over time, leading to dimensional
changes and reduced structural integrity.
Poor UV Stability: Many polymers are susceptible to
degradation by ultraviolet (UV) radiation from
sunlight, resulting in discoloration, embrittlement, and
loss of mechanical properties.
Limited Adhesion: Polymers may have poor
adhesion properties, making it challenging to bond
them to other materials or surfaces using
conventional adhesives or bonding techniques.
Complex Recycling: While many polymers are
recyclable, the recycling process can be complex
and costly, requiring specialized equipment and
infrastructure. Additionally, certain polymers are not
easily recyclable or compatible with existing
recycling systems.