INTRODUCTION TO POLYMER

Lecture note
The word polymer has a Greek origin. which means many units (parts). Polymer is defined as
a chemical substance of a high molecular mass formed by the combination of a large number
of simple molecules, called monomers. e.g., Polymerisation The process by which the
monomers get combined and transformed into polymers. is known as polymerisation. n
[Monomer] → Polymer Difference between Polymers and Macromolecules Polymers are also
called macromolecules due to their large size but converse is not always true. A macromolecule
mayor may not contain monomer units, e.g., chlorophyll (C55H72O5N4Mg) is a
macromolecule but not a polymer since there are no monomer units present so we can conclude
that all polymers are macromolecules while all macromolecules may not be polymers in nature
Polymers are all created by the process of polymerization wherein their constituent elements
called monomers, are reacted together to form polymer chains, i.e 3-dimensional networks
forming the polymer bonds.
The type of polymerization mechanism used depends on the type of functional groups attached
to the reactants. In the biological context, almost all macromolecules are either completely
polymeric or are made up of large polymeric chains.

Synthetic polymers can be classified according to their response to heat. A thermoplastic polymer can
be softened by heating and then transformed into desired shapes/products by moulding. In contrast,
thermosetting polymers are permanently hard at elevated temperatures and pressures. They cannot be
softened and remoulded. Polymers can be divided mainly into four types depending on their properties
– plastics (e.g. PVC), fibres (e.g. polyamides), elastomers (e.g. rubber) and adhesives (e.g. resins). One
of the most interesting uses of polymers (e.g. biomedical polymers) has been as replacements for
diseased, worn out or missing parts of the human body such as leg, arm, lung, heart, liver, kidney,
arteries, teeth, knee joints and hip joints. Synthetic polymers could pose a serious threat to environment
unless we make them biodegradable. All polymers are macromolecules with the same repeating unit,
but all macromolecules are not polymers. For example, proteins and nucleic acids (DNA and RNA) are
macromolecules but they do not have the same repeating unit. Natural polymers and macromolecules
such as polysaccharides (e.g. cellulose, starch, etc) and nucleic acids (responsible for heredity) based
on sugars and phosphates. When naming homopolymers (i.e. polymers with one monomer unit), the
name of the monomer is written after the prefix poly, e.g. polyethylene. If the name of the monomer is
not a one word the name of the monomer is written within brackets, e.g. poly (vinyl chloride).

HISTORICAL DEVELOPMENENT OF POLYMERS

Polymers have existed in natural form since life began and those such as DNA ,RNA,
Proteins and polysaccharides play crucial roles in plant and animal life. Natural polymers like
wood, cotton and leathers has been in use foe ages, Natural rubbery materials was used
reference in the bible days as been used as adhesive ,coating and fillers . The birth of polymer
science may be traced back to the mid-nineteenth century. In the 1830s, Charles Goodyear
developed the vulcanization process that transformed the sticky latex of natural rubber into a
useful elastomer for tire use. In 1847, Christian F. Schönbein reacted cellulose with nitric acid
to produce cellulose nitrate. This was used in the 1860s as the first man-made thermoplastic,
celluloid. In 1907, Leo Hendrik Baekeland 1 produced Bakelite (phenol−formaldehyde resin).
Glyptal (unsaturated-polyester resin) was developed as a protective coating resin by General
Electric in 1912.
By the 1930s, researchers at DuPont in the United States had produced a variety of new
polymers including synthetic rubber and more “exotic” materials such as nylon and Teflon. By
1938, Dow had produced polystyrene in commercial scale for the first time and, in 1939,
polyethylene (low-density) was made by scientists at ICI in England. Efforts to develop new
polymeric materials, particularly synthetic rubber, were intensified during World War II when
many naturally occurring materials such as Hevea rubber were in short supply. In the 1950s,
Karl Ziegler and Giulio Natta independently developed a family of stereospecific transition-
metal catalysts that made possible the commercialization of polypropylene as a major
commodity plastic. The 1960s and 1970s witnessed the development of a number of high-
performance engineering plastics polymers that could compete favourably with more
traditional materials, such as metals, for automotive and aerospace applications. These included
polycarbonate, poly (phenylene oxide), polysulfones, polyimides, aromatic polyamides such
as Kevlar, and other high-temperature rigid-chain polymers. More recently, specialty polymers
with electrically conducting, photoconducting, and liquid-crystalline properties have appeared
for a variety of applications.
Today, polymeric materials are used in nearly all areas of daily life and their production and
fabrication are major worldwide industries. Among plastics, the largest shares of the total
production in 2012 were the polyethylenes, followed by polypropylene, poly(vinyl chloride)
(PVC), and polystyrene., thermosetting resins (principally phenolic, urea, and melamine resins)
typically represent around 10% of the total plastics production while synthetic rubbers, such as
styrene–butadiene rubber (SBR) and polybutadiene, represent only about 6% of the total
production in recent years.
Polyethylene (PE) -Let us first study the chemistry of well-known polymer polyethylene or polyethene
or polythene, in which a large number of ethylene or ethene [𝐶𝐻2 − 𝐶𝐻2 ] molecules are linked to form
a long hydrocarbon chain or the hydrocarbon backbone. Ethylene or ethene is called the monomer
(mono = one; mer = parts) and −CH2CH2− is the repeating unit. In the polymer formula, the repeating
monomer unit is placed within brackets with bonds extending to both sides. The subscript n indicates
the number of repeating units. Thus, [𝐶𝐻2 − 𝐶𝐻2 ]𝑛 is the formula used to represent polyethylene, with
n repeating units. Note that n is a large integer. Figure 1 Formation of polyethylene We know that
ethylene is a gas produced in petroleum industry. Both carbon atoms are sp 2 -hybridized and it has a
planar geometry. During polymerisation ethylene gas containing two sp2 -carbon atoms (with a carbon-
carbon double bond, C=C) is converted into a white solid with a long hydrocarbon chain in which each
tetrahedral carbon atom (-CH2-) is sp 3 -hybridized and forms two carbon-carbon single bonds to
adjacent carbon atoms.

TYPES OF POLYETHYLENE
There are two types of polyethylene depending on the density of the resulting polymer. 1.
Low density polyethylene (LDPE) which is produced at high temperatures over (200 oC) and high
pressure (1000 atm). 2.
High density polyethylene (HDPE) which is produced at ambient temperatures and low pressure (100
atm) in the presence of a catalyst.

PHYSICAL PROPERTIES AND USES OF POLYETHLENE

HDPE has a higher density, greater rigidity and greater strength as well as a higher melting point. It is
used for the preparation of threaded bottle caps, radio and television cabinets, toys and large-diameter
pipes. LDPE is a flexible, waxy, translucent material which has a relatively low melting point. LDPE
is used in insulation for electric wiring, plastic/shopping bags, refrigerator dishes, squeeze bottles, and
many other common household articles. HDPE consists primarily of linear molecules, that is, long un-
branched chains (with molar mass ca. 3,000,000). The chains can run alongside one another in close
contact over relatively great distances. This permits strong intermolecular forces of attraction between
the chains. The overall effect is to produce an ordered (crystalline) structure that imparts rigidity,
strength, and a higher melting temperature to the polymeric material. LDPE has branched chains that
prevent the macromolecules from assuming a crystalline structure. This weakens the attraction between
chains and produces a more flexible material and lower melting temperature than HDPE. Density,
tensile strength and relative elongation

KELVER-POLY(PARA-PHENYLENE TEREPHTHALAMIDE) - Kevlar is a very strong

material, about five times as strong as steel in equivalent weight. Kevlar is made when amide groups
are linked by a benzene ring instead of long carbon chains. The presence of benzene ring imparts
extreme strength to Kevlar and hence it is used for metal replacement. Besides all the advantages a
major issue with polyamides is their affinity to absorb moisture. Moisture uptake causes variation in
the dimensions. Amides are also easily attacked by acids or alkalis even in dilute concentrations in case
of acids. The reaction is catalysed by high temperatures. The reason is that amide linkage is readily
broken down by dilute acid, and the elastomer fibers in the material are detached and destroyed. The
net result is a hole in the mate rial. Kevlar is more resistant to acid or alkali attack as compared to
nylon. Nylon is used in textiles for clothing and car- pets, tire cords, ropes. Kevlar is used in bulletproof
vests, lightweight skis, in replacement of metals in many applications like space and aircraft bodies,
light weight automobiles. Applications are also found in bullet proof vest, body armour and sportswear
etc

KEVLER
SOME POLYMERS AND THEIR MONOMERS
• Polypropene, also called polypropylene, is comprised of monomer propene.
• Polystyrene is an aromatic polymer, naturally transparent, made up of monomer
styrene.
• Polyvinyl chloride (PVC) is a plastic polymer made from monomer vinyl
chloride.
• The urea-formaldehyde resin is a non-transparent plastic obtained by heating
formaldehyde and urea.
• Glyptal is comprised of monomers ethylene glycol and phthalic acid.
• Bakelite or polyoxybenzylmethylenglycolanhydride is a plastic that is made up
of monomers phenol and aldehyde.
STRUCTURE OF POLYMERS
Most of the polymers around us are made up of a hydrocarbon backbone.
A Hydrocarbon backbone being a long chain of linked carbon and hydrogen atoms, possible
due to the tetravalent nature of carbon.

TYPES OF POLYMERS
On the basis of the type of the backbone chain, polymers can be divided into:
Organic Polymers: Carbon backbone.
Inorganic Polymers: Backbone constituted by elements other than carbon.

CHARACTERISTICS OF POLYMERS
1. Polymeric molecules are very big molecules. There average molecular weights may
approach 105 or more. That's why, they are also known as macromolecules.
2. Polymers are semi-crystalline materials. It means they have both amorphous and
crystalline regions. In fact, polymers have regions of crystallinity, called crystallites,
embedded in amorphous regions. Crystallites provide strength and hardness and the
amorphous regions provide flexibility to the polymeric material.
3. The intermolecular forces in polymers can be Vander Waals' forces, dipole-di-pole
attractions or hydrogen bonding. These intermolecular forces are in addition to covalent
bonds which connect the repeating units into a macromolecule.
4. The chemical, electrical, optical, mechanical and thermal properties of polymers depend
on (i) size and shape of polymers, and (ii) the presence or absence of characteristic
 intermolecular forces. These parameters not only determine the properties of the polymers,
but also the performance of these materials in a given applications.
5. Polymers show time-dependent properties.
6. Polymers are combustible materials.
7. Polymers have low densities and they show excellent resistance to corrosion .
8. Generally, polymers are thermal and electrical insulators .
9. Polymeric materials are easily mouldable even into complex shapes with reproducible
dimensions with a minimum of fabrication and finishing cost.

CLASSIFICATION OF POLYMERS
Since Polymers are numerous in number with different behaviours 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.
We can compare the properties of different polymers in many ways based on
A) SOURCE/ORIGIN
B) STRUCTURE
• Atomic level
• Molecular level
✓ Linear/branched.
✓ Network
✓ Secondary structure
✓ Chain length
✓ Homo/ co-polymer
• Crystallinity
• Phase behaviours
C) REACTION/ ENVIRONMENT INTERACTION
• Thermoplastics
• Thermoset
D) PYSICAL STATE/STEREOREGULARITY
• Tacticity
• Conformation
• Configuration
E) MOLECULAR WEIGHT
 • Number
• Weight
• Viscosity (AVG)
• Poly dispersity
• Degree of polymerisation

CLASSIFICATION BASED ON SOURCE

The first classification of polymers is based on their source of origin,
1. 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 ).
2. 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 Fibres (commonly used in our clothes, fishing nets etc.)
3. 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.
Classification Based on Structure of Polymers
Atomic level-This deals with the nature of the atoms that are on the atom that are on the
polymer chain and how they are distributed.
Molecular level-This deals with the architecture of the polymer chain.

• Linear structure in polymer molecules: In general, linear molecular structures occur

in thermoplastics. In this molecular structure, molecules are occurred in linear alignments, and
there are nearly no cross-linking or branched structure.

• Branched structure in polymer molecules: Branched structures in polymer molecules occur with
replacement of ‘H’ atoms with ‘C’ atoms in linear molecules, and because of this replacement with
 ‘C’, this ‘C’ makes additional and same chemical reactions with other ‘C’ atoms. Because of this
phenomenon in polymer molecules, branched structures occur. Polyethylene is the example of this
branched structure.

• Cross-linked structure in polymer molecules: This structure is the main type of structure that affects
the polymer properties. Cross-linking occurs in polymer structures with the same logic with
branched structure that explained above. When the branches that created by ‘C’ atoms are linked
with each other, as shown in illustration, cross-linked structure occurs.

THERMOSET -Thermoset is a polymer that is cured by heat or chemical reaction and becomes
infusible and in- soluble material. Thermoset polymers have a permanent irreversible polymerization.
Thermoset polymers posses a cross linked molecular structure and are formed in two stage
polymerization . The first stage is formation of a polymer with linear chains. The second stage of
polymerization results in final cross-linked structure. The end product can be made rigid or flexible.
The Polymerization is controlled to result in heavily cross-linked short chains for hard product and
lightly cross-linked long chains for soft and flexible products .
THERMOPLASTIC -Thermoplastic is a plastic that softens upon heating and hardens when cooled.
Thermoplastics are made up of linear molecular chains and can be shaped by flow into articles by
molding or extrusion without need of any chemical processing before molding. The most useful
physical property of a thermoplastic is its glass transition temperature at which it begins to soften.
There are three types of thermoplastics crystalline, amorphous and semi- crystalline
Crystalline thermoplastics - They are usually translucent, and their molecular chains have a regular
arrangement. They have high and sharp melting temperature. Compared to amorphous thermoplastics
they have more mechanical impact resistance. Their load bearing capacity can be enhanced considerable
with addition of fibers. Upon curing they shrink more as compared to amor- phous thermoplastics.
Examples are polypropylene (PP), polyethylene (PE). Amorphous thermoplastics
They are usually transparent and have diffused melting point. The molecules are arranged randomly
and that’s why they do not flow easily into mold compared to crystalline polymers, to crystalline
polymers. Upon curing they shrink less as compared to crystalline thermoplastics . Examples are
polycarbonate (PC), polymethylmethacrylate (PMMA), polystyrene (PS), polyphenylene oxide (PPO),
acrylonitrile butadiene styrene (ABS)
Elastomers – Elastomers are rubber-like solid polymers that are elastic in nature.When we say elastic it
simply means that the polymercan be easily stretched by applying little force .Elastomer polymers possess
both viscosity and elasticity. For example, rubber, are elastic solids. The polymer is held by weak
intermolecular forces. They have the property to retract to its original position after being stretched.

Difference Between Thermoplastics and Thermosetting Plastics :

Sl No Thermoplastics Thermosetting plastics
1. Thermoplastics are linear Thermosetting Plastics are cross-linked
polymers. polymers
2. They undergo no chemical change They undergo chemical change in the molding molding
in the molding operation. operation.
3. They can be softened again and They cannot be re-softened once they hard.
again.
4. These plastics can be reused. These plastics cannot be reused.
5. These are soft and flexible. These are hard and brittle.
6. They are affected by certain They are unaffected by any solvent.
solvents.
7. Thermoplastics are not fireproof. Thermosetting Plastics are fireproof.

USES OF POLYMERS
Here we will list some of the important uses of polymers in our everyday life.

• Polypropene finds usage in a broad range of industries such as textiles, packaging, stationery,
plastics, aircraft, construction, rope, toys, etc.
• Polystyrene is one of the most common plastic, actively used in the packaging industry. Bottles,
toys, containers, trays, disposable glasses and plates, tv cabinets and lids are some of the daily-used
products made up of polystyrene. It is also used as an insulator.
• The most important use of polyvinyl chloride is the manufacture of sewage pipes. It is also used as
an insulator in the electric cables.
• Polyvinyl chloride is used in clothing and furniture and has recently become popular for the
construction of doors and windows as well. It is also used in vinyl flooring.
• Urea-formaldehyde resins are used for making adhesives, moulds, laminated sheets, unbreakable
containers, etc.
• Glyptal is used for making paints, coatings, and lacquers.
• Bakelite is used for making electrical switches, kitchen products, toys, jewellery, firearms,
insulators, computer discs, etc.