Polymer Science & Technology Unit 1

▪Introduction & Basic concepts

▪Polymer based industries and feedstock
▪Classification of Polymers
Introduction
• Polymers are now well-accepted for a wide variety of applications, both
structural and non-structural, and for mass-manufactured as well as one-
off speciality products.
• The growth in their use has continued in the last two decades or more,
despite the effects of several recessions in industrial activity.
• In the same period the demand for traditional materials like metals,
ceramics and glasses has remained static or even fallen.
• In one of the most active areas, that of thermoplastic polymers,
consumption is divided between packaging, building, and a wide range of
other applications.
Source: ICC Conference
US Plastic Market Size
Global Scenario
Indian Scenario
Applications

Source: data from BPF Statistics

History
▪ Polymers have been with us from the beginning of time; they form the very
basis (building blocks) of life.
▪ However, it was not until the middle of the 20th century that we began to
understand the true nature of polymers.
▪ This understanding came with the development of plastics, which are true
man-made materials that are the ultimate tribute to man’s creativity and
ingenuity..
Beginnings
▪ In 1868, synthesis of cellulose nitrate
▪ Shortage of ivory from which billiard balls made
▪ John Wesley Hyatt (in the U.S.) mixed pyroxin made from cotton (a natural
polymer) and nitric acid with camphor. The result was cellulose nitrate,
which he called celluloid.
▪ Alexander Parkes, seeking a better insulating material for the electrical
industry, had discovered that camphor was an efficient plasticizer for
cellulose nitrate in 1862.
▪ Cellulose nitrate is derived from cellulose, a natural polymer.
Beginnings
▪ The first truly man-made plastic came 41 years later (in 1909) when Dr. Leo
Hendrick Baekeland developed phenol–formaldehyde plastics (phenolics):
electric iron and cookware handles, grinding wheels, and electrical plugs.
Beginnings
▪ Other polymers — cellulose acetate (toothbrushes, combs, cutlery handles,
eyeglass frames); urea–formaldehyde (buttons, electrical accessories); poly(vinyl
chloride) (flooring, upholstery, wire and cable insulation, shower curtains); and
nylon (toothbrush bristles, stockings, surgical sutures) — followed in the 1920s.
▪ During the first half of the 20th century, extensive organic and physical
developments led to the first understanding of the structural concept of
polymers — long chains or a network of covalently bonded molecules.
▪ German chemist Hermann Staudinger on polyoxymethylene and rubber and of
the American chemists W. T. Carothers on nylon.
▪ Staudinger first proposed the theory that polymers were composed of giant
molecules, and he coined the word macromolecule to describe them.
▪ Carothers classification of polymers as condensation or addition polymers
persists today.
Beginnings
▪ The Nobel-prize-winning development of stereo-specific catalysts by Professors
Karl Ziegler of Germany and Giulio Natta of Italy led to the ability of polymer
chemists to “order” the molecular structure of polymers.
▪ As a consequence, a measure of control over polymer properties now exists;
polymers can be tailor-made for specific purposes.
▪ The 1950s also saw the development of two families of plastics — acetal and
polycarbonates.
▪ Together with nylon, phenoxy, polyimide, poly(phenylene oxide), and
polysulfone they belong to the group of plastics known as the engineering
thermoplastics.
▪ They have outstanding impact strength and thermal and dimensional stability —
properties that place them in direct competition with more conventional
materials like metals.
Beginnings
▪ The 1960s and 1970s witnessed the introduction of thermoplastic
polyesters (exterior automotive parts, bottles); high-barrier nitrile resins;
and the so-called high-temperature plastics, including such materials as
polyphenylene sulfide, polyether sulfone, etc.
▪ The high-temperature plastics were initially developed to meet the
demands of the aerospace and aircraft industries.
Polymer
▪ The word polymer is derived from classical Greek poly meaning “many”
and meres meaning “parts.”
▪ Polymer is a large molecule (macromolecule) built up by the repetition of
small chemical units
Polymer
▪ The conversion of the monomer to the polymer involves a rearrangement
of electrons.
▪ The residue from the monomer employed in the preparation of a polymer
is referred to as the structural unit.
▪ In the case of polystyrene, the polymer is derived from a single monomer
(styrene) and, consequently, the structural unit of the polystyrene chain is
the same as its repeating unit.
Polymer
▪ Some polymers are derived from the mutual reaction of two or more
monomers that are chemically similar but not identical.
▪ For example, poly(hexamethylene adipamide) or nylon 6,6 is made from
the reaction of hexamethylenediamine and adipic acid.

▪ The repeating unit in this case consists of two structural units: the residue
from hexamethylenediamine and the residue from adipic acid
Degree of Polymerization
▪ The subscript designation, n, indicates the number of repeating units strung
together in the polymer chain (molecule). This is known as the degree of
polymerization (DP).
▪ It specifies the length of the polymer molecule.
▪ Polymerization occurs by the sequential reactions of monomers
▪ Monomers to dimer to trimer and so on.
▪ Reaction may also be between dimers, trimers, or any molecular species within
the reaction mixture to form a progressively larger molecule.
▪ A series of linkages is built between the repeating units, and the resulting
polymer molecule is often called a polymer chain, a description which
emphasizes its physical similarity to the links in a chain.
▪ Low-molecular-weight polymerization products such as dimers, trimers,
tetramers, etc., are referred to as oligomers.
▪ A high degree of polymerization is normally required for a material to develop
useful properties
▪ Polystyrene, with a degree of polymerization of 7, is a viscous liquid whereas
commercial grade polystyrene is a solid and the DP is typically in excess of 1000.
▪ It must be emphasized, however, that no clear demarcation has been
established between the sizes of oligomers and polymers.
▪ The degree of polymerization represents one way of quantifying the molecular
length or size of a polymer other is by term molecular weight (MW).
▪ MW(Polymer) = DP × MW(Repeat Unit).
▪ PS: There are eight carbon atoms and eight hydrogen atoms in the repeating
unit.
▪ MW of the repeating unit is 104 (8 × 12 + 1 × 8).
▪ For commercial grade polystyrene, DP of 1000.
▪ MW of this type of polystyrene is 104,000
Feed stocks
▪ About 80 per cent of all petrochemicals end up in polymers, the most important building
blocks being ethylene, propylene, butadiene and benzene.
▪ Ethylene is the progenitor of most vinyl monomers.
▪ The C2 and C3 building blocks can be combined with benzene to form another set of
monomers and intermediates.
▪ Other chemicals are also produced, such as plasticizers which are then added in a subsequent
stage to polymers to modify their properties.
▪ Primary sources of synthetic polymers are crude oil, natural gas and, to a minor extent, coal.
▪ Following distillation of petroleum into the major fractions (gasoline C5 up to 95 °C, naphtha
75–175 °C, kerosene 175–225 °C), the naphtha cut is subjected to cracking to yield smaller,
double bonded molecules.
▪ The reaction is conducted at high temperatures (400–800 °C), but under low pressure using
steam for cracking.
▪ This process can yield monomers directly, such as ethylene (C2), propylene (C3) and butadiene
(C4), but often further reactions are required to add other elements such as oxygen and
chlorine.
 Classification of Polymers

Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Natural Semi-Synthetic Synthetic

➢Polymers either obtained from plants or animal are called natural polymers.
➢They are called plant and animal polymers. Ex. Cellulose, Jute, Lichen, Silk, Wool,
Leather, RNA, DNA, Natural rubber.
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Natural Semi-Synthetic Synthetic

➢ The polymers obtained by simple chemical treatment of natural fibres to

improve their physical properties like lustrous nature, tensile strength are called
semisynthetic fibres.
➢ Ex. Acetate rayon, ammonium silk, viscous rayon
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Natural Semi-Synthetic Synthetic

➢The fibers obtained by polymerization of simple chemical molecules in laboratory

are synthetic fibers.
➢Ex. Nylon, terylene, polyethene, polystyrene, synthetic rubber, nylon, PVC,
bakelite, teflon etc.
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Homo-polymer Co-Polymer

➢A polymer consist of identical monomers is called homo polymer.

➢E.g. Polyethylene, PVC, Polypropylene
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Homo-polymer Co-Polymer

➢ A polymer consist of monomers of different chemical structure are called

copolymers.
➢ E.g. Nylon 6,6
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Thermoplastic Thermosetting

➢ They are easily molded in desired shapes by heating and subsequent cooling at
room temperature.
➢ They are soft in hot and hard on cooling.
➢ They may be linear or branched chain polymers.
➢ Ex. PE, PVC, PS, PP
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Thermoplastic Thermosetting

➢ These polymers are hard and infusible on heating. They do not soften on heating
under pressure and they are not remolded.
➢ These are cross linked polymers and cannot reused.
➢ E.g. Bakelite
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Addition Condensation

➢ The polymers formed by the addition of monomers repeatedly without removal

of by products are called addition polymers.
➢ These polymers contains all the atoms of monomers hence their molecular
weight are integral multiple of monomer unit.
➢ E.g. Teflon, Polyethylene, Polypropylene, PVC
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Addition Condensation

➢They are formed by the combination of two monomers by removal of small

molecules like H2O, Alcohol or NH3.
➢Their molecular mass is not the integral multiple of monomer units.
➢They have ester and amide linkage in their molecules. E.g. Polyamides(Nylons),
Polyesters(PET)
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Linear Branched Cross-linked

➢ In these polymers monomers are linked with each other and form a long straight
chain.
➢ These chains has no any side chains.
➢ Their molecules are closely packed and have high density, tensile strength, and
melting point.
➢ E.g. HDPE, Nylons
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Linear Branched Cross-linked

➢ They have a straight long chain with different side chains.

➢ Their molecules are irregularly packed hence they have low density, Tensile
strength and melting point.
➢ E.g. LDPE, LLDPE
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Linear Branched Cross-linked

➢ In these monomeric units are linked together to constitute a 3D network.

➢ The links involved are called cross links.
➢ They are hard, rigid .and brittle due to their network structure.
➢ E.g. Bakelite, Melamine, Formaldehyde resins, Vulcanized rubber
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Fibre Plastic Elastomer Resin

➢ If polymer is drawn into long filament like material whose length is at least 100
times it’s diameter, are said to be converted into fiber.
➢ They have high tensile strength because of high intermolecular attractive force
like Hydrogen bonding.
➢ Highly crystalline.
➢ E.g. Nylon, Terylene.
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Fibre Plastic Elastomer Resin

➢Polymer is shaped into hard and tough utility articles by application of heat and
pressure, is known as plastics.
➢Here the intermolecular force between polymeric chains are intermediate
between elastomers and fibers.
➢They are partially crystalline.
➢E.g. Polystyrene, PVC, PMMA
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Fibre Plastic Elastomer Resin

➢ They are solids with rubber like elastic properties.

➢ Here the polymeric chains are held together by the weakest intermolecular
forces so they are highly amorphous in nature.
➢ These weak binding forces permit them to be stretched.
➢ E.g. Natural rubber, BUNA-S, BUNA-N, Vulcanized rubber
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Fibre Plastic Elastomer Resin

➢Low molecular weight.

➢Polymers which are used as adhesives, sealants etc., in a liquid form are
described as liquid resins.
➢E.g. Epoxy adhesives and polysulphides sealants
 Polymer
s
Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Isotactic Syndiotactic Atactic

➢ The head to tail configuration in which the functional groups are all deposited on
the same side of the chain, is called isotactic polymers.
 Polymer
s
Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Isotactic Syndiotactic Atactic

➢ If the deposition of side groups is in alternating fashion, it is called syndiotactic

polymers.
 Polymers

Thermal Mode of
Origin Monomer Structure Application Tacticity
Response formation

Isotactic Syndiotactic Atactic

➢ If the deposition of side groups are at random around the main chain, it is called
atactic polymer.