Polymers

Dr. Jitendra Satam

• A polymers are macromolecule with high molecular mass
compound ranging from 5000 to one million
• Formed by combination of one or more low molecular weight
compounds. The smallest unit from which polymer is obtained is
called monomer.
• The process by which polymers are obtained is called
polymerization
• For e.g. polyethylene is obtained by repeating ethylene unit as
a result of polymerization.
 Classification based on source
• Naturally occurring Polymers: These occur in plants and
animals and are very essential for life e.g. starch, cellulose, amino
acids, etc.

• Synthetic polymers: These polymers are prepared in laboratory

they are man made polymers e.g. plastics, synthetic rubbers, etc.

• Semi synthetic polymers: These are derived from naturally

occurring polymers by chemical modification. e.g. vulcanized
rubber, Cuprammonium silk and Cuprammonium rayon, etc.
 Classification based on Molecular forces
Polymers are classified into four categories based on magnitude of
intermolecular forces
• Elastomers: In these polymers, chain are held by weakest intermolecular
forces which permits the polymers to be stretched. The polymer regains its
original position when forces are released.
• Fibers: In these polymers the inter molecular forces are strong due to
hydrogen bonding, cross linking, cyclic structure
• Thermoplastics: These are polymers for which inter molecular forces
between elastomers and fibers. Due to this they can be easily molded by
heating.
• Thermosetting polymers: Thermosetting polymers undergo chemical
changes and cross linking on heating and become permanently hard and
infusible.
 Classification based on Tacticity
• Isotactic polymers: In isotactic, all the functional group lie
on the same side of chain
COOME COOME COOME COOME COOME

ME ME ME ME ME

• Syndiotactic polymers: In syndiotatactic, functional group

arrangement is alternate
COOME ME COOME ME

ME COOME ME COOME ME
 Atactic polymers: In atactic, functional group arrangement
is random
COOME COOME ME COOME ME

ME ME COOME ME COOME

Every other carbon in the chain is a stereo-center

 Classification based on Polymerization method
• Addition Polymerization: A polymer formed by direct repeated addition of
monomers is called addition polymerization. In this types of polymers monomers
are unsaturated compounds or derivatives of alkenes.

• Condensation Polymerization: Condensation polymerization involves

condensation of two different monomers which are normally bi functional group.
During the process there is loss of small molecule such as water
 Plastics
• Plastic is a substance that can be easily moulded into a desired shape by the
effect of mechanical force & heat.
• In the manufacturing of plastic raw materials like coal, petroleum, cellulose, salt,
sulphur, limestone, air, water etc. are used.
Plastics as engineering materials:-
• Low fabrication cost, low thermal & electrical conductivities, high resistance to
corrosion, Plastics are resistant to chemicals & solvents
• Plastics reduce noise & vibrations in machines
• Plastics are bad conductors of heat are useful for making handles used for hot
objects, most plastics are inflammable.
• Plastics are electrical insulators & find large scale use in the electrical industry.
• Plastics are clear & transparent so they can be given beautiful colors.
 Compounding of plastics
The process of mechanical mixing of various additives with
polymers (resin) to impart some special properties to the plastics.
The additives gets incorporated with resins to give homogeneous
mixture.
The principle Additives / Ingredients used in compounding are:
• Resin or Binder
• Fillers or extenders
• Plasticizers
• Pigments or Dyes
• Activators, catalysts or accelerators
• Lubricants
• Stabilizers
 Fabrication (Molding) of Plastics
Giving any desired shape to the plastics (granules or powders) by using
mould under the application of heat and pressure. A proper method is to
be selected depending on the shape and type of resin used. Methods
involves partial melting of resinous mass by heating.
In case of thermo-plasts molten resin is introduced in die/mould and
desired shape could be achieved by compression and further cooling.
In case of thermo-sets partially polymerized mass or raw materials are
introduced in the die/mould, which further cured at high temperature in
the mould itself to achieve desired shape.
Note:
• In case of thermoplasts, curing is done at room temperature (low
temperature), while in case of thermosets, curing is done at high
temperature to obtain desired cross-linking
 Four important types of
fabrication Methods
• Compression Molding : (Suitable for Thermosets /
Thermoplasts)
• Injection Molding : (Suitable for Thermoplasts)
• Transfer Molding : (Suitable for Thermosets)
• Extrusion Molding : (Suitable for Thermoplasts)
 Compression Molding
1. Common and oldest method for molding thermosetting / thermoplastic materials
2. Compression of raw materials or soften resinous mass is done in the mould/die under
heat and pressure
3. Predetermined quantity of raw materials is introduced carefully in the mould, further
compressed by hydraulic pressure (2000 to 10000 psi)
4. Molten or soften resinous mass gets filled in the cavity of mould.
5. Curing is done by heating (Thermosetting) or by cooling (Thermoplastics)
6. Finally moulded article is separated from the mould by opening the mould apart.
7. Applications : Electric switch boxes, Ash trays, cabinets for radio, television,
computers etc.
 Injection Molding
• Especially used for thermoplastic materials
• Powder or granular resin is heated in a cylinder and injected at a controlled rate in a mould
• Piston plunger or screw is used to force the material in mould.
• Pressure upto 1758 kg/cm2 (125 psi) is used
• Once the article is formed mould is cooled and half mould is opened to remove the finished article.
• Disadvantage of the method is formation of air bubbles or cavities in the articles
• Applications: Smaller but large volume articles such as, pen caps, bottle caps, cups, containers,
mechanical parts
 Transfer Molding
• The method combines features of both Compression Molding (hydraulic
pressing of molding materials - thermosets) and Injection Molding (ram-
plunger and filling the mold through a sprue).
• The method is used especially for molding thermosetting resins (thermosets)
• Products with relatively intricate designs could be fabricated with this method
• Powdered raw materials are heated at certain low temperature to soften and
then introduced through an orifice or sprue in the mould
• Then it is cured in the mould at high temperature for certain time
• Finally the moulded article is removed by separation of mould

Advantages:
• Articles with intricate shapes could be designed
• Aerospace and automobile parts, car body, helmets
• The articles produced are blister free
• Fine wires and glass fibers can be inserted in the mould
• Even thick pieces can be cured completely and uniformly
Transfer Molding
 Extrusion Molding (Horizontal)
• The method is used for the manufacturing of continuous type of thermoplastic
articles with constant cross-section. Eg. Tubes, rods, strips, insulated electric
cables
• Dry powder or granules of thermoplastic materials are introduced through
hopper and further melted by heating.
• There are two types of extrusion moulding:
1. Vertical extruder moulding
2. Horizontal extruder moulding
• Molten mass is pushed through the orifice of the die by using screw
• Once the article leaves the orifice, it is allowed to pass through water for
solidification
• Proper temperature control of heating chamber and the speed of the screw are
the major factors behind successful operation
Extrusion Molding
(Horizontal)
Extrusion Molding (Vertical)
 Condensation polymerisation Addition polymerisation

(1) It is also known as step growth (1) It is also known as chain growth
polymerisation polymerization

(2) It takes place in monomers having (2) It takes place only in monomers
reactive functional groups having multiple bonds.

(3) It takes place with elimination of (3) It takes place without elimination of
simple molecule like H2O,NH3,HCl simple molecule.
etc.,

(4) Repeat units of monomers are (4) Repeat units & monomers are same.
different

(5) The polymer is formed in gradual (5) Reaction is fast and polymer is formed
steps at once.

(6) The molecular mass of polymer (6) There is very little change in the
increases throughout the reaction molecular mass throughout the
reaction

(7) Product obtained may be (7) Product obtained are thermoplastic

thermosetting/thermoplastic

(8) E.g.:- Bakelite, polyester ,polyamides (8) E.g:-Polyethylene, PVC, poly styrene.
etc.,
 Conducting Polymers
• Generally polymers are insulators because of the absence of free
electrons.
• But they can be made conductive in certain cases by the process
called doping.
• Two conditions for the polymer to become conducting are:
1. Polymers should possess conjugated double bonds
2. Polymer structure has to be disturbed either by adding or
removing electrons by the process of doping.
• There are 3 major classes of conducting polymers
1. Intrinsically conducting polymers
2. Doped conducting polymers
3. Extrinsically conducting polymers
 1. Intrinsically conducting polymers
• This belong to a class of organic materials consist of Conjugated
pi-electrons in the backbone of their macromolecules which is
responsible for high electrical conductivity.
• In an electric field, conjugated pi-electrons of the polymer gets
excited and can be transported through the solid polymer.
• Overlapping of orbitals of conjugated pi-electrons over the entire
backbone of the polymer results in the formation of valence bands
and conduction bands. This induces conductivity in the presence
of electric field.
For example:
Poly-acetylene, poly-aniline, poly-pyrolle and poly-thiophene etc.
Polyacetylene
• Due to their high electrical properties, ICPs are intensively
investigated for application in electronics, microelectronics,
optoelectronics mainly for areas in aerospace and
automobile industries.
• Among the most promising applications of the ICPs are
corrosion protection, solid-state charge storage devices,
electromagnetic screens, antistatic coatings and gas
separation coatings.
• However, poor mechanical properties, environmental
sensitivity, moderate stability of electrical properties with
temperature significantly limit the industrial applicability of
ICPs.
 2. (DCP) Doped conducting polymer
• While the addition of a donor or an acceptor molecule to the polymer is
called "doping", the reaction that takes place is actually a redox
reaction.
• The first step is the formation of a cation (or anion), which is called a
soliton or a polaron.
Pn ⇔ [Pn + A – ] (reduction - oxidation)
• As synthesized conductive polymers exhibit very low conductivities. It
is not until an electron is removed from the valence band (p-doping) or
added to the conduction band (n-doping, which is far less common)
does a conducting polymer become highly conductive.
• Doping (p or n) generates charge carriers which move in an electric
field. Positive charges (holes) and negative charges (electrons) move to
opposite electrodes. This movement of charge is what is actually
responsible for electrical conductivity.
 (DCP) Doped conducting polymer
• This is obtained by exposing a polymer to a charge
transfer agent in a gas phase or in solution.
• Conductivity of ICPs can be increased by creating
positive or negative charges on the polymer backbone
by oxidation or reduction by the process of doping.
p-doping involves treating intrinsically conducting
polymer with a Lewis acid thereby oxidation takes place
and positive charges on the polymer backbone are
created. Some common P-dopants are I2, Br2, AsF5, PF6
etc.
n-doping involves treating intrinsically conducting
polymer with a Lewis base thereby reduction takes
place and negative charges on the polymer backbone
are created. Some common N-dopants are Li, Na, Ca
etc.
 3. Extrinsically Conducting Polymer
This type of conducting polymers possesses conductivity due to the
presence of externally mixed conducting elements or compounds.
These are of the following two types:
1. Conductive element filled polymer: Such polymers contains
non-conducting polymers (behaving as binder) holds the
conducting elements or compounds (behaving as conducting
filler) such as carbon black, metals, metal oxides, etc. Such
polymers possesses good bulk conductivity, low cost, light
weight, mechanically tough and easily processable.
2. Blended conducting polymer: Such polymers are obtained by
blending conventional polymers with conducting polymers
either through physical or chemical process.
 Applications of conducting polymers

• In rechargeable light weight batteries

• In optical display devices
• In aircrafts and aerospace components
• In diodes and transistors
• In solar cells
BIODEGRADBALE POLYMER
 Biodegradable Polymer

• Biodegradable polymers are polymers in which

monomers are joined to one another by functional
group linkage and has unstable link in backbone.
• They are broken down to biologically accepted
molecules that are metabolized and removed from
the body via normal metabolic pathway.
 Biodegradation

• It is process of converting polymer material into

harmless, simple and gaseous products by the action of
enzymes, micro-organism and water.
• The process of biodegradation is threefold: first an
object undergoes bio-deterioration, which is the
mechanical weakening of its structure; then follows bio-
fragmentation, which is the breakdown of materials by
microorganisms; and finally assimilation, which is the
incorporation of the old material into new cells.
 Advantages of Biodegradable polymer
• Biodegradable Plastics Produce Less Emissions
• Biodegradable Plastics = Less Waste
• Petroleum Will Eventually Run Out
• Growing crops to create biodegradable plastics can theoretically last
forever, if there is good farmland available.
• Combine this with renewable energy use and you have a winning
combination for environmentally friendly production.
• Biodegradable Plastics Can Decompose Quickly
• Over the cycle of their decomposition, traditional plastics can release
pollutants such as methane or bisphenol-A (BPA) (other than
that phthalates such as BBP, DBP and DIBP), which can harm both the
environment and human health. Bio-polymers don’t contain these
chemicals and so when they biodegrade, our environment and our
health aren’t affected.
• Biodegradable products are usually seen as a key part of
sustainable business practices.
• Application in agriculture: time controlled
biodegradable olefin can be used in agriculture for
mulching, netting , twine, etc.
• Biopolymer can be used as absorbable surgical
implants, controlled release of drug, absorbable skin
grafts and bone places to support the body recovery
system.
 Biodegradable polymers-Polylactic acid
Polylactic acid, also known as poly(lactic acid) or polylactide
(abbreviation PLA) is a thermoplastic polyester with backbone formula
(C3H4O2)n or [–C(CH3)HC(=O)O–]n, formally obtained by
condensation of lactic acid C(CH3)(OH)HCOOH with loss of water
(hence its name).
It can also be prepared by ring-opening polymerization of lactide [–
C(CH3)HC(=O)O–]2, the cyclic dimer of the basic repeating unit.
 Properties
• PLA polymers range from amorphous glassy polymer to semi-crystalline and highly
crystalline polymer with a glass transition 60–65 °C, a melting temperature 130-180 °C,
and a Young's modulus 2.7–16 GPa.
• Heat-resistant PLA can withstand temperatures of 110 °C. The basic mechanical properties
of PLA are between those of polystyrene and PET.
• The melting temperature of PLLA can be increased by 40–50 °C and its heat deflection
temperature can be increased from approximately 60 °C to up to 190 °C by physically
blending the polymer with PDLA (poly-D-lactide).
• PDLA and PLLA form a highly regular stereocomplex with increased crystallinity. The
temperature stability is maximised when a 1:1 blend is used, but even at lower
concentrations of 3–10% of PDLA, there is still a substantial improvement.
• Biodegradation of PDLA is slower than for PLA due to the higher crystallinity of PDLA.
• Racemic PLA and pure PLLA have low glass transition temperatures, making them
undesirable because of low strength and melting point. A stereocomplex of PDLA and
PLLA has a higher glass transition temperature, lending it more mechanical strength.
 Uses
• PLA is used in a large variety of consumer products such as disposable
tableware, cutlery, housings for kitchen appliances and electronics such as
laptops and handheld devices, and microwavable trays.
• It is used for compost bags, food packaging and loose-fill packaging material
that is cast, injection molded, or spun.
• In the form of a film, it shrinks upon heating, allowing it to be used in shrink
tunnels. In the form of fibers, it is used for monofilament fishing line and
netting. In the form of nonwoven fabrics, it is used for upholstery, disposable
garments, awnings, feminine hygiene products, and diapers.
• PLA has applications in engineering plastics, where the stereocomplex is
blended with a rubber-like polymer such as ABS. Such blends have good form
stability and visual transparency, making them useful in low-end packaging
applications.
• PLA is used for automotive parts such as floor mats, panels, and covers. Its
heat resistance and durability are inferior to the widely used polypropylene
(PP), but its properties are improved by means such as capping of the end
groups to reduce hydrolysis.
• In the form of fibers, PLA is used for monofilament fishing line and netting
for vegetation and weed prevention. It is used for sandbags, planting pots,
binding tape and ropes .
• PLA can degrade into innocuous lactic acid, so it is used as medical implants
in the form of anchors, screws, plates, pins, rods, and mesh. Depending on
the exact type used, it breaks down inside the body within 6 months to 2
years. This gradual degradation is desirable for a support structure, because
it gradually transfers the load to the body (e.g. to the bone) as that area heals.
The strength characteristics of PLA and PLLA implants are well
documented.