POLYMERS

SUB-TOPICS
 Definition of Polymer
 Polymer Classification
 Functionality
 Plastics
 Polyethylene Plastics
 Vinyl Plastics
 Specialty Polymers
Polymer:
Polymers = Poly (many) + mer (unit)

composed of large number of repeating units of Identical

structures called monomers.
 Classification of Polymers
1. On the basis of Origin

• Natural Polymers – occurs in nature

eg starch, cellulose, protein, natural rubber

• Synthetic Polymers – man-made polymers

eg polyethylene, polyvinylchloride, bakelite, nylon 66
2. On the basis of monomer composition

• Homopolymer - identical monomers

nA → (A)n

eg polyethylene, polyvinylchloride

• Copolymer – more than one type of

monomers nA + mB → A-A-B-B-A-B

eg bakelite, nylon66
Depending on the arrangement of the monomeric units, the
copolymers are further divided as:

Random copolymers monomeric units arranged randomly A — B — B — A —B — A

—A—B—B—A—B——

Alternating copolymers type of monomer units arranged in an alternating manner.

A—B—A—B—A—B

Block copolymers monomeric units arranged in blocks. A—A—A—A—B—B—B—B

Graft copolymers branched copolymers where backbone is formed of one type of

monomer and the branches are formed of another

*
3. On the basis of Chain Structure
• Linear Polymer
• Branched Polymer
• Cross Linked Polymer
5. Based on polymerisation mechanism

• Addition polymers - addition of

monomeric units
• eg polyethene, PVC, polypropylene,
polybutadiene
• Non-biodegradable and hard to recycle
• Unsaturated molecules
• Formed by addition reaction
• Involves one monomer unit
• CONDENSATION POLYMERS
- condensation of two or more than two
monomers with
the elimination of simple molecules like water,
ammonia and hydrochloric acid
eg Phenol, Formaldehyde Polymer,
Polyamides, Melamine Formaldehyde
Polymer,Nylon 66 etc.

Nylon 66 is obtained by condensation of two

monomers, hexa-methylene diamine and adipic
acid with the loss of water molecules
7. Based on tacticity –

Tacticity - spatial arrangement of the substituent

groups on the asymmetric carbon atom.
Based on the orientation of side groups in space .

Isotactic polymers – orientation of side groups

(R) on all asymmetric carbon atoms is the
same
• Syndiotactic polymer - side groups on
alternate asymmetric carbon atoms is the
same

• Atactic polymer- side groups

randomly arranged
8.Based on degree of polymerisation
• Oligopolymers - low degree of polymerisation
• Macromolecules - high degree of
polymerisation

9. Based on chemical composition

• Organic polymers -backbone chain is made
mainly of carbon atoms and the side chains
of oxygen, nitrogen, sulphur, etc.
eg include polythene, PVC, nylon, etc.

• Inorganic polymers -No carbon in the

backbone chain.
eg silicone rubbers (Silly Putty, and water
proofing sealant), phosphazene, etc.
Mechanism of Polymerisation T
Two types of polymerisation processes:
1. Addition polymerisation or Chain polymerisation
2. Condensation Polymerisation

1. Addition polymerisation or Chain polymerisation

-monomers are added to each other without the formation
of any byproduct.
Bifunctional molecules like ethylene, propylene (olefins),
vinyl compounds and allyl compounds generally undergo this
type of polymerisation. As majority of these monomers fall
under the ‘vinyl’ category; hence, chain polymerisation is also
customarily termed as ‘vinyl polymerisation’. Addition
polymerisation consists of three important step
Three important steps
(i) Chain initiation:
formation of active molecules (chain initiators)
These chain initiators then attack the monomer to
initiate the chain formation.
I—I →2 I* (Chain initiator)
I* + M → I—M* (Monomer) (Chain is initiated)
(ii) Chain propagation:
Initiated chain then attacks more monomeric
molecules leading to the increase in the length
of the chain.
I—M* + M → I—M—M* I—M
—M* + M → I—M—M—M*
I—M—M—M* + M → I—M—
M—M—M* (Chain
propagates)
(iii) Chain termination:
 Plastics
• Term ‘plastic’ refers to class of polymers that
can be shaped into hard and tough utility
articles by the application of heat and
pressure.

• Properties - light in weight, highly dielectric,

durable, less brittle, good strength, non
hygroscopic, low maintenance cost and
corrosion-resistant.

Replacing metals and glass in all walks of life.

Types of plastics:
Speciality polymers-

Chemically modified used as coupling agents,

polymers
compatibilizers, impact modifiers, tie-layer adhesive resins,
metal adhesion promoters, flow modifiers and chain
extenders for polymer compounds, blends and alloys.
1.Conducting Polymers :

Polymers do not conduct electricity but conductivity of

the doped polymer approaches the conductivity of one
of the best conductors.
Conductance of Intrinsic conducting polymers is due to
• extensive conjugation in their backbone
• presence of conjugated pi electrons (e-s are
delocalised)
• doped by adding either electron donors or electron
acceptors on the polymeric backbone (p or n type)

Conductance of Extrinsic conducting polymers is due to

• Presence of externally added ingredients like carbon
black, metallic fibres, metal oxides → ↑conductivity.
Polymer acts as binder for conducting elements.
• Blending of conducting polymers with conventional
polymers, which have better physical, chemical and
Some of the conducting
polymers are
Applications
Used in
• Electronics, solar display illuminati
cells, sources and s, on
microchips. batteries which
• perchlorate-doped
rechargeable light have
polyacetylene-lithium
• system.
weight
Photovoltaic devices in Al/
photovoltaic
like cells. polymer/Au
• Telecommunication systems.
• Antistatic coatings, smart windows use
Electrically conducting polyaniline.
Polyaniline shows different colors in different
oxidation states → color changes in response to
sunlight or temperature changes.
• Organic light-emitting diodes (OLEDs).
• Electronic devices such as transistors and
2.Electroluminescent Polymers :

Structure
Polyphenyle
ne vinylene
(PPV)

Preparation
Electroluminescent
Light emission
Polymers : is stimulated by electric current.
Devices at low voltages →practical amounts of
light. This property → development of flat panel
displays using organic LEDS, solar panels and
optical amplifiers.
• Light-emitting diode (LED) is a crystalline
semiconductor chip that glows.
• OLED is made of sheets of polymer
semiconductor material resembling plastic
using polyphenylene vinylene (PPV) as the
emissive layer.
Polyphenylene vinylene is the simplest and
cheapest and the only polymer which has so far
been successfully processed into a highly
Applications
• Stability, process ability, electrical and optical
properties have made PPV to be considered for
a variety of uses.
• Capable of electroluminescence, so it is used
in polymer-based OLEDs.
• Devices based on PPV emit yellow green
light.
Derivatives obtained by substitution of PPV
are used when light of a different color is
desired.
• Electron-donating material in organic solar
cells.
• Susceptibl to photodegradation and
e
Limitations oxidative in the presence of
degradati
precautions have oxygen.
to So,
be taken to
on
prevent oxygen contamination during
4.Liquid crystalline polymers:
Polymers that are capable of forming regions of
highly ordered structure while in liquid phase.

Degree of Order of Liquid Crystalline

Polymers < Regular Solid Crystal.

Properties:
• High Mechanical Strength at high
temperatures
• Extremely Chemical Resistant, inherent flame
retardant & good weather ability and
• Commonl known
exceptionally inert. liquid crystalline
y kevlar. polymer
(p- is poly
-
aromatic phenyleneterephthalamide
4. Biodegradable Polymers

Degradation of polymers by environmental

factors such as sunlight, temperature changes
or by the action of microbes (bacteria, fungi,
etc.).

eg i) natural polymers like rubber and cellulose

degrade gradually by bacterial action.
ii) synthetic polymers like polyvinyl
hydroxyethy alcohol, cellulose polymer,
polyhydroxybutyr
l polycaprolactone,
polymer,
ate
polymer and polyhydroxyvalerate
hydroxyvalera
poly(hydroxybutyrate
a copolymer(PHBV) te)
of hydroxybutyrate
hydroxyvalera
and
Applications of Biodegradable polymers

• Extensive use in the medical field.

• Commercially in tissue engineering and
drug delivery field of biomedicine.
• Orthopedic fixation devices.
• Join fractured bones as they provide the
required strength to the bone and after the
bone heals and can take the load.
• Harmlessly degrade over time.
• Prevents the patient from an additional
operation for removal, as was required earlier
when metallic device was used.
Addition Polymers
Polyethylene

• Polyethylene (PE), light, versatile synthetic resin prepared

by the addition polymerization of ethylene.
• Polyethylene is a member of the important family
of polyolefin resins.
• It is the most widely used plastic in the world, being
made into products ranging from clear food wrap and
shopping bags to detergent bottles and automobile fuel
tanks.
• It can also be slit or spun into synthetic fibres or modified
to take on the elastic properties of a rubber.
Low density Polyethylene (LDPE)

• LDPE is prepared from gaseous ethylene under very

high pressures (up to about 1000-3000 atmospheres)
and high temperatures (up to about 250 °C ) in the
presence of free radical initiators like benzoyl peroxide.
• Traces of oxygen catalyse the reaction.
Properties

• These processes yield a polymer structure with both

long and short branches. Because the branches prevent
the polyethylene molecules from packing closely
together in hard, stiff, crystalline arrangements, LDPE is
a very flexible material.
• Its density is low (0.91-0.925 g/cm3).
• It is a waxy solid that floats on water.
• It is not polar and has weak intermolecular forces.
• Its melting point is approximately 110 °C (230 °F).
• It is tough, flexible, chemically inert and has excellent
electrical insulation properties.
Applications
• LDPE is for storing a variety of
used
foodstuffs.
• Principal uses are in packaging film, trash and
grocery bags, agricultural mulch, wire and
cable insulation, squeeze bottles, toys, and
houseware.
High density Polyethylene (HDPE)

• HDPE is manufactured at low temperatures (60-70 °C) and

pressures (6-8 atms), using Ziegler-Natta and metallocene
catalysts or activated chromium oxide (known as a Phillips
catalyst).
• At 35 atm pressures, 60-200 °C and in the presence of metal
oxide catalyst like CrO3 supported on silica alumina, ethylene
polymerises to give HDPE.
Properties

• The polymeric chains are linear. The lack of branches in

its structure allows the polymer chains to pack closely
together, resulting in a dense, highly crystalline
material of high strength and moderate stiffness.
• Hence, it has high density (0.95-0.97 g/cm3).
• With a melting point more than 20 °C (36 °F) higher
than LDPE, it can withstand repeated exposure to 120
°C (250 °F) so that it can be sterilized.
• It has excellent electrical insulation properties, has low
water and gas permeability, excellent chemical
resistance and is free from odor and toxicity.
Applications

• Used for making insulations, pipes, products like

blow-molded bottles for milk and household
cleaners; blow-extruded grocery bags, construction
film, and injection-molded pails, caps, and toys.

• It is also used for manufacturing of crates, industrial

containers and overhead tanks.

• HDPE sheets are used for packing materials and for

making toys.
Linear low-density Polyethylene (LLDPE)

• LLDPE is structurally similar to LDPE.

• It is made by copolymerizing ethylene with 1-butene and
smaller amounts of 1-hexene and 1-octene, using Ziegler-Natta
or metallocene catalysts.
• The resultant structure has a linear backbone, but it has short,
uniform branches that, like the longer branches of LDPE,
prevent the polymer chains from packing closely together.
• Overall, LLDPE has similar properties to LDPE and competes for
the same markets.
• The main advantages of LLDPE are that the polymerization
conditions are less energy-intensive and that the polymer’s
properties may be altered by varying the type and amount of its
chemical ingredients.
Uses

• Used in making golf ball cover, orthopaedic devices,

blending with LDPE, packing films and bottles.
Ultrahigh molecular-weight polyethylene
(UHMWPE)

• Linear polyethylene can be produced ultrahigh-

molecular-weight
in versions, with molecular weights of
30,00,000 to 60,00,000 atomic units, as opposed to
5,00,000 atomic units for HDPE.

• These polymers can be spun into fibres and then

drawn, or stretched, into a highly crystalline state,
resulting in high stiffness and a tensile strength many
times that of steel.
Uses

• Used in making surgical prostheses,machine

parts, and heavy- duty liners.

• Yarns made from these fibres are woven

into bulletproof vests.
Condensation Polymers
Nylon

• They are polyamide polymers having recurring amide groups.

• When adipic acid monomer and hexamethylene
diamine monomer reacts, then the final product is nylon 6,6 and
water.
Properties

• It is a linear polymer and the polymeric chains are held together

by hydrogen bonding.
• Nylons are Lustrous, elastic and are very strong.
• Moreover, they are very Resilient and do not absorb water. They
also dry quickly.
• They have a more compact molecular structure and at the same
time, have better sunlight and water resistance
• They have a high melting point at 256 °C or 492.8 °F.
• Additionally, they are Excellent abrasion-resistant.
• Nylons can be very lustrous, semi-lustrous or dull.
• Nylons also have a high resistance to fungi, insects,
animals, mildew, moulds, rot and various kinds of chemicals.
• These polyamides have Good Specific Strengths.
Applications
• Nylon 6,6 is used for making fibres that are used for making
decorative carpets, socks and stockings.
• They are used for making many military-grade applications.
• It is used for making strings of musical instruments and as a
thread in bristles for toothbrushes.
• Because of its high thermal & abrasion resistance nylons
are used in mechanical engineering applications
like gears, bearings, machine parts where greater
friction is
there. Nylon 6 is mainly used for making tyre cords,
seat belts, ballistic cloth, etc.
• Nylon 11 and 12 are used for making flexible tubings
for
conveying petrol.
Bakelite
Bakelite is a polymer made up of the monomers phenol and
formaldehyde in the presence of acidic/alkaline catalyst. This phenol-
formaldehyde resin is a thermosetting polymer.

Preparation:
It is normally prepared
by two different methods.

i. Base catatysed using

excess of formaldehyde
over phenol.

ii. Acid catalyzed method

using excess of phenol.
Applications
• It is used for making electric insulator parts
like switches, plugs, switch boards etc.
• For making moulded articles like telephone
parts cabinet of radio and television
• As an anion exchanger in water purification by
ion exchange method in boilers
• As an adhesive (binder) for grinding wheels etc.
• In paints and varnishes
• For making bearings used in propeller shafts,
paper industry and rolling mills
Glyptal
Preparation:
Cross-linked, thermoset polymer prepared by condensing
glycerol (a triol) with phthalic anhydride.
Applications
• Glyptal and other alkyl polyesters are useful as coating
materials and are not used for making fibres and plastic
products.

• Glyptal is insoluble in alcohol and is added in paints to

improve their washability and adhesion.

• Its fast drying time and along with its good dielectric
strength makes it an excellent general-purpose adhesive
for many electrical and non-electrical applications.

• It is also used as a sealing wax.