POLYMERS

Contents

▪ Definition of Polymer
▪ Polymer Classification
▪ Functionality
▪ Plastics
▪ Polyethylene Plastics
▪ Vinyl Plastics
▪ Specialty Polymers
Definition Polymer
Polymers = Poly (many) + mer (unit)
Macromolecule built from smaller units (monomers)

Monomer/Monomers Polymer
Ethylene Polyethylene
Vinyl chloride Polyvinylchloride
Amino acid Protein
1,3 Butadiene + Styrene Buna S
hexa-methylene diamine + adipic Nylon 6,6
acid
Phenol + Formaldehyde Bakelite
 Classification of Polymers
1. On the basis of Origin

• Natural Polymers – occurs in nature

eg starch, cellulose, protein, natural rubber

• Synthetic Polymers – man made

eg polyethylene, polyvinylchloride, bakelite, nylon 66
• Natural Polymers
DNA

Starch

Sugar

Proteins
• Synthetic Polymers – prepared artificially
eg polyethylene, polyvinylchloride, bakelite, nylon

LDPE

HDPE
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 monomeric 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 type of monomer
A—A—A—A—A—A—A–A
B
B
3. On the basis of Chain Structure
• Linear Polymer
• Branched Polymer
• Cross Linked Polymer
4. Based on chain composition

• Homochain polymer - all carbon atoms along their

backbone of polymer
eg polyethene, PVC, rubber

• Heterochain polymer chain contains a heteroatom

eg nylon (polymeric chain has nitrogen atom)
and terylene (polymeric chain has oxygen atom)
5. Based on polymerisation mechanism

• Addition polymers - addition of monomeric units

eg polyethene, PVC, polypropylene, polybutadiene,
polystyrene

(Polythene (two types)

Chain Length: 1000 - 2000

Low-Density Polyethylene (LDPE)

Chain Length: 10,000 – 100,000

High-Density Polyethylene (HDPE)

Teflon( Polytetrafluoroethene)
Nonstick coating chemically inert and resistance to
attack by reagents.

Polyacrylonitrile
(Good resistance to stain, chemicals, insects and fungi)

Substitute for wool in making commercial fibers as orlon

or acrilan.
 Buna S

A Copolymer of 1, 3, butadiene and styrene

Good substitute for natural rubber used for making

foot wear components, cable insulator etc…
Poly vinylchloride
• 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
Polyester

Nylon 6

Temp=533-543K

H 2O
 PHENOL FORMALDEHYDE POLYMER
(BAKELITE).

phen formaldyhyd o-
ol e hydroxymethylphenol
6. Based on molecular forces

• Elastomers - have weakest intermolecular forces

and have elastic behavior.
eg natural rubber can be stretched to at least thrice of
original length but returns to their original shape and
dimension as soon as the stretching force is removed.

• Fibres - held by strong intermolecular forces like

hydrogen bonds or dipole–dipole interactions.
eg nylon 66, polyster, silk
.
• Thermoplastics -linear, long-chain polymers that
soften on heating and hardens on cooling. The
intermolecular forces of these polymers are
intermediate between those of elastomers and fibres.
There is no cross-linking between the polymeric
chains. They can be processed again and again.
eg polyethene, polystyrene, PVC, teflon, polypropylene

• Thermosetting plastics - changes irreversibly into

hard and rigid materials on heating and cannot be
reshaped once they set. They form hard, infusible,
insoluble products because of cross-linkages.
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.
Functionality
- Number of reactive sites in a molecule

Any molecule acts as a monomer if it has at least two

reactive sites, i.e. functionality = 2.

eg, ethylene can add two molecules of hydrogen or

halogen. So, it is bifunctional (functionality 2).

IIly, acetylene is tetrafunctional (functionality 4), as it

can react with four atoms of hydrogen or halogen.

lIly, phenol is trifunctional (functionality 3) (2-ortho

and 1 para). It undergoes substitution reaction at
these sites.
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:
Active centers are removed or they combine with each other
and the chain propagation comes to an end.
I — M — M — M* + M* —M—I → I—M—M—M—M—M—I
 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:

(i) Thermoplastics
(ii) Thermosetting plastics.
Thermoplastics softens on heating and can be moulded
into desired shape. On cooling, they become hard. They
can be resoftened and remoulded by the application of heat
and pressure as they are composed of linear or long-chain
molecules. On heating the intermolecular bonds weaken,
the material softens and thus can be moulded again
without any damage.
eg polyethene, polypropylene, polystyrene, polyamides etc

Thermosetting plastics, when subjected to heat and

pressure, change into a hard and rigid substance. They
set and cannot be softened again by the application of
heat as their three-dimensional cross-linked structure
will not soften on heating but may decompose or
disintegrate at high temperatures.
eg bakelite, melamine formaldehyde, epoxy resins, etc.
Speciality polymers-

Chemically modified polymers used as coupling agents,

compatibilizers, impact modifiers, tie-layer adhesive resins,
metal adhesion promoters, flow modifiers and chain
extenders for polymer compounds, blends and alloys.
1. Polycarbonates -polyesters of phenols and carbonic acid.
Structure

Preparation:
condensation 2,2-bis(4-hydroxyphenyl) propane (bisphenol-A)
with diphenyl carbonate → polycarbonate
Properties:
• High-performance engineering thermoplastic, is a
tough, strong, generally transparent, amorphous
solid with outstanding impact resistance.
• Maintains its shape and size even under great stress
over a wide range of temperature.
• Resistant to water, acids, detergents, oils and
greases, but is attacked by bases, halogenated
solvents (chloroform, carbon tetrachloride), ketones
(acetones, acetonitrile), organic solvents like
benzene, benzylalcohol, dimethyl ether,
carbondisulphide, etc.
• Excellent resistance upto 140°C and maintains
toughness even at low temperature −20°C.
• Good electrical insulation properties
Uses:
• Electrical properties and dimensional stability enables it to
be used for mouldings for computers, calculating machines, for
making hair driers, electric razors, CDs and DVDs.
• Excellent impact resistance, helps it to be used in
automobile industry for making police shields, motorcycle
windshields, headlight covers, car bumpers, front panels,
safety helmets, etc.
• Stain resistant to oils, greases and domestic beverages
promotes its use for making blenders, food processing bowls,
coffee maker, food mixer housings.
• Temperature resistant, stability and chemical inertness,
helps it to find use in the manufacture of baby bottles,
syringes.
• Outstanding impact resistant enables its use for making
water dispensers, furniture (office and institutional), vacuum
cleaner bases, cord hooks, impellers, spectacles, cameras and
also for the manufacture of other unbreakable items
2.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 mechanical
properties.
Some of the conducting polymers are
Applications
Used in
• Electronics, solar cells, displays, illumination
sources and microchips.
• rechargeable light weight batteries which have
perchlorate-doped polyacetylene-lithium system.
• Photovoltaic devices like in Al/polymer/Au
photovoltaic cells.
• 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 diodes.
3.Electroluminescent Polymers :

Structure
Polyphenylene
vinylene (PPV)

Preparation
Electroluminescent Polymers :
Light emission 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 ordered crystalline
thin film.
Properties
• PPV is a bright yellow, fluorescent polymer.
• Emission max 551 nm (2.25 eV) & 520 nm (2.4 eV).
• Lies in yellow green region of the visible spectrum.
• Insoluble, intractable and infusible.
Incorporation of side groups like alkyl, alkoxy or phenyl
↑ solubility of the polymer.
• Diamagnetic material with low intrinsic electrical
conductivity (of the order of 10–13 S cm–1).
Electrical conductivity ↑ upon doping with iodine, ferric
chloride, alkali metals or acids.
Stability of these doped materials is low. Alkoxy
substituted PPVs get easily oxidised than the parent
PPV, so have much higher conductivities.
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.

Limitations
• Susceptible to photodegradation and oxidative
degradation in the presence of oxygen. So,
precautions have to be taken to prevent oxygen
contamination during manufacturing.
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 exceptionally
inert.
• Commonly known liquid crystalline polymer is
kevlar. - poly (p-phenyleneterephthalamide),
aromatic polyamide.
Liquid Crystalline Polymers
Preparation
Polycondensation of aromatic dichloride + aromatic
diamines
Properties

• Extraordinary mechanical properties

• High elastic modulus
• High tensile strength
• Kevlar can be spun into fibres that have 5 times the
tensile strength of steel and 10 times that of Al on a
weight to weight basis.
• High tensile strength is due to extensive hydrogen
bonding between the adjacent polymeric chains.
• Extreme chemical inert
• High heat stability and flexibility.
• Extremely resistant to fire.
 Uses
• It is used in the fabrication of protective wear including
bullet-proof vests.
• It is extensively used in aerospace and aircraft
industries, boat hulls, drum heads, sports equipments,
car parts (such as tyres, brakes, clutch linings),
helmets, brake pads, ropes, cables, etc.
• LCPs are generally used as reinforced (composite)
materials with carbon or glass fibres.
• Presently, the high cost of liquid crystalline polymers
limits its use to speciality applications like electronic
components (e.g., computer memory modules),
housings for light wave conductors and various
aerospace applications
 Kevlar

Strong Network of Covalent bonds

and Polar Hydrogen Bonds
5. 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 alcohol,

hydroxyethyl cellulose polymer, polycaprolactone,
polyhydroxybutyrate polymer, polyhydroxyvalerate
polymer and poly(hydroxybutyrate hydroxyvalerate)
(PHBV) a copolymer of hydroxybutyrate and
hydroxyvalerate.
 Preparation of PHBV- biodegradable

1.P.H.B.V (Poly B – hydroxy – Co – B hydroxy valerate

P.H.B.V)
Monomers – 3 – hydroxy butanoic acid + 3 hydroxy pentanoic
acid.
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.
• Good biocompatibility, controlled biodegradability and
good process ability makes Poly(α-hydroxyl ester),
a biodegradable materials to be used in biomedical
applications.
• Polylactic acid(PLA), polyglycolic acid (PGA), and
polylactic-co-glycolic acid (PLGA) too are widely used
in medical purposes like tissue engineering scaffolds
and related areas.
• PLGA is a combination of PLA and PGA. The
degradation rate, crystallinity, and mechanical
strength can be altered by changing the percentages
of each unit in the copolymer.
• Physical properties of poly (propylene fumarate) are
enhanced by composite with calcium phosphate-
degradable bio-ceramics for application as a bone
substitute material.
• In controlled drug delivery, polymer slowly
degrades into smaller fragments releasing the
drug gradually and in a controlled manner.
• Dental devices, biodegradable vascular stents,
biodegradable soft tissue anchors, etc.
• ↑Manufacture of plastic bags, toys and other
plastic products.
• Gradually degrade in the environment (or in
landfills) and leave the environment green.
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 used for storing a variety of
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 in ultrahigh-

molecular-weight 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.
Nylon 6
Preparation:
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.
• Glass-reinforced nylon plastics find use in domestic
appliances, radiator parts of cars, etc.
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.
Preparation:
i. .

Resole

Bakelite
Preparation:
ii. .
Properties

• Phenol resins are hard, rigid and strong materials

• They have excellent heat and moisture resistance
• They have good chemical resistance
• They have good abrasion resistance
• They have electrical insulation characteristics
• They are usually dark coloured
• Lower molecular weight grades have excellent bonding
strength and adhesive properties.
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.
Properties

• It is a thermosetting polymer and is tough in nature and has a

high degree of polymerisation.

• It does not soften when heated. The cross-linking keeps the

polymer chains from moving with respect to one another when
heated.

• It is a fast drying thermoplastic that can bond a variety of

materials.

• It has strong, durable bonds that have excellent resistance to oil,

gasoline and moisture.
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.