A1950219738 - 16842 - 3 - 2018 - Chapter 13 Polymers 2

Engineering Chemistry
Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.

pearl necklace
pearl necklace
Polymers
You may think of polymers as being a relatively

modern invention however naturally occurring
polymers have been used for thousands of years
– wood, rubber, cotton, wool, leather, silk,.. etc
• Artificial polymers are, indeed, relatively
recent and mostly date from after WWII
in many cases, the artificial material is both
better and cheaper than the natural alternative
Preapred by: Mr. Harminder Singh 3

A polymer is a large molecule made by linking together
repeating units of small molecules called monomers

Polymers
A macromolecule is a very large molecule consisting of repeating units called monomers.
These structural units are bound together by covalent bonds.
A collection of macromolecules is called a polymer. For example, polyethylene
Polymerization
Polymers are prepared by polymerizing a monomer. The reaction is called polymerization
Polymerization of ethylene to form polyethylene
Ethylene monomer units
H 2C CH2 -CH2CH2-CH2CH2-CH2CH2-CH2CH2-
ethylene
polyethylene
Some Important Terms
• Degree of polymerization: The number of repeating units
present in a polymer is called degree of polymerization.
• “n” is called degree of polymerization. When n is large,
the polymers are called high polymers. For low values of
n, less than 10, the polymers are called oligomers.
Classification of polymers
1. Natural and Synthetic Polymers:

(Based on occurrence)
2. Thermoplastic and thermosetting polymers (Based on thermal
behavior)
3. Addition and condensation polymers (Based on polymerization
reaction)
Fig. Examples of addition polymers.
4. Linear, branched and cross-linked polymers (Based on
chemical structure)
5. Organic and inorganic polymers (Based on backbone material)
6. Atactic, isotactic and syndiotactic polymers (Based on Stereo
chemistry)
Based on mechanical behavior
7. Elastomers (undergo elongation on pulling and return to
original length when relesed, Ex- rubber)
Fibers (long, thin, thread like, Ex- jute, wood, silk)
Resins (low MW polymer used as adhesive)
Plastics (which can be molded onto desired shape)
8. Homopolymers and copolymers
Fig. Homopolymers and Copolymers
Classification of polymers
1. Natural and Synthetic Polymers: (Based on occurrence)

Natural polymers: wood, cellulose,, jute, cotton, wool etc.
Synthetic polymers: PE, PVC, epoxy resin etc.
2. Thermoplastic and thermosetting polymers
(Based on thermal behavior)
Thermoplastic polymers: The polymers that soften on
heating and which can be converted into any shape on
cooling are called thermoplastics. The process of heating,
reshaping, and retaining the shape on cooling can be
repeated several times without affecting their properties
much. Ex: PE, PolyCarbonate(PC), Polytetrafluoro ethylene
(PTEE) etc.
Thermosetting polymers: Polymers that undergo chemical
changes and cross-linking on heating and become
permanently hard, rigid and infusible on cooling, are called
thermosetting polymers. They do not soften on reheating;
instead they undergo degradation. Ex: phenol-formaldehyde
(bakelite), urea-formaldehyde etc.
3. a) Addition polymers (Based on type of polymerization)
The polymers formed by self-addition of several monomers to
each other without elimination of byproducts are called
addition polymers. Ex: PVC, PE etc.
•Monomers add successively to a growing polymer chain

•Polyethylene and polystyrene are addition polymers.
•Only olefinic or vinyl compounds can undergo addition polymerization.
•No elimination of byproducts.
•Double bond provides required bonding sites.
•The elemental composition of the polymer is the same as that of monomer.
•The addition of monomers takes place rapidly.
•Polymerization is brought about by initiators like free radicals.
Addition Polymerization Example
In this type of polymerization C=C bonds of monomers react to form larger

monomers until the unit is a larger polymer chain as seen here.
Table on the next slide shows ethylene monomer based polymers
Fig. Examples of addition polymers.
3. b) Condensation Polymer (Based on type of
polymerization)
The polymers formed by intermolecular condensation reaction by the functional
groups of monomers with continuous elimination of small molecules such as
ammonia, water etc. Ex: nylon-6,6; polyester etc.
•Polymer chain grows when monomers combine and split out water or other small
molecule.
•Nylon 6,6 and polyurethane are condensation polymers.
•The monomers having two or more reactive functional groups can undergo
condensation polymerization.
•There is continuous elimination of byproducts.
•Polymerization proceeds through intermolecular condensation.
•Polymerization is catalyzed by acids or alkali.
•The polymer chain built up is slow and stepwise.
•The elemental composition of the polymer is different from that of the monomers.
Condensation Polymer Example
Adipic acid
4. Linear, branched and cross-linked polymers (Based
on chemical structure)

5. Organic and Inorganic polymer
Organic
Inorganic
6. Atactic, isotactic and syndiotactic polymers (Based on
stereochemistry)
Side Group is random
Side Groups are on same side
Side Groups are on

alternating fashion
Fig. Atactic, isotactic and syndiotactic polymers.
Homopolymers and copolymers
Fig. Homopolymers and Copolymers

Homo Polymerization Example
In this type of polymerization C=C bonds of monomers react to form larger

monomers until the unit is a larger polymer chain as seen here.
Table on the next slide shows ethylene monomer based polymers
Copolymerization
The polymerization of two or more different monomers resulting in the formation of a
polymer containing both monomers linked in one chain is called copolymerization. It is
considered as a type of condensation polymerization. The polymers so formed are called
copolymers.
A copolymer is a polymer that has two types of monomer units in its chain .
•Block copolymer: When repeating units of each kind appear in blocks, it is called a
block copolymer.
•Random copolymer: If the various repeating units occur randomly along the chain
structure, the polymer is called a random copolymer.
•Graft copolymers: They are formed when chains of one kind are attached to the
backbone of a different polymer.
7. Elastomers, fibers, resins and plastics
(Classification based on end use of polymer)
Elastomers: Polymers that undergo very long elongation
when pulled apart and return to their original length on
release are called elastomers. Ex natural rubber, silicone
rubber etc.
Fibres: These are long, thin and thread-like ploymers. Ex:
jute, wood, silk etc.
Resins: These are low molecular weight polymers used as
adhesives. They can be in the form of liquids or powders.
Ex: phenol-formaldehyde, urea-formaldehyde etc.
Plastics: These are polymers which can be molded into
desired shapes by the application of heat and pressure.
Ex: PE, PVC etc.
Advanced polymeric materials (plastic)
30
31
Classification of plastic
32
Structure-property relationship
The Structure of the polymers depends upon:
1. Size and shape of the polymer chain .
2. Chemical nature of the monomers.
The Structure of the polymers further effects the physical and mechanical
properties of polymers.
• Strength
• Crystalinity
• Elasticity
• Non-elastic Nature of Fibers
• Plastic deformation
• Chemical Resistivity
34
The tensile strength of a material
quantifies how much stress the
material will endure before
suffering permanent deformation.
For example, a rubber band with
a higher tensile strength will hold
a greater weight before snapping
35
For a polymer to be commercially useful , It should have low melt viscosity, high
tensile strength and impact strength
36
Crystallinity
Amorphous and crystalline regions in a polymer. The crystalline region

(crystallite) has an orderly arrangement of molecules. The higher the 37
crystallinity, the harder, stiffer.
Crystallinity
Linear polymers have higher crystallinity, because the atoms along the chain
Permit closer approach, branched polymer will have low crystallinity.
Polymers containing polar groups can form H-bonding, so have higher

crystallinity.
38
• Elasticity: Elasticity of a polymer is due to uncoiling and
recoiling of the molecular chains on application of force. For
a polymer to show elasticity, the individual chains do not
break on prolonged stretching .Breaking takes place when
the chains slip past each other and get separated. Elasticity
can be increased by
1. Cross linking
2. Avoiding bulky groups
• Non-elastic Nature of Fibers : Here chain mobility is

reduced by very close packing of the polymer chain
backbone without cross linking. Polar groups and cyclic
rings in the backbone chain give high strength to polymer
fibre. Ex. In Nylon 6,6,PET
• Plastic deformation : It is studied by applying heat and P. Thermoplastic
polymer on applying heat and P first become soft, flexible and undergo
deformation. On further heating above their M.P they melt and flow.
Such a property is called plastic deformation. On cooling they returned
to original state.
• On the other hand thermosetting polymers do not show deformation
because On strong heating they undergo degradation.
• Chemical Resistivity: It depends upon structure of polymer and nature

of attacking reagents. During chemical attack it first softens, swells and
losses its strength and then dissolves. It depends on
• Presence of polar-non polar group, decides their solubility.
• Molar mass higher, lower solubility.
• Degree of crystallinity higher, resistivity higher.
• Extent of cross linking higher, resistivity higher.
Glass transition temperature and
melting point
41
Higher flexibility, lower Tg,
More side group- less flexible- Higher Tg,
Stronger intermoleculer force-higher Tg
 Higher branching- higher Tg
P= plasticizer
 More plasticizer- lower Tg
F = flexibility
 More stereogegularity- Higher Tg
Lowers Tg
 Higher molecular weight- Higher Tg. 42
Some Important Commercial Thermoplastics
Polythylene (PE): LDPE and HDPE

LDPE: Lots of branching-
Used in Food packaging
HDPE: No branching- Used for

Cans, milk bottle, fuel tank.
44
45
46
47
Polypropylene
Application:-
For making packaging container, furniture and toys.
Polystyrene (PS)
Used in making video cassettes,

radio and television parts.
Polyvinylchloride (PVC)
Used in making cable insulator,

Rigid pipes etc.
Polyvinyl Acetate (PVA)
Used in making adhesive for

textiles, paper and woods.
Polytetrafluoroethylene/Teflon (TFE)
Used for insulation of coil,

capasitor, wires.
Some Important Synthetic and Semi-synthetic Fibers
Nylons (polyamides) are polyamide.
Adipic acid
Application: Making sports gear, fishing lines, sports equipments

Making brushes and combs.
Some Important Commercial Thermosetting Resins
Phenol–Formaldehyde Resins
Novolac resin
Resol resin
Both resol and novolac on curing with wood flour filler give highly cross-linked
product called Bakelite. (Cross linking Novolac polymer)
Making golf balls.
54
Elastomers (Rubber)
Natural rubber is prepared from latex of Hevea rubber trees or gutta-

percha and balata. It is a linear polymer of isoprene and is called polyisoprene.
Properties of vulcanized rubber-
1. Good tensile strength

2. Excellent electrical insulation
property
3. It’s resistance to organic solvent
4. Low water absorption
5. Resistance to oxidation.
Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are
organic polymers that conduct electricity. Such compounds may have metallic conductivity
or can be semiconductors
58
Polyacetylene
59
60
61
Before doping there is sufficient energy gap between Valence band and Conduction
band. Upon doping, the polarons and solitons are formed.
Upon formation of large amount of solitons and polarons, a new energy band is
created between VB and CB, so that helps the electron to jump from VB to CB, as a
result the conductivity increases.
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64
65
Prep. By : Dr. Ashish kumar
Extrusion Moulding
• Extrusion molding is a manufacturing process used to make pipes, hoses, drinking
straws, curtain tracks, rods, and fibre. The granules melt into a liquid which is forced through a die,
forming a long 'tube like' shape. The shape of the die determines the shape of the tube. The
extrusion is then cooled and forms a solid shape. The tube may be printed upon, and cut at equal
intervals. The pieces may be rolled for storage or packed together. Shapes that can result from
extrusion include T-sections, U-sections, square sections, I-sections, L-sections and circular
sections.
• Raw materials in the form if thermoplastic pallets, granules,or

powder, placed into a hopper and fed into extruder barrel.
• The barrel is equipped with a screw that blends the pallets and
conveys them down the barrel
• Heaters around the extruder’s barrels heats the pellets and

liquefies them
Screw has 3-sections

• Feed section
• Melt or transition section
• Pumping section. Prep. By : Dr. Ashish kumar
• Advantages:
• 1. Low initial setup cost
• 2. Fast set up time.
• 3. Low production cost.
Applications:
Used for manufacturing Solid rods, channels, tubing, pipe,
window frames, architectural components can be extruded
due to continuous supply and flow.
• Plastic coated electrical wire, cable, and strips are also

extruded

Thank You

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Engineering Chemistry

Copyright  2012 Wiley India Pvt. Ltd. All rights reserved.

You may think of polymers as being a relatively

Preapred by: Mr. Harminder Singh 3

Preapred by: Mr. Harminder Singh 5

A collection of macromolecules is called a polymer. For example, polyethylene

Polymers are prepared by polymerizing a monomer. The reaction is called polymerization

Polymerization of ethylene to form polyethylene

Ethylene monomer units

1. Natural and Synthetic Polymers:

Fig. Examples of addition polymers.

8. Homopolymers and copolymers

Fig. Homopolymers and Copolymers

1. Natural and Synthetic Polymers: (Based on occurrence)

•Monomers add successively to a growing polymer chain

In this type of polymerization C=C bonds of monomers react to form larger

Table on the next slide shows ethylene monomer based polymers

Preapred by: Mr. Harminder Singh 22

Side Group is random

Side Groups are on same side

Side Groups are on

Fig. Homopolymers and Copolymers

In this type of polymerization C=C bonds of monomers react to form larger

Table on the next slide shows ethylene monomer based polymers

Amorphous and crystalline regions in a polymer. The crystalline region

Polymers containing polar groups can form H-bonding, so have higher

• Non-elastic Nature of Fibers : Here chain mobility is

• Chemical Resistivity: It depends upon structure of polymer and nature

Polythylene (PE): LDPE and HDPE

HDPE: No branching- Used for

Used in making video cassettes,

Used in making cable insulator,

Used in making adhesive for

Used for insulation of coil,

Nylons (polyamides) are polyamide.

Application: Making sports gear, fishing lines, sports equipments

Natural rubber is prepared from latex of Hevea rubber trees or gutta-

1. Good tensile strength

• Raw materials in the form if thermoplastic pallets, granules,or

• Heaters around the extruder’s barrels heats the pellets and

Screw has 3-sections

• Plastic coated electrical wire, cable, and strips are also

Prep. By : Dr. Ashish kumar

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