Introduction to Polymers

POLYMERS

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 WHAT ARE POLYMERS, MONOMERS
AND
POLYMERIZATIONS?
 Polymers : A polymer (Greek poly, "many" + -mer, "parts") is a
large molecule, or macromolecule, composed of many repeated
subunits. 
 Polymerization : The process of linking the repeating units (monomers)
is termed as polymerization

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 WHAT ARE POLYMERS, MONOMERS
AND
POLYMERIZATIONS?
The small molecules which combine with each other to form
polymer molecules are termed monomers.
Monomer : A monomer is a molecule that may bind chemically

Introduction to Polymers
to other molecules to form a polymer.

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Introduction to Polymers
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TYPES OF POLYMERS & POLYMERIZATIONS

Classification
of Polymers

Polymerization
Polymer Structure
Mechanism

Condensation Addition Step- Chain-

Polymers Polymers Polymerization Polymerization

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TYPE OF POLYMERIZATION
 Monomers undergo polymerizaton by two types. They
are:

Introduction to Polymers
• Addition or chain polymerization
• Condensation or step polymerization

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THE ADDITION-CONDENSATION
SYSTEM

What are addition polymers?

Introduction to Polymers
Addition polymers are those formed from monomers without the
loss of a small molecule.

Y Y

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Polymer Structure

The addition-condensation system

Introduction to Polymers
Polymers whose repeating units are joined together
by functional units such as ester (-OCO-),
amide (-NHCO-), urethane (-OCONH-), sulfide (-
SO2-) and other linkages.

-R-Z-R-Z-R-Z-R-Z-R-Z-

R is aliphatic or aromatic grouping and Z is functional unit. 8

Polymer Structure

The addition system

Introduction to Polymers
The major addition polymers are those formed by polymerization
of monomers containing carbon-carbon double bond; such
monomers are called vinyl monomers or substituted ethylenes.

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ADDITION POLMERIZATION
 Self addition of several bifunctional monomers to each
ohter takes place by chain reaction without the
elimination of any simple molecules.

Introduction to Polymers
 GENERAL REACTION:

n [CH2=CH]  [-CH2-CH-]n
| |
Y Y

Where Y=H,Ethylene,CH3,Propylene,Cl, Vinyl Chloride, C6H5,

Sterene, CN , Acrylonitrile 10
Addition polymerization is initiated by
small qty of substance called Initiators.

Introduction to Polymers
E.g.-Zeigler-Natta catalyst, potassium
persulphate , dibenzoyl sulphat e.

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MECHANISM OF ADDITION POLYMERIZATION
{FREE RADICLE REACTION MECHANISM}

 Free Radical Mechanism of chain reaction involves 3

stages namely

Introduction to Polymers
I. Initiation

II. Propagation

III. Termination

 SCHEMATIC REPRESENTATION
[ R* - Free radical
M* - Unsaturated Monomer]

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• Generation of free radical :
I  2R E.g. I  CH2=CH2
• Initiation :
R + M  RM1

Introduction to Polymers
• Propagation :
RM1 + M  RM2
RM2 + M  RM3
RM( x – 1 ) + M  RM x
RM( y – 1 ) + M  RM y
• Termination :
RM x + RM y  RM x + y (COUPLING)
RM x + RM y  RM x + RM y (DISPROPORTIONATION) 13
MECHANISM OF ADDITION
POLYMERIZATION OF POLY-ETHYLENE
Synthesis of poly-ethylene -(CH2-CH2)- n from
Ethylene, CH2=CH2 using di-benzoyl peroxide (C6H5COO)2

Introduction to Polymers
as the indicator
n CH2=CH2  -(CH2-CH2)- n
(C6H5COO)2

Generation of free radical

(C6H5COO)2 2C6H5COO 2CO2 + 2C6H5 or (R)
Initiation
R + CH2=CH2 R-CH2-CH2
In General : R-(CH2-CH2)X-CH2-CH2
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R-(CH2-CH2)Y-CH2-CH2
Termination
 By coupling (by the combination of two radicals)

R-(CH2-CH2)X-CH2-CH2 + CH2-CH2-(CH2-CH2)Y-R

Introduction to Polymers
R-(CH2-CH2)X-CH2-CH2-CH2-CH2-(CH2-CH2)Y-R
By disproportionation
R-(CH2-CH2)X-CH2-CH2 + R-(CH2-CH2)Y-CH2-CH2

R(CH2CH2)X-CH2-CH3 + R(CH2CH2)Y-CH=CH2

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CONDENSATION POLYMERIZATION
• Self addition of several bifunctional monomer to each
other takes place accompanying elimination of simple
molecues like H2O,NH3 & HCL

Introduction to Polymers
• General reaction:
n[HOOC-X-COOH] + n[HO-Y-OH]

HO-[….OC-X-COO-Y-O]n-H + (2n-1)H20

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E.g..
 Terylene is obtained by condensing terpthalic acid

Introduction to Polymers
[HOOC-C6H4-COOH] with ethylene glycol [HO-C2H4-
OH]
 Nylon is made by the condensation of adipic acid
[HOOC-(CH2)4-COOH] with hexamethylene diamine
[NH2-(CH2)6-NH2]

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PLASTIC
 Plastic is a material consisting of any of a wide range
of synthetic or semi-synthetic organics that
are malleable and can be molded into solid objects of

Introduction to Polymers
diverse shapes.

 The processibility of a plastic is classified as either

'thermoplastic' and 'thermosetting'.

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 THERMOPLASTICS AND THERMOSETS
 The response of a polymer to mechanical forces at elevated
temperature is related to its dominant molecular structure.
 One classification of polymers is according to its behavior and
rising temperature. Thermoplastics and Thermosets are the 2

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categories.
 A thermoplastic is a polymer that turns to a liquid when heated and
freezes to a very glassy state when cooled sufficiently.
 Most thermoplastics are high-molecular-weight polymers whose
chains associate through weak Van der Waals forces (polyethylene);
stronger dipole-dipole interactions and hydrogen bonding (nylon).
 THERMOPLASTICS AND THERMOSETS
 Thermoplastic polymers differ from thermosetting polymers
(Bakelite, vulcanized rubber) since thermoplastics can be
remelted and remolded.

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 Thermosetting plastics when heated, will chemically
decompose, so they can not be recycled. Yet, once a thermoset is
cured it tends to be stronger than a thermoplastic.
 Typically, linear polymers with minor branched structures (and
flexible chains) are thermoplastics. The networked structures are
thermosets.
Examples of Thermoplastics

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MORE EXAMPLES OF
THERMOPLASTICS
Polymer

PTFE
THERMOPLASTICS
 Thermoplastics generally have a linear or branched
macromolecular structure.  

Introduction to Polymers
 A thermoplastic may be repeatedly heated and cooled.
 Upon heating, the plastic softens.  
 Upon cooling, the plastic hardens.  

 It is the non-cross-linked molecular structure of these

plastics which gives them their fusible properties.  

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 Examples of thermoplastics include:
 Acrylics

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 Cellulosics

 Polyamides

 Polyolefins

 Styrenes

 Vinyls

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PROPERTIES AND APPLICATIONS OF
SOME THERMOPLASTICS
 Hydrocarbon Plastics
 Polyethylene (PE)

Introduction to Polymers
 Polypropylene (PP)
 Polystyrene (PS)

 Chlorocarbon and Flurocarbon polymers

 Polyvinyl Chloride (PVC)
 Polytetrafluoro ethylene (PTFE)

 Acrylic Materials
 Polymethyl Methacrylate (PMMA)
 Polyacrylonitrile (PAN)

 Polyamides (PA) 25
 Heterochain Polymers
 Acetal (POM)

Introduction to Polymers
 Polycarbonate (PC)
 Polyethylene teraphthalate (PET)

 Polyether ether ketone (PEEK)

 Polyphenylene oxide (PPO)

 Polyphenylene Sulphide (PPS)

 Polyimides

 Polyamide – imide (PAI)

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 Polyethylene (PE) : Polyethylene (PE), light, versatile
synthetic resin made from the polymerization of
ethylene. Polyethylene is a member of the important

Introduction to Polymers
family of polyolefin resins.
 Uses

Film, Packaging, Bags, Industrial Applications, Piping,

Containers, Food Packaging, Wire & Cable Applications.

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 Polypropylene (PP) : Polypropylene (PP) is similar in
many respects to high-density polyethylene (HDPE).
However, instead of forming a long polymer chain made
up of repeating –CH2 components, the porous
polypropylene molecule has a series of CH3 groups that
hang off the main carbon backbone.

Introduction to Polymers
 Polypropylene is recyclable and has the number "5“.

 USES

As polypropylene is resistant to fatigue, most plastic living

hinges, such as those on flip-top bottles, are made from
this material. However, it is important to ensure that
chain molecules are oriented across the hinge to
maximise strength.  

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 Polystyrene : Polystyrene is obtained by reacting
ethylene with benzene in the presence of aluminum
chloride to yield ethylbenzene. The benzene group in this

Introduction to Polymers
compound is then dehydrogenated to yield
phenylethylene, or styrene, a clear liquid hydrocarbon
with the chemical structure CH2=CHC6H5.

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THERMO SETTING POLYMER
 A thermosetting polymer (or plastic), also known as
a thermoset, is petrochemical material that
irreversibly cures. The cure may be induced by heat,

Introduction to Polymers
generally above 200 °C (392 °F), through a chemical
reaction, or suitable irradiation.
 Thermoset materials are usually liquid or malleable prior
to curing and designed to be molded into their final
form, or used as adhesives.
 Others are solids like that of the molding compound used
in semiconductors and integrated circuits (IC). Once
hardened a thermoset resin cannot be reheated and
melted to be shaped differently. 30
 Thermosetting resin may be contrasted with
thermoplastic polymers which are commonly produced
in pellets and shaped into their final product form by

Introduction to Polymers
melting and pressing or injection molding.
 After these plastics have been formed, thermosets
undergo a chemical reaction (by heat, catalyst, ultraviolet
light) that results in a final cross-linking within the
plastic.  
 As a result of this cross-linking, thermosets harden when
they are heated; they cannot easily be molded after their
initial formation.  
 Most phenolics are thermosets. 31
PROPERTIES AND APPLICATIONS OF
SOME THERMO SETTING POLYMER
 Phenolics
 Poly formaldehyde (PF)

Introduction to Polymers
 Amino – Formaldehyde
 Ueraformaldehyde (UF)
 Melamine formaldehyde (MF)

 Polyester
 Epoxides (EP)

 Polyurethanes (PUR)

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