R. S.

INSTITUTE OF TECHNOLOGY

Polymers
Presented By
Dr. Harisha S
Assistant Professor
Department of Chemistry
K S Institute of Technology
Bengaluru - 09

POLYMERS

Polymers are macromolecules,formed by the combinationof many smaller repeating molecules. These
smaller molecules are termed as monomers.

The word "polymer" is derived from Greek language poly means many, meros means molecules.

"Deoxyribonucleicacid (DNA), ribonucleicacid (RNA) and proteins are macromoleculesand are essential
forms of life and hence polymers are 'inked to life.

Cellulose, lignin, starch and natural rubber are other examples

of natural polymers. Polypropylene, Polyester, PTFE,
Polyethylene are the well-known synthetic polymers.

Example: Polyethylene, Nylon, PVC, Teflon, Polyester, Bakelite, etc.

 is defined as a simple molecule
and •mer (part). Monomer
The word monomer comes from mono-(one)
with other monomer molecules to
It forms covalent linkages
with two oc more binding sites through which
form the macromolecule,

and glycol with two bonding sites act as monomers,

Examples: Alkenes, vinyl chloride, adlplc acid,

to its number of polymerizable groups.

In polymer chemistry, the functionality of a monomer refer

CHfCH2 has one functional group and two functionalities (A true monomer)

HO.CH$CHÜOH has two functional groups and two functionalities (A true monomer)

A Process In which formation of polymer is called polymerization.

Of

The no of repeating units or monomer units in the chain of a polymer is called degree of polymerization (DP).

The molecularweight of an addition polymeris the product of the molecularweight of the repeating unit
and the degree of polymerization (DP).

Molecular weight of the polynrer

Molecular weight of the monomer

Molecular weigh! of Polvmer

"Molecular weight Of a polymer is defined as sum of the atomic weight of each of the atoms in the
molecules, which Is present in the polymer"

I) Number —average molecular mass (Mn)

Different molecular weights

2) Weight - average molecular weight (Mw)
 (Mnl
1) Number—average molecular mass

molecules of a sample to the total number Of molecules.

It is the ratioof total mass of all the

NI molecules have molecular mass MI each.

N2 molecules have molecular mass M2 each.

In general, Ntmolecules have molecular mass Mi each.

Then, Totalmass of all the molecules

Total number of Molecules
Total mass of all the NI molecules = NIMI
NIMI + + + NiMi
Total mass of all the N2 molecules = N2M2

In general, Total mass of all the Nt molecules.= N M

2) Weight average molecular weight (Mw)

It is the ratio of products of total mass of groups of molecules to

the total mass of all molecules.

N: molecules have molecular mass NIMI each.

N2 molecules have molecular mass N2M2each.

In general, N, molecules have molecular mass Nitvl,

each.

Then, Products of total mass of groups of molecules

Total mass of all the NI molecules = NIM 2 Totalmass of all the molecules

Total mass of all the N2 molecules = N2M22 + N2M22 + + NiMi2

+ N2M2 + + N'vli
In general, Total mass of all the N, molecules = N tv1i2
Polydispersitv Index:

It is the measure of number of molecular species having different sizes, equal to the ratio of weight average
molecular mass to number average molecular mass.

tvlw
PDI =

If PDI = I polymer is mono disperse & Homogeneous.

PDI > 1 polymer is polydisperse & less Homogeneous.

Numerical Problems:

QI. In a sample of a polymer, 100 molecules have molecularmass 103g/mol, 200 moleculeshave molecular
mass 104 g/mol and 250 molecules have molecular mass IOS g/mol. Calculate the number average, weight
average molecular mass of the polymerand PDI.

Solution

Given, + N2M2 + + NiMi

NI = 100, Ml = 103g/mol

N2= 200, M2 = 104 g/mol

(100 x 103) + (200 x 104) + (250 x IO S)
N3 = 250, M3 = IO S g/mol
100 + 200 + 250

49272g/mol
 too 200
(100 10') (200 x 104) (250*10 9)

MF 92992g/mol

92992
PDI = 1.89
49272

02. In a polymer sample, 20 % of molecules have molecularmass 12000 g/mol 30% molecules have molecular mass
20000 g/mol, remaining molecules have molecularmass 22000 g/mol. Calculate the number average, weight average
molecular mass of the polymer and PDI.

Solution

Given, NIMI + N2M2+

NI 20, Ml - 12000g/mol

30, rv12- 20000 g/mol

(20 x 12000)+ (30 x 20000) + (50 x 22000)
- SO, M3 - 22000 g/mol 20 + 30 + 50

19400g/mol
 NIM, +

20 x (12000)2+ 30 x (20000)?+ so x (22000)?

(20 x 12000) + (30 x 20000) + (50 x 22000)

MF 20144g/mol

20144
PDI = 1.04
19400

POLYMER COMPOSITES

The combination of two or more distinct componentsto form a new

class
of materialsuitable for structural
applications is referred to as compositematerials.When one of the
componentsis a polymer,resulting
composite called as polymer composite.

Kevlar

Kevlar is synthesized in solution of N-methyl-pyrrolidone& calcium chloride from the

monomers 1, 4-
phenylene-diamine (para-phenylenediamine)& Terphthaloylchloride through a condensationreaction with
liberation of HCI as a byproduct.

n Cl.—c n H2N c NH
-2nHCl

Terepthaloyl Chloride P-phenylene diamine Kelvar

Professor,
 Properties:

It has very light weight.

It has high tensile strength and stiffness.

It has very good corrosion resistance.

li ns K VI

It is used to make light weight boat hulls.

Aircraft fuselage panels, pressure vassals, high performance race car, bullet proof vests.

Used in puncture resistance bicycle tyres etc.

Kevlar is crystalline, light weight and Nonflammable. Used in reinforcement material for some tyres.

Resistant to heat, impact and scratch. Used in making of light weight boat hulls and Aerospace industry.

Good Chemical resistance. Used in formula one rating car .

Good tensile strength. Used in bullet proof vests and combat Helmets.

Abrasion & Corrosion resistant Used in making puncture resistant tyres

BULLET ! STAB DIVINGGLOVES WALKINGBOOTS MILITARYHELMET

PROOFVESTS

povtCG

CUT RESISTANT BICYCLE TYRES CAR TYRES FIRE pROOF

GLOVES CLOTHING
 "An organic polymer with highly delocalized pi-electron
system having electrical conductance Of the order Of a
conductor is called conducting polymer".

Polyacetylene, polypyrrole, polythiophene, polyphenylene,

polyaniline, etc.

In this method polyacetylene is Synthesized

by using monomergaseous acetylene in the presence Of Ziegler-
Natta catalyst such as Titanium isopropaxide
and triethyl aluminium (Al(C2Hsh) at 120 oc.

n CHECH
-2nHCl

Commercial Applications of Polvacetvlene:

IJsed in the manufacture of chemical sensors, corrosion inhibitors.

Used in compact electronic devices such as polymer based transistors, LEDs etc.

Conducting polymers are generally produced by doping an oxidizingor a reducing agent into an organic polymer
with conjugated back bone consisting of pi-electron system.

An organic polymer can be converted into a conducting polymer if it has

I) Linear structure

2) Extensive conjugation in polymeric back bone (Pi-back bone)

The conducting polymers are synthesized by doping, in which charged species are introduced in organic polymers
having pi-back bone. The important doping reactions are;

Oxidative doping (p-doping)

* Reductive doping (n-doping)

$.37.
Mechanism Of conduction in Poty•cetylene

the conduCtivityOf polyacetVleneIS S/tfi

the doped polyacetyleneshows the tOnduCtivityOf S/m.

electron from
When polyacetyleneis partially oxidized with an oxidativedopant like in CCla, it takes away an
the n-backbone of polyacetylene chain producing a free radical and positive charge (hole).

this combination of charge site and free radical is called polaron.

this would create new localized electronic state in the energy gap. On further oxidation, a bipolaron is formed.

If the polyacetylene Chain is heavily oxidized, polaronscondensepair-wise to form solitons which merge with
the edges of conduction bond (CB) and valence bond (VB) exhibitingconductivity.

and thus making a conductive polymer.

As positive Charges are mobile, on applying potential they move

12in CC14

Polaron

.e- 12in

Bipolaron

Rearrangement

Conducting from polyacetalene

 (n-<QQinz)
In reductive doping technique, reducingagent
pi-backboneof a polymeris partial* reducedby a

This facilitates the formation of negative for

charged Sites on the ppbaObone and ere responsW,e

The most commonly used reducing agents are: sodium naptha%dein tetra hydro furan,

Qfgnoyctien.

+ The addition of an electron to the polymer back bone by using a reducingagentgeneratesz

+ A second reduction of chain containing polaron, followed by the recombinationof yieldstwochased (-%j
carriers on each chain.

formed the redudng zsent

+ These charge sites on the polymer chains are compensated caticr,s(%2+ions)

j Redudon Na - Naphth.2Ede

Naphthaze
Il Reductzn Na -

Recombinat.ooof
Commercial Applications:

Fabrication of organic thin transistors

Non-volatile memory devices based on organic transistors

Fabrication Of organic photovoltaic cells

Fabrication Of organic light-emittingdevices (OLED)

Conducting polymer actuators and Micropumps

Focused upon polymer membranes that incorporated electronically conducting polymers and piezoelectric polymers

Ferroelectric polymers for thin film devices

Gene Sensors

Printed electronics

Responsive membranes/Hybrid Plastics

Thank You