POLYMERS

Definitions

(1) Monomers:

“Building blocks of polymer.These are simple molecules that combine with each other to
form polymer Eg. Ethylene

(2) Polymer:

It is a macro molecule formed by the covalent linkage of a large number of monomer

unit. Eg. Polyethylene

(3) Degree of polymerization (DP):

 The number of repeating units (n) in the polymer chain is called degree of
polymerization.

 If the chain have high degree of polymerization (>10,000) then it is high polymer, if it
is <10,000, then it is oligopolymers.

(4) Functionality:

 The number of bonding sites or functional groups(active sites) in a monomer is

referred to as its functionality.

 For a substance to act as a monomer, it must have at least two reactive sites.

Ex: (i) the double bonds (C=C) in all vinyl compounds (CH 2 = CHX) provide two
bonding sites; it is bifunctional.

(ii) Adipic acid COOH-(CH2)4-COOH -bifunctional(2-COOH groups)

(iii) Hexamethylene diamine H2N-(CH2)6-NH2 - bifunctional(2-NH2 groups)

(iii) Malic acid HOOC-CH2-CH(OH)-COOH -trifunctional(2-COOH,1-OH

groups)

(iv)Tartaric acid HOOC-(CHOH)2-COOH -tetrafunctional(2-COOH,2-

OH groups)

(5) Polymerization
The fundamental chemical process by which the monomers (low molecular weight) are
converted into polymers (high molecular weight).

nM ---(M)n---

Classification:

1) Based on the origin of the polymers, they are classified in to

(i)Natural polymers: They are obtained from natural sources Eg: Starch, Cellulose and
proteins..etc

(ii)Synthetic polymers: They are man-made polymers Eg: Polyethylene, Polypropylene,

polystyrene, PVC, Polyester, Polyamides…etc.

2)Based on the way the repeating units are linked, polymers are classified into

(i) Linear polymers.

-M-M-M-M-M-M- Eg.polyethylene,PVC

(ii)Branched polymers.

-M-M-M-M-M

M Eg.Polyethylene formed under high pressure.

(iii)Cross-linked polymers.

-M-M-M-M-M-M-

-M-M-M-M-M-M- Eg.phenol-formaldehyde resin

-M-M-M-M-M-M-

3) Based on thermal behavior polymers are classified into

(i) Thermoplastics-The polymers which become soft on heating and hard on cooling.
This cycle can be carried out many times without affecting their chemical properties.
Eg. Polythene, PVC.

(ii) Thermosetting plastics-The polymers which undergo chemical changes and cross-
linking on heating and become permanently hard, rigid and infusible.They will not soften
on heating once they are set. Eg.Phenol-formaldehyde resin and epoxy resin.

4) Based on structure and uses polymers are classified into

(i)Elastomers-undergo very large elongation when pulled, but return to original length
on release of force.Eg.Natural rubber, Synthetic rubbers.

(ii)Fibres-These are long,thin and thread like polymer chains which do not undergo
strtching or deformation like elastomers.Eg.Silk,Cotton,Nylon6,Nylon66 etc.

(iii)Plastics-The polymers which can be moulded into desired articles by the application
of heat and pressure are called plastics. Eg.PVC,Teflon etc.

(iv)Resins-These are low molecular weight polymers and are the base materials used in
the manufacture of plastics. Eg. Phenol-formaldehyde resin and epoxy resin.

TYPES OF POLYMERISATION

(i)ADDITION POLYMERIZATION OR CHAIN POLYMERIZATION: The processes

in which rapid self addition of several bifunctional monomers to each other takes place
by chain reaction without elimination of any byproduct.

nCH2 CH2 (-CH2-CH2-CH2-CH2-)n

Ethylene Polyethylene

(ii)CONDENSATION(STEP) POLYMERIZATION: The process in which , bi or poly

functional monomers undergo inter molecular condensation with continuous elimination
of by products (water, HCl, ammonia, alcohol..etc) is called condensation
polymerization.

Eg.Formation of polyester,terylene from terephthalic acid and ethylene glycol.

HOOC-C6H4-COOH + HO-C2H4-OH --(-OC-C6H4-CO-O-C2H4-O-)n--

Terephthalic acid ethylene glycol Terylene

 DIFFERENCE BETWEEN ADDITION AND CONDENSATION POLYMERISATION

Addition polymerization Condensation polymerization

(i) Polymerization due to addition reaction

(i) Polymerization due to
condensation Reaction

(ii) No elimination of byproducts (ii)Elimination of byproducts like H2O,NH3

(iii) Ziegler-Nutta (TiCl4) catalyst may be (iii) Acid or Alkali may be used as Catalyst
used catalyst

(iv)Linear structure is obtained. (iv) Linear or branched or cross linked

polymers are obtained.

(v) Molecular weight of polymer is (v) It is different with weight of .

Integral multiple of that of monomer monomer.

(vi)Self addition takes place very rapidly (vi) The polymer chain build up is slow
and stepwise.

Mechanism of polymerization. (Free Radical mechanism)

This mechanism explains the addition polymerization.

It involves four steps

1. Generation of Free radical 2.Initiation. 3. Propagation 4.Termination

1. Generation of free radical:-

Initiators are thermally unstable compound and decompose into products are called free
radicals.

When energy is supplied to initiatorR-R, say, in the from heat, the molecule split into two
symmetrical components as show below
 hυ /∆

R-R 2R.

2. Initiation:

*Free radical having a lone pair electron, is very reactive, and can attack any molecule which has
a lone electron or with double bond monomer molecules.

*The free radical R attracts the double bond in the monomer resulting a new free radical .

R. +M RM1.

3. Propagation:

*In this step, the new free-radical attacks another monomer molecule to produce yet another new
free radical. Many repetitions of this step lead to polymer chain growth and continue until
termination occurs.

RM1. +M RM2.

RM2. +M RM3.

RM(x-1). +M RMx.

RM(y-1). +M RMy.

4. Termination;

In the termination process the growing polymer chain is transformed into a dead polymer
molecule.

There exists a statistical probability of the two growing chain coming close and collide with each
other when such collision takes place the following two reaction occurs resulting the arrest of
the chain growth .

a. Termination by coupling:-

Here, two growing chains combined by the coupling of the lone electron present in each chain to
form an electron pair and, this nullify their reactivity. Since this process involves the coupling of
the two lone electron this kind of termination is known as” Termination by coupling”.

RMx. +RMy. RMx+y. (Dead polymer)

b.Termination by dis-proportionation :-

Here, one H form one growing chain is abstracted by the other growing chain and utilized by
the lone electron for getting stabilized, while the chain, which had donated the H, get stabilized
by the formation of a double bond.

Termination process result is the formation of two polymer molecules shorter chain length.

RMx. +RMy. RMx + RMy (Dead polymers)

Free radical mechanism taking Vinyl chloride as example

Glass transition temperature (Tg):-

All amorphous polymers, when cooled below a certain temperature, become stiff, hard,
brittle and glassy but above this temperature, they are soft, flexible and rubbery. This
transition temperature of a polymer is called ‘’glass transition temperature”.

The temperature at which the polymer abruptly transfers from glassy to rubbery state in called Tg

Glassy state Viscoelastic state Viscofluid state

(Hard and brittle) (Rubbery) (Polymer melt)

Tg Tm

Tm is melting point of polymer. The temperature below which it is in rubbery state and above
which it behaves like a viscous liquid is melting point of polymer.
Parameters influencing Tg value:-

i.Flexibility

* The factors which lowering chain flexibility of polymer increases Tg.

* Linear polymer chain made of C-C, C-O and C-N single bonds have higher degree of
freedom of rotation, increases chain flexibility and thus decrease Tg.

* Presence of rigid structures in polymer chain such as aromatic or cyclic structure hinder
freedom of rotation thus lowering of chain flexibility and increase in Tg.

Eg.Tg of polyethylene -1100C

Tg of polystyrene 1000C

ii.Intermolecular forces

Strong intermolecular cohesive forces restrict molecular mobility. This leads to an increase in Tg.

Eg.Tg of polypropylene -180C

Tg of nylon 66 570C

iii.Branching and cross-linking

A high density of branching brings the polymer chains closer, lowers the free volume thus
reducing the chain mobility and resulting in an increase in Tg.

Whereas small branching provides volume for free rotation.Therefore lower Tg value.

iv.Molecular mass:-

The Tg values of all polymers, Increase with molecular weight, because when molecular mass is
high,long polymer chain coil and entangle with one another.This restricts free mobility of chains
and Tg increases.

Significances of Tg

 Tg can be used to evaluate the flexibility of a polymer and predict its response to
mechanical stress.

 Polymers show an abrupt change in their physical properties at their Tg.

COMMERCIALLY IMPORTANT POLYMERS

1. TEFLON [POLY TETRA FLUOROETHYLENE (PTFE)]:

STRUCTURE: -[----CF2-CF2----]n-

PREPARATION

(b) Preparation of polymer (Teflon)

It is obtained by heating the monomer under pressure with ammonium per sulphate as initiator.

n[CF2=CF2] ammonium per sulfate(or)peroxide --[---CF2-CF2-CF2-CF2----]—

PROPERTIES:

(i)It is highly crystalline and orientable polymer.

(ii)It is a linear polymer and a thermoplastic.

(iii)It is a very good insulator and high chemical resistance to almost all solutions.

(iv)It is not wetted by oil or water.

(v)High Boiling Point and high density.

(vi)High thermal stability and mechanical strength.

Teflon is therefore called “wonder plastic”

APPLICATIONS:

(i)It is used as insulating material for motors, generators, coils, transformers and capacitors.

(ii)Anticorrosive coating in army weapons

(iii)As lubricant

(iv)Oil and water do not wet Teflon and this property is used in coating nonstick cooking wears.

2.POLYMETHYL METHACRYLATES(or)Plexi glass or Lucite (PMMA)

PREPARATION
PMMA is obtained when methyl methacrylate is polymerized at 60-70 0C in presence of
hydrogen peroxide.

CH3 CH3

n CH2=C-CH3 polymerization/H2O2 CH2 C CH2 C

COOCH3 60-700C COOCH3 COOCH3

Polymethylmethacrylate

PROPERTIES:

(i)It is hard, fairly rigid material with a high softening point of about 130-140 oC, but it becomes
rubber like at a temperature about 65 oC.It account for the outstanding shape forming properties
of polymethylmethacrylate.

(ii)It has an excellent optical clarity and has a good stability.

(iii)It has low chemical resistance to hot acids and alkalis and low scratch-resistant.

APPLICATIONS:

(i)For making lenses, air craft windows, artificial eyes, TV screens, attractive sign boards etc.

(ii)It is also used for making transparent bottles, tubes etc

POLYMER COMPOSITES:

DEF:A combination of two or more distinct components to form a new class of material suitable
for structural applications is referred to as composite materials.

When one of the components is a polymer, the resulting composite is called a polymer
composite.While each component retains its parent constituents, particularly in terms of
mechanical properties.

PROPERTIES:

(i)They have low density.

(ii)They have high strength to weight ratio.

(iii)They are much stronger and durable than conventional metals like steel and aluminium.
(iv)They are most suitable for aerospace applications due to their light weight.

(v)They have good corrosion resistance.

(vi)Theh have good abrasion resistance and impact resistance.

PRODUCTION OF POLYMER COMPOSITES:

(I)These polymer composites are obtained by suitably bonding a fiber material with a polymer
resin matrix and the same under pressure and heat.

(II)The common fiber material used in polymer composites are glass fiber, boron filament,
carbon/graphite fibers , kevlar etc.

(III)The common resin matrix used are polyesters, epoxy, phenolic, silicon, vinyl derivatives and
polyamides.

(a)Phenolic resins are used wherever resistance to high temperature is needed.

(b)Epoxy resins imparts high mechanical properties.

(c)Silicon resins impart high excellent electrical and thermal properties.

Production of polymer composites involves the following steps

(a)The mould is coated with oil or wax to prevent the final article from sticking to the mould.

(b)The mould is then coated with a resin matrix and over which a precut glass fiber is lide.

(c)Another layer of the resin coating is given over the glass cloth.

(d)Alternative layer of resin and glass cloth are laid in a similar sequence until the required
thickness is built up.

(e)The whole set up is then cured at either normal temperature or elevated temperature.

(f)So formed composite is removed from the mould and subjected to trimming and finishing.

TWO IMPORTANT TYPES OF FIBER-REINFORCED POLYMER COMPOSITE ARE

(I)Kevlar: It is an aromatic polyamide with the name poly(para-phenyleneterepthamide).It is

prepared by condensation reaction of para-phenylenediamine and terepthaloylchloride.

O O
H H
Cl C C N N H
n

poly(paraphenylene terepthalamide)
The linkage through para positions of the phenyl rings gives Kevlar a strong ability to stretch and
hence its extra strength.

Properties and applications:

 It forms even better fibres than non-aromatic polyamides.

 It has high tensile strength and modulus than fibre glass.

 These are used for structures which require stiffness, high abrasion resistance and light
weight.

 Applications include lightweight boat hulls, aircraft fuselage panels, pressure vessels,
high performance race cars, bullet proof vests and puncture resistant bicycle tyres.