UNIT: IV POLYMERS

POLYMERS

Polymer is the word derived from two Greek words

Poly=many; Mers=units

Polymer: - Polymer is a macromolecule built up by the linking together of large no

of smaller molecules called monomers.

Ex: Polythene is a polymer formed by linking together of large [Link] Ethene

molecules.

Monomer: The Small Molecule which combines with each other to form polymer
molecules are known as monomers.

Degree of polymerization: The number of repeating units in a polymer chain is

known as the degree of polymerization.

Depending upon the degree of polymerization there are two types of polymers.

1. Oligo polymers: Those polymers whose degree of polymerization is less than

600 are called oligo polymers.
2. High polymers: when the degree of polymerization is more than 600 it is
called high polymer.

Functionality of monomer: The number of reactive sites in a monomer is called

functionality of the monomer.

If two reactive sites are there in a monomer then it is called bifunctional, then it
gives straight chain polymer.

If three reactive sites are there in a monomer then it is called trifunctional, then it
gives branched chain polymer.

Glycol (Bifunctional) Glycerol (Trifuctional)

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Classification of polymers:

Polymers can be classified in several ways

i. Based on structure: on the basis of structure polymers can be classified into three types

1. Liner chain polymers: in this polymers monomers are joined together in a chain

-M1- M1- M1- M1- M1- M1- M1-

Eg: poly ethylene, nylon etc.

2. Branched chain polymers: in these polymers the chain of polymer contains branches of
monomers

-M1- M1- M1- M1- M1- M1- M1-

M1

M1

3. Cross-linked polymers: in the cross – linked polymers monomers are cross-linked

together in all the three dimensions.

-M1- M1- M1- M1- M1-

-M1- M1- M1- M1- M1-

ii. Based on the types of monomer: On the basis of type of monomers polymers are
classified into two types

1. Homo polymers: these are formed by the polymerization of same type of monomers
-M1- M1- M1- M1- M1- M1- M1-
Eg: PE, PVC etc
2. Co-polymers: when two or more types of monomers are joined then the polymer is
called co-polymer.

-M1- M2- M1- M2- M1- M2- M1-

Eg : Bakelite

iii. Based on Tacticity of polymers:

The arrangement of functional groups on carbon back bone of the polymer is called tacticty
of the polymer. Depending on the tacticity, there are three different types of polymers.

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Isotactic polymers: Those polymers in which the functional groups are arranged on the
same side of carbon back bone are called isotactic polymers
Ex: Poly vinyl chloride.

Atactic polymers: When there is no regular arrangement of functional groups on the back
bone of the polymer chain, then it is called atactic polymer.
Ex: Poly vinyl chloride.

Syndiotactic polymers: The polymers with alternate arrangement of functional groups

are called syndiotactic polymers.
Ex. Poly vinyl chloride.

Polymerisation: - It is defined as the process of linking or joining together smaller molecules i.e
monomers to make large molecule.

There are mainly two types of polymerisation reactions.

I. Chain polymerisation (or) Addition Polymerisation.

II. Step polymerisation (or) Condensation polymerisation.

I. Chain polymerisation (or) Addition polymerisation:

A chain Polymarisation is a reaction that yields a polymer product which is exact multiple of
monomers. Thus the mechanism is also called addition polymerisation.

Characteristics:

 The functionality of the monomer is two or bifunctional.

An initiator is required to start the polymerisation reaction.

 The polymerisation takes place by self-addition of the monomer molecules to each other.


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 The conversion of “=” to” –“takes place during the polymerisation liberating
20 Kcal/mole of energy. Hence it is exothermic reaction.


The molecular weight of the polymer is the exact multiple of the monomers.
This mechanism is carried out in three steps. i.e.


i) Initiation. ii)Propagation. iii)Termination.



Chain polymerisation is of three types

1. Free radical chain polymerisation.

2. Ionic chain polymerisation.
3. Co-ordination chain polymerisation.

1) Free radical chain polymerisation: The homolytic fission of a bond gives free
radicals

a.)Initiation: Initiators are unstable compounds and undergo homolytic fission to

produce free radicals which reacts with π electrons of the monomer to produce
monomer free radicals.

Monomer free radical

b.) Propagation: The monomer free radicals react with a number of monomers
rapidly resulting the chain growth with free radical site at the end of the chain
producing a living polymer.

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By adding fresh monomer to the living polymer with free radical site again chain
growth starts. Hence it is known as living polymer

c) Termination

Self-termination: In this step one growing polymer combine with other growing
polymer produce a dead polymer.

Dead polymer

II. Step polymerisation (or) Condensation polymerisation:

Step polymerisation takes place by condensation reaction of the functional groups

of the monomers, hence known as condensation polymerisation.

Characteristics: -

The monomers contain functional groups like -OH, -COOH, -NH2, -RCOORI,
Halides etc.


The functionality of the monomer must be two (or) more than two.
The polymer is built up by a slow stepwise condensation reaction of the


functional groups of the monomer.



The polymerisation reaction is accompanied by the elimination of bi products

like HCl, CH3OH, H2O etc.


The reactions are not exothermic.

The molecular weight of the polymer is not the sum of the molecular weights


of the monomers.


The polymers produced are living polymers containing functional groups at

the end of the chain.


Ex: The polymerisation of a diacid with diol produces Terylene.

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 Terepthalic acid Ethylene glycol
Terylene

Plastics:

Plastics are the organic materials of high molecular weight which can be moulded
into any desired form, when subjected to heat and pressure in the presence of a
catalyst.

The term plastic must be differentiated from the resin. Plastic and resin are
considered as synonymous.

Resin: The product formed by polymerisation is ‘Resin’

Plastics characterized by the following properties:

Light weight and high strength to weight ratio.

Good thermal and electrical insulation.


High corrosion resistance.



High chemical inertness.



Low maintenance cost.



Some plastics have special properties like transparency, shock absorbing



capacity, etc.


Depending upon activity towards heat plastics are classified as two types.

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 Thermoplastic resins Thermosetting resins
1. These resins become soft on
heating and rigid on cooling. 1. This resin doesn’t respond to heat.

2. These resins are formed by chain 2. These resins are formed by step
Polymerisation. Polymerisation.

3. These resins are made of long 3. These resins have three

chains attached by weak dimensional network structures.
vanderwaal’s force of attraction.
4. The resins are not easily soluble in
4. The resins are soluble easily in organic solvents.
some
4. 5. These are not Eco-Friendly.
The resins are not easily soluble in
Organic solvents. 6. Thermoset resins are hard strong
and more brittle.
5. These are Eco-Friendly plastics.
7. The scrap of the plastic cannot be
6. Thermoplastic resins are soft weak reused.
and less brittle.
8. These plastics cannot be reclaimed
7. The scrape of the plastic can be from wast.
reused.
Ex: Bakelite, Nylon, Epoxy Resins
8. These plastics can be reclaimed etc..
from waste.

Ex: PE, PVC, PS, Teflon. Etc…

Poly vinyl chloride (PVC):

Poly vinyl chloride is produced by free radical chain polymerisation of vinyl

chloride in presence of benzoyl peroxide or hydrogen peroxide.

Properties:

PVC is a colorless, non-inflammable and chemically inert powder.

It has specific gravity 1.33 and melting point 148oc.



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 It is resistant to atmospheric conditions.
PVC is strong and brittle.


It is resistant to atmospheric conditions like O2, CO2 and moisture.



PVC is not stable to heat and [Link], it undergoes degradation.




Applications:

PVC treated with plasticizers is called plasticized PVC.

Plasticized PVC is used for electrical insulations, injection moulding articles


like tool handles, radio and telephone components, cameras and aircrafts.


Un plasticized PVC is rigid, highly resistant to chemicals and brittle.

This PVC is used for making safety helmets, refrigerator components, tyres,


cycle and motor cycle mudguards.



TEFLON (Poly tetra fluoro ethylene) or Fluon:-

TEFLON is obtained by the chain polymerisation of tetrafluoro ethylene in

presence of Benzoyl peroxide as an initiator.

Properties:-

Due to presence of highly electronegative Fluorine atoms, TEFLON has got

High melting point and High density.


It is very strong, hard polymer that can be machined to drilling, punching

etc.


It has high melting point (>350oc).

TEFLON is very good electrical insulator.


It possesses high density 2.1 – 2.3 gm/cc.




Applications:

TEFLON is a very good insulating material for motors, transformers, cables,

wires, etc.


 It is used for making gaskets, pump parts, tank linings etc.

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 Due to its extreme chemical resistance, it is used for making chemical carry
pipes.


Non-lubricating bearings and non-stick stop cock for burettes are made from
TEFLON.


 It is used for coating as impregenating glass fiber, asbestos fibers.

Bakelite or (Phenol- Formaldehyde Resin):

Bakelite is an important Thermoset resin. It is prepared by the step polymerisation

of phenol with formaldehyde in presence of an acid or alkali as a catalyst.

The polymerisation takes place in three stages:

Stage-i:

Phenol is made to react with formaldehyde in presence of acid/alkali to produce

mono, di, tri methylol phenols depending on the phenol formaldehyde ratio (P/F
ratio)

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Stage-ii:

The mono, di, and tri methylol phenols are heated to produce two types of straight
chain resins by condensation of the methyl group with hydrogen atom of benzene
ring or another methyl group.

Stage iii:

This stage of preparation includes heating of ‘A’ stage resin and ‘B’ stage resin
together which develops cross linking and produce Bakelite plastic resin.

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Properties:-

Bakelite is hard, rigid and strong, it is a scratch resistant and water resistant
polymer.


It is resistant to chemicals but it is attacked by alkalis due to presence of OH

group.


Bakelite is an excellent electrical insulator and has very good corrosion

resistance.


It is a good anion exchange resin, exchanges –OH group with any other
anion.


Applications:

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 It is used for making electrical insulator parts like switches, heater handles.
It is used for moulded articles like telephone parts, cabinets for radio and


television.


It is used for making bearings used in propeller shafts, paper industry and
rolling mills.


 It is used in paints and varnishes

Nylon 6:6

Nylon 6:6 is produced by the co-polymerisation of hexamethylene diamine with

adipic acid.

Properties:

Nylon possesses high strength, hardness and high melting point. The high
melting point of the nylon is due to the hydrogen bonding between the


hydrogen atom of the amide group and oxygen of c = o groups.

Nylon possesses good chemical resistance and electrical resistance.
Nylon possesses good resistance to environmental conditions.


They are good insulators.




Applications:

The major application is in the textile industry.

Because of its high thermal and abrasion resistance nylons are used in


mechanical engineering applications like gears, bearings etc..



Flexible tubings for conveying petrol etc are made from nylons.
Nylons are used as electrical insulators.


Nylon 6 is used for making tyre cords.



Nylons are used in automobile industry and telecommunication industry for



making radiator parts and coil formers respectively.



Terylene:

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 Terepthalic acid Ethylene glycol
Terylene

Properties:

as it is a strong fiber, bleaching or dry cleaning agents have no effect on it

it absorbs very little quantity of water; it dries up quickly


it is stable at high temperature



it is resistant to acid and bases due to insolubility in most organic solvents




Uses:

it is used in making of plastic bottles

terylene is widely used in textile industry



Rubbers:

Those polymers which possess the property of elasticity are called rubber. The
elasticity of rubber is due to its coiled helix structure. Based on origin rubbers are
of two types

1. Natural rubbers.
2. Synthetic rubbers or Elastomers.

1. Natural rubber:

The rubber obtained from natural source is called natural rubber. Natural rubber
is processed from the cell sap of three main types of trees. 1. Hevea brasiliensis
[Link] [Link] percha found in tropical and semi-tropical countries.

The main composition of natural rubber is polyisoprene, which is in the form of

long coiled chains, responsible for the elasticity of natural rubber as shown.

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Processing of natural rubber:
 Natural rubber is made from latex
 Latex is collected by making diagonal cut on the outer layer of rubber tree (Hevea
brasiliensis).
 The latex looks like a milky colloidal suspension contains 30-40% of Rubber and 55-70% of
water.
 The Latex is diluted with water and an enzymatic hydrolysis is done.
 After completion of the reaction, formic acid/Acetic acid is added to the reaction mass to
get the precipitate of raw natural rubber.
 The precipitated raw natural rubber is separated from the reaction mass and passed
through rollers to get sheets of rubber.
 Wet grinded natural rubber is dried to get pure natural rubber.
 Rubber sheets are finally dried by smoking. This rubber is called smoked rubber.
 During coagulation of rubber, sodium bisulphate is also added to prevent the oxidation of
rubber. This is called Creep rubber.

Draw backs of natural rubber

 It is soft at high temperature and hard; easily broken at low temperature. Its usage
temperature range is very limited. It becomes hard and brittle during winter. It becomes
soft and sticky during summer.
 Weak and low tensile (means extension) strength (200 Kg/Cm2).
 It absorbs more water.
 It is not stable in mineral oils, solvents and oxidizing agents. It swells up in oils.
 Its shape is completely spoiled under outside force.
 When stretched to greater extent, it suffers from permanent deformation.
 It is not durable
 It possesses tackiness (under pressure two sheets becomes one)

introduced by Charles Good in 1839

 The properties of natural rubber are improved by Vulcanization process which is

Vulcanization of rubber
 The vulcanization changes natural rubber into a heavily cross-connected and hard
thermosetting polymer.
 When raw rubber is heated with sulfur at 140-1800C, it becomes high quality rubber. This
process is called vulcanization. The suphur forms cross links between the chains of the

Compounding and Vulcanization of Rubber:

rubber molecules.

1. Vulcanisers: The most important vulcaniser is sulphur. When sulphur was

added to rubber it combines chemically at the double bonds of the different
chains producing sulphur cross linking and imparts strength.

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 The percentage of sulphur added for vulcunisation is in the range of 1 to
35%. If the percentage of rubber is more than 32, that rubber is called
ebonite rubber

2. Plasticizers:-
Plasticizers impart plasticity to the rubber. The commonly used plasticizers
are vegetable oils, waves etc.
3. Accelerators:-
Accelerators catalyses the vulcanization process by reducing the time
required for vulcanization. Magneisa and white lead are used as
[Link], 0.5 to 1% of accelerators are added.
4. Anti oxidants:-
They retard the deterioration of rubber by light and air. Complex organic
amines like phenyl napthyl amine, phenolic substances and phosphites are
added as antioxidants.
5. Reinforcing agents:-
They give strength, rigidity, and toughness to the rubber. Commonly used
reinforcing agents are Zno, Mgco3, Baso4, and caco3.
6. Coloring agents:-
They impart desired color to the rubber as Ferric oxide – Red color, Lead
chromate – Yellow, carbon black – black, and Titanium dioxide – white.

The natural rubber processed, is mixed with the different compounding and
vulcanizing material after grinding as a mix it is converted to sheets by passing
between rolls.

Advantages of vulcanization:-

Vulcanized rubber has good tensile strength and load bearing capacity.
Vulcanized rubber has higher resistance to oxidation and atmospheric gases


like CO2 , O2, moisture, light and u.v radiation



Vulcanized rubbers possess good impact resistance.

Vulcanized rubber has good elasticity depending on the extent of


vulcanization.


Vulcanized rubber is a good electrical insulator and ebonite is a best

electrical insulator.


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Properties of Natural rubber:

Natural rubber is a strong and tough engineering material.

Natural rubber is resistant to atmospheric conditions, water, dilute acids


and bases.


Natural rubber is not attacked by organic solvents, petrol, CS2 ,CCl4,

Turpentine etc .


 Rubber reacts with chlorine to give chlorinated rubber.

Applications of Natural rubber:

The major application of natural rubber is in the manufacture of tyres.

It is used for preparing V belts for power transmission.


The tank linings in chemical plants where corrosive chemicals are stored are


prepared from rubber



To reduce machine vibrations, rubber is used for sandwiching between two

metal surfaces.


Foamed rubber is used for making cushions, mattresses etc.

Toys and sports items are manufactured from natural rubber.



Synthetic rubbers (or) Elastomers

Synthetic rubbers are called Elastomers, because they are characterized by the
property of elasticity.

BuNa-S: it is also called styrene rubber or GRS.

BuNa – s stands for the composition of monomers and catalyst.

Bu – Stands for Butadiene

Na – Stands for Sodium Catalyst

S – Stands for Styrene

BuNa – s is prepared by the co-polymerisation of butadiene with styrene using

sodium as catalyst.

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Properties:

Styrene rubber is strong and tough polymer.

BuNa-s Possess excellent abrasion resistance.


It is vulcanized by sulphur mono chloride (S2Cl2)



It is good electrical insulator.



Styrene possess high load bearing capacity




Applications:

 Major application of styrene rubber is in the manufacture of tyres

 It is used in the foot wear industry for making shoe soles and footwear
components.
 It is also used for making wire and cable insulations.

Butyl Rubber:

Butyl rubber is also known as GR – I, Produced by copolymerization of isobutene

with 1-5% of isoprene of anhydrous aluminum chloride in methyl chloride as a
catalyst.

Properties:

 It is a strong and tough synthetic rubber with low permeability to air and
other gases.
 Butyl rubber can be vulcanized with sulphur but it possesses low hardness
due to less number of double bonds.
 Butyl rubber has excellent resistance to heat, abrasion and chemicals.

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Applications:

 Butyl rubber is used for making cycle tyres and automobiles tubes.
 It is used for making automobile parts, and conveyor belts.
 It is used as an insulator for high voltage wire and cables

Thiokol rubber/polysulphide rubber or GRP:

Thiokol rubber is prepared by the co-polymerisation of sodium polysulphide

(Na2S4) and Ethylene dichloride.

Properties:

 Thiokol rubber possesses strength and impermeability to gases.

 Thiokol rubber cannot be vulcanized and it cannot form hard rubber.
 It possesses extremely good resistance to mineral oils, fuels, oxygen,
solvents, ozone and sunlight.
 Thiokol rubber possesses low abrasion resistance.

Applications:

 Fabrics coated with Thiokol are used for barrage balloons, life rafts and
jackets which are inflated by CO2.
 Thiokol is used for lining hoses for conveying gasoline and oil.
 It is used for making gaskets and seals for printing rolls.

Conducting polymers

The polymers which conduct electricity is called conducting polymers. The

conduction of the polymers may be due to unsaturation or due to the presence of
externally added ingredients in them.

The conducting polymers can be classified in the following way.

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 Conducting polymers

Intrinsic conducting polymers Extrinsic conducting polymers

Intrinsic polymer Doped conducting Conductivity Blended

conducting with conjugation Polymer Element
polymer

Doped conducting polymers:-

The conductance of a polymer can be increased by introducing a positive charge or

negative charge on polymer backbone by oxidation reduction. This process is
similar to semiconductor technology and is called doping.

Doping is two types:-

1. Creating a positive site on polymer backbone called p-doping.

2. Creating a negative site on the polymer backbone called n-doping.

Doping and conductivity of polyacetylene

P-doping: -

P-doping is done by oxidation of a conducting polymer like polyacetylene with a

Lewice acid or iodine vapor.

This is also called oxidative doping.

1.

2.

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In the above reaction the Iodine molecules attract an electron from polyacetylene

chain and become now the polyacetylene becomes positively charged and
termed as radical cat ion or polaron.

The polarons on doping forms solitions i.e . Further oxidations of polaron give
solitions.

The delocalized charges of solition are responsible for the transport of charge
along the polymer chain.

N-doping:

N-doping is carried out by reduction process by the addition of an electron to

polymer backbone by using reducing agents like sodium naphtalide Na+(C10H8).
Formation of polaron, bipolaron takes place in two steps, followed by
recombination of radical which yields two charge carriers on the polyacetylene
chain responsible for conduction as shown below

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The electron added to polyacetylene by reductive doping doesn’t go into the
conductivity band but goes into an intermediate electronic state within the band
gap of radical anion (polaron).

The bi anion lowers the energy by segregating into two negative solitions at the
mid gap energy levels. This leads to the generation of conduction pathways. As a
consequence, the conductivity increases significantly.

Applications of conducting polymers: -

 The conducting polymers are used in rechargeable batteries, small in size

producing current density up to 50 mA/cm2
 Conducting polymer are also used for making analytical sensors for pH
 The conducting polymers are used for making ion exchangers. These
membranes made of conducting polymers show selective permeability for
ions and gases hence they are used for control release of drug.
 The conducting polymers are used for making electric displays and optical
fibers; they are used for electron beam lithography.
 The conducting polymers are applicable in photovoltaic devices.

Biodegradable polymer

The polymer which can be degraded by the enzymatic action of naturally occurring
microorganisms and bacteria are called biodegradable polymers.

The basic requirement of the biodegradable polymers should be

 Production of non-toxic products.

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  Capable of maintaining good mechanical integrity until degradation.
 Controlled rates of degradation.

The biodegradable polymers are classified as naturally occurring and synthesized polymer.

1) Naturally occurring biodegradable polymer:

Examples:

1. Polysaccherides – e.g. starch and cellulose.

2. Proteins – e.g. gelatin, silk, wool.
3. Polyesters – e.g. polyhydroxy alkanoates
4. Other – e.g. natural rubbers.

2). Synthetic biodegradable polymers:

Examples:

1. Poly lactic acid

2. Poly vinyl alcohol

3.16.1. Poly lactic acid (or) polylactide (PLA)

Poly lactic acid is a biodegradable thermoplastic polyester belonging to the class of poly
hydroxy alkanoates, derived from renewable source such as Starch or Sugarcane

Industrially PLA is produced by microbial fermentation of sugar or glucose. It is processed

mainly by injection molding and extrusion molding into films.

Properties: -

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 PLA polymer is thermoplastic and is stable to U.V radiations
 PLA possess good melting point 173-1780 c
 The crystallinity lies in the range of 70%.
 PLA possess good biocompatibility as well as high strength
 PLA is a chiral compound existing as poly L-lactic acid.
 PLA possess good resistance to moisture.

Applications: -

The potential application of PLA is in the medical and pharmaceutical industries like
fixation and orthopedic applications, skin substitutes, bone graft substitutes etc.

Preparation of Poly vinyl alcholo (PVA)

Polyvinyl alcohol is prepared from hydrolysis of polyvinyl acetate.

Properties: -

 It is belonging to the class of vinyl polymers.

 It is water soluble.
 Possess excellent mechanical properties.

Applications:

 PVA is used in variety of medical applications because of its biocompatibility.

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  PVA is used in cartilage replacement, contact lenses and eye drops
 PVA is used in household sponges that absorb more water

Prepared by:
[Link]
[Link] Chemistry
Basic sciences & Humanities
Padmasri dr [Link] Institute of technology

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