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HIGH POLYMER for Engineering

Applications
Module- 4

Dr L Sukanya Ravishankar
CHEMISTRY Professor
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POLYMERS
Polymers are macromolecules built-up by linking a large number of small molecules called monomers.
Ex: Polyethylene, Teflon, plexiglass.

The Monomer can be linked together to generate a polymer. Monomers may be of same type or
different. If all the monomers are of same type, then the polymer formed is called homoploymer. If the
monomers are of different type, then they are called as co-polymers.

homopolymer

Random copolymer

Properties:

1. High strength
2. Light weight and high strength to weight ratio
3. Processing advantage
4. Corrosion resistance
5. Flexible

Uses:

1. Food packing
2. Clothing
3. Home furnishing
4. Transportation
5. Medical devices, etc.

Functionality:-

It is defined as the number of bonding sites or functional group present in a molecule of the monomer.
Depending on the number of bonding sites, the monomers are called bifunctional, trifunctional or polyfunctional.
A simple molecule should possess at least bifunctionality, to undergo polymerization.
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Polymerization

Polymerization is defined as the chemical reaction in which a monomer is converted to the polymer
under specific conditions. All polymerization reactions need suitable initiators.

Degree of Polymerization (DP)

It is defined as the total number of repeating units present in a polymer molecule.

Where ‘n’ is the degree of polymerization.

The molecular weight of a polymer can be calculated using the formula-

Mol. Wt. of polymer= degree of polymerization X mol.wt. of monomer.

CLASSIFICATION OF POLYMERS

Several different methods of classification of polymers are possible. The important methods are given
below.

1. Based on sources.

Polymers

Natural polymers Synthetic polymers (manmade)

(Which are found in nature in animals and plants) (Which are synthesized from simple molecules)

Ex: Starch, cellulose, proteins, silk, jute, Ex: polythene, polypropene, polystyrene,
Wool, rubber, nucleic acids PVC, Bakelite, nylon, polyester etc.

2. Based on mechanism of polymerization

a) Addition polymers: Ex- polyethylene, polypropylene, Plexiglass, PVC, etc.
b) Condensation polymers: Ex- Bakelite, nylon, polyester.
3. Based on thermal behavior
a) Thermoplastics: Ex- polyethylene, PVC, plexiglass etc.,
b) Thermosetting: Ex- epoxy resins, Bakelite, urea-formaldehyde, etc.
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4. Based on chemical structure

a) Linear polymer. Ex: High Density Polyethylene (HDPE)
b) Branched polymer. Ex: LDPE, Polystyrene and PMMA
c) Cross linked polymer. Ex: Bakelite.

5. Based on properties
a) Fibers – wool, silk, cotton, nylon, etc.
b) Plastics- PVC, plexiglass, Teflon, etc.
c) Elastomers-natural rubber, Buna-s rubber, etc.
d) Resins- epoxy resin, urea-formaldehyde

ADDITION POLYMERIZATION (chain polymerization)- preparation, properties and applications of

TEFLON

– Formed by an addition reaction, where many monomers bond together via rearrangement of
bonds without the loss of any atom or molecule is called addition polymerization.

– Teflon-
Polytetrafluoroethylene, better known as Teflon, is made up of a long string of tetrafluoroethylene
monomers. It has structural formula (-CF2-CF2-) and is also a thermoplastic.

CONDENSATION POLYMERIZATION –

Condensation is an intermolecular combination and takes place through different functional groups
having affinity towards each other. Also defined as the reaction occurring between simple polar groups
containing monomers which form the polymer by eliminating simple molecules like NH3, H2O, HCl.
Example: Bakelite

Methods of polymerization

 Bulk polymerization:

This polymerization method occurs in homogenous system. A monomer in the liquid state is
mixed with a small quantity of initiator to form a homogenous mixture. Initiation is carried out either thermally
or photo chemically. The mixture is constantly agitated and heated to the polymerization temperature. Once the
reaction starts, heating is stopped since the reaction is exothermic. The polymer product formed is free from
any contamination and hence can be used without purification.
This method is used for the manufacture of plexiglass, PVC, polystyrene.
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Advantages-

 The product is highly pure

 This method is very simple.
 The conversion factor is very high.
 The products need neither purification nor isolation.

Disadvantages –

 The heat control and the agitation are difficult.

 This method has to carry for relatively less exothermic polymerization reactions.
 As the polymerization progresses, the viscosity increases, the termination becomes difficult and a gel
effect is observed. This phenomenon is called as “gel effect” or “auto acceleration”.

 Solution Polymerization

 Some of the disadvantages of bulk polymerization are eliminated in solution polymerization. In this
method, monomer and the initiator are dissolved in a solvent to form a homogenous mixture. The presence
of solvent facilitates heat and reduces the viscosity build up. The mixture is kept at the polymerization
temperature and constantly agitated. After completion of the reaction, the product is isolated from the
solvent by evaporation or used as such in solution form.

This method is used for the manufacture of PVC, polystyrene, polyethene, polyacrylonitrile.

Advantages-

 The heat control and agitation is easy.

 The viscosity build up is negligible.
 The product obtained can be directly used as adhesive and coatings.

Disadvantages-

 Polymers of high molar mass cannot be formed as the solvent molecules may act as chain terminators.
 The method become costlier since it uses costly solvents.
 The product is contaminated by solvent.
 Requires solvent recovery and recycling.

 Suspension Polymerization-

In this method polymer is produced in a heterogeneous medium. The solvent used in this method is water.
The use of aqueous media facilitates agitation and heat control. The water insoluble monomer is suspended in
water as tiny droplets by continuous agitation. The droplets are prevented from coalescing by using small
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quantities of a water soluble polyvinyl alcohol. The initiator soluble only in the monomer droplets is added and
the mixture is heated and agitated constantly. The method is like bulk polymerization technique. Polymerization
takes place inside the droplet and product being insoluble in water produces spherical pearls or beads of polymer.
Hence the method is also called pearl polymerization. They are isolated by the easy method of filtration, followed
by washing.
This method is used for the manufacture of PVC, polyvinyl acetate, polystyrene.

Advantages-

 The process is cheap since it involves only water instead of solvents.

 Viscosity increase is negligible.
 Agitation and heat control are easy.
 The product isolation is easy since the product is insoluble in water.
 The product is pure.

Disadvantages-

 It is difficult to control the particle size.

 The method can be adopted only for water insoluble monomers.

 Emulsion Polymerization.

MICELLE

The essential ingredients are-

 Water insoluble monomer.
 Water soluble initiator; such as potassium persulfate, H2O2 etc.
 Water.
 Surfactant (emulsifier) such as soap (RCOOH) and detergents (RSO3Na).

Monomer molecules and free-radical initiators are added to a water-based emulsion bath along with soap
like materials known as surfactants, or emulsifier. The surfactant molecules composed of a hydrophilic (water-
loving-head) polar end and hydrophobic (water-hating- tail) non-polar end, form a stabilizing emulsion before
polymerization by coating the monomer droplets. Other surfactant molecules clump together into smaller
aggregates called micelles, which also absorb monomer molecules.
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Mechanism:

I. Aggregation of soap molecules to form ‘micelle’.

II. Initiator forms free radicals in the water, where they may find a few monomers to react with.
III. These radicals diffuse into the micelles and initiate the polymerization in each micelle.
IV. Growing of the polymer chain inside the micelle takesplace. The polymer growth inside the
micelle causes its swelling. The polymer growth continues until the growing chain is
encountered by a radical and gets terminated.
V. The product so formed is isolated either by coagulation using electrolytes or by freezing.

This method is used for the manufacture of PVC, polyvinyl acetate, Teflon, elastomers.

Advantages of emulsion polymerization include:[1]

 High molecular weight polymers can be made at fast polymerization rates.

 Agitation and heat control is easy.
 Molecular weight control is possible.
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Disadvantages of emulsion polymerization include:

 Surfactants and other polymerization adjuvants remain in the polymer are difficult to remove which
decreases the quality of the fabricated wares.
 This method requires rapid agitation.
 For dry (isolated) polymers, water removal is an energy-intensive process
 The polymer needs additional purification.

PREPARATION, PROPERTIES AND APPLICATIONS OF POLYMERS

Epoxy resins
1. Trade name Araldite and Epon
2. Prepared by condensation polymerization of Bis-phenol-A and Epichlorohydrin
3. Reaction is carried out in the presence of alkali

4. The epoxy pre polymer resin so obtained is linear, of low molecular weight and is a soluble liquid.
5. Epoxy resins further cured or hardened at room temperature on mixing with hardeners like diamine,
dicarboxylic acid or acid anhydrides.

Epoxy prepolymer + hardeners cross linked epoxy resins

Properties
Excellent chemical resistance and heat resistance, good mechanical properties and electrical insulating properties,
Highly water resistant, Offers excellent adhesion to surfaces.

Applications:
1. The major use of epoxy resins are as adhesive for joining many surfaces such as glass, metals, wood etc
2. They are used in industrial flooring as skid resistance, highway surfacing and patching materials
3. Used as laminating materials
4. Used in paints and coatings.
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5. Molds made-up of epoxy resins are employed for the production of aircraft and automobile
components.
6. They are used as matrix, towards the fabrication of fibre reinforced plastics.

Polyurethane
Polyurethane (PUR and PU) is a polymer composed of organic units joined by carbamate (urethane, -NH-CO-
O-) links. While most polyurethanes are thermosetting polymers that do not melt when heated, thermoplastic
polyurethanes are also available.

Prepared by the poly addition reaction between diisocyanate and a diol or a triol. During the addition reaction the
H atom of OH group migrates to and adds to nitrogen atom. The presence of extra oxygen in urethane linkage
offers increased flexibility to the polymer chains.
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PROPERTIES

 It offers high mechanically flexibilities.

 It is highly resistant to water, oil and other corrosive chemicals.
 It offers excellent abrasion resistance.
 It has high tensile strength and crystallizes upon stretching.

USE OF POLYURETHANES
Polyurethanes are used in
 Used as gymnasium and dance flooring material.
 Used as surface coatings, films, foams and adhesives.
 PU foams are used as cushions for furniture's and automobiles seating's.
 PU fabrics are used in the manufacturing of swim suits and lightweight garments.
 Used as soles for shoes.
 PU elastomers are used as gaskets, seals, tires and in industrial wheels.

Kevlar
(Poly-paraphenylene terephthalamide – branded Kevlar)
Kevlar is a heat-resistant para-aramid synthetic fiber

Kevlar is synthesized by condensation polymerization of 1,4-phenylene-diamine(para-

phenylenediamine) and terephthaloylchloride in solution medium.

N-methyl-pyrrolidone and calciumchloride are used as solvents.

1,4-diaminobenzene Terephthaloyl chloride Synthesis of Kevlar

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Molecular structure of Kevlar: bold represents a monomer unit, dashed lines indicate hydrogen bonds.
Properties

 Very high tensile strength, five times stronger than steel.

 Kevlar can resist attacks from many different chemicals, however long exposure to strong acids
or bases will degrade it over time.
 Unlike most plastics it does not melt. It is reasonably good at withstanding temperatures and
decomposes only at temperature ≤450°C.
 High tensile strength-to-weight ratio.
 Very low co-efficient of thermal expansion.

Applications

 Bullet proof vests.

 Cut-resistant gloves.
 Kevlar fibers are used in woven ropes and in cables.
 Inner lining for some bicycle tires to prevent punctures.
 Plastic reinforcement for boat hulls, airplanes and bicycles.

Glass Transition Temperature (Tg)

The temperature below which a polymer is hard, brittle and above which it is soft and flexible is called the
glass transition temperature. It is denoted by Tg

The hard, brittle state is known as glassy state. In glassy state, there is no segmental and molecular motion.
Soft flexible state is called the rubbery state. In rubbery state there is only segmental motion but no molecular
mobility.

On heating much above Tg both segmental as well as molecular motion become possible and the
polymer flows like viscous liquid. This temperature is usually called a flow temperature and has no sharp
melting point.
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Parameters affecting Tg value

1. Crystalline:

In crystalline polymers the polymer chains are arranged in a parallel fashion. Each chain is bound to the other
by strong forces like H-bonding, van der walls forces, polar interactions, etc. such type of close packing
imparts has high degree of crystallinity. Hence crystalline polymers have higher Tg than amorphous polymers.

Example: High Density Poly Ethylene (HDPE), PVC are highly crystalline

2. Molecular weight
The Tg value of a polymer is also influenced by its molecular weight. Tg values of all polymers, in general,
increase with molecular weight up to 20,000 and beyond which the effect is negligible.

3. Effect of side groups (Pendant groups):

The presence of side group can change the glass transition temperature.
(a) Bulky pendant groups: the presence of bulky side group, such as a benzene ring, can restrict rotational
freedom, leading to higher glass transition temperature.
As in polystyrene, the presence of benzene ring increases the Tg

Atactic Polypropylene Tg = -20oC

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Atactic Polystyrene Tg = 100oC

(b) Flexible side groups: the presence of flexible pendant groups, for example, aliphatic chains, limits the
packing of the chains and hence increases the rotational motion, thereby lessening the Tg value.

Cross-Linking and branching

The presence of cross-links between chains restricts rotational motion and raises Tg.

Branching – for example, the Tg values of polymethylacrylate, (100 C), polyethylacrylate (-240 C) and
polybutylacrylate (-540C). In this the side chains themselves are flexible and as the side chain length
increases from methyl to butyl, their flexibility also increases. Also as the side chain length increases, they
push the neigbhouring main chains further apart, thereby increasing the free volume and, hence, flexibility.
Therefore Tg value decreases.

4. Plasticizers:

Plasticizers are high molecular weight compounds added to plastics to increase their flexibility and
workability. They weaken the intermolecular forces between the polymer chains and decrease T g. Plasticizers
often are added to semi-crystalline polymers to lower the value of Tg below room temperature. In this case the
amorphous phase of the polymer will be rubbery at normal temperatures, reducing the brittleness of the material.

Significance of Tg:

1. Tg value is a measure of flexibility of a polymer and predict its response to mechanical stress.
2. Its value gives an idea of thermal expansion, heat capacity, refractive index, electrical and mechanical
properties of the polymer.
3. Knowledge of Tg is useful in choosing the right temperature for fabrication of material.
4. Tg value helps us to understand, whether the given polymer is flexible or rigid at the given temperature.

DETERMINATION OF MOLECULAR WEIGHT OF POLYMERS

Molecular weight(MW) of macromolecules(polymers) are always expressed as an average, while,
MW of small molecules are always definite.
i.e.,MW of NaOH is 40, while PVA is 80000–100000.
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Polymers normally contain a mixture of chains, with different lengths or different degree of
polymerization. Thus, it is not possible to assign a definite MW to polymers.
Consequently, different statistical(averaging) methods are adopted to determine the MW of
polymers.
The three important averaging methods adopted are;
Determination of MW, using number averaging technique.
Determination of MW, using weight averaging technique.
Determination of MW, using viscosity averaging technique.
The MW of polymer is however named after the technique adopted towards its determination, thus we
have 3 types of molecular weights namely; Number average MW; Weight average MW and Viscosity
average MW

̅̅̅̅̅)
Number average molecular weight (Mn) or (𝑴𝒏

 The number average molecular weight is defined as the total molar masses of polymer divided
by the total number of molecules in the mixture.
 The number average molecular mass is determined by the measurement of colligative
properties.
 The number average molecular mass is a good index of physical properties such as “impact”
and tensile strength.

Where, Ni is the number of molecules having molecular weight Mi units.

𝑛1𝑀1+𝑛2𝑀2+𝑛3𝑀3+𝑛4𝑀4
Mn= 𝑛1+𝑛2+𝑛3+𝑛4

W=NM, W1=N1M1, W2=N2M2

̅̅̅̅̅)
Weight average molecular weight (Mw) or (𝑴𝒘

 Weight average molecular mass is the mass obtained when sum of the products of
total mass of group of molecules (Having different molecular masses) and their
respective molecular masses are divided by total mass of all the molecules.
 This type of molecular weight is determined by light scattering and ultra-
centrifugation techniques, which essentially measure molecular size.
 The weight average molecular mass is always greater than the number average
molecular mass.
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 Therefore, ratio of these two is greater than one. This ratio is called distribution
index or “Polydispersity index”(PDI).

The weight average molecular weight depends not only on the number of molecules present, but also on
the weight of each molecule. To calculate this, Ni is replaced with NiMi.

In mixture, if w is the mass of polymers with molar mass M1, w2 with molar mass M2… up to wi with
molar mass Mi then,

𝑤
But number of moles N=𝑀 and w=NM, therefore replacing wi by Ni ,

Conducting polymers

An organic polymer with highly delocalized pi-electron system (or conjugated double bonds) having
electrical conductance of the order of conductors are called conducting polymers.

Polyaniline

Conducting polyaniline
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Conducting polyacetylene

Polyacetylene consists of chains of hundreds to thousands of carbon atoms linked by alternating single and double
bonds. They conduct electricity when doped with oxidizing or reducing agents or protonic acids. Conductivity of
pure polyacetylene is about 4.4 X 10-5S/cm.

Mechanism:
1. Oxidative doping (p-doping)

In this process, pi-backbone of polymer is partially oxidized using a suitable oxidizing agent. This creates
positively charged sites on polymer backbone, which are current carriers for conduction. The oxidizing agents
used in p-doping are iodine vapour, iodine in CCl4, HBF4, perchloric acid.

a. The oxidative dopant such as iodine is added.

b. It takes away an electron from the pi- backbone of the polyacetylene chain and creates a positive hole on one
of the carbon.

c. The other pi electron resides on the other carbon making it a radical

d. The radical ion formed is called polaron

e. A dipolaron ( solitron) is formed on further oxidation

f. These radicals migrate and combine to establish a back bone double bond.

g. As the two e- are removed the chain will have two positive centers

h. The chain as a whole is neutral but holes are mobile and when potential is applied they migrate from one
carbon and account for conductivity.
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Reductive doping [n-doping]:

In this process, pi-backbone of polymer is partially reduced using a suitable reducing agent.
This creates negatively charged sites on polymer backbone, which are current carriers for
conduction.