Engineering Chemistry(PTCY3151)

Regulation 2023 (PT)

Unit 1 – Polymer Chemistry
Polymer - Polymers are large chain molecules having a high molecular weight in the range of 103 to 107. These are made
up of a single unit or a molecule, which is repeated several times within the chained structure. The process by which the
simple molecules (monomers) are converted into polymers is called polymerization. For example, many ethylene
molecules combine to form a giant molecule of polythene.

Monomer Name Monomer Formula Polymer Name Polymer Formula Properties Uses
ethylene CH2=CH2 Polyethylene (low density (LDPE)) –(CH2-CH2)n– soft, waxy solid film wrap, plastic bags
electrical insulation, bottles,
ethylene CH2=CH2 Polyethylene(high density (HDPE)) –(CH2-CH2)n– rigid, translucent solid
toys
atactic: soft, elastic solid similar to LDPE carpet,
propylene CH2=CHCH3 Polypropylene((PP) different grades) –[CH2-CH(CH3)]n–
isotactic: hard, strong solid upholstery
vinyl chloride CH2=CHCl Poly(vinyl chloride) (PVC) –(CH2-CHCl)n– strong rigid solid pipes, siding, flooring
vinylidene chloride CH2=CCl2 Poly(vinylidene chloride)(Saran A) –(CH2-CCl2)n– dense, high-melting solid seat covers, films
hard, rigid, clear solid toys, cabinets, packaging
styrene CH2=CHC6H5 Polystyrene(PS) –[CH2-CH(C6H5)]n–
soluble in organic solvents (foamed)
high-melting solid soluble
acrylonitrile CH2=CHCN Polyacrylonitrile(PAN, Orlon, Acrilan) –(CH2-CHCN)n– rugs, blankets, clothing
in organic solvents
non-stick surfaces,
tetrafluoroethylene CF2=CF2 Polytetrafluoroethylene(PTFE, Teflon) –(CF2-CF2)n– resistant, smooth solid
electrical insulation
Poly(methyl methacrylate)(PMMA, Lucite, lighting covers, signs,
methyl methacrylate CH2=C(CH3)CO2CH3 –[CH2-C(CH3)CO2CH3]n– hard, transparent solid
Plexiglas) skylights
vinyl acetate CH2=CHOCOCH3 Poly(vinyl acetate)(PVAc) –(CH2-CHOCOCH3)n– soft, sticky solid latex paints, adhesives
requires vulcanization for
isoprene CH2=CH-C(CH3)=CH2 cis-Polyisoprene(natural rubber) –[CH2-CH=C(CH3)-CH2]n– soft, sticky solid
practical use
synthetic rubber, oil
chloroprene CH2=CH-CCl=CH2 Polychloroprene (cis + trans)(Neoprene) –[CH2-CH=CCl-CH2]n– tough, rubbery solid
resistant

Monomer : A monomer is the single unit or the molecule which is repeated in the polymer chain. It is the basic unit
which makes up the polymer.

Macromolecules : Macromolecules are very large molecules that are formed by the polymerization of smaller molecules
called monomers. Examples are Carbohydrates, Nucleic acid, Proteins & Lipids

Polymerization - Polymerization is a process in which large number of small molecules (called monomers) combine to
give a big molecule (called a polymer) with or without elimination of small molecules like water.

Degree of Polymerization - The number of repeating units (n) in a polymer chain is known as degree of polymerization
in other words the functionality of a monomer or its degree of polymerization determines the final polymer that will be
formed due to the combination of the monomers. The number of reactive bonds or groups that are available for coupling
will determine whether the monomer will be mono-, bi-, tri-, or polyfunctional. . It is represented by the following
relationship.

Degree of polymerization(n), DPn = Molecular weight of the polymeric network / Molecular weight of the repeating unit

Examples –

1) LDPE= 20,000 amu, Molecular weight of Polyethylene= 28.05 amu

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DPn= 20,000/28.05 amu
DPn=713
2) HDPE= 3,00,000 amu, Molecular weight of Polyethylene= 28.05 amu
DPn= 3,00,000 /28.05 amu
DPn=10,695
3) Polystyrene = 50,00,000 amu, Molecular weight of Polyethylene= 104.15 amu
DPn= 50,00,000 / 104.15 amu
DPn=48,007

Monofunctional or unifunctional - When a single reactive group is present in the monomer molecule, then it is termed
as monofunctional or unifunctional. However, a monofunctional group cannot lead to the propagation of a polymer chain.
For example , in carboxylic acid, CH3COOH, the –COOH group is the monofunctional group.

Bifunctional - When two reactive groups are present in the monomer molecule, then it is termed as bifunctional. More
often than not, polymerization reaction with bifunctinal groups occur when a double bond splits to couple with another
double bonded monomer. If a double bonded molecule is present, then the polymer would be –

Trifunctional - When a monomer contains three groups that are reactive, then it is termed as trifunctional.It is important
to note that a trifunctional polymer may be a mixture of monofunctional and bifunctional monomer structures.

Let us consider the reaction of phenol and formaldehyde to form trimethyl phenol. In the figure , the three formaldehyde
molecules contain three reactive groups in the form of -OH groups. These reactive groups get attached to the positions 1,
2 and 3 in the phenol molecule.

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Types of Polymers based on Degree of Polymerization

(a) Oligopolymers Polymers with low degree of polymerization are called ‘oligopolymers’.
(b) Macromolecules Polymers with a high degree of polymerization are called ‘high polymers’. They have very
high molecular weights (104–106) and hence are called macromolecules

Classification of Polymers
• Classification of polymers based on Source
• Classification of polymers based on Structure
• Classification of polymers based on Synthesis
• Classification of polymers based on Intermolecular Forces

Classification of polymers based on Source – Polymers based on its source/origin are of two types:
(a) Natural Polymers (b) Synthetic Polymers

(a) Natural Polymers - They are polymers that occur in nature. For example, starch (polymer of a-D-glucose),
cellulose (a polymer of b-D-glucose), proteins (polymer of a-amino acids) and natural rubber (a polymer of
poly-cis-isoprene).

(b) Synthetic Polymer - It is a polymer that is prepared artificially in the laboratory. For example, polyethylene
(PE), polyvinylchloride (PVC), nylon, terylene, bakelite, synthetic rubber, etc.

Classification of polymers based on Structure – Polymers based on its structure are of three types:
(a) Linear Polymers (b) Branched Polymers (c) Cross-linked Polymers

(a) Linear polymer - It has no branching other than the pendant groups associated with the monomer. Linear
polymers are well packed and therefore have high densities. For example, polythene, nylons and polyesters.

(b) Branched polymers - These are polymers in which the monomers are joined to form long chains with side
chains or branches of different lengths. They are irregularly packed and have low densities. If the side chain
is different from parent chain, they are called graft polymers. For example, low-density polyethene,
glycogen, etc.

(c) Cross-linked polymers - These are polymers in which the monomer units are linked together to form a three-
dimensional network. These polymers are hard, rigid and brittle. They are also called network polymers. For
example, bakelite, vulcanised rubber, etc.

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Classification of polymers based on Synthesis – Polymers based on its synthesis are of two types:
(a) Addition Polymers (b) Condensation Polymers

(a) Addition Polymer – Those polymers that are obtained by the addition of monomeric units are called addition
polymers. The molecular weight of such a polymer is an exact multiple of the molecular weight of the
monomer.

n (monomer) ----------> polymer

Molecular weight of polymer = n × molecular weight of monomer.

For example, polyethene, PVC, etc.

(b) Condensation polymers - A polymer formed by the condensation of two or more than two monomers with
the elimination of simple molecules like water, ammonia and hydrochloric acid is termed as a condensation
polymer. The molecular weight of such a polymer is not an exact multiple of the molecular weight of the
monomer. For example, Nylon 66 is obtained by the condensation of two monomers, hexamethylenediamine
and adipic acid with the loss of water molecules.

Classification of polymers based on Intermolecular Forces – Polymers based on its intermolecular forces are of four
types:

(a) Elastomers (b) Fibres (c) Thermoplastics (d) Thermosetting Plastics

(a) Elastomers - They are polymers held by weakest intermolecular forces and have elastic behavior. For example,
natural rubber. These can be stretched to at least thrice of their original length but return to their original
shape and dimension as soon as the stretching force is removed.

(b) Fibres - These are polymers whose polymeric chains are held together by strong intermolecular forces like
hydrogen bonds or dipole–dipole interactions. They are crystalline in nature and have high tensile strength.
For example, nylon 66, polyster, silk, etc.

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 (c) Thermoplastics - They are linear, long-chain polymers that soften on heating and harden when cooled. The
intermolecular forces of these polymers are intermediate between those of elastomers and fibres. There is
no cross-linking between the polymeric chains. They can be processed again and again.
For example, polyethene (PE), polystyrene, PVC, teflon, polypropylene, etc.

(d) Thermosetting Plastics - They are polymers that can change irreversibly into hard and rigid materials on
heating and cannot be reshaped once they set. They form hard, infusible, insoluble products because of cross-
linkages. For example, bakelite, melamine, etc.

Mechanism of Polymerization
There are two types of polymerization processes:

1. Addition polymerization or chain polymerization

2. Condensation polymerization

1. Addition polymerization or chain polymerization - In this type of polymerization, the monomer molecules
are added to each other without the formation of any byproduct. The elemental composition of polymer is
similar to that of the monomer and its molecular weight is an exact multiple of the molecular weight of the
original monomeric molecule.

Bifunctional molecules like ethylene, propylene (olefins), vinyl compounds and allyl compounds generally
undergo this type of polymerization. As majority of these monomers fall under the ‘vinyl’ category; hence,
chain polymerization is also customarily termed as ‘vinyl polymerization’.
Addition polymerization consists of three important steps

(a) Chain initiation - This step involves the formation of active molecules called chain initiators.

These chain initiators then attack the monomer to initiate the chain formation.

(b) Chain propagation - The initiated chain then attacks more monomeric molecules leading to the increase in
the length of the chain.

Hence the polymeric chain propagates.

(c) Chain termination - The active centers are removed, or they combine with each other and the chain
propagation comes to an end.

The addition polymerization reaction can take place by three methods.

1. Free radical mechanism

2. Ionic mechanism (anionic and cationic) – Not in Syllabus

3. Coordination mechanism – Not in Syllabus

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1. Free radical mechanism – It has three steps

Initiation - The first step of which involves two reactions. The first is the spontaneous decomposition of an
initiator into free radicals. A variety of peroxides act as initiator such as benzoyl peroxide, tertiary butyl
hydroperoxide etc.

The next part of initiation involves the addition of this radical to the monomer molecule (M) to initiate the
chain.

The M* is the initiator radical or primary radical.

Propagation - The mechanism of propagation is the reaction of the radical M* with its own monomer M.

Continuous addition of new monomer in this manner will finally produce a polymer

chain in which the substituents are located on alternate atoms.

Terminations - The most common terminations are the effect of

(a) Collision between two growing chains

(b) Collision of a growing chain with an initiator radical when the latter is proportionately in excess.

(c) Collision between a growing chain with impurities. Sometimes the chain length of the polymer is controlled
by deliberately adding inhibitors.

More rarely, by disproportionation an H atom of one radical is transferred to another resulting in two polymers
one saturated and the other unsaturated.

2. Condensation polymerization - In condensation polymerization, the polymerization reaction proceeds step

by step through reaction between the functional groups of the monomers with the removal of small
molecules like water. For example, consider the formation of Nylon 6,

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 The reaction proceeds step by step and the chain elongates.

Properties of Polymers
1. Glass Transition Temperature (Tg)
The Glass Transition Temperature (Tg) is a critical property of amorphous materials (like polymers) that marks
the transition between a hard and brittle "glassy" state and a more flexible, rubbery state. Below is an
overview of methods and models for calculating or estimating Tg.

Experimental Measurement:
The most reliable way to determine Tg is through experimental techniques such as:
• Differential Scanning Calorimetry (DSC): Measures heat flow into or out of the material as it is heated
or cooled, detecting changes in heat capacity at Tg.
• Dynamic Mechanical Analysis (DMA): Measures changes in mechanical properties (e.g., modulus) as
a function of temperature.
• Thermomechanical Analysis (TMA): Tracks dimensional changes (e.g., expansion) as temperature
varies.
Theoretical Models for Estimation:
Several theoretical and semi-empirical models are available for estimating Tg, particularly for polymers. These
models are useful when experimental data are lacking.

a. Fox Equation (for polymer blends):

For polymer blends, the Tg can be estimated by the Fox equation:

where:
• 𝑇𝑔 blend is the glass transition temperature of the polymer blend,
• 𝑤1 and 𝑤2 are the weight fractions of the two components,
• 𝑇𝑔1 and 𝑇𝑔2 are the glass transition temperatures of the pure components.

b. Gordon-Taylor Equation (for polymer mixtures):

The Gordon-Taylor equation refines the Fox equation for more accurate results, especially when the
interaction between polymer chains is significant.

where k is an empirical parameter representing the interaction between the polymers.

c. Group Contribution Methods:

For new or custom-designed polymers, group contribution methods can be used. These methods estimate Tg
by summing contributions from different structural groups in the polymer.
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 Van Krevelen Group Contribution: The Tg of a polymer can be estimated by:

where 𝐹𝑖 are the contribution factors from the various molecular groups.

Factors Affecting Tg:

• Molecular Weight: For low molecular weight polymers, Tg can increase with molecular weight up to
a plateau.

where 𝑇𝑔∞ is the glass transition temperature at infinite molecular weight, 𝑀𝑤 is the molecular weight, and
𝐾 is a constant.
• Crosslinking: Increasing crosslink density typically raises Tg.
• Plasticizers: Additives like plasticizers lower Tg by increasing free volume and chain mobility.

2. Tacticity
Tacticity refers to the spatial arrangement of side chains attached to the main polymer chain in stereoregular
polymers. It plays a crucial role in determining the physical properties of polymers such as crystallinity, melting
point, and mechanical strength. There are three main types of tacticity in polymers:

Isotactic: All the substituent groups (side chains) are positioned on the same side of the polymer chain.
Isotactic polymers tend to crystallize well and have higher melting points due to their regular structure.

Syndiotactic: The substituent groups alternate sides along the polymer chain in a regular pattern. Syndiotactic
polymers also tend to be crystalline but are generally more flexible than isotactic polymers.

Atactic: The substituent groups are randomly placed on either side of the polymer chain, leading to an
amorphous structure. Atactic polymers are usually less crystalline and have lower melting points and softer
mechanical properties compared to isotactic or syndiotactic polymers.

Tacticity is especially important in the synthesis of polymers like polypropylene, where controlling the tacticity
can lead to significantly different material properties.

Tacticity Calculation:
To calculate the tacticity of a polymer sample, you typically analyze the sequence of stereocenters (usually
through NMR or similar techniques). You can calculate the percentage of isotactic, syndiotactic, or atactic
placements in a polymer as follows:

Step 1: Identify Sequences

For a polymer chain, identify the stereochemical sequence of the monomers. This is typically done with NMR
data (specifically 13C NMR or 1H NMR), which allows you to distinguish isotactic, syndiotactic, and atactic
triads (groups of three repeating units).

Isotactic Triad: All stereocenters are aligned in the same direction.

Syndiotactic Triad: Stereocenters alternate direction.
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 Atactic Triad: The arrangement is random.

Step 2: Count the Triads

Count the number of isotactic, syndiotactic, and atactic triads in the polymer chain from the NMR data.

Step 3: Calculate Percentages

Once you have counted the triads, the tacticity can be calculated using the following formula:

Where: Number of Triads of a Given Type is the count for either isotactic, syndiotactic, or atactic triads.
Total Number of Triads is the sum of all triads (isotactic + syndiotactic + atactic).
Example:
If NMR analysis shows:
• 50 isotactic triads
• 30 syndiotactic triads
• 20 atactic triads
Then:

This method helps in determining the stereochemical composition of the polymer chain, providing insights
into its properties.

3. Molecular Weight - Number Average

If n1, n2, n3, … are the numbers of molecules with molecular masses M1, M2, M3, …, respectively, then the
number average molecular weight is

where ni is the number of molecules or number of moles of molecules having molecular weight Mi.
Number average molecular weight can be measured on the basis of colligative property like osmotic pressure.

Example –
Calculate the number average and weight average Molecular masses and PDI of a Polyethylene Polymer with
a following composition. (CH2-CH2)400 is 25%, (CH2-CH2)800 is 35%, (CH2-CH2)600 is 40%

Molecular mass of repeating Unit=28

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 =(25x11200)+(35x22400)+(40x16800)
25+35+40
Mn = 17360

4. Molecular Weight - Weight Average

If m1, m2, m3,... are the weights of species with molecular masses M1, M2, M3, …, respectively, then the
weight average molecular weight is

Example –
=25(11200) 2+35(22400) 2+40(16800) 2
25(11200)+35(22400)+40(16800)

Mw= 18426

5. Viscosity Average
The viscosity average molecular weight 𝑀𝑣 is a common way to determine the average molecular weight of
polymers based on their viscosity in solution. It is determined using the Mark-Houwink equation, which
relates the intrinsic viscosity of a polymer solution to its molecular weight.

Mark-Houwink Equation:

Where:
• [η] = intrinsic viscosity
• K and a = constants that depend on the polymer-solvent system and temperature
• Mv = viscosity average molecular weight

Steps to Calculate Viscosity Average Molecular Weight:

1. Determine Intrinsic Viscosity: Intrinsic viscosity [η] is determined by measuring the viscosity of a
polymer solution at different concentrations and extrapolating to zero concentration.
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 2. Obtain Mark-Houwink Constants: The constants K and a are specific to the polymer-solvent system and
are typically provided in literature or determined experimentally.
3. Solve for Mv: Rearranging the Mark-Houwink equation:

Using the values of [η], K, and a, calculate the viscosity average molecular weight Mv.

Example:
• Let’s say:
• [η]=0.45 dL/g
• K=0.0002 dL/g
• a=0.6
The viscosity average molecular weight Mv would be calculated as:

6. Polydispersity Index
The ratio of mass average molecular mass to the number average molecular mass is called polydispersity index
PDI. This gives an idea about the homogeneity of the polymer.

Where:
𝑀𝑤 = Weight-average molecular weight
𝑀𝑛 = Number-average molecular weight

Example –
=18426
17360
PDI = 0.94

Techniques of Polymerization
1. Bulk Polymerization
2. Emulsion Polymerization
3. Solution Polymerization
4. Suspension Polymerization

1. Bulk Polymerization - Bulk polymerization is simpler from the standpoint of formulation and equipment, but
it is very difficult to control because the polymerization is highly exothermic. In this method, the monomer is
taken in liquid state and the free radical initiator is dissolved in it. The chain transfer agent, used to control
molecular weight, is also dissolved in the monomer. The homogenous reaction mixture is then heated or
exposed to radiation for initiating the polymerization. The mixture is stirred well because the reaction is highly
exothermic. As the reaction proceeds, the viscosity of the medium increases and mixing becomes difficult.
However, the polymer is insoluble in the monomer, polymer precipitates and the viscosity of the medium
does not change appreciably.

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 Disadvantage - The reaction mixture becomes viscous, the probability of chain collision becomes less, and
chain termination becomes difficult. Active radicals accumulate increasing the rate of polymerization to such
an extent that it may become uncontrolled and lead to explosion.
However, this method gives the polymer of highest purity because except chain initiator and chain transfer
agents no other additive is used in the process.
Bulk polymerization technique is used in the polymerization of methyl methacrylate or styrene and vinyl
chloride.

2. Emulsion Polymerization - This method was developed by Goodyear Tire and Rubber Company in the
1920s. Like suspension polymerization, this technique also uses water as a dispersing medium. However,
unlike suspension polymerization, here the monomer is dispersed in the aqueous phase by an emulsifying
agent such as soap or detergent. Redox type initiator radicals like hydrogen peroxide and persulphates are
generated in the aqueous phase and they diffuse into soap micelles containing monomer molecules. As the
polymerization proceeds, more and more monomers migrate into micelles to continue the reaction. When
new radical diffuses into the micelle, radical combination occurs, and the polymerization reaction is
terminated. This method results in the formation of extremely high molecular weight polymers. Chain
transfer agents are added to control the degree of polymerization.
Emulsion polymerization is widely used in industry for manufacturing water-based (latex) paints or
adhesives in which the emulsified product is directly used. It is also used for preparing tacky polymers.
Monomers such as vinyl chloride, butadiene, chloroprene and vinyl acetate are polymerized by this
technique.

3. Solution Polymerization - In this method, the monomer, free radical initiator and the chain transfer agent
(whenever used) are dissolved in an inert solvent. The ionic or coordination catalysts are either dissolved or
suspended. The polymer formed is in solution form. It is separated from solution either by evaporation of
the solvent or by precipitation in a nonsolvent. The inert solvent controls viscosity and promotes proper
heat transfer.

Disadvantages
(i) It is difficult to get high molecular weight polymers because no matter how inert the solvent is, chain
transfer to the solvent cannot be completely ruled out.
(ii) It is often difficult to remove the solvent completely from the finished polymer. Solution polymerization
is used to manufacture polyacrylonitrile by free radical polymerization and polyisobutylene by cationic
polymerization. Block co-polymers are also made exclusively by the technique.

4. Suspension Polymerization - This technique finds use in heterogeneous systems and is used only for water
insoluble monomers. The monomer is first mechanically dispersed in a non-compatible liquid, usually water
to form a suspension. The resultant monomer droplets are then polymerized using an initiator soluble in the
monomer. The monomer is kept in suspension by continuous agitation and by the addition of stabilizers
such as polyvinyl alcohol or methylcellulose. The polymer obtained is in the form of granular beads that are
isolated by filtration or by spraying into a heated chamber (spray drying). As the polymer is granular in the
form of beads or pearls, this method is also referred to as beads or pearls polymerization.
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 Disadvantage - This technique cannot be used for tacky polymers such as elastomers because of the
tendency of agglomeration of polymer particles.
Suspension methods are used to prepare a number of granular polymers like polystyrene, styrene
divinylbenzene beads (used for ion exchange resins), polymethylmethacrylate, polyvinyl acetate, etc.

Engineering Plastics
Plastics
The term ‘plastic’ refers to the class of polymers that can be shaped into hard and tough utility articles by
the application of heat and pressure. They are strong, light, highly dielectric, durable and corrosion-
resistant. Because of these properties, the use of plastics is increasing tremendously. Plastic materials are
replacing metals in all walks of life. The reason for using plastics over metals is that
• They are light in weight and at the same time possess good strength, toughness and rigidity.
• They are corrosion-resistant and also resist the action of chemicals.
• They are less brittle than glass and can be made equally smooth and transparent.
• They do not absorb moisture.
• They can be easily moulded into desired shape.
• They can take a variety of colors, are heat-resistant and abrasion-resistant, and have good
dimensional stability. Their maintenance cost is low.

Types of plastics - Plastics are generally classified into two categories:

• Thermoplastics
• Thermosetting plastics

Thermoplastics They are plastic materials that soften on heating and can be moulded into desired shape.
On cooling, they become hard. However, they can be resoftened and remoulded by the application of heat
and pressure. The reason for resoftening of thermoplastic is that they are composed of linear or long-chain
molecules. On heating the intermolecular bonds weaken, the material softens and thus can be moulded
again without any damage. Common examples of thermoplastics are polyethene, polypropylene,
polystyrene, teflon, polyamides, etc.

Thermosetting plastics They are those plastic materials that, when subjected to heat and pressure, change
into a hard and rigid substance. Once they set, they cannot be softened again by the application of heat. The
reason is that during moulding they acquire three-dimensional cross-linked structure. Such three-
dimensional polymers will not soften when heated but may decompose or disintegrate at high
temperatures. Common examples are bakelite, melamine formaldehyde, epoxy resins, etc.

Difference between the thermoplastics and thermosetting plastics

Thermoplastics Thermosetting plastics

Once moulded, they can be resoftened and Once moulded, they set permanently. They do
reused not soften again on heating

They are softer and less strong. -e polymeric They are strong and hard. There are cross-
chains are held together by weak van der Waals linkages and covalent bond formation between
forces the adjacent polymeric chains

They are generally formed by These are formed by condensation

additionpolymerisation reaction polymerization reaction

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 As they soften again and again, they can They cannot be recycled, reused or reclaimed
berecycled, reused and reclaimed from waste from waste

Examples include polythene, Examples include bakelite, melamine

polypropylene,teon, nylon, natural rubber formaldehyde, epoxy resins, vulcanised rubber

Examples of Plastics, Properties & Applications

1. Polyamides
2. Polycarbonates
3. Polyurethanes

1. Polyamides - Polyamides are synthetic polymers, having recurring amide groups, which have a structure
similar to that of polypeptides. Nylon belonging to this class is used for making fibres. Nylon 66 is obtained by
the polymerization of adipic acid with hexamethylene diamine. Adipic acid is commercially produced by
oxidation of cyclohexane derived from either benzene or petroleum.

Hexamethylene is made by final hydrogenation of the adiponitrile.

Adipic acid and hexamethylene diamine mixed in equimolecular proportions in aqueous solution in an
autoclave and heated at 100°C. The compounds react to form nylon salt in solution. Nylon salt is then heated
at 265°C with Dow therm vapours to remove water and molten nylon results. Nylon fibre is obtained by melt
spinning process.

Nylon can be extruded as a heavy ribbon, in an atmosphere of nitrogen which is chilled and chipped. The
polymer can be remelted to spin into fibre and can be used for extrusion of molded objects.

Properties - Nylon is strong, tough, elastic and can be dyed easily. Nylon possesses high abrasion resistance
and is chemically stable. It possesses high temperature stability and also high melting (160°C-264°C). It is
insoluble in common organic solvents but soluble in phenol, formic acid.

Applications - The polymer can be run directly to spinning machines to produce fibre, hence nylon 66 is
primarily used for fibres, which find use in making socks, undergarments, dresses, carpets etc.

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2. Polycarbonates - Polycarbonates are polyesters of phenols and carbonic acid. They can be prepared by the
condensation of diphenoxymethylene derivatives with diphenyl carbonate. 2,2-bis(4-hydroxyphenyl) propane
(bisphenol-A) on reaction with diphenyl carbonate gives polycarbonate.

Properties - Polycarbonate, a high-performance engineering thermoplastic, is a tough, strong, generally

transparent, amorphous solid with outstanding impact resistance. It maintains its shape and size even under
great stress over a wide range of temperature. It is resistant to water, acids, detergents, oils and greases, but
is attacked by bases, halogenated solvents (chloroform, carbon tetrachloride), ketones (acetones,
acetonitrile), organic solvents like benzene, benzylalcohol, dimethyl ether, carbondisulphide, etc. It has
excellent resistance to high temperatures upto 140 °C and maintains toughness at low temperatures upto -20
°C. It has good electrical insulation properties.

Applications - Owing to its electrical properties and dimensional stability, it is used for mouldings for
computers, calculating machines, for making hair driers, electric razors, CDs and DVDs. Owing to its excellent
impact resistance, it is used in automobile industry for making motorcycle windshields, police shields,
headlight covers, car bumpers, front panels, safety helmets, etc.
As it is not stained by oils, greases and domestic beverages, it is used for making blenders, food processing
bowls, coffee maker, food mixer housings.
Owing to its temperature resistance, stability and chemical inertness, it finds use in the manufacture of baby
bottles, syringes.
It is also used for making water dispensers, furniture (office and institutional), vacuum cleaner bases, cord
hooks, impellers, spectacles, cameras and also for the manufacture of other unbreakable items.

3. Polyurethanes - Polyurethanes were developed by Otto Bayer and co-workers in 1937. They are characterized
by the presence of urethane group —N—C—O linkage.
| ||
H O

They are obtained by condensing di-isocyanate and diol. When ethylene glycol reacts with p-phenyldi-
isocyanate polyurethane is formed.

1, 4-butanediol and 1,6-hexanediisocyanate react to yield Perlon- U (a crystalline polymer).

General reaction

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 Properties - They have high strength; good resistance to gas, oil and aromatic hydrocarbons; high abrasion
resistance; excellent resistance to oxygen and ozone, but are susceptible to microbial attack. They are also
less stable at high temperatures.

Applications - Polyurethanes are used to make foams used in cushions for automobiles and furniture, they
are also used for coatings, as adhesives and as elastomers. Polyurethane fibres are used for making
swimsuits. They also find use in the manufacture of shoe soles, solid tyres and impellers.

Compounding and Fabrication Techniques

Compounding - Plastics for manufacturing of finished articles are always mixed with 4-10% of other
materials, which impart some durable properties to the moulded material. These materials
are known as additives which not only impart some properties to plastics but also make the processing easy.
The process of mixing these additives to virgin plastics is called Compounding. Additives and their functions
are discussed below:
(i) Resin – Resin is the binding constituent, which binds all the additives together. Thermosetting
resins are added as linear low molecular weight polymers, which actually form crosslinking during
the moulding process in presence of catalyst.
(ii) Fillers - Fillers can modify the properties of plastics to give the final plastic, better hardness,
tensile strength, finish and workability. Fibrous fillers such as wood flour, cotton fibre, chopped
rags impart improved mechanical strength to the plastic; asbestos increases heat resistance; mica
or slate powder improves electrical properties. Percentage of fillers may vary and can be upto
50%. Solidified filaments of glass are bundled into strands, compressed to produce a glass mat.
Plastics embedded with these mats are known as fibre reinforced plastics (FRP). FRP is very strong
and can be used to make gates of dam, corrosion-resistant pipes and tanks, safety helmets, jeep
bodies. PVC laminated to steel or aluminium are called “Composites”.
(iii) Plasticizers - Plasticizers are small molecules which penetrate into the polymer matrix and
neutralize a part of the intermolecular forces of attraction between macromolecules and increase
the mobility of the polymer segments so that chains can slide over each other. Thus, plasticizers
act as an internal lubricant and improve the plasticity and flexibility of the polymer. Commonly
used plasticizers include vegetable oils, camphor, dibutyl/dioctyl phthalate etc.
(iv) Lubricants - Waxes, oils, stearates and soaps are used to improve the finish and reduce the
sticking tendency of the plastic to the moulds.
(v) Catalysts or accelerators - They are added to accelerate the polymerisation process. They are
particularly used for thermosetting plastics. Commonly used catalysts are hydrogen peroxide,
benzoylperoxides, metals like Ag, Cu and Pb and oxides like ZnO.
(vi) Stabilizers - They improve the thermal stability during processing. Stabilisers are added to those
polymers which have a tendency to decompose at moulding temperature. For example, vinyl
polymers. Commonly used stabilisers are salts of lead and stearates of lead, cadmium and barium.
(vii) Coloring materials - Organic dye stuffs and opaque inorganic pigments are commonly used to
impart color to the plastic products.

Fabrication or Plastic Moulding Techniques - Plastic materials supplied in granular, powder or other forms are
moulded into articles by various methods. The commonly used methods are as follows:

1. Injection Moulding - It is used for producing articles made of thermoplastic materials like mugs,
buckets, dust bins, chairs, etc.
The mould consists of a two-part system; one part is movable, and the other is stationary. The
stationary part is fixed to the end of the cylinder, whereas the movable part can be opened or closed
on to the stationary part.

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 In this process, a correct amount of plastic material as granules, pellets or powder is fed from the
hopper into the cylinder. The piston pushes the plastic material into the heating chamber where it
melts to form a viscous liquid. Again, with the help of the piston the molten plastic material is injected
through the nozzle into the mould cavity. Pressure is maintained in the mould cavity. The material is
cooled by water circulation. It solidifies. Finally, the mould is opened, the piece is ejected, the mould
is closed, and the entire cycle is repeated. The most outstanding feature of this technique is the speed
with which the pieces may be produced.

2. Extrusion moulding - This method is used for making elongated and continuous articles such as rods,
pipes, tubes, hose pipes films, filaments and sheets. An extruder resembles the injection moulding
apparatus, except that the mould cavity is replaced with a die.

In this process, the compounded plastic material in the form of powder or granules is fed into the
electrically heated cylinder using a hopper. A helically rotating screw inside the cylinder further works
the plastic charge. During the journey from hopper to the die, the plastic material passes through
three zones namely feed zone, compression zone and metering zone. The feed zone receives the
charge from the hopper. No heating takes place in the feed zone. In the compression zone, the
powdered charge melts because of heating and compression by the moving screw. The pasty molten
mass enters the metering zone. The pressure in this region enables the molten polymer to enter the
die and come out of it with the desired shaped. The material extruded out of the die is quite hot
(usually 125–350 °C) and is carried over the conveyor belt through a tub containing cold water.

The process of extrusion is also used for coating wires and cables with PVC or rubber. This method
gives products of good surface finish and dimensional stability.
This process is widely used to encapsulate or enclose items such as coils, plugs, integrated circuits,
utensil handles, etc.

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3. Blow Moulding - It is used for producing hollow articles like bottles and hollow toys. Thermoplastic
articles such as PE, polycarbonate, PVC, nylon and styrene are blow-moulded.

In this process a hot, softened thermoplastic tube called ‘parison’ is properly placed inside the two-
piece hollow mould. The split mould is then closed, sealing the bottom. This joint is usually seen at
the bottom of the plastic bottles. Air is then blown in the hot parison. It is inflated and acquires the
shape of the mould. The mould is allowed to cool and the rigid thermoplastic article formed is
removed by opening the mould.

4. Calendaring - For production of continuous films or sheets this process is adopted. The compounding
material is run between two highly polished metallic rollers rotating in opposite direction. While
passing through the gap between the rollers the sheet is formed, whose thickness varies with the gap.
Engraved rollers offer beautiful designs of embossed plastics.

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