POLYMERS

RC 2019-20
 UNIT IV
POLYMERS

1. Define Polymer

A polymer is a giant or macro molecule formed by the repeated union of several simple
molecules (monomers). The repeat units in a polymer chain are linked through strong covalent
bonds. The properties of polymers are entirely different from those of its monomers.
e.g. Polyethylene, polyvinyl chloride etc.

CH2 CH2 H2C CH

n n

Polyethylene Cl
Polyvinyl chloride

2. Define Monomer
.
A monomer is a simple molecule having two or more bonding sites through which each can link
to the other monomers to form a polymer chain. Monomers are often called ‘’building blocks’’
of a polymer chain.

e.g. Ethylene (CH2=CH2), Vinyl chloride (CH2=CH-Cl) etc.

3. Define polymerization.

The process by which the monomers are transformed into a polymer is called
polymerization.

Polymerization
n CH2 CH CH2 CH
Initiator
n
Cl Cl

Polyvinylchloride
Vinyl chloride

4. How polymers are classified?

Polymers are classified in different ways based on their sources, thermal behavior, mechanism
of polymerization and properties as under:

(a) Natural and synthetic polymers

(b) Thermoplastic and thermosetting polymers

(c) Addition and condensation polymers

(d) Elastomers, fibers, resins and plastics

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 (a) Natural and Synthetic Polymers: This type of classification is based on the source of
polymers. The polymers which are obtained from natural sources such as plants and animals
are called natural polymers.

e.g. cotton, wool, silk, starch, cellulose, proteins, natural rubber, leather, etc.

The polymers which are synthesized from simple molecules are called synthetic polymers.
Majority of modern day commercial polymers are synthetic polymers.

e.g. Polyethylene, Polystyrene, Teflon, PVC, Plexiglass, Nylons, Polyesters, etc., belong to
synthetic polymers family.

(b) Thermoplastics and Thermosettings: The basis for this classification is the thermal behavior
of the polymers.

Thermoplastics: The polymers which become soft on heating and hard on cooling are called
thermoplastics. This cycle can be carried out many times without affecting their chemical
properties.

e.g. Polyethylene, plexiglass, polyvinyl chloride, teflon, etc., are thermoplastic.

Thermosettings: The polymers which undergo chemical changes and cross linking on heating
and become permanently hard, rigid and infusible are called thermosettings. They will not
soften on heating, once they are set.

e.g. Phenol-formaldehyde resin, urea-formaldehyde resin, epoxy resins, etc., are typical
examples of thermosettings.

(c) Addition and condensation polymers: The basis for this classification is their polymerization
Mechanism.

i) Addition (chain) polymerization: A polymerization reaction in which monomers

containing one or more double bonds are linked to each other without the elimination of any
by-products, usually in the presence of free radical initiator is called addition or chain
polymerization .
Eg: Formation of polyethylene.

n CH2 CH2 Polymerization

CH2 CH2
Initiator
Ethylene n

Polyethylene

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 ii) Condensation (step) polymerization: A polymerization reaction in which bi or poly
functional monomers undergo intermolecular condensation with continuous elimination of
by-products such as H2O, HCl, NH3 etc. is called condensation or step polymerization. They
are normally catalyzed by acids or bases.

(d) Elastomers, Fibers, Plastics, and Resins: Polymers can also be classified based on their
structure and end uses.

(i) Elastomers: The polymer which undergo a very large elongation when pulled but return to
the original length on release of force is called an elastomer. The polymer chains of elastomers
are long, coiled and entangled.

e.g. Natural rubber, Buna-S, Neoprene rubber, Nitrile rubber, Silicone rubber, etc.

(ii) Fibers: Fibers are long, thin and thread like polymer chains which do not undergo stretching
or deformation like elastomers. These long chain molecules are lined up and held together by
hydrogen bonding.
e.g. Wood, silk, cotton, jute, etc., are the examples of natural fiber forming materials.

(iii) Plastics: The polymers which can be molded into desired articles by the application of heat
and pressure are called plastics. Plexiglass, Polyvinyl chloride, Teflon, etc., are familiar examples
of plastics.

(iv) Resins: Low molecular mass polymers either in the liquid or solid form are called resins.
Resins are used as adhesives or molding powders.

Examples: P-F resin, U-F resin, Epoxy resin, M-F resin.

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5. Define functionality.
The total number of functional groups or bonding sites present in a monomer molecule is called
the functionality of the monomer. Depending on the number of bonding sites, the monomers
are called bifunctional, trifunctional or poly functional. A simple molecule should possess at
least bifunctionality, which is the basic requirement to qualify as a monomer and to undergo
polymerization.
e.g. 1: The double bonds (C = C) in all vinyl compounds provide two bonding sites. Therefore, all
vinyl compounds are bifunctional monomers.

n CH2=CH2 [Ethylene] & nCH2=CH-Cl [Vinyl chloride]

e.g. 2: The functionality of adipic acid (HOOC - [CH]4 - COOH) and Hexamethylene diamine (NH2
- [CH]6 - NH2) is two because each contains two reactive functional groups.

6. Degree of polymerization.

The degree of polymerization is a number which expresses the total number of repeat units in a
polymer chain. It is denoted by DP.

n[CH2 = CH2] ⟶ [-CH2 - CH2-]n

Ethylene Polyethylene

Where n is the degree of polymerization. The value of DP indicates the length of a polymer
chain. The DP can also be used to compute the molecular weight of a polymer.

Molecular weight of polymer = DP x Mol.wt of repeat unit.

i) If the DP of polyethylene is 500, its molecular weight is calculated as under:

Mot. wt of polyethylene = DP x Mol. wt. of ethylene.
500 x 28= 14,000.

Mol.wt of polymer =14,000.

(Calculation of molecular weight of Ethylene: 2 C atoms = 4X12= 24

4 H atoms = 4X1=4

Total= 24+4=28)

ii) If the DP of polyvinylchloride is 250, its molecular weight is calculated as under.

Mot. wt of polyethylene = DP x Mol. wt. of vinyl chloride.
250 x 62.45= 15,612.5
(Calculation of molecular weight of Ethylene: 2 C atoms = 4X12= 24

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 3 H atoms = 3X1=3

1 Cl atom= 35.45

Total= 24+3+35.45=62.45)

7. Write a note on methods of Polymerization.

Industrial polymerization can be carried out by different techniques. The principal
polymerization methods are:

(a) Bulk polymerization

(b) Suspension polymerization
The choice of a method depends on the nature of monomer, the polymer formed, and the
polymerization mechanism followed. Each method has its inherent advantages and
disadvantages.

(a) Bulk polymerization

In this method, polymerization occurs in homogeneous system. The method is used for the
polymerization of liquid monomers. The reaction mixture consists of a liquid monomer which
acts as solvent for the added initiator and chain transfer agent if any used. The entire reaction
mass is kept under constant agitation for effective heat and mass transfer. It is heated initially
to polymerization temperature to initiate the reaction. The polymer product formed, being free
from any contamination except the monomer, can be used without purification.

Advantages
 The method is relatively simple and requires simple equipment.
 The conversion is extremely high (= 100%).
 The purity of the product is high.
 The product needs neither isolation nor purification.
 The product has high optical clarity.

Disadvantages

 The agitation is difficult

 The heat control is more difficult. As the reaction progresses, the viscosity increases,
and hot spots tend to develop due to the difficulty in agitation. The uncontrolled
exothermic reactions may lead to explosion.

Applications: The bulk polymerization is mainly used for the manufacture of condensation
polymers where the reactions are mildly exothermic. The method can also be used fo the
production of plexiglass and polystyrene.

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 (b) Suspension (Pearl) polymerization
In this method polymerization occurs in heterogeneous system and the method is used only for
water insoluble monomers. Since the product separates out is spherical pearls or beads, the
method is often called "pearl polymerization". The use of aqueous media facilitates agitation
and heat control.

The water insoluble monomer it suspended in water as several tiny droplets by continuous
agitation. These droplets are prevented from coalescing using small amounts of water soluble
polymers such as polyvinyl alcohol or colloids. The initiators used are soluble in monomers.
Each monomer droplet containing dissolved initiator, being discrete, the method in effect is
bulk polymerization. The reaction mass is heated to initiate the polymerization. The product
formed being water insoluble separates out in the form of beautiful spherical 'pearls' or 'beads'.
They are isolated by the easy method of filtration, followed by washing.

Advantages

 The viscosity buildup of polymer is negligible.

 Efficient thermal control.
 Isolation of product is easy as it needs only filtration and washing.
 Higher purity product.
 The process is more economical since water is used in place of costly solvents.
 Isolated products need no further purification.

Disadvantages

 The method is applicable only for polymerization of water insoluble monomers.

 It is difficult to control particle size.

Applications: The method is used for commercial production of polyvinyl chloride, polyvinyl
acetate, styrene-divinyl benzene (ion exchanger), etc.

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8 What are conducting polymers? Discuss the mechanism of conductance in
Polyacetylene. Mention its applications.

Polymers with highly delocalized pi-electron system, whose conductivity is comparable with
that of metals, are called conducting polymers.
The basic requirement for organic polymer to be inherently conducting is
a) They should have linear structure with relatively rigid chains.
b) They should have continuous conjugation (alternative single and double bonds)
through the polymer chain.
c) Presence of oxidizing and reducing agent.

e.g. Polyacetylene, polyaniline, polypyrrole, etc.

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Applications: It is used
1. As electrode material for commercial rechargeable batteries. Eg: Lead-Acid
battery.
2. For making sensors for pH, O2, SO2, NH3 and glucose.

3. In telecommunications systems.
4. In electronic devices such as transistors and diodes.
5. In fuel cells as the electro catalytic materials.

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Mechanism of conduction in Polyacetylene: Oxidative doping (p-doping)
1. Polyacetylene consists of chains of hundreds to thousands of carbon atoms linked by
alternating single and double bonds.
2. When a suitable oxidizing agent such as iodine vapour or iodine in CCl4 or perchloric
acid is added, it takes away an electron from the pi-backbone of the polyacetylene
chain.
3. It creates a +ve charge on one of the carbon. The other electron resides on another
carbon making it a radical. So a radical ion called polaron is formed.
4. A bipolaron (soliton) is formed on second oxidation.

5. These two radicals (electrons) migrate and combine to establish back one double
bond.
6. As two electrons are removed the chain will have two +ve centers (holes). These
positive charges are mobile and when a potential is applied they migrate accounting
for conductivity. Hence it behaves as p-type conductor.
7. Conductivity of pure polyacetylene is about 4.4 x 10-5 S/cm. Upon doping with
oxidizing agent such as iodine, it increases to about 400 S/cm.

9. What is glass transition temperature? Discuss factors affecting glass transition

temperature. Mention its significance
 The temperature, below which a polymer is hard, brittle and above which it is soft
and flexible is called the glass transition temperature, which is denoted by ‘Tg’.
 The hard, brittle state is known as the glassy state and soft flexible state as the
rubbery state.
 In the glassy state, there will be no segmental and molecular motion. But in rubbery
state, there is only segmental motion but no molecular mobility.
 The temperature at which the polymer melts and starts flowing is called flow
temperature(Tm).

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Tg and Tm of some polymers:

Polymer Tg (0C) Tm (oC)

Nylon 6 50 250
PVC 80 310
PE -125 146

Importance (significance) of Tg:

a) Tg value is a measure of flexibility of a polymer and predicts its response to
mechanical stress.
b) Tg value gives the idea of the thermal expansion, heat capacity, refractive index,
electrical and mechanical properties of the polymer.
c) The Tg value gives information of polymer which could be used as rubber or plastic.
d) Knowledge of Tg and Tm is useful in choosing right temperature range for fabrication.

Factors affecting Tg:

1) Crystallinity: In crystalline polymers, each chain is bound to the other by strong
forces like H- bonding i.e. chains are arranged in regular parallel manner. Hence
they have higher Tg than amorphous polymers. Ex: Polyethylene (-110 ºC) has
lower Tg than Nylon 6,6 (57 ºC) because of H-bonding.
2) Molecular mass: Generally Tg of a polymer increases with molecular mass up to
20,000 and above that there is no change.

3) The presence of plasticizers: The presence of plasticizers reduces Tg of a

polymer. Ex: Diisooctyl phthalate is added to PVC to reduce its Tg from 80ºC to
below room temperature.

4) Effect of side groups: The presence of side groups which hinders the free rotation,
and restricts the chain mobility. Hence increases Tg value. Ex: Poly [- methyl
styrene] has higher Tg (170ºC) value than polystyrene (100ºC).

5) Flexibility: Higher the degree of freedom of rotation of the polymer, the lower will
be its Tg. Ex: Polyethylene (-110ºC) has lower Tg compared to Polystyrene (100ºC).

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10. There is a relation between structure and property of polymers. Sub stantiate
this statement by relating the following properties with structure i) strength ii)
crystallinity iii) chemical resistance. iv) Optical properties

i) Strength: Melt viscosity, impact and tensile strength determine the usefulness of a
polymer. The properties of a polymer could be varied by varying its structure.
a) Tensile strength and impact strength increases with molecular mass up to a certain
point and then become constant.
b) The melt viscosity of a polymer also increases initially gradually at first and then
steeply with increase in molecular mass.
c) For polymer to be commercially useful it should have low melt viscosity, high tensile
and impact strength.

ii) Crystallinity: Polymers made up of linear chains without much bulky side groups and
high degree of symmetry imparts a high degree of crystallinity.
a) Polymers such as HDPE, stereo regular isotactic and syndiotactic isomers of
polyethylene, PVC are highly crystalline.
b) Isotactic PS has a regular structure and is more crystalline than atactic PS where
bulky groups are arranged randomly on the polymer backbone.
c) Polymer chains which are linked by hydrogen bonding are highly crystalline. Eg:
Nylons (polyamides) show higher crystallinity due to hydrogen bonding.
d) Polyethylene terephthalate is more crystalline than polyethylene phthalate. This is
because PETP (para substituted) is highly symmetrical compared to PEP (ortho
substituted).

Note: HDPE: High-density polyethylene

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Higher crystallinity leads to:
1. Sharper melting point.
2. Greater density, rigidity and strength.
3. Greater brittleness and heat resistance.
4. Lesser solubility and greater chemical resistance.
5. Lesser permeability to gases and liquids.

iii) Chemical Property: The chemical resistance of a polymer depends on the

composition and structure of the polymer and also on the nature of attacking reagents.
a) Polymers with polar groups such as –OH, –COOH etc. are attacked by polar solvents
like water, alcohols and ketones.
b) Polymers with non-polar groups such as -CH3, -C6H5 etc. are generally swell or
dissolve in non-polar solvents like benzene, toluene and CCl4.

c) Higher the degree of cross linking and molecular weight, higher is the chemical
resistance.
d) More crystalline the polymer, higher is the chemical resistance.
e) Polymer containing functional groups such as –OH, –COOH and unsaturation
undergo oxidative degradation when exposed to air and light.
f) Polymer containing ester groups (-COO) and amide linkages (-NHCO) undergo
hydrolysis with strong acid or alkalis at high temperature.

iv) Optical Properties. The interactions of electromagnetic radiation with polymers involve, at the

most, the cooperative movement of small groups of atoms. Optical properties of polymers,
such as, gloss, transparency, clarity, haze, colour, surface aspect and refractive index, are
closely linked to our perception of a plastic product’s quality and visual performance. Optical
properties are dependent on the specific polymer or copolymer material, the formulation
(colourants, fillers, plasticizers and other additives) and the crystallinity of the materials. But
also, mechanical and chemical degradation or aging processes and the mechanical conditions
and / or temperature treatments applied during processing influence the optical properties of
polymers and polymer formulations.

12. Polymer degradation is a change in the properties tensile strength, colour, shape, etc.
Polymer-based product under the influence of one or more environmental factors such as heat,
light or chemicals such as acids, alkalis and some salts. These changes are usually undesirable,
such as cracking and chemical disintegration of products.

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 a) Oxidation
The polymers are susceptible to attack by atmospheric oxygen, especially at elevated
temperatures encountered during processing to shape. Many process methods such as
extrusion and injection moulding involve pumping molten polymer into tools, and the high
temperatures needed for melting may result in oxidation unless precautions are taken.

Atmospheric Oxygen i) Photooxidation occurs when solar radiation combines with oxygen. ii)
Free radicals, formed as a result of the cleavage of chemical bonds by solar radiation, react with
oxygen to form peroxy radicals that initiate a series of radical chain reactions. iii)The extent of
photochemical reactions involving oxygen differ in the inner and outer layers of both aromatic
and aliphatic polymers due to their dependence on the diffusion of oxygen through the
polymer. iv)Photooxidation is significantly reduced at depths.

b) Weathering
The aging of natural and artificial polymeric materials is a natural phenomenon in metals, glass,
minerals and other inorganic materials. The main environmental parameters influencing the
degradation of polymeric materials is daylight combined with the effects of temperature,
moisture and oxygen. These act as the main parameters of stress for outdoor weathering.

i) Ozonolysis typically results in stiffening and cracking, particularly under mechanical stress.
ii)Atmospheric pollutants such as sulphur dioxides + solar radiation + oxygen = crosslinking of
polyethylene and polypropylene & rapid loss of color in pigmented coatings
iii)Moisture + temperature = microbial growth, may cause material degradation.

Atmospheric Oxygen i) Photooxidation occurs when solar radiation combines with oxygen. ii)
Free radicals, formed as a result of the cleavage of chemical bonds by solar radiation, react with
oxygen to form peroxy radicals that initiate a series of radical chain reactions. iii)The extent of
photochemical reactions involving oxygen differ in the inner and outer layers of both aromatic
and aliphatic polymers due to their dependence on the diffusion of oxygen through the
polymer. iv)Photooxidation is significantly reduced at depths.

c) Environmental Stress Cracking (ESC) is one of the most common causes of unexpected brittle
failure of thermoplastic (especially amorphous) polymers known at present. Environmental
stress cracking may account for around 15-30% of all plastic component failures in service.
Research shows that the exposure of polymers to liquid chemicals tends to accelerate the
crazing process, initiating crazes at stresses that are much lower than the stress causing crazing
in air. The action of either a tensile stress or a corrosive liquid alone would not be enough to
cause failure, but in ESC the initiation and growth of a crack is caused by the combined action of
the stress and a corrosive environmental liquid.

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d) Thermal degradation of polymers is molecular deterioration as a result of overheating. At
high temperatures the components of the long chain backbone of the polymer can begin to be
broken (chain scission) and react with one another to change the properties of the polymer.
Thermal degradation can present an upper limit to the service temperature of plastics as much
as the possibility of mechanical property loss. Indeed, unless correctly prevented, significant
thermal degradation can occur at temperatures much lower than those at which mechanical
failure is likely to occur. The chemical reactions involved in thermal degradation lead to physical
and optical property changes relative to the initially specified properties. Thermal degradation
generally involves changes to the molecular weight (and molecular weight distribution) of the
polymer and typical property changes include reduced ductility and embrittlement, chalking,
color changes, cracking, general reduction in most other desirable physical properties. Thermal
breakdown products may include a complex mixture of compounds, including but not limited to
carbon monoxide, ammonia, aliphatic amines, ketones, nitriles, and hydrogen cyanide, which
may be flammable, toxic and/or irritating. The specific materials generated will vary depending
on the additives and colorants used, specific temperature, time of exposure and other
immediate environmental factors.

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