Polymers

Index
Topic
Page
Introduction
Learning Objectives
Concept Map
Prerequisite Vocabulary
Classification
Polymerisation - Mechanisms
10
Important Addition Polymers
14
Important Condensation Polymers
15
Polymerisation Technology
17
Glass Transition Temperature
24
Tacticity
28
Average Molecular Weight
29
References
33
Material prepared by: Chemistry Faculty
Page 1 of 33
Introduction
Is there a common factor in the following things?
All These Materials Are Made up of Polymers i.e., Macro Molecules

Do you know?
Which synthetic fiber was discovered first?
What natural fiber was nylon initially developed to replace?
Page 2 of 33
Guess what this is
FOR CHECKING YOUR ANSWER SCROLL DOWN TO PAGE 33
Page 3 of 33
Learning Objectives
On completion of this chapter you will be able to:
1. Define monomer and polymer

2. Understand the difference between molecule and monomer
3. Define functionality
4. Find out the functionality of various molecules and justify the statement All
molecules are not monomers but all monomers are molecules
5. Define polymerization
6. Classify polymers based on skeleton, method of preparation, properties etc.,
7. Mechanism and Techniques of polymerization
8. Understand the unique properties of polymer which makes them a wonderful
structural material
9. Understand the method of preparation, properties and utilities of Nylon 6:6 and
epoxy resin
Page 4 of 33
Page 5 of 33
Prerequisite Vocabulary
Molecule
The smallest part of a substance that has all the properties of the substance.
Molecules can be made up of one or more atoms of same kind (Hydrogen, oxygen etc.,)
or different kinds of atoms ( Water , Carbon di oxide etc.,).
Compound
A substance made of more than one element (water, carbon di oxide)
In other words hetero atomic molecules are generally called compounds
Elastic
Capable of resuming former size and shape after being stretched
Monomer and Polymer
Mer in Greek means unit.
Mono and Poly mean single and many respectively.
Try to put the words together and define monomer and polymer now! (Check answer in
page #)
Molecule and Monomer
Any molecule capable of joining with other molecules to form a macro molecule, whose
property is totally different from that of the molecule, is called monomer. For example
ethylene can combine with one more ethylene and form a dimmer (two units) which can
continue to become polyethylene by joining with many ethylenes. The properties of
Page 6 of 33
ethylene and poly ethylene are radically different. This is because, a covalent bond binds
the two adjacent molecules ( ethylene in this case) .
Though water is a molecule, it cannot form a covalent bond with another water molecule.
Two adjacent water molecules are held together by Hydrogen bond, and not covalent
bond.
Hence water is just a molecule and not a monomer.
Is it possible to differentiate molecule and monomer?
The answer is yes.
But, how?
Looking at the structure and taking stock of functionality makes it possible to
differentiate a monomer and a polymer.
The concept of functionality can be understood with a little imagination.
To form a human chain, many people join their hands together. Each person holds one
persons hand on either side. This results in a long human chain.
Now, if each individual is considered as a molecule then, if then each molecule should
able form at least two new bonds (one on either side). Thus functionality can be defined
as the number of active sites / bonding sites in a molecule. In other words, functionality is
the measure of capacity of a molecule to form new bonds.
If the functionality is at least two, then the molecule can form a polymer.
Hence if the functionality is 2 or >2, the molecule becomes a monomer and if the
functionality is <2 (0, 1) then it is remains only as a molecule.
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Consider the following examples

Functionality
Examples
CH4 , CCl4 , C6H6
ROH , RCl , RCOOR, RNH2
Amino Acids , CH2 = CH2 (ethene),

CH2OH CH2OH (glycol)
CH2OH CHOH CH2OH (glycerol)

C6H5OH (phenol)
CH CH (acetylene)
Thus all monomers are molecules but all molecules are not monomers. Only those
molecules whose functionality is 2 / >2 are called monomers.
Polymers are classified based on
1. Type of monomers joined together ( homo polymer and hetero polymer)

2. Skeleton Back bone ( homo chain and hetero chain polymer)
3. Polymerisation process ( addition and condensation polymers)
4. Tacticity ( iso , syndio and atactic)
5. Thermal property ( thermo plastic and thermosettes)
6. Application ( fiber, elastomer, resin and plastic)
Page 8 of 33
The process of conversion of a monomer to a polymer is called polymerization
Mechanism of polymerization
Reaction mechanism is defined as an insight into a chemical reaction , which is usually
supported by proof.
Polymerisation can occur in a carbonium ion intermediate / a carbanion intermediate / a
free radical intermediate.
Cationic polymerization
Initiators
Lewi Acids or any one of the below
Chain initiation
Chain Propagation
Page 9 of 33
Chain Termination
One hydrogen from the carbon leaves as proton, giving a lively polymer
Free Radical Polymerisation

Reaction is initiated using a peroxide initiator
The propagation / chain growth proceeds through a carbon radical
The reaction is terminated using nitrobenzene as a terminator
Termination can occur by coupling / combination or by diproportionation
Combination leads to a dead or a saturated end polymer
Disproportion leads to a mixture of live or unsaturated end and dead or saturated end
polymer
Initiation
Page 10 of 33
Propagation
Termination by Coupling / Combination
<
Page 11 of 33
Page 12 of 33
Polymerisation Summary
Polymerisation
conditions
Initiator
Propagating
Species
Terminator
Cationic
Lewis acid and

Water
Carbo cation
(C+)
Toluene
Anionic
Lewis base and

Water
Carb anion
(C)
Ammonia and
EtOH
Free radical
AIBN (Azobis Iso Butyro Nitrile )

, Peroxides
(acetyl or benzoyl
peroxide )
Free radical
(C)
Nitrobenzene / alcohols /
ketones
(i) Coupling : Dead

polymer
Product
Live polymer
Dead polymer
(ii) Disproportionation :
Mixture of live and dead
polymers
Example
PP
PVC
LDPE
Page 13 of 33
Page 14 of 33
Page 15 of 33
Page 16 of 33
Polymerisation Technology
Bulk polymerization or mass polymerization is carried out by adding a soluble initiator

to pure monomer in liquid state. The initiator should dissolve in the monomer. The
reaction is initiated by heating or exposing to radiation. As the reaction proceeds the
mixture becomes more viscous. The reaction is exothermic and a wide range of molecular
masses are produced.
Bulk polymerization has several advantages over other methods, these advantages are
The system is simple and requires thermal insulation.
The polymer is obtained pure.
Large castings may be prepared directly.
Molecular weight distribution can be easily changed with the use of a chain
transfer agent.
The product obtained has high optical clarity
Disadvantages
Heat transfer and mixing become difficult as the viscosity of reaction mass
increases.
The problem of heat transfer is compounded by the highly exothermic nature of

free radical addition polymerization.
The polymerization is obtained with a broad molecular weight distribution due to

the high viscosity and lack of good heat transfer.
Very low molecular weights are obtained.
Page 17 of 33
Emulsion polymerization is a type of radical polymerization that usually starts with an

emulsion incorporating water, monomer, and surfactant. The most common type of
emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer (the
oil) are emulsified (with surfactants) in a continuous phase of water. Water-soluble
polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used
to act as emulsifiers/stabilizers.
These latex particles are typically 100 nm in size, and are made of many individual
polymer chains. The particles are stopped from coagulating with each other because each
particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other
particles electrostatically. When water-soluble polymers are used as stabilizers instead of
soap, the repulsion between particles arises because these water-soluble polymers form a
'hairy layer' around a particle that repels other particles, because pushing particles
together would involve compressing these chains.
Page 18 of 33
Emulsion polymerization is used to manufacture several commercially important

polymers. Many of these polymers are used as solid materials and must be isolated from
the aqueous dispersion after polymerization. In other cases the dispersion itself is the end
product. A dispersion resulting from emulsion polymerization is often called a latex
(especially if derived from a synthetic rubber) or an emulsion (even though "emulsion"
strictly speaking refers to a dispersion of an immiscible liquid in water). These emulsions
find applications in adhesives, paints, paper coating and textile coatings. They are finding
increasing acceptance and are preferred over solvent-based products in these applications
as a result of their eco-friendly characteristics due to the absence of VOCs (Volatile
Organic Compounds) in them.
Emulsion polymerization: Polymerization whereby monomer(s), initiator, dispersion
medium, and possibly colloid stabilizer constitute initially an inhomogeneous system
resulting in particles of colloidal dimensions containing the formed polymer.
Note: With the exception of mini-emulsion polymerization, the term emulsion
polymerization
does not mean that polymerization occurs in the droplets of a monomer emulsion. [1]
Batch emulsion polymerization: Emulsion polymerization in which all the ingredients
are
placed in a reactor prior to reaction.[2]
Advantages of emulsion polymerization include:[3]
High molecular weight polymers can be made at fast polymerization rates. By

contrast, in bulk and solution free radical polymerization, there is a tradeoff
between molecular weight and polymerization rate.
Page 19 of 33
The continuous water phase is an excellent conductor of heat and allows the heat to
be removed from the system, allowing many reaction methods to increase their
rate.
Since polymer molecules are contained within the particles, the viscosity of the
reaction medium remains close to that of water and is not dependent on molecular
weight.
The final product can be used as is and does not generally need to be altered or
processed.
Disadvantages of emulsion polymerization include:
Surfactants and other polymerization adjuvants remain in the polymer or are

difficult to remove
For dry (isolated) polymers, water removal is an energy-intensive process
Emulsion polymerizations are usually designed to operate at high conversion of

monomer to polymer. This can result in significant chain transfer to polymer.
Can not be used for condensation, ionic or Ziegler-Natta polymerization, although

some exceptions are known.
Page 20 of 33
Solution polymerization is a method of industrial polymerization. In this procedure, a

monomer is dissolved in a non-reactive solvent that contains a catalyst.
The reaction results in a polymer which is also soluble in the chosen solvent. Heat
released by the reaction is absorbed by the solvent, and so the reaction rate is reduced.
Moreover the viscosity of the reaction mixture is reduced, not allowing autoacceleration
at high monomer concentrations. Once the maximum or desired conversion is reached,
excess solvent has to be removed in order to obtain the pure polymer. Hence, solution
polymerization is mainly used for applications where the presence of a solvent is desired
anyway, as is the case for varnish and adhesives. It is not useful for the production of dry
polymers because of the difficulty of complete solvent removal.
This process is one of two used in the production of sodium polyacrylate, a
superabsorbent polymer used in disposable diapers.
Page 21 of 33
Notable polymers produced using this method are polyacrylonitrile (PAN) and
polyacrylic acid (PAA).
Suspension polymerization is a heterogeneous radical polymerization process that uses

mechanical agitation to mix a monomer or mixture of monomers in a liquid phase, such
as water, while the monomers polymerize, forming spheres of polymer.
This process is used in the production of many commercial resins, including polyvinyl
chloride (PVC), a widely used plastic, styrene resins including polystyrene, expanded
polystyrene, and high-impact polystyrene, as well as poly(styrene-acrylonitrile) and
poly(methyl methacrylate).
The reaction mixture consists of two phases, a liquid matrix and monomer droplets. The
monomer and initiator are insoluble in the liquid phase, so they form drops within the
liquid matrix. A suspension agent is usually added to stabilize the monomer droplets and
Page 22 of 33
hinder monomer drops from coming together. The reaction mixture usually has a volume
ratio of monomer to liquid phase of 0.1 to 0.5. The liquid phase acts as a heat transfer
agent, enabling high rates of polymerization with little change in the temperature of the
polymerizing solution. The reactions are usually done in a stirred tank reactor that
continuously mixes the solution using turbulent pressure or viscous shear forces. The
stirring action helps to keep the monomer droplets separated and creates a more uniform
suspension, which leads to a more narrow size distribution of the final polymer beads.
The polymerization is usually carried to completion. The kinetics of the polymerization
within an individual bead are similar to those of typical radical polymerization.
Page 23 of 33
Properties of Polymers
The glass transition temperature is a function of chain flexibility. The glass transition
occurs when there is enough vibrational (thermal) energy in the system to create
sufficient free-volume to permit sequences of 6-10 main-chain carbons to move together
as a unit. At this point, the mechanical behavior of the polymer changes from rigid and
brittle to tough and leathery.
Actually, the glass transition temperature is more important in plastics applications than
the melting point, because it tells us a lot about how the polymer behaves under ambient
conditions. The melting temperature is often referred to as the first-order transition
thats where the polymer changes state from solid to liquid. Technically, only crystalline
polymers have a true melting point; thats the temperature at which the crystallites melt
and the total mass of plastic becomes amorphous.
Amorphous polymers do not have a true melting point; however, they do have a firstorder transition where their mechanical behavior transitions from a rubbery nature to
viscous rubbery flow.
All polymers have some temperature at which their physical properties are rigid and
glassy material, similar to crystal polystyrene (Tg = 100oC).
If polypropylene (Tg = 0oC) is cooled down to -40oC and it becomes brittle like glass. In
its glassy state, the mechanical behavior of the polymer is relatively stable. The material
is very hard and brittle, and the properties dont change significantly with temperature.
Modulus remains high and impact strength is almost nil. However, as the temperature
rises, there will be a point where the behavior of the polymer will fairly rapidly change
from glassy to a very tough and leathery behavior. This change in behavior is evidenced
Page 24 of 33
by a sharp decline in modulus (stiffness), or increase in impact strength as the ambient

temperature is increased. This region is termed the glass transition region. The
temperature at the midpoint of the transition from glassy to rubbery, the glass transition
region, is defined as the glass transition temperature, Tg.
If the ambient temperature is elevated further, the material behavior becomes similar to a
rubber. In this region, called the rubbery plateau, the low modulus and high impact
strength again become less significantly affected by temperature. However, at some
point the material becomes so soft that it will flow under very low pressure; this is the
final transition to viscous rubbery flow. This is considered the melting temperature of
the polymer, or the first-order transition temperature.
Basically if a polymers glass transition temperature is well above (say, 50oC above)
ambient room temperature, the material will behave like a brittle glassy polymer .Itll be
stiff with low impact resistance. Conversely, if the Tg is well below room temperature,
the material is what is commonly termed a rubber or elastomer ; soft and easily stretched;
and those materials whose Tg is reasonably close to the ambient temperature will exhibit
plastic material behavior (ie) They are strong and tough with good impact resistance.
In applications that can experience temperature extremes, it is important to know what

the potential exposure temperatures are and how they will affect the mechanical behavior
of the material. Polypropylene, a tough plastic in room-temperature applications, turns
glassy and brittle at low temperatures, while at elevated temperatures, the material
becomes soft and easily deformed under low loads (ie) rubber-like. This change in
properties is simply the effect of temperature on the mechanical behavior of the material
as it proceeds from well below its Tg, through its glass transition and into the rubbery
Page 25 of 33
plateau. At even higher temperatures, the crystallites will melt and the material will flow
under moderate pressure
Page 26 of 33
Material
Tg (C)
Acrylonitrile butadiene styrene (ABS) 105

Low-density polyethylene (LDPE)
125
145
Poly(carbonate)
Poly(methyl methacrylate) (atactic) 105
Poly(vinyl acetate) (PVAc)
30
85
Poly(vinyl alcohol) (PVA)
Poly(vinyl chloride) (PVC)
80]
Poly-3-hydroxybutyrate (PHB)
15
Polychlorotrifluoroethylene (PCTFE) 45
Polyethylene terephthalate (PET)
70
Polynorbornene
215]
Polypropylene (atactic)
20
Polypropylene (isotactic)
0
Polystyrene
95
Polytetrafluoroethylene (PTFE)
115
Polyvinyl fluoride (PVF)
-20
Polyvinylidene fluoride (PVDF)
35]
Tyre rubber
70]
Page 27 of 33
Tacticity
Tacticity (from Greek taktikos "of or relating to arrangement or order") is the
relative stereochemistry of adjacent chiral centers within a macromolecule.
The practical significance of tacticity rests on the effects on the physical properties of the
polymer. The regularity of the macromolecular structure influences the degree to which it
has rigid, crystalline long range order or flexible, amorphous long range disorder.
Iso tactic
(All same side cis)
Syndiotactic
(Alternate side trans)
Atactic
(Random)
Page 28 of 33
Average Molecular Weight of polymer

In linear polymers the individual polymer chains rarely have exactly the same degree of
polymerization and molar mass, and there is always a distribution around an average
value.
The molar mass distribution (or molecular weight distribution) in a polymer describes
the relationship between the number of moles of each polymer species (Ni) and the molar
mass (Mi) of that species.
Different average values can be defined depending on the statistical method that is
applied
Page 29 of 33
Illustration of Average Molecular weight Calculation

The number of chains having specific mass is given as below
Number of Molecules
1
3
5
8
10
13
20
13
10
8
5
3
1
Mass of each Molecule

800,000
750,000
700,000
650,000
600,000
550,000
500,000
450,000
400,000
350,000
300,000
250,000
200,000
From the above data, We can arrive at number average as below

Number of Molecules, Ni
1
3
5
8
10
13
20
13
10
8
5
3
1
Total number of molecules =
100
Mass of Each Molecule, Mi

800,000
750,000
700,000
650,000
600,000
550,000
500,000
450,000
400,000
350,000
300,000
250,000
200,000
Total Mass =
Total Mass of Each Type of

Molecule, NiMi
800,000
2,250,000
3,500,000
5,200,000
6,000,000
7,150,000
10,000,000
5,850,000
4,000,000
2,800,000
1,500,000
750,000
200,000
NiMi = 50,000,000
Page 30 of 33
To get the number average molecular weigh, divide the total weight of the sample
by the total number of the molecules. The number average molecular weight for
this sample is given by
NiMi/
Ni = 50,000,000/100 = 500,000.
We can arrive at the mass average as below

Number of
Molecules
Mass of Each
Molecule
Total Mass of
Each
Type of Molecule
Weight Fraction Weight Average of

Type of Molecule
each molecule
NiM I
(Ni)
1
3
5
8
10
13
20
13
10
8
5
3
1
(Mi)
800,000
750,000
700,000
650,000
600,000
550,000
500,000
450,000
400,000
350,000
300,000
250,000
200,000
(NiMi)
800,000
2,250,000
3,500,000
5,200,000
6,000,000
7,150,000
10,000,000
5,850,000
4,000,000
2,800,000
1,500,000
750,000
200,000
Total Mass =
Total number of
molecules = 100
NiMi =
50,000,000
WiMi
Wi=
NiMi
0.016
0.045
0.070
0.104
0.120
0.143
0.200
0.117
0.080
0.056
0.030
0.015
0.004
12,800
33,750
49,000
67,600
72,000
78,650
100,000
52,650
32,000
19,600
9,000
3,750
800
Weight Average
Molecular Weight
= WiMi
= 531,600
Page 31 of 33
Polydispersity Index
The number average and the weight average molecular are not the same.
The distribution of molecular weights in a polymer sample is often described by
the ratio of the weight average molecular weight to the number average molecular
weight. This ratio is the Polydispersity Index (or PDI).
In the above example the ratio is (PDI) = 531,600/500,000 = 1.063.
Answer for question in page 3
_ Synthetic fibres are a part of our everyday life. Do you know which synthetic fibre
was discovered first?
Polyester. Even though Rayon was first introduced at the end of the 19th century it is not
considered a true synthetic fibre as it is derived from naturally occurring cellulose.
Polyesters were discovered before nylon and are synthetics but had major drawbacks.
They weren't developed to their full potential until later. Nylon, as we know it today, was
discovered in 1935 and is considered the worlds first true synthetic fibre.
_ What natural fibre was nylon initially developed to replace?

Silk. Nylons structure was very similar to that of natural silk.
The figure shows a white strand of a nylon polymer formed at the junction of two
layers of a solution containing a diacid (bottom layer) and a diamine (top layer)
Page 32 of 33
Check questions
1. Define monomer and polymer.
2. What are the differences between molecule and monomer?
3. Define functionality
4. Justify the statement All molecules are not monomers but all monomers are
molecules
5. Define polymerization .
6. What is AIBN
7. Classify polymers based on skeleton, method of preparation, properties etc.,
8. Describe the preparation, properties and utilities of Nylon 6.6
9. Describe the preparation, properties and utilities of epoxy resin
Source
1. Polymer Science by Gowariker V.R. , Viswanathan N.V. and JayadevSreedhar , New
Age International P (Ltd.,).
2. Text book of Polymers by Bill Meyer,Wiley India Edition
3. Introductory Polymer Chemistry by G.S.Mishra,Wiley Eastern Ltd
4. Principles of Polymer Science by Bahadur and Sastry, Narosa Publication
Page 33 of 33

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Index

Important Addition Polymers

Important Condensation Polymers

Glass Transition Temperature

Average Molecular Weight

Material prepared by: Chemistry Faculty

All These Materials Are Made up of Polymers i.e., Macro Molecules

Which synthetic fiber was discovered first?

What natural fiber was nylon initially developed to replace?

Material prepared by: Chemistry Faculty

Guess what this is

FOR CHECKING YOUR ANSWER SCROLL DOWN TO PAGE 33

Material prepared by: Chemistry Faculty

On completion of this chapter you will be able to:

1. Define monomer and polymer

Material prepared by: Chemistry Faculty

Material prepared by: Chemistry Faculty

Material prepared by: Chemistry Faculty

Material prepared by: Chemistry Faculty

Consider the following examples

CH4 , CCl4 , C6H6

ROH , RCl , RCOOR, RNH2

Amino Acids , CH2 = CH2 (ethene),

CH2OH CHOH CH2OH (glycerol)

Polymers are classified based on

1. Type of monomers joined together ( homo polymer and hetero polymer)

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The process of conversion of a monomer to a polymer is called polymerization

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Free Radical Polymerisation

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Termination by Coupling / Combination

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Lewis acid and

Lewis base and

AIBN (Azobis Iso Butyro Nitrile )

(i) Coupling : Dead

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Bulk polymerization or mass polymerization is carried out by adding a soluble initiator

The system is simple and requires thermal insulation.

The polymer is obtained pure.

Large castings may be prepared directly.

The product obtained has high optical clarity

The problem of heat transfer is compounded by the highly exothermic nature of

The polymerization is obtained with a broad molecular weight distribution due to

Very low molecular weights are obtained.

Material prepared by: Chemistry Faculty

Emulsion polymerization is a type of radical polymerization that usually starts with an

Material prepared by: Chemistry Faculty

Emulsion polymerization is used to manufacture several commercially important

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

Material prepared by: Chemistry Faculty

Disadvantages of emulsion polymerization include:

Surfactants and other polymerization adjuvants remain in the polymer or are

For dry (isolated) polymers, water removal is an energy-intensive process

Emulsion polymerizations are usually designed to operate at high conversion of

Can not be used for condensation, ionic or Ziegler-Natta polymerization, although

Material prepared by: Chemistry Faculty

Solution polymerization is a method of industrial polymerization. In this procedure, a

Material prepared by: Chemistry Faculty