POLYMER SCIENCE MODULE TENG1111

Developed By:
ASHENAFI ALEBACHEW (MSC IN MATERIALS SCIENCE AND ENGINEERING)
& FEKADU TADESSE (MSC IN MATERIALS SCIENCE AND ENGINEERING)

April, 2023
Chapter One

INTRODUCTION TO POLYMERS
1.1. Definition of Terms
The word ‗polymer‘ is coined from two Greek words: poly means many and mer
means unit or part. The term polymer is defined as very large molecules having high
molecular mass. These are also referred to as macromolecules, which are formed by
joining of repeating structural units on a large scale. The repeating structural units
are derived from some simple and reactive molecules known as monomers and are
linked to each other by covalent bonds. This process of formation of polymers from
respective monomers is called polymerisation. The transformation of ethene to
polythene and interaction of hexamethylene diamine and adipic acid leading to the
formation of Nylon 6, 6 are examples of two different types of polymerisation
reactions.

Differences with low molecular weight compounds

o
Solid benzene, for instance, melts to become liquid benzene at 5.5 C and further
heating it is converted into gaseous benzene. In contrast to this, polymers do not
melt sharply at one particular temperature. Instead, it becomes softer and then into a
viscous liquid i.e. molten mass. Polymers, also, are converted into gases but no
longer they remain in polymeric form. When low molecular weight compounds are
dissolved in a solvent, the viscosity do not change significantly even after saturation.
Whereas, polymers take longer time to dissolve and results in increase in viscosity.
Also, saturation point is not observed easily.
1.2. Fundamental Requirements of Fibre Forming Polymers
Life as we know it could not exist without polymers. Proteins, with large numbers of
amino acids joined by amide linkages, perform a wide variety of vital roles in plants
and animals. Carbohydrates, with repeating units derived from simple sugars, are
among the most plentiful compounds in plants and animals. Both carbohydrates and
proteins are important fiber forming natural polymers. Proteins are the basis for
wool, silk and other animal-derived filaments. Cellulose as a carbohydrate occurs as
cotton, linen and other vegetable fibers. Before the days of synthetic fibers, man
relied on the plant and animal fibers for clothing materials. These natural materials
have a great deal in common. Cotton, and other plant fibers are all cellulose; wool,
silk, furs and feathers are all keratins; leather hide is mostly collagen. The common
factor shared by cellulose, keratin and collagen is that they all have similar
molecular structures and all are fibrous polymers. The formation of these polymer
fibers require making of a long thin chain of covalent bonds, stacking alongside
each other with tight packing using more covalent bonds, tying them in a bundle
and positioning the bundles all along the line of tension. The free ends of each chain
in the bundle need to be linked up to those in the bundle in front and behind. The
recipe is the same whether it is for a spider's web or a bird's feather. If a material is
being pulled out, it is less likely to break if it is made from a bundle of long fibers
than if it is one solid block. Molecules linked together in a chain, by covalent bonds
are very difficult to break if pulled along their length, so the orientation of the chain
when tension occurs is crucial. If several chains are stacked next to one another, the
bundle (or fibril) will be a useful unit for building a fiber, provided that the chains of
molecules cannot slide past each other. In order to prevent this they need to be tied
to each other by cross-linkages and also should be reasonably long. Hence for a
polymer to form a fiber, the three requirements are stacking, physical cross-linking
and sufficient length. However there is a diminishing return from excessive length.
When chains get too long they are difficult to stack and orientate. The ideal length-
width ratio of the polymer should be about 100 to 1 for successful fiber formation.
If chains lying next to each other have cross linkages they are unable to slip past
each other, and this increases their resistance to being physically torn from each
other. The insolubility and strength of the cellulose in plant fibers is due to the

2|Page
frequent physical cross-linking which occurs between strait, long chains of sugar
molecules. Hence only a few bacteria (sheltering in the stomachs of cows and
termites) can break it down and get to the sugar. Starch which has a chemical make
up to similar cellulose cannot form fiber, because there is no opportunity for chain
alignment and physical cross linkage due to branching and curling (coiling) up of the
molecule into a ball. Hence Starch has no structural strength and is used as a food
source.

1.3. Classification of Polymers

There are several ways of classification of polymers based on some special
considerations. The following are some of the common classifications of polymers:
Classification Based on Source:
Under this type of classification, there are three sub categories:-
1. Natural polymers: These polymers are found in plants and animals. Examples
are proteins, cellulose, starch, some resins and rubber.
2. Semi-synthetic polymers: cellulose derivatives as cellulose acetate (rayon) and
cellulose nitrate, etc. are the usual examples of this sub category.
3. Synthetic polymers: a variety of synthetic polymers as plastic (polythene),
synthetic fibres (nylon 6,6) and synthetic rubbers (Buna - S) are examples of
manmade polymers extensively used in daily life as well as in industry

Classification Based on Structure of Polymers:

There are three different types based on the structure of the polymers.
1. Linear polymers
These polymers consist of long and straight chains. The examples are high
density polythene, polyvinyl chloride, etc. These are represented as:

2. Branched chain polymers

These polymers contain linear chains having some branches, e.g., low
density polythene. These are depicted as follows:

3|Page
 3. Cross linked or Network polymers
These are usually formed from bi-functional and tri-functional monomers
and contain strong covalent bonds between various linear polymer chains,
e.g. bakelite, melamine, etc. These polymers are depicted as follows:

Classification Based on Mode of Polymerization

Polymers can also be classified on the basis of mode of polymerization into two sub
groups.
1. Addition polymers
The addition polymers are formed by the repeated addition of monomer
molecules possessing double or triple bonds, e.g., the formation of
polythene from ethene and polypropene from propene. However, the addition
polymers formed by the polymerisation of a single monomeric species are
known as homopolymers, e.g., polythene.

The polymers made by addition polymerisation from two different

monomers are termed as copolymers, e.g., Buna-S, Buna-N, etc

2. Condensation polymers
The condensation polymers are formed by repeated condensation reaction
between two different bi-functional or tri-functional monomeric units. In
these polymerisation reactions, the elimination of small molecules such as
water, alcohol, hydrogen chloride, etc. take place. The examples are terylene

4|Page
 (dacron), nylon 6, 6, nylon 6, etc. For example, nylon 6, 6 is formed by the
condensation of hexamethylene diamine with adipic acid.

Classification Based on Molecular Force

A large number of polymer applications in different fields depend on their unique
mechanical properties liketensile strength, elasticity, toughness, etc. These
mechanical properties are governed by intermolecular forces, e.g., van der Waals
forces and hydrogen bonds, present in the polymer. These forces also bind the
polymer chains. Under this category, the polymers are classified into the following
four sub groups on the basis of magnitude of intermolecular forces present in them.
1. Elastomers
These are rubber – like solids with elastic properties. In these elastomeric
polymers, the polymer chains are held together by the weakest
intermolecular forces. These weak binding forces permit the polymer to be
stretched. A few ‗crosslinks‘ are introduced in between the chains, which
help the polymer to retract to its original position after the force is released
as in vulcanised rubber. The examples are buna-S, buna-N, neoprene, etc
2. Thermoplastic polymers
These are the linear or slightly branched long chain molecules capable of
repeatedly softening on heating and hardening on cooling. These polymers
possess intermolecular forces of attraction intermediate between elastomers
and fibres. Some common thermoplastics are polythene, polystyrene,
polyvinyls, etc.

3. Thermosetting polymers
These polymers are cross linked or heavily branched molecules, which on
heating undergo extensive cross linking in moulds and again become
infusible. These cannot be reused. Some common examples are bakelite,
urea-formaldelyde resins, etc

5|Page
Chapter one: Multiple choice Questions

1. Pick out the false statement

a) More monomer molecules joined in units of long polymer.
b) Polymer is long chain giant organic molecules assembled from many
small molecules called monomers.
c) Polymer is a large molecule consisting of a number of repeating units
with molecular weight typically several thousand or higher.
d) The word micromolecule is a synonym for polymer.
2. Which of the following polymers are not classified under natural polymers?
a) Polysaccharides
b) Epoxy
c) Proteins
d) DNA
3. The characteristics of low molecular weight compounds are given below-
i. When it dissolved in a solvent, the viscosity do not change
significantly even after saturation.
ii. It melts to become liquid and further heating it is converted into
gaseous.
iii. It takes longer time to dissolve and results in increase in viscosity..

Which of the following is True?

a) I, II, III
b) II and III
c) I and II
d) Only III
4. Which of the following is wrong combination?
a) Natural polymers  plastic
b) Thermosetting polymers Bakelite
c) Synthetic polymers nylon 6,6
d) Thermoplastic polymers polystyrene

6|Page
 5. If you are interested in designing polymeric material with three dimensional
networked and a high degree of cross-linking, among the basic structure of
polymers, which one can you prefer for your design?
a) Network polymers
b) Linear polymers
c) Branched polymers
d) Cross-link polymers
6. Pick out the correct statement
a) Block copolymer are made of alternating sequences of the different
monomers.
b) Linear polymer is a polymer that includes interconnections between
chains.
c) Condensation polymers are formed by the repeated addition of monomer
molecules.
d) Elastomeric polymers, the polymer chains are held together by the
weakest intermolecular forces.
7. Nylon 11 has the following structure

If the number-average degree of polymerization, Xn, for nylon is 100 and Mw

= 120,000, what is its polydispersity?
a) 7.45
b) 6.56
c) 5.65
d) 8.03
8. Which of the following is Thermoplastic Polymer?
a) Epoxy
b) Bakelite
c) Nylon
d) Phenolic resins

7|Page
Chapter one : Descriptive Questions
1. What are monomers and polymers? Give suitable examples.
2. Polypropylene (PP) is an example of a polymer. The structure of Polypropylene
(PP) molecule is shown below. This polymer is made from monomers. Draw the
structures of the monomer molecules showing all the covalent bonds.

3. Identify the special characteristics and applications of polymers?

4. What are the important Mechanical Properties of polymers?
5. Draw A typical molecular weight distribution curve of a polymer? Discuss the
practical significance of the molecular weight of a polymer? What is the difference
between number
average and weight average molecular weight? How is the polydispersity index,
PDI, obtained from the curve?
6. How can Polymers be Biodegraded? Give an example.
7. Classify the polymers with respect to their Monomer Composition. Give
examples of each with structure?
8. Give an account of classification of polymers based on the source of availability
or origin?
9. What are the advantages of thermoplastic polymer over thermosetting polymer?
What could be the drawback of thermosetting polymer?
10. Discuss the effect of cross-linking and branching of the chains on the properties
of polymers.

8|Page
CHAPTER TWO

POLYMER SYNTHESIS
Polymerization in which the polymer forms by addition of monomeric unit to the
growing chain is called as addition polymerization. Generally, a monomer
containing double bond and an initiator creates the first active unit; they are needed
to start the chain growth. The active group, which is the chain carrier group, may be
a free radical, an anion, or a cation.
2.1 Chain Polymerisation
A. Free Radical Polymerisation
Free radicals are unpaired electrons that are highly reactive and have short lifetimes.
In free radical polymerizations, each polymer chain grows by addition of monomer
to the free radical of the growing chain. Upon addition of the monomer, the free
radical is transferred to the new chain end. Free radical polymerization has three
stages: initiation, propagation, and termination.
Initiation
In the initiation step free radicals are formed from an initiator and then these free
radicals bind to a monomer. Initiators can be peroxides or azo compounds in which
scission of a single bond creates radicals, or a redox reaction in which radicals are
created by an electron transfer to or from an ion or molecule. Dissociation can be
affected by the application of heat or electromagnetic radiation (e.g., UV, g).
Peroxides and hydroperoxides are frequently used as initiators because of the
instability of the O–O bond. In the case of azo compounds, the process is driven by
the release of N2. Redox reactions are preferred especially when the polymerization
is needed to be carried out at low temperatures.6,10 Heat and electromagnetic
radiations can also start polymerization by breaking the double bond of the
monomeric units and creating two active radicals. In this case, the chain adds to
monomeric units from both ends. The free radical initiation step can be shown as
follows:
Dissociation of an initiator (I) such as benzoyl peroxide yields two radicals (R*)
with a dissociation rate constant kd:

9|Page
This radical then attacks to a monomer molecule to create the first radical M*.

where ki is the rate constant of initiation.

Some of the most widely used initiator systems:-

Propagation
The free radicals formed are very active and immediately add on monomer
molecules leading to growing macroradicals. Each addition creates a new radical
that has the same identity as the previous one, except that it is larger by one
monomer unit. In the polymerization mechanism, it is assumed that all growing
chains have the same propagation constant (kp). The successive additions may be
represented by:

10 | P a g e
Propagation with growth of the chain takes place in milliseconds and kp for most
monomers is in the range of 102–104lmol -1s-1
Termination
Termination usually occurs by combination or disproportionation reactions.
Combination is coupling of two growing chains to form a single polymer molecule.

where ktc is the rate constant for termination by combination.

In disproportionation reaction, a hydrogen atom is abstracted and exchanged
between the growing chains leaving behind two terminated chains:

where ktd is the rate constant for termination by disproportionation.

Termination by disproportionation forms one polymer molecule with a saturated
end-group and another with an unsaturated end-group. Type of termination affects
the molecular weight. If it is through combination, average molecular weight will be
two times higher than that of polymers terminated by disproportionation. In general,
both types of termination reactions take place in different proportions depending
upon the monomer and the polymerization condition. For example, polystyrene
chains terminate by combination whereas poly(methyl methacrylate) chains
terminate by disproportionation, especially at temperatures above 600C.
Kinetics of radical polymerization
In radical polymerization reactions, decomposition of the initiator (such as
peroxides and azo compounds) proceeds much more slowly than the reaction of the
free radical with the monomer. This step is therefore the rate-determining step. The
rate of initiation (Ri) is

where f is the initiator efficiency, the fraction of the radicals successful in initiating
chains, kd is the rate constant for initiator dissociation, and [I] is the concentration of
11 | P a g e
the initiator. The constant 2 defines that two radicals are formed from one initiator
molecule. The initiator efficiency is in the range of 0.3–0.8 due to side reactions.
The initiator efficiency decreases when side reactions terminates the radicals.
The rate of termination is represented as

where kt is the overall rate constant for termination. The constant 2 shows that the
two growing chains are terminated by each termination reaction. At the start of the
polymerization, the rate of formation of radicals greatly exceeds the rate of
termination. As the reaction proceeds, the rate of formation and the rate of loss of
radicals by termination becomes equal and it can be stated that there is no change in
the concentration of M*. This is the steady state (d[M*]/dt=0). At steady state, the
rates of initiation (Ri) and termination (Rt) are equal, leading to

The rate of propagation is represented as

Rp can be obtained as

If the initiator efficiency is high (close to 1) and if f is independentofmonomer,

rateofpolymerization isproportional tothe first power of the monomer concentration.
In chain polymerization, one important phenomenon is ‗gel effect‘ or ‗Trommsdorff
– Norrish effect‘ which is autoacceleration of the polymerization. In these cases,
viscosity of the reaction medium increases and the mobility of the growing chains
are restricted. Chains continue to grow with addition of monomers, but they cannot
terminate. Therefore, the system is no longer in steady state. Fast polymerization
causes heat evolution and local hot spots, leading to cross-linking and gel formation.
Degree of polymerization
Kinetic chain length n is defined as the number of monomer molecules used per
active center. It is, therefore, represented as Rp/Ri = Rp/Rt. Therefore,

12 | P a g e
The number average degree of polymerization, Xn, is the average number of
monomer molecules added to the polymer molecule. If the propagating radicals
terminate by combination Xn =2v, and if termination is by disproportionation! Xn =
v.
Chain transfer is the reaction of a growing chain with an inactive molecule to
produce a dead polymer chain and a molecule with a radical. The transfer agent may
be the initiator, monomer, polymer, solvent, or an impurity. When the transfer does
not lead to new chain growth, it is called inhibition. If the newly formed radical is
less reactive than the propagating radical, then it is called retardation.
B. Ionic Polymerization
Addition polymerization of olefinic monomers can also be achieved with active
centers possessing ionic charges. These can be either cationic polymerizations or
anionic polymerizations depending on the type of the chain carrier ion. The ionic
charge of the active center causes these polymerizations to be more selective unlike
free radical polymerization. They proceed only with monomers that have appropriate
substituent groups which can stabilize the active center. Since the required activation
energy for ionic polymerization is small, these reactions may occur at very low
temperatures. High rate of polymerization at low temperatures is a characteristic of
ionic polymerizations. For cationic active centers, electron-donating substituent
groups are needed. For anionic polymerization, the substituent group must be
electron withdrawing to stabilize the negative charge. Thus, most monomers can be
polymerized either by cationic or by anionic polymerization but not by both. Only
when the substituent group has a weak inductive effect and is capable of
delocalizing both positive and negative charges (e.g., styrene and 1,3-dienes) both
cationic and anionic polymerization can be achieved. Another important difference
between free radicalic and ionic polymerizations is that many ionic polymerizations

13 | P a g e
proceed at much higher rates than free radical polymerization, mainly because the
concentration of propagating chains is much higher (by a factor of 104–106).
Another difference is that an ionic active center is accompanied by a counter ion of
opposite charge. Both the rate and stereochemistry of propagation are influenced by
the counter ion and the strength of interaction with the active center. Finally,
termination does not occur by a reaction between two ionic active centers because
they are of similar charge.
Cationic polymerization
Typical catalysts for cationic polymerization are strong electron acceptors and
include Lewis acids, Friedel–Crafts halides, Bro¨nsted acids, and stable carbenium-
ion salts. Many of them require a co catalyst, usually a proton donor, to initiate
polymerization. Those monomers with electron donating 1-1-substituents that can
form stable carbenium ions are polymerized by cationic mechanisms. For these
systems, the polymerization rate is very high; for isobutylene initiated by AlCl3 or
BF3, in few seconds at 100(C0) chains of several million daltons can form. Both the
rate and the molecular weight decrease with temperature and are much lower at
room temperature. In certain cationic polymerizations, a distinct termination step
may not take place; therefore ‗living‘ cationic polymers are formed. However, chain
transfer to a monomer, polymer, solvent, or counterion can terminate the growth of
chains. Cationic polymerizations are usually conducted in solution, at low
temperature, typically 80 to 100(C0). The solvent is important because it determines
the activity of the ion at the end of the growing chain. There is a linear increase in
polymer chain length and an exponential increase in polymerization rate as the
dielectric strength of the solvent increases.
Anionic polymerization
The initiator in an anionic polymerization needs to be a strong nucleophile,
including Grignard reagents and other organo metallic compounds like n-butyl (n-
C4H9) lithium. When the starting reagents are pure and the polymerization reactor is
free of traces of oxygen and water, the chain can grow until all the monomer is
consumed. For this reason, anionic polymerization is sometimes called ‗living‘
polymerization. Termination occurs only by the deliberate introduction of oxygen,
carbon dioxide, methanol, or water.

14 | P a g e
C. Coordination Polymerization

Use of some special catalysts may lead to the formation of very orderly structured
polymers with high stereospecificity. For example, the processes used in the
polymerization of both isotactic polypropylene (i-PP) and high density polyethylene
(HDPE) employ transition-metal catalysts called Ziegler–Natta catalysts, which
utilize a coordination type mechanism during polymerization. In general, a Ziegler–
Natta catalyst is anorganometallic complex with the cation from Groups I to III in
the Periodic Table, (e.g., Al(C2H5)3), a hallide of transition metal from Groups IV
to VIII, (e.g., TiCl4). HDPE can be prepared by bubbling ethylene gas into a
suspension of Al(C2H5)3 and TiCl4 in hexane at room temperature. Although the
exact mechanism is still unclear, it is proposed that the growing polymer chain is
bound to the metal atom of the catalyst and that monomer insertion involves a
coordination of the monomer with the atom. It is this coordination of the monomer
that results in the stereospecificity of the polymer. Coordination polymerizations can
be terminated by introduction of water, hydrogen, aromatic alcohol, or metals.
2.2 Step Polymerisation
Step-growth polymerization involves a series of reactions in which any two species
(monomers, dimers, trimers, etc.) can react at any time, leading to a larger molecule.
Most step-growth polymerizations, as we shall see presently, involve a classical
condensation reaction such as esterification, ester interchange, or amidization. In
step-growth polymerization, the stepwise reaction occurs between pairs of
chemically reactive or functional groups on the reacting molecules. In most cases,
step-growth polymerization is accompanied by the elimination of a small molecule
such as water as a by-product. A typical step-growth polymerization of the
condensation type is the formation of a polyester through the reaction of a glycol
and a dicarboxylic acid, as shown in Equation

15 | P a g e
where R and R ′ are the unreactive part of the molecules.
Step-growth polymerizations generally involve either one or more types of
monomers. In either case, each monomer has at least two reactive (functional)
groups. In cases where only one type of monomer is involved, which is known as A-
B step-growth polymerization, the functional groups on the monomer are different
and capable of intramolecular reactions. An example is the formation of an aliphatic
polyester by the self-condensation of ω -hydroxycaproic acid
Equation

Step-growth polymerizations can be divided into two main categories:

polycondensation, in which a small molecule is eliminated at each step and poly-
addition, in which, as the name suggests, monomers react without the elimination of
a small molecule.

An example of polyaddition-type step-growth polymerization is the preparation of

polyurethane by the ionic addition of diol (1,4 butanediol) to a diisocyanate (1,6
hexane diisocyanate)
Equation

16 | P a g e
Another example of polyaddition-type step-growth polymerization is the preparation
of polyurea from the reaction of diisocyanate and diamine, as shown in Equation

Distinguishing Features of Chain and Step Polymerization Mechanisms

Chain Polymerisation Step Polymerisation
Only growth reaction adds repeat units Any two molecular species present can
one at a time react
Monomer concentration decreases Monomer disappears early in reaction at
steadily throughout the reaction DP 10 less than 1% monomer remains
High polymer is formed at once, Polymer molecular weight rises steadily
polymer molecular weight changes little
throughout reaction
Long reaction times give high yields but Long reaction times are essential to
affect molecular weight little obtain high molecular weight

17 | P a g e
Reaction mixture contains only At any stage all molecular species are
monomer, high polymers present in a measurable distribution e.g.
monomer, dimer, trimer
No small molecule is split off Low molecular weight by-products are
obtained
Higher molecular weight can be Higher molecular weight is difficult to
achieved (>25000) achieve
More likely to cross links Cross linking is not favoured

2.3 Copolymerizationand Copolycondensation

Copolymerisation is a polymerisation reaction in which a mixture of more than one
monomeric species is allowed to polymerise and form a copolymer. The copolymer
can be made not only by chain growth polymerisation but by step growth
polymerisation also. It contains multiple units of each monomer used in the same
polymeric chain. For example, a mixture of 1, 3 – butadiene and styrene can form a
copolymer.

Copolymers are polymers formed from two or more monomeric units. The
arrangement of repeating units can be in various ways along the chain. Some
copolymers are very similar to homopolymers, because they have one type of
repeating units. But proteins and some polysaccharides are copolymers of a number
of different monomers. Copolymers constitute the vast majority of commercially
important polymers. Compositions of copolymers may vary fromonly asmall
percentageofonecomponenttocomparable proportions of both monomers. Such a
wide variation in composition permits the production of polymer products with
vastly different properties for a variety of end uses. The minor constituent of the
copolymer may, for example, be a diene introduced into the polymer structure to
provide sites for such polymerization reaction as vulcanization; it may also be a

18 | P a g e
trifunctional monomer incorporated into the polymer toensure cross-linking,
orpossibly it maybeamonomer containing carboxyl groups to enhance product
solubility, dyeability, or some other desired properties.
Copolycondensation
If the reactants in the polycondensation reaction are more than a single pair, there is
a copolycondensation that takes place.
Simple Polycondensation reaction:

Copolycondensation reaction:

Where A and B are functional groups capable of undergoing condensation reaction.

The polymers are also known as mixed polycondensates e.g. DMT, EG and
Dimethyl isophthalate.

Here para linkages are interposed with metalinkages at random. This reduces chain
rigidity and crystallinity. Introducing terephthalic acid in nylon 6,6 polymerisation
increases the crystallinity and melting point.

2.4 Polymerization Techniques

Factors such as the nature of the monomer, type of polymerisation mechanism
chosen, the required physical form of polymer and the viability of the process for
industrial production are some of those dictating the physical conditions. Varying
19 | P a g e
physical conditions lead to different polymerisation techniques. Different
techniques include:-
 Bulk polymerisation
 Solution polymerisation
 Suspension polymerisation
 Emulsion polymerisation
 Melt condensation
 Solution condensation
 Interfacial condensation
 Solid and gas phase condensation

Bulk Polymerisation
Monomer is taken in the liquid state and the initiator is dissolved in the monomer.
The chain transfer agent used to control the molecular weight is also dissolved in the
monomer. The whole system is therefore in the homogeneous phase. The reaction
mixture is heated or exposed to radiation source for initiating the polymerisation and
is kept under agitation for proper mass and heat transfer. As the polymerisation
proceeds the viscosity of the medium increases and mixing becomes progressively
difficult, leading to products with very broad molecular weight distribution.
Another disadvantage of bulk polymerisation is that the medium gets viscous, the
diffusibility of the growing polymer chain becomes restricted. The probability of
collision becomes less, termination becomes difficult. Active radical sites
accumulate and the rate of polymerisation increase enormously. The above
phenomenon is known as ―auto-acceleration‖ and some times the uncontrolled
exothermic reaction lead to an explosion. Bulk polymerisation is simple and product
obtained has a high purity since, except the initiator and the chain transfer agent, no
other additive that could contaminate the product. No isolation or cleaning of the
polymer is required e.g. free radical polymerisation with MMA, styrene.

Solution Polymerisation
In solution polymerisation, the monomer is dissolved in a suitable inert solvent
along with the chain transfer agent, whenever used. Free radical initiator is also

20 | P a g e
dissolved in the solvent medium while ionic coordination catalysts can be
suspended. The presence of inert solvent medium helps to control the viscosity
increase and promote proper heat transfer. The major disadvantages of this system
include
 There is a possibility of chain transfer to the solvent, cannot be ruled out.
 The polymer formed in the reaction needs to be isolated from the solvent by
precipitation or by evaporation. However, the traces remain with polymer.
Polymer required in the solution stage can be obtained e.g. PAN

The reaction can be carried out at comparatively lower temperatures during which
heat and mass transfer is easier. The solvent is used for entrapping the byproduct is
easier. Owing to the presence of the solvent phase, however, kinetic probability of
chain growth is low and this leads to a reduce rate and a low DP e.g. liquid polyester
resins.

Suspension Polymerisation
Only water insoluble monomers can be polymerized using this technique. The
monomer is suspended in water, in the form of fine droplets, which are stabilized or
prevented from coalescing by using suitable water-soluble colloids, surface active
agents and stirring. The size of monomer droplets formed depends on the monomer
to water ration, type and concentration of stabilizing agent and also on the type and
speed of agitation employed. The initiators are monomer soluble. Since each
droplet is isolated and independent of each droplet, it can be visualized to act as an
independent bulk polymerisation nucleus. Presence of liquid phase controls the heat
of exothermicity e.g. water. The process is economical since water is used as the
medium of heat transfer. Since the polymerisation takes place inside the droplets,
the number of monomers added to radical is higher i.e. kinetic chain length is
higher. Narrow molecular weight distribution is possible. Polymerisation proceeds
to 100% conversion and the product is obtained as spherical beads or pearls. For
this reason, this technique is also known as ―pearl polymerisation‖. Separation of
polymer is possible by simple filtration and removal of surface active agent is

21 | P a g e
possible by water washing e.g. expanded polystyrene, styrene-divinyl benzene-
block copolymer, PVA beads.

Emulsion Polymerisation
As in the case of suspension polymerisation, in the emulsion polymerisation also,
the monomer is dispersed in aqueous phase. Not as a droplet but as a uniform
emulsion. Emulsion is stabilized by certain surface active agents, protective colloids
and certain buffers. The surfactants can be
 Anionic – alkali salts of fatty acids
 Cationic – alkyl amines
 Non-ionic – esters of fatty acids
Surfactants serve the purpose of lowering the surface tension at monomer water
interface and facilitate emulsification of monomer. Surfactants are fully soluble
only at low concentrations and beyond certain concentration they do not disperse
molecularly but form aggregates known as ―micelles‖. The highest concentration
beyond which micelle formation takes place is known as ―critical micelle
concentration (CMC)‖. Emulsifier molecules are made of two parts namely a long
non-polar hydrocarbon and a polar groups such as COONa,, SO3 Na. In micelle
formation, the emulsifier molecules aggregates in such a way that the polar end of
the molecules align themselves outward and hydrocarbon ends come close to each
other at the interior. Due to close proximity of the hydrocarbon ends of all
emulsifier molecules, the interior of micelles acts as hydrocarbon phase where the
monomer can be solubilized.

Now, when the monomer is added and agitated, emulsification takes place. The
resultant emulsion is a complex system i.e. a molecular solution of emulsifier in
water is the continuous phase where in monomer droplets and micelles are
uniformly dispersed. If the monomer is slightly soluble in water, then aqueous
emulsifier will have monomers dissolved in it. This is the difference with
suspension polymerisation i.e. if the quantity of emulsifier added is less than CMC,
then it becomes suspension polymerisation. Emulsion polymers uses water soluble
initiators like hydrogen peroxide, persulphates. Therefore the monomer is present as

22 | P a g e
suspended droplets and solubilized in the interior of micelles. When monomer is
insoluble and initiator water soluble, no initiator can approach monomers and
polymerisation will not take place. At micelle, favrourable condition exists for
polymerisation to occur. The surface of micelle hydrophilic which can attract
initiator and the polymerisation starts from surface and proceeds inward.

As when the monomer is consumed for polymerisation, more monomers diffuse

inside the micelle from monomers present outside as droplets. The reaction
continues till the termination reaction and as the size grows, the micelle size also
enlarges and after particular stage, the micelles burst and lose its identity. This gives
more access to monomers. Therefore monomer droplets in the aqueous phase act as
a reservoir. At the end of the polymerisation, fine particles of the polymer,
stabilized by emulsifier layer and dispersed uniformly in the aqueous phase is
obtained. This milky white dispersion is often called ―latex‖. This can be either
used as such for making adhesives, water-soluble emulsion paints and etc. The
polymer can be separated using electrolytes, spray drying or freezing e.g. acrylates,
MMA, vinyl acetate.

Interfacial Condensation
Polymerisation is allowed to proceed at the interface between an aqueous and an
organic medium. Reactants having highly reactive functional groups, which can
readily react at ambient temperatures to form condensation products are suited to
this techniques e.g. aromatic polyamides. The diamine is dissolved in water and
acid chloride in chloroform or carbon tetrachloride. When the two solutions are
brought together, at the interface, the diamine molecules diffuse into the organic
phase and react. The resulting polymer precipitates out. The byproduct formed in
the reaction i.e. hydro chloric acid diffuses into the reacting medium. Since the
polymer formation at the interface is diffusion controlled process, very high
molecular weight products can be achieved by this technique. Higher agitation is
employed to achieve higher interface / volume ratio and so the DP and rate of
reaction. Due to agitation employed in the process, the polymer formed in the
process forms slurry, which is washed free of other reactants.

23 | P a g e
Solution Polymerisation
In this, the reactants are taken as a solution in a suitable inert solvent. The reaction
can be carried out at comparatively lower temperatures during which heat and mass
transfer is easier. The solvent is used for entrapping the byproduct is easier. Owing
to the presence of the solvent phase, however, kinetic probability of chain growth is
low and this leads to a reduce rate and a low DP e.g. liquid polyester resins.

Melt Polycondensation
This is suitable for monomers which have at least one solid component and do not
decompose around their melting point. The temperature involved in melt
polycondensation is higher and hence the reaction has to be carried out in an inert
atmosphere of nitrogen or carbon dioxide to avoid side reactions that can lead to
oxidation, decarboxylation and degradation.

In some cases, the reaction is carried out under reduced pressure to facilitate the
removal of the byproduct, which is necessary to achieve high molecular weight.
Also, removal of the byproduct will be difficult to achieve at later stages as the
viscosity increases. The polymer under molten state is removed from the reactor in
the same condition since it will be difficult to remove after solidification. In many
situations, hot melt is directly passed into processing equipment for extrusion,
spinning, casting e.g. PET, Nylon

24 | P a g e
Chapter Two: Multiple choice Questions
1. Polymerization is the process of :-
a) The synthesis of the large molecular weight polymers.
b) Monomer units are joined over and over, to generate each of the constituent
giant molecules.
c) Chain-growth and step-growth polymerization are the most common methods of
polymerization process.
d) All
2. The Feature of Polymerization Mechanism are given below:-
I. No small molecule is split off
II. Polymer molecular weight rises steadily
III. Only growth reaction adds repeat units one at a time
IV. Any two molecular species present can react
V. Monomer concentration decreases steadily throughout the reaction
VI. Low molecular weight by-products are obtained

Which of the following is feature of Step-Growth polymerization?

a) I, II, III
b) IV,VI,II
c) V,VI,III
d) IV,I,V
3. Which of the feature of polymerization in question 2 would be most explain for
Chain-Growth polymerization?
a) II,VI,III
b) IV,V,I
c) I,III,V
d) IV,VI,II
4. Which of the following is wrong combination?
a) Free Radical Chain Polymerization  Benzoyl Peroxide
b) Cationic polymerization Boron tri fluoride with Water
c) Chain-growth polymerization polyester
d) Step-growth polymerization nylon 6,6

5. Consider the following polymers;

i.

25 | P a g e
 ii.

iii.

iv.

Which of these will possess Anionic polymerization?

a) iii
b) iv
c) i
d) ii
6. Which of the polymers in question 5 would be most suitable for step growth
polymerization ?
a) i and ii
b) i and iv
c) iii
d) iii and i
7. When choosing an initiator for free-radical polymerization, which important
parameters are must be considered :-
a) The temperature range to be used for polymerization and the nature of the
monomer
b) The reactivity of the radicals formed
c) The presence of certain promoters and accelerators
d) All

8. Which of the following is the right sequence of fundamental steps of free radicals
polymerization?
a) Initiation, propagation, and termination.
b) Propagation, initiation, and termination.
c) Initiation, termination, and propagation.
d) Termination, propagation, and Initiation.
26 | P a g e
 9. Which of the following polymers has been produced from the ring-opening of cyclic
organic compounds?
a) Ethylene Oxides
b) Propylene Oxides
c) Poly(ethylene terephthalate)
d) a and b
10. The data for bulk chain polymerization having potassium persulfate as initiator is
given-
[I] = 5 mol/m3
[M] = 5.3*103 mol/m3
kp2/kt = 0.85*10-6 m3/ mol-s
What is the initial rate of polymerization, if potassium persulfate decomposes at a
rate of 2.2*10-6 m3 s/ mol?
a) 0.0261m3/mol-s
b) 0.0462m3/mol-s
c) 1m3/mol-s
d) 0.0162 m3/ mol-s.

Chapter two: Descriptive Questions

1. Write a note on polymerization?
2. What are the basic requirements of a monomer(s) to take part in condensation
polymerization/ Addition polymerization?
3. Explain the kinetic of free radical chain polymerization and Derive an expression
for the
overall rate of free radical Chain-growth polymerization?
4. Explain the fundamental steps in free radical chain polymerization in detail. 5.
List the differences between chain growth and step growth polymerization
6. Write a note on kinetic chain length in free radical polymerization.
7. What are LDPE and HDPE? How they are prepared?
8. Explain the applications of polymers obtained from ring-opening polymerization
process?
9. Compare the merits and demerits of different polymerization Methods?

27 | P a g e
Chapter Three

MANUFACTURING OF IMPORTANT POLYMERS AND

POLYMER PROCESSING

3.1. Polymer Production: Polyester (PET, PBT, PTT)

Polyethylene terephthalate (PET) is the most outstanding member of the family of

polyester. Polyester is defined as a polymer comprising synthetic linear
macromolecule having in the chain, at least 85% (by mass) of an ester of a diol and
terephthalic acid.

The initial efforts in making the polyester include

1. Sabacic acid + Ethylene Glycol : HOOC (CH2)8 COOH + HO (CH2)2OH

(WH Carothers)
2. Terephthalic acid + Ethylene Glycol: (Winfield and Dickson)

Polymer Production:
PET, a step growth (condensation) polymer, is produced industrially by one of the
following routes.

DMT Route: raw materials are dimethyl terephthalate and monoethylene glycol.
PTA / TPA Route: raw materials are terephthalic acid and monoethylene glycol.

Raw Materials
In earlier days, TPA (polymer grade) was not available and so PET was
manufactured using DMT and EG. By early 1960s, processes for TPA were
commercialized. Since then PET manufacturing using TPA has been increasing
steadily.

28 | P a g e
DMT MEG
Melting Point (o C) – 141 Boiling Point (o C) – 195 to 198o C
Boiling Point (o C) – 280
Ester Interchange value – 96% in 2 hours

High molecular PET is essential prerequisite for fibre formation and to obtain high
moleculare PET, it is necessary for the presence of both the monomers in equimolar
(1:1) proportion. To ensure stoichiometry ratio of 1:1, an intermediate reaction is
conducted between the two monomers (DMT + MEG) or (PTA + MEG) to produce
an intermediate diglycol terephthalate (DGT). In DGT, the acid: glycol ratio is
chemically fixed at 1:2. This is the first stage in Pet production.

Once DGT is formed, the second stage of polycondensation is similar for both the
routes.

The intermediate DGT formation leads to number of advantages compared with a

direct mixture of monomers subjected to polycondensation. The advantages include:
 The polycondensation process is applied to a uniform chemically
pure, monomeric starting material.
 Wider choice of catalysts
 Fewer side reactions
 High speed of reaction
 Good colour of polyester
 Better thermostability
 Better post treatment

29 | P a g e
The process involved in the reaction between DMT and MEG is referred to as Ester
Interchange or Trans-esterification.

On the other hand direct esterification (DE) can be carried out as given below:

30 | P a g e
Transesterification involving DMT and MEG is a slow process and requires a
catalyst for the process e.g. metal, metal oxides, metal salts (upto < 2.0%) like Zn,
Co, Pb, Ca and Mn. The powerful catalysts also results in unwanted side reactions.
Catalysts enhancing transesterification results in degradation in the
polycondensation step.

Antimony based catalysts are active in polycondensation step and not in ester-
interchange step.

Polycondensation
The rate of reaction is decided by temperature, vacuum, agitation, type of reactor
and concentration of catalysts used.
 As the temperature increases, the rate of polycondensation also increases.
However, at above 280o C, the degradation takes place.
 Longer duration inside the reactor may degrade the polymer.
 The increase in agitation also increase the viscosity of the melt (40 – 60 rpm)
 Application of vacuum results in more efficient and quicker removal of MEG
vapour and attainment of required melt viscosity at shorter time.
 Increase in carboxyl groups can deactivate the catalysts and slow down the
polycondensation.
PTA route
TPA itself accelerates the direct esterification step. However, if necessary, stronger
acids or esters of titanic acid can be used as additional catalysts.Due to absence of
metal catalyst, no side reactions can occur in this. But higher temperature used in
the polycondensation reaction some times degrades the PET. Generally, higher
DEG formation takes place in PTA route. This results in lower average molecular
weight, high dye affinity and lower melting point.Directesterification can be carried
out in the reactors used for transesterification reactions.

The solubility of TPA in MEG is low and requires a temperature of 240 – 260o Cat
400 kPa pressure. TPA and MEG are mixed in the proportion of 1:1 to 1:1.3. The
process proceeds smoothly and water, which is produced as a byproduct is allowed

31 | P a g e
to distill-off from the system. Hence no reflux system attachment is necessary as
required for methanol reflux in ester-interchange system.

When the process is complete, a thermal stabilizer is added to the melt and then
transferred to polycondensation vessel. Polycondensation is common to both DMT
and PTA processes. Vacuum is maintained to achieve higher molecular weight.

3.2. Poly (trimethylene terephthalate) (PTT)

Poly (trimethylene terephthalate) (PTT) is an aromatic polyester made by the

polycondensation of 1,3-propanediol (PDO) and terephthalic acid. Poly
(trimethylene terephthalate) is a semicrystalline polymeric material developed by
Shell Chemical Co., in various forms like fibre, films and plastic grade version.
Poly(trimethylene terephthalate) (PTT) was first synthesized and patented in 1941
but it was not produced commercially because of the expensive nature of one of the
precursors used in the synthesis i.e. 1, 3-propanediol. It is an odd-numbered
aromatic polyester compared to Poly(ethylene terephthalate) and poly(butylenes
terephthalate. Commercialisation of PTT fibre has become possible on account of
possible synthesis of 1,3 propanediol in a large scale. The PTT has a similar
molecular weight and characteristics as that of other polyesters. PTT fibres show
promising future in the field of carpets, textiles, films and packaging. Because of its
unusual mechanical and fiber properties, PTT has been widely studied in the past.

Fig. 1 Structure of PTT

Manufacturing of PTT involves the liquid feed mixtures comprising bis-3-

hydroxypropyl terephthalate and/or low molecular weight polyesters of 1,3-
32 | P a g e
propanedioI and terephthalic acid. Bis-3-hydroxypropyI terephthalate and the low
molecular weight polyesters are continuously polymerized to form a poly
(trimethylene terephthalate) pre-polymer and, subsequently, is continuousIy
polymerized to form a higher molecular weight poly (trimethylene terephthalate).

The PTT fibres show relatively lower melting temperature compared to normal poly
(ethylene terephthalate) and the molten polymer shows rapid crystallizing property
also. The PTT/PP based bico-melt-blown webs show enhanced barrier properties
and heat resistance and the PTT spun-bonded nonwovens showed better drapability
and elastic recovery. Nonwovens using hydro-entangling, thermo-bonding and
needle-punching have also been manufactured on laboratory using staple PTT fibers.
Poly (trimethylene terephthalate) has high stretchability, soft hand and low
processing temperature compared to the poly (ethylene terephthalate) fibres. PTT
fibers have optical properties similar to that of PET fibers i.e. high-refractive
indices. The refractive indices of PTT fibers have been found to be 1.626 in parallel
and 1.566 in perpendicular).

The melting point exists between 245 – 265o C during extrusion, which is lesser than
polyethylene terephthalate fibres. Although initially targeted for the carpeting
market, PTT can be spun and drawn at high speeds, resulting in a fiber suitable for
fine denier applications such as sportswear, activewear, and other specialty textiles.

3.3. Polybutylene terephthalate (PBT)

Polybutylene terephthalate (PBT) is a thermoplastic engineering polymer that is
used as an insulator inthe electrical andelectronics industries. It is
a thermoplastic (semi-)crystalline polymer, and a type of polyester. PBT is resistant
to solvents, shrinks very little during forming, is mechanically strong, heat-resistant
up to 150 °C (or 200 °C) and can be treated with flame retardants to make it
noncombustible.

PBT is closely related to other thermoplastic polyesters. Compared to PET

(polyethylene terephthalate), PBT has slightly lower strength and rigidity, slightly

33 | P a g e
better impact resistance, and a slightly lower glass transition temperature. PBT and
PET are sensitive to hot water above 60 °C (140 °F). PBT and PET
need UV protection if used outdoors, and most grades of these polyesters are
flammable, although additives can be used to improve both UV and flammability
properties.

Summary of the structures

Additives used in polyester production include:

 Optical whiteners (1%)
 Delustring agent – TiO2 (<1%)
 Pigments (organic, inorganic)
 Comonomers – salts of sodium
 Aliphatic glycol – to improve the dyeability
 Antibacterial agent
 Natural oils – for fragrance
 Flame retardants – phosphorous based additives

Amount of delustrant (titanium dioxide) used in Polyester and Nylon

34 | P a g e
 Type of fibre produced Quantity of TiO2 (%)
Bright 0.0 - 0.05%
Semi-matt 0.06 – 0.4
Matt 0.4 – 1.0
Strong matt 1.01 – 2.1
Super strong matt 2.1 and above

When the fibres are exposed to light, they loose their strength. Ultraviolet
component of light and moisture content of the samples are very much important in
such decomposition. Matt fibres are damaged more strongly than bright fibres
because TiO2 acts as catalyst and accelerates decomposition.

35 | P a g e
 3.4. Polyamides (Nylon 6, Nylon 6, 6)

Nylon 6, Nylon 66
Nylon 6 and Nylon 6, 6 are two important members of a group of polymers, known
as polyamides. The structural units of a polyamide are joined together by an amide
group – CO – NH - . Nylon 6,6 was the first synthetic fibres introduced
commercially (W.H. Carothers). Subsequently, Paul Schlack (Germany) discovered
nylon 6 in 1939.

Nylon is defined as a manufactured fibre in which the fibre forming substance is

long chain synthetic polyamide in which less than 85% of amide linkages are
attached to two aromatic rings, while at least 85% of amide linkage are joined to two
aromatic groups is known as aramids.

Nylon 6 Polymer Production

A polyamide that is derived from a diacid and a diamine is categorized as AABB
e.g. nylon 6,6. On the other hand, polyamide synthesized from an amino acid or a
lactum is termed as AB type e.g. nylon 6.

Caprolactum Amino caproic acid

Caprolactum (CL) can be synthesized via a number of methods using phenols,

benzene, toluene or cyclohexane. The main properties of caprolactum include:
Freezing point – 69o C and Moisture Content (%) – 0.10. Caprolactum does not
polymerize in a completely dry condition. It requires a catalyst which converts a
small amount of caprolactum to aminocaproic acid (ACA). This is followed by
polymerization. The catalyst can be an acid, base or simply water.

36 | P a g e
 Catalyst System
Acid Base Water
Type Strong Acids Carbonates, hydroxides ---
(HCl)
Rate of Reaction Fast Very Fast Slow
Yield (Output) Low High High
Commercial Use Not Used Shows Promise Commercially
Used

As the water concentration increases, the molecular weight decreases, time of

polymerization decreases, number of end groups increases.Water solubility in
caprolactum at constant temperature is proportional to water vapour pressure.
Increase in operating temperature decreases the amount of water in dissolved phase.

As the reaction temperature increases, molecular weight decreases, time decreases

and end groups decreases.

As the stabilizer concentration increases the molecular weight decreases.

The base catalyst system has the advantage of high production rate, high molecular
weight and narrow molecular weight distribution. However, it is difficult to
controlling the reaction is difficult.In industrial practice, the polymerization is
controlled by temperature in the range of 225 – 280o C and amount of water present
in the dissolved phase is kept around 5 – 10%.

Control of Molecular Weight

The molecular weight of nylon 6 is related to the degree of polymerization by the

relationship: MW= DP x 113.

37 | P a g e
The principal factors which control the molecular weight are temperature, amount of
water present in the system, time of polymerization and stabilizer used in the
reaction.

The stabilizer can be either acidic (acetic acid, benzoic acid) or basic (benzylamine).
An acid stabilizer leaves the carboxyl end groups in the polymer free end and thus
making it reactive to basic dyes. Basic stabilizers yield and acid dyeable nylon.

Thermal stabilizers are added in the case of tyre cord production.

Mechanism: Caprolactum polymerization is preceded by a hydrolysis step.

ACA adds to further monomer units, initiating polymerization. This is known as

step addition.

After polymerization has proceeded for some time, the process reaches equilibrium.
In industrial practice, under equilibrium conditions, the reaction forms equilibrium
with 90% in favor of polycaprolactum.

Once the equilibrium is reached, which usually takes about 4 – 6 hours in a VK tube,
a step growth (condensation) polymerization occurs. The reaction leads to an
increase in molecular weight.

Cyclic oligomers form as a by-product during the reaction.Due to higher solubility,

these oligomers can be extracted using boiling methanol. The optional ingredients
added during the process include:

 Delustrant (titanium dioxide TiO2) for dull or semi dull grade polymer

38 | P a g e
  An antistatic agent to reduce the static electricity
 Light stabilizer against ultra violet rays
 Heat stabilizers for tyre cord (copper salts, alkali metal oxides)
 Organic or inorganic pigments for mass colouration

As the feed enters the top zone, the molten mixture appears to boil due to water
bubbles escaping the liquid phase. The course of polymerization is decided by the
temperature in this zone. The step addition process is complete within 6 hours but
the residence time of 12 – 24 hours is allowed to increase the degree of
polymerization.

Caprolactum CL Melter (75o CL + Acetic acid + VK Tube Extruder

C) TiO2 + Water

CL Extraction Wash Cutter Cooler

High water content is required for the conversion of CL to ACA, step addition
polymerization process. While PC stage, the water concentration is to be maintained
at low level and also the by-product has to be eliminated (water). Two VK tubes are
used in series with each other instead of single tube. One for prepolymerising and
another for polymerization.

39 | P a g e
Washing
The nylon 6 polymer chips contain 90% PCL, 8-9% CL and 3% oligomers. The
chips are subjected to counter-current water wash at 95o C to remove CL. This is
necessary to prevent post polymerization of residual CL during spinning operation.

The residues after the final wash remain at 0.5%. The chips are dried in rotary drum
at 1-5 rpm at 100-120o C under vacuum or in nitrogen atmosphere for 20 – 50 hours.

40 | P a g e
Nylon 6, 6

The raw materials used in this are hexamethylene diamine and adipic acid. The
properties of the raw materials include:

Hexamethylene diamine Adipic Acid

Colourless Crystals White Crystals
Melting Point - 40o C Melting Point – 152o C
Boiling Point – 204 – 205o C Boiling Point – 216 o C
Molecular Weight – 116

It is necessary to maintain the molar ration of 1:1 of both to ensure high molecular
weight. This is achieved by reacting the two components in methanol solution at an
elevated temperature. This results in adipic acid – HMD Salt (AH Salt or Nylon 6, 6
Salt), which precipitates out.

41 | P a g e
About 13.5% of the weight of the monomer used is lost in the form of water whereas
only 2.0% of CL is lost in the case nylon 6 during recovery.

Polycondensation
This is carried out in an autoclave under nitrogen atmosphere under high
temperature. AH salt is introduced along with monofunctional agent (acetic acid)
acting as a molecular weight stabilizer. This is heated to 260 – 280o C. The
presence during the reaction is reduced to high vacuum to increase the DP of the
polymer.

Continuous Polymerisation
AH solution is prepolymerised in the reactor heated by the jacket. Then the mass is
conveyed through the pump into the flasher while moving forward, the pressure
decreases and so the polymerization takes place gradually. This is then transferred
to the screw pumping device.

42 | P a g e
Polymerisation using Dry Nylon 6,6 salt
It is a batch process and needs more time for the removal of water. The heating
process is carried out at 240o C.

Direct Polymerisation
Molten Adipic Acid and HMDA is added in equimolar proportion in a low
temperature polymeriser. Then the mass is transferred to PC reactor.

3.5. Polyacrylonitrile (Acrylic and Modacrylics)

Acrylic Fibres

Next to polyester and nylon, acrylic fibres occupy an eminent position in the
synthetic fibres. Acrylic fibres have replaced wool in many major applications,
particularly in knitted garments. Acrylic fibres are made using acrylonitrile as one
of the major monomers. Among vinyl monomers, acrylonitrile is the only monomer
used for the production of commodity synthetic fibres. Other vinyl monomers lack
cohesive forces between the molecular chains of their polymers and therefore cannot
compete with acrylonitrile.

Originally, acrylic fibres posed three main problems namely processability,

dyeability, degradability and to overcome this, comonomers are added. The term
―acrylic fibres‖ refers to a fibre containing at least 85% acrylonitrile monomer while
in modacrylics the percer of the acrylonitrile must be less than 85% but greater than
35%. All acrylic fibres are made from acrylonitrile (90-94%) combined with at least
one or two comonomers. Acrylics are manufactured, composed of at least 85% by
weight acrylonitrile units and remaining 15% with acidic monomers (0 -5%), neutral
monomers (5-10%) and vinyl pyridine (to open the structure).

43 | P a g e
 Methyl Acrylate (MA)
Opens up the structure, improves
Neutral Comonomers
Methyl Methacrylate (MMA) solubility and dyeability.

Vinyl Acetate (VA)

Ionic Comonomers
Sodium allylsulphonate, Sodium
(Sodium Salts of vinyl Basic dyes dyeability
styrene suplhonate
compounds)
Ionic Comonomers Allylamines, thiocyanates Acid dyes dyeability

Chloroethyl acrylonitrile Increases flame retardancy

Functional Additives Acrylamide, hydroxyl methyl or Improves antistatic properties,
propyl methacrylate hydrophilicity

Carboxylic acids such acrylic acid and methacrylic acids have, also, been used.

Polymerisation Methods
Three general polymerization methods are used in the case of acrylics namely,
solution polymerization, suspension and emulsion polymerization methods. Of
these, solution and suspension methods are used for fibre production.

Solution Polymerisation
Homogeneous solution polymerization in dimethyl formamide (DMF), dimethyl
acetamide (DMAc), dimethyl sulphoxide (DMSO) and zinc chloride (ZnCl2) have
the advantage of direct production of spinning dope. Monomers with highly reactive
functional groups can be polymerized at low temperature levels.
Solvent Time required for
polymerization (hrs)
DMF, DMAc 10 – 18, 2 – 4
NaSCN 1.5

AIBN, benzoyl peroxide are used as initiators and also the initiators with sulphonate
groups.

44 | P a g e
DMF, DMAc have higher chain transfer activity compared to DMSO and zinc
chloride and so latter are preferred. Of the conomonomers used, methacrylate is the
least active in chain transfer while vinyl acetate is as active as DMF and DMAc in
chain transfer.

To reduce the chain transfer activity of solvents, organic diluents are suggested like
acetone. The polymerization mixture containing DMF + Acetone + Acrylonitrile +
Methacrylate + AIBN is heated to 60o c for 20 hours.

 Because of high chain mobility in solution polymerisatin, chain termination

is rapid.
 Solution of insoluble monomers prior to polymerization is essential.
 Reaction rates of VA, vinly chloride are low and the polymer colour is
inferior.
 Choice of solvent is also decided by the type of spinning. DMF is used for
dry spinning as other organic solvents have higher boiling points.

Suspension /Dispersion Polymerisation

This is the most widely used method of polymerization using persulphates,
perchlorates or hydrogen peroxide as radical initiators. Depending upon the
initiators used, the end groups o of the polymer changes e.g. OH, SO4, SO3.

The initiation and primary radical growth steps occur in the aqueous phase. The
chain growth is limited in the aqueous phase because the monomer concentration is
normally very low and the polymer is in soluble in water. During polymerization,
water : monomer feed ratio vary from 3 to 5. EDTA or oxalic acid is used as the
chain stopper in the reaction.

45 | P a g e
Natural Product Polymers
Regenerated Cellulosic Fibre – Viscose Rayon
Production of viscose rayon involves treating the pulp, which is of higher degree of
polymerization than the final yarn, in caustic soda to get a uniform solution of lower
DP level. The pulp undergoes various unit operations like steeping, pressing,
shredding, xanthation, dissolving, ripening, filteration, deaeration and finally
spinning of filaments.
Steeping
Pulp sheets are soaked in aqueous solution of sodium hydroxide having the
concentration of 18% at ambient temperature or slightly higher. During steeping, the
pulp swells by capillary action and the reaction with caustic results in the formation
of sodium cellulosate.

Cell .OH + NaOH Cell. ONa+ H2O

Because of the chemical and physical changes, during steeping, heat is evolved,
approximately 2 KCal/kg, which may vary due to fill rate and may result in localized
temperature variation to several degrees.

Shredding
Pressing tends to compress the alkali cellulose, which needs to be opened to provide
uniform access to air and CS2 vapor/liquid in subsequent xanthation operation.
Ageing
Viscosity of viscose and final properties of rayon are dependent on average chain
length or DP of cellulose, which is controlled by ageing of alkali cellulose crumbs to
appropriate extent, depending on the type of rayon produced. There are atleast two
chemical reactions that will result in reducing the DP, viz., hydrolysis and oxidation.
Oxidation leads to random cleavage of the chains; hydrolysis involves end group
attack and removes single units from the ends of the cellulose chains.
Depolymerisation by hydrolysis occurs more slowly than that by oxidation.
Xanthation
In Xanthation, the reaction with CS2 leads to formation of soluble Sodium Cellulose
Xanthate (SCX), which is normally carried out in reactor creating a vacuum and
then introducing CS2. Orange colour formation is generally considered as an
indication of the end of xanthate formation.
46 | P a g e
 Cell OH + OH- Cell. O- + H2O
Cell O- + CS2 Cell O CS2-
CS2 also reacts with alkali, forming sulphur-containing byproducts such as sodium
trithiocarbonate and sulphide. The xanthation reaction is exothermic so the
temperature is maintained below 32o C by using cold-water circulation.
2 CS2 + 6 NaOH Na2 CS3 + Na2CO3 +Na2 S + 3 H2O
Ripening
Viscose ripening is the longest stage in the production of viscose, involving a
temperature range as low as 10 -16o C. Removal of air is essential for avoiding
bubbles that would interfere with smooth spinning. This is accomplished either
simultaneously with ripening in a tank or continuously by exposing a thin film of
viscose to relatively a high vacuum immediately prior to ripening tank and air is
removed gradually during the process. The extent of the ripening can be measured
by viscosity and Salt Index or Hottenroth Number.
CellO CS= Cell O- + CS2 (Decomposition)
Cell O- + CS2 + Cell O CS2- (Rexanthation)
Cell O CS2- + Cell OH Cell OCS2- + Cell OH (Transxanthation)
2CS2 + 6 NaOH Na2CS3 + Na2S + 3 H2O (Byproduct formation)

Structure Development during Spinning

Spin bath and its components, spinning method and post spinning operation play a
major role in the development of the morphological structure. Spin bath includes

Sulphuric acid 8-10%

Sodium Sulphate 22-24%
Zinc Sulphate 1-2.5%
Water - Balance
Initially, action of acid/salt present in the spin bath causes the viscose to coagulate
and forms a skin around the filament. Then as the acid penetrates in to the viscose
filaments, neutralization of alkali occurs. At the same time cellulose xanthate is
regenerated and CS2 is liberated. The principal reactions beginning at the spinneret
are coagulation, neutralization and regeneration. In the coagulation process, viscose
sets up a gel rapidly and can be regarded as the major step.
47 | P a g e
 2 Cell O CS2 Na + ZnSO4 (Cell O CSS)Zn + Na2SO4 (Coagulation)
2Cell OCS2 + H2SO4 2 Cell OH + Na2SO4 + 2 CS2
(Regeneration)
The products of these reactions, together with those from the neutralization of the
alkali as the acid penetrates the forming fibre, diffuse in to the spin bath. Sodium
sulphate, the neutralization product, is also one of the spin bath components that
mainly affect removal of water from the gel filament i.e. dehydration. Zinc sulphate,
being a coagulation and dehydration agent, also influence the cellulose regeneration.
The forces that act to shape the filament have been classified into
 Osmotic pressure, developing as a result of diffusion process
 Tensile and compressive forces from the mechanical action of spinning and
stretching
 Collapse of the structure by dehydration and shrinkage

Alternatives to Spin Bath with Zinc Sulphate

During spinning of viscose rayon 2-4 kg/ton of rayon of zinc gets carried over with
the filaments after spinning. This result in zinc bearing effluents and zinc pollution
affects marine and aquatic life. The other drawback with zinc is the formation of
encrustation on the spinneret surface due to the formation of some complex ZnS
salts, which can affect spinning performance.
Aluminium scores over zinc as well as other alternative chemicals. Aluminium in
the form of aluminium sulphate is widely used in water treatment plants and does
not pose any hazard to human, animal, plant and marine life. The various reactions
taking place in presence of aluminium compound are:
2 NaOH + H2SO4 Na2SO4 + 2 H2O

6 NaOH + Al2 (SO4)3 2 Al (OH)3 + 3 Na2 SO4

2 Al (OH)3 + 3 H2 SO4 Al2 (SO4)3 + 6 H2 O

Third reaction also reduces the rate of hydrolysis of cellulose xanthate as this
reaction also consumes sulphuric acid. In a bath containing both aluminium and zinc
sulphate, increase in zinc sulphate resulted in increase in elongation, also decrease in
aluminium sulphate content.
48 | P a g e
Magnesium sulphate, being more soluble than sodium sulphate, permits high salt
concentration in bath without crystallization difficulties. These additives are tested
for LD50 oral toxicity, skin compatibility, irritation to mucus membrane.
Cuprammonium rayon and Acetate rayon
Cellulose Acetate (Dry Spun)
The starting material for acetate fibres was formerly cotton linters, the shorter fibres
attached to the cotton seed. Wood pulp is used now to obtain superior fibre
properties. The purified fibres are steeped in glacial acetic acid so that they become
more reactive. They are thoroughly mixed with an excess of glacial acetic acid and
acetic anhydride. Addition of sulpuric acid is used to accelerate the acetylation
reaction.
The reaction is strongly exothermic and in order to avoid degradation of the polymer
molecules and needs cooling. The process is carried out at 20 – 30o C for 8 hours
and a gelatinour mass is obtained.
In order to make the secondary acetate, sufficient water is added to the mixture,
which contains excess acetic acid and acetic anhydride to give a solution of 95%
acetic acid. The reaction is carried out for 20 hours and stopped when 1/6th of
acetate groups have been randomly changed to OH groups. It is essential to remove
the sulphate radicals during the hydrolysis process. Excess water is added and
secondary acetate is precipitated. It takes 24 hours and stirring to dissolve the
secondary acetate in about 3 times its weight of acetone mixed with alcohol or
water.
“S” Finishing – Surface saponification of triacetate fibres is called ―S Finishing‖,
treated with 0.35% sodium hydroxide and wetting agent at 90o C for one hour. It
has the following advantages. 1) Improved anti-static properties as its hydroxyl
groups increases due to saponification, 2) Improved resistant to glazing during
ironing since no softening takes place, 3) handle is improved and saponifiedfibre is
more receptive to soft finish and 4) Rubbing fastness is improved after dyeing.
Fortisan
This is made by stretiching cellulose acetate in steam under pressure then
saponifying the stretched yarn. During saponification , it losses 38% of its weigh. It

49 | P a g e
is the most highly oriented and strongest of any cellulosic fibres with tenacity 5.8
g/den in dry condition and 5.56 g/den under wet condition.
Durafil
It is extremely fine rayon with about 0.3 denier i.e. all skin type. Its dry strength is
about 5.5 g/den (wet – 3.9 g/den) and elongation at break is about 7% (wet contition
– 8%).
Cuprammonium Rayon
Cotton linters are used as raw material in the production of cuprammonium rayon.
Mechanically opened and purified cotton linters are boiled with 2% sodium
carbonate with little amount of sodium hydroxide. Both are removed by washing
and is followed by bleaching of cotton fibres with hypochlorites at room temperature
for 1-2 hours. Cuprammonium hydroxide solution is added to the purified linters
and is dissolved to a solution. Thus, copper-cellulose is formed and then is filtered.
Spinning solution is prepared by dissolving the cellulose at low temperature in
aqueous ammonia containing basic copper sulphate, which is again filtered. Pure
spinning solution is blue in colour and is highly stable. Spinning of cuprammonium
rayon is done by two methods, namely, stretch spinning or continuous spinning.
Difference exists only in post spinning methods. In stretch spinning, filaments are
collected in Topham box while in continuous form they are collected in the form of
sheet. The spinnerette is made of nickel and has large holes 0.8 mm (viscose
0.5mm).
Spinning solution is extruded through holes into a long glass funnel. In between
spinneret and this funnel, filaments are subjected to stretch and so called ―stretch
spinning‖. At top of the funnel soft, slightly alkaline water is introduced and runs
out at bottom. Then it is taken to acid bath where the coagulation is completed.

Property Viscose Acetate Triacetate Cuprammonium

rayon rayon rayon
Dry Tenacity (g/d) 2.6 1.3 – 1.2 ---
1.7
Wet Tenacity (g/d) 1.4 0.9 0.8 1.2
Elongation at Break 15 25 --- 15

50 | P a g e
(%) (EAB)- Dry
Wet EAB (%) 25 35 --- 25
Moisture Content (%) 12 - 13 1.32 --- ---
Specific Gravity (g/cc) 1.52 1.32 --- ---
Melting point (o C) -- --- 290 – 300 ---

Modified high wet modulus – Polynosic yarn & super high wet modulus yarn

Spin Bath with zinc sulphate

Spin bath for conventional process include Sulphuric acid (8-10%), Sodium
Sulphate (22-24%), Zinc Sulphate (1-2.0%) and Water (Balance Quantity). The
diameter of the filament has a considerable effect on the rate of diffusion and the
decomposition of cellulose xanthate and in turn affects the structure and properties
of the fibre. The alkaline viscose solution is exposed to an acidic spin bath under
carefully controlled conditions. Initially, action of acid/salt present in the spin bath
causes the viscose to coagulate and forms a skin around the filament. Then as the
acid penetrates in to the viscose filaments, neutralization of alkali occurs. At the
same time cellulose xanthate is regenerated and CS2 is liberated. The continuous
buildup of sodium sulphate and water will have to be removed from the system for
maintaining a material balance.

2Cell OCS2 + H2SO4 2 Cell OH + Na2SO4 + 2 CS2

Poly nosic fibers

The term ―polynosic‖ was coined in 1959 to stress the high polymeric nature of
material. The polynosicfibrespossesss a high degree of wet modulus than ordinary
rayons. The extension is not more than 3.5% in water. Polynosics are high strength
51 | P a g e
viscose rayon fibres with particularly higher wet strength. Earlier researches on
viscose processes were aimed at rapid coagulation and regeneration following
extrusion. Polynosics require reversal of this trend and employ a weak spinning
bath with dilute acid, sodium sulphate without zinc sulphate. This allows slow
xanthate decomposition while appreciable stretch is applied before complete
regeneration. A highly ordered (crystalline) and oriented structure is developed with
higher modulus characteristics in both dry and wet conditions. The absence of zine
ions results in a structure without a skin structure. The degree of polymerization is
maintained about twice the level of ordinary rayon, through the elimination of
ageing stage and ripening of cellulose xanthate which is dissolved in water instead
of alkali. The spin bath composition include
Sulphuric Acid – 2 – 3%
Sodium Sulphate – 4 – 6%&Temperature – 25o C
The stretch given to the filaments is as high as 150 – 300% at a speed of 100 m/min.

Modified Rayons

Addition of certain chemical to the viscose serve to stabilize xanthate

decomposition, thereby prolonging the period during which effective stretch may be
applied. The examples of the modifiers include tertiary amines, dithiocarbamates.

Action of Modifiers
Modifiers do not influence the process independently and are effective only in
presence of zinc in the spin bath. Modifiers are added up to 1-3% by weight of
cellulose and added to viscose prior to the extrusion. They are also added into the
spin bath. Sometimes, spin bath proportion is also modified e.g. reducing acid
concentration, increasing the zinc salt concentration. Formation of semipermeable
membrane by the combined action of zinc and modifier retards the penetration of H+
(acid) is significantly increased in the presence of the modifier.

Modified High Wet Modulus Rayon (HWM)

52 | P a g e
The conditions of viscose solution and spinning bath composition are similar to tyre
cord yarns..
Sulphuric Acid – 8 – 10%
Sodium Sulphate – 16 – 24%
Zinc Sulphate – 6%
Temperature <350C

The fibres can be stretched up to 125 - 150%.

Super High Wet Modulus Rayon

It has been reported that addition of about 1% of formaldehyde to the spin bath or to
the viscose solution, substantially increases the toughness, plasticity of viscose gel.
This permits the stretch levels up to 500 – 600%. Compound gel formed by
xanthated cellulose and formaldehyde has stability against sulphuric acid in the
presence of excess formaldehyde.

This reduces relative mobility of the molecules but increases the mobility of
individual molecules and forms transient cross linking. This enhances the stretch
and so the toughness. In the next bath regeneration is carried out which may not
contain formaldehyde. Fibres with a tenacity of 10 g/d with 6% elongation can be
obtained using this process. But toxic nature of formaldehyde prevents the
commercial exploitation of the fibres.

Principle of manufacture: Casein fibre – Properties

Casein (Milk Fibre)
Milk Fiber was firstly introduced in 1930 in Italy & America to compete the wool. It
is new generation of innovative Fiber & a kind of synthetic Fiber made of milk
casein Fiber through bio-engineering method with biological health which has
passed international ecological certification of oeko-tex standard 100. There are also

53 | P a g e
some different brands for the same fiber manufactured from milk casein known as
Aralac, Lanatil and Merinova.

Milk protein contains 18 amino acids and has natural and permanent antimicrobial
effect, used for top-grade apparels.

Manufacturing
Milk is skimmed to remove the cream. Skimmed milk is heated to 40o C and acid is
added to coagulate the proteins which separate as the curd, liquid part is separated.
The curd is washed to remove acids, salts. Most water is removed mechanically and
curd is dried. The curd consists of casein. 100 lbs of milk yields 3 lbs of casein and
about same amount of fibre can be produced.10 kg of casein is dispersed in 50 L of
water containing 0.2 kg of NaOH (i.e. 2.7% of NaOH on weight of water), the
resultant solution is clarified, extruded through spinneret.Extruded fibres are drawn,
dried and often cross-linked using formaldehyde and then cut into the staple fibre
form. The coagulation bath consists of
Water – 100 parts
H2SO4 - 2 parts
HCHO – 5 parts
Glucose – 20 parts

After drawing, the fibres are rinsed, dried and crimped before cutting into staple
form.

Advantages
Today's Milk Fiber is environmentally friendly, high strength & much more superior
as compare to man-made fibers. Some of the benefits of having Milk Fiber are as
given below:
 As it is having continues graft polymerization technique hence it is totally
eco-friendly in nature.

54 | P a g e
  It can be considered as "Green Product" as no formaldehyde is present in the
product.
 Milk fiber is made from milk casein instead of fresh milk. We may use acid,
reactive or cationic dyes for this kind of specialty fiber.
 pH of milk fiber is 6.8 which are same as that of human skin. Hence the
products made up from them are more compatible to human skin.
 Milk Fiber contains seventeen amino acids & natural anti-bacterial rate is
above eighty percent. Hence milk fiber has sanitarian function.
 It is a new synthetic Fiber having milk protein as main material based on
high technical process. Milk Fiber has the advantages natural Fiber
combined with synthetic Fiber.
 These are more comfortable, excellent water transportation & air
permeability

Soybean Protein
Soybean protein fibres are praised as the healthy, comfortable and green fibre of the
new century. Its major material is soybean protein, which is obtained from soy
bean. Soya bean has high protein content (35%).
Soy beans are crushed, meal is extracted with solvent hexane to remove oily
substances. Protein is dissolved out the remaining materials by dilute sodium
sulphate solution. The protein is recovered by acidification of solution. Enzymes
and auxiliaries are added which alters spherical proteins into a linear one.

55 | P a g e
Chapter three: - Multiple choice Questions
1. Which of the following is not true about polyester?
a) It forms a large class of commercially important polymers.
b) poly(ethylene terephthalate) is the largest volume synthetic fiber.
c) It characterized by the presence of amide linkages.
d) It used as film (Mylar) and in bottle applications.
2. Which of the following functional group would you expect to be most
suitable for the synthesize of polyamide?
a) Condensation reaction between a dicarboxylic acid and a diamine
b) Addition reaction between a dicarboxylic acid and a diamine
c) Reaction between a diacid chloride and a diamine
d) a and c
3.

This polymer produce by the reaction of :-

a) Dimethyl terephthalate + ethylene glycol
b) Adipic acid + Hexamethylenediamine
c) Hydrolytic polymerization of caprolactam
d) Dimethyl formamide + ammonium persulfate
4. Which of the functional group in question 3 would be most suitable for the
production of nylon6,6 ?
5. Which one is a Natural Product Polymers?
a) Acrylic fibers and Modacrylic
b) Cellulose fibers and starch
c) Poly(ethylene terephthalate )
d) Nylon6,6 and nylon 6
6. Which of the polymers in question 5 would be include in
POLYACRYLONITRILE (PAN) ?
7. Which of the following is wrong combination?

56 | P a g e
 a) Polyacrylonitrile (pan) Acrylic fibers
b) Natural Product PolymersStarch
c) Polycaprolactam Nylon 6
d) poly(ethylene terephthalate) Nylon6,6
8. Why mixing and heat transfer are the main difficulties in bulk
polymerization?
a) Because viscosity of the reaction mass increases.
b) Because viscosity of the reaction mass decreases.
c) Because viscosity of the reaction mass constant.
d) None
9. Which of the following is not true about polymerization processes?
a) In homogeneous polymerization, all the reactants including monomers,
initiators, and solvents are mutually soluble and compatible with the
resulting polymer.
b) In heterogeneous polymerization, the catalyst, the monomer, and the
polymer product are mutually insoluble.
c) Heterogeneous polymerization comprises bulk (mass) or solution
systems.
d) Heterogeneous polymerization reactions may be categorized as,
suspension , precipitation, emulsion, and interfacial polymerization
10. Which of the following polymerization techniques are classified under
homogeneous polymerization?
a) Interfacial polymerization
b) Solution polymerization
c) Suspension polymerization
d) Emulsion polymerization
11. Which of the following are disadvantages of Bulk Polymerization?
a) The polymer is obtained pure
b) Heat transfer and mixing become difficult
c) The system is simple and requires thermal insulation
d) Molecular weight distribution can be easily changed with the use of a
chain transfer agent.
57 | P a g e
12. Which system consists of water insoluble monomer, dispersion medium and
emulsifying agents or surfactants (soaps and detergents) and a water
soluble initiator (potassium persulphate / H2O2).
a) Suspension polymerization
b) Bulk polymerization
c) Emulsion polymerization
d) Solution polymerization

Chapter three: Descriptive Questions

1. Write the polymerization reaction of the following polymers :-
a) Polyester (PET)
b) Nylon 6,6
c) Polycaprolactam (Nylon 6)
2. Why the numbers 6, 6 and 6 are put in the name of nylon-6, 6 and nylon-6?
3. Explain the difference and similarity of starch and cellulose?
4. Why mixing and heat transfer are the main difficulties in bulk polymerization?
5. Compare the merits and demerits of different polymerization techniques?
6. Explain the principle of the following addition polymerization techniques :-
a) Bulk polymerization
b) Solution polymerization
c) Suspension polymerization
d) Emulsion polymerization

58 | P a g e
CHAPTER 4

STRUCTURE OF POLYMERS
Microstructure of a polymer can be defined in terms of its conformation and
configuration.Polymer morphology, which may be defined as the study of the
structure and relationships of polymer chains on a scale large compared with that of
the individual repeat unit or the unit cell, i.e. on the scale at which the polymer
chains are often represented simply by lines to indicate the path of the backbone
through various structures. morphology is concerned with such matters as the
directions of the chain axes with respect to the crystallite faces and with the
relationship between the crystallites and the non-crystalline material, a particular
aspect of which is the nature of the crystalline ‗amorphous‘ interface .

The shape of the polymer molecule will be influenced naturally by the nature of the
repeating unit and the manner in which these units are linked together. A particular
state of tacticity is a particular configuration of the molecule and cannot be changed
without breaking and reforming bonds and, at ordinary temperatures; there is not
enough thermal energy for this to happen. Rotations around bonds produce only
different conformations. It is therefore convenient to consider polymer shape in two
contexts:

1. Configuration or cis-trans isomerism : Arrangement fixed by primary

valence bonds; can be altered only through the breaking or reforming of
chemical bonds.A change in configuration require the rupture of covalent
bond
2. Conformation: Arrangement established by rotation about primary valence
bonds. Is defined by its sequence of bonds and torsion angles. The change in
shape of a given molecule due to torsion about single (σ ) bonds.
Configurations – to change must break bonds

59 | P a g e
4.1. Structure and Conformation of Polymer molecules
The term conformation refers to the different arrangements of atoms and substituents
of the polymer chain brought about by rotations about single bonds. The term
conformation has taken on two separate meanings: (a) the long-range shape of the
entire chain.Molecular orientation can be changed by rotation around the bonds
without bond breaking. Moreover, while maintaining the 109 degree angle between
bonds polymer chains can rotate around single C-C bonds (double and triple bonds
are very rigid).

4.1.1. Isomerism
The term configuration includes its composition, sequence distribution, steric
configuration, geometric and substitutional isomerism. Isomerism are hydrocarbon
compounds with same composition may have different atomic
arrangements.Physical properties may depend on isomeric state (e.g. boiling
temperature of normal butane is -0.5 oC, of isobutane -12.3 oC)

Vinyl polymers are addition polymers that have the general formula (CHX—CH2)n,
where X may be any group and is, for example, a chlorine atom for poly(vinyl
chloride) (PVC). Slightly more complicated polymers are those such as poly(methyl
methacrylate) (PMMA), which has the formula (CXY—CH2)n, where X is a methyl
group (CH3) and Y is the methacrylate group ((CO)OCH3) (see fig. 1.2). These
polymers are sometimes also classed as vinyl polymers. Both types of polymer may
have two principal kinds of irregularity or configurational isomerism:(i) the
monomer units may add head-to-head or tail-to-tail and (ii) the chains need not
exhibit a regular tacticity. The two mirror image configurations remain
distinguishable, however. The different possible spatial arrangements are called the
tacticity of the polymer.

60 | P a g e
It is a geometrical requirement that if a polymer is to be potentially capable of
crystallising, its chains must be able, by undergoing suitable rotations around single
bonds, to take up an arrangement with translational symmetry. If a polymer is
actually to crystallise there is also a physical requirement:the crystal structure must
usually have a lower Gibbs free energy than that of the non-crystalline structure at
the same temperature. Consideration of this physical requirement is deferred to later
sections;the present section deals only with the geometrical requirement.Geometrical
regularity can be considered to require(i) chemical regularity of the chain and (ii)
stereoregularity of the chain.

4.1.2. Stereoregularity and Geometrical isomerism

Stereoregularity means that the chain must be capable (by rotations about single
bonds) of taking up a structure with translational symmetry. Translational symmetry
means that the chain is straight on a scale large compared with the size of the
chemical repeat unit and consists of a regular series of translational repeat units, so
that the chain can be superimposed upon itself by translation parallel to the axis of
the chain by the length of one translational repeat unit Stereoisomerism which atoms
are linked together in the same order, but can have different spatial arrangement.
Isotactic configuration all side groups R are on the same side of the chain. If the R
groups on successive pseudochiral carbons all have the same configuration,the
polymer is called isotactic.Syndiotactic configuration: side groups R alternate sides
of the chain. Atactic configuration: random orientations of groups R along the chain.

Geometrical isomerism: The most important examples in this class are the cis and
trans isomerism about double bonds. Take polybutadiene as an example, The cis–
trans isomerism arises because rotation about the double bond is impossible without
disrupting the structure. Thus the formula on the left of equation is written cis-
polybutadiene. The cis and trans formulas are both crystallizable when appearing in
pure form, but with different melting temperatures. If a mixture of cis and trans
isomers occurs, crystallization may be suppressed, similar to the atactic polymers.

4.1.2. Tacticity in Polymers

The polymerization of a monosubstituted ethylene, such as a vinyl compound, leads
to polymers in which every other carbon atom is a chiral center. This is often
marked with an asterisk for emphasis:

61 | P a g e
Such carbon atoms are referred to as pseudochiral centers in long-chain polymers
because the polymers do not in fact exhibit optical activity (12). The reason for the
lack of optical activity can be seen through a closer examination of the substituents
on such a pseudochiral center:

The two chain segments are indicated by and and in general will be of unequal
length. The first few atoms of the two chain segments attached to C* are responsible
for the optical activity, not those farther away. These near atoms are seen to be the
same, and hence the polymer is optically inactive.The two mirror image
configurations remain distinguishable, however.The different possible spatial
arrangements are called the tacticity of the polymer. If the R groups on successive
pseudochiral carbons all have the same configuration, the polymer is called
isotactic( below figure a). When the pseudochiral centers alternate in configuration
from one repeating unit to the next, the polymer is called syndiotactic (below figure
b). If the pseudochiral centers do not have any particular order, but in fact are
statistical arrangements, the polymer is said to be atactic (below figure c).

In specifying the tacticity of the polymer, the prefixes it and st are placed before the
name or structure to indicate isotactic and syndiotactic structures, respectively. For
example, it-polystyrene means that the polystyrene is isotactic.Such polymers are
known as stereoregular polymers.The absence of these terms denotes the
corresponding atactic structure.The second point is the stereoregularity displayed by
monosubstituted vinyl polymers of olefins. Isotactic and syndiotactic polymers
possess stereoregular structures.

62 | P a g e
Tacticity affects the physical properties:The isotactic and syndiotactic structures are
both crystallizable because of their regularity along the chain.However, their unit
cells and melting temperatures are not the same. Atactic polymers, on the other
hand, are usually completely amorphous unless the side group is so small or so polar
as to permit some crystallinity. Atactic polymers will generally be amorphous, soft,
flexible materials, low melting and easily soluble.Isotactic and syndiotactic
polymers will be more crystalline, harder, less flexible (rigid), high melting and
relatively insoluble. Polypropylene (PP) is a good example. Atactic PP is a low
melting, gooey (soft) material. Isoatactic PP is high melting (176º), crystalline,
tough material that is industrially useful. Syndiotactic PP has similar properties, but
is very clear. It is harder to synthesize.

4.2. Major Transitions in Polymer Molecules

When a block of ice is heated, its temperature increases until at a certain temperature
(depending on the pressure) it starts to melt. No further increase in temperature will
be observed until all the ice has melted (solid becomes liquid).If heating is
continued, the same phenomenon is observed as before and as the liquid starts to
boil (liquid turns to vapor).However, the transitions in polymers are somewhat
different and certainly more complex.In the first place, those molecules large enough
to be appropriately termed polymers do not exist in the gaseous state.At high
temperatures, they decompose rather than boil since what we would consider
conventionally as their ―boiling points‖ are generally higher than their
decomposition temperatures.Second, a given polymeric sample is composed of a
mixture of molecules having different chain lengths (molecular weights).
In contrast to simple molecules, therefore, the transition between the solid and liquid
forms of a polymer is rather diffuse and occurs over a temperature range whose
63 | P a g e
magnitude (of the order of 2 to 10°C) depends on the polydispersity of the
polymer.On melting, polymers become very viscous (viscoelastic) fluids, not freely
flowing as in the case of low-molecular-weight materials.Two important
temperatures at which certain physical properties of polymers undergo drastic
changes have been identified:The glass transition temperature, Tg and crystalline
melting point, Tm. If a polymer is amorphous, the solid-to-liquid transition occurs
very gradually, going through an intermediate ―rubbery‖ state without a phase
transformation.The transition from the hard and brittle glass into a softer, rubbery
state occurs over a narrow temperature range referred to as the glass transition
temperature. In the case of a partially crystalline polymer, the above transformation
occurs only in the amorphous regions.The crystalline zones remain unchanged and
act as reinforcing elements thus making the sample hard and tough.If heating is
continued, a temperature is reached at which the crystalline zones begin to melt. The
equilibrium crystalline melting point, Tm, for polymers corresponds to the
temperature at which the last crystallite starts melting.

Atomic arrangement in polymer crystals is more complex than in metals or ceramics

(unit cells are typically large and complex). Polymers can be divided into two broad
classes, amorphous and semicrystalline. If observations are made at a fixed
frequency, or isochronally,crystalline polymers often exhibit three major transitions
as the temperature is varied, usually labelled a, b and g in decreasing order of
temperature, whereas amorphous polymers generally exhibit two major
transitions,labelled a and b in decreasing order of temperature. If other relaxations
are seen at lower temperatures, they are labelled g or d,respectively. These labels are
arbitrary and do not indicate any fundamental relationship between the relaxations

64 | P a g e
given the same label in different polymers. For an amorphous polymer the transition
at the highest temperature, labelled a, always corresponds to the glass transition,
whereas for polymers of low crystallinity it is often the transition labelled b that
corresponds to the glass transition. For this reason the glass transition in amorphous
polymers is sometimes labelled aa to distinguish it from the a transition in
crystalline polymers, which can sometimes be assigned to the crystalline material.
At the glass transition temperature, Tg, the amorphous portions of a polymer soften.
The most familiar example is ordinary window glass, which softens and flows at
elevated temperatures. Yet glass is not crystalline, but rather it is an amorphous
solid. It should be pointed out that many polymers are totally amorphous. Carried
out under ideal conditions, the glass transition is a type of second-order transition.
The basis for the glass transition is the onset of coordinated molecular motion is the
polymer chain. At low temperatures, only vibrational motions are possible, and the
polymer is hard and glassy In the glass transition region, region 2, the polymer
softens, the modulus drops three orders of magnitude, and the material becomes
rubbery. Regions 3, 4, and 5 are called the rubbery plateau, the rubbery flow, and the
viscous flow regions, respectively. Examples of each region are shown below
figures .

65 | P a g e
4.2.1. Polymer Crystallinity
The development of crystallinity in polymers depends on the regularity of structure
in the polymer. Thus isotactic and syndiotactic polymers usually crystallize, whereas
atactic polymers, with a few exceptions (where the side groups are small or highly
polar), do not. Regular structures also appear in the polyamides (nylons), polyesters,
and so on, and these polymers make excellent fibers. Nonregularity of structure first
decreases the melting temperature and finally prevents crystallinity. Mers of
incorrect tacticity tend to destroy crystallinity, as does copolymerization. Thus
statistical copolymers are generally amorphous. Blends of isotactic and atactic
polymers show reduced crystallinity, with only the isotactic portion crystallizing.
Under some circumstances block copolymers containing a crystallizable block will
crystallize;again, only the crystallizable block crystallizes.Polymer molecules are
often partially crystalline (semi- crystalline), with crystalline regions dispersed
within amorphous material.

Most crystallizing polymers are semicrystalline; that is, a certain fraction of the
material is amorphous, while the remainder is crystalline. The reason why polymers
fail to attain 100% crystallinity is kinetic,resulting from the inability of the polymer
chains to completely disentangle and line up properly in a finite period of cooling or
annealing.More crystallinity is an indication of higher density, more strength, higher
resistance to dissolution and softening by heating.Degree of crystallinity is
determined by:
I. Rate of cooling during solidification: time is necessary for chains to move
and align into a crystal structure.

66 | P a g e
 II. Mer-complexity: crystallization less likely in complex structures, but simple
polymers, such as polyethylene, crystallize relatively easily.
III. Chain configuration: linear polymers crystallize relatively easily, branches
inhibit crystallization, network polymers almost completely amorphous,
cross- linked polymers can be both crystalline and amorphous.
IV. Isomerism: isotactic, syndiotactic polymers crystallize relatively easily -
geometrical regularity allows chains to fit together, atactic polymers is
difficult to crystallize.
V. Co-polymerism: easier to crystallize if mer arrangements are more regular -
alternating, block can crystallize more easily as compared to random and
graft.
There are several methods for determining the percent crystallinity in such
polymers. The first involves the determination of the heat of fusion of the whole
sample by calorimetric methods such as DSC; The heat of fusion per mole of
crystalline material can be estimated independently by melting point depression
experiments; A second method involves the determination of the density of the
crystalline portion via X-ray analysis of the crystal structure, and determining the
theoretical density of a 100% crystalline material. The density of the amorphous
material can be determined from an extrapolation of the density from the melt to the
temperature of interest. Crystalline polymers are denser than amorphous polymers,
so the degree of crystallinity can be obtained from the measurement of density

Where

- represents the experimental density, and

- are the densities of the amorphous and crystalline

portions, respectively.

A third method stems from the fact that the intensity of X-ray diffraction depends on
the number of electrons involved and is thus proportional to the density. Besides
Bragg diffraction lines for the crystalline portion, there is an amorphous halo caused
by the amorphous portion of the polymer. This last occurs at a slightly smaller angle
than the corresponding crystalline peak, because the atomic spacings are larger. The
amorphous halo is broader than the corresponding crystalline peak, because of the
molecular disorder.

67 | P a g e
4.2.2. The glass transition Temperature (Tg)
At a characteristic temperature, Tg, the rate of volume expansion increases suddenly
to a higher constant level, i.e., there is a change in the slope of the volume–
temperature curve from a lower to a higher volume coefficient of expansion.At the
same time, there is an abrupt change in physical behavior from a hard, brittle, glassy
solid below Tg to a soft, rubbery material above Tg.On further heating, the polymer
changes gradually from the rubbery state to a viscous liquid whose viscosity
decreases with increasing temperature until decomposition sets in.For a crystalline
polymer, the changes at Tg are less drastic. This is because these changes are
restricted mainly to the amorphous domains while the crystalline zones remain
relatively unaffected between the glass transition (Tg) and the melting temperature
(Tm).The semi-crystalline polymer is composed of rigid crystallites immersed
(dispersed) in a rubbery amorphous matrix. In terms of mechanical behavior, the
polymer remains rigid, pliable, and tough. At the melting temperature, the
crystallites melt, leading to a viscous state . Above Tm the crystalline polymer, like
the amorphous polymer, exists as a viscous liquid.
For amorphous polymers, the glass transition temperature, tg, constitutes their most
important mechanical property. in fact, u qualitatively, the glass transition region
can be interpreted as the onset oflong-range, coordinated molecular motion pon
synthesis of a new polymer, the glass transition temperature is among the first
properties measured. the glass transition temperature itself varies widely with
structure and other parameters the following are the major factors affecting glass
transition temperature
a. Chain Flexibility: Chain flexibility is determined by the ease with which rotation
occurs about primary valence bonds.Polymers with low hindrance to internal
rotation have low Tg values.Long-chain aliphatic groups —ether and ester
68 | P a g e
 linkages — enhance chain flexibility, while Rigid groups like cyclic structures
stiffen the backbone.Bulky side groups that are stiff and close to the backbone
cause steric hindrance, decrease chain mobility, and hence raise Tg.The
influence of the side group in enhancing chain stiffness depends on the
flexibility of the group and not its size. In fact, side groups that are fairly flexible
have little effect within each series; instead polymer chains are forced further
apart. This increases the free volume, and consequently Tg drops.
b. Inter-chain Attractive Forces: It is to be expected that the presence of strong
intermolecular bonds in a polymer chain, i.e., a high value of cohesive energy
density, will significantly increase Tg.
c. Cross-Linking and Branching: By definition, cross-linking involves the
formation intermolecular connections through chemical bonds.This process
necessarily results in reduction in chain mobility. Consequently, Tg increases.
For lightly cross-linked systems like vulcanized rubber, Tg shows a moderate
increase over the uncross-linked polymer.In this case, Tg and the degree of
cross-linking have a linear dependence, as shown by the following approximate
empirical equation:

 where Tg = the glass transition temperature of the uncross-linked polymer

having the same chemical composition as the cross-linked polymer
 Mc = the number-average molecular weight between cross-linked points
d. Like long and flexible side chains, branching increases the separation between
chains, enhances the free volume, and therefore decreases Tg.

4.2.1. The crystalline melting point

The crystalline plateau extends until the melting point of the polymer. The melting
temperature, Tf, is always higher than Tg, Tg being from one-half to two-thirds of Tf
on the absolute temperature scale. Melting involves a change from the crystalline
solid state into the liquid form for low-molecular-weight (simple) materials. This
concept has been extended to melting in crystalline polymeric systems, however,in
the case of crystalline polymers:The macromolecular nature of polymers and the
existence of molecular weight distribution (PDI) lead to a broadening of Tm.The
process of crystallization in polymers involves chain folding. This creates inherent
defects in the resulting crystal. Consequently, the actual melting point is lower than
the ideal thermodynamic melting point.Because of the macromolecular nature of
polymers and the conformational changes associated with melting, the process of
melting in polymer is more rate sensitive than that in simple molecules.No polymer
is 100% crystalline. The use of polymers in many practical applications is often
limited by their relatively low melting temperatures. Because of this there has been
considerable interest in determining the factors which control the value of Tm and in
synthesizing polymers which have high melting temperatures.For a particular type of
polymer the value of Tm depends upon the molar mass and degree of chain
69 | P a g e
branching. This is because there is a higher proportion of chain ends in low-molar-
mass polymers and the branches in non-linear polymers both have the effect of
introducing defects into the crystals and so lower their Tm. If the molar mass of the
polymer is sufficiently high that the polymer has useful mechanical properties the
effect of varying M upon Tm is not strong. In contrast, the presence of branches in a
high-molar-mass sample of polyethylene can reduce Tm by 30°C.

The following are the major factors affecting the crystalline melting point, tm
a. Chain Flexibility:Polymers with rigid chains would be expected to have
higher melting points than those with flexible molecules.This is because, on
melting, polymers with stiff backbones have lower conformational entropy
changes than those with flexible backbones.As we saw earlier, chain
flexibility is enhanced by the presence of such groups as –O– and –(CO·O)–
and by increasing the length of (–CH2–) units in the main chain. Insertion of
polar groups and rings restricts the rotation of the backbone and
consequently reduces conformational changes of the backbone,
b. Intermolecular Bonding: The cohesive forces in polymers involve the
secondary bonding forces ranging from the weak van der Waals forces
through the much stronger hydrogen bonds. In some cases, these forces even
include primary ionic bonds.The decrease in the cohesive energy density
associated with the decrease in the density of sites for intermolecular
bonding (increased space between polar groups) leads to a reduction in the
melting points.
c. Chain ends and branches can be thought of as impurities which depress the
melting points of polymer crystals.

The following tables summarises the Approximate equilibrium melting points of some
common polymers

70 | P a g e
71 | P a g e
Chapter four : Multiple choice Questions
1. Pick out the correct statement
a. All polymers are highly crystalline
b. Amorphous polymers are denser than crystalline polymers
c. Atactic polymers will generally be amorphous, soft, flexible materials,
low melting and easily soluble.
d. Isoatactic PP is a low melting, gooey material

2. If a polymer is amorphous the transition from the hard and brittle glass into a
softer, rubbery state occurs over a narrow temperature range referred to as
a. crystalline melting point, Tm
b. glass transition temperature, Tg
c. transition temperature
d. none
3. more crystalline polymer shows all properties except
a. higher density
b. stronger and less flexible it becomes
c. higher resistance to dissolution and softening by heating
d. none
4. Identify the correct order for amorphous phases of polymeric material with a
characteristic five regions of viscoelastic behaviour

5. Thermal characteristics (Tg and Tm) of a polymer increase with

a. Chain stiffness (Double bonds and aromatic groups) and Bulky side
groups
b. Polar side groups
c. Increased linearity
d. Longer chains
e. All
6. At a characteristic temperature, Tg, what will happen to the polymer
a. There is an abrupt change in physical behavior from a hard, brittle, glassy
solid below Tg to a soft, rubbery material above Tg.
b. there is a change in the slope of the volume–temperature curve from a
lower to a higher volume coefficient of expansion
c. the rate of volume expansion decreases suddenly to a higher constant
level
d. all except C

72 | P a g e
7. Which of the following is NOT a type of isomerism found in polymers?
a) Stereoisomerism
b) Geometric isomerism
c) Configurational isomerism
d) Magical isomerism

8. Which of the following is a major transition occurring in polymer molecules?

a) Glass transition
b) Melting transition
c) Crystallization transition
d) All of the above
9. What is the term used to describe the ordered structure of polymer molecules in
solid polymer materials?
a) Polymer crystallinity
b) Polymer isomerism
c) Polymer transition
d) Polymer chaos
10. Which of the following factors do NOT affect the glass transition temperature
(Tg) of polymers?
a) Molecular weight
b) Flexibility of the polymer chain
c) Presence of plasticizers
d) Color of the polymer
11. Configuration isomerism in polymers is due to:
a) Different spatial arrangements of atoms or groups in a polymer chain
b) The presence of double bonds in polymer chains
c) The difference in rotation around single or double bonds in a polymer chain
d) None of the above
12. In a semi-crystalline polymer, what percentage of the polymer chains are in the
crystalline region?
a) 100%
b) 50% – 95%
c) 0% – 100%
d) 0% – 50%
73 | P a g e
13. What is the main factor affecting the polymer's melting temperature?
a) Chain flexibility
b) Temperature
c) Pressure
d) Presence of plasticizers
14. In stereoisomerism, the two types of configurations that can occur are:
a) Isotactic and syndiotactic
b) Syndiotactic and atactic
c) Isotactic and atactic
d) Geometric and conformational

15. Which of the following refers to isomerism in polymers?

a) Different monomers combining to form the same polymer
b) Same monomers combining to form different polymers
c) Formation of polymers in different shapes and structures
d) Formation of polymers from different isomers of a monomer
16. What is the glass transition temperature (Tg) in a polymer?
a) Temperature at which a polymer changes from a glassy to a rubbery state
b) Temperature at which a polymer starts to degrade
c) Temperature at which a polymer begins to soften and melt
d) Temperature at which a polymer undergoes crystallization
17. Which of the following has a significant effect on the glass transition
temperature (Tg) of a polymer?
a) Molecular weight
b) Monomer structure
c) Chain branching
d) All of the above
18. What is the primary reason for the formation of polymer crystallinity?
a) Regular arrangement of chains due to the presence of double bonds
b) Folding and self-assembly of polymer chains due to attractive forces between chains
c) The presence of cross-links between different polymer chains
d) The crystallization process of the solvent used in the polymer solution

74 | P a g e
19. Which of the following transitions can be observed in a polymer molecule?
a) Glass transition
b) Crystallization
c) Melting
d) All of the above
20. What is the significance of increasing the degree of branching in a polymer?
a) Increases the glass transition temperature (Tg)
b) Decreases the glass transition temperature (Tg)
c) Has no effect on the glass transition temperature (Tg)
d) Results in completely amorphous polymers
21. Which of the following factors can decrease the crystallinity of a polymer?
a) Increasing molecular weight
b) Increasing the degree of branching
c) Reducing chain flexibility
d) Reducing the rate of cooling during solidification
22. The process of generating different stereo structures of a polymer chain using
different geometric placement of functional groups in a monomer is called:
a) Geometric isomerism
b) Diastereoisomerism
c) Configurational isomerism
d) Stereospecific polymerization
23. Which of the following is an example of configurational isomerism in polymers?
a) Atactic and isotactic polymers
b) Cis and trans polymers
c) Linear and branched polymers
d) Polymers with different molecular weights
24. In a polymer, which of the following factors can increase the melting
temperature?
a) Lower molecular weight
b) Greater chain branching
c) Higher degree of crystallinity
d) Higher glass transition temperature (Tg)

75 | P a g e
Chapter Four : Descriptive Questions:
1. How can we determine the shape of polymer?
2. How to explain isomerism in polymer And State the difference between
stereoisomerism and geometrical isomerism?
3. With the help of neat diagrams of the spatial arrangement of polymer, explain the
type of stereoisomerism with reference to polymer structure.
4. Explain briefly the formation of stereoregular polypropylenes in the
polymerization of propylene. What is the role of tacticity on the properties of
polypropylenes.
5. Why the transition in polymer is complex regarding to other small molecules?
6. Explain the physical states of amorphous polymers? What are the characteristics
of these polymers ?
7. What do you understand by term Polymer Crystallinity? How is degree of
crystallinity of a
polymer determined? Show density method for measurement of crystallinity
percentage?
8. Explain the idea of semi-crystalline polymer‖? Show the effect of crystallinity on
the
mechanical properties of a polymer ?
9. Distinguish between amorphous and crystalline polymers with examples?
10. When a polymer is heated does it shows any transition? Draw and label the
transitions.
What will happen the polymer when glass transition temperature increase?
11. What is the effect of molecular weight on glass transition temperature?
12. What is glass transition temperature (Tg)? Discuss various factors influencing
the glass
transition temperature of polymers and comment on Tg of Isotactic and atactic
Polypropylene (PP)?
13. Discuss various factors influencing the crystalline melting point of polymers?

76 | P a g e
Chapter 5

Polymer Properties and Testing

5.1. Properties of Polymers
Relationships between the synthesis and molecular properties of polymers and
between their molecular and bulk properties provide the foundations of Polymer
Science. In order to establish these relationships, and to test theories, it is essential to
accurately and thoroughly characterize the polymers under investigation. Since the
physical and mechanical properties of polymers composed of various mers and their
isomers differ, careful determination of the configuration of each preparation is
made daily in many chemical industries.The physical properties of a polymer, such
as its strength and flexibility depend on Chain length - in general, the longer the
chains the stronger the polymer;Side groups - polar side groups give stronger
attraction between polymer chains, making the polymer stronger;Branching
:straight, un branched chains can pack together more closely than highly branched
chains, giving polymers that are more crystalline and therefore stronger;Cross-
linking if polymer chains are linked together extensively by covalent bonds, the
polymer is harder and more difficult to melt.
5.1.1. Techniques of Polymer Characterization of properties of polymers
The mechanical properties of polymers are highly dependent on temperature and on
the time-scale of any deformation; polymers are viscoelastic and exhibit some of the
properties of both viscous liquids and elastic solids.At low temperatures or high
frequencies a polymer may be glass-like, with a value of Young‘s modulus in the
region 109–1010 Pa, and it will break or yield at strains greater than a few per cent.
At high temperatures or low frequencies it may be rubber-like, with a modulus in the
region 105–106 Pa, and it may withstand large extensions of order 100% or more
with no permanent deformation. Figure 6.1 shows schematically how Young‘s
modulus of a polymer varies with temperature in the simplest case. At still higher
temperatures the polymer may undergo permanent deformation under load and
behave like a highly viscous liquid.In an intermediate temperature range, called the
glass-transition range,the polymer is neither glassy nor rubber-like; it has an
intermediate modulus and has viscoelastic properties. This means that, under
constant load, it undergoes creep, i.e. the shape gradually changes with time,
whereas at constant strain it undergoes stress-relaxation, i.e. the stress required to
maintain the strain at a constant value gradually falls.

At very low molecular weights the tensile stress to break, sb, is near zero. As the
molecular weight increases, the tensile strength increases rapidly, and then gradually
levels off. Since a major point of weakness at the molecular level involves the chain
ends, which do not transmit the covalent bond strength, it is predicted that the tensile
77 | P a g e
strength reaches an asymptotic value at infinite molecular weight. In general, the
longer the polymer chain, the stronger the polymer. There are two reasons longer
chains are more tangled and there are more intermolecular forces between the
chains because there are more points of contact. These forces, however, are quite
weak for polyethene.

Areas in a polymer where the chains are closely packed in a regular way are said to
be crystalline. The percentage of crystallinity in a polymer is very important in
determining its properties. The more crystalline the polymer, the stronger and less
flexible it becomes.When a polymer is stretched (cold-drawn), a neck forms. In the
neck the polymer chains line up producing a more crystalline region. Cold-drawing
leads to an increase in strength.The first polyethene which was made contained
many chains which were branched. This resulted in a relatively disorganized
structure of low strength and density. This was called low density polyethene
(LDPE).In the crystalline form, the methyl groups all have the same orientation
along the chain. This is called the isotactic form. In the amorphous form, the methyl
groups are randomly orientated. This is called the atactic form.Polymers with a
regular structure are said to be stereo-regular.The mechanical properties of polymers
are not single-valued functions of the chemical nature of the macromolecules.They
will vary also with molecular weight, branching, cross-linking, crystallinity, and
other additives, orientation, and other consequences of processing history and
sometimes with the thermal history of the particular sample.

5.1.2. POLYMER VISCOELASTICITY

Visco-elasticity implies that the material has the characteristics both of a viscous
liquid which cannot support a stress without flowing and an elastic solid in which
removal of the imposed stress results in complete recovery of the imposed
deformation.Polymeric solids and liquids are intermediate in behavior between
Hookean, elastic solids, and Newtonian, purely viscous fluids. They often exhibit
elements of both types of response, depending on the time scale of the experiment.
Application of stresses for relatively long times may cause some flow and
permanent deformation in solid polymers while rapid shearing will induce elastic
behavior in some macromolecular liquids. It is also frequently observed that the
value of a measured modulus or viscosity is time dependent and reflects the manner
in which the measuring experiment was performed.These phenomena are examples
of viscoelastic behavior.
Polymers exhibit viscoelastic behavior. The mechanical properties of solid polymers
show marked sensitivity to time compared with traditional materials like metals and
ceramics. Viscoelastic material such as polymers combine the characteristics of both

78 | P a g e
elastic and viscous materials.. They often exhibit elements of both Hookean elastic
solid and pure viscous flow depending on the experimental time scale.Application of
stresses of relatively long duration may cause some flow and irrecoverable
(permanent) deformation, while a rapid shearing will induce elastic response in
some polymeric fluids.Three types of experiments are used in the study of Visco-
elasticity. These involve creep, stress relaxation, and dynamic techniques.
In creep studies a body is subjected to a constant stress and the sample dimensions
are monitored as a function of time.When the polymer is first loaded an immediate
deformation occurs, followed by progressively slower dimensional changes as the
sample creeps towards a limiting shape. The processing of polymers involves

rheological phenomena.

Depending on the region of viscoelastic behavior, the mechanical properties of

polymers differ greatly. Model stress–strain behavior is illustrated in Figure below.
Glassy polymers are stiff and often brittle, breaking after only a few percent
extension. Polymers in the glass transition region are more extensible, sometimes
exhibiting a yield point (the hump in the tough plastic stress–strain curve)

The figure below shows Stress–strain behavior of various polymers. While the initial
slope yields the modulus, the area under the curve provides the energy to fracture.

5.4. Testing Polymer Properties

Three types of experiments are used in the study of Visco-elasticity. These involve
creep, stress relaxation, and dynamic techniques. In creep studies a body is subjected
to a constant stress and the sample dimensions are monitored as a function of
time.When the polymer is first loaded an immediate deformation occurs, followed

79 | P a g e
by progressively slower dimensional changes as the sample creeps towards a
limiting shape.The following are the major mechanical experiments.
5.4.1. STRESS–STRAIN EXPERIMENTS
In stress–strain tests the specimen is deformed (pulled) at a constant rate, and the
stress required for this deformation is measured simultaneously.Polymers exhibit a
wide variation of behavior in stress–strain tests, ranging from hard and brittle to
ductile, including yield and cold drawing. The utility of stress–strain tests for design
with polymeric materials can be greatly enhanced if tests are carried out over a wide
range of temperatures and strain rates. In stress–strain experiments, a polymer
sample is pulled (deformed) at a constant elongation rate, and stress is measured as a
function of time.

In stress–strain experiments, a polymer sample is pulled (deformed) at a constant

elongation rate, and stress is measured as a function of time. Generally the polymer
specimen, which may be rectangular or circular in cross-section, is molded or cut in
the form of a dog bone.It is clamped at both ends and pulled at one of the clamped
ends (usually downward) at constant elongation. The shape of the test specimen is
designed to encourage failure at the thinner middle portion. The central section
between clamps is called the initial gauge length, L0. The load or stress is measured
at the fixed end by means of a load transducer as a function of the elongation, which
is measured by means of mechanical, optical, or electronic strain gauges.The
experimental data are generally stated as engineering (nominal) stress (σ) vs.
engineering (nominal) strain(ε). The engineering stress is defined as:
80 | P a g e
5.4.2. CREEP EXPERIMENTS
In creep tests, a specimen is subjected to a constant load, and the strain is measured
as a function of time. The test specimen in a laboratory setup can be a plastic film or
bar clamped at one end to a rigid support while the load is applied suddenly at the
other end. The elongation may be measured at time intervals using a cathetometer or
a traveling microscope.Measurements may be conducted in an environmental
chamber. Creep data provide important information for selecting a polymer that
must sustain dead loads for long periods. Creep experiments are conducted in the inverse
manner. A constant stress is applied to a sample, and the dimensions are recorded as a function of
time. Of course, these experiments can be generalized to include shear motions, compression, and so
on.

5.4.3. STRESS RELAXATION EXPERIMENTS

Stress relaxation experiments were used to determine the mechanism of degradation
in synthetic polymers during World War II, when these materials were first being
made.In stress relaxation experiments, the specimen is rapidly (ideally,
instantaneously) extended a given amount, and the stress required to maintain this
constant strain is measured as a function of time. The stress that is required to
81 | P a g e
maintain the strain constant decays with time. When this stress is divided by the
constant strain, the resultant ratio is the relaxation modulus (Er(t,T), which is a
function of both time and temperature. Stress relaxation data provide useful
information about the viscoelastic nature of polymers. In this case the strain is held
constant and the stress decays slowly with time whereas in an elastic solid it would
remain constant.

82 | P a g e
Chapter Five : Multiple choice Questions
1. In which case the specimen is rapidly (ideally, instantaneously) extended a given
amount, and the stress required to maintain this constant strain is measured as a
function of time.
a.. stress relaxation experiments c. creep
experiments
b.. stress–strain experiments d. none
2. Identify the incorrect statement about physical properties of a polymer and the
different factors
a. if polymer chains are linked together extensively by covalent bonds, the
polymer is harder and more difficult to melt
b. straight, un branched chains can pack together more closely than highly
branched chains, giving polymers that are more crystalline and therefore
stronger
c. polar side groups give stronger attraction between polymer chains, making
the polymer stronger
d. the longer the chains the stronger the polymer
e. none
3. Based on the graph (a-d) which option best describe the stress-strain behavior of
polymer materials listed as P,Q,R and S

83 | P a g e
4. Which of the following is NOT a mechanical test for polymers?
a) Tensile testing
b) Compression testing
c) Impact testing
d) Ultraviolet testing
5. What is the state of a viscoelastic material when the energy input is at low strain
rates?
a) Brittle
b) Ductile
c) Rubber-like
d) Fluid-like
6. What is the main advantage of using a dynamic mechanical analyzer (DMA) for
characterizing the viscoelastic behavior of polymers?
a) It can measure the stress-strain relationship under a constant strain rate.
b) It can measure viscoelastic behavior in real-world applications.
c) It can measure the hardening rate of the material.
d) It can measure the stress-strain behavior of a thin film.
7. What term is used to define the resistance of a viscoelastic material to
deformation?
a) Stress
b) Strain
c) Elastic modulus
d) Viscosity
8. Which of the following properties does NOT play a significant role in
determining the mechanical performance of a polymer?
a) Molecular weight
b) Degree of polymerization
c) Molecular structure
d) Presence of impurities
9. Which of the following is not a common polymer property?

84 | P a g e
 a) Density
b) Hardness
c) Viscosity
d) Acidity
10. Glass transition temperature (Tg) is a measure of the:
a) Polymer's melting point
b) Temperature at which the polymer becomes brittle
c) Temperature at which the polymer changes from a glassy to a rubbery behavior
d) Maximum usable temperature of a polymer
11. What is the most common method of measuring the molecular weight of a
polymer?
a) Size exclusion chromatography (SEC)
b) Nuclear magnetic resonance (NMR) spectroscopy
c) Mass spectrometry (MS)
d) Ultraviolet-visible (UV-Vis) spectroscopy
12. Viscoelasticity is the property of a material that exhibits both:
a) Viscosity and elasticity
b) Strength and flexibility
c) Hardness and toughness
d) Ductility and brittleness
13. Which of the following tests is commonly used to measure the viscoelastic
behavior of the polymers?
a) Creep testing
b) Tensile testing
c) Compression testing
d) Hardness testing
14. Which mechanical test is used to measure a material's resistance to permanent
indentation or penetration by another material?
a) Tensile test
b) Hardness test
c) Compression test
d) Fatigue test

85 | P a g e
15. In a tensile test, the elongation at break of a polymer specimen is reported as
a) Fraction of the original length
b) Percentage of the original length
c) Change in length
d) Ratio of the final length to the original length

Chapter Five : Descriptive Questions:

1. Explain the reasons why longer polymers have higher strength?
2. Why do polymers have different physical properties?
3. How the structures of polymers affect their physical properties?
4. What is the role of branching and chain length on the properties of polymer?
5. Explain How to study visco-elasticity behavior of a polymer?
6. Explain the fundamentals of polymer melt rheology!What kind of rheology
models describe the relation between shear stress and the shear rate?

86 | P a g e
References
1. L. H. Sperling: Introduction to Physical Polymer Science, John Wiley & Sons,
Inc., 2006.
2. D. I. Bower: An Introduction to Polymer Physics, Cambridge, 2002.
3. 3. R.J. Young, and Lovell, P.A., Introduction to Polymers, Second Edition,
Chapman and Hall Pub. Co., New York, ISBN 0-412-30630-1 (1991).

87 | P a g e